CN112920306B - Resin for adsorbing parachloroaniline in para-ester, synthetic method and application thereof - Google Patents
Resin for adsorbing parachloroaniline in para-ester, synthetic method and application thereof Download PDFInfo
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- CN112920306B CN112920306B CN202110317688.6A CN202110317688A CN112920306B CN 112920306 B CN112920306 B CN 112920306B CN 202110317688 A CN202110317688 A CN 202110317688A CN 112920306 B CN112920306 B CN 112920306B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention relates to a resin for adsorbing p-chloroaniline in p-ester, a synthetic method and application thereof. The synthesis method comprises the following steps: mixing a polystyrene polymer, aluminum trichloride and dimethyl fumarate for reaction to obtain a dimethyl fumarate modified polymer; and cleaning and drying the dimethyl fumarate modified polymer to obtain the resin for adsorbing the parachloroaniline. Through covalent bonding of dimethyl fumarate molecules on the surface of the polystyrene polymer, a hydrogen bond effect or an adsorption effect can be generated on the amino group of p-chloroaniline, and the p-chloroaniline has a very small adsorption effect on the p-ester, so that differential adsorption can be generated between the p-chloroaniline and the p-ester, and the p-chloroaniline in the p-ester product can be removed very conveniently.
Description
Technical Field
The invention relates to the technical field of dye intermediates, in particular to a resin for adsorbing p-chloroaniline in para-ester, a synthetic method and application thereof.
Background
Para- (beta-hydroxyethyl sulfone sulfate) aniline, also known as para-ester, is an important intermediate for the synthesis of reactive dyes. In the synthesis of para-ester, the prior synthesis process mainly comprises the steps of sulfonating aniline by chlorosulfonic acid thionyl chloride, reducing the sulfonated product, condensing with ethylene oxide, and finally carrying out sulfation, wherein the final product contains a certain amount of para-chloroaniline which is one of arylamines. With the improvement of the national requirement on the green environmental protection property of printing and dyeing textile products, the requirement on the forbidden arylamine in the textile products is more and more strict, so that the most direct influence is the control of the textile printing and dyeing industry on the related indexes of the used dyeing dye, and the national also establishes the standard of the forbidden arylamine in the dye and the dye intermediate.
In order to control the parachloroaniline in the para- (beta-hydroxyethyl sulfone sulfate) aniline to reach the national standard, the existing process comprises the improvement of the synthesis process of para-ester, for example, the para-beta-hydroxyethyl sulfone sulfate aniline is obtained by using acetanilide as a starting material and sequentially carrying out chlorosulfonation, reduction, condensation, esterification and the like. The method has the advantages of high yield of para-ester, excellent amino value and ester value, and difficult reduction of para-chloroaniline in the product to meet the requirements of national standards.
In addition, the content of parachloroaniline is reduced by adsorption filtration, which is commonly used by various manufacturers, and can dispose of parachloroaniline by-product generated in the synthesis of para-ester, but the cost is relatively high, and solid waste is generated, which not only increases the production cost, but also increases the risk of environmental pollution.
Disclosure of Invention
In view of the above, there is a need to provide a resin for adsorbing p-chloroaniline in para-ester, which can effectively reduce the content of p-chloroaniline in the synthesized para-ester, improve the product quality of para-ester, reduce the production cost, and reduce the risk of environmental pollution, so as to meet the national standard for banning arylamine in dyes and dye intermediates.
The invention provides a synthetic method of resin for adsorbing parachloroaniline in para-ester, which comprises the following steps:
mixing a polystyrene polymer, aluminum trichloride and dimethyl fumarate to react to obtain a dimethyl fumarate modified polymer; and
and cleaning and drying the dimethyl fumarate modified polymer to obtain the resin for adsorbing p-chloroaniline in the para-ester.
Wherein the polystyrene polymer is a styrene-divinylbenzene polymer.
Wherein the mass ratio of the polystyrene polymer to the aluminum trichloride to the dimethyl fumarate is (4-6): 1, (0.8-1.2).
Specifically, the reaction temperature of the polystyrene polymer, the aluminum trichloride and the dimethyl fumarate is 80-130 ℃.
