WO2023103333A1 - Method for preparing environment-friendly pet polyester having good hue quality on continuous polymerization device - Google Patents

Method for preparing environment-friendly pet polyester having good hue quality on continuous polymerization device Download PDF

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WO2023103333A1
WO2023103333A1 PCT/CN2022/100292 CN2022100292W WO2023103333A1 WO 2023103333 A1 WO2023103333 A1 WO 2023103333A1 CN 2022100292 W CN2022100292 W CN 2022100292W WO 2023103333 A1 WO2023103333 A1 WO 2023103333A1
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Prior art keywords
titanium
continuous polymerization
pet polyester
polymerization device
environmentally friendly
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PCT/CN2022/100292
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French (fr)
Chinese (zh)
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徐锦龙
梅锋
王华平
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江苏新视界先进功能纤维创新中心有限公司
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Publication of WO2023103333A1 publication Critical patent/WO2023103333A1/en

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Definitions

  • the invention belongs to the technical field of polymer material synthesis, and relates to a method for preparing environmentally friendly PET polyester with good hue and phase quality on a continuous polymerization device.
  • titanium-based catalysts instead of antimony-based catalysts to produce PET can obtain environmentally friendly polyester materials that do not contain heavy metal antimony.
  • titanium-based catalysts are generally added before precondensation and most of them are added before or during esterification.
  • titanium-based catalysts have the characteristics of high catalytic activity, and they can also catalyze the main reaction of PET polymerization. The intensity of the side reaction will increase accordingly. Studies have shown that the higher the catalyst concentration, the stronger the side reaction, resulting in a higher hue index b value of the synthetic PET than that of the PET synthesized by the antimony catalyst, and the appearance is yellowish, which affects the quality of the product.
  • the traditional solution is to add a phosphorus-containing compound as a stabilizer while using a titanium-based catalyst to reduce the activity of the titanium-based catalyst, thereby reducing the degree of side reactions and obtaining a better hue, but the use of a phosphorus-containing compound stabilizer will make
  • the hue index L value of the PET product decreases, which is manifested as a decrease in whiteness.
  • Document 2 Synthesis Technology and Application, 2007 Vol22-4: 32-37
  • Document 3 discloses a green titanium-based catalyst.
  • the present invention provides a method for preparing environmentally friendly PET polyester with good hue and phase quality on a continuous polymerization device.
  • a method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device The raw materials are composed of dibasic acid, dibasic alcohol and titanium series catalyst, excluding stabilizers and toners;
  • the titanium-based catalyst is added in two times in the continuous polymerization device; the timing of the first addition is before the pre-condensation reaction, and the timing of the second addition is after the pre-condensation reaction and before the final polycondensation reaction;
  • the weight ratio of the titanium element of the titanium-based catalyst added for the first time relative to the total amount of PET is 2-6ppm, and the weight ratio of the titanium element of the titanium-based catalyst added for the second time relative to the total amount of PET is 1-4ppm;
  • a small amount of titanium-based catalyst can ensure the smooth progress of the reaction.
  • a certain amount of titanium-based catalyst is added to maintain the polymerization reaction. Normal speed; the principle of setting the catalyst addition amount is to add as little amount as possible under the condition that the polycondensation reaction can be carried out normally.
  • the timing of adding the titanium catalyst for the first time is before the esterification reaction, or during the esterification reaction, or after the esterification reaction , Before the precondensation reaction.
  • the titanium-based catalyst is added for the second time in the logistics pipeline that transports the PET polyester obtained by pre-condensation to the final polycondensation tank, and in the logistics pipeline
  • the cost of joining equipment is the lowest, and the operation is the easiest to control.
  • the method for preparing environmentally friendly PET polyester with good color phase quality on the continuous polymerization device before adding the titanium-based catalyst to the logistics pipeline, extract the PET polyester obtained by partial pre-condensation from the kettle in front of the final polycondensation tank Oligomer material a, mix the titanium series catalyst to be added with the PET polyester oligomer material a, the mixing temperature is the same as the temperature of the logistics pipeline, and the temperature of the logistics pipeline depends on the PET polymer obtained by precondensation.
  • the temperature of the ester because the addition amount of the titanium-based catalyst is very small, it cannot be accurately measured without mixing the reaction materials, and there is no such a small addition device, and it is beneficial to improve the dispersion of the catalyst in the system after pre-mixing with the reaction materials before adding it to the system effect, so first mix the titanium-based catalyst to be added with the PET polyester oligomer material a and then add it to the system.
  • the method for preparing environmentally friendly PET polyester with good hue quality on the continuous polymerization device is mixed in a fully mixed stirring tank or a dynamic mixer.
  • the present invention is equivalent to adding a fully mixed stirring tank or a dynamic mixer outside the continuous polymerization device.
  • the mixer, the fully mixed stirring tank or the dynamic mixer is connected with the logistics pipeline that transports the PET polyester obtained by precondensation to the final polycondensation tank in the continuous polymerization device.
  • the quality of the PET polyester oligomer material a obtained by partial precondensation is the whole PET polyester oligomer material b obtained by precondensation 1/10 to 1/20 of the total mass, setting the ratio in this range can avoid poor dispersion and avoid increasing the load on the adding device.
  • the titanium-based catalyst is titanate, titanium ethylene glycol, titanium-silicon composite catalyst or titanium chloride hydrolysis complex.
  • the continuous polymerization device is a three-pot continuous polymerization device, a four-pot continuous polymerization device or a five-pot continuous polymerization device.
  • the dibasic acid is terephthalic acid
  • the dibasic alcohol is ethylene glycol
  • the temperature of the esterification reaction is 220-250 ° C, the pressure 0.15-0.35MPa, the time is 1-5h
  • the temperature of the pre-condensation reaction is 260-270°C
  • the pressure is 300-1000Pa
  • the time is 0.5-2h
  • the temperature of the final polycondensation reaction is 270-285°C
  • the pressure is 20- 100Pa
  • the time is 0.5 ⁇ 3h.
