CN109521146A - A kind of measuring method of the method and ester group equivalent that avoid carbon dioxide to interfere in ester hydrolysis reaction - Google Patents
A kind of measuring method of the method and ester group equivalent that avoid carbon dioxide to interfere in ester hydrolysis reaction Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 48
- 238000010931 ester hydrolysis Methods 0.000 title claims abstract description 34
- 125000004185 ester group Chemical group 0.000 title claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001868 water Inorganic materials 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- -1 ester compounds Chemical class 0.000 claims abstract description 16
- 238000005259 measurement Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- 238000009835 boiling Methods 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 208000011580 syndromic disease Diseases 0.000 claims description 4
- 230000002452 interceptive effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 14
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 18
- 230000007062 hydrolysis Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FHESUNXRPBHDQM-UHFFFAOYSA-N diphenyl benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OC=2C=CC=CC=2)=CC=1C(=O)OC1=CC=CC=C1 FHESUNXRPBHDQM-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QYAIYPDHHRBYRW-UHFFFAOYSA-N nitric acid;propan-2-ol Chemical compound CC(C)O.O[N+]([O-])=O QYAIYPDHHRBYRW-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 206010049244 Ankyloglossia congenital Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention provides a kind of method for avoiding carbon dioxide to interfere in ester hydrolysis reaction and the measuring methods of ester group equivalent, described method includes following steps: (1) mixing alkaline aqueous solution with ester compounds, then organic reagent is added, so that organic reagent is formed organic reagent membrane on alkaline aqueous solution surface, carries out ester hydrolysis reaction；Wherein, the density of the density ratio water of the organic reagent is small, and the organic reagent and water are immiscible, meanwhile, the organic reagent does not chemically react during ester hydrolysis reaction.In the present invention, using smaller than water density and form organic reagent membrane on aqueous solution surface with the immiscible organic reagent of water, therefore it can be contacted to avoid air with hydrolyzate, consumption so as to avoid the carbon dioxide in air to hydroxide, also carbon dioxide can be avoided to react with hydroxide and generate carbonate impurities, therefore the accuracy that the measurement of ester compounds ester group content can be significantly improved, avoids the generation of side reaction in hydrolytic process.
Description
Technical field
The invention belongs to the technical field of ester hydrolysis control and application, it is related to avoiding carbon dioxide in a kind of ester hydrolysis reaction
The method of interference and the measuring method of ester group equivalent.
Background technique
Ester hydrolysis reaction has extensive industrial application, such as can produce isopropanol, ethylene glycol etc. by ester hydrolysis.Separately
Outside, it is reacted by ester hydrolysis, it can also be used to the measurement of fat saponification value.
In the industrial production, mostly reaction is hydrolyzed in (sodium hydroxide/potassium hydroxide) to ester under alkaline condition.But water
It solves in reaction process, sodium hydroxide, potassium hydroxide are easy to be influenced by Carbon Dioxide in Air, and side reaction (such as reaction equation I occurs
Sodium carbonate or potassium carbonate impurity are generated with reaction equation II), on the one hand leads to the meaningless loss of hydroxide, on the other hand also donor
Frenulum enters new impurity.
Reaction equation I:NaOH+CO2→Na2CO3+H2O；
Reaction equation II:KOH+CO2→K2CO3+H2O。
Standard GB/T/T 5534-2008 " measurement of animal and plant fat saponification number " at present, the principle of measurement is: returning
Sample and potassium hydroxide-ethanol solution are boiled together under the conditions of stream, then with the hydrogen-oxygen of the hydrochloric acid solution overtitration of calibration
Change potassium.In GB/T 5534-2008, do not take measures to avoid in hydrolytic process NaOH or KOH by Carbon Dioxide in Air
Consumption.But the carbon dioxide-depleted part potassium hydroxide in air, large error can be brought to measurement result.Below with experiment
It is illustrated:
It is cooled to after pure water (pure water refers to that deionized water is cooled to room temperature after boiling, similarly hereinafter) is heated to boiling
Room temperature prepares the aqueous solution of KOH, and concentration is about 1.0mol/L, stirs evenly.Take same volume KOH solution, in two kinds of situation into
After row processing, titrated with the ethanol solution hydrochloride that concentration is about 1.0mol/L.
