CN111517995A - Method and device for continuously producing polyester modified tri-monomer - Google Patents
Method and device for continuously producing polyester modified tri-monomer Download PDFInfo
- Publication number
- CN111517995A CN111517995A CN202010428523.1A CN202010428523A CN111517995A CN 111517995 A CN111517995 A CN 111517995A CN 202010428523 A CN202010428523 A CN 202010428523A CN 111517995 A CN111517995 A CN 111517995A
- Authority
- CN
- China
- Prior art keywords
- tank
- monomer
- esterification
- polyester modified
- esterification kettle
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method and a device for continuously producing polyester modified tri-monomer, wherein the method does not use a catalyst and has the chemical reaction formula as follows:
the polyester modified monomer is m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate. The invention has the beneficial effects that: the process method for continuously producing the polyester modified tri-monomer adopts the isophthalic acid-5-sodium sulfonate and the ethylene glycol to directly esterify, and overcomes the problem of unstable ester exchange rate of ester exchange reaction in the traditional SIPE production process for preparing SIPE by SIPM. In addition, the process method does not need to add a catalyst in the production process, and the byproduct is water, so that the pollution to the environment is effectively reduced. Hair brushThe process method and the device for continuously producing the polyester modified tri-monomer realize the continuous production of the SIPE, can stably produce the SIPE with high esterification rate, improve the quality of products and optimize the production process.
Description
Technical Field
The invention belongs to the technical field of modified polyester production, and particularly relates to a process method and a device for continuously producing a polyester modified tri-monomer.
Background
The polyester modified monomer is dihydroxy ethyl isophthalate-5-sodium Sulfonate (SIPE), and is used in producing Cationic Dyeable Polyester (CDP), easy-to-dye cationic dyeable polyester (ECDP) and anti-pilling polyester. The appearance is as follows: a pale yellow transparent viscous liquid. The melting point of the cationic terylene prepared by copolymerization of the m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate as a modifier is lower than that of the common terylene, and the crystallinity of the cationic terylene is lower than that of the common terylene, so that dye molecules are easy to permeate, the fiber is easy to dye, the color absorption rate is improved, and the moisture absorption is correspondingly improved.
The traditional SIPE production process is prepared by carrying out ester exchange reaction on dimethyl isophthalate-5-sodium Sulfonate (SIPM) and Ethylene Glycol (EG), and because the ester exchange reaction is a reversible equilibrium reaction, the ester exchange reaction product of the production process not only contains SIPE, but also contains monoester exchange product of methyl ethyl isophthalate-5 sodium Sulfonate (SIPM), and in addition, part of SIPM which does not participate in the reaction is contained, namely the ester exchange rate is an important investigation index in the SIPE preparation process.
CN204999829U discloses a system for continuously synthesizing a third monomer of sodium ethylene glycol isophthalate-5-sulfonate, which comprises a slurry blending tank and an ester exchange reactor which are connected in sequence, three monomer surge tanks and three monomer storage tanks, three monomer storage tanks are equipped with the bottom discharge mouth, the top of thick liquids surge tank still is equipped with the SIPM import, ethylene glycol import and additive import, the top of three monomer surge tanks is equipped with ethylene glycol import and additive import, be connected slurry pipeline between the bottom discharge mouth of thick liquids surge tank and the top feed inlet of ester exchange reactor, be equipped with thick liquids delivery pump on the slurry pipeline, be equipped with the three-way valve on the low reaches pipeline of slurry delivery pump, be equipped with thick liquids backflow pipeline between the top backward flow mouth of three-way valve and thick liquids surge tank, all the pipelines from ester exchange reactor to three monomer surge tanks and from three monomer surge tanks to three monomer storage tanks all adopt the heat tracing pipeline. However, the byproduct obtained in the systematic production process is still methanol, and the reaction still needs to use a catalyst, so that the production cost of the synthesis process and the treatment cost of the byproduct are high, and the methanol pollutes the environment and is not easy to produce on a large scale.
As known from the prior art, in the traditional SIPE preparation production process, when the ester exchange rate is too high, the obtained SIPE is easy to generate self-polymerization, so that the content of coagulated particles in materials is easy to increase in the process of preparing cationic dye dyeable terylene, and the service cycle of a filter, a spinning assembly and the like is shortened; when the ester exchange rate is too low, the residual quantity of the by-product methanol is increased, and when the materials are added into a high-temperature polymerization system, the methanol is easy to explode and accumulate on the wall of a kettle, so that a large amount of black foreign matters are generated in the system, and finally, the appearance color of the product becomes dark, the performance becomes poor, the availability is low, and the selling price is low; in addition, in the traditional SIPE production process, harmful gas methanol is generated to pollute the environment, and a corresponding treatment device is required to be arranged for separately treating the methanol, so that the production and maintenance costs are increased.
