CN110467563B - Fluorine-containing nitroxide free radical polymerization inhibitor, preparation method thereof and continuous refining process of 4-hydroxybutyl acrylate - Google Patents

Fluorine-containing nitroxide free radical polymerization inhibitor, preparation method thereof and continuous refining process of 4-hydroxybutyl acrylate Download PDF

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CN110467563B
CN110467563B CN201910762239.5A CN201910762239A CN110467563B CN 110467563 B CN110467563 B CN 110467563B CN 201910762239 A CN201910762239 A CN 201910762239A CN 110467563 B CN110467563 B CN 110467563B
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polymerization inhibitor
fluorine
refining process
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hydroxybutyl acrylate
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CN110467563A (en
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郑京涛
李俊平
黎源
孙亚明
安丽艳
康学青
鞠昌迅
郭华
陆国太
李付国
赵文娟
王勤隆
潘世伟
刘岩
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention relates to a fluorine-containing nitroxide free radical polymerization inhibitor, a preparation method thereof and a continuous refining process of 4-hydroxybutyl acrylate. The fluorine-containing nitroxyl radical polymerization inhibitor is a polymerization inhibitor with no color number and high boiling point, is added in the process of distilling light components and products of a 4-hydroxybutyl acrylate refining process, and can realize the continuous refining operation of the 4-hydroxybutyl acrylate by combining the three-step operations of continuous extraction, rectification for removing the light components, short-range distillation and the like.

Description

Fluorine-containing nitroxide free radical polymerization inhibitor, preparation method thereof and continuous refining process of 4-hydroxybutyl acrylate
Technical Field
The invention belongs to the field of organic compound preparation, relates to a refining process of hydroxy acrylate, and particularly relates to a fluorine-containing nitroxide free radical polymerization inhibitor and a preparation method thereof, and a continuous refining process of 4-hydroxybutyl acrylate.
Background
4-hydroxy butyl acrylate (4-HBA) is mainly used in surface coating baking varnish for automobile metal coating, the rapid development of the automobile coating industry is driven by the rapid advance of the automobile industry, wherein a bi-component acrylic polyurethane coating consisting of Hydroxy Acrylic Resin (HAR) and isocyanate curing agent becomes a main variety of finishing varnish in the automobile repair industry due to the characteristics of room-temperature or low-temperature baking curing, good polishing and polishing performance and the like.
Related process reports exist for refining 4-hydroxybutyl acrylate by adopting extraction and rectification processes, research and optimization of a process for synthesizing 4-hydroxybutyl acrylate by a direct esterification method of Lanjun Yu and the like mention that hydroquinone and p-hydroxyanisole compounded polymerization inhibitor are selected as a reaction polymerization inhibitor, cyclohexane is used as an extractant of 1, 4-butanediol diacrylate, dichloromethane is used as an extractant for extracting 4-hydroxybutyl acrylate from a water phase, the extraction temperature is selected to be 20 ℃, reaction and separation process flows are simulated by virtue of penAs Plus, and the purity of the 4-hydroxybutyl acrylate product can reach 99.4%. In the process, hydroquinone and p-hydroxyanisole added into a reaction system cannot be removed in the extraction process, and are evaporated into a product in the rectification stage to influence the downstream polymerization application of the product, meanwhile, the hydroquinone and the p-hydroxyanisole are oxidized into quinones in the rectification stage and are carried into the product to influence the color number of the product, in addition, residual acrylic acid in the reaction stage and the extraction stage accelerates the polymerization and decomposition of 4-hydroxybutyl acrylate in the rectification stage, and the process flow is not feasible in actual production.
The synthesis and application research of 4-hydroxybutyl acrylate, the aging and application of synthetic materials, 2018, 47 (3): 110-114. it is mentioned that the acidic homogeneous catalyst and the polymerization inhibitor can be removed by washing with water and alkali, the polymerization inhibitor can be removed by activated carbon adsorption, 1, 4-butanediol diacrylate is removed by nonpolar solvents such as cyclohexane, benzene, n-hexane or toluene, 1, 4-butanediol and 4-hydroxybutyl acrylate are separated by strongly polar solvents such as dichloromethane, butyl acetate, trichloromethane, etc., and the polymerization inhibitor is adsorbed by activated carbon.
CN109053449A provides a production process and equipment for preparing 4-hydroxybutyl acrylate by extraction separation, 1, 4-butanediol and acrylic acid react under the conditions of catalysts of p-toluenesulfonic acid, hydroquinone as a polymerization inhibitor and p-hydroxyanisole to obtain main products of 4-hydroxybutyl acrylate and 1, 4-butanediol diacrylate, cyclohexane is used for extracting 1, 4-butanediol diacrylate from a water phase, dichloromethane is used for extracting 4-hydroxybutyl acrylate from the water phase, and finally, the finished product is prepared by reduced pressure distillation.
CN109053450A provides a method for preparing hydroxybutyl acrylate by extraction separation, which comprises the steps of reacting 1, 4-butanediol with acrylic acid under the action of a catalyst, hydroquinone serving as a polymerization inhibitor and p-hydroxyanisole to obtain an esterification reaction liquid, extracting 1, 4-butanediol diacrylate from a water phase by using an extractant cyclohexane, extracting 4-hydroxybutyl acrylate from the water phase by using dichloromethane and the like, and finally carrying out reduced pressure distillation to obtain a finished product.
Disclosure of Invention
The invention aims to provide a fluorine-containing nitroxide free radical polymerization inhibitor and a preparation method thereof, and a continuous refining process of 4-hydroxybutyl acrylate by adopting the polymerization inhibitor. The fluorine-containing nitroxyl radical-containing polymerization inhibitor is a colorless high-boiling point polymerization inhibitor, is added in the process of distilling light components and products in the 4-hydroxybutyl acrylate refining process, and can realize continuous refining operation on the 4-hydroxybutyl acrylate product by combining three-step continuous extraction, rectification for removing the light components, short-range distillation and other operations, so that the labor intensity is low, the obtained product has high purity, low color number and low acid content, and continuous industrial production is easy to realize.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a fluorine-containing nitroxide free radical polymerization inhibitor which is at least one of the following structural formulas:
Figure BDA0002170700660000031
wherein m and n are respectively and independently 5-50, preferably 8-15;
in the present invention, the fluorine-containing nitroxide radical-containing polymerization inhibitor is preferably
Figure BDA0002170700660000032
In the invention, the number average molecular weight of the fluorine-containing nitroxide free radical polymerization inhibitor is 2000-4000, preferably 2500-3000;
in the invention, the fluorine content in the fluorine-containing nitroxide free radical polymerization inhibitor is 3-62 wt%, preferably 14-35 wt%;
in the invention, the content of nitroxide radical in the fluorine-containing nitroxide radical polymerization inhibitor is 2-13 wt%, preferably 7-11 wt%;
in the invention, the boiling point of the fluorine-containing nitroxide free radical polymerization inhibitor is 500-800 ℃, and preferably 550-700 ℃.
In the invention, the fluorine-containing nitroxide free radical polymerization inhibitor is a white solid with the color number of 0.
The fluorine-containing nitroxide free radical polymerization inhibitor is a 4-hydroxybutyl acrylate polymerization inhibitor and can also be used for inhibiting polymerization of other hydroxyl acrylates.
The invention also provides a preparation method of the fluorine-containing nitroxide free radical polymerization inhibitor, which comprises the following steps:
(1) carrying out ester exchange reaction on methyl acrylate and 2,2,6, 6-tetramethyl piperidinol to obtain 2,2,6, 6-tetramethyl piperidineacrylate;
(2) adding perfluoroolefin into the reaction liquid obtained in the step (1) to perform copolymerization with 2,2,6, 6-tetramethyl piperidine acrylate;
(3) and (3) adding sodium tungstate and hydrogen peroxide into the reaction liquid obtained in the step (2) to carry out oxidation reaction, thereby obtaining the fluorine-containing nitroxide free radical polymerization inhibitor.
In the step (1), the temperature of the ester exchange reaction is 90-120 ℃, and preferably 100-110 ℃; the time is 6-12 h, preferably 8-10 h;
the molar ratio of the methyl acrylate to the 2,2,6, 6-tetramethyl piperidinol is 1.5-5: 1, and preferably 2-3: 1;
preferably, after the transesterification reaction is completed, a post-treatment process such as distillation is further included to remove methyl acrylate, methanol by-product of the reaction, and the like in the reaction solution;
in the step (2), the copolymerization polymerization reaction is carried out at the reaction temperature of 30-60 ℃, preferably 40-50 ℃; the reaction time is 5-15 h, preferably 7-10 h, the reaction pressure is 4-8 MPaG, preferably 5-7 MPaG, and the pressure is released to normal pressure after the reaction is finished;
the mol ratio of the perfluoroolefin to the 2,2,6, 6-tetramethylpiperidine acrylate is 0.5-3: 1, preferably 1-2.5: 1.