  • the invention adopts the method of adding titanium series catalyst twice without adding stabilizer, and by controlling the catalyst content of PET in different polymerization stages, the progress of side reactions is controlled while ensuring the progress of the polymerization reaction.
  • a small amount of titanium-based catalyst can ensure the smooth progress of the reaction.
  • a certain amount of titanium-based catalyst is added to maintain the polymerization reaction. proceed at normal speed.
  • the method of adding catalysts in stages in the present invention reduces the concentration of catalyst viscosity in the reaction system, reduces the degree of side reactions as a whole, and the hue index of the product is significantly improved .
  • the method for preparing environmentally friendly PET polyester with good hue quality in the continuous polymerization device of the present invention adopts the corresponding method of differential catalysis by utilizing the relatively large viscosity difference and the difference in reaction kinetic mechanism between the pre-condensation stage and the final polycondensation stage. Measures, the overall low catalyst concentration process makes the reaction process more stable, milder, and more controllable than the traditional process; while controlling the yellowing of the product, it does not affect the brightness and luster of the product, and the appearance quality of the product is completely comparable to that when using antimony-based catalysts s level.
  • the present invention is applicable to all titanium-based catalysts in principle. Since there are countless kinds of titanium-based catalysts in theory, it is impossible to list them one by one.
  • the titanium-based catalysts used in the examples are just examples.
  • the continuous polymerization device is a three-pot continuous polymerization device, including an esterification tank, a pre-condensation tank and a final polycondensation tank. The specific steps are as follows:
  • Dibasic acid terephthalic acid
  • Diol ethylene glycol
  • Titanium catalyst tetrabutyl titanate
  • the dibasic acid and the dibasic alcohol are mixed at a molar ratio of 1:2 to carry out the esterification reaction; the temperature of the esterification reaction is 250°C, and the pressure is 0.35MPa; wherein, before the esterification reaction, titanium is added to the esterification kettle series catalyst, the weight ratio of the titanium element of the added titanium series catalyst relative to the PET total amount is 5ppm;
  • step (2) The product of step (2) is pre-condensed; the temperature of the pre-condensation reaction is 270 ° C, and the pressure is 1000 Pa; a part of the PET polyester oligomer material a is extracted from the pre-condensation kettle, and the titanium series catalyst is mixed with the PET polyester low
  • the polymer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank and the final polycondensation tank, wherein, the PET polyester oligomer material a is all PET polyester low polymer obtained by pre-condensation 1/10 of the total mass of the polymer material b, the weight ratio of the titanium element of the titanium-based catalyst to the total amount of PET is 1ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
  • the final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 285 ° C, and the pressure is 100 Pa.
  • the finally obtained environmentally friendly PET polyester with good hue quality has a hue index b value of 4.6, a hue index L value of 88.2, and an intrinsic viscosity of 0.648 dL/g.
  • the method for preparing PET polyester on a continuous polymerization device is basically the same as in Example 1, except that the titanium element of the titanium series catalyst added in the step (2) accounts for 6 ppm by weight relative to the total amount of PET, and the step ( 3) no titanium-based catalyst was added; Comparative Example 1 was equivalent to adding all the titanium-based catalysts in Example 1 before the esterification reaction.
  • the hue index b value of the finally prepared PET polyester is 6.2, and the intrinsic viscosity is 0.645dL/g.
  • Example 1 can significantly reduce the hue index b value of polyester relative to Comparative Example 1, because the method of adding catalyst in sections in Example 1 reduces the viscosity of the catalyst during the reaction.
  • the concentration in the system generally reduces the degree of side reactions, so that the hue index of the product can be significantly improved.
  • the continuous polymerization device is a three-pot continuous polymerization device, including an esterification tank, a pre-condensation tank and a final polycondensation tank. The specific steps are as follows:
  • Dibasic acid terephthalic acid
  • Diol ethylene glycol
  • Titanium catalyst titanium ethylene glycol
  • step (2) The product of step (2) is subjected to pre-condensation; the temperature of the pre-condensation reaction is 268°C, and the pressure is 900Pa; part of the PET polyester oligomer material a is extracted from the pre-condensation kettle, and the titanium series catalyst is mixed with the PET polyester low
  • the polymer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank and the final polycondensation tank, wherein, the PET polyester oligomer material a is all PET polyester low polymer obtained by pre-condensation 1/11 of the total mass of the polymer material b, the weight ratio of the titanium element of the titanium-based catalyst to the total amount of PET is 2ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
  • the final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 282° C., and the pressure is 90 Pa.
  • the finally obtained environmentally friendly PET polyester with good hue quality had a hue index b value of 5.2, a hue index L value of 88.4, and an intrinsic viscosity of 0.644 dL/g.
  • the method for preparing PET polyester on a continuous polymerization device is basically the same as in Example 2, except that the titanium element of the titanium series catalyst added in step (2) accounts for 6 ppm by weight relative to the total amount of PET, and the step ( 3) no titanium-based catalyst was added; Comparative Example 2 was equivalent to adding all the titanium-based catalysts in Example 2 before the esterification reaction.
  • the hue index b value of the finally prepared PET polyester is 6.5, and the intrinsic viscosity is 0.646dL/g.
  • Example 2 can significantly reduce the hue index b value of polyester relative to Comparative Example 2, because the method of adding catalyst in sections in Example 2 reduces the viscosity of the catalyst during the reaction.
  • the concentration in the system generally reduces the degree of side reactions, so that the hue index of the product can be significantly improved.
  • the continuous polymerization device is a four-pot continuous polymerization device, including an esterification kettle I, an esterification kettle II, a pre-condensation kettle and a final polycondensation kettle.
