CN111187409B - Method and apparatus for reduced pressure polymerization of semi-aromatic polyamide - Google Patents

Method and apparatus for reduced pressure polymerization of semi-aromatic polyamide Download PDF

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CN111187409B
CN111187409B CN202010021112.0A CN202010021112A CN111187409B CN 111187409 B CN111187409 B CN 111187409B CN 202010021112 A CN202010021112 A CN 202010021112A CN 111187409 B CN111187409 B CN 111187409B
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reaction
semi
acid
reaction kettle
reaction vessel
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CN111187409A (en
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苑先佩
刘彪
曲振
高斌
潘现路
杨伟翔
陈海波
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C08G69/30—Solid state polycondensation

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyamides (AREA)

Abstract

The application discloses polymerization method of semi-aromatic polyamide and device used by the same, and the process route has the advantages of short polymerization time, low content of organic matters in condensed waste liquid, capability of realizing continuous polymerization and the like by expanding and reducing the pressure of the series-connected reaction kettles with pressure equalizing pipelines arranged between the reactors.

Description

Method and apparatus for reduced pressure polymerization of semi-aromatic polyamide
Technical Field
The present invention relates generally to a process and apparatus for the reduced pressure polymerization of semi-aromatic polyamides, and more particularly to a process and apparatus for the reduced pressure polymerization of semi-aromatic polyamide materials using a reaction vessel.
Background
The semi-aromatic polyamide is prepared by the polycondensation of aliphatic diamine and aromatic diacid or aromatic diamine and long carbon chain aliphatic diacid. Currently, the semi-aromatic polyamide varieties mainly comprise nylon 4T, nylon 46, nylon 6T/6, nylon 6T/66, nylon 6T/6I/66, nylon 9T, nylon 10T, nylon MXD6 and the like. Compared with aliphatic polyamide, the main chain of the polyamide molecule introduces an aromatic ring structure, so that the heat resistance and the mechanical property of the polyamide product are improved, and the water absorption is reduced to different degrees. Compared with the wholly aromatic polyamide, the main chain segment of the molecule of the wholly aromatic polyamide contains the aliphatic chain, so that the performances such as forming processability, solubility and the like are improved, and the wholly aromatic polyamide has better cost performance and is widely applied to the automobile and the electronic and electrical industries.
The synthesis method of semi-aromatic polyamide mainly comprises a low-temperature solution polycondensation method, an ester-amine exchange polycondensation method, a direct melt polycondensation method and a high-temperature high-pressure solution polycondensation method, but the methods have certain defects. For example, the patent US 6355769 adopts an organic solvent with a high price as a solvent system for the reaction, so that the production cost is high, and meanwhile, the hydrogen chloride gas as a byproduct in the reaction process is dissolved in the solvent to corrode reaction equipment, so that the service life of the equipment is short; in patent CN 101768266, organic solvents such as methanol/ethanol/acetone and the like are used as a solvent system for reaction, so that the production cost is increased, the operation risk is also brought, and the industrial production is not facilitated; patent US 5837803 uses macromolecular polyester as raw material to prepare semi-aromatic polyamide by ester-amine exchange polycondensation, the relative molecular weight of the final product is difficult to control, the molecular weight of the product at the later stage of the reaction is difficult to increase and the molecular weight distribution is wider. Nylon MXD6 was developed by Toyo Boseki Kabushiki Kaisha in Japan by the direct melt polycondensation method, and application of this method to the synthesis of semi-aromatic nylon was reported in patent CN1624021A by Mitsubishi corporation in Japan, but this method was only applicable to products having a relatively low melting point (< 280 ℃) such as nylon MXD6, and could not be used for the synthesis of semi-aromatic polyamides having a relatively high melting point (> 300 ℃) such as nylon 6T. Most of the semi-aromatic polyamides which are industrially produced at present adopt a high-temperature high-pressure solution polycondensation method, when the semi-aromatic polyamides are produced by adopting the method, prepolymers are prepared at high temperature and high pressure in the presence of a large amount of solvents (generally water), pressure is released, water is discharged to normal pressure, and then polycondensation is carried out after vacuum or materials are discharged, and then tackifying is carried out continuously to improve the molecular weight; the preparation method of semi-aromatic polyamide adopts similar methods to prepare semi-aromatic polyamide in patents of US6140459 and US4076664 of Dupont, US2012245283A1 and US5688901A of BASF, US5177178 of EMS, US4022756 and US4113708A of Monsanto and US20090098325 of Kuraray, and has the advantages of multiple process steps, complex operation and high production cost, and simultaneously causes the degradation and oxidation of products at high temperature and reduces the product performance. The high-temperature high-pressure solution polymerization method is improved by DSM patent US20100063245, EMS patent US2008274355A1, Mitsui Petrochemical Industries patent US5849826A, and golden hair patent US8420772, wherein the operation of pressure relief to normal pressure is improved to pressure relief to a certain specific pressure (generally > 2MPaG), the prepolymer is flashed by utilizing the self pressure after equilibrium reaction, and then solid phase or melt tackifying is carried out to obtain a high molecular weight product. The flash evaporation discharging method avoids the oxidation and degradation of the material in a high-temperature state in the traditional method, and can better maintain the performance of the material; however, the operation of pressure relief and condensation in the method not only takes a long time, but also can cause the diamine which is not completely reacted to escape, thereby causing the organic content of the condensed waste liquid to be high and causing the waste water to be difficult to treat.