Specifically, after a polystyrene polymer is mixed with a part of aluminum trioxide, dimethyl fumarate and the remaining aluminum trioxide are added to the mixture to react sufficiently.
Furthermore, the temperature condition for mixing part of aluminum trioxide of the polystyrene polymer is 80-95 ℃, and the treatment time is not less than 4 h.
Further, the temperature condition for adding dimethyl fumarate and the rest aluminum trioxide into the mixture to carry out sufficient reaction is 120-130 ℃, and the reaction time is not less than 4 hours.
Further, the mass of the aluminum trioxide and the polystyrene polymer which are mixed together is 30-40% of the total amount required for synthesis.
The invention also provides a resin prepared by the synthesis method.
The invention also provides application of the resin in removing or reducing the content of parachloroaniline in a synthesized para-ester product.
Has the advantages that:
according to the p-chloroaniline adsorbing resin provided by the invention, dimethyl fumarate molecules are covalently bonded on the surface of a polystyrene polymer, so that a hydrogen bond effect or an adsorption effect can be generated on the amino group of p-chloroaniline, a very small adsorption effect is realized on the p-ester, differential adsorption can be generated between the p-chloroaniline and the p-ester, and the p-chloroaniline in the p-ester product can be removed very conveniently.
Drawings
FIG. 1 is a dynamic permeation diagram of a resin-packed chromatography column prepared according to the present invention, wherein C0For initial content of upper column solution, CtThe content of the effluent liquid at the time t after the column is loaded.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a synthetic method for adsorbing p-chloroaniline resin in para-ester, which comprises the following steps:
mixing a polystyrene polymer, aluminum trichloride and dimethyl fumarate for reaction to obtain a dimethyl fumarate modified polymer; and
and cleaning and drying the dimethyl fumarate modified polymer to obtain the resin for adsorbing the parachloroaniline.
The resin synthesized by the method effectively reduces the content of parachloroaniline in the synthesized para-ester product, improves the product quality of the para-ester, reduces the production cost, and simultaneously can reduce the risk of environmental pollution, thereby reaching the national standard of forbidding arylamine in dyes and dye intermediates.
The polystyrene polymer may be a polymer synthesized by free radical addition polymerization of styrene monomer, and specifically may include common polystyrene, Expanded Polystyrene (EPS), High Impact Polystyrene (HIPS) and Syndiotactic Polystyrene (SPS), or styrene-divinylbenzene polymer.
The styrene-divinylbenzene polymer is in a microsphere structure and can adopt a suspension polymerization method, a seed swelling method, a precipitation polymerization method and a micro-engineering emulsification technology. The method for preparing the monodisperse porous styrene-divinylbenzene microsphere by the micro-engineering emulsification technology comprises a microporous membrane/microchannel emulsification method and a micro-fluidic technology. The microporous membrane/microchannel emulsification method is characterized in that an organic phase (comprising a monomer, a cross-linking agent, an initiator and a pore-forming agent) passes through a microporous membrane or a microchannel under the action of pressure to form liquid drops under the action of interfacial tension, and the liquid drops enter a continuous phase to form a suspension system under the action of the shearing force of a flowing continuous phase and then are polymerized. The particle size of the microspheres can be regulated and controlled by changing the pore diameter of the microporous membrane/microchannel. The microporous membrane is different from the microchannel emulsification method in that the microporous membrane reduces the particle size distribution by a certain technology during the preparation of materials, the variation coefficient of the particle size is generally between 10% and 17%, and the microchannel emulsification technology is to prepare micropores on silica gel, metal or polymer materials, and the variation coefficient of the particle size is generally less than 5%. The micro-fluidic technology is that the mutual shearing force between the dispersed phase micro-fine streamline and the flowing continuous phase is utilized to continuously obtain monodisperse liquid drops in a micro-scale range, then polymerization is carried out, and the pore-making agent is removed after the reaction is finished to obtain the porous microspheres. The particle size of the microspheres is typically from a few microns to several hundred microns, with a coefficient of variation of the particle size typically less than 3%.