The perfluoroolefin is at least one of tetrafluoroethylene and/or hexafluoropropylene, and preferably tetrafluoroethylene.
In the step (3), the oxidation reaction is carried out at the temperature of 100-110 ℃ for 36-48 h;
the mass ratio of the sodium tungstate to the 2,2,6, 6-tetramethyl piperidine acrylate is 0.05-0.5: 1, preferably 0.08-0.15: 1;
the molar ratio of the hydrogen peroxide to the 2,2,6, 6-tetramethyl piperidinol is 0.8-2: 1, and preferably 1-1.5: 1.
Preferably, the copolymerization reaction in the step (2) and/or the oxidation reaction in the step (3) are carried out in a nitrogen atmosphere.
Preferably, after the oxidation reaction is finished, the post-treatment processes such as washing, extraction, distillation or drying are also included; the washing and extraction temperature is 20-30 ℃, and the distillation or drying temperature is 80-90 ℃. The specific method adopted in some embodiments of the invention is as follows: and sequentially adding hot water and toluene into the reaction solution, washing at 20-30 ℃ to remove salt and extract the toluene, standing for phase splitting, taking an oil phase, and distilling at 80-90 ℃ to remove the solvent to obtain the white solid fluorine-containing nitroxide free radical polymerization inhibitor.
The invention also aims to provide a continuous refining process of 4-hydroxybutyl acrylate by using the fluorine-containing nitroxide free radical polymerization inhibitor, which comprises the following steps:
1) extracting and separating the coarse reaction liquid of the 4-hydroxybutyl acrylate continuously in three steps to obtain an extraction liquid containing the 4-hydroxybutyl acrylate;
2) step 1), carrying out alkali liquor neutralization and water washing on the extract liquor to obtain a washed oil phase;
3) and 2) adding a fluorine-containing nitroxide free radical polymerization inhibitor into the oil phase after water washing, rectifying to remove light components, and performing short-path distillation to obtain the 4-hydroxybutyl acrylate.
Further, in the step 1), the crude reaction liquid of 4-hydroxybutyl acrylate comprises, based on 100% of the total mass of the crude reaction liquid of 4-hydroxybutyl acrylate: 0.5-5 wt% of acrylic acid, 40-60 wt% of 1, 4-butanediol, 40-50 wt% of 4-hydroxybutyl acrylate, 1-10 wt% of 1, 4-butanediol diacrylate, 0.5-2 wt% of catalyst and 0.1-1 wt% of polymerization inhibitor;
the catalyst is at least one of concentrated sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid;
the polymerization inhibitor is at least one of phenothiazine, hydroquinone, p-methoxyphenol, ZJ-701, ZJ-705 and N, N-di-N-butyl copper dithiocarbamate.
Further, in the step 1), the three-step continuous extraction separation comprises tower separation or centrifugal separation, and the adopted equipment is at least one of a filler extraction tower, a sieve plate extraction tower, a rotary disc extraction tower and a centrifugal extractor, preferably the centrifugal extractor;
the three-step continuous extraction comprises the following steps: a 1, 4-butanediol diacrylate (BDDA) removal and extraction unit, a 4-hydroxybutyl acrylate (4-HBA) extraction and extraction unit and a 1, 4-Butanediol (BDO) removal and extraction unit; in some embodiments of the present invention, the three-step continuous extraction includes sequentially removing and extracting a 1, 4-butanediol diacrylate (BDDA) unit, a 4-hydroxybutyl acrylate (HBA) unit, and a 1, 4-Butanediol (BDO) unit;
the extracting agent used in the 1, 4-butanediol diacrylate removing and extracting unit is at least one or a mixture of more of cyclohexane, normal hexane, normal heptane, normal pentane, xylene and toluene, and the normal hexane is preferred;
the extractant used in the 4-hydroxybutyl acrylate extraction unit is at least one or a mixture of dichloromethane, butyl acetate, trichloromethane and carbon tetrachloride, preferably dichloromethane;
the extracting agent used in the 1, 4-butanediol removing and extracting unit is at least one or a mixture of water, a 5-10 wt% NaCl aqueous solution and a 5-10 wt% KCl aqueous solution, and preferably water.
Further, in the step 1), the mass ratio of the 1, 4-butanediol diacrylate removing and extracting unit to the 4-hydroxybutyl acrylate crude reaction liquid to the extracting agent is 1: 2-3, the number of extraction stages is 5-10, and the temperature is 20-30 ℃;
in the 4-hydroxybutyl acrylate extraction unit, the mass ratio of the crude reaction liquid of the 4-hydroxybutyl acrylate to the extractant is 1: 1-3, the extraction stage number is 2-5, and the temperature is 20-30 ℃;
the mass ratio of the 1, 4-butanediol removal extraction unit to the 4-hydroxybutyl acrylate crude reaction liquid to the extractant is 1: 1-3, the extraction stage number is 5-10, and the temperature is 20-30 ℃.
Further, in the step 1), the composition of the extract containing 4-hydroxybutyl acrylate is calculated by taking the total mass of the extract containing 4-hydroxybutyl acrylate excluding the mass of the extractant as 100%, and the extract contains 0.1-0.5 wt% of acrylic acid, 0.1-0.5 wt% of 1, 4-butanediol, 99.0-99.5 wt% of 4-hydroxybutyl acrylate, 0.1-0.5 wt% of 1, 4-butanediol diacrylate, 0.2-0.5 wt% of a catalyst, and 0.05-0.1 wt% of a polymerization inhibitor.
Further, in the step 2), the alkali liquor is neutralized, and the used alkali liquor is at least one of 1-10 wt% of NaOH aqueous solution and 1-10 wt% of KOH aqueous solution; preferably aqueous NaOH solution;
neutralizing the alkali liquor, wherein the pH is controlled within the range of 7-10, and preferably 8-9;
the alkali liquor is neutralized at the temperature of 15-40 ℃, preferably 20-35 ℃, and more preferably 20-30 ℃.
Further, in the step 2), the washing step number of the obtained neutralization solution by water is 1-8, preferably 2-4;
and (3) washing, wherein the mass ratio of the water consumption to the neutralizing solution is 0.1-2: 1, preferably 0.3-1: 1;
and washing with water at the temperature of 15-40 ℃, preferably at the temperature of 20-35 ℃, and more preferably at the temperature of 20-30 ℃.
Further, in the step 2), the oil phase after washing comprises, by taking the total mass of the oil phase excluding the mass of the extractant as 100%, 0.01 to 0.05 wt% of acrylic acid, 0.1 to 0.5 wt% of 1, 4-butanediol, 99.0 to 99.5 wt% of 4-hydroxybutyl acrylate, 0.1 to 0.5 wt% of 1, 4-butanediol diacrylate, 0.01 to 0.05 wt% of a catalyst, and 0.01 to 0.05 wt% of a polymerization inhibitor.
Further, in the step 3), the amount of the fluorine-containing nitroxide radical polymerization inhibitor added is 0.1-5 wt%, preferably 1-2 wt% of the total amount of the oil phase after washing.
Further, in the step 3), the number of theoretical plates of a rectifying tower adopted for rectifying is 10-20, preferably 12-18;
the rectifying tower adopts a continuous feeding mode; the tower top temperature of the rectifying tower is 15-35 ℃, and preferably 20-30 ℃; the pressure at the top of the tower is 40-85 KPa (A), preferably 45-70 KPa (A).
Further, in the step 3), the light component is the extractant remained in the three-step continuous extraction and separation operation in the step 1), and preferably, the light component is a mixture of n-hexane, dichloromethane and water.
Further, in the step 3), the short path distillation is carried out under the pressure of 0.01-1 KPa (A), preferably 0.02-0.1 KPa (A), and the temperature is 70-180 ℃, preferably 90-150 ℃.
The short-path distillation is carried out in a short-path evaporator, the short-path evaporator comprises an internal condenser, and the tube side temperature of the internal condenser is-60-10 ℃, preferably-25-5 ℃;
a gas phase outlet of the short-range evaporator is provided with a two-stage condenser, and the tube side temperature of the first-stage condenser is 28-40 ℃, preferably 30-38 ℃; the tube side temperature of the second-stage condenser is-60-10 ℃, and preferably-25-5 ℃.
Preferably, the tube pass of the first-stage condenser is a circulating water refrigerant, the temperature is 28-40 ℃, preferably 30-38 ℃, and the tube pass of the second-stage condenser is a 30-60 wt% glycol aqueous solution, the temperature is-60-10 ℃, preferably-25-5 ℃.