Disclosure of Invention
Aiming at the problems in the prior art, the application aims to provide the preparation method of the semi-aromatic polyamide, which realizes the polymerization reaction of the semi-aromatic polyamide without pressure relief, ensures the stability of diamine in a reaction system and is beneficial to industrial production. To achieve the purpose, the following technical scheme is adopted in the application.
One or more embodiments of the present application provide a process for the reduced pressure polymerization of a semi-aromatic polyamide comprising the steps of:
(1) reacting an aromatic dibasic acid and a mixture of an aliphatic dibasic acid and an aliphatic diamine or a mixture of an aliphatic dibasic acid and an aromatic diamine, pure water in an amount of 30 to 100% by weight (e.g., 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%) of the total weight of the acid and the amine, an auxiliary in an amount of 0.1 to 1.5% by weight (e.g., 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, or 1.5%) of the total weight of the acid and the amine in a first reaction tank for 1 to 3 hours (e.g., 1, 2, or 3 hours) at a reaction temperature of 80 to 150 ℃ (e.g., 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, or 150 ℃), and a reaction pressure of 0 to 0.5MPaG (e.g., 0MPaG, 0.1MPaG, 0.2MPaG, 0,3MPaG, 0.4MPaG or 0.5MPaG) to obtain a polyamide salt solution; wherein the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 40:60-80:20, the mixed acid of the aromatic dibasic acid and the aliphatic dibasic acid is equimolar with the aliphatic diamine, and the aliphatic dibasic acid is equimolar with the aromatic diamine;
(2) after the step (1) is finished, equalizing the pressure of a second reaction kettle and the first reaction kettle through an equalizing line, then transferring the polyamide salt solution in the first reaction kettle into the second reaction kettle, and carrying out prepolymerization reaction for 1-5h (for example, 1, 2, 3, 4, 5h) at the temperature of 240-280 ℃ (for example, 240 ℃, 250 ℃, 260 ℃, 270 ℃, or 280 ℃) and the pressure of 3.3-6.5MPaG (for example, 4MPaG, 5MPaG, 6MPaG, 6.2MPaG, or 6.5 MPaG);
(3) after the step (2) is finished, equalizing the pressure of a third reaction kettle and the pressure of a second reaction kettle through an equalizing pipeline; then transferring the prepolymer obtained in the second reaction kettle to a third reaction kettle for polymerization reaction for 1-3h (such as 1, 2, 3h), wherein the reaction temperature is 240-280 ℃ (such as 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃), the reaction pressure is 2.5-3.4MPaG (such as 2.5MPaG, 2.8MPaG, 3MPaG, or 3.2MPaG), and the volume of the third reaction kettle is larger than that of the second reaction kettle;
(4) and carrying out solid-phase polycondensation or melt polycondensation on the prepolymer obtained in the third reaction kettle to obtain a final product.
In one or more embodiments of the present application, the volume of the second reaction vessel is the same as the volume of the first reaction vessel.
In one or more embodiments of the application, the ratio of the volume of the third reaction vessel to the vessel volume of the second reaction vessel is greater than 1 and equal to or less than 80, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, or 80.
In one or more embodiments of the application, the ratio of the volume of the third reaction vessel to the vessel volume of the second reaction vessel is in the range of 2 to 50, such as 4 to 20.
In one or more embodiments of the application, the design pressure of the first reactor is 6.5 to 10MPaG, the design pressure of the second reactor is 6.5 to 10MPaG, and the design pressure of the third reactor is 5 to 8 MPaG.
In one or more embodiments of the application, the aromatic dibasic acid in the step (1) is a dicarboxylic acid having a benzene ring in the main chain.
In one or more embodiments of the application, the dicarboxylic acid having a benzene ring in the backbone is selected from one or more of terephthalic acid, isophthalic acid, phthalic acid, 4 ' -biphenyldicarboxylic acid, 4 ' -dicarboxybiphenylsulfone, 4 ' -dicarboxybiphenylether.
In one or more embodiments of the application, the dicarboxylic acid having a benzene ring in the main chain is terephthalic acid or isophthalic acid.
In one or more embodiments of the application, the aliphatic dibasic acid is a dicarboxylic acid having a main chain containing 4 to 18 (e.g., 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18) carbon atoms, such as adipic acid.
In one or more embodiments of the application, wherein the aliphatic diamine in step (1) is an aliphatic diamine having a main chain of 4 to 18 carbon atoms, for example, an aliphatic diamine having a main chain of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms.
In one or more embodiments of the present application, wherein the aliphatic diamine in step (1) is hexamethylene diamine.
In one or more embodiments of the application, the aromatic diamine is a diamine having a benzene ring in the main chain, such as one or more of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and 1, 4-naphthalenediamine.
In one or more embodiments of the application, the aliphatic diamine is m-phenylenediamine.
In one or more embodiments of the application, the coagent described in step (1) includes a catalyst and a molecular weight regulator.
In one or more embodiments of the application, the catalyst is selected from one or more of potassium phosphate, magnesium phosphate, calcium phosphate, zinc phosphate, potassium phosphite, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, potassium hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite, and zinc hypophosphite.
In one or more embodiments of the application, the catalyst is sodium hypophosphite.
In one or more embodiments of the application, the molecular weight regulator is selected from one or more of acetic acid, benzoic acid, terephthalic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, hexamethylenediamine, decamethylenediamine, dodecanediamine.
In one or more embodiments of the application, the molecular weight regulator is benzoic acid.