A: pipetting the aqueous solution of 5mL KOH with liquid-transfering gun, and the acidic alcohol for being about at once then 1.0mol/L with concentration is molten
Liquid is titrated.
The reaction condition of B:(ester hydrolysis) it is taken in the aqueous solution addition boiling flask of 5mL KOH with liquid-transfering gun, slowly it is put into
Boiling object is helped, condensation reflux unit is accessed, boiling is heated to and is kept for one hour；Use pure water 10mL from condenser pipe after being cooled to room temperature
Top is rinsed obtain mixed solution down, titration.
Same volume KOH solution consumes hydrochloric acid solution volume under the conditions of different disposal and is shown in Table 1:
Table 1
| Condition | Consume hydrochloric acid solution volume/mL |
| A | 5.103 |
| B | 4.745 |
| (A-B)/A | 7.01% |
As a result illustrate, KOH solution during heating, touches air, can lead to potassium hydroxide because of carbon dioxide
Consumption.
Active ester is in CCL (copper-clad plate) using in the ascendant.Select polyfunctional group active ester can as curing accelerator
Free hydroxyl is formed when solidifying to avoid epoxy resin, to efficiently reduce the water imbibition of solidified resin.Moreover, multiple
CCL producer is proposed the performance requirement of the copper-clad plate product reply antenna substrate material of Modified Products By Modification of Active Esters And Epoxy Resin, and obtains
Preferable market effect.Modified Products By Modification of Active Esters And Epoxy Resin, active ester groups (- C=O-O-) are reacted with epoxy group 1:1, the two it is anti-
Answer formula III as follows,
Therefore, Accurate Determining active ester groups content suffers from design and the raw material quality control of glue formula significant
Meaning.
CN106966863 discloses a kind of method of hydrolysis process nitric acid isopropanol, i.e., by nitric acid isopropanol and hydroxide
The aqueous solution of sodium or potassium hydroxide is fitted into autoclave, is warming up to 140-160 DEG C, pressure control is anti-at 0.8-1.8MPa
Answer 20-40min.Although isopropanol is successfully prepared, it does not mention how avoiding Carbon Dioxide in Air to hydrogen
The problem of oxide influences.
When avoiding the problem that carbon dioxide or water etc. interfere reaction system, the method generallyd use is control reactant
System is vacuum condition or to be passed through inert gas in the reaction system, under the higher reaction environment of vacuum degree, the boiling point of water compared with
It is low, being not easily controlled for reaction change, and the reaction condition of control vacuum degree realization side during large-scale industrial production can be made
Method is more complex, will increase manpower and material resources cost, and the method for a straight-through inert gas is also difficult to extensive in the reaction system
Using being used in production.
It is convenient and simple therefore, it is necessary to develop a kind of new method for avoiding carbon dioxide interference ester hydrolysis, it is easily controllable,
And then further increase the accuracy of measurement ester compounds ester group equivalent.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for avoiding carbon dioxide to interfere in ester hydrolysis reaction and ester group to work as
The measuring method of amount, the measuring method of ester group equivalent provided by the invention effectively prevent ester compounds and hydrolyze under alkaline condition
When, side reaction problem occurs for hydroxide and Carbon Dioxide in Air；The measuring method of ester group equivalent provided by the invention is available
In production control, experimental analysis etc., it is remarkably improved the accuracy of ester compounds ester group determination of equivalent.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of method for avoiding carbon dioxide to interfere in ester hydrolysis reaction, the method
Include the following steps:
(1) alkaline aqueous solution is mixed with ester compounds, organic reagent is then added, make organic reagent in alkaline aqueous solution
Surface forms organic reagent membrane, carries out ester hydrolysis reaction；
Wherein, the density of the density ratio water of the organic reagent is small, and the organic reagent and water are immiscible, meanwhile, institute
Organic reagent is stated not chemically react during ester hydrolysis reaction.