According to the continuous refining process of the 4-hydroxybutyl acrylate, the purity of the prepared 4-hydroxybutyl acrylate is more than 99%, the refining yield is more than 90%, the color number is below 5(APHA), and the acid value is extremely low and is less than 0.05 mgKOH/g; the content of the polymerization inhibitor carried in the prepared 4-hydroxybutyl acrylate product is lower than 10ppm, wherein the polymerization inhibitor carried in the crude reaction liquid can be completely removed by alkali liquor neutralization and washing after being refined.
The technical scheme of the invention has the beneficial effects that:
1. by adopting multi-stage continuous extraction equipment and a multi-stage continuous extraction process, the removal rate of 1, 4-butanediol diacrylate, the removal rate of 1, 4-butanediol and the extraction rate of the product 4-hydroxybutyl acrylate are higher and reach more than 99 percent, so that the purity of the product is ensured, the operation intensity of personnel is reduced, and the labor cost is reduced;
2. residual acrylic acid and acid catalyst in the extracted oil phase are removed by using an alkali liquor neutralization process, and the decomposition and polymerization of the 4-hydroxybutyl acrylate product in the distillation process can be accelerated by the presence of the acid liquor neutralization process, so that the 4-hydroxybutyl acrylate product with low acid value and high purity can be further obtained;
3. adding fluorine-containing nitroxide free radical polymerization inhibitor into the oil phase after extraction, neutralization and water washing, wherein the fluorine-containing nitroxide free radical polymerization inhibitor has a high boiling point (higher than that of 4-hydroxybutyl acrylate by more than 200 ℃), a colorless number and a large molecular weight, and can be prevented from being carried into a product by a gas phase, so that a low-color-number product (the color number is less than 5) is obtained;
4. a rectification process is adopted, the extractant is removed from the top of the tower, and a high-purity 4-hydroxybutyl acrylate heavy component is obtained from the bottom of the tower, so that conditions are provided for preparing a high-purity 4-hydroxybutyl acrylate product;
5. according to the molecular distillation principle, 4-hydroxybutyl acrylate is distilled in a short path, the heat-sensitive material 4-hydroxybutyl acrylate is short in heating time, the operation process is simple, equipment is few, the energy consumption of products is low, and the purity of the products can reach more than 99%;
6. the whole refining process uses continuous extraction and rectification and distillation equipment, and can be used for large-scale continuous production of the 4-hydroxybutyl acrylate.
Drawings
FIG. 1 is a GPC chart of a fluorine-containing nitroxide-containing radical polymerization inhibitor prepared in example 1;
FIG. 2 is a GPC chart of a fluorine-containing nitroxide-containing radical polymerization inhibitor prepared in example 2;
FIG. 3 is a GPC chart of a fluorine-containing nitroxide-containing radical polymerization inhibitor prepared in example 3;
FIG. 4 is a GPC chart of a fluorine-containing nitroxide-containing radical polymerization inhibitor prepared in example 4;
FIG. 5 is an IR spectrum of the fluorine-containing nitroxide radical-containing polymerization inhibitor prepared in example 1;
FIG. 6 is an IR spectrum of the fluorine-containing nitroxide radical-containing polymerization inhibitor prepared in example 4;
FIG. 7 is a schematic view of the process for continuously refining hydroxybutyl 4-acrylate according to the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
First, the main raw material sources in the example:
1. methyl acrylate, Shanghai Aladdin Biotechnology Ltd, analytically pure;
2. 2,2,6, 6-tetramethylpiperidinol, Alfa Aesar, analytical grade;
3. toluene, national pharmaceutical group chemical reagents ltd, analytically pure;
4. xylene, west longa science ltd, analytically pure;
5. benzene, Shanghai Aladdin Biotechnology GmbH, analytically pure;
6. tetrafluoroethylene, Dalian specialty gas Co., Ltd, analytically pure;
7. hexafluoropropylene, carbofuran technologies ltd, analytical purity;
8. anhydrous sodium tungstate, lark technologies ltd, 99%;
9. hydrogen peroxide, national pharmaceutical group chemical reagents ltd, analytically pure.
Secondly, the product analysis method in the embodiment:
1. the gas chromatography is used for analyzing components and contents of reaction liquid and products, and a correction factor method is adopted, so that the method comprises the following steps: shimadzu 1020-plus;
2. the structure of the fluorine-containing nitroxide free radical polymerization inhibitor is determined by a Fourier infrared spectrometer, and the structure comprises the following instruments, manufacturers and models: thermo (USA) 470 FTIR.
3. The molecular weight of the fluorine-containing nitroxide free radical polymerization inhibitor is measured by a gel chromatograph (GPC), and the manufacturer and the model of the apparatus are as follows: shimadzu (Japan) LC-20 AD;
4. the boiling point of the fluorine-containing nitroxide free radical polymerization inhibitor is measured by a thermogravimetric analyzer (TGA), and the manufacturer and the model of the apparatus are as follows: METTLER (Switzerland) TGA/DSC 1;
5. measuring the content of fluorine in the fluorine-containing nitroxide free radical polymerization inhibitor by using an Atomic Absorption Spectrometer (AAS), wherein the content of fluorine in the fluorine-containing nitroxide free radical polymerization inhibitor is determined by the following instruments and manufacturers and models: perkin Elmer (U.S. PinAAcle 900T;
6. measuring the color number of the 4-hydroxybutyl acrylate product by using a color number instrument, wherein the instrument manufacturer and the model are as follows: hash HACH LICO 620.
Example 1:
the preparation of the fluorine-containing nitroxide free radical polymerization inhibitor comprises the following steps:
1) adding methyl acrylate and 2,2,6, 6-tetramethyl piperidinol into a reaction kettle according to the amount of 2:1(mol), reacting for 9 hours at the temperature of 102 ℃, and after the ester exchange reaction is finished, distilling the methyl acrylate and the reaction byproduct methanol in the methyl acrylate under the pressure of 20KPaA to obtain a reaction liquid containing 2,2,6, 6-tetramethyl piperidineacrylate;
2) cooling the reaction liquid in the step (1) to 45 ℃ by adopting circulating water at 28 ℃, adding tetrafluoroethylene into a reaction kettle, wherein the addition amount of the tetrafluoroethylene is as follows: 2,2,6, 6-tetramethyl piperidine acrylate is 2:1(mol), then high-pressure nitrogen is filled to ensure that the pressure in the reaction kettle is 5.5MPaG, the reaction is finished after 8 hours, the pressure in the reaction kettle is relieved, and the reaction kettle is replaced by nitrogen for three times;
3) adding sodium tungstate and hydrogen peroxide into a reaction kettle, wherein the adding amount of the hydrogen peroxide is as follows: the ratio of 2,2,6, 6-tetramethyl piperidinol to sodium tungstate is 1.2:1(mol), and the addition amount of sodium tungstate is as follows: the 2,2,6, 6-tetramethyl piperidine acrylate is 0.1:1(wt), and the reaction is finished after the reaction temperature is raised to 105 ℃ and the reaction lasts for 40 h;
4) and cooling the reaction liquid to room temperature, sequentially adding hot water and toluene into the reaction liquid, washing and extracting at 20-30 ℃, shaking uniformly, standing for 1h, taking an oil phase at 80-90 ℃, and performing reduced pressure distillation (removing the toluene solvent therein to obtain a white heavy component, namely the fluorine-containing nitroxide free radical polymerization inhibitor.
The fluorine-containing nitroxide-containing radical polymerization inhibitor prepared in example 1 (GPC spectrogram is shown in FIG. 1, and infrared spectrogram is shown in FIG. 5) has a structure of
Figure BDA0002170700660000121
Wherein m is about 8 to 9, n is about 8 to 9, fluorine is about 25 to 26 wt%, nitroxide radical is about 8.5 to 9.5 wt%, molecular weight is about 2680(Mn), boiling point is 640 ℃, and color number is 0.
Example 2:
the preparation of the fluorine-containing nitroxide free radical polymerization inhibitor comprises the following steps:
1) adding methyl acrylate and 2,2,6, 6-tetramethyl piperidinol into a reaction kettle according to the amount of 3:1(mol), reacting for 8 hours at the temperature of 100 ℃, and after the ester exchange reaction is finished, distilling the methyl acrylate and the reaction byproduct methanol in the methyl acrylate under the pressure of 20KPaA to obtain a reaction liquid containing 2,2,6, 6-tetramethyl piperidineacrylate;
2) cooling the reaction liquid in the step (1) to 40 ℃ by adopting circulating water at 28 ℃, adding tetrafluoroethylene into a reaction kettle, wherein the addition amount of the tetrafluoroethylene is as follows: 2,2,6, 6-tetramethyl piperidine acrylate is 1:1(mol), then high-pressure nitrogen is filled to ensure that the pressure in the reaction kettle is 5.0MPaG, the reaction is finished after 7 hours, the pressure in the reaction kettle is relieved, and the reaction kettle is replaced by nitrogen for three times;
3) adding sodium tungstate and hydrogen peroxide into a reaction kettle, wherein the adding amount of the hydrogen peroxide is as follows: the ratio of 2,2,6, 6-tetramethyl piperidinol to sodium tungstate is 1:1 (mol): the 2,2,6, 6-tetramethyl piperidine acrylate is 0.15:1(wt), and the reaction is finished after the reaction temperature is raised to 105 ℃ and the reaction is carried out for 36 hours;
4) and cooling the reaction liquid to room temperature, sequentially adding hot water and toluene into the reaction liquid, washing and extracting at 20-30 ℃, shaking uniformly, standing for 1h, taking an oil phase at 80-90 ℃, carrying out reduced pressure distillation, removing the solvent toluene in the oil phase, and obtaining a white heavy component, namely the fluorine-containing nitroxide free radical polymerization inhibitor.