In one or more embodiments of the application, each reaction vessel is free of a pressure relief line, and the entire process is free of a condensation dehydration operation.
In one or more embodiments of the present application, the prepolymer obtained in the third reaction vessel is flashed off the third reaction vessel.
In one or more embodiments of the application, after the third reaction kettle is discharged, the prepolymer in the second reaction kettle is transferred to the third reaction kettle, then the polyamide solution in the first reaction kettle is transferred to the second reaction kettle, and then reactants are added into the first reaction kettle, so that the first reaction kettle, the second reaction kettle and the third reaction kettle are reacted simultaneously.
One or more embodiments of the application provide a device for semi-aromatic polyamide decompression polymerization, which comprises a first reaction kettle, a second reaction kettle and a third reaction kettle, wherein a pressure equalizing pipeline is arranged between the first reaction kettle and the second reaction kettle and between the second reaction kettle and the third reaction kettle.
In one or more embodiments of the application, pressure equalization lines are disposed between the top of the first reaction vessel and the top of the second reaction vessel, and between the top of the second reaction vessel and the top of the third reaction vessel.
In one or more embodiments of the present application, the volume of the first reaction vessel is the same as the volume of the second reaction vessel, and the volume of the third reaction vessel is greater than the volume of the second reaction vessel.
In one or more embodiments of the application, the second and third reaction vessels are provided with insert pipes to prevent splashing when transferring the material.
In one or more embodiments of the application, an anchor paddle, a gate paddle, a screw paddle, and/or a ribbon paddle is provided in each reaction vessel.
In one or more embodiments of the application, the first reaction vessel and the second reaction vessel are provided with anchor paddles and/or gate paddles.
In one or more embodiments of the application, the third reaction vessel is provided with a screw paddle and/or a ribbon paddle.
In one or more embodiments of the application, the apparatus further comprises a vacuum drum dryer, a vacuum double-cone dryer, or a tower continuous tackifying reactor for solid phase polycondensation reactions, or a vented twin screw extruder for melt polycondensation reactions.
Detailed Description
In one or more embodiments of the present application, a multi-kettle series expansion and depressurization method is adopted to quickly achieve the purpose of reactant dehydration, shorten the reaction time, and improve the production efficiency; the whole process has no operations such as cooling, pressure relief and the like, and the un-fixed diamine continuously participates in the reaction in the third reaction kettle, so that the problem that the content of organic matters in the condensed waste liquid is high and the condensed waste liquid is difficult to treat is solved.
The process for the reduced pressure polymerization of semi-aromatic polyamides in one or more embodiments herein comprises the steps of:
(1) putting a mixture of aromatic dibasic acid and aliphatic dibasic acid with aliphatic diamine or a mixture of aliphatic dibasic acid with aromatic diamine, pure water accounting for 30-100% of the total weight of the acid and the amine and an auxiliary agent accounting for 0.1-1.5% of the total weight of the acid and the amine into a first reaction kettle at normal temperature, heating to 80-150 ℃ to prepare a polyamide salt solution, wherein the reaction time is 1h, and the design pressure of the first reaction kettle is 7 MPaG; the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 40:60-80:20, the molar ratio of mixed acid of the aromatic dibasic acid and the aliphatic dibasic acid to the aliphatic diamine is 50:50, and the molar ratio of the aliphatic dibasic acid to the aromatic diamine is 50: 50;
(2) transferring the polyamide salt solution to a second reaction kettle at the temperature of 240 ℃ and 280 ℃ for high-pressure polymerization reaction, wherein the design pressure of the second reaction kettle is 7 MPaG; carrying out prepolymerization reaction at constant temperature and constant pressure for 1-5 h;
(3) equalizing the pressure of the third reaction kettle and the second reaction kettle by using an equalizing pipeline, transferring the material in the second reaction kettle into a third reaction kettle 3 at the temperature of 240 plus 280 ℃, wherein the volume of the third reaction kettle is larger than that of the second reaction kettle, the design pressure of the third reaction kettle is 5MPaG, and the material is sprayed out after reacting for a certain time at constant temperature and constant pressure in the third reaction kettle;
(4) and carrying out solid phase polycondensation or melt polycondensation on the sprayed solid prepolymer to obtain a final product.
In one or more embodiments of this application, first reation kettle and second reation kettle are independent reation kettle respectively, thereby carry out salification and high-pressure polymerization respectively and promote polymerization efficiency.
In one or more embodiments herein, a process for the reduced pressure polymerization of a semi-aromatic polyamide comprises the steps of:
(1) synthesis of polyamide salts: putting mixed acid (mixture of aromatic dibasic acid and aliphatic dibasic acid) and aliphatic diamine with the same mole as the mixed acid or mixture of aliphatic dibasic acid and aromatic diamine with the same mole as the mixed acid, pure water accounting for 30-100% of the total weight of the acid and the amine and an auxiliary agent accounting for 0.1-1.5% of the total weight of the acid and the amine into a first reaction kettle at normal temperature, heating to 80-150 ℃ to prepare a polyamide salt solution, wherein the design pressure of the first reaction kettle is 7 MPaG;
(2) high-pressure prepolymerization of polyamide salt solution: opening a pressure equalizing line between the first reaction kettle and the second reaction kettle, transferring the polyamide salt solution to the second reaction kettle at the temperature of 240-280 ℃ for high-pressure prepolymerization reaction, wherein the pressure of the second reaction kettle is 7 MPaG;
(3) carrying out expansion and depressurization polymerization on the prepolymer: pressure of a third reaction kettle and a second reaction kettle is balanced by using a pressure equalizing pipeline, then the prepolymer in the second reaction kettle is transferred into the third reaction kettle at the temperature of 240-280 ℃, the volume of the third reaction kettle is larger than that of the second reaction kettle, the design pressure of the third reaction kettle is 5MPaG, and the material is sprayed out after being subjected to constant-temperature and constant-pressure reaction in the third reaction kettle for a period of time;
(4) post-polycondensation of prepolymer: and carrying out solid-phase polycondensation or melt polycondensation on the solid material sprayed out of the third reaction kettle to obtain a final product.