In conclusion, how to overcome the problems existing in the SIPE production process, while ensuring the quality of the SIPE, the intrinsic quality of the modified polyester and the subsequent spinnability, dyeing property, fiber and other physical and mechanical properties are the key research directions of the polyester modified three-monomer production process and the urgent technical problems to be solved.
Disclosure of Invention
In order to solve the problems in the prior art for producing the polyester modified tri-monomer (SIPE), the invention provides a brand-new direct esterification synthesis method and a device matched with the method for use.
The invention provides a method for continuously producing polyester modified tri-monomer, which does not use catalyst and has the chemical reaction formula:
the polyester modified monomer is m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate.
Further, weighing the sodium m-diformate-5-sulfonate and the excessive glycol, and uniformly mixing and stirring to obtain slurry;
and continuously conveying the obtained slurry to an esterification kettle for esterification reaction to obtain the polyester modified tri-monomer, wherein the excessive glycol also plays a role of a reaction solvent.
Further, step (1): weighing raw materials according to the molar ratio of the isophthalic acid-5-sodium sulfonate to the ethylene glycol of 1:20-1:5, adding the ethylene glycol into a pulping tank, starting stirring, then keeping the stirring state, adding the isophthalic acid-5-sodium sulfonate, and continuing stirring to uniformly mix the materials to obtain a material A;
step (2): and conveying the material A to an esterification kettle for esterification reaction to obtain the polyester modified tri-monomer product.
Further, an ether inhibitor can be added in the step (1), and the adding amount is controlled to be 1:2000-1:100 of the molar ratio of the ether inhibitor to the isophthalic acid-5-sodium sulfonate.
Further, in the step (1), the temperature of the pulping tank is between room temperature and 130 ℃, and the pressure is normal pressure.
Further, the method of the invention comprises the following steps:
step (1): putting the 5-sodium sulfoisophthalate, the glycol and the ether inhibitor into a pulping tank in proportion, starting a stirrer of the pulping tank to stir, keeping pulping operation for 30-90 min after all materials are added, keeping the temperature in the pulping tank at-130 ℃ and the pressure at normal pressure, and obtaining a material A after the pulping operation is finished;
step (2): and introducing the material A into the esterification kettle for esterification reaction at the temperature of 170-210 ℃ and the pressure of 0-0.1 MPa (gauge pressure), wherein the reduced reaction residence time is 2-3.5h, thereby obtaining the polyester modified tri-monomer product.
Further, after the beating operation is finished, the material A is conveyed to a pulp supply tank, and in order to ensure the continuous production, the volume of the pulp supply tank is at least 1.5 times of that of the beating tank; and conveying the material A from the slurry supply tank into the esterification kettle for esterification reaction.
Furthermore, the esterification rate of the m-phthalic acid-5-sodium sulfonate in the method of the invention reaches 85-95%. Wherein, the esterification rate refers to the amount of the isophthalic acid-5-Sodium Sulfonate (SSIPA) and the Ethylene Glycol (EG) undergoing esterification reaction in the reaction process, and accounts for the percentage of the total amount of the added isophthalic acid-5-Sodium Sulfonate (SSIPA).
The invention also provides a device for continuously producing the modified polyester tri-monomer, which is used for implementing the method and comprises a pulping tank and an esterification kettle in sequence according to the material supply sequence; optionally, the esterification kettle is connected with a subsequent polyester production line system, and provides the polyester modified tri-monomer material for the polyester production line system.
The device further comprises a slurry supply tank, wherein the pulping tank is connected with the slurry supply tank, the slurry supply tank is connected with the esterification kettle, the pulping tank, the slurry supply tank and the esterification kettle comprise stirring paddles, a separation tower is further arranged at the upper part of the esterification kettle, the gas substances in the esterification kettle flow back ethylene glycol into the esterification kettle through the separation tower, and meanwhile, water in the gas substances is collected to a collection tank connected with the top of the separation tower after being extracted from the top of the separation tower (6) and condensed.
Further, a slurry pump is optionally arranged between the pulping tank and the slurry supply tank;
a slurry conveying pump is optionally arranged between the slurry supply tank and the esterification kettle;
and a product conveying pump is optionally arranged between the esterification kettle (5) and the polyester production line system.