  • the specific steps are as follows:
  • Dibasic acid terephthalic acid
  • Diol ethylene glycol
  • Titanium-based catalyst STiC-01 titanium-silicon composite catalyst (Shanghai Petroleum Research Institute);
  • step (2) The product of step (2) is pre-condensed; the temperature of the pre-condensation reaction is 264 ° C, and the pressure is 800 Pa; a part of the PET polyester oligomer material a is extracted from the pre-condensation kettle, and the titanium series catalyst is mixed with the PET polyester low
  • the polymer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank and the final polycondensation tank, wherein, the PET polyester oligomer material a is all PET polyester low polymer obtained by pre-condensation 1/13 of the total mass of the polymer material b, the weight ratio of the titanium element of the titanium-based catalyst to the total amount of PET is 3ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
  • the final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 276° C., and the pressure is 80 Pa.
  • the finally prepared environmentally friendly PET polyester with good hue quality has a hue index b value of 3.9, a hue index L value of 87.1, and an intrinsic viscosity of 0.648 dL/g.
  • the continuous polymerization device is a four-pot continuous polymerization device, including an esterification kettle I, an esterification kettle II, a pre-condensation kettle and a final polycondensation kettle.
  • the specific steps are as follows:
  • Dibasic acid terephthalic acid
  • Diol ethylene glycol
  • Titanium catalyst titanium chloride hydrolysis complex (India DORF KETAL company ACtivate TM 436);
  • step (2) The product of step (2) is subjected to pre-condensation; the temperature of the pre-condensation reaction is 266°C, and the pressure is 700Pa; part of the PET polyester oligomer material a is extracted from the pre-condensation kettle, and the titanium series catalyst is mixed with the PET polyester low
  • the polymer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank and the final polycondensation tank, wherein, the PET polyester oligomer material a is all PET polyester low polymer obtained by pre-condensation 1/15 of the total mass of the polymer material b, the weight ratio of the titanium element of the titanium-based catalyst to the total amount of PET is 3ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
  • the final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 279 ° C, and the pressure is 60 Pa.
  • the finally obtained environmentally friendly PET polyester with good hue quality has a hue index b value of 2.8, a hue index L value of 86.9, and an intrinsic viscosity of 0.648 dL/g.
  • the continuous polymerization device is a five-pot continuous polymerization device, including esterification kettle I, esterification kettle II, precondensation kettle I, precondensation kettle II and final polycondensation kettle, the specific steps are as follows:
  • Dibasic acid terephthalic acid
  • Diol ethylene glycol
  • Titanium catalyst tetrabutyl titanate
  • step (2) The product of step (2) is pre-condensed; the temperature of the pre-condensation reaction is 262 ° C, and the pressure is 500 Pa; a part of the PET polyester oligomer material a is extracted from the pre-condensation kettle II, and the titanium-based catalyst and the PET polyester The oligomer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank II and the final polycondensation tank, wherein, the PET polyester oligomer material a is all the PET polymer obtained by pre-condensation 1/17 of the total mass of the ester oligomer material b, the weight ratio of the titanium element of the titanium series catalyst to the total amount of PET is 2ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
  • the final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 270°C, and the pressure is 20Pa.
  • the finally obtained environmentally friendly PET polyester with good hue quality has a hue index b value of 1.6, a hue index L value of 88, and an intrinsic viscosity of 0.647dL/g.
  • the continuous polymerization device is a five-pot continuous polymerization device, including esterification kettle I, esterification kettle II, precondensation kettle I, precondensation kettle II and final polycondensation kettle, the specific steps are as follows:
  • Dibasic acid terephthalic acid
  • Diol ethylene glycol
  • Titanium catalyst titanium ethylene glycol
  • the product of step (2) is pre-condensed; the temperature of the pre-condensation reaction is 260 ° C, and the pressure is 300 Pa; a part of the PET polyester oligomer material a is extracted from the pre-condensation kettle II, and the titanium-based catalyst and the PET polyester
  • the oligomer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank II and the final polycondensation tank, wherein, the PET polyester oligomer material a is all the PET polymer obtained by pre-condensation 1/20 of the total mass of the ester oligomer material b, the weight ratio of the titanium element of the titanium series catalyst to the total amount of PET is 2ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
  • the final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 280 ° C, and the pressure is 30 Pa.
  • the finally obtained environmentally friendly PET polyester with good hue quality has a hue index b value of 2.2, a hue index L value of 86.8, and an intrinsic viscosity of 0.650 dL/g.

Abstract

The present invention relates to a method for preparing environment-friendly PET polyester having good hue quality on a continuous polymerization device. Raw materials are composed of dibasic acid, dibasic alcohol, and a titanium catalyst. The titanium catalyst is added twice in the continuous polymerization device. The first adding opportunity is before a pre-polycondensation reaction, and the second adding opportunity is after the pre-polycondensation reaction and before a final polycondensation reaction. The weight ratio of a titanium element of the titanium catalyst added for the first time relative to the total amount of PET is 2-6 ppm, and the weight ratio of the titanium element of the titanium catalyst added for the second time relative to the total amount of the PET is 1-4 ppm. The environment-friendly PET polyester having good hue quality has a hue index b value of smaller than or equal to 6 and a hue index L value of greater than or equal to 86. The method does not affect the brightness and luster of a product while controlling the yellowing of the product, and the appearance quality of the product completely reaches the level when an antimony catalyst is used.

Description

在连续聚合装置上制备色相品质良好的环保PET聚酯的方法Method for preparing environmentally friendly PET polyester with good color phase quality on continuous polymerization device 技术领域technical field
本发明属于高分子材料合成技术领域，涉及在连续聚合装置上制备色相品质良好的环保PET聚酯的方法。The invention belongs to the technical field of polymer material synthesis, and relates to a method for preparing environmentally friendly PET polyester with good hue and phase quality on a continuous polymerization device.
