CN111153796B - Method for preparing ultraviolet curing reactive diluent from rectification by-product - Google Patents
Method for preparing ultraviolet curing reactive diluent from rectification by-product Download PDFInfo
- Publication number
- CN111153796B CN111153796B CN201911413923.9A CN201911413923A CN111153796B CN 111153796 B CN111153796 B CN 111153796B CN 201911413923 A CN201911413923 A CN 201911413923A CN 111153796 B CN111153796 B CN 111153796B
- Authority
- CN
- China
- Prior art keywords
- solution
- esterification
- rectification
- reaction kettle
- proper amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing ultraviolet curing reactive diluent by rectification byproducts, which comprises a, firstly, putting a proper amount of rectification byproducts and a decoloring agent into a reaction kettle, and heating the reaction kettle to 94-96 ℃ for pretreatment; b, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, and adjusting the temperature of the reaction kettle to 90-93 ℃ to perform reflux dehydration esterification reaction to obtain an esterification solution; c, adding deionized water, a sodium hydroxide solution and a sodium chloride solution into the esterification solution step by step, uniformly stirring, standing for layering, and removing layered lower-layer liquid to obtain a cleaned esterification solution; and d, distilling the washed esterification solution to separate the solvent, thereby obtaining a finished product of the active diluent. The method can recycle the rectification by-products, reduce the difficulty of waste treatment and reduce the preparation cost of the reactive diluent.
Description
Technical Field
The invention relates to a preparation method of a reactive diluent, in particular to a method for preparing an ultraviolet curing reactive diluent by rectifying byproducts.
Background
Rectification is a separation process for separating each component by utilizing different volatility of each component in a mixture, and a single chemical product with higher purity can be obtained usually by a rectification process, for example, the rectification process is required in the preparation process of common tripropylene glycol and trimethylolpropane. Although the rectification process can separate high-purity chemical substances from the mixture, a large amount of byproducts are generated in the rectification process, for example, a large amount of heavy component byproducts are separated under a high-temperature condition in the process of preparing tripropylene glycol; in the process of preparing trimethylolpropane, a large amount of light-component byproducts are separated at low temperature. The heavy component by-product or the light component by-product generally contains various complex components, has dark color and large smell, is difficult to recycle, not only improves the treatment cost, but also is not beneficial to environmental protection.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing an ultraviolet curing reactive diluent by rectifying byproducts, which comprises the following steps:
a. firstly, putting a proper amount of rectification by-products and a decoloring agent into a reaction kettle, and heating the reaction kettle to 94-96 ℃ for pretreatment;
b. then cooling to 40-50 ℃, then respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, and then adjusting the temperature of the reaction kettle to 90-93 ℃ to perform reflux dehydration esterification reaction to obtain esterification liquid;
c. b, sequentially eluting the esterification solution obtained in the step b by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain a cleaned esterification solution;
d. and (3) carrying out reduced pressure distillation on the washed esterification solution to separate the solvent, thus obtaining the finished product of the active diluent.
Further, the step c comprises the following sub-steps:
(1) Adding a proper amount of deionized water into the esterification solution, uniformly stirring, standing for layering, and removing layered lower-layer liquid to obtain the esterification solution after primary cleaning;
(2) Adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, and removing layered lower-layer liquid to obtain esterification solution after the secondary cleaning;
(3) And (3) continuously adding a proper amount of sodium chloride solution into the esterification liquid after the secondary cleaning, uniformly stirring, standing for layering, and removing the layered lower-layer liquid to obtain the cleaned esterification liquid.
Further, the decolorizing agent is hypophosphorous acid.
Further, the catalyst is methanesulfonic acid or p-toluenesulfonic acid.
Furthermore, the polymerization inhibitor is one or more of p-hydroxyanisole, hydroquinone, copper chloride and copper sulfate.
Further, the reflux agent is cyclohexane or toluene; the solvent is acrylic acid.
Further, in the step b, the acid value of the reaction kettle is 28-36mgKOH/g.
Further, in the step c, the mass concentration of the sodium oxide solution is 8-12wt%; the mass concentration of the sodium chloride solution is 3-7wt%.
Further, in the step d, the temperature of distillation separation is 72-78 ℃, and the pressure of distillation separation is-0.7 MPa to-0.9 MPa.
Further, the mass ratio of the rectification by-product, the decolorizing agent, the solvent, the catalyst, the polymerization inhibitor and the reflux agent is as follows: 480 to 650, wherein the weight ratio is (wt%) in the range of 5.7 to 5.7.
The invention has the following beneficial technical effects:
compared with the prior art, the invention discloses a method for preparing an ultraviolet curing reactive diluent from a rectification byproduct, and the method can recycle the rectification byproduct to prepare the usable ultraviolet curing reactive diluent, thereby reducing the difficulty of chemical waste treatment, simultaneously reducing the preparation cost of the ultraviolet curing reactive diluent and being beneficial to improving the economic benefit of enterprises. In addition, the invention adopts hypophosphorous acid as a decoloring agent to pretreat the rectification by-products, obviously improves the decoloring effect, avoids the defect of darker color, ensures that the prepared ultraviolet curing reactive diluent is more acceptable by users, and is beneficial to opening the market.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more clearly understand the advantages and features of the present invention and to clearly define the scope of the present invention.
Example 1:
the embodiment provides a method for preparing an ultraviolet curing reactive diluent from rectification byproducts, which mainly takes the rectification byproducts as raw materials to prepare the ultraviolet curing reactive diluent so as to realize the recycling of rectification wastes.
A method for preparing an ultraviolet curing reactive diluent by rectifying byproducts specifically comprises the following steps:
a. firstly, putting a proper amount of rectification by-products and a decoloring agent into a reaction kettle, and carrying out pretreatment by keeping the temperature of the reaction kettle at 94 ℃ for 3 hours.
b. Then cooling to 40 ℃, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, then adjusting the temperature of the reaction kettle to 90 ℃ and the acid value to be 28mgKOH/g, and carrying out reflux dehydration esterification reaction to obtain esterified liquid, wherein the reflux time is 5h.
c. And c, sequentially eluting the esterification solution obtained in the step b by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain a cleaned esterification solution.
d. And (3) carrying out reduced pressure distillation on the washed esterification solution at 72 ℃ and under the condition of-0.7 MPa to separate the solvent, thus obtaining the finished product D1 of the active diluent.
The distillation by-product in this embodiment is a distillation by-product generated in the process of preparing tripropylene glycol, and the tripropylene glycol is generally synthesized by using propylene oxide and dipropylene glycol as raw materials to perform a condensation reaction and purifying the tripropylene glycol by using a distillation tower. And the decolorizing agent in the step a adopts hypophosphorous acid. In the step b, the solvent adopts acrylic acid, the catalyst adopts methanesulfonic acid, the polymerization inhibitor is formed by mixing p-hydroxyanisole and copper chloride according to the mass ratio of 1:8, and the reflux agent adopts cyclohexane. And the mass ratio of the rectification by-products, the decolorant, the solvent, the catalyst, the polymerization inhibitor and the reflux agent is controlled to be 630.
In addition, in the step c, a step-by-step elution method is adopted in the elution process of the esterification solution by using deionized water, a sodium hydroxide solution and a sodium chloride solution, specifically, a proper amount of deionized water is added into the esterification solution at first, the mixture is stirred uniformly, then is kept stand for layering, and the layered lower layer liquid is removed, so that the esterification solution after primary cleaning is obtained. Then, adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after the secondary cleaning. And finally, continuously adding a proper amount of sodium chloride solution into the esterification solution after the secondary cleaning, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the cleaned esterification solution. In this embodiment, the concentration of the sodium hydroxide solution is 8%; the concentration of the sodium chloride solution is 3wt%, and the dosage of the deionized water, the sodium hydroxide solution and the sodium chloride solution is 70g respectively.
Of course, when the esterification solution is eluted by using deionized water, a sodium hydroxide solution and a sodium chloride solution, repeated washing may be performed for multiple times according to actual needs, for example, repeated washing may be performed by using deionized water, repeated washing may be performed by using a sodium hydroxide solution or repeated washing may be performed by using a sodium chloride solution, the washing sequence is not limited, and the specific washing operation process for each time is similar to that described above, and will not be described in detail here.
Example 2:
the embodiment provides a method for preparing an ultraviolet curing reactive diluent from a rectification byproduct, which comprises the following steps:
a. firstly, putting a proper amount of rectification by-products and a decoloring agent into a reaction kettle, and carrying out pretreatment by keeping the temperature of the reaction kettle at 95 ℃ for 4 hours.
b. Then cooling to 50 ℃, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, then adjusting the temperature of the reaction kettle to 92 ℃ and the acid value to be 30mgKOH/g, and carrying out reflux dehydration esterification reaction to obtain esterified liquid, wherein the reflux time is 6h.
c. And (c) sequentially eluting the esterification solution obtained in the step (b) by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain the cleaned esterification solution.
d. And (3) carrying out reduced pressure distillation on the washed esterification solution at 75 ℃ and under the pressure of-0.8 MPa to separate the solvent, thus obtaining a finished product D2 of the active diluent.
The rectification byproduct in this embodiment is a rectification byproduct generated in the process of preparing tripropylene glycol, and the tripropylene glycol is generally synthesized by using propylene oxide and dipropylene glycol as raw materials to perform a condensation reaction and purifying the product by using a rectification tower. The decolorizing agent in the step a adopts hypophosphorous acid. In the step b, the solvent adopts acrylic acid, the catalyst adopts methanesulfonic acid, the polymerization inhibitor is formed by mixing p-hydroxyanisole and copper chloride according to the mass ratio of 1:8, and the reflux agent adopts cyclohexane. And the mass ratio of the rectification by-products, the decolorant, the solvent, the catalyst, the polymerization inhibitor and the reflux agent is controlled to be 640.4.
And c, eluting the esterification solution by using deionized water, a sodium hydroxide solution and a sodium chloride solution by using a step-by-step elution method, specifically, firstly adding a proper amount of deionized water into the esterification solution, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after primary cleaning. Then, adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, and removing layered lower layer liquid to obtain the esterification solution after the secondary cleaning. And finally, continuously adding a proper amount of sodium chloride solution into the esterification solution after the secondary cleaning, uniformly stirring, standing for layering, and removing layered lower layer liquid to obtain the cleaned esterification solution. In this embodiment, the concentration of the sodium hydroxide solution is 10%; the concentration of the sodium chloride solution is 5wt%, and the dosage of the deionized water, the sodium hydroxide solution and the sodium chloride solution is 70g respectively.
Example 3:
the embodiment provides a method for preparing an ultraviolet curing reactive diluent from a rectification byproduct, which comprises the following steps:
a. firstly, putting a proper amount of rectification by-products and a decoloring agent into a reaction kettle, and carrying out pretreatment by keeping the temperature of the reaction kettle at 96 ℃ for 5 hours.
b. Then cooling to 45 ℃, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, then adjusting the temperature of the reaction kettle to 93 ℃ and the acid value to be 32mgKOH/g, and carrying out reflux dehydration esterification reaction to obtain esterified liquid, wherein the reflux time is 7h.
c. And (c) sequentially eluting the esterification solution obtained in the step (b) by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain the cleaned esterification solution.
d. And (3) carrying out reduced pressure distillation on the washed esterification solution at 78 ℃ and under the condition of-0.9 MPa to separate the solvent, thus obtaining the finished product D3 of the active diluent.
The rectification byproduct in this embodiment is a rectification byproduct generated in the process of preparing tripropylene glycol, and the tripropylene glycol is generally synthesized by using propylene oxide and dipropylene glycol as raw materials to perform a condensation reaction and purifying the product by using a rectification tower. The decolorizing agent in the step a adopts hypophosphorous acid. In the step b, acrylic acid is used as a solvent, p-toluenesulfonic acid is used as a catalyst, and p-hydroxyanisole, copper chloride and hydroquinone are used as polymerization inhibitors in a mass ratio of 1:8:1, and the reflux agent adopts toluene. And the mass ratio of the rectification by-products, the decolorant, the solvent, the catalyst, the polymerization inhibitor and the reflux agent is controlled to be 650.7.
And c, eluting the esterification solution by using deionized water, a sodium hydroxide solution and a sodium chloride solution by using a step-by-step elution method, specifically, firstly adding a proper amount of deionized water into the esterification solution, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after primary cleaning. Then, adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after the secondary cleaning. And finally, continuously adding a proper amount of sodium chloride solution into the esterification solution after the secondary cleaning, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the cleaned esterification solution. In this embodiment, the concentration of the sodium hydroxide solution is 12%; the concentration of the sodium chloride solution is 7wt%, and the dosage of the deionized water, the sodium hydroxide solution and the sodium chloride solution is 70g respectively.
Example 4:
the embodiment provides a method for preparing an ultraviolet curing reactive diluent from a rectification byproduct, which comprises the following steps:
a. firstly, putting a proper amount of rectification by-products and a decoloring agent into a reaction kettle, and carrying out pretreatment by keeping the temperature of the reaction kettle at 95 ℃ for 4 hours.
b. Then cooling to 50 ℃, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, then adjusting the temperature of the reaction kettle to 91 ℃ and the acid value to be 30mgKOH/g, and carrying out reflux dehydration esterification reaction to obtain esterified liquid, wherein the reflux time is 6h.
c. And (c) sequentially eluting the esterification solution obtained in the step (b) by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain the cleaned esterification solution.
d. And (3) carrying out reduced pressure distillation on the washed esterification solution at 75 ℃ and under the pressure of-0.8 MPa to separate the solvent, thus obtaining a finished product D4 of the active diluent.
The distillation byproduct in this embodiment is a distillation byproduct generated in the process of preparing tripropylene glycol, and the tripropylene glycol is generally synthesized by using propylene oxide and dipropylene glycol as raw materials to perform a condensation reaction and then purifying the resulting product in a distillation tower. The decolorizing agent in the step a adopts hypophosphorous acid. In step b, acrylic acid is used as a solvent, and methanesulfonic acid is used as a catalyst. The polymerization inhibitor may be any one of p-hydroxyanisole, hydroquinone, copper chloride and copper sulfate, and p-hydroxyanisole is selected as the polymerization inhibitor in this embodiment. Toluene was used as a reflux agent. And the mass ratio of the rectification by-products, the decolorant, the solvent, the catalyst, the polymerization inhibitor and the reflux agent is controlled to be 640.
And c, eluting the esterification solution by using deionized water, a sodium hydroxide solution and a sodium chloride solution by using a step-by-step elution method, specifically, firstly adding a proper amount of deionized water into the esterification solution, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after primary cleaning. And then, adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, removing layered lower-layer liquid, adding a proper amount of sodium hydroxide solution into the reaction kettle again for repeated cleaning, namely cleaning the esterification solution after the primary cleaning twice by using the sodium hydroxide solution, and obtaining the esterification solution after the sodium hydroxide solution is cleaned. And finally, continuously adding a proper amount of sodium chloride solution into the esterification solution cleaned by the sodium hydroxide solution, uniformly stirring, standing for layering, and removing layered lower layer liquid to obtain the cleaned esterification solution. In this embodiment, the concentration of the sodium hydroxide solution is 10%; the concentration of the sodium chloride solution is 5wt%, and the dosage of the deionized water, the sodium hydroxide solution and the sodium chloride solution is 70g respectively.
Example 5:
the embodiment provides a method for preparing an ultraviolet curing reactive diluent by rectifying byproducts, which comprises the following steps:
a. firstly, putting a proper amount of rectification by-products and a decoloring agent into a reaction kettle, and carrying out pretreatment by keeping the temperature of the reaction kettle at 94 ℃ for 3 hours.
b. Then cooling to 40 ℃, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, then adjusting the temperature of the reaction kettle to 90 ℃ and the acid value to be 34mgKOH/g, and carrying out reflux dehydration esterification reaction to obtain esterified liquid, wherein the reflux time is 5h.
c. And (c) sequentially eluting the esterification solution obtained in the step (b) by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain the cleaned esterification solution.
d. And (3) carrying out reduced pressure distillation on the washed esterification solution at 72 ℃ and under the condition of-0.7 MPa to separate the solvent, thus obtaining the finished product D5 of the active diluent.
The rectification byproduct in this embodiment is a rectification byproduct generated in the process of preparing trimethylolpropane, and the trimethylolpropane is usually synthesized by using n-butyl aldehyde and formaldehyde as raw materials, performing a condensation reaction, and then performing solvent extraction, extraction separation, and purification in a rectification tower. In the rectification process by using the rectification tower, a large amount of light component byproducts, namely the rectification byproducts in the embodiment, can be separated at low temperature. The decolorizing agent in the step a adopts hypophosphorous acid. In the step b, the solvent adopts acrylic acid, the catalyst adopts methanesulfonic acid, the polymerization inhibitor is formed by mixing p-hydroxyanisole and copper chloride according to the mass ratio of 1:4, and the reflux agent adopts cyclohexane. And the mass ratio of the rectification by-products, the decolorant, the solvent, the catalyst, the polymerization inhibitor and the reflux agent is controlled to be 480.7.
And c, eluting the esterification solution by using deionized water, a sodium hydroxide solution and a sodium chloride solution by using a step-by-step elution method, specifically, firstly adding a proper amount of deionized water into the esterification solution, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after primary cleaning. Then, adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after the secondary cleaning. And finally, continuously adding a proper amount of sodium chloride solution into the esterification solution after the secondary cleaning, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the cleaned esterification solution. In this embodiment, the concentration of the sodium hydroxide solution is 8%; the concentration of the sodium chloride solution is 3wt%, and the dosage of the deionized water, the sodium hydroxide solution and the sodium chloride solution is 70g respectively.
Example 6:
the embodiment provides a method for preparing an ultraviolet curing reactive diluent by rectifying byproducts, which comprises the following steps:
a. firstly, putting a proper amount of rectification by-products and a decoloring agent into a reaction kettle, and carrying out pretreatment by keeping the temperature of the reaction kettle at 95 ℃ for 4 hours.
b. Then cooling to 50 ℃, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, then adjusting the temperature of the reaction kettle to 92 ℃ and the acid value to 35mgKOH/g, and carrying out reflux dehydration esterification reaction to obtain esterified liquid, wherein the reflux time is 6h.
c. And (c) sequentially eluting the esterification solution obtained in the step (b) by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain the cleaned esterification solution.
d. And (3) carrying out reduced pressure distillation on the washed esterification solution at 75 ℃ and under the pressure of-0.8 MPa to separate the solvent, thus obtaining the finished product D6 of the active diluent.
The rectification byproduct in this embodiment is a rectification byproduct generated in the process of preparing trimethylolpropane, and the trimethylolpropane is usually synthesized by using n-butyl aldehyde and formaldehyde as raw materials, performing a condensation reaction, and then performing solvent extraction, extraction separation, and purification in a rectification tower. In the rectification process by using the rectification tower, a large amount of light component byproducts, namely the rectification byproducts in the embodiment, can be separated at low temperature. The decolorizing agent in the step a adopts hypophosphorous acid. In the step b, acrylic acid is used as a solvent, methanesulfonic acid is used as a catalyst, p-hydroxyanisole and copper chloride are mixed according to a mass ratio of 1. And the mass ratio of the rectification by-products, the decolorant, the solvent, the catalyst, the polymerization inhibitor and the reflux agent is controlled to be 492.6.
And c, eluting the esterification solution by using deionized water, a sodium hydroxide solution and a sodium chloride solution by using a step-by-step elution method, specifically, firstly adding a proper amount of deionized water into the esterification solution, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after primary cleaning. Then, adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, and removing layered lower layer liquid to obtain the esterification solution after the secondary cleaning. And finally, continuously adding a proper amount of sodium chloride solution into the esterification solution after the secondary cleaning, uniformly stirring, standing for layering, and removing layered lower layer liquid to obtain the cleaned esterification solution. In this embodiment, the concentration of the sodium hydroxide solution is 10%; the concentration of the sodium chloride solution is 5wt%, and the dosage of the deionized water, the sodium hydroxide solution and the sodium chloride solution is 70g respectively.
Example 7:
the embodiment provides a method for preparing an ultraviolet curing reactive diluent from a rectification byproduct, which comprises the following steps:
a. firstly, putting a proper amount of rectification byproducts and a decoloring agent into a reaction kettle, and heating the reaction kettle to 96 ℃ and preserving heat for 5 hours for pretreatment.
b. Then cooling to 45 ℃, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially adding into a reaction kettle, then adjusting the temperature of the reaction kettle to 93 ℃ and the acid value to 36mgKOH/g, and carrying out reflux dehydration esterification reaction to obtain esterified liquid, wherein the reflux time is 7h.
c. And c, sequentially eluting the esterification solution obtained in the step b by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain a cleaned esterification solution.
d. And (3) carrying out reduced pressure distillation on the washed esterification solution at 78 ℃ and under the condition of-0.9 MPa to separate the solvent, thus obtaining a finished product D7 of the active diluent.
The rectification byproduct in this embodiment is a rectification byproduct generated in the process of preparing trimethylolpropane, and the trimethylolpropane is usually synthesized by using n-butyl aldehyde and formaldehyde as raw materials, performing a condensation reaction, and then performing solvent extraction, extraction separation, and purification in a rectification tower. In the rectification process by using the rectification tower, a large amount of light component byproducts, namely the rectification byproducts in the embodiment, can be separated at low temperature. The decolorizing agent in the step a adopts hypophosphorous acid. In the step b, acrylic acid is used as a solvent, p-toluenesulfonic acid is used as a catalyst, and p-hydroxyanisole, copper chloride and hydroquinone are used as polymerization inhibitors in a mass ratio of 1:4:1, and the reflux agent adopts toluene. And the mass ratio of the rectification by-products, the decolorant, the solvent, the catalyst, the polymerization inhibitor and the reflux agent is controlled to be 500.
And c, eluting the esterification solution by using deionized water, a sodium hydroxide solution and a sodium chloride solution by using a step-by-step elution method, specifically, firstly adding a proper amount of deionized water into the esterification solution, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the esterification solution after primary cleaning. Then, adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, and removing layered lower layer liquid to obtain the esterification solution after the secondary cleaning. And finally, continuously adding a proper amount of sodium chloride solution into the esterification solution after the secondary cleaning, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the cleaned esterification solution. In this embodiment, the concentration of the sodium hydroxide solution is 12%; the concentration of the sodium chloride solution is 7wt%, and the dosage of the deionized water, the sodium hydroxide solution and the sodium chloride solution is 70g respectively.
And respectively weighing a proper amount of the finished reactive diluent D1-D7, and mixing with a proper amount of urethane acrylate and a photoinitiator to obtain the ultraviolet curing adhesive G1-G7. Then, QUV test, brittleness test, salt spray test, cold and hot impact test and pencil hardness test were performed on the UV curable adhesives G1 to G7, respectively, and the test results are shown in Table 1. In this embodiment, the QYV test, the brittleness test, the salt spray test, the cold and hot impact test, and the pencil hardness test all adopt the existing test technologies, and are not described herein.
TABLE 1
As can be seen from Table 1, the ultraviolet curing adhesive obtained by mixing the reactive diluent prepared by the invention, a proper amount of urethane acrylate and light initiation has good ultraviolet resistance, is obviously low in brittleness, and also shows excellent performances in salt spray tests, cold and hot impact, hardness and the like.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. A method for preparing an ultraviolet curing reactive diluent by rectifying byproducts is characterized by comprising the following steps:
a. firstly, putting a proper amount of rectification by-products and a decoloring agent into a reaction kettle, and heating the reaction kettle to 94-96 ℃ for pretreatment;
b. then cooling to 40-50 ℃, respectively weighing a proper amount of solvent, catalyst, polymerization inhibitor and reflux agent, sequentially putting into a reaction kettle, and then adjusting the temperature of the reaction kettle to 90-93 ℃ to perform reflux dehydration esterification reaction to obtain an esterification solution;
c. b, sequentially eluting the esterification solution obtained in the step b by using deionized water, a sodium hydroxide solution and a sodium chloride solution respectively to obtain a cleaned esterification solution;
d. distilling the washed esterification solution under reduced pressure to separate the solvent, and obtaining a finished product of the active diluent;
the rectification by-product is a heavy component by-product separated at high temperature in the rectification process for preparing the tripropylene glycol;
the decolorizing agent is hypophosphorous acid;
the catalyst is methanesulfonic acid or p-toluenesulfonic acid;
the polymerization inhibitor is one or more of p-hydroxyanisole, hydroquinone, copper chloride and copper sulfate;
the reflux agent is cyclohexane or toluene;
the solvent is acrylic acid.
2. The method for preparing uv curable reactive diluent from rectified by-products according to claim 1, wherein the step c comprises the sub-steps of:
(1) Adding a proper amount of deionized water into the esterification solution, stirring uniformly, standing for layering, and removing layered lower layer liquid to obtain the esterification solution after primary cleaning;
(2) Adding a proper amount of sodium hydroxide solution into the esterification solution after the primary cleaning, uniformly stirring, standing for layering, and removing layered lower-layer liquid to obtain esterification solution after the secondary cleaning;
(3) And (3) continuously adding a proper amount of sodium chloride solution into the esterification liquid after the secondary cleaning, uniformly stirring, standing for layering, and removing the layered lower layer liquid to obtain the cleaned esterification liquid.
3. The method for preparing UV-curable reactive diluent from rectification byproducts as claimed in claim 1, wherein in step b, the acid value of the reaction kettle is 28-36mgKOH/g.
4. The method for preparing the ultraviolet curing reactive diluent by rectifying the byproducts as claimed in claim 1, wherein in the step c, the mass concentration of the sodium oxide solution is 8-12wt%; the mass concentration of the sodium chloride solution is 3-7wt%.
5. The method for preparing the ultraviolet curing reactive diluent from the rectification byproduct as claimed in claim 1, wherein in the step d, the temperature of the distillation separation is 72-78 ℃, and the pressure of the distillation separation is-0.7 MPa to-0.9 MPa.
6. The method for preparing the ultraviolet curing reactive diluent by the rectification by-product according to claim 1, wherein the rectification by-product, the decolorant, the solvent, the catalyst, the polymerization inhibitor and the reflux agent are in the following mass ratio: 480 to 650.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911413923.9A CN111153796B (en) | 2019-12-31 | 2019-12-31 | Method for preparing ultraviolet curing reactive diluent from rectification by-product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911413923.9A CN111153796B (en) | 2019-12-31 | 2019-12-31 | Method for preparing ultraviolet curing reactive diluent from rectification by-product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111153796A CN111153796A (en) | 2020-05-15 |
| CN111153796B true CN111153796B (en) | 2022-11-25 |
Family
ID=70560091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911413923.9A Active CN111153796B (en) | 2019-12-31 | 2019-12-31 | Method for preparing ultraviolet curing reactive diluent from rectification by-product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111153796B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621468B (en) * | 2022-03-25 | 2023-08-11 | 湖北科林博伦新材料有限公司 | Synthesis method of chlorine-free environment-friendly toughening diluent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250093A (en) * | 2008-03-22 | 2008-08-27 | 江苏三木集团 | Preparation method of tripropylene glycol |
| CN108947779A (en) * | 2018-08-15 | 2018-12-07 | 南京红宝丽聚氨酯有限公司 | A kind of preparation method of tripropylene glycol |
-
2019
- 2019-12-31 CN CN201911413923.9A patent/CN111153796B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250093A (en) * | 2008-03-22 | 2008-08-27 | 江苏三木集团 | Preparation method of tripropylene glycol |
| CN108947779A (en) * | 2018-08-15 | 2018-12-07 | 南京红宝丽聚氨酯有限公司 | A kind of preparation method of tripropylene glycol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111153796A (en) | 2020-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104496819B (en) | A kind of method that environment-friendly plasticizer is prepared in waste resource recycling | |
| CN104610063A (en) | Novel preparation method of dioctyl terephthalate | |
| CN101029122A (en) | Production and use for acrylic ester modified polyester resin | |
| CN111153796B (en) | Method for preparing ultraviolet curing reactive diluent from rectification by-product | |
| CN102584582B (en) | Preparing technology of hydroxyethyl acrylate | |
| CN111170836B (en) | Preparation method of pentaerythritol triallyl ether | |
| CN102584579B (en) | Preparation process of hydroxyethyl methacrylate | |
| CN108359031A (en) | A kind of water borne UV curing resin and its application | |
| CN111099996A (en) | Preparation method of tert-butyl acrylate | |
| CN110713438B (en) | Production process of ethylene glycol di (meth) acrylate | |
| CN104559750A (en) | UV hand feeling coating based on elastic urethane acrylate and preparation method of UV hand feeling coating | |
| CN105503501A (en) | Butanol-cyclohexane azeotropic mixture extractive distillation method | |
| JPH06219991A (en) | Production of polyfunctional @(3754/24)meth)acrylate | |
| CN117185973A (en) | Acrylic monomer and application thereof in photo-curing functional coating | |
| JPH0616594A (en) | Production of @(3754/24)meth)acrylic ester | |
| CN105481691B (en) | The synthetic method of double cyclopentenyl oxygen ethylmethyl acrylate | |
| CN107177314B (en) | Method for preparing rosin diene addition product polyol ester resin from rosin | |
| CN101932547A (en) | Be used for reclaiming the method for sulfonic acid catalyst and noble products from acrylate heavy ends | |
| CN105541552B (en) | A kind of glycol dimethyl ether azeotropic mixture extraction rectifying method | |
| CN113387493B (en) | Wastewater treatment process in reactive diluent production | |
| CN109456452B (en) | Polyaryletherketone modified core-shell structure acrylic resin emulsion and preparation method thereof | |
| CN112079714A (en) | Preparation method of 2-phenylethyl acrylate | |
| CN102381996A (en) | Preparation method of diethylaminoethyl methacrylate | |
| CN114292187B (en) | Organic compound extracted from waste generated in production of hydroxyalkyl acrylate and method thereof | |
| JPH069496A (en) | Production of @(3754/24)meth)acrylic acid esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |