阅读说明：本技术 量热分析技术在聚羧酸减水剂工业放大过程中的应用 (Application of calorimetric analysis technology in industrial amplification process of polycarboxylate superplasticizer ) 是由 何旭斌 陈浩 陈玉丽 竹林贤 徐伟 于 2020-06-10 设计创作，主要内容包括：本发明提供了量热分析技术在聚羧酸减水剂工业放大过程中的应用,通过在实验室立升规模下测量聚羧酸减水剂聚合反应过程中释放的热量,由此指导工业放大过程中工艺变量的控制,实现聚羧酸减水剂质量稳定的生产；本发明通过引入全自动量热分析仪,测量聚合反应实验过程中释放的热量,模拟优化聚合反应温度,减少工业化放大过程中产品质量不稳定的问题,提供一种实验室研发成果快速转移至工厂生产的方法。(The invention provides application of a calorimetric analysis technology in an industrial amplification process of a polycarboxylate water reducer, and the heat released in the polymerization reaction process of the polycarboxylate water reducer is measured in a laboratory at a vertical liter scale, so that the control of process variables in the industrial amplification process is guided, and the stable quality production of the polycarboxylate water reducer is realized; the invention provides a method for rapidly transferring laboratory research and development results to factory production by introducing a full-automatic momentum thermal analyzer, measuring heat released in a polymerization reaction experiment process, simulating and optimizing polymerization reaction temperature, and reducing the problem of unstable product quality in an industrial amplification process.)

1. The application of the thermal quantitative analysis technology in the industrial amplification process of the polycarboxylate superplasticizer is characterized in that the application method comprises the following steps: the heat released in the polymerization reaction process of the polycarboxylate superplasticizer is measured in a laboratory at a rising scale, so that the control of process variables in the industrial amplification process is guided, and the production of the polycarboxylate superplasticizer with stable quality is realized.

2. The application of the calorimetric analysis technology in the industrial amplification process of the polycarboxylate superplasticizer according to claim 1 is characterized in that the application method comprises the following steps:

(1) the fully automated laboratory reactor RC1e is ready;

(2) preparing raw material monomers and additives of the polycarboxylate superplasticizer, and preparing a base material in a solution form and dropwise adding the base material for later use;

(3) setting experimental parameters, and measuring the heat released in the polymerization reaction process of the polycarboxylate superplasticizer by adopting a full-automatic laboratory reactor RC1 e; according to the measured thermal data and the real-time calorimetry diagram in the polymerization process, the reaction temperature required by the preparation of the polycarboxylic acid water reducing agent of different types is combined, the temperature control treatment is carried out on the reaction process by regulating and controlling the refrigeration intensity and the starting time period of a cooling system and regulating the dropping rate of dropping materials in the industrial amplification process, and the production of the polycarboxylic acid water reducing agent with stable quality is realized.

3. The application of the calorimetric analysis technology in the industrial amplification process of the polycarboxylate water reducer as the claim 2, wherein in the step (2), raw material monomers and additives of the polycarboxylate water reducer are prepared according to the product formula of a common water-reducing type, high water-reducing type, slump-retaining type, slow-release type or ester polycarboxylate water reducer;

the raw material monomer is selected from one or the combination of isobutylene polyethylene glycol ether, isopentenyl polyethylene glycol ether, ethylene glycol monovinyl polyethylene glycol ether, 4-hydroxybutyl vinyl polyoxyethylene ether and methoxy polyethylene glycol ether;

the additive comprises: unsaturated carboxylic acid and its derivatives, initiator, chain transfer agent and catalyst.

4. The application of the calorimetric analysis technique in the industrial scale-up process of the polycarboxylate water reducer as claimed in claim 3, wherein the unsaturated carboxylic acid and the derivative thereof are selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, monomethyl maleic anhydride, monoethyl maleic anhydride and dimethyl maleic anhydride.

5. The application of the calorimetric analysis technology in the industrial amplification process of the polycarboxylate water reducer as set forth in claim 3, wherein the initiator comprises an oxidant and a reducing agent, and the oxidant is selected from one of hydrogen peroxide and ammonium persulfate; the reducing agent is at least one selected from ascorbic acid, sodium formaldehyde sulfoxylate, sodium sulfite, rongalite, ferrous sulfate and sodium hypophosphite.