In a preferred embodiment, the ether inhibitor is added during the pulping process, because glycol can undergo self-etherification reaction during the reaction process to generate diethylene glycol, which affects the reaction efficiency and the conversion rate of raw materials, the addition of the ether inhibitor can effectively inhibit the self-etherification reaction of glycol, greatly improve the reaction efficiency and the conversion rate of raw materials, which is completely different from the action object and action principle of adding a catalyst in the prior art to accelerate the reaction speed, and the catalyst added in the prior art, like carboxyl on sodium 5-sulfoisophthalate (SSIPA), is to increase the positive charge on the carbonyl carbon atom by using metal cations, thereby facilitating the combination of alcohol and further playing a role in catalysis. Preferably, the ether inhibitor is selected from any one or a combination of any two or more of zinc acetate, potassium acetate and sodium acetate. The addition mode of the ether inhibitor can be directly adding in a solid form or adding in a solution with the mass concentration of 2-6% prepared by using ethylene glycol as a solvent.
The esterification product obtained by the invention can be used for the synthetic reaction of producing Cation Dyeable Polyester (CDP) and dyeable cation dyeable Ester (ECDP) by a terephthalic acid diethyl ester mixed copolymerization method.
Compared with the intermittent production process in the prior art, the production method of the polyester modified tri-monomer is a continuous and direct esterification production mode by improving the synthesis process and adjusting the reaction device system, and solves the problems of different batch-to-batch quality and high defective rate caused by the conventional intermittent process. Meanwhile, the processing method is more suitable for realizing large-scale production, is more favorable for meeting the increasing demand of the market for the polyester modified tri-monomer, and can make outstanding contribution to the polyester industry.
The invention has the beneficial effects that:
1. the invention opens up a new third monomer synthesis process, SSIPA and ethylene glycol are used as raw materials, and the third monomer can be continuously produced under the condition of not using a catalyst by adjusting the synthesis process and innovating reaction conditions, so that the corresponding third monomer raw material is continuously provided for a subsequent polyester processing production line;
2. compared with the synthesis route of methanol which is the byproduct in the prior art, the synthesis route of the invention is more environment-friendly, and greatly saves the production cost;
3. the invention improves the reaction equipment and is matched with the adjustment of reaction process parameters, so that the synthesis reaction in the reactor can be continuously carried out under the condition of not adding a catalyst in the reaction process, the principle is that the balance relation of the chemical reaction in the reactor is broken, the reaction is continuously carried out towards the direction of generating a target product, the use cost of the catalyst can be greatly saved, the energy waste and the potential safety hazard caused by equipment parking and driving in the catalyst replacement process are greatly reduced, and the production safety of an enterprise is greatly improved while the production cost of the enterprise is saved.
Drawings
FIG. 1 is a flow diagram of a process for the continuous production of polyester modified tri-monomers according to the present invention;
in the figure: 1. a pulping tank; 2. a slurry pump; 3. a slurry supply tank; 4. a slurry delivery pump; 5. an esterification kettle; 6. a separation column; 7. a product delivery pump; 8. a collection tank; 9. polyester production line system.
Detailed description of the preferred embodiments
The invention is illustrated in detail below with reference to examples:
example 1
A method for the continuous production of a polyester modified tri-monomer, the method comprising the steps of:
step (1): firstly, adding ethylene glycol into a pulping tank, and sequentially adding isophthalic acid-5-sodium sulfonate and an ether inhibitor into the stirring tank under the stirring condition, wherein the molar ratio of the isophthalic acid-5-sodium sulfonate to the ethylene glycol is 1:20, the mass ratio of the ether inhibitor to the isophthalic acid-5-sodium sulfonate is 1:2000, the stirring temperature is kept at 20 ℃, the pulping operation is kept for 60min, the pressure is normal pressure, and a material A is obtained after the pulping operation is finished; the ether inhibitor is zinc acetate, and the ether inhibitor can be added directly or mixed into 2-6% glycol solution by a random adding mode;
step (2): and introducing the material A into the esterification kettle for esterification reaction, wherein the esterification reaction temperature is 170 ℃, the pressure is 0.1MPa (gauge pressure), and the reduced reaction residence time is 2.5h to obtain the polyester modified tri-monomer product, and the esterification rate of the m-phthalic acid-5-sodium sulfonate is 85%.
Optionally, step (1) after completing the pulping operation, the material A can be conveyed to a pulp supply tank in the presence of a pulp supply tank, and the volume of the pulp supply tank is at least 1.5 times of the volume of the pulping tank for ensuring continuous production; and conveying the material A from the slurry supply tank into the esterification kettle for esterification reaction.
During the reaction, the conveying flow rate of the slurry A is as follows: 1028Kg/h, the output flow of the materials contained in the esterification kettle is as follows: 1007Kg/h, 20.8Kg/h of water produced by the separation tower; the ratio of the total mass of the materials contained in the esterification kettle to the output flow of the materials is 2.5, the materials contained in the esterification kettle are ensured to be in a constant value by utilizing the material conservation principle, and a continuous and direct esterification synthesis production system is realized.
