CN102087233B - Method for characterizing progress and conversion rate of chemical reaction - Google Patents
Method for characterizing progress and conversion rate of chemical reaction Download PDFInfo
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- CN102087233B CN102087233B CN 200910200010 CN200910200010A CN102087233B CN 102087233 B CN102087233 B CN 102087233B CN 200910200010 CN200910200010 CN 200910200010 CN 200910200010 A CN200910200010 A CN 200910200010A CN 102087233 B CN102087233 B CN 102087233B
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Abstract
The invention belongs to the technical field of chemical industry control and detection and relates to a method for characterizing progress and conversion rate of a chemical reaction, in particular a solid-phase reaction. The method comprises the following steps of: measuring melting curves of reaction mixtures in different reaction stages by utilizing a thermal analysis method; and determining the progress and the conversion rate of the reaction by comparing a melting peak of a certain reactant or the change of a melting peak area of the product. The method is easy and convenient to operate and intuitive in result, can be used for characterizing the progress of the reaction, particularly the solid-phase reaction, the optimizing reaction conditions, and the like, and can be widely applied to the fields of fine chemical engineering and the like.
Description
Technical field
The invention belongs to chemical industry control and detection technique field, be specifically related to a kind of characterize chemical reaction particularly solid phase reaction carry out the method for degree and conversion ratio.The invention reside in and utilize heat analysis method, measure the melting curve of differential responses reaction mixture during the stage, the variation of melting peak or product melting peak area by more a certain reactant, that determines to react carries out degree and conversion ratio.
Background technology
Measure degree and conversion ratio that chemical reaction carries out quickly and accurately, for the industrial condition of determining, optimizing chemical reaction, formulate rational technology and have meaning.Traditional chemical reaction carries out in solution or gas phase often, adopt method assaying reaction processes such as spectrum and chromatogram according to architectural feature, as online Fourier transform infrared technology, but on-line monitoring reaction system, the mensuration process does not have destructiveness, be conducive to find intermediate and research dynamics, use obtaining aspect the detection reaction process widely, disturb big, poor signal to noise and spectrogram complexity, be difficult for shortcoming such as analysis but the traditional detection means also face solvent simultaneously.
In addition, the normal solid phase reaction of using in the present chemosynthesis, because solid phase reaction is not used solvent, have advantages such as high selectivity, high yield, course of reaction be simple, at some special solid-phase reaction systems, can judge the solid phase reaction process according to the phenomenons such as release of change in color, gas, but in most of solid phase reaction processes, can't directly observe these phenomenons.Reported in literature is arranged, measure the solid phase reaction process with methods such as X-ray diffraction (XRD), mass spectrum (MS), spectral component analysers, but shortcomings such as applicable surface is narrow, interpretation of result complexity that those methods face equally, make the solid phase reaction degree be difficult to monitor in real time, limited the optimization of reaction conditions and technology.Therefore, development a kind of characterize simply and easily chemical reaction particularly solid phase reaction carry out degree methods and seem particularly necessary.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method that chemical reaction carries out degree and conversion ratio that characterizes is provided.Relate in particular to a kind of method of utilizing the extent of reaction and conversion ratio in the heat analysis method fast detecting solid state reaction.
Studies show that the generation of chemical reaction originates in the diffusion contact of two reactant molecules usually, and chemical action takes place, and generates the product molecule.The product molecule that generate this moment is dispersed in the reaction system, and just the dispersion as a kind of impurity or defective exists.In solid phase reaction, when product molecule aggregation arrives some levels size, the nucleus of product can appear, thus the nucleation process of finishing.Nucleus is long to certain final independent crystalline phase that forms product in size back.Simultaneously, solid phase reaction is in case generation can be carried out fully, and there is not intermediate in no chemical equilibrium in the system.The reactant of solid phase reaction or form the product of independent crystalline phase can melt in heating or cooling procedure, solidifies, physicochemical change such as crystal transfer, decomposition.These variations are attended by the change of system enthalpy, thereby produce thermal effect.Differential scanning calorimetry (DSC) can effectively record the thermal effect in these processes, and shows with the form at neither endothermic nor exothermic peak.
The inventive method is utilized the extent of reaction and conversion ratio in the heat analysis method fast detecting chemical reaction, it comprises: the fusion or the crystallization curve that adopt differential scanning calorimetry (DSC) record differential responses reaction mixture during the stage, by the relatively variation of reactant or product melting peak area, simply and intuitively determine the degree of carrying out of reaction.