Because the benzene ring of the styrene-divinylbenzene microsphere has higher reaction activity, different functional groups such as chloromethyl, carboxyl, hydroxyl, nitro, amino, sulfonic group and the like can be introduced into the surface of the benzene ring by utilizing the substitution reaction of the benzene ring. The resin prepared by the invention is obtained by the method provided by the embodiment of the invention, namely, one carbonyl group of dimethyl fumarate is bonded to the surface of the microsphere through the action of aluminum trichloride. Since the dimethyl fumarate molecule contains two carbonyl groups and two ether bonds, namely a double bond, the dimethyl fumarate can generate hydrogen bonding action or adsorption action on the amino group of p-chloroaniline, and is extremely favorable for removing the p-chloroaniline.
Specifically, the mass ratio of the polystyrene polymer to the aluminum trichloride to the dimethyl fumarate is (4-6): 1, (0.8-1.2). The polystyrene polymer prepared by the method has the average particle size of 100um, the variation coefficient of the particle size of 4.8 percent and monodispersity. The aluminum trichloride is anhydrous aluminum chloride, and can be a product of Jiangsu Reheng chemical industry Co. Dimethyl fumarate is available from Shanghai Michell chemical technology, Inc.
Specifically, the reaction temperature of the polystyrene polymer, the aluminum trichloride and the dimethyl fumarate is 80-130 ℃. Specifically, when the polystyrene polymer is styrene-divinylbenzene microspheres, anhydrous aluminum trioxide and the styrene-divinylbenzene microspheres can be mixed at the temperature of 80-95 ℃ and treated for not less than 4 hours; and adding dimethyl fumarate, controlling the temperature to be 120-130 ℃, and then treating for not less than 4 hours to complete the reaction.
Specific examples of the synthesis of a typical p-chloroaniline adsorbing resin are as follows:
1. weighing styrene-divinylbenzene polymer, soaking in acetone for 4h, washing with water, vacuum-filtering, drying, placing into a three-neck flask, and adding phenyl solvent to swell the microspheres for more than 20 h;
2. under the mechanical stirring, adding a part of anhydrous aluminum trichloride into the swollen microsphere system, controlling the temperature to be 80-95 ℃, stirring for 4 hours, then adding dimethyl fumarate, simultaneously adding another part of anhydrous aluminum trichloride, continuously stirring for 4 hours at 120-130 ℃, stopping the reaction, and obtaining the p-chloroaniline adsorbing resin. And filtering the product, washing the resin with dilute hydrochloric acid, then sequentially washing with 4% sodium hydroxide solution, deionized water and methanol, drying at the constant temperature of 80-100 ℃ for 12 hours, and storing for later use.
Wherein the reactant and the aluminum trichloride meet the limited range, for example, the mass ratio of the polystyrene polymer, the aluminum trichloride and the dimethyl fumarate is (4-6): 1, (0.8-1.2). And the anhydrous aluminum trioxide is added in two times, and the proportion of the first addition accounts for 30-40% of the total amount of aluminum trioxide, so that the reaction speed and the worth of resin modification degree can be controlled.
To specifically illustrate the statistics of the specific examples of the synthesis process of p-chloroaniline resin provided by the present invention, the parameters of the synthesis process are shown in table 1.
The sequence of addition in table 1 is the order of addition of reactants and aluminum trichloride: a1, the reactants are added together with aluminum trichloride; a2 shows that 30-40% of aluminum trioxide is added to the swollen microspheres, and then dimethyl fumarate and the rest of aluminum trioxide are added; a3 shows that 20% of aluminum trioxide was added to the swollen microspheres, followed by dimethyl fumarate and the remaining aluminum trioxide; a4 shows that 50% of aluminum trioxide was added to the swollen microspheres, followed by dimethyl fumarate and the remaining aluminum trioxide; a5 shows that 30-40% of aluminum trioxide was mixed with fumaric acid and then mixed with microspheres for reaction. The charging temperature in table 1 corresponds to the step temperature of a1, a2, A3, a4 and a5 and the time of each step control, wherein only the direct one-step mixing indicated by a1 corresponds to the temperature of only one step control.