As a preferred embodiment, the esterification reaction temperature is 170 ℃ and the pressure is 0.1MPa, under which conditions the reaction residence time is 2.5 h.
Example 2
A method for the continuous production of a polyester modified tri-monomer, the method comprising the steps of:
step (1): firstly, adding ethylene glycol into a pulping tank, and sequentially adding isophthalic acid-5-sodium sulfonate and an ether inhibitor into the stirring tank under the stirring condition, wherein the molar ratio of the isophthalic acid-5-sodium sulfonate to the ethylene glycol is 1:15, the mass ratio of the ether inhibitor to the isophthalic acid-5-sodium sulfonate is 1:1500, the stirring temperature is kept at 50 ℃, the pulping operation is kept for 50min, the pressure is normal pressure, and a material A is obtained after the pulping operation is finished; the ether inhibitor is potassium acetate, and the ether inhibitor can be added directly or mixed into 2-6% glycol solution by a random adding mode;
step (2): and introducing the material A into the esterification kettle for esterification reaction, wherein the esterification reaction temperature is 180 ℃, the pressure is 0.1MPa (gauge pressure), and the reduced reaction residence time is 2.2h, so as to obtain the polyester modified tri-monomer product, and the esterification rate of the m-phthalic acid-5-sodium sulfonate is 88%.
Optionally, step (1) after completing the pulping operation, the material A can be conveyed to a pulp supply tank in the presence of a pulp supply tank, and the volume of the pulp supply tank is at least 1.5 times of the volume of the pulping tank for ensuring continuous production; and conveying the material A from the slurry supply tank into the esterification kettle for esterification reaction.
During the reaction, the conveying flow rate of the slurry A is as follows: 816.8 kg/h; the output flow of the materials contained in the esterification kettle is as follows: 795.2Kg/h, 21.6Kg/h of water produced by the separation tower, and the ratio of the total mass of the materials contained in the esterification kettle to the output flow of the materials is 2.2; the invention ensures the material contained in the esterification kettle to be in a constant value by utilizing the material conservation principle, realizes a continuous and direct esterification synthesis production system, and ensures the stability of the production of the polyester modified tri-monomer by setting the reaction process and conditions.
Example 3
A method for the continuous production of a polyester modified tri-monomer, the method comprising the steps of:
step (1): firstly, adding ethylene glycol into a pulping tank, and sequentially adding isophthalic acid-5-sodium sulfonate and an ether inhibitor into the stirring tank under the stirring condition, wherein the molar ratio of the isophthalic acid-5-sodium sulfonate to the ethylene glycol is 1:12, the mass ratio of the ether inhibitor to the isophthalic acid-5-sodium sulfonate is 1:1500, the stirring temperature is kept at 70 ℃, the pulping operation is kept for 45min, the pressure is normal pressure, and a material A is obtained after the pulping operation is finished; the ether inhibitor is zinc acetate, and the ether inhibitor can be added directly or mixed into 2-6% glycol solution by a random adding mode;
step (2): and introducing the material A into the esterification kettle for esterification reaction, wherein the esterification reaction temperature is 190 ℃, the pressure is 0MPa (gauge pressure), and the reduced reaction residence time is 2.0h to obtain the polyester modified tri-monomer product, and the esterification rate of the m-phthalic acid-5-sodium sulfonate is 86%.
Optionally, step (1) after completing the pulping operation, the material A can be conveyed to a pulp supply tank in the presence of a pulp supply tank, and the volume of the pulp supply tank is at least 1.5 times of the volume of the pulping tank for ensuring continuous production; and conveying the material A from the slurry supply tank into the esterification kettle for esterification reaction.
In the reaction process, the delivery flow rate of the slurry A is 690 kg/h; the output flow of the materials contained in the esterification kettle is as follows: 668.9kg/h, 21.6kg/h of separating tower produced water, and the ratio of the total mass of the materials contained in the esterification kettle to the output flow of the materials is 2.0; the invention ensures the material contained in the esterification kettle to be in a constant value by utilizing the material conservation principle, realizes a continuous and direct esterification synthesis production system, and ensures the stability of the production of the polyester modified tri-monomer by setting the reaction process and conditions.