6. The application of the calorimetric analysis technique in the industrial amplification process of the polycarboxylate water reducer as the claim 3, wherein the chain transfer agent is at least one selected from mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite, sodium allyl sulfonate and sodium methallyl sulfonate.

7. The application of the calorimetric analysis technology in the industrial amplification process of the polycarboxylate water reducer as the claim 3, wherein the catalyst is one or more selected from ferrous sulfate, ammonium ferrous sulfate, titanium trichloride, 98% concentrated sulfuric acid, zinc chloride and copper chloride.

8. The application of the calorimetric analysis technique in the industrial scale-up process of the polycarboxylate water reducer as set forth in claim 2, wherein in the step (3), the experimental parameters comprise: polymerization temperature, stirring rate, dropping time and dropping mode;

the polymerization temperature is 5-65 ℃;

the stirring speed is 80-250 r/min;

the dripping time is 30-180 min;

the dropping mode is single dropping or double dropping.

Technical Field

The invention relates to the field of polycarboxylic acid water reducing agents, in particular to a method for guiding heat transfer problem in the industrial production process of a series of polycarboxylic acid water reducing agents by using a calorimetric analysis technology.

Background

The polycarboxylate superplasticizer serving as a new-generation high-performance water reducing agent has the advantages of low mixing amount, high water reducing rate, good slump retentivity and the like, is strong in molecular structure designability, easy to realize function regulation and control, and suitable for market demands, and is a key material for promoting the development of domestic and foreign concrete admixtures to high fields for many years.

Most of the existing polycarboxylic acid water reducing agents are produced by aqueous solution free radical polymerization, the polycarboxylic acid water reducing agents of different types select proper reaction temperature according to the factors such as the activity of a polymerization monomer, the type of an oxidation reduction system and the like, the system temperature change in different reaction processes has important influence on the product performance, and the sensitivity of different types of products to the temperature change is different. For example, the reaction temperature of the novel six-carbon polycarboxylate superplasticizer needs to be controlled below 30 ℃, the temperature exceeds 30 ℃, the activity of a redox system is reduced, so that more raw materials of polyether macromonomer are remained, and the product performance is rapidly reduced; the reaction temperature for synthesizing most of the four-carbon and five-carbon polycarboxylate superplasticizers is between 10 and 50 ℃, and the reaction temperature for synthesizing the polyester polycarboxylate superplasticizers is controlled to be above 55 ℃. In the existing industrial production of polycarboxylic acid, a common enamel reaction kettle is generally adopted in the industry, a cooling device is restricted by the stirring form (capability) and the heating and cooling form (capability), the transfer rate of reaction heat is slow, even a part of manufacturers do not have a heat exchange device, and the produced polycarboxylic acid water reducing agent product has the problem of unstable quality along with the change of seasonal temperature. Comprehensive understanding of heat release information in the polymerization process of the polycarboxylate superplasticizer becomes an important basis for solving product performance fluctuation caused by polymerization temperature change.

In order to better simulate the scale of industrial production, a reaction amplification experiment becomes the mainstream of industrial research on the polycarboxylate superplasticizer. However, the reaction amplification experiment is restricted by equipment, so that raw materials are wasted, and the thermochemical characteristics of the process cannot be comprehensively and accurately known. The conventional small experiment reaction equipment has high heat transfer efficiency, is difficult to realize strict heat insulation, and cannot accurately provide heat information in the synthesis process of the polycarboxylic acid water reducing agent, so that the search for a proper reaction amplification experiment process method is particularly important.

Disclosure of Invention

The invention provides a method for rapidly transferring laboratory research and development results to factory production by introducing a full-automatic momentum thermal analyzer, measuring heat released in a polymerization reaction experiment process, simulating and optimizing polymerization reaction temperature, and reducing the problem of unstable product quality in an industrial amplification process.

The technical scheme of the invention is as follows:

the application of a thermal quantitative analysis technology in the industrial amplification process of the polycarboxylate superplasticizer is realized by measuring the heat released in the polymerization reaction process of the polycarboxylate superplasticizer in a laboratory at a vertical liter scale, so as to guide the control of process variables in the industrial amplification process and realize the stable quality production of the polycarboxylate superplasticizer.