In the step (1), the aromatic dibasic acid is one or more of dicarboxylic acids having a benzene ring structure in the main chain, such as terephthalic acid, isophthalic acid, phthalic acid, 4 ' -biphenyldicarboxylic acid, 4 ' -dicarboxybiphenylsulfone, 4 ' -dicarboxybiphenylether, etc., preferably terephthalic acid and isophthalic acid; the aliphatic diamine is one or more of aliphatic diamines with 4-18 carbon atoms in the main chain of the molecule; the aromatic diamine is one or more of m-phenylenediamine, o-phenylenediamine and 1, 4-naphthalene diamine, and preferably m-phenylenediamine; the auxiliary agent is mainly a catalyst and a molecular weight regulator, wherein the catalyst is selected from one or more of potassium phosphate, magnesium phosphate, calcium phosphate, zinc phosphate, potassium phosphite, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, potassium hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite, and preferably the sodium hypophosphite; the molecular weight regulator is selected from one or more of acetic acid, benzoic acid, terephthalic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine, and is preferably benzoic acid.
The first reaction kettle and the second reaction kettle are high-pressure reaction kettles, and the design pressure is 7 MPaG.
The volume of the first reaction kettle is the same as that of the second reaction kettle.
The first reaction kettle and the second reaction kettle are independent reaction kettles respectively, and salt forming reaction and high-pressure polymerization reaction are carried out respectively;
the third reaction kettle is a high-pressure reaction kettle with the design pressure of 5 MPaG.
The volume of the third reaction kettle is N times of the volume of the second reaction kettle, and N is 1-80, preferably 2-50, and more preferably 4-20 times.
In one or more embodiments herein, the polyamide salt solution is transferred to the second reaction vessel immediately after opening the pressure equalization line when transferring the polyamide salt solution from the first reaction vessel to the second reaction vessel.
In one or more embodiments of the present application, before transferring the prepolymer in the second reaction kettle to the third reaction kettle, the pressure equalization line is opened to equalize the pressures of the third reaction kettle and the second reaction kettle, so that the prepolymer is not separated out due to flash evaporation when transferring the prepolymer to the third reaction kettle.
In one or more embodiments of the present application, the second reaction vessel and the third reaction vessel are provided with an insert pipe to prevent splashing when the material is transferred.
In one or more embodiments of the present application, after the material transferred to the third reaction kettle is subjected to a constant temperature and pressure reaction for a period of time, the material is sprayed out by means of the steam pressure in the reaction kettle, and the material is flash-evaporated and cooled into a powdery solid prepolymer.
In one or more embodiments herein, the powdered solid prepolymer is solid-phase tackified or melt-tackified to increase molecular weight to yield a final product.
In one or more embodiments of the present application, the solid-phase tackifying equipment includes, but is not limited to, a vacuum drum tackifying device, a vacuum double-cone tackifying device, a tower-type continuous tackifying device, etc.; the melt tackifying equipment includes, but is not limited to, devolatilizing screw tackifying devices.
In one or more embodiments of this application, the third reation kettle ejection of compact finishes, transfers the second reation kettle material to the third reation kettle, then transfers the material of first reation kettle to the second reation kettle, and later first reation kettle can advance the raw materials and continue the reaction. The continuous polymerization reaction is realized by the above flow.
One or more technical solutions of the present application have at least one of the following advantageous effects:
(1) by increasing the pressure of the first reaction kettle and arranging the pressure equalizing pipeline between the first reaction kettle and the second reaction kettle, the second reaction kettle can quickly transfer the low-temperature polyamide salt solution in the first reaction kettle to the second reaction kettle without cooling, so that the operation time of heating and cooling the second reaction kettle is saved;
(2) liquid water in the second reaction kettle is quickly transferred to a gas phase space of a third reaction kettle by utilizing a pressure equalizing pipeline without the operation of pressure relief and condensation, so that the aim of pressure reduction and dehydration of the prepolymer is fulfilled in a short time;
(3) the stable transition of a high-pressure reaction section and a balance reaction section is quickly realized through the capacity expansion and pressure reduction of the reaction kettles connected in series;
(4) the whole polymerization process before discharging the prepolymer is carried out in a closed manner, no pressure relief operation is carried out in the whole process before discharging the prepolymer in the third reaction kettle, the process route has the advantages of shorter polymerization time, lower content of organic matters in condensed waste liquid and reduction of the treatment difficulty of waste water;
(5) continuous polymerization can be achieved.
Detailed Description
Comparative example and example, the starting material terephthalic acid was from Hemicanite (Dalian) Inc., the starting material adipic acid was from Shenma group, Inc., the starting material hexamethylenediamine was from Envida, the starting material m-phenylenediamine was from northern Red Special chemical, Inc., Sichuan; the auxiliary agent consists of benzoic acid serving as a molecular weight regulator and sodium hypophosphite serving as a catalyst in a mass ratio of 8:1, and the two are both from chemical reagents of national medicine group, Inc.