Example 4
A method for the continuous production of a polyester modified tri-monomer, the method comprising the steps of:
step (1): firstly, adding ethylene glycol into a pulping tank, and sequentially adding isophthalic acid-5-sodium sulfonate and an ether inhibitor into the stirring tank under the stirring condition, wherein the molar ratio of the isophthalic acid-5-sodium sulfonate to the ethylene glycol is 1:10, the mass ratio of the ether inhibitor to the isophthalic acid-5-sodium sulfonate is 1:800, the stirring temperature is kept at 80 ℃, the pulping operation is kept for 38min, the pressure is normal pressure, and a material A is obtained after the pulping operation is finished; the ether inhibitor is sodium acetate, and the ether inhibitor can be added directly or mixed into 2-6% glycol solution by a random adding mode;
step (2): and introducing the material A into the esterification kettle for esterification reaction, wherein the esterification reaction temperature is 190 ℃, the pressure is 0.05MPa (gauge pressure), and the reduced reaction residence time is 3h to obtain the polyester modified tri-monomer product, and the esterification rate of the m-phthalic acid-5-sodium sulfonate is 92%.
Optionally, step (1) after completing the pulping operation, the material A can be conveyed to a pulp supply tank in the presence of a pulp supply tank, and the volume of the pulp supply tank is at least 1.5 times of the volume of the pulping tank for ensuring continuous production; and conveying the material A from the slurry supply tank into the esterification kettle for esterification reaction.
During the reaction, the conveying flow rate of the slurry A is as follows: 605.5 kg/h; the output flow of the materials contained in the esterification kettle is as follows: 583kg/h, the separation tower produced water 22.6kg/h, the ratio of the total mass of the materials in the esterification kettle to the output flow of the materials is 2.1; the invention ensures the material contained in the esterification kettle to be in a constant value by utilizing the material conservation principle, realizes a continuous and direct esterification synthesis production system, and ensures the stability of the production of the polyester modified tri-monomer by setting the reaction process and conditions.
Example 5
A method for the continuous production of a polyester modified tri-monomer, the method comprising the steps of:
step (1): firstly, adding ethylene glycol into a pulping tank, and sequentially adding isophthalic acid-5-sodium sulfonate and an ether inhibitor into the stirring tank under the stirring condition, wherein the molar ratio of the isophthalic acid-5-sodium sulfonate to the ethylene glycol is 1:8, the mass ratio of the ether inhibitor to the isophthalic acid-5-sodium sulfonate is 1:500, the stirring temperature is kept at 110 ℃, the pulping operation is kept for 35min, the pressure is normal pressure, and a material A is obtained after the pulping operation is finished; the ether inhibitor is a mixture of zinc acetate and potassium acetate, the molar ratio of the zinc acetate to the potassium acetate is 3:2, and the ether inhibitor can be added in a solid manner or a glycol solution with the mass concentration of 2-6% by blending, optionally;
step (2): introducing the material A into the esterification kettle for esterification reaction at 200 deg.C under 0.1MPa (gauge pressure) for 3h to obtain the polyester modified tri-monomer product with esterification rate of 5-sodium sulfoisophthalate95% of the total weight of the composition. The byproducts obtained from the esterification reaction are water and ethylene glycol with volatility, the ethylene glycol can be recycled after being treated by a separation tower, and the collected water can be held in a collection tank
Optionally, step (1) after completing the pulping operation, the material A can be conveyed to a pulp supply tank in the presence of a pulp supply tank, and the volume of the pulp supply tank is at least 1.5 times of the volume of the pulping tank for ensuring continuous production; and conveying the material A from the slurry supply tank into the esterification kettle for esterification reaction.
During the reaction, the conveying flow rate of the slurry A is as follows: 521.1 kg/h; the output flow of the materials contained in the esterification kettle is as follows: 498.6kg/h, 22.6kg/h of water produced by the separation tower, and the ratio of the total mass of the materials in the esterification kettle to the output flow of the materials is 3; the invention ensures the material contained in the esterification kettle to be in a constant value by utilizing the material conservation principle, realizes a continuous and direct esterification synthesis production system, and ensures the stability of the production of the polyester modified tri-monomer by setting the reaction process and conditions.
Example 6
In combination with the reaction device system of the invention, another method for continuously producing the polyester modified tri-monomer comprises the following steps:
step (1): firstly, adding ethylene glycol into a pulping tank 1, sequentially adding 500 parts of isophthalic acid-5-sodium sulfonate and 0.5 part of sodium acetate as an ether inhibitor into the pulping tank 1 under the stirring condition, keeping the stirring temperature at 25 ℃ for pulping for 60min, keeping the pressure at normal pressure, and obtaining a material A after the pulping operation; the ether inhibitor is sodium acetate, the ether inhibitor is zinc acetate, and the ether inhibitor can be added in a mode of directly adding solid or blending into 2-6% of glycol solution by mass concentration optionally;
step (2): and (2) introducing the material A into the esterification kettle 5 for esterification reaction at the temperature of 180 ℃ and the pressure of 0.2MPa (gauge pressure) by taking a slurry pump 2 as power from the pulping tank 1 through a pipeline, wherein the reaction residence time is 1.8h in terms of conversion, thus obtaining the polyester modified tri-monomer product, wherein the esterification rate of the m-phthalic acid-5-sodium sulfonate is 93%.