Among the present invention, it is the material with fusion or crystallization behavior that described chemical reaction refers to have at least in reactant or the product a kind of, namely exists to have the material that phase transformation takes place in heating or cooling procedure.
Among the present invention, described chemical reaction is solid phase reaction.
Among the present invention, if reactant is crystallizable material, then can by the corresponding melting peak area of reactant on the DSC curve reduce to characterize reaction carry out degree or transforming degree; If product is crystallizable material, what then can characterize reaction by the increase of the corresponding melting peak area of product on the DSC curve carries out degree or transforming degree; Then, by reactant on each bar curve or product melting peak area, calculate reactant or the relative content of product in reaction system, obtain differential responses during the stage concrete reaction carry out degree; The extent of reaction that determines according to said method, in conjunction with the reaction conditions that each stage adopts, can be for formulating rational technology, the condition of optimizing chemical reaction provides technical guarantee.
The differential scanning calorimetry (DSC) that the present invention adopts is a kind of heat analysis method of classics, have fast, accurately, characteristics such as precision height, can be used for research and development, quality inspection Quality Control and the failure analysis etc. of various types of materials and chemical field.Adopted differential scanning calorimetry analytical reactions process in the inventive method, technology realizes easily, detection time is short, advantages such as having simple, intuitive as a result, be easy to analyze, speed easy and simple to handle, that reaction process is analyzed is fast, both can be used for characterizing the degree of carrying out of reaction, also can be used for the aspect such as preferred of reaction conditions.
Description of drawings
Fig. 1 be reaction system at differential responses stage differential scanning calorimetry (DSC) curve, wherein, G represents to grind, H represents 90 ℃ of heating in vacuum, the numeral time (minute).
Fig. 2 is heptandioic acid (pimelic acid) with calcium stearate (calcium stearate) at differential responses stage differential scanning calorimetry (DSC) curve.
Below further describe the present invention by specific embodiment.
Embodiment
For samarium trichloride (SmCl
37H
2O) with hindered amine part two (2,2,6,6-tetramethyl-4-piperidyl) sebacate (is called for short 770, structure is shown below) carry out solid phase, generate the reaction system of coordination compound, operate as follows: at first adopt abrasive method to promote the carrying out of reaction, grind the potpourri of getting in the 5mg reaction system after 15 minutes and carry out dsc analysis, the result is shown in the G15 curve, and system only endothermic peak occurs near 85 ℃, and this peak belongs to the fusion heat absorption of part 770 in the reactant, simultaneously, do not observe another reactant SmCl on the curve
37H
2The thermal effect of O and product.Show that independent being ground to play the effect that reactant is mixed, can not make reaction begin to carry out.Consider that nucleation stage is controlled by temperature mainly in the solid phase reaction, after system is ground evenly, added the program of heating, adopt fusion method, system is heated to more than the fusing point of one of reactant part 770 90 ℃.After the 120min, to sample sampling and carry out dsc analysis, the result is shown in curve G15H120, and a less endothermic peak also appears near the endothermic peak except 85 ℃ near 110 ℃, belong to SmCl
37H
2O and the 770 solid phase complexs that form show that the heating steps of employing is conducive to the carrying out of nucleation stage.Continue after the heating reactant is ground, promote the carrying out of reaction.Respectively at 15min, 30min, the reaction system sample analysis of 45min, the result is shown in curve G15H120G15, G15H120G30, G15H120G45, the reactant melting peak of representative constantly reduces along with milling time near 85 ℃, and near the peak 110 ℃ but constantly increases along with milling time by contrast.After milling time reached 45min, the reactant melting peak almost disappeared on the system DSC curve, and near the endothermic peak remaining 110 ℃ only shows that degree that this moment, solid phase reaction was carried out has approached to finish.
Reaction system is separated, purified and carries out spectroscopy analysis, and the result shows that product is that target complex and productive rate reach 86%, shows that the result who adopts detection technique proposed by the invention to obtain is directly perceived and believable.If further calculate reactant on each bar curve or product endothermic peak area and contrasted, in conjunction with to reaction conditions refined control more, just can obtain the data that the quantitative extent of reaction changed with reaction conditions, reaction time, significant for process detection and the condition optimizing of this type reaction.