背景技术Background technique
使用钛系催化剂替代锑系催化剂生产PET可以获得不含重金属锑的环保聚酯材料。现有技术中钛系催化剂一般是在预缩聚前而且大部分都是在酯化前或酯化过程中加入的，然而钛系催化剂具有催化活性高的特点，在催化PET聚合主反应的同时也会使副反应的强度相应增加，研究表明催化剂浓度越高副反应越强烈，导致合成的PET的色相指标b值相对锑系催化剂合成的PET高，外观表现是发黄色，影响产品的质量。文献1(北京化工学院学报，1980-1：109-115)研究了钛系催化剂对聚酯聚合反应的影响，该文献表明钛系催化剂对聚酯主、副反应都具有很高的催化活性，会导致产品色相发黄。Using titanium-based catalysts instead of antimony-based catalysts to produce PET can obtain environmentally friendly polyester materials that do not contain heavy metal antimony. In the prior art, titanium-based catalysts are generally added before precondensation and most of them are added before or during esterification. However, titanium-based catalysts have the characteristics of high catalytic activity, and they can also catalyze the main reaction of PET polymerization. The intensity of the side reaction will increase accordingly. Studies have shown that the higher the catalyst concentration, the stronger the side reaction, resulting in a higher hue index b value of the synthetic PET than that of the PET synthesized by the antimony catalyst, and the appearance is yellowish, which affects the quality of the product. Document 1 (Journal of Beijing Institute of Chemical Technology, 1980-1: 109-115) has studied the impact of titanium series catalysts on polyester polymerization. This document shows that titanium series catalysts have high catalytic activity for polyester main and side reactions. May cause the product to appear yellowish in color.
传统应对方法是在使用钛系催化剂的同时添加含磷的化合物作为稳定剂来降低钛系催化剂的活性从而使副反应程度降低并获得较好的色相，但是含磷的化合物稳定剂的使用会使PET产物的色相指标L值下降，表现为白度降低。例如，文献2(合成技术及应用，2007 Vol22-4：32-37)提到磷系稳定剂在反应过程中容易产生沉淀及凝絮，从而一定程度上影响L值指标。文献3(CN110606946A)公开的一种绿色钛系催化剂，通过同时加入200～400ppm含磷稳定剂制备出b值在2～6之间的聚酯，但L值相应在85以下。文献4(CN106832241A)公开了一种用钛酸四丁酯与苯基膦酸等复配的催化剂，b值可以控制在6以下，但L值只有30～40。The traditional solution is to add a phosphorus-containing compound as a stabilizer while using a titanium-based catalyst to reduce the activity of the titanium-based catalyst, thereby reducing the degree of side reactions and obtaining a better hue, but the use of a phosphorus-containing compound stabilizer will make The hue index L value of the PET product decreases, which is manifested as a decrease in whiteness. For example, Document 2 (Synthesis Technology and Application, 2007 Vol22-4: 32-37) mentioned that phosphorus-based stabilizers are prone to precipitation and flocculation during the reaction process, which affects the L value index to a certain extent. Document 3 (CN110606946A) discloses a green titanium-based catalyst. By adding 200-400 ppm phosphorus-containing stabilizer at the same time, a polyester with a b value between 2 and 6 is prepared, but the L value is correspondingly below 85. Document 4 (CN106832241A) discloses a catalyst compounded with tetrabutyl titanate and phenylphosphonic acid. The b value can be controlled below 6, but the L value is only 30-40.
发明内容Contents of the invention
为解决现有技术中存在的问题，本发明提供一种在连续聚合装置上制备色相品质良好的环保PET聚酯的方法。In order to solve the problems in the prior art, the present invention provides a method for preparing environmentally friendly PET polyester with good hue and phase quality on a continuous polymerization device.
为达到上述目的，本发明采用的技术方案如下：In order to achieve the above object, the technical scheme adopted in the present invention is as follows:
在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，原料由二元酸、二元醇和钛系催化剂组成，不包括稳定剂和调色剂；A method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device. The raw materials are composed of dibasic acid, dibasic alcohol and titanium series catalyst, excluding stabilizers and toners;
钛系催化剂在连续聚合装置中分2次加入；第1次加入的时机为预缩聚反应之前，第2次加入的时机为预缩聚反应之后、终缩聚反应之前；The titanium-based catalyst is added in two times in the continuous polymerization device; the timing of the first addition is before the pre-condensation reaction, and the timing of the second addition is after the pre-condensation reaction and before the final polycondensation reaction;
第1次加入的钛系催化剂的钛元素相对于PET总量的重量占比为2～6ppm，第2次加入的钛 系催化剂的钛元素相对于PET总量的重量占比为1～4ppm；在预缩聚阶段，由于反应体系粘度较低，少量的钛系催化剂就能够保证反应的顺利进行，在进入终缩聚阶段由于反应体系粘度较高，再补充一定量的钛系催化剂以维持聚合反应以正常速度进行；催化剂添加量的设定原则是保证缩聚反应可以正常进行的情况下添加尽可能少的量，不同钛系催化剂品种有不同的添加量范围，在预聚阶段如果低于设定下限将无法保证预聚合反应顺利进行，超过最大设定值范围则视同一次添加工艺，失去二次添加的意义；在终缩聚阶段如果低于设定下限将同样失去二次添加的意义而且可能导致终缩聚反应无法顺利进行，超过最大设定值范围会使产品色相变差。The weight ratio of the titanium element of the titanium-based catalyst added for the first time relative to the total amount of PET is 2-6ppm, and the weight ratio of the titanium element of the titanium-based catalyst added for the second time relative to the total amount of PET is 1-4ppm; In the pre-polycondensation stage, due to the low viscosity of the reaction system, a small amount of titanium-based catalyst can ensure the smooth progress of the reaction. In the final polycondensation stage, due to the high viscosity of the reaction system, a certain amount of titanium-based catalyst is added to maintain the polymerization reaction. Normal speed; the principle of setting the catalyst addition amount is to add as little amount as possible under the condition that the polycondensation reaction can be carried out normally. Different titanium series catalysts have different addition amount ranges. It will not be able to guarantee the smooth progress of the pre-polymerization reaction. If it exceeds the maximum set value range, it will be regarded as a one-time addition process and lose the meaning of the second addition; if it is lower than the set lower limit in the final polycondensation stage, it will also lose the meaning of the second addition and may cause The final polycondensation reaction cannot be carried out smoothly, and the hue of the product will deteriorate if it exceeds the maximum set value range.