TABLE 1
In order to analyze the properties of the resins synthesized in the above examples 1 to 10 and comparative examples 1 to 4, the following experiments were conducted in the examples of the present invention.
First, static isothermal adsorption experiment
Weighing 0.100g of the pretreated resin in a 250mL conical flask, wetting the resin with 0.5mL of methanol, rinsing the resin with distilled water for 3 times after 30min, adding 100mL of p-chloromethamine aqueous solution and p-ester aqueous solution (10mg/L, 200mg/L, 40mg/L, 60mg/L, 80mg/L and 100mg/L, the concentrations of the two are the same) with different contents, oscillating the resin in a constant-temperature oscillator for 24h at room temperature to balance adsorption, and measuring the equilibrium concentration of p-chloroaniline in each conical flask at 291nm by using an ultraviolet spectrophotometry method. And the equilibrium adsorption quantity Q of the adsorbent is calculated by the following formulae(mg/g)；
Qe＝V(C0-Ce)/WM；
Wherein V is the volume of the solution (L), C0And CeThe initial concentration and the adsorption equilibrium concentration (mg/L) of the parachloroaniline solution are respectively, W is the dry resin mass (g), and M is the molecular weight of the parachloroaniline.
Specifically, in the two-component static experiment, the adsorption amount of Qe includes the adsorption amount of para-ester and the adsorption amount of para-chloroaniline.
Second, dynamic adsorption experiment
In order to examine the stability of the resins prepared in the above examples and comparative examples, the dynamic adsorption test was conducted at a temperature of 303K using a 20cm X16 mm glass column with a sand core filter plate having a pore size of 20 μm, 10.00g of dry resin was weighed and charged into the column by a wet method, driven by a Lange peristaltic pump, and the dynamic adsorption-desorption stability test was continuously conducted at a concentration of 56mg/L (8.95% by weight of p-chloroaniline) as the starting concentration of the p-diester solution, at a flow rate of 50mL/h, through the adsorption column, after saturation of adsorption, by desorption at 333K using a 40% methanol solution, and the dynamic permeation test was plotted as shown in FIG. 1.
Third, experimental results
1. Adsorption capacity and adsorption kinetics
The adsorption isothermal adsorption curves of the two substances on the resin at different temperatures are drawn, the maximum adsorption amounts of the para-ester and the para-chloroaniline on various resins in competitive adsorption can be calculated through fitting the isothermal adsorption curves, and the competitive adsorption results of the para-ester and the para-chloroaniline on the different resins can be found in the process of comparing the values of the maximum adsorption amounts.
TABLE 1
As can be seen from Table 1:
1) the two-component static adsorption experiment shows that the maximum adsorption capacity of the resin corresponding to the examples 1-10 is greatly different between p-chloroaniline and p-ester, and the difference is more obvious than the comparison ratio, which indicates that the resin prepared in the examples 1-10 can be beneficial to the difference of the maximum adsorption capacity to differentially adsorb the p-chloroaniline and the p-ester so as to achieve the purpose of separation.
2) Specifically, comparative examples 1 to 4 were not sufficiently studied about the reactants for resin synthesis and aluminum trioxide, resulting in a decrease in the ability of the resin prepared therefrom to adsorb p-chloroaniline (compared to example 1). On the other hand, comparative examples 5 and 6, which are not modified or modified with dimethyl fumarate, not only significantly reduce the ability of the prepared resin to adsorb p-chloroaniline (compared to example 1), but also significantly increase the adsorption amount of the p-ester to be close to the adsorption amount of p-chloroaniline (compared to example 1), so that the resins prepared in comparative examples 5 and 6 can hardly separate p-chloroaniline and p-ester effectively, and thus the aim of removing p-chloroaniline in the p-ester product can not be achieved. This is probably because dimethyl fumarate contains two carbonyl groups and two ether bonds, i.e., a double bond, in the molecule, and thus both of them can produce a hydrogen bond or an adsorption to the amino group of p-chloroaniline, which is extremely advantageous for removing p-chloroaniline.