The polymerization inhibitor containing fluorine and nitroxide radical prepared in example 2 (GPC spectrum is shown in FIG. 2), wherein m is about 8-9, n is about 8-9, fluorine is about 23-24 wt%, nitroxide radical is about 9-10 wt%, molecular weight is about 2540(Mn), boiling point is 620 ℃, and color number is 0.
Example 3:
the preparation of the fluorine-containing nitroxide free radical polymerization inhibitor comprises the following steps:
1) adding methyl acrylate and 2,2,6, 6-tetramethyl piperidinol into a reaction kettle according to the amount of 2:1(mol), reacting for 9 hours at the temperature of 110 ℃, and after the ester exchange reaction is finished, distilling the methyl acrylate and the reaction byproduct methanol in the methyl acrylate under the pressure of 20KPaA to obtain a reaction liquid containing 2,2,6, 6-tetramethyl piperidineacrylate;
2) cooling the reaction liquid in the step (1) to 40 ℃ by adopting circulating water at 28 ℃, adding tetrafluoroethylene into a reaction kettle, wherein the addition amount of the tetrafluoroethylene is as follows: 2,2,6, 6-tetramethyl piperidine acrylate is 1:1(mol), then high-pressure nitrogen is filled to ensure that the pressure in the reaction kettle is 7.0MPaG, the reaction is finished after 7 hours, the pressure in the reaction kettle is relieved, and the reaction kettle is replaced by nitrogen for three times;
3) adding sodium tungstate and hydrogen peroxide into a reaction kettle, wherein the adding amount of the hydrogen peroxide is as follows: the ratio of 2,2,6, 6-tetramethyl piperidinol to sodium tungstate is 1.5:1(mol), and the addition amount of sodium tungstate is as follows: the 2,2,6, 6-tetramethyl piperidine acrylate is 0.08:1(wt), and the reaction is finished after the reaction temperature is raised to 110 ℃ and the reaction is carried out for 48 hours;
4) and cooling the reaction liquid to room temperature, sequentially adding hot water and toluene into the reaction liquid, washing and extracting at 20-30 ℃, shaking uniformly, standing for 1h, taking an oil phase at 80-90 ℃, carrying out reduced pressure distillation, removing the solvent toluene in the oil phase, and obtaining a white heavy component, namely the fluorine-containing nitroxide free radical polymerization inhibitor.
The polymerization inhibitor containing fluorine and nitroxide radical prepared in example 3 (GPC spectrum is shown in FIG. 3), wherein m is about 8-9, n is about 8-9, fluorine is about 21-22 wt%, nitroxide radical is about 9-10 wt%, molecular weight is about 2800(Mn), boiling point is 670 deg.C, and color number is 0.
Example 4:
the preparation of the fluorine-containing nitroxide free radical polymerization inhibitor comprises the following steps:
1) adding methyl acrylate and 2,2,6, 6-tetramethyl piperidinol into a reaction kettle according to the amount of 2.5:1(mol), reacting at 105 ℃ for 10 hours, and after the ester exchange reaction is finished, distilling the methyl acrylate and a reaction byproduct methanol in the methyl acrylate under the pressure of 20KPaA to obtain a reaction liquid containing 2,2,6, 6-tetramethyl piperidineacrylate;
2) cooling the reaction liquid in the step (1) to 50 ℃ by adopting circulating water at 28 ℃, adding hexafluoropropylene into the reaction kettle, wherein the adding amount of the hexafluoropropylene is as follows: 2,2,6, 6-tetramethyl piperidine acrylate is 2.5:1(mol), then high-pressure nitrogen is filled to ensure that the pressure in the reaction kettle is 7.0MPaG, the reaction is finished after 15 hours, the pressure in the reaction kettle is relieved, and the reaction kettle is replaced by nitrogen for three times;
3) adding sodium tungstate and hydrogen peroxide into a reaction kettle, wherein the adding amount of the hydrogen peroxide is as follows: 2,2,6, 6-tetramethylpiperidinol is 1.2:1(mol), sodium tungstate addition: the 2,2,6, 6-tetramethyl piperidine acrylate is 0.15:1(wt), and the reaction is finished after the reaction temperature is raised to 110 ℃ and the reaction lasts for 40 h;
4) and cooling the reaction liquid to room temperature, sequentially adding hot water and toluene into the reaction liquid, washing and extracting at 20-30 ℃, shaking uniformly, standing for 1h, taking an oil phase at 80-90 ℃, carrying out reduced pressure distillation, removing the solvent toluene in the oil phase, and obtaining a white heavy component, namely the fluorine-containing nitroxide free radical polymerization inhibitor.
The fluorine-containing nitroxide-containing radical polymerization inhibitor prepared in example 4 (GPC chromatogram is shown in FIG. 4, and IR spectrum is shown in FIG. 6) has the following IR analysis structure,
Figure BDA0002170700660000141
wherein m is about 8 to 9, n is about 8 to 9, fluorine is about 30 to 31 wt%, nitroxide radical is about 7.5 to 8.5 wt%, molecular weight is about 3000(Mn) by GPC spectrogram analysis, boiling point is 660 ℃, and color number is 0.
Example 5
A continuous refining process of 4-hydroxybutyl acrylate (shown in FIG. 7) comprises the following steps:
the raw material 4-hydroxybutyl acrylate crude reaction liquid comprises the following components: 1.2 wt% of acrylic acid, 42.5 wt% of 1, 4-butanediol, 48.2 wt% of 4-hydroxybutyl acrylate, 6.7 wt% of 1, 4-butanediol diacrylate, 0.8 wt% of catalyst p-toluenesulfonic acid and 0.6 wt% of polymerization inhibitor hydroquinone;
1) a 1, 4-butanediol diacrylate removing and extracting unit, wherein a five-stage centrifugal extractor is used for extracting the coarse reaction liquid of the 4-hydroxybutyl acrylate to remove the by-product of the 1, 4-butanediol diacrylate and the coarse reaction liquid of the 4-hydroxybutyl acrylate: extracting agent cyclohexane is 1:2.1(wt), the extraction temperature is 25 ℃, and the removal rate of 1, 4-butanediol diacrylate is 99.3%;
4-hydroxybutyl acrylate extraction and extraction unit, extracting the water phase obtained in the step 1) by using a two-stage centrifugal extractor, wherein the reaction solution is as follows: the extraction temperature is 25 ℃, and the extraction rate of 4-hydroxybutyl acrylate is 99.1 percent;
removing and extracting a unit by using 1, 4-butanediol, extracting the oil phase obtained in the step 2) by using a five-stage centrifugal extractor, and reacting: extracting agent water is 1:1.3(wt), the extraction temperature is 25 ℃, and the removal rate of 1, 4-butanediol is 99.1%;
the composition of the extract containing 4-hydroxybutyl acrylate obtained in step 1) is calculated by taking the total mass of the extract containing 4-hydroxybutyl acrylate excluding the mass of the extractant as 100 percent, and comprises 0.14 percent of acrylic acid, 0.15 percent of 1, 4-butanediol, 99.2 percent of 4-hydroxybutyl acrylate, 0.2 percent of 1, 4-butanediol diacrylate, 0.25 percent of catalyst p-toluenesulfonic acid and 0.06 percent of polymerization inhibitor hydroquinone;
2) an alkali liquor neutralizing unit, wherein 2 wt% of NaOH aqueous solution is used for neutralizing the extracted oil phase obtained in the step 1), the neutralizing temperature is 20 ℃, and the pH value of the titration end point is 8.1;
and a water washing unit, wherein the obtained neutralized liquid is washed by water, the water washing temperature is 20 ℃, the number of stages is 2, the mass ratio of the water consumption to the neutralized liquid is 0.4:1, and the oil phase after water washing comprises the following components in terms of 100 percent of the total mass of the oil phase excluding the extractant: 0.02 wt% of acrylic acid, 0.35 wt% of 1, 4-butanediol, 99.1 wt% of 4-hydroxybutyl acrylate, 0.45 wt% of 1, 4-butanediol diacrylate, 0.04 wt% of catalyst and 0.04 wt% of polymerization inhibitor;
3) adding the fluorine-containing nitroxide free radical polymerization inhibitor prepared in the example 1 into the oil phase obtained by water washing in the step 2), wherein the adding amount is 1.5 wt% of the total amount of the oil phase after water washing, using a rectifying tower, the number of tower plates is 16, the temperature at the top of the tower is 28 ℃, the pressure at the top of the tower is 50KPaA, the content of light component cyclohexane in the obtained tower bottom liquid is 0.47 wt%, continuously transferring the tower bottom liquid into a short-path evaporator through a pump, the short-path evaporator is internally provided with a condenser, the temperature of the ethylene glycol aqueous solution with the weight percent in a tube pass is-10 ℃, the temperature of the circulating water in the tube pass of a first-stage condenser at the top of the short-path evaporator is 30 ℃, the temperature of the ethylene glycol aqueous solution with the weight percent in the tube pass of a second-stage condenser is-15 ℃, the separation pressure of the product is controlled to be 0.05KPaA, the separation temperature is 105 ℃, obtaining refined 4-hydroxybutyl acrylate, the purity is 99.17%, and the color number is 3, the refining yield was 91.7%, the acid value was 0.009mgKOH/g, the content of the fluorine-containing nitroxide radical polymerization inhibitor entrained in the product was 4ppm, and the polymerization inhibitor hydroquinone was 0 ppm.