In a preferred embodiment, step (1) is further provided with a slurry supply tank 3 after completing the pulping operation, wherein the material a is supplied to the slurry supply tank 3 from the slurry tank 1 through a pipeline and powered by a slurry pump 2, and then supplied to the esterification kettle 5 from the slurry supply tank 3 through a pipeline and powered by a slurry delivery pump 4; to ensure continuous production, the volume of the pulp supply tank is at least 1.5 times of the volume of the beating tank; and conveying the material A from the slurry supply tank into the esterification kettle for esterification reaction.
The invention not only ensures the stability of the production of the polyester modified tri-monomer, but also improves the esterification rate by setting the reaction process and conditions, and the specific conditions are as follows:
firstly, EG 1736kg is put into a pulping tank 1, and then SSIPA 500kg and ether inhibitor NaAC (sodium acetate) 0.5kg are added into the pulping tank 1 together for pulping to obtain a material A; a material A is conveyed to a slurry supply tank 3 through a pipeline and powered by a slurry pump 2, and then conveyed to an esterification kettle 5 through a pipeline and continuously esterified in an esterification kettle 6, the amount of the material A prepared by each batch of the pulping tank 1 is 2236.5kg, the hourly feeding amount of the esterification kettle 5 is 93.2kg, and 2236.8kg is supplied to the esterification kettle 5 by the slurry supply tank 3 every day, so that a batch of slurry prepared by the pulping tank 1 every day is conveyed to the slurry supply tank for storage, and continuous esterification reaction can be ensured.
And reacting in an esterification kettle 5 to obtain a generated solution of dihydroxy ethyl isophthalate-5-sodium Sulfonate (SIPE) with the mass concentration of 30%, and continuously extracting the solution.
After EG, SSIPA and an anti-ether agent NaAC are pulped in a pulping tank 1 at room temperature and normal pressure, a material A is introduced into a slurry supply tank 3 by a slurry pump 2; wherein, the capacity of the pulping tank 1 is designed according to a batch of material A prepared in one day, and the capacity of the pulp supply tank 3 is designed according to the material A which can be stored by 1.5 times.
The materials in the slurry supply tank 4 are continuously conveyed into the esterification kettle 5 by the slurry conveying pump 4 at the speed of 93.2kg/H, and stay in the esterification kettle 5 for 2H to 3.5H to finish the esterification reaction, wherein the esterification byproduct is H2O; the esterification reaction temperature is 190 ℃, the pressure is normal pressure, the SIPE solution SSIPA esterification rate after the esterification reaction is 95 percent, and the esterification product is continuously extracted and supplied to an esterification pipeline of a 8000 ton polyester production line system 9 produced in year by a product delivery pump 7 at 90.5 kg/h.
Wherein, the retention time refers to the ratio of the total amount of the materials in the reactor to the conveying flow of the materials.
From the gaseous material of 5 upper mouths of esterifying kettle draws, through knockout tower 6, retrieve collection tank 8 after separating out ethylene glycol therein, can be used to recycle, improve ethylene glycol's utilization efficiency more, greatly practice thrift manufacturing cost.
Compared with the esterification rate of less than 90 percent in the prior art, the esterification rate of the invention is obviously improved, particularly in the embodiment, the esterification rate reaches 95 percent, the record of the esterification rate in the process condition of synthesizing the three monomers is refreshed, and the invention has development.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, but any modifications or equivalent variations made according to the technical spirit of the present invention are within the scope of the present invention as claimed.
Claims (10)
1. A method for continuously producing polyester modified tri-monomer is characterized in that no catalyst is used, and the chemical reaction formula is as follows:
the polyester modified monomer is m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate.
2. The method of claim 1, comprising weighing sodium m-phthalate-5-sulfonate and excessive ethylene glycol, mixing and stirring uniformly to obtain slurry;
and continuously conveying the obtained slurry to an esterification kettle for esterification reaction to obtain the polyester modified tri-monomer, wherein the excessive glycol also plays a role of a reaction solvent.
3. The method of claim 2,
step (1): weighing raw materials according to the molar ratio of the isophthalic acid-5-sodium sulfonate to the ethylene glycol of 1:20-1:5, adding the ethylene glycol into a pulping tank, starting stirring, then keeping the stirring state, adding the isophthalic acid-5-sodium sulfonate, and continuing stirring to uniformly mix the materials to obtain a material A;
step (2): and conveying the material A to an esterification kettle for esterification reaction to obtain the polyester modified tri-monomer product.