In the present invention, using smaller than water density and formed on aqueous solution surface with the immiscible organic reagent of water organic
Reagent membrane, therefore can be contacted to avoid air with hydrolyzate, disappear so as to avoid the carbon dioxide in air to hydroxide
Consumption can also avoid carbon dioxide from reacting with hydroxide and generate carbonate impurities, therefore can significantly improve ester compounds ester group
The accuracy of assay, and can be to avoid the generation of side reaction in hydrolytic process.
Meanwhile present invention employs water as solvent that reaction is hydrolyzed, and avoids and uses methanol or ethyl alcohol as solvent,
More economically, environmentally friendly；Hydrolysis time is shorter, and hydrolysis is more thorough, this is because ester hydrolyzes under the action of hydroxide, generation
Carboxylate is substantially insoluble in alcohol, and has good dissolubility in water, and product dissolves in water can promote hydrolysis
Forward direction it is mobile, and then be conducive to improve hydrolysis efficiency, keep hydrolysis more thorough.
Preferably, the organic reagent in ethylo benzene, butyl benzene, toluene or dimethylbenzene any one or at least two
The combination of kind.
Preferably, alkaline reagent used in the alkaline aqueous solution includes sodium hydroxide and/or potassium hydroxide.
Preferably, in alkaline aqueous solution, the concentration of the alkaline reagent is 0.1mol/L or more, such as 0.2mol/L,
0.3mol/L, 0.5mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.2mol/L, 1.5mol/L etc..
In the present invention, it as long as ensuring that the additive amount of alkaline reagent can make ester hydrolysis completely, is specifically testing
When ester group equivalent, even if not knowing the theoretical ester group equivalent of ester compounds, but ester output may infer that by the structure of ester compounds
The probable ranges of base equivalent make hydrolysis of ester group completely as long as guaranteeing that the additive amount of alkaline reagent is greater than this range.
Preferably, the ester hydrolysis reaction carries out under stirring conditions.
Preferably, the rate of the stirring is 50-100r/min, such as 60r/min, 70r/min, 80r/min, 90r/
Min etc..
Preferably, the condition of the ester hydrolysis reaction is that reaction system is heated to boiling reflux state and keeps 20-
40min, such as 25min, 30min, 35min etc..
As optimal technical scheme, described method includes following steps:
(1) alkaline aqueous solution that the concentration of alkaline reagent is 0.1mol/L or more is mixed with ester compounds, is then added
Organic reagent makes organic reagent form organic reagent membrane on alkaline aqueous solution surface, will under the stirring rate of 50-100r/min
Reaction system is heated to boiling reflux state and keeps 20-40min, carries out ester hydrolysis reaction；
Wherein, the density of the density ratio water of the organic reagent is small, and the organic reagent and water are immiscible, meanwhile, institute
Organic reagent is stated not chemically react during ester hydrolysis reaction.
Second aspect, the present invention provides a kind of measuring methods of ester group equivalent, utilize ester water as described in relation to the first aspect
The method for avoiding carbon dioxide from interfering in solution reaction carries out the measurement of ester group equivalent.
The measuring method that ester group equivalent is carried out using the method for the ester hydrolysis of first aspect offer, can be to avoid titanium dioxide
Consumption of the carbon to hydroxide, and then the accuracy of ester group determination of equivalent can be improved.
Preferably, the measuring method includes the following steps:
(A) alkaline aqueous solution is mixed with ester compounds, organic reagent is then added, make organic reagent in alkaline aqueous solution
Surface forms organic reagent membrane, carries out ester hydrolysis reaction；
(B) solution system for completing ester hydrolysis reaction is titrated using ethanol solution hydrochloride, the acidic alcohol of consumption
Liquor capacity is denoted as V1, mL；
(C) ester compounds are added without, successively carry out blank test by step (A), (B), the acidic alcohol for recording consumption is molten
The volume of liquid is V0, mL；
(D) it is calculated by Formulas I, obtains ester group equivalent；
A=1000m/ [(V0-V1)×c]；
Formulas I；
Wherein, the ester group equivalent of A- ester compounds, g/mol；The quality of m- ester compounds, g；Institute in c- ethanol solution hydrochloride
Substance withdrawl syndrome containing HCl, mol/L.