Example 6
A continuous refining process of 4-hydroxybutyl acrylate comprises the following steps:
the raw material 4-hydroxybutyl acrylate crude reaction liquid comprises the following components: 1.2 wt% of acrylic acid, 42.5 wt% of 1, 4-butanediol, 48.2 wt% of 4-hydroxybutyl acrylate, 6.7 wt% of 1, 4-butanediol diacrylate, 0.8 wt% of catalyst p-toluenesulfonic acid and 0.6 wt% of polymerization inhibitor hydroquinone;
1) a 1, 4-butanediol diacrylate removing and extracting unit, wherein a five-stage centrifugal extractor is used for extracting the coarse reaction liquid of the 4-hydroxybutyl acrylate to remove the by-product of the 1, 4-butanediol diacrylate and the coarse reaction liquid of the 4-hydroxybutyl acrylate: extracting agent cyclohexane is 1:3(wt), the extraction temperature is 20 ℃, and the removal rate of 1, 4-butanediol diacrylate is 99.8%;
4-hydroxybutyl acrylate extraction and extraction unit, extracting the water phase obtained in the step 1) by using a two-stage centrifugal extractor, wherein the reaction solution is as follows: extracting agent dichloromethane of 1:2(wt), extraction temperature of 20 ℃, extraction rate of 4-hydroxybutyl acrylate of 99.5%;
removing and extracting a unit by using 1, 4-butanediol, extracting the oil phase obtained in the step 2) by using a five-stage centrifugal extractor, and reacting: extracting agent water is 1:2(wt), the extraction temperature is 20 ℃, and the removal rate of 1, 4-butanediol is 99.3%;
the composition of the extract containing 4-hydroxybutyl acrylate obtained in step 1) comprises 0.15 wt% of acrylic acid, 0.11 wt% of 1, 4-butanediol, 99.33 wt% of 4-hydroxybutyl acrylate, 0.15 wt% of 1, 4-butanediol diacrylate, 0.21 wt% of catalyst and 0.05 wt% of polymerization inhibitor, wherein the total mass of the extract containing 4-hydroxybutyl acrylate excluding the mass of the extractant is 100%;
2) an alkali liquor neutralizing unit, wherein 2 wt% of NaOH aqueous solution is used for neutralizing the extracted oil phase obtained in the step 1), the neutralizing temperature is 20 ℃, and the pH value of the titration end point is 8.3;
and a water washing unit, wherein the obtained neutralized liquid is washed by water, the water washing temperature is 20 ℃, the number of stages is 2, the mass ratio of the water consumption to the neutralized liquid is 0.4:1, and the oil phase after water washing comprises the following components in terms of 100 percent of the total mass of the oil phase excluding the extractant: 0.02 wt% of acrylic acid, 0.3 wt% of 1, 4-butanediol, 99.3 wt% of 4-hydroxybutyl acrylate, 0.3 wt% of 1, 4-butanediol diacrylate, 0.04 wt% of catalyst and 0.04 wt% of polymerization inhibitor;
3) adding the fluorine-containing nitroxide free radical polymerization inhibitor prepared in the example 2 into the oil phase obtained by water washing in the step 2), wherein the adding amount is 1.5 wt% of the total amount of the oil phase after water washing, using a rectifying tower, the number of tower plates is 16, the temperature at the top of the tower is 28 ℃, the pressure at the top of the tower is 50KPaA, the content of light component cyclohexane in the obtained tower bottom liquid is 0.41 wt%, continuously transferring the tower bottom liquid into a short-path evaporator through a pump, the short-path evaporator is internally provided with a condenser, the temperature of the ethylene glycol aqueous solution with the weight percent in a tube pass is-10 ℃, the temperature of the circulating water in the tube pass of a first-stage condenser at the top of the short-path evaporator is 30 ℃, the temperature of the ethylene glycol aqueous solution with the weight percent in the tube pass of a second-stage condenser is-15 ℃, the separation pressure of the product is controlled to be 0.05KPaA, the separation temperature is 105 ℃, obtaining refined 4-hydroxybutyl acrylate, the purity is 99.31%, and the color number is 2, the refining yield was 91.1%, the acid value was 0.005mgKOH/g, the content of the fluorine-containing nitroxide radical polymerization inhibitor entrained in the product was 3ppm, and the polymerization inhibitor hydroquinone was 0 ppm.
Example 7
A continuous refining process of 4-hydroxybutyl acrylate comprises the following steps:
the raw material 4-hydroxybutyl acrylate crude reaction liquid comprises the following components: 1.2 wt% of acrylic acid, 42.5 wt% of 1, 4-butanediol, 48.2 wt% of 4-hydroxybutyl acrylate, 6.7 wt% of 1, 4-butanediol diacrylate, 0.8 wt% of catalyst p-toluenesulfonic acid and 0.6 wt% of polymerization inhibitor hydroquinone;
1) a 1, 4-butanediol diacrylate removing and extracting unit, wherein a five-stage centrifugal extractor is used for extracting the coarse reaction liquid of the 4-hydroxybutyl acrylate to remove the by-product of the 1, 4-butanediol diacrylate and the coarse reaction liquid of the 4-hydroxybutyl acrylate: extracting agent cyclohexane is 1:2.5(wt), the extraction temperature is 25 ℃, and the removal rate of 1, 4-butanediol diacrylate is 99.4%;
4-hydroxybutyl acrylate extraction and extraction unit, extracting the water phase obtained in the step 1) by using a two-stage centrifugal extractor, wherein the reaction solution is as follows: the extraction temperature is 25 ℃, and the extraction rate of 4-hydroxybutyl acrylate is 99.2%;
removing and extracting a unit by using 1, 4-butanediol, extracting the oil phase obtained in the step 2) by using a five-stage centrifugal extractor, and reacting: extracting agent water is 1:1.5(wt), the extraction temperature is 25 ℃, and the removal rate of 1, 4-butanediol is 99.3%;
the extract containing 4-hydroxybutyl acrylate obtained in step 1) is calculated by taking the total mass of the extract containing 4-hydroxybutyl acrylate excluding the mass of the extractant as 100 percent, and comprises 0.2 percent by weight of acrylic acid, 0.12 percent by weight of 1, 4-butanediol, 99.3 percent by weight of 4-hydroxybutyl acrylate, 0.13 percent by weight of 1, 4-butanediol diacrylate, 0.2 percent by weight of catalyst and 0.05 percent by weight of polymerization inhibitor;
2) an alkali liquor neutralizing unit, wherein 2 wt% of NaOH aqueous solution is used for neutralizing the extracted oil phase obtained in the step 1), the neutralizing temperature is 20 ℃, and the pH value of the titration end point is 8.5;
and a water washing unit, wherein the obtained neutralized liquid is washed by water, the water washing temperature is 20 ℃, the number of stages is 2, the mass ratio of the water consumption to the neutralized liquid is 0.4:1, and the oil phase after water washing comprises the following components in terms of 100 percent of the total mass of the oil phase excluding the extractant: 0.01 wt% of acrylic acid, 0.33 wt% of 1, 4-butanediol, 99.17 wt% of 4-hydroxybutyl acrylate, 0.43 wt% of 1, 4-butanediol diacrylate, 0.03 wt% of catalyst and 0.03 wt% of polymerization inhibitor;
3) adding the fluorine-containing nitroxide free radical polymerization inhibitor prepared in the example 3 into the oil phase obtained by water washing in the step 2), wherein the adding amount is 1.5 wt% of the total amount of the oil phase after water washing, using a rectifying tower, the number of tower plates is 16, the temperature at the top of the tower is 28 ℃, the pressure at the top of the tower is 50KPaA, the content of light component cyclohexane in the obtained tower bottom liquid is 0.42 wt%, continuously transferring the tower bottom liquid into a short-path evaporator through a pump, the short-path evaporator is internally provided with a condenser, the temperature of the ethylene glycol aqueous solution with the weight percent in a tube pass is-10 ℃, the temperature of the circulating water in the tube pass of a first-stage condenser at the top of the short-path evaporator is 30 ℃, the temperature of the ethylene glycol aqueous solution with the weight percent in the tube pass of a second-stage condenser is-15 ℃, the separation pressure of the product is controlled to be 0.05KPaA, the separation temperature is 105 ℃, obtaining refined 4-hydroxybutyl acrylate, the purity is 99.34%, and the color number is 2, the refining yield is 90.9%, the acid value is 0.008mgKOH/g, the content of fluorine-containing nitroxide free radical polymerization inhibitor carried in the product is 3ppm, and the content of polymerization inhibitor hydroquinone is 0 ppm.