Comparative example
The reaction is carried out in two steps: salifying reaction and prepolymerization reaction. The design pressure of the salification reaction kettle is 0.5MPaG, and the design pressure of the prepolymerization reaction kettle is 7 MPaG.
Putting a mixture of terephthalic acid and adipic acid (the molar ratio of the terephthalic acid to the adipic acid is 50:50) and equimolar hexamethylene diamine, pure water accounting for 60% of the total weight of the terephthalic acid, the adipic acid and the hexamethylene diamine and an auxiliary agent accounting for 1% of the total weight of the phthalic acid, the adipic acid and the hexamethylene diamine into a salt forming reaction kettle at normal temperature, heating to 110 ℃ within 2h to prepare a polyamide salt solution, wherein the pressure of the first reaction kettle is 0.13MPaG, and the salt forming reaction lasts for 1 h; transferring the polyamide salt solution into a prepolymerization reaction kettle preheated to 110 ℃, heating to 280 ℃ within 4 hours after the material is transferred, controlling the pressure in the reaction kettle to be 5.75MPaG, reacting for 2 hours at constant temperature and constant pressure, then starting constant temperature pressure release, releasing the pressure to be 3.1MPaG within 5 hours, maintaining the temperature to be 280 ℃, reacting for 2 hours under 3.1MPaG, and then spraying the material; and cooling the solid powder, and then performing solid phase polycondensation or melt polycondensation for tackifying. From the beginning of the transfer of the polyamide salt solution to the time before discharging, the whole polymerization process takes about 13 hours, and the COD value of the condensed waste liquid is 2168 ppm.
Example 1
Carrying out reduced pressure polymerization according to the material ratio of the comparative example, and the volume (V) of a third reaction kettle3) Is the volume (V) of the second reaction kettle2) 8 times (V)3＝10V2)。
Putting a mixture of terephthalic acid and adipic acid (the molar ratio of the terephthalic acid to the adipic acid is 50:50) and equimolar hexamethylene diamine, pure water accounting for 60% of the total weight of the terephthalic acid, the adipic acid and the hexamethylene diamine and an auxiliary agent accounting for 1% of the total weight of the terephthalic acid, the adipic acid and the hexamethylene diamine into a first reaction kettle at normal temperature, heating to 110 ℃ within 2h to prepare a polyamide salt solution, wherein the pressure of the first reaction kettle is 0.13MPaG, and the salt forming reaction lasts for 1 h; opening a pressure equalizing line between the first reaction kettle and the second reaction kettle, transferring the polyamide salt solution to the second reaction kettle preheated to 280 ℃, heating the material to 280 ℃ within 1h, wherein the pressure of the second reaction kettle is 5.75MPaG, and reacting for 2h at constant temperature and constant pressure; after the constant-temperature and constant-pressure reaction is finished, opening a pressure equalizing line between the second reaction kettle and the third reaction kettle, after about 2 hours, equalizing the pressure of the second reaction kettle and the third reaction kettle to 3.4MPaG, after the material is transferred to the third reaction kettle, maintaining the conditions of 280 ℃ and 3.4MPaG, and after 2 hours of reaction, spraying the material; after the solid powder is cooled, solid phase/melt polycondensation and tackifying are carried out. From the beginning of the transfer of the polyamide salt solution to the time before the discharge, the whole polymerization process takes about 7 hours, and the COD value of the condensed waste liquid is 1397 ppm.
Example 2
The polymerization under reduced pressure was carried out according to the feed ratio of example 1, third reactor volume (V)3) Is the volume (V) of the second reaction kettle2) 15 times (V)3＝20V2)。
Putting a mixture of terephthalic acid and adipic acid (the molar ratio of the terephthalic acid to the adipic acid is 80:20) and equimolar hexamethylene diamine, pure water accounting for 60% of the total weight of the phthalic acid, the adipic acid and the hexamethylene diamine and an auxiliary agent accounting for 1% of the total weight of the terephthalic acid, the adipic acid and the hexamethylene diamine into a first reaction kettle in a normal temperature state, heating to 150 ℃ within 2 hours to prepare a polyamide salt solution, wherein the pressure of the first reaction kettle is 0.5MPaG, and the salt forming reaction lasts for 1 hour; opening a pressure equalizing line between the first reaction kettle and the second reaction kettle, transferring the polyamide salt solution to the second reaction kettle preheated to 280 ℃, heating the material to 280 ℃ within 1h, wherein the pressure of the second reaction kettle is 5.75MPaG, and reacting for 5h at constant temperature and constant pressure; after the constant-temperature and constant-pressure reaction is finished, opening a pressure equalizing pipeline between the second reaction kettle and the third reaction kettle, after about 1.5 hours, equalizing the pressure of the second reaction kettle and the third reaction kettle to 2.5MPaG, after the material is transferred to the third reaction kettle, maintaining the conditions of 280 ℃ and 2.5MPaG, and after the reaction is carried out for 1 hour, spraying the material; after the solid powder is cooled, solid phase/melt polycondensation is carried out for thickening. From the beginning of the salt solution transfer to the time before discharging, the whole polymerization process takes about 8.5h, and the COD value of the condensed waste liquid is 1844 ppm.