3) In addition, examples 6 to 10 were also investigated on the order of addition of aluminum trioxide as a catalyst to a polymer, dimethyl fumarate, the amount of aluminum trioxide added in portions, and the reaction temperature of the addition in portions, and the results showed that the resin prepared in example 6 obtained differential adsorption effects on p-chloroaniline and para-ester, and also obtained optimal differential adsorption rates during differential adsorption of p-chloroaniline and para-ester. This differential adsorption rate has a positive effect on the actual removal in the process of using the resin as chromatographic packing for separation and decontamination.
2. Dynamic adsorption experiment
TABLE 2
As can be seen from Table 2:
1) the dynamic adsorption experiments showed that the trend of the dynamic adsorption amounts of the resins of examples 1 to 10 and comparative examples 1 to 6 was consistent with that of the two-component static adsorption experiments, but the dynamic adsorption amounts of the respective resins were decreased.
2) In addition, the chromatographic dynamic penetration times of the examples 1 to 10 are greatly different between the para-ester and the para-chloroaniline, so that the para-chloroaniline can be effectively collected in different time periods in the actual chromatographic process, and the para-chloroaniline can be effectively removed from the para-ester tea product.
In conclusion, the resin for adsorbing parachloroaniline provided by the invention can effectively and reversibly adsorb, and dynamic chromatography experiments verify that the resin can generate differential adsorption with para-ester, so that parachloroaniline can be effectively removed.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (9)
1. The synthesis method of the resin for adsorbing p-chloroaniline in the p-ester is characterized by comprising the following steps of:
mixing a polystyrene polymer, aluminum trichloride and dimethyl fumarate to react to obtain a dimethyl fumarate modified polymer; and
cleaning and drying the dimethyl fumarate modified polymer to obtain resin for adsorbing p-chloroaniline in the para-ester;
the polystyrene polymer is a styrene-divinylbenzene polymer.
2. The synthesis method according to claim 1, wherein the mass ratio of the polystyrene polymer to the aluminum trichloride to the dimethyl fumarate is (4-6): 1 (0.8-1.2).
3. The method as claimed in claim 1, wherein the reaction temperature of the polystyrene polymer, the aluminum trichloride and the dimethyl fumarate is 80-130 ℃.
4. The method of claim 3, wherein the polystyrene polymer is mixed with a portion of aluminum trichloride, and then dimethyl fumarate and the remaining aluminum trichloride are added to the mixture to react thoroughly.
5. The synthesis method of claim 4, wherein the polystyrene polymer is mixed with aluminum trichloride at 80-95 deg.C for 4h or longer.
6. The synthesis method of claim 4, wherein the temperature condition for adding dimethyl fumarate and the rest aluminum trichloride into the mixture to carry out the full reaction is 120-130 ℃, and the reaction time is not less than 4 h.
7. The synthesis method of claim 4, wherein the mass of the aluminum trichloride mixed with the polystyrene polymer is 30-40% of the total mass required for synthesis.
8. A resin made by the synthesis method of any of claims 1-7.
9. Use of the resin of claim 8 to remove or reduce the amount of parachloroaniline in the synthesized para-ester product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012073A (en) * | 2007-01-30 | 2007-08-08 | 南京大学 | Treatment for waste water of benzidine production by two-section adsorbing method an d resource recovery method |
| CN102786446A (en) * | 2012-08-23 | 2012-11-21 | 楚源高新科技集团股份有限公司 | New production process for chlorosulfonation of para-ester by using thionyl chloride |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012073A (en) * | 2007-01-30 | 2007-08-08 | 南京大学 | Treatment for waste water of benzidine production by two-section adsorbing method an d resource recovery method |
| CN102786446A (en) * | 2012-08-23 | 2012-11-21 | 楚源高新科技集团股份有限公司 | New production process for chlorosulfonation of para-ester by using thionyl chloride |
Non-Patent Citations (1)
| Title |
|---|
| 孙越等.3种树脂对水溶液中对氯苯胺吸附性能的比较研究.《离子交换与吸附》.2010,第26卷(第2期),第139-144页. * |
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