Example 8
A continuous refining process of 4-hydroxybutyl acrylate comprises the following steps:
the raw material 4-hydroxybutyl acrylate crude reaction liquid comprises the following components: 1.2 wt% of acrylic acid, 42.5 wt% of 1, 4-butanediol, 48.2 wt% of 4-hydroxybutyl acrylate, 6.7 wt% of 1, 4-butanediol diacrylate, 0.8 wt% of catalyst p-toluenesulfonic acid and 0.6 wt% of polymerization inhibitor hydroquinone;
1) a 1, 4-butanediol diacrylate removing and extracting unit, wherein a five-stage centrifugal extractor is used for extracting the coarse reaction liquid of the 4-hydroxybutyl acrylate to remove the by-product of the 1, 4-butanediol diacrylate and the coarse reaction liquid of the 4-hydroxybutyl acrylate: extracting agent cyclohexane is 1:3(wt), the extraction temperature is 25 ℃, and the removal rate of 1, 4-butanediol diacrylate is 99.5%;
4-hydroxybutyl acrylate extraction and extraction unit, extracting the water phase obtained in the step 1) by using a two-stage centrifugal extractor, wherein the reaction solution is as follows: the extraction temperature is 25 ℃, and the extraction rate of 4-hydroxybutyl acrylate is 99.5 percent;
removing and extracting a unit by using 1, 4-butanediol, extracting the oil phase obtained in the step 2) by using a five-stage centrifugal extractor, and reacting: extracting agent water is 1:3(wt), the extraction temperature is 25 ℃, and the removal rate of 1, 4-butanediol is 99.4%;
the extract containing 4-hydroxybutyl acrylate obtained in the step 1) is calculated by taking the total mass of the extract containing 4-hydroxybutyl acrylate excluding the mass of the extractant as 100 percent, and comprises 0.1 percent by weight of acrylic acid, 0.1 percent by weight of 1, 4-butanediol, 99.45 percent by weight of 4-hydroxybutyl acrylate, 0.15 percent by weight of 1, 4-butanediol diacrylate, 0.15 percent by weight of catalyst and 0.05 percent by weight of polymerization inhibitor;
2) an alkali liquor neutralizing unit, wherein 2 wt% of NaOH aqueous solution is used for neutralizing the extracted oil phase obtained in the step 1), the neutralizing temperature is 20 ℃, and the pH value of the titration end point is 8.0;
and a water washing unit, wherein the obtained neutralized liquid is washed by water, the water washing temperature is 20 ℃, the number of stages is 2, the mass ratio of the water consumption to the neutralized liquid is 0.4:1, and the oil phase after water washing comprises the following components in terms of 100 percent of the total mass of the oil phase excluding the extractant: 0.01 wt% of acrylic acid, 0.20 wt% of 1, 4-butanediol, 99.5 wt% of 4-hydroxybutyl acrylate, 0.25 wt% of 1, 4-butanediol diacrylate, 0.02 wt% of catalyst and 0.02 wt% of polymerization inhibitor;
3) adding the fluorine-containing nitroxide free radical polymerization inhibitor prepared in the example 4 into the oil phase obtained by water washing in the step 2), wherein the adding amount is 1.5 wt% of the total amount of the oil phase after water washing, using a rectifying tower, the number of tower plates is 16, the temperature at the top of the tower is 28 ℃, the pressure at the top of the tower is 50KPaA, the content of light component cyclohexane in the obtained tower bottom liquid is 0.40 wt%, continuously transferring the tower bottom liquid into a short-path evaporator through a pump, the short-path evaporator is internally provided with a condenser, the temperature of the ethylene glycol aqueous solution with the weight percent in a tube pass is-10 ℃, the temperature of the circulating water in the tube pass of a first-stage condenser at the top of the short-path evaporator is 30 ℃, the temperature of the ethylene glycol aqueous solution with the weight percent in the tube pass of a second-stage condenser is-15 ℃, the separation pressure of the product is controlled to be 0.05KPaA, the separation temperature is 105 ℃, obtaining refined 4-hydroxybutyl acrylate, the purity is 99.39%, and the color number is 1, the refining yield is 92.74%, the acid value is 0.004mgKOH/g, the content of fluorine-containing nitroxide free radical polymerization inhibitor carried in the product is 2ppm, and the content of polymerization inhibitor hydroquinone is 0 ppm.
Comparative example 1
The process for refining 4-hydroxybutyl acrylate (batch type) was performed in the same manner as in example 5 using the raw material, namely, the crude reaction mixture of 4-hydroxybutyl acrylate, and the steps were as follows:
1) the method comprises the following steps of (1), removing an extraction unit from 1, 4-butanediol diacrylate, extracting reaction liquid by using a separating funnel, removing 1, 4-butanediol diacrylate as a byproduct, and reacting the reaction liquid: extracting agent cyclohexane is 1:2.1(wt), the extraction temperature is 25 ℃, and the removal rate of 1, 4-butanediol diacrylate is 71.1%;
2) 4-hydroxybutyl acrylate extraction unit, extracting the water phase obtained in the step 1) by using a separating funnel, wherein the reaction solution is as follows: the extraction temperature is 25 ℃, and the extraction rate of 4-hydroxybutyl acrylate is 89.3 percent;
3) removing an extraction unit from 1, 4-butanediol, extracting the oil phase obtained in the step 2) by using a separating funnel, and reacting: extracting agent water is 1:1.3(wt), the extraction temperature is 25 ℃, and the removal rate of 1, 4-butanediol is 73.4%;
4) an alkali liquor neutralizing unit, wherein 2 wt% NaOH aqueous solution is used for neutralizing the oil phase obtained in the step 3), the neutralizing temperature is 20 ℃, and the titration end point is 8.2;
5) a water washing unit, washing the neutralized liquid obtained in the step 4) with water, wherein the water washing temperature is 20 ℃, the number of stages is 2, the mass ratio of the water consumption to the neutralized liquid is 0.4:1, and the oil phase after water washing comprises the following components by 100 percent of the total mass of the oil phase excluding the extractant: 0.02 wt% of acrylic acid, 11.8 wt% of 1, 4-butanediol, 86.2 wt% of 4-hydroxybutyl acrylate, 1.9 wt% of 1, 4-butanediol diacrylate, 0.04 wt% of catalyst and 0.04 wt% of polymerization inhibitor;
6) adding the fluorine-containing nitroxide radical polymerization inhibitor prepared in the example 1 into the oil phase obtained by water washing, wherein the amount of the fluorine-containing nitroxide radical polymerization inhibitor is 1.5 wt% of the total amount of the oil phase after water washing, using a rectifying tower, the number of tower plates is 16, the temperature of the tower top is 28 ℃, the pressure of the tower top is 50KPaA, the content of light component cyclohexane in the obtained tower bottom liquid is 0.47 wt%, continuously transferring the tower bottom liquid into a short-range evaporator through a pump, arranging a condenser in the short-range evaporator, wherein the temperature of an ethylene glycol aqueous solution is 45 wt% in a pipe pass, the temperature is-10 ℃, the temperature of circulating water in the pipe pass of a first-stage condenser at the top of the short-range evaporator is 30 ℃, the temperature of an ethylene glycol aqueous solution is 45 wt% in the pipe pass of a second-stage condenser is-15 ℃, controlling the separation pressure of the product to be 0.05KPaA and the separation temperature to be 105 ℃, obtaining refined 4-hydroxybutyl acrylate, the purity is 87.3%, the color number is 4, the purification yield was 68.2%, and the acid value was 0.019 mgKOH/g.