Example 3
Referring to example 1, the molar ratio of terephthalic acid to adipic acid was adjusted to 40:60, third reaction tank volume (V)3) Is the volume (V) of the second reaction kettle2) 4 times (V)3＝4V2)。
Putting a mixture of terephthalic acid and adipic acid (the molar ratio of the terephthalic acid to the adipic acid is 40:60) and equimolar hexamethylene diamine, pure water accounting for 60% of the total weight of the terephthalic acid, the adipic acid and the hexamethylene diamine and an auxiliary agent accounting for 1% of the total weight of the terephthalic acid, the adipic acid and the hexamethylene diamine into a first reaction kettle at normal temperature, heating to 80 ℃ within 1h to prepare a polyamide salt solution, wherein the pressure of the first reaction kettle is 0MPaG, and the salt forming reaction lasts for 1 h; opening a pressure equalizing line between the first reaction kettle and the second reaction kettle, transferring the polyamide salt solution to the second reaction kettle preheated to 280 ℃, heating the material to 240 ℃ within 2 hours, wherein the pressure of the second reaction kettle is 3.3MPaG, and reacting for 3 hours at constant temperature and constant pressure; after the constant-temperature and constant-pressure reaction is finished, opening a pressure equalizing line between the second reaction kettle and the third reaction kettle, after about 1 hour, equalizing the pressure of the second reaction kettle and the third reaction kettle to 2.9MPaG, after the materials are transferred to the third reaction kettle, maintaining the conditions of 240 ℃ and 2.9MPaG, and after the materials are reacted for 3 hours, spraying out the materials; after the solid powder is cooled, solid phase/melt polycondensation and tackifying are carried out. From the beginning of the salt solution transfer to the time before the discharge, the whole polymerization process takes about 9 hours, and the COD value of the condensed waste liquid is 987 ppm.
Example 4
Referring to example 1, the molar ratio of terephthalic acid to adipic acid was adjusted to 80:20, the third reaction tank volume (V)3) Is the volume (V) of the second reaction kettle2) 4 times (V)3＝4V2)。
Putting a mixture of terephthalic acid and adipic acid (the molar ratio of the terephthalic acid to the adipic acid is 80:20) and equimolar hexamethylene diamine, pure water accounting for 30% of the total weight of the terephthalic acid, the adipic acid and the hexamethylene diamine and an auxiliary agent accounting for 1% of the total weight of the phthalic acid, the adipic acid and the hexamethylene diamine into a first reaction kettle in a normal temperature state, heating to 100 ℃ within 1h to prepare a polyamide salt solution, wherein the pressure of the first reaction kettle is 0.1MPaG, and the salt forming reaction lasts for 1 h; opening a pressure equalizing line between the first reaction kettle and the second reaction kettle, transferring the polyamide salt solution to the second reaction kettle preheated to 260 ℃, heating the material to 260 ℃ within 2 hours, and reacting for 2 hours under constant temperature and constant pressure, wherein the pressure of the second reaction kettle is 4.7 MPaG; after the constant-temperature and constant-pressure reaction is finished, opening a pressure equalizing pipeline between the second reaction kettle and the third reaction kettle, after about 1.5 hours, equalizing the pressure of the second reaction kettle and the third reaction kettle to 3.22MPaG, after the materials are transferred to the third reaction kettle, maintaining the conditions of 260 ℃ and 3.22MPaG, and after 2 hours of reaction, ejecting the materials; after the solid powder is cooled, solid phase/melt polycondensation and tackifying are carried out. The whole polymerization process takes about 7.5 hours from the beginning of the salt solution transfer to the time before discharging, and the COD value of the condensed waste liquid is 776 ppm.
Example 5
According to the process conditions of example 4, the starting materials were replaced by adipic acid and m-phenylenediamine in a molar ratio of 50:50 and a third reaction vessel volume (V)3) Is the volume (V) of the second reaction kettle2) 4 times (V) of3＝4V2)。
Putting adipic acid, equimolar m-phenylenediamine, pure water accounting for 60 percent of the total weight of the adipic acid and the m-phenylenediamine and an auxiliary agent accounting for 1 percent of the total weight of the adipic acid and the m-phenylenediamine into a first reaction kettle at normal temperature, heating to 100 ℃ within 1h to prepare a polyamide salt solution, wherein the pressure of the first reaction kettle is 0.1MPaG, and the salt forming reaction lasts for 1 h; opening a pressure equalizing line between the first reaction kettle and the second reaction kettle, transferring the polyamide salt solution to the second reaction kettle preheated to 260 ℃, heating the materials to 260 ℃ within 2h, and reacting for 2h under constant temperature and constant pressure, wherein the pressure of the second reaction kettle is 4.7 MPaG; after the constant-temperature and constant-pressure reaction is finished, opening a pressure equalizing line between the second reaction kettle and the third reaction kettle, after about 1.5 hours, equalizing the pressure of the second reaction kettle and the third reaction kettle to 3.22MPaG, after the materials are transferred to the third reaction kettle, maintaining the conditions of 260 ℃ and 3.22MPaG, and after 2 hours of reaction, spraying out the materials; after the solid powder is cooled, solid phase polycondensation or melt polycondensation is carried out for tackifying. From the beginning of the salt solution transfer to the time before the discharge, the whole polymerization process takes about 7.5h, and the COD value of the condensed waste liquid is 493 ppm.