色相品质良好的环保PET聚酯的色相指标b值小于等于6，达到了《聚对苯二甲酸乙二醇酯切片国家标准》，色相指标L值大于等于86，色相指标L值大于等于86即达标，这是行业共识。Environmentally friendly PET polyester with good hue quality has a hue index b value less than or equal to 6, which meets the "National Standard for Polyethylene Terephthalate Chips". The hue index L value is greater than or equal to 86, and the hue index L value is greater than or equal to 86. This is the industry consensus.
作为优选的技术方案：As a preferred technical solution:
如上所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，钛系催化剂第1次加入的时机为酯化反应之前，或者为酯化反应过程中，或者为酯化反应之后、预缩聚反应之前。As mentioned above, the method for preparing environmentally friendly PET polyester with good color phase quality on a continuous polymerization device, the timing of adding the titanium catalyst for the first time is before the esterification reaction, or during the esterification reaction, or after the esterification reaction , Before the precondensation reaction.
如上所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，钛系催化剂第2次加入在将预缩聚得到的PET聚酯输送至终缩聚釜的物流管道，在物流管道中加入设备成本最低、操作最容易控制。As mentioned above, the method for preparing environmentally friendly PET polyester with good hue and quality on the continuous polymerization device, the titanium-based catalyst is added for the second time in the logistics pipeline that transports the PET polyester obtained by pre-condensation to the final polycondensation tank, and in the logistics pipeline The cost of joining equipment is the lowest, and the operation is the easiest to control.
如上所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，将钛系催化剂加入到物流管道中之前，从终缩聚釜前面的釜中抽取出来部分预缩聚得到的PET聚酯低聚物物料a，将待加入的钛系催化剂与PET聚酯低聚物物料a混合，混合的温度与所述物流管道的温度相同，所述物流管道的温度取决于预缩聚得到的PET聚酯的温度；因为钛系催化剂加入量非常少，不用反应物料混合无法精确计量同时也没有这么小的添加装置，而且用反应物料进行预混合后再加入系统中有利于提高催化剂在体系中的分散效果，因此先将待加入的钛系催化剂与PET聚酯低聚物物料a混合再加入到体系中。As mentioned above, the method for preparing environmentally friendly PET polyester with good color phase quality on the continuous polymerization device, before adding the titanium-based catalyst to the logistics pipeline, extract the PET polyester obtained by partial pre-condensation from the kettle in front of the final polycondensation tank Oligomer material a, mix the titanium series catalyst to be added with the PET polyester oligomer material a, the mixing temperature is the same as the temperature of the logistics pipeline, and the temperature of the logistics pipeline depends on the PET polymer obtained by precondensation. The temperature of the ester; because the addition amount of the titanium-based catalyst is very small, it cannot be accurately measured without mixing the reaction materials, and there is no such a small addition device, and it is beneficial to improve the dispersion of the catalyst in the system after pre-mixing with the reaction materials before adding it to the system effect, so first mix the titanium-based catalyst to be added with the PET polyester oligomer material a and then add it to the system.
如上所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，混合在全混搅拌釜或动态混合器内进行，本发明相当于在连续聚合装置外增加全混搅拌釜或动态混合器，全混搅拌釜或动态混合器与连续聚合装置中将预缩聚得到的PET聚酯输送至终缩聚釜的物流管道连接。As mentioned above, the method for preparing environmentally friendly PET polyester with good hue quality on the continuous polymerization device is mixed in a fully mixed stirring tank or a dynamic mixer. The present invention is equivalent to adding a fully mixed stirring tank or a dynamic mixer outside the continuous polymerization device. The mixer, the fully mixed stirring tank or the dynamic mixer is connected with the logistics pipeline that transports the PET polyester obtained by precondensation to the final polycondensation tank in the continuous polymerization device.
如上所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，部分预缩 聚得到的PET聚酯低聚物物料a的质量为预缩聚得到的全部PET聚酯低聚物物料b总质量的1/10～1/20，比例设置在此范围既可以避免分散较差，又可以避免增加添加装置的负荷。As mentioned above, the method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device, the quality of the PET polyester oligomer material a obtained by partial precondensation is the whole PET polyester oligomer material b obtained by precondensation 1/10 to 1/20 of the total mass, setting the ratio in this range can avoid poor dispersion and avoid increasing the load on the adding device.
如上所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，钛系催化剂为钛酸酯类、乙二醇钛、钛硅复合催化剂或氯化钛水解络合物。As mentioned above, the method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device, the titanium-based catalyst is titanate, titanium ethylene glycol, titanium-silicon composite catalyst or titanium chloride hydrolysis complex.
如上所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，连续聚合装置为三釜连续聚合装置、四釜连续聚合装置或五釜连续聚合装置。The above-mentioned method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device, the continuous polymerization device is a three-pot continuous polymerization device, a four-pot continuous polymerization device or a five-pot continuous polymerization device.
如上所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，二元酸为对苯二甲酸，二元醇为乙二醇；酯化反应的温度为220～250℃，压力为0.15～0.35MPa，时间为1～5h；预缩聚反应的温度为260～270℃，压力为300～1000Pa，时间为0.5～2h；终缩聚反应的温度为270～285℃，压力为20～100Pa，时间为0.5～3h。As mentioned above, the method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device, the dibasic acid is terephthalic acid, and the dibasic alcohol is ethylene glycol; the temperature of the esterification reaction is 220-250 ° C, the pressure 0.15-0.35MPa, the time is 1-5h; the temperature of the pre-condensation reaction is 260-270℃, the pressure is 300-1000Pa, the time is 0.5-2h; the temperature of the final polycondensation reaction is 270-285℃, the pressure is 20- 100Pa, the time is 0.5~3h.