Comparative example 2
Preparing a fluorine-containing nitroxide free radical polymerization inhibitor, wherein in the step 2), the molar ratio of perfluoroolefin to 2,2,6, 6-tetramethylpiperidine acrylate is not within the range of 0.5-3: 1, and the steps are as follows:
1) adding methyl acrylate and 2,2,6, 6-tetramethylpiperidinol into a reaction kettle according to the amount of 2.5:1(mol), reacting at 105 ℃ for 10 hours, and after the ester exchange reaction is finished, distilling the methyl acrylate and the reaction byproduct methanol in the methyl acrylate under the pressure of 20KPaA to obtain 2,2,6, 6-tetramethylpiperidineacrylate;
2) cooling the reaction liquid in the step (1) to 50 ℃ by adopting circulating water at 28 ℃, adding tetrafluoroethylene into a reaction kettle, wherein the addition amount of the tetrafluoroethylene is as follows: 2,2,6, 6-tetramethyl piperidine acrylate is 1:3(mol), then high-pressure nitrogen is filled to ensure that the pressure in the reaction kettle is 2.0MPaG, the reaction is finished after 10 hours, the pressure in the reaction kettle is relieved, and the reaction kettle is replaced by nitrogen for three times;
3) adding sodium tungstate and hydrogen peroxide into a reaction kettle, wherein the adding amount of the hydrogen peroxide is as follows: the 2,2,6, 6-tetramethylpiperidine acrylate is 1:1.2(mol), and the addition amount of sodium tungstate is: 2,2,6, 6-tetramethyl piperidinol is 0.15:1(wt), and the reaction is finished after the reaction temperature is increased to 110 ℃ and the reaction is carried out for 40 h;
4) cooling the reaction liquid to room temperature, adding hot water and toluene, shaking uniformly, standing for 1h, taking an oil phase, carrying out reduced pressure distillation to remove a solvent toluene in the oil phase, and preparing the fluorine-containing nitroxide radical polymerization inhibitor, wherein in the structural formula, the m value is about 2-3, the n value is about 55-56, the molecular weight is about 11800(Mn), the fluorine content is about 1.4-1.5 wt%, the nitroxide radical content is about 13.1-13.2 wt%, the color number is 49, and the boiling point is 635 ℃;
the preparation process of the comparative example changes the proportion of perfluoroolefin and 2,2,6, 6-tetramethyl piperidine acrylate, so that the obtained fluorine-containing nitroxide free radical polymerization inhibitor has m and n values, molecular weight, fluorine content and nitroxide free radical content which are beyond the range of the invention, and the polymerization inhibitor has higher color number.
The polymerization inhibitor added in the step 3) of the example 5 is replaced by the fluorine-containing nitroxide radical-containing polymerization inhibitor obtained in the step 4 of the comparative example 2, and the purified 4-hydroxybutyl acrylate has the purity of 99.05%, the color number of 35, the purification yield of 90.5% and the acid value of 0.009 mgKOH/g.
Comparative example 3
Changing the sequence of three-step continuous extraction, comprising the following steps:
the raw material 4-hydroxybutyl acrylate crude reaction liquid comprises the following components: 1.3 wt% of acrylic acid, 41.8 wt% of 1, 4-butanediol, 47.9 wt% of 4-hydroxybutyl acrylate, 7.4 wt% of 1, 4-butanediol diacrylate, 0.9 wt% of catalyst p-toluenesulfonic acid and 0.7 wt% of polymerization inhibitor hydroquinone;
1) 4-hydroxybutyl acrylate extraction unit, extracting a reaction liquid phase by using a separating funnel, wherein the reaction liquid: the extraction temperature is 25 ℃, the extraction rate of 4-hydroxybutyl acrylate is 68.1 percent, and the extraction rate of 1, 4-butanediol diacrylate is 79.9 percent;
2) removing an extraction unit from the 1, 4-butanediol diacrylate, extracting the oil phase obtained in the step 1) by using a separating funnel, removing a 1, 4-butanediol diacrylate byproduct, and obtaining a reaction solution: the extraction temperature is 25 ℃, the two phases are miscible, and the aim of continuously separating phases cannot be fulfilled.
Comparative example 4
A continuous purification process of 4-hydroxybutyl acrylate, using a high boiling point radical polymerization inhibitor containing nitrogen and oxygen but not containing fluorine, was different from example 5 in that: in the step 3), ZJ-701 polymerization inhibitor is adopted, the content of light component cyclohexane in the obtained tower bottom liquid is 0.52 wt%, the purity of the refined 4-hydroxybutyl acrylate product is 99.01%, and the color number is 58. After the ZJ-701 polymerization inhibitor is used for replacing the high-boiling-point polymerization inhibitor containing fluorine and nitroxide free radicals, although the purity of the product obtained by refining is basically consistent, the color number of the obtained product is obviously higher, and the refining effect of the method cannot be realized.
Comparative example 5
The continuous refining process of 4-hydroxybutyl acrylate is different from that of example 5 in that: in the step 3), a p-methoxyphenol polymerization inhibitor is adopted, the content of light component cyclohexane in the obtained tower bottom liquid is 0.55 wt%, the purity of the refined 4-hydroxybutyl acrylate product is 98.98%, the color number is 52, and the content of p-methoxyphenol in the product is 0.22 wt%. After the high-boiling-point polymerization inhibitor containing fluorine and nitroxide free radicals is replaced by the p-methoxyphenol polymerization inhibitor, the color number of the product is higher, and the content of the polymerization inhibitor carried by the product is higher, so that the downstream use is influenced.

Claims (40)

1. A fluorine-containing nitroxide free radical polymerization inhibitor is at least one of the following structural formulas:
Figure FDA0003040334200000011
wherein m and n are 5 to 50 independently.
2. The fluorine-containing nitroxide radical-containing polymerization inhibitor according to claim 1, characterized in that: the structure is as follows
Figure FDA0003040334200000012
3. The fluorine-containing nitroxide radical-containing polymerization inhibitor according to claim 1, characterized in that: the m and n values are respectively and independently 8-15.
4. The fluorine-containing nitroxide radical-containing polymerization inhibitor according to claim 1, characterized in that: the number average molecular weight of the fluorine-containing nitroxide free radical polymerization inhibitor is 2000-4000; and/or
The fluorine content in the fluorine-containing nitroxide free radical polymerization inhibitor is 3-62 wt%; and/or
The content of nitroxide free radicals in the fluorine-containing nitroxide free radical polymerization inhibitor is 2-13 wt%; and/or
The boiling point of the fluorine-containing nitroxide free radical polymerization inhibitor is 500-800 ℃; and/or
The fluorine-containing nitroxide free radical polymerization inhibitor is a white solid with the color number of 0.
5. The fluorine-containing nitroxide radical-containing polymerization inhibitor according to claim 4, characterized in that: the number average molecular weight of the fluorine-containing nitroxide free radical polymerization inhibitor is 2500-3000; and/or
The fluorine content in the fluorine-containing nitroxide free radical polymerization inhibitor is 14-35 wt%; and/or
The content of nitroxide free radicals in the fluorine-containing nitroxide free radical polymerization inhibitor is 7-11 wt%; and/or
The boiling point of the fluorine-containing nitroxide free radical polymerization inhibitor is 550-700 ℃.
6. A process for producing a fluorine-containing nitroxide radical-containing polymerization inhibitor according to any one of claims 1 to 5, which comprises the steps of:
(1) carrying out ester exchange reaction on methyl acrylate and 2,2,6, 6-tetramethyl piperidinol to obtain 2,2,6, 6-tetramethyl piperidineacrylate;
(2) adding perfluoroolefin into the reaction liquid obtained in the step (1) to perform copolymerization with 2,2,6, 6-tetramethyl piperidine acrylate;
(3) and (3) adding sodium tungstate and hydrogen peroxide into the reaction liquid obtained in the step (2) to carry out oxidation reaction, thereby obtaining the fluorine-containing nitroxide free radical polymerization inhibitor.
7. The method of claim 6, wherein: in the step (1), the transesterification reaction is carried out at the temperature of 90-120 ℃ for 6-12 h;
the molar ratio of the methyl acrylate to the 2,2,6, 6-tetramethyl piperidinol is 1.5-5: 1; and/or
In the step (2), the copolymerization polymerization reaction is carried out at the reaction temperature of 30-60 ℃ for 5-15 h and at the reaction pressure of 4-8 MPaG;
the mol ratio of the perfluoroolefin to the 2,2,6, 6-tetramethyl piperidine acrylate is 0.5-3: 1; and/or
In the step (3), the oxidation reaction is carried out at the temperature of 100-110 ℃ for 36-48 h;
the mass ratio of the sodium tungstate to the 2,2,6, 6-tetramethyl piperidine acrylate is 0.05-0.5: 1;
the molar ratio of the hydrogen peroxide to the 2,2,6, 6-tetramethyl piperidinol ester is 0.8-2: 1.