Carbon Dioxide in Air can be reduced or avoided to hydroxide in the measuring method of ester group equivalent provided by the invention
Consumption, with experiments have shown that as follows:
The aqueous solution of KOH is prepared, concentration is about 1.0mol/L, is stirred evenly.Take same volume KOH solution, point or less three
After kind situation is handled, titrated with the ethanol solution hydrochloride that concentration is about 1.0mol/L.
A0: pipetting 5mL with liquid-transfering gun, is then titrated at once with ethanol solution hydrochloride.
B1: it takes the aqueous solution of 5mL KOH to be added in boiling flask with liquid-transfering gun, is carefully added into and helps boiling object, access is condensed back to
Device is flowed, boiling is heated to and keeps 30min；It is titrated after being cooled to room temperature.
B2: it is added in boiling flask with the aqueous solution that liquid-transfering gun pipettes 5mL KOH, is carefully added into and helps boiling object, toluene is added
0.5mL accesses condensation reflux unit, is heated to boiling and keeps 30min；It is titrated after being cooled to room temperature.
2 are shown in Table to the titration results of three of the above disposition:
Table 2
| Condition | Consume hydrochloric acid solution volume, mL |
| A0 | 5.105 |
| B1 | 4.752 |
| B2 | 5.102 |
It is almost the same using consumption of the A0 and B2 condition to hydrochloric acid solution volume, but the hydrochloric acid solution volume of B1 consumption is bright
It is aobvious to tail off, illustrate KOH solution during heating, ingress of air can lead to the consumption of potassium hydroxide because of carbon dioxide；And
After toluene is added, because there is toluene air-isolation in solution top layer, during heating, carbon dioxide can not be with hydrogen for KOH solution
Nak response is aoxidized, and then avoids consumption of the carbon dioxide to hydroxide.
Compared with the existing technology, the invention has the following advantages:
(1) in the present invention, using smaller than water density and formed with the immiscible organic reagent of water on aqueous solution surface
Organic reagent film, therefore can be contacted to avoid air with hydrolyzate, so as to avoid the carbon dioxide in air to hydroxide
Consumption, can also avoid carbon dioxide and hydroxide can generate carbonate impurities, therefore ester compounds ester can be significantly improved
The accuracy of base assay.
(2) present invention employs water as solvent is hydrolyzed reaction, avoids and uses methanol or ethyl alcohol as solvent, more
Add economic, environmental protection；Hydrolysis time is shorter, and hydrolysis is more thorough, this is because ester hydrolyzes under the action of hydroxide, the carboxylic of generation
Hydrochlorate is substantially insoluble in alcohol, and has good dissolubility in water, and product dissolves in water can promote hydrolysis
Forward direction is mobile, and then is conducive to improve hydrolysis efficiency, keeps hydrolysis more thorough.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of measuring method of active ester (Japanese DIC production, HPC-8000) ester group equivalent is as follows:
(1) sodium hydrate aqueous solution that compound concentration is about 1.0mol/L；The active ester sample learnt from else's experience after being dried is about
0.20-0.80g, correct amount simultaneously record weight, are accurate to after decimal point four, unit g；Flat burning is added in active ester sample
In bottle, it is slowly put into electromagnetic agitation, 5 milliliters of NaOH aqueous solutions is pipetted with liquid-transfering gun and is added in flask, it is then pure in addition
Toluene 0.5mL is added in water 30mL.Then boiling flask is accessed into condensation reflux unit, starting is heated, and is added under electromagnetic agitation state
Heat is extremely boiled, and stops heating after keeping boiling reflux 20min.