Comparative and example data statistics
Figure BDA0002360800740000091
From the above statistical data, it can be seen that the polymerization processes of examples 1 to 5 took less time than the comparative examples, and the COD values of the condensed waste liquids were also less than those of the comparative examples. Through the process control in the patent, the polymerization time can be reduced to about one-half of that of the comparative example, and the COD value can be reduced to about one-third of that of the comparative example. Therefore, the decompression polymerization method and the decompression polymerization device can shorten the whole reaction time and reduce the content of organic matters in the condensed waste liquid.
Example 6
Based on example 4, the continuous polymerization of semi-aromatic polyamide under reduced pressure was carried out by process adjustment, the time consumption of the whole polymerization process and the COD value were the same as those of example 4.
The method comprises the following steps: putting a mixture of terephthalic acid and adipic acid (the molar ratio of the terephthalic acid to the adipic acid is 80:20) and equimolar hexamethylene diamine, pure water accounting for 30% of the total weight of the phthalic acid, the adipic acid and the hexamethylene diamine and an auxiliary agent accounting for 1% of the total weight of the phthalic acid, the adipic acid and the hexamethylene diamine into a first reaction kettle in a normal temperature state, heating to 100 ℃ within 1h to prepare a polyamide salt solution, wherein the pressure of the first reaction kettle is 0.1MPaG, and the salt forming reaction lasts for 1 h; and opening a pressure equalizing line between the first reaction kettle and the second reaction kettle, and transferring the polyamide salt solution to the second reaction kettle preheated to 260 ℃. After the transfer of the polyamide salt solution is finished, starting to provide the next batch of raw materials for the first reaction kettle;
step two: after the polyamide salt solution is transferred to a second reaction kettle, heating the material to 260 ℃ within 2h, and reacting the material in the second reaction kettle for 2h under the constant temperature and the constant pressure, wherein the pressure of the second reaction kettle is 4.MPaG 4.7MPaG; after the constant-temperature and constant-pressure reaction is finished, opening a pressure equalizing pipeline between the second reaction kettle and the third reaction kettle, after about 1.5 hours, equalizing the pressure of the second reaction kettle and the third reaction kettle to 3.22MPaG, transferring the material to the third reaction kettle for polymerization reaction, and then transferring the newly prepared polyamide salt solution in the first reaction kettle to the second reaction kettle to start the polymerization reaction;
step three: after the materials in the second reaction kettle are transferred to a third reaction kettle, the conditions of 260 ℃ and 3.22MPaG are maintained, and the materials are sprayed out after 2 hours of reaction; and after the materials in the third reaction kettle are emptied, opening a pressure equalizing pipeline between the third reaction kettle and the second reaction kettle, and transferring the materials in the second reaction kettle to the third reaction kettle.

Claims (29)

1. A process for the reduced pressure polymerization of a semi-aromatic polyamide comprising the steps of:
(1) reacting a mixture of aromatic dibasic acid, aliphatic dibasic acid and aliphatic diamine or a mixture of aliphatic dibasic acid and aromatic diamine, pure water accounting for 30-100% of the total weight of the acid and the amine and an auxiliary agent accounting for 0.1-1.5% of the total weight of the acid and the amine in a first reaction kettle for 1-3 hours at the temperature of 80-150 ℃ and the pressure of 0-0.5MPaG to obtain a polyamide salt solution; wherein the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 40:60-80:20, the mixed acid of the aromatic dibasic acid and the aliphatic dibasic acid is equimolar with the aliphatic diamine, and the aliphatic dibasic acid is equimolar with the aromatic diamine;
(2) after the step (1) is finished, equalizing the pressure of a second reaction kettle and the pressure of a first reaction kettle through an equalizing pipeline, transferring the polyamide salt solution in the first reaction kettle into the second reaction kettle, and carrying out prepolymerization reaction at the temperature of 240-280 ℃ and the pressure of 4-6.5MPaG for 1-5 h;
(3) after the step (2) is finished, equalizing the pressure of a third reaction kettle and the pressure of a second reaction kettle through an equalizing pipeline, then transferring the prepolymer obtained in the second reaction kettle into the third reaction kettle for polymerization reaction for 1-3h, wherein the reaction temperature is 240-280 ℃, the reaction pressure is 2.5-3.4MPaG, and the volume of the third reaction kettle is larger than that of the second reaction kettle; and
(4) carrying out solid-phase polycondensation or melt polycondensation on the prepolymer obtained in the third reaction kettle to obtain a final product; wherein,
the volume of the second reaction kettle is the same as that of the first reaction kettle;
the ratio of the volume of the third reaction kettle to the volume of the second reaction kettle is more than 1 and less than or equal to 80.
2. The process for the reduced pressure polymerization of semi-aromatic polyamides according to claim 1, wherein the ratio of the volume of the third reaction vessel to the volume of the second reaction vessel is 2 to 50.
3. The process for the reduced pressure polymerization of semi-aromatic polyamides according to claim 2, the ratio of the volume of the third reaction vessel to the volume of the second reaction vessel is 4-20.
4. The semi-aromatic polyamide pressure-reducing polymerization method according to claim 1, wherein the aromatic dibasic acid in the step (1) is a dicarboxylic acid having a benzene ring in the main chain.
5. The semi-aromatic polyamide reduced pressure polymerization process according to claim 4, wherein the aromatic dibasic acid in step (1) is one or more of terephthalic acid, isophthalic acid, phthalic acid, 4 ' -biphenyldicarboxylic acid, 4 ' -dicarboxybiphenylsulfone, 4 ' -dicarboxybiphenylether.