Heptandioic acid (Pimelic acid) is with calcium stearate (CaSt) and can generate heptandioic acid calcium (CaPim) by solid phase reaction, and as polypropylene nucleater.For this reaction, adopt abrasive method to promote the carrying out of reaction equally.Two kinds of materials are mixed, get when two kinds of reactants have just mixed and ground 1,2,3 minute respectively respectively that potpourri carries out dsc analysis in the 5mg reaction system.The result as shown in Figure 2, in the system of just mixing, an endothermic peak respectively appears in the DSC curve near 108 and 126 ℃, represent the fusion of calcium stearate and heptandioic acid respectively.Mixed system is ground, sampling and carry out dsc analysis behind the 1min, the result shows the endothermic peak complete obiteration of calcium stearate and heptandioic acid, occurs a wideer endothermic peak in 64-99 ℃ of scope, belongs to the more formed intermediates of calcium stearate and heptandioic acid reaction.Dwindle through 64-99 ℃ of interior endothermic peak scope of scope after the grinding of 2min, and 170 ℃ of endothermic peaks that go out to represent heptandioic acid calcium.Grind after the 3min, the endothermic peak scope is further dwindled in the 64-99 ℃ of scope, goes out to represent stearic endothermic peak at 78 ℃, and 170 ℃ located heptandioic acid calcium endothermic peak and continue to strengthen.In other temperature ranges, do not find to represent the endothermic peak of other materials, only have heptandioic acid calcium and stearic acid in the explanation system.Monitoring by the entire reaction course of DSC, can find that the solid phase reaction of heptandioic acid and calcium stearate is very fast, and mainly form intermediate product in initial reaction stage, through further grinding, regeneration product stearic acid and heptandioic acid calcium gradually in intermediate product.
Claims (3)
1. one kind characterizes the method that chemical reaction carries out degree and conversion ratio, it is characterized in that utilizing heat analysis method, detect the melting curve of differential responses reaction mixture during the stage, by the variation of more a certain reactant or product melting peak area, that determines reaction carries out degree and conversion ratio
Described chemical reaction is solid phase reaction, and having at least a kind of in the reactant in this reaction or the product is the material with fusion or crystallization behavior;
Described heat analysis method is differential scanning calorimetry.
2. method according to claim 1 is characterized in that, when reactant is crystallizable material, by the corresponding melting peak area of reactant on the thermal analysis curve reduce to characterize reaction carry out degree or transforming degree.
3. method according to claim 1 is characterized in that, when product was crystallizable material, what the increase by the corresponding melting peak area of product on the thermal analysis curve characterized reaction carried out degree or transforming degree.
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| CN106940331A (en) * | 2017-03-21 | 2017-07-11 | 山东京博石油化工有限公司 | Intermittent liquid phase bulk polymerization prepares the measuring method of polyacrylic polymerisation conversion |
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| CN105527320A (en) * | 2015-12-18 | 2016-04-27 | 盐城师范学院 | Four-way solid state chemical reaction conductivity analysis method |
| CN106248722B (en) * | 2016-07-25 | 2019-09-06 | 成都慧成科技有限责任公司 | A method of the water suction of prediction polyvinyl alcohol resin work in-process and dewatering |
| CN107832970A (en) * | 2017-11-23 | 2018-03-23 | 扬州大学 | Synthesis path automatic generating method in Chemical Manufacture problem is decomposed based on recurrence |
| CN115403687A (en) * | 2022-08-12 | 2022-11-29 | 国科广化精细化工孵化器(南雄)有限公司 | Method for monitoring thermal runaway process of butyl acrylate polymerization on line and application |
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| CN1553173A (en) * | 2003-06-04 | 2004-12-08 | 中国科学院大连化学物理研究所 | Ageing progress testing method in insoluble sulfur preparing process |
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| CN1553173A (en) * | 2003-06-04 | 2004-12-08 | 中国科学院大连化学物理研究所 | Ageing progress testing method in insoluble sulfur preparing process |
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| Title |
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| 王东亮等.α、β成核剂复配对聚丙烯性能的影响.《中国塑料》.2007,第21卷(第12期),全文. * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106940331A (en) * | 2017-03-21 | 2017-07-11 | 山东京博石油化工有限公司 | Intermittent liquid phase bulk polymerization prepares the measuring method of polyacrylic polymerisation conversion |
| CN106940331B (en) * | 2017-03-21 | 2019-09-06 | 山东京博石油化工有限公司 | Intermittent liquid phase bulk polymerization prepares the measurement method of polyacrylic polymerisation conversion |
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