(2) it after being cooled to room temperature, rinses condensation down at the top of condenser pipe with about 20mL pure water and is in control clear
Mixed solution, it is to be titrated；It is titrated using ethanol solution hydrochloride as titer, consumption volume is V1Milliliter.
(3) ester compounds are added without, successively carry out blank test by step (1), (2), the acidic alcohol for recording consumption is molten
The volume of liquid is V0, mL；
(4) it is calculated by Formulas I, obtains ester group equivalent；
A=1000m/ [(V0-V1)×c]；
Formulas I；
Wherein, the ester group equivalent of A- ester compounds, g/mol；The quality of m- ester compounds, g；Institute in c- ethanol solution hydrochloride
Substance withdrawl syndrome containing HCl, mol/L.
It is tested twice in parallel, the results are shown in Table 3.
Comparative example 1
It is tested by the operating method of embodiment 1, the difference with embodiment 1 is only that, is added without toluene.
It is tested twice in parallel, the results are shown in Table 3.
3 are shown in Table to the test and calculated result of embodiment 1 and comparative example 1:
Table 3
By the comparison of embodiment 1 and comparative example 1 it is found that after adding organic reagent, the ester group equivalent result that finally measures
It is more stable.
Embodiment 2
A kind of measuring method of the ester group equivalent of diphenyl iso-phthalate is as follows:
(1) sodium hydrate aqueous solution that compound concentration is about 1.0mol/L；The M-phthalic acid two learnt from else's experience after being dried
Phenyl ester sample about 0.25-0.30g, correct amount simultaneously record weight, are accurate to after decimal point four, unit g；Sample is added flat
In the flask of bottom, it is slowly put into electromagnetic agitation, 5mL NaOH aqueous solution is pipetted with liquid-transfering gun and is added in flask, it is then pure in addition
Toluene 0.5mL is added in water purification 30mL.Then boiling flask is accessed into condensation reflux unit, starting is heated, under electromagnetic agitation state
It is heated to boiling, and stops heating after keeping boiling reflux 30min.
(2) it after being cooled to room temperature, rinses condensation down at the top of condenser pipe with about 20mL pure water and is in control clear
Mixed solution, it is to be titrated；It is titrated using ethanol solution hydrochloride as titer, consumption volume is V1Milliliter.
(3) ester compounds are added without, successively carry out blank test by step (1), (2), the acidic alcohol for recording consumption is molten
The volume of liquid is V0, mL；
(4) it is calculated by Formulas I, obtains ester group equivalent；
A=1000m/ [(V0-V1)×c]；
Formulas I；
Wherein, the ester group equivalent of A- ester compounds, g/mol；The quality of m- ester compounds, g；Institute in c- ethanol solution hydrochloride
Substance withdrawl syndrome containing HCl, mol/L.
It is tested twice in parallel, the results are shown in Table 4.
Comparative example 2
It is tested by the operating method of embodiment 2, the difference with embodiment 2 is only that, is added without toluene.
It is tested twice in parallel, the results are shown in Table 4.
4 are shown in Table to the test and calculated result of embodiment 2 and comparative example 2:
Table 4
The relative molecular weight of diphenyl iso-phthalate is 318.32, and theoretical ester group equivalent is 159.16g/mol, by reality
The comparison of example 2 and comparative example 2 is applied it is found that while accuracy higher using the data stability of measuring method measurement of the invention
It is higher.
Embodiment 3
Difference with embodiment 2 is only that, in the present embodiment, toluene is replaced with dimethylbenzene (about containing meta-xylene
40%, ortho-xylene about 20%, paraxylene about 20%, ethylo benzene is about 20%).
It is tested twice in parallel, the results are shown in Table 5.
Comparative example 3
It is tested by the operating method of embodiment 3, the difference with embodiment 3 is only that, is added without dimethylbenzene.
It is tested twice in parallel, the results are shown in Table 5.
5 are shown in Table to the test and calculated result of embodiment 3 and comparative example 3:
Table 5
The relative molecular weight of diphenyl iso-phthalate is 318.32, and theoretical ester group equivalent is 159.16g/mol, by reality
The comparison of example 3 and comparative example 3 is applied it is found that while accuracy higher using the data stability of measuring method measurement of the invention
It is higher.