6. The semi-aromatic polyamide pressure-reducing polymerization process according to claim 5, wherein the aromatic dibasic acid in the step (1) is terephthalic acid or isophthalic acid.
7. The semi-aromatic polyamide pressure-reducing polymerization process according to any one of claims 4 to 6, wherein the aliphatic dibasic acid in step (1) is a dicarboxylic acid having a main chain of 4 to 18 carbon atoms.
8. The semi-aromatic polyamide pressure-reducing polymerization method according to claim 7, wherein the aliphatic dibasic acid in the step (1) is adipic acid.
9. The semi-aromatic polyamide pressure-reducing polymerization process according to any one of claims 4 to 6 and 8, wherein the aliphatic diamine in step (1) is an aliphatic diamine having a main chain of 4 to 18 carbon atoms.
10. The semi-aromatic polyamide pressure-reducing polymerization process according to claim 9, wherein the aliphatic diamine in step (1) is hexamethylenediamine.
11. The semi-aromatic polyamide pressure-reducing polymerization method according to any one of claims 4 to 6, 8 and 10, wherein the aromatic diamine in the step (1) is a diamine having a benzene ring in the main chain.
12. The semi-aromatic polyamide pressure reduction polymerization process according to claim 11, wherein the aromatic diamine in step (1) is one or more of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1, 4-naphthalenediamine.
13. The semi-aromatic polyamide reduced pressure polymerization process according to claim 12, wherein the aromatic diamine in step (1) is m-phenylenediamine.
14. The process for the polymerization of a semi-aromatic polyamide under reduced pressure according to claim 1, wherein the auxiliary in the step (1) comprises a catalyst and a molecular weight regulator.
15. The semi-aromatic polyamide reduced pressure polymerization process of claim 14, the catalyst being selected from one or more of potassium phosphate, magnesium phosphate, calcium phosphate, zinc phosphate, potassium phosphite, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, potassium hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite, and zinc hypophosphite.
16. The semi-aromatic polyamide reduced pressure polymerization process of claim 15, the catalyst being sodium hypophosphite.
17. The semi-aromatic polyamide reduced pressure polymerization process according to claim 14, wherein the molecular weight regulator is selected from one or more of acetic acid, benzoic acid, terephthalic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, hexamethylenediamine, decamethylenediamine, and dodecanediamine.
18. The semi-aromatic polyamide reduced pressure polymerization process of claim 17, wherein the molecular weight regulator is benzoic acid.
19. The process for the polymerization under reduced pressure of semiaromatic polyamides according to any one of claims 1 to 6, 8, 10 and 12 to 18, wherein each reaction vessel has no pressure relief line and the whole process has no concentration dehydration operation.
20. The semi-aromatic polyamide reduced pressure polymerization process according to any one of claims 1 to 6, 8, 10 and 12 to 18, wherein the prepolymer obtained in the third reaction vessel is flashed off the third reaction vessel.
21. The semi-aromatic polyamide reduced pressure polymerization process according to any one of claims 1 to 6, 8, 10 and 12 to 18, wherein after the third reaction tank is discharged, the prepolymer in the second reaction tank is transferred to the third reaction tank, then the polyamide salt solution in the first reaction tank is transferred to the second reaction tank, and then reactants are added to the first reaction tank, thereby allowing the first reaction tank, the second reaction tank and the third reaction tank to simultaneously react.
22. The semi-aromatic polyamide reduced pressure polymerization method according to any one of claims 1 to 6, 8, 10 and 12 to 18, wherein the reduced pressure polymerization is carried out by using an apparatus for semi-aromatic polyamide reduced pressure polymerization, the apparatus comprising a first reaction vessel, a second reaction vessel and a third reaction vessel, and pressure equalizing lines are disposed between the first reaction vessel and the second reaction vessel and between the second reaction vessel and the third reaction vessel.
23. The process for the reduced pressure polymerization of semi-aromatic polyamide according to claim 22, wherein an equalization line is provided between the top of said first reaction vessel and the top of said second reaction vessel, and between the top of said second reaction vessel and the top of said third reaction vessel.
24. The process for the reduced pressure polymerization of semi-aromatic polyamide according to claim 22, wherein in said apparatus, the volume of said first reaction vessel is the same as the volume of said second reaction vessel, and the volume of said third reaction vessel is larger than the volume of said second reaction vessel.
25. The process for the reduced pressure polymerization of semi-aromatic polyamide according to claim 24, wherein the second reaction vessel and the third reaction vessel are provided with an insert pipe to prevent the occurrence of splash during the transfer of the materials.
26. The process for the polymerization under reduced pressure of semi-aromatic polyamides according to claim 22, wherein in the apparatus, anchor paddles, gate paddles, screw paddles and/or ribbon paddles are provided in each reaction vessel.
27. The process for the reduced pressure polymerization of semi-aromatic polyamides according to claim 26, wherein in the apparatus, the first reaction vessel and the second reaction vessel are provided with anchor paddles and/or frame paddles.
28. The process for the reduced pressure polymerization of semi-aromatic polyamides according to claim 27, wherein the third reaction vessel is equipped with a screw and/or ribbon-type paddle.
29. The process for the reduced pressure polymerization of semi-aromatic polyamide according to claim 28, wherein the apparatus further comprises a vacuum drum dryer, a vacuum double-cone dryer or a tower-type continuous viscosity increasing reactor for the solid phase polycondensation reaction, or a vented twin-screw extruder for the melt polycondensation reaction.
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