本发明的原理如下：Principle of the present invention is as follows:
本发明采用2次加入钛系催化剂的方法，不需要添加稳定剂，通过控制PET在不同聚合阶段的催化剂含量，在保证聚合反应进行的同时控制副反应的进行。在预缩聚阶段，由于反应体系粘度较低，少量的钛系催化剂就能够保证反应的顺利进行，在进入终缩聚阶段由于反应体系粘度较高，再补充一定量的钛系催化剂以维持聚合反应以正常速度进行。与传统的在缩聚反应之前全部加入催化剂的工艺相比，本发明中分段加入催化剂的方法，减少了催化剂粘度在反应体系中的浓度，总体降低了副反应程度，产品的色相指标得到明显改善。The invention adopts the method of adding titanium series catalyst twice without adding stabilizer, and by controlling the catalyst content of PET in different polymerization stages, the progress of side reactions is controlled while ensuring the progress of the polymerization reaction. In the pre-polycondensation stage, due to the low viscosity of the reaction system, a small amount of titanium-based catalyst can ensure the smooth progress of the reaction. In the final polycondensation stage, due to the high viscosity of the reaction system, a certain amount of titanium-based catalyst is added to maintain the polymerization reaction. proceed at normal speed. Compared with the traditional process of adding all catalysts before the polycondensation reaction, the method of adding catalysts in stages in the present invention reduces the concentration of catalyst viscosity in the reaction system, reduces the degree of side reactions as a whole, and the hue index of the product is significantly improved .
有益效果Beneficial effect
本发明的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，通过利用预缩聚阶段、终缩聚阶段反应体系较大的粘度差及反应动力学机理的差异，采用差异化催化的对应措施，总体的低催化剂浓度工艺使反应过程相对于传统工艺更稳定、更温和、更可控；在控制产品发黄的同时不影响产品的亮度和光泽，产品外观质量完全达到使用锑系催化剂时的水平。The method for preparing environmentally friendly PET polyester with good hue quality in the continuous polymerization device of the present invention adopts the corresponding method of differential catalysis by utilizing the relatively large viscosity difference and the difference in reaction kinetic mechanism between the pre-condensation stage and the final polycondensation stage. Measures, the overall low catalyst concentration process makes the reaction process more stable, milder, and more controllable than the traditional process; while controlling the yellowing of the product, it does not affect the brightness and luster of the product, and the appearance quality of the product is completely comparable to that when using antimony-based catalysts s level.
具体实施方式Detailed ways
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
本发明从原理上适用于所有钛系催化剂，由于钛系催化剂理论上有无数种，不可能一一列举，实施例中的所使用的钛系催化剂，只是举例。The present invention is applicable to all titanium-based catalysts in principle. Since there are countless kinds of titanium-based catalysts in theory, it is impossible to list them one by one. The titanium-based catalysts used in the examples are just examples.
实施例1Example 1
在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，连续聚合装置为三釜连续聚合装置，包括酯化釜、预缩聚釜和终缩聚釜，具体步骤如下：A method for preparing environmentally friendly PET polyester with good hue and quality in a continuous polymerization device. The continuous polymerization device is a three-pot continuous polymerization device, including an esterification tank, a pre-condensation tank and a final polycondensation tank. The specific steps are as follows:
(1)原料的准备：(1) Preparation of raw materials:
二元酸：对苯二甲酸；Dibasic acid: terephthalic acid;
二元醇：乙二醇；Diol: ethylene glycol;
钛系催化剂：钛酸四丁酯；Titanium catalyst: tetrabutyl titanate;
(2)酯化；(2) Esterification;
将二元酸和二元醇以1:2的摩尔比混合后进行酯化反应；酯化反应的温度为250℃，压力为0.35MPa；其中，酯化反应之前，向酯化釜中添加钛系催化剂，加入的钛系催化剂的钛元素相对于PET总量的重量占比为5ppm；The dibasic acid and the dibasic alcohol are mixed at a molar ratio of 1:2 to carry out the esterification reaction; the temperature of the esterification reaction is 250°C, and the pressure is 0.35MPa; wherein, before the esterification reaction, titanium is added to the esterification kettle series catalyst, the weight ratio of the titanium element of the added titanium series catalyst relative to the PET total amount is 5ppm;
(3)预缩聚；(3) Precondensation;
将步骤(2)的产物进行预缩聚；预缩聚反应的温度为270℃，压力为1000Pa；从预缩聚釜中抽取出部分PET聚酯低聚物物料a，将钛系催化剂与PET聚酯低聚物物料a在全混搅拌釜内混合，将混合物加入到预缩聚釜与终缩聚釜之间的物流管道中，其中，PET聚酯低聚物物料a为预缩聚得到的全部PET聚酯低聚物物料b总质量的1/10，钛系催化剂的钛元素相对于PET总量的重量占比为1ppm，混合的温度与物流管道的温度相同；The product of step (2) is pre-condensed; the temperature of the pre-condensation reaction is 270 ° C, and the pressure is 1000 Pa; a part of the PET polyester oligomer material a is extracted from the pre-condensation kettle, and the titanium series catalyst is mixed with the PET polyester low The polymer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank and the final polycondensation tank, wherein, the PET polyester oligomer material a is all PET polyester low polymer obtained by pre-condensation 1/10 of the total mass of the polymer material b, the weight ratio of the titanium element of the titanium-based catalyst to the total amount of PET is 1ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
(4)终缩聚；(4) final polycondensation;
进行终缩聚，制得色相品质良好的环保PET聚酯；终缩聚反应的温度为285℃，压力为100Pa。The final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 285 ° C, and the pressure is 100 Pa.
最终制得的色相品质良好的环保PET聚酯的色相指标b值为4.6，色相指标L值为88.2，特性粘度为0.648dL/g。The finally obtained environmentally friendly PET polyester with good hue quality has a hue index b value of 4.6, a hue index L value of 88.2, and an intrinsic viscosity of 0.648 dL/g.