8. The method of claim 7, wherein: in the step (1), the transesterification reaction is carried out at the temperature of 100-110 ℃ for 8-10 h.
9. The method of claim 7, wherein: in the step (1), the molar ratio of the methyl acrylate to the 2,2,6, 6-tetramethyl piperidinol is 2-3: 1.
10. The method of claim 7, wherein: in the step (2), the copolymerization reaction is carried out at the reaction temperature of 40-50 ℃ for 7-10 h and at the reaction pressure of 5-7 MPaG.
11. The method of claim 7, wherein: in the step (2), the molar ratio of the perfluoroolefin to the 2,2,6, 6-tetramethylpiperidine acrylate is 1-2.5: 1.
12. The method of claim 7, wherein: in the step (3), the mass ratio of the sodium tungstate to the 2,2,6, 6-tetramethyl piperidine acrylate is 0.08-0.15: 1; the molar ratio of the hydrogen peroxide to the 2,2,6, 6-tetramethyl piperidinol ester is 1-1.5: 1.
13. A continuous refining process of 4-hydroxybutyl acrylate is characterized by comprising the following steps:
1) extracting and separating the coarse reaction liquid of the 4-hydroxybutyl acrylate continuously in three steps to obtain an extraction liquid containing the 4-hydroxybutyl acrylate;
2) step 1), carrying out alkali liquor neutralization and water washing on the extract liquor to obtain a washed oil phase;
3) adding the fluorine-containing nitroxide free radical polymerization inhibitor which is described in any one of claims 1-5 or prepared by the method described in any one of claims 6-12 into the oil phase after the step 2) water washing, removing light components by rectification, and obtaining the 4-hydroxybutyl acrylate by short-path distillation.
14. The continuous refining process of claim 13, characterized by: in the step 1), the crude reaction liquid of 4-hydroxybutyl acrylate comprises the following components by taking the total mass of the crude reaction liquid of 4-hydroxybutyl acrylate as 100 percent: 0.5-5 wt% of acrylic acid, 40-60 wt% of 1, 4-butanediol, 40-50 wt% of 4-hydroxybutyl acrylate, 1-10 wt% of 1, 4-butanediol diacrylate, 0.5-2 wt% of catalyst and 0.1-1 wt% of polymerization inhibitor;
the catalyst is at least one of concentrated sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid;
the polymerization inhibitor is at least one of phenothiazine, hydroquinone, p-methoxyphenol, ZJ-701, ZJ-705 and N, N-di-N-butyl copper dithiocarbamate.
15. The continuous refining process of claim 13, characterized by: in the step 1), the three-step continuous extraction separation comprises tower separation or centrifugal separation, and equipment adopted is at least one of a filler extraction tower, a sieve plate extraction tower, a rotary disc extraction tower and a centrifugal extractor;
the three-step continuous extraction comprises a 1, 4-butanediol diacrylate removing and extracting unit, a 4-hydroxybutyl acrylate extracting and extracting unit and a 1, 4-butanediol removing and extracting unit;
the extracting agent used in the 1, 4-butanediol diacrylate removing and extracting unit is at least one or a mixture of more of cyclohexane, normal hexane, normal heptane, normal pentane, xylene and toluene;
the extractant used in the 4-hydroxybutyl acrylate extraction unit is at least one or a mixture of dichloromethane, butyl acetate, trichloromethane and carbon tetrachloride;
the extracting agent used in the 1, 4-butanediol removing and extracting unit is at least one or a mixture of water, 5-10 wt% of NaCl aqueous solution and 5-10 wt% of KCl aqueous solution.
16. The continuous refining process of claim 15, characterized by: the equipment is a centrifugal extractor.
17. The continuous refining process of claim 15, characterized by: the extracting agent used in the 1, 4-butanediol diacrylate removing and extracting unit is n-hexane.
18. The continuous refining process of claim 15, characterized by: the mass ratio of the 4-hydroxybutyl acrylate crude reaction liquid to the extractant of the 1, 4-butanediol diacrylate removing and extracting unit is 1: 2-3, the number of extraction stages is 5-10, and the temperature is 20-30 ℃.
19. The continuous refining process of claim 15, characterized by: the extractant used in the extraction unit for extracting the 4-hydroxybutyl acrylate is dichloromethane.
20. The continuous refining process of claim 15, characterized by: in the 4-hydroxybutyl acrylate extraction unit, the mass ratio of the crude reaction liquid of the 4-hydroxybutyl acrylate to the extractant is 1: 1-3, the extraction stage number is 2-5, and the temperature is 20-30 ℃.
21. The continuous refining process of claim 15, characterized by: the extracting agent used in the 1, 4-butanediol removing and extracting unit is water.
22. The continuous refining process of claim 15, characterized by: the mass ratio of the 1, 4-butanediol removal extraction unit to the 4-hydroxybutyl acrylate crude reaction liquid to the extractant is 1: 1-3, the extraction stage number is 5-10, and the temperature is 20-30 ℃.
23. The continuous refining process of claim 13, characterized by: in the step 2), the alkali liquor is neutralized, and the alkali liquor used is at least one of NaOH aqueous solution and KOH aqueous solution; neutralizing the alkali liquor, wherein the pH is controlled within the range of 7-10, and the temperature is 15-40 ℃; and/or
And (3) washing, wherein the mass ratio of the water consumption to the neutralizing solution is 0.1-2: 1; the temperature is 15-40 ℃.
24. The continuous refining process of claim 23, wherein: the alkali liquor is NaOH aqueous solution.
25. The continuous refining process of claim 23, wherein: and neutralizing the alkali liquor, wherein the pH control range is 8-9.
26. The continuous refining process of claim 23, wherein: and neutralizing the alkali liquor at the temperature of 20-35 ℃.
27. The continuous refining process of claim 26, wherein: and neutralizing the alkali liquor at 25-30 ℃.
28. The continuous refining process of claim 23, wherein: and washing with water, wherein the mass ratio of the water consumption to the neutralizing solution is 0.3-1: 1.
29. The continuous refining process of claim 23, wherein: and washing with water at the temperature of 20-35 ℃.
30. The continuous refining process of claim 29, wherein: and washing with water at the temperature of 25-30 ℃.
31. The continuous refining process of claim 13, characterized by: in the step 3), the adding amount of the fluorine-containing nitroxide free radical polymerization inhibitor is 0.1-5 wt% of the total amount of the oil phase after washing.
32. The continuous refining process of claim 31, wherein: the addition amount of the fluorine-containing nitroxide free radical polymerization inhibitor is 1-2 wt% of the total amount of the oil phase after washing.
33. The continuous refining process of claim 13, characterized by: in the step 3), the number of theoretical plates of a rectifying tower adopted for rectifying is 10-20; the rectifying tower adopts a continuous feeding mode; the tower top temperature of the rectifying tower is 15-35 ℃; the pressure at the top of the tower is 40-85 KPaA; and/or
The light component is an extractant remained in the three-step continuous extraction and separation operation in the step 1); and/or
The short-path distillation is carried out at the pressure of 0.01-1 KPaA and the temperature of 70-180 ℃; the short-path distillation is carried out in a short-path evaporator, the short-path evaporator comprises a built-in condenser, and the tube side temperature of the built-in condenser is-60-10 ℃.
34. The continuous refining process of claim 33, wherein: and in the rectification, the number of theoretical plates of a rectifying tower is 12-18.
35. The continuous refining process of claim 33, wherein: the top temperature of the rectifying tower is 20-30 ℃, and the top pressure is 45-70 KPaA.
36. The continuous refining process of claim 33, wherein: the light component is a mixture of n-hexane, dichloromethane and water.
37. The continuous refining process of claim 33, wherein: the short-path distillation is carried out at the pressure of 0.02-0.1 KPaA and the temperature of 90-150 ℃.
38. The continuous refining process of claim 33, wherein: the tube side temperature of the built-in condenser is-25-5 ℃.
39. The continuous refining process of claim 33, wherein: a gas phase outlet of the short-path evaporator is provided with a two-stage condenser, and the tube side temperature of the first-stage condenser is 28-40 ℃; the tube side temperature of the second-stage condenser is-60-10 ℃.
40. The continuous refining process of claim 33, wherein: a gas phase outlet of the short-range evaporator is provided with a two-stage condenser, and the tube side temperature of the first-stage condenser is 30-38 ℃; the tube side temperature of the second-stage condenser is-25-5 ℃.
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