4. The method according to claim 3, wherein an ether inhibitor is further added in the step (1), and the molar ratio of the ether inhibitor to the sodium 5-sulfoisophthalate is controlled to be 1:2000-1: 100.
5. The method according to claim 3, wherein in the step (1), the temperature of the pulping tank is room temperature to 130 ℃ and the pressure is normal pressure.
6. The method according to claim 4, characterized in that it comprises the following steps:
step (1): putting the 5-sodium sulfoisophthalate, the glycol and the ether inhibitor into a pulping tank in proportion, starting a stirrer of the pulping tank to stir, keeping pulping operation for 30-90 min after all materials are added, keeping the temperature in the pulping tank at-130 ℃ and the pressure at normal pressure, and obtaining a material A after the pulping operation is finished;
step (2): and introducing the material A into the esterification kettle for esterification reaction at the temperature of 170-210 ℃ and the pressure of 0-0.1 MPa (gauge pressure), wherein the reduced reaction residence time is 2-3.5h, thereby obtaining the polyester modified tri-monomer product.
7. The method according to claim 6, wherein the step (1) is that after completing the beating operation, the material A is transferred to a pulp supply tank, and the volume of the pulp supply tank is at least 1.5 times of the volume of the beating tank for ensuring the continuous production;
and conveying the material A from the slurry supply tank into the esterification kettle for esterification reaction.
8. A device for continuously producing polyester modified tri-monomer is characterized by comprising a beating tank (1) and an esterification kettle (5) in sequence according to the material supply sequence; optionally, the esterification kettle is connected with a subsequent polyester production line system (9) to provide the polyester modified tri-monomer material for the polyester production line system.
9. The device according to claim 8, characterized by further comprising a slurry supply tank (3), wherein the pulping tank (1) is connected with the slurry supply tank (3), the slurry supply tank (3) is connected with the esterification kettle (5), the pulping tank (1), the slurry supply tank (3) and the esterification kettle (5) comprise stirring paddles, a separation tower (6) is further arranged at the upper part of the esterification kettle (5), the gas substances in the esterification kettle (5) are refluxed with ethylene glycol into the esterification kettle through the separation tower (6), and simultaneously, water in the gas substances is extracted from the top of the separation tower (6) and condensed and collected to a collection tank (8) connected with the top of the separation tower.
10. The arrangement according to claim 9, characterized in that between the beating tank (1) and the slurry supply tank (3), optionally also a slurry pump (2) is provided;
a slurry conveying pump (4) is optionally arranged between the slurry supply tank and the esterification kettle;
and a product conveying pump (7) is optionally arranged between the esterification kettle (5) and the polyester production line system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010428523.1A CN111517995A (en) | 2020-05-20 | 2020-05-20 | Method and device for continuously producing polyester modified tri-monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010428523.1A CN111517995A (en) | 2020-05-20 | 2020-05-20 | Method and device for continuously producing polyester modified tri-monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111517995A true CN111517995A (en) | 2020-08-11 |
Family
ID=71909247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010428523.1A Pending CN111517995A (en) | 2020-05-20 | 2020-05-20 | Method and device for continuously producing polyester modified tri-monomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111517995A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057612A (en) * | 2021-12-27 | 2022-02-18 | 江苏恒科新材料有限公司 | Method for preparing diethylene glycol isophthalate-5-sodium sulfonate by using isophthalic acid-5-sodium sulfonate direct esterification method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3899470A (en) * | 1973-08-01 | 1975-08-12 | Monsanto Co | Continuous process for preparation of basic dyeable polyester |
| US4803625A (en) * | 1986-06-30 | 1989-02-07 | Buddy Systems, Inc. | Personal health monitor |
| CN101265218A (en) * | 2007-03-12 | 2008-09-17 | 厦门翔鹭化纤股份有限公司 | Method for preparing SIPE from SIPA by direct esterification method |
| CN204999829U (en) * | 2015-08-17 | 2016-01-27 | 中国昆仑工程公司 | System for in succession synthetic third monomer m phthalic acid glycol ester -5 - sodium sulfonate |
| CN107881580A (en) * | 2016-09-29 | 2018-04-06 | 中国石化仪征化纤有限责任公司 | A kind of continuous producing method of fire-retardant polyester fibre |