The Applicant declares that avoiding carbon dioxide in the present invention is explained by the above embodiments ester hydrolysis reaction of the invention
The method of interference and the measuring method of ester group equivalent, but the invention is not limited to above-mentioned method detaileds, that is, do not mean that this
Invention, which must rely on above-mentioned method detailed, to be implemented.It should be clear to those skilled in the art, appoints to of the invention
What is improved, addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all falls within this
Within the protection scope and the open scope of invention.
Claims (10)
1. a kind of method for avoiding carbon dioxide to interfere in ester hydrolysis reaction, which is characterized in that described method includes following steps:
(1) alkaline aqueous solution is mixed with ester compounds, organic reagent is then added, make organic reagent on alkaline aqueous solution surface
Organic reagent membrane is formed, ester hydrolysis reaction is carried out；
Wherein, the density of the density ratio water of the organic reagent is small, and the organic reagent and water are immiscible, meanwhile, it is described to have
Machine reagent does not chemically react during ester hydrolysis reaction.
2. the method according to claim 1, wherein the organic reagent be selected from ethylo benzene, butyl benzene, toluene or
In dimethylbenzene any one or at least two combination.
3. method according to claim 1 or 2, which is characterized in that alkaline reagent used in the alkaline aqueous solution includes
Sodium hydroxide and/or potassium hydroxide.
4. method described in any one of -3 according to claim 1, which is characterized in that in alkaline aqueous solution, the alkalinity
The concentration of reagent is 0.1mol/L or more.
5. method described in any one of -4 according to claim 1, which is characterized in that item of the ester hydrolysis reaction in stirring
It is carried out under part.
6. according to the method described in claim 5, it is characterized in that, the rate of the stirring is 50-100r/min.
7. method described in any one of -6 according to claim 1, which is characterized in that the condition of the ester hydrolysis reaction is will
Reaction system is heated to boiling reflux state and keeps 20-40min.
8. method described in any one of -7 according to claim 1, which is characterized in that described method includes following steps:
(1) alkaline aqueous solution that the concentration of alkaline reagent is 0.1mol/L or more is mixed with ester compounds, is then added organic
Reagent makes organic reagent form organic reagent membrane on alkaline aqueous solution surface, will reaction under the stirring rate of 50-100r/min
System is heated to boiling reflux state and keeps 20-40min, carries out ester hydrolysis reaction；
Wherein, the density of the density ratio water of the organic reagent is small, and the organic reagent and water are immiscible, meanwhile, it is described to have
Machine reagent does not chemically react during ester hydrolysis reaction.
9. a kind of measuring method of ester group equivalent, which is characterized in that utilize the ester water as described in any one of claim 1-8
The method for avoiding carbon dioxide from interfering in solution reaction carries out the measurement of ester group equivalent.
10. measuring method according to claim 9, which is characterized in that the measuring method includes the following steps:
(A) alkaline aqueous solution is mixed with ester compounds, organic reagent is then added, make organic reagent on alkaline aqueous solution surface
Organic reagent membrane is formed, ester hydrolysis reaction is carried out；
(B) solution system for completing ester hydrolysis reaction is titrated using ethanol solution hydrochloride, the ethanol solution hydrochloride of consumption
Volume is denoted as V1, mL；
(C) ester compounds are added without, successively blank test is carried out by step (A), (B), records the ethanol solution hydrochloride of consumption
Volume is V0, mL；
(D) it is calculated by Formulas I, obtains ester group equivalent；
A=1000m/ [(V0-V1)×c]；
Formulas I；
Wherein, the ester group equivalent of A- ester compounds, g/mol；The quality of m- ester compounds, g；It is contained in c- ethanol solution hydrochloride
HCl substance withdrawl syndrome, mol/L.
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| CN101511963A (en) * | 2006-08-04 | 2009-08-19 | 奥特梅特诺米尼斯有限公司 | Protective surface film for a liquid |
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