对比例1Comparative example 1
在连续聚合装置上制备PET聚酯的方法，基本同实施例1，不同之处仅在于步骤(2)中加入的钛系催化剂的钛元素相对于PET总量的重量占比为6ppm，步骤(3)中不加入钛系催化剂；对比例1相当于将实施例1中所有的钛系催化剂都调整到酯化反应之前添加。The method for preparing PET polyester on a continuous polymerization device is basically the same as in Example 1, except that the titanium element of the titanium series catalyst added in the step (2) accounts for 6 ppm by weight relative to the total amount of PET, and the step ( 3) no titanium-based catalyst was added; Comparative Example 1 was equivalent to adding all the titanium-based catalysts in Example 1 before the esterification reaction.
最终制得的PET聚酯的色相指标b值为6.2，特性粘度为0.645dL/g。The hue index b value of the finally prepared PET polyester is 6.2, and the intrinsic viscosity is 0.645dL/g.
将实施例1与对比例1对比可以看出，实施例1相对于对比例1能够明显降低聚酯的色相指标b值，这是因为实施例1分段加入催化剂的方法减少了催化剂粘度在反应体系中的浓度，总体降低了副反应程度，使得产品的色相指标能够得到明显改善。Comparing Example 1 with Comparative Example 1, it can be seen that Example 1 can significantly reduce the hue index b value of polyester relative to Comparative Example 1, because the method of adding catalyst in sections in Example 1 reduces the viscosity of the catalyst during the reaction. The concentration in the system generally reduces the degree of side reactions, so that the hue index of the product can be significantly improved.
实施例2Example 2
在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，连续聚合装置为三釜连续聚合装置，包括酯化釜、预缩聚釜和终缩聚釜，具体步骤如下：A method for preparing environmentally friendly PET polyester with good hue and quality in a continuous polymerization device. The continuous polymerization device is a three-pot continuous polymerization device, including an esterification tank, a pre-condensation tank and a final polycondensation tank. The specific steps are as follows:
(1)原料的准备：(1) Preparation of raw materials:
二元酸：对苯二甲酸；Dibasic acid: terephthalic acid;
二元醇：乙二醇；Diol: ethylene glycol;
钛系催化剂：乙二醇钛；Titanium catalyst: titanium ethylene glycol;
(2)酯化；(2) Esterification;
将二元酸和二元醇以1:1.8的摩尔比混合后进行酯化反应；酯化反应的温度为245℃，压力为0.3MPa；其中，酯化反应之前，向酯化釜中添加钛系催化剂，加入的钛系催化剂的钛元素相对于PET总量的重量占比为4ppm；Mix the dibasic acid and the dibasic alcohol with a molar ratio of 1:1.8 and then carry out the esterification reaction; the temperature of the esterification reaction is 245°C, and the pressure is 0.3MPa; among them, before the esterification reaction, titanium is added to the esterification kettle series catalyst, the weight ratio of the titanium element of the added titanium series catalyst relative to the PET total amount is 4ppm;
(3)预缩聚；(3) Precondensation;
将步骤(2)的产物进行预缩聚；预缩聚反应的温度为268℃，压力为900Pa；从预缩聚釜中抽取出部分PET聚酯低聚物物料a，将钛系催化剂与PET聚酯低聚物物料a在全混搅拌釜内混合，将混合物加入到预缩聚釜与终缩聚釜之间的物流管道中，其中，PET聚酯低聚物物料a为预缩聚得到的全部PET聚酯低聚物物料b总质量的1/11，钛系催化剂的钛元素相对于PET总量的重量占比为2ppm，混合的温度与物流管道的温度相同；The product of step (2) is subjected to pre-condensation; the temperature of the pre-condensation reaction is 268°C, and the pressure is 900Pa; part of the PET polyester oligomer material a is extracted from the pre-condensation kettle, and the titanium series catalyst is mixed with the PET polyester low The polymer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank and the final polycondensation tank, wherein, the PET polyester oligomer material a is all PET polyester low polymer obtained by pre-condensation 1/11 of the total mass of the polymer material b, the weight ratio of the titanium element of the titanium-based catalyst to the total amount of PET is 2ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
(4)终缩聚；(4) final polycondensation;
进行终缩聚，制得色相品质良好的环保PET聚酯；终缩聚反应的温度为282℃，压力为90Pa。The final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 282° C., and the pressure is 90 Pa.
最终制得的色相品质良好的环保PET聚酯的色相指标b值为5.2，色相指标L值为88.4，特性粘度为0.644dL/g。The finally obtained environmentally friendly PET polyester with good hue quality had a hue index b value of 5.2, a hue index L value of 88.4, and an intrinsic viscosity of 0.644 dL/g.
对比例2Comparative example 2
在连续聚合装置上制备PET聚酯的方法，基本同实施例2，不同之处仅在于步骤(2)中加入的钛系催化剂的钛元素相对于PET总量的重量占比为6ppm，步骤(3)中不加入钛系催化剂；对比例2相当于将实施例2中所有的钛系催化剂都调整到酯化反应之前添加。The method for preparing PET polyester on a continuous polymerization device is basically the same as in Example 2, except that the titanium element of the titanium series catalyst added in step (2) accounts for 6 ppm by weight relative to the total amount of PET, and the step ( 3) no titanium-based catalyst was added; Comparative Example 2 was equivalent to adding all the titanium-based catalysts in Example 2 before the esterification reaction.
最终制得的PET聚酯的色相指标b值为6.5，特性粘度为0.646dL/g。The hue index b value of the finally prepared PET polyester is 6.5, and the intrinsic viscosity is 0.646dL/g.
将实施例2与对比例2对比可以看出，实施例2相对于对比例2能够明显降低聚酯的色相指标b值，这是因为实施例2分段加入催化剂的方法减少了催化剂粘度在反应体系中的浓度，总体降低了副反应程度，使得产品的色相指标能够得到明显改善。Comparing Example 2 with Comparative Example 2, it can be seen that Example 2 can significantly reduce the hue index b value of polyester relative to Comparative Example 2, because the method of adding catalyst in sections in Example 2 reduces the viscosity of the catalyst during the reaction. The concentration in the system generally reduces the degree of side reactions, so that the hue index of the product can be significantly improved.
实施例3Example 3
在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，连续聚合装置为四釜连续聚合装置，包括酯化釜I、酯化釜II、预缩聚釜和终缩聚釜，具体步骤如下：A method for preparing environmentally friendly PET polyester with good hue and quality in a continuous polymerization device. The continuous polymerization device is a four-pot continuous polymerization device, including an esterification kettle I, an esterification kettle II, a pre-condensation kettle and a final polycondensation kettle. The specific steps are as follows:
(1)原料的准备：(1) Preparation of raw materials:
二元酸：对苯二甲酸；Dibasic acid: terephthalic acid;
二元醇：乙二醇；Diol: ethylene glycol;
钛系催化剂：STiC-01钛硅复合催化剂(上海石油科学研究院)；Titanium-based catalyst: STiC-01 titanium-silicon composite catalyst (Shanghai Petroleum Research Institute);
(2)酯化；(2) Esterification;
将二元酸和二元醇以1:1.6的摩尔比混合后进行酯化反应；酯化反应的温度为240℃，压力为0.25MPa；其中，酯化反应过程中，向酯化釜I中添加钛系催化剂，加入的钛系催化剂的钛元素相对于PET总量的重量占比为4ppm；Mix the dibasic acid and the dibasic alcohol with a molar ratio of 1:1.6 to carry out esterification reaction; the temperature of the esterification reaction is 240°C, and the pressure is 0.25MPa; Adding a titanium-based catalyst, the weight ratio of the titanium element of the added titanium-based catalyst relative to the total amount of PET is 4ppm;
(3)预缩聚；(3) Precondensation;
将步骤(2)的产物进行预缩聚；预缩聚反应的温度为264℃，压力为800Pa；从预缩聚釜中抽取出部分PET聚酯低聚物物料a，将钛系催化剂与PET聚酯低聚物物料a在全混搅拌釜内混合，将混合物加入到预缩聚釜与终缩聚釜之间的物流管道中，其中，PET聚酯低聚物物料a为预缩聚得到的全部PET聚酯低聚物物料b总质量的1/13，钛系催化剂的钛元素相对于PET总量的重量占比为3ppm，混合的温度与物流管道的温度相同；The product of step (2) is pre-condensed; the temperature of the pre-condensation reaction is 264 ° C, and the pressure is 800 Pa; a part of the PET polyester oligomer material a is extracted from the pre-condensation kettle, and the titanium series catalyst is mixed with the PET polyester low The polymer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank and the final polycondensation tank, wherein, the PET polyester oligomer material a is all PET polyester low polymer obtained by pre-condensation 1/13 of the total mass of the polymer material b, the weight ratio of the titanium element of the titanium-based catalyst to the total amount of PET is 3ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
(4)终缩聚；(4) final polycondensation;
进行终缩聚，制得色相品质良好的环保PET聚酯；终缩聚反应的温度为276℃，压力为80Pa。The final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 276° C., and the pressure is 80 Pa.
最终制得的色相品质良好的环保PET聚酯的色相指标b值为3.9，色相指标L值为87.1，特性粘度为0.648dL/g。The finally prepared environmentally friendly PET polyester with good hue quality has a hue index b value of 3.9, a hue index L value of 87.1, and an intrinsic viscosity of 0.648 dL/g.
实施例4Example 4
在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，连续聚合装置为四釜连续聚合装置，包括酯化釜I、酯化釜II、预缩聚釜和终缩聚釜，具体步骤如下：A method for preparing environmentally friendly PET polyester with good hue and quality in a continuous polymerization device. The continuous polymerization device is a four-pot continuous polymerization device, including an esterification kettle I, an esterification kettle II, a pre-condensation kettle and a final polycondensation kettle. The specific steps are as follows:
(1)原料的准备：(1) Preparation of raw materials:
二元酸：对苯二甲酸；Dibasic acid: terephthalic acid;
二元醇：乙二醇；Diol: ethylene glycol;
钛系催化剂：氯化钛水解络合物(印度DORF KETAL公司
Figure PCTCN2022100292-appb-000001
ACtivate TM 436)； Titanium catalyst: titanium chloride hydrolysis complex (India DORF KETAL company
Figure PCTCN2022100292-appb-000001
ACtivate ™ 436);
(2)酯化；(2) Esterification;
将二元酸和二元醇以1:1.4的摩尔比混合后进行酯化反应；酯化反应的温度为235℃，压力 为0.15MPa；其中，酯化反应过程中，向酯化釜I中添加钛系催化剂，加入的钛系催化剂的钛元素相对于PET总量的重量占比为3ppm；Mix the dibasic acid and the dibasic alcohol with a molar ratio of 1:1.4 to carry out the esterification reaction; the temperature of the esterification reaction is 235° C., and the pressure is 0.15 MPa; Adding a titanium series catalyst, the weight ratio of the titanium element of the added titanium series catalyst relative to the total amount of PET is 3ppm;
(3)预缩聚；(3) Precondensation;
将步骤(2)的产物进行预缩聚；预缩聚反应的温度为266℃，压力为700Pa；从预缩聚釜中抽取出部分PET聚酯低聚物物料a，将钛系催化剂与PET聚酯低聚物物料a在全混搅拌釜内混合，将混合物加入到预缩聚釜与终缩聚釜之间的物流管道中，其中，PET聚酯低聚物物料a为预缩聚得到的全部PET聚酯低聚物物料b总质量的1/15，钛系催化剂的钛元素相对于PET总量的重量占比为3ppm，混合的温度与物流管道的温度相同；The product of step (2) is subjected to pre-condensation; the temperature of the pre-condensation reaction is 266°C, and the pressure is 700Pa; part of the PET polyester oligomer material a is extracted from the pre-condensation kettle, and the titanium series catalyst is mixed with the PET polyester low The polymer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank and the final polycondensation tank, wherein, the PET polyester oligomer material a is all PET polyester low polymer obtained by pre-condensation 1/15 of the total mass of the polymer material b, the weight ratio of the titanium element of the titanium-based catalyst to the total amount of PET is 3ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
(4)终缩聚；(4) final polycondensation;