Specifically, the application method comprises the following steps:

the application of the thermal quantitative analysis technology in the industrial amplification process of the polycarboxylate superplasticizer comprises the following steps:

(1) the fully automated laboratory reactor RC1e is ready;

(2) preparing raw material monomers and additives of the polycarboxylate superplasticizer, and preparing a base material in a solution form and dropwise adding the base material for later use;

(3) setting experimental parameters, and measuring the heat released in the polymerization reaction process of the polycarboxylate superplasticizer by adopting a full-automatic laboratory reactor RC1 e; according to the measured thermal data and the real-time calorimetry diagram in the polymerization process, the reaction temperature required by the preparation of the polycarboxylic acid water reducing agent of different types is combined, the temperature control treatment is carried out on the reaction process by regulating and controlling the refrigeration intensity and the starting time period of a cooling system and regulating the dropping rate of dropping materials in the industrial amplification process, and the production of the polycarboxylic acid water reducing agent with stable quality is realized.

Further:

in step (1), the fully automated laboratory reactor RC1e comprises: automatic thermostat and control device, iControl^TMSoftware, a reaction kettle device and a UCB comprehensive control box.

In the step (2), raw material monomers and additives of the polycarboxylate superplasticizer are prepared according to the formula of common polycarboxylate superplasticizer products such as common water reducers, high water reducers, slump loss preventers, slow release reducers, esters and the like;

the raw material monomer is preferably one of or the combination of isobutylene polyethylene glycol ether (HPEG), isopentenyl polyethylene glycol ether (TPEG), ethylene glycol monovinyl polyethylene glycol ether (EPEG), 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) and methoxy polyethylene glycol ether (MPEG);

the additive comprises: unsaturated carboxylic acid and its derivatives, initiator, chain transfer agent and catalyst;

wherein: the unsaturated carboxylic acid and the derivative thereof are preferably one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, monomethyl maleic anhydride, monoethyl maleic anhydride and dimethyl maleic anhydride;

the initiator comprises an oxidant and a reducing agent, wherein the oxidant is preferably one of hydrogen peroxide and ammonium persulfate; the reducing agent is preferably at least one of ascorbic acid, sodium formaldehyde sulfoxylate, sodium sulfite, rongalite, ferrous sulfate and sodium hypophosphite;

the chain transfer agent is preferably at least one of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite, sodium allyl sulfonate and sodium methallyl sulfonate;

the catalyst is preferably one or more of ferrous sulfate, ammonium ferrous sulfate, titanium trichloride, 98% concentrated sulfuric acid, zinc chloride and copper chloride.

In the step (3), the experimental parameters include: polymerization temperature, stirring rate, dropping time and dropping mode;

the polymerization temperature is preferably 5 to 65 ℃;

the stirring speed is preferably 80-250 r/min;

the dripping time is preferably 30-180 min;

the dripping mode is preferably single dripping or double dripping.

The synthesis of the polycarboxylic acid water reducing agent generally adopts aqueous solution free radical polymerization, and the adopted raw materials comprise unsaturated polyether macromonomer, redox initiator, chain transfer agent and some comonomers. The invention relates to more than 3 comonomers, the self-polymerization rate of the high-activity monomer is higher under the high-temperature condition, the distribution uniformity of each functional group on a polymer molecular chain is influenced, the polymerization degree of the polymer is influenced by high-temperature reaction, the heat released by the whole polymerization reaction needs to be tested in order to effectively transfer the heat generated by polymerization, prevent implosion and control the reaction rate of each monomer, so that a proper cooling system is selected to perform temperature control treatment on the reaction process, and the polycarboxylic acid water reducer product with excellent performance is prepared.

The invention has the beneficial effects that:

1. the invention provides a method for measuring heat released in a polymerization reaction experiment process under a laboratory condition by using a full-automatic reactor RC1e, optimizing polymerization reaction temperature, reducing the problem of unstable product quality in an industrial amplification process and quickly transferring laboratory research and development results to factory production.

2. The full-automatic reaction calorimeter RC1e is used for small-scale screening, a small amount of accurate raw materials are used for realizing heat testing, waste is greatly reduced, the yield in development can be increased, and key information is provided for industrial decision.

Detailed Description

The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited thereto.

In the following examples, a fully automated laboratory reactor RC1e manufacturer: mettler Toriledo Co.