| CN109485841A (en) * | 2018-09-20 | 2019-03-19 | 浙江恒澜科技有限公司 | A kind of continuous polymerization method of the alkali soluble copolymer polyester of not antimony-containing catalyst |
| CN109485839A (en) * | 2018-11-16 | 2019-03-19 | 泰山医学院 | A method of water-soluble polyester is prepared using three monomer production technology Waste water concentrating material |
| CN110387596A (en) * | 2019-07-18 | 2019-10-29 | 新凤鸣集团股份有限公司 | A kind of preparation method of the CDP fabrics long filament |
-
2020
- 2020-05-20 CN CN202010428523.1A patent/CN111517995A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3899470A (en) * | 1973-08-01 | 1975-08-12 | Monsanto Co | Continuous process for preparation of basic dyeable polyester |
| US4803625A (en) * | 1986-06-30 | 1989-02-07 | Buddy Systems, Inc. | Personal health monitor |
| CN101265218A (en) * | 2007-03-12 | 2008-09-17 | 厦门翔鹭化纤股份有限公司 | Method for preparing SIPE from SIPA by direct esterification method |
| CN204999829U (en) * | 2015-08-17 | 2016-01-27 | 中国昆仑工程公司 | System for in succession synthetic third monomer m phthalic acid glycol ester -5 - sodium sulfonate |
| CN107881580A (en) * | 2016-09-29 | 2018-04-06 | 中国石化仪征化纤有限责任公司 | A kind of continuous producing method of fire-retardant polyester fibre |
| CN109485841A (en) * | 2018-09-20 | 2019-03-19 | 浙江恒澜科技有限公司 | A kind of continuous polymerization method of the alkali soluble copolymer polyester of not antimony-containing catalyst |
| CN109485839A (en) * | 2018-11-16 | 2019-03-19 | 泰山医学院 | A method of water-soluble polyester is prepared using three monomer production technology Waste water concentrating material |
| CN110387596A (en) * | 2019-07-18 | 2019-10-29 | 新凤鸣集团股份有限公司 | A kind of preparation method of the CDP fabrics long filament |
Non-Patent Citations (2)
| Title |
|---|
| GUAN LI TAO ET AL: "Influence of the Catalyst on the Synthesis of SIPE", 《APPLIED MECHANICS AND MATERIALS》 * |
| 刘春福等: "直接酯化法制备SIPE-EG溶液的工艺研究", 《聚酯工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057612A (en) * | 2021-12-27 | 2022-02-18 | 江苏恒科新材料有限公司 | Method for preparing diethylene glycol isophthalate-5-sodium sulfonate by using isophthalic acid-5-sodium sulfonate direct esterification method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832397B (en) | The method of online reuse PET Polymerization Waste | |
| CN102286544B (en) | A kind of clean preparation method of starch base alcohol fuel | |
| CN102008922B (en) | Process method and method for regenerating methyl nitrite in production of dimethyl oxalate | |
| CN103451027B (en) | Esterification method for preparing biodiesel using waste oils and fats | |
| CN105001091A (en) | Esterification reaction process for plasticizer DOTP (dioctyl terephthalate) | |
| CN107090606A (en) | A kind of method for producing multifunctional different polyester fiber | |
| CN102559396A (en) | Biodiesel esterification ester exchange reaction device | |
| CN111517995A (en) | Method and device for continuously producing polyester modified tri-monomer | |
| CN101245252B (en) | Method for producing biological diesel oil by using waste oil | |
| CN103304788B (en) | Preparation method of polybutylene terephthalate polyester resin | |
| CN102701985A (en) | Method for preparing epoxy resin curing agent by performing alcoholysis on PET (Polyethylene Terephthalate) polyester | |
| CN106854262A (en) | Moisture absorption can contaminate low melting point polyester chip and preparation method thereof | |
| CN109456194A (en) | A kind of preparation method of fatty alcohol polyol acid esters | |
| CN103834477B (en) | The production method of a kind of glycerine fuel | |
| CN102030625B (en) | Method for synthesizing vanillin | |
| CN2820864Y (en) | Polyester catalyst mixing device | |
| CN101973884A (en) | Method for preparing triisononyl trimellitate (TINTM) | |
| CN215429031U (en) | Synthetic device for preparing water-soluble polyester resin | |
| CN104651060A (en) | Biodiesel continuous ester interchange technology | |
| CN108727308A (en) | A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel | |
| CN202509071U (en) | Biodiesel esterification ester exchange reaction device | |
| CN112374961A (en) | Four alkali wash deacidification devices of carbon behind ether | |
| CN113402382A (en) | Method for adjusting water content in iridium catalytic system oxo-synthesis acetic acid system | |
| CN111943872A (en) | Continuous process and device for synthesizing high-ester exchange rate sodium bis (hydroxyethyl) isophthalate-5-sulfonate through catalytic reaction rectification | |
| CN107245035B (en) | Clean production device for low-carbon acid high-boiling-point alcohol ester and use process |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200811 |
|
| RJ01 | Rejection of invention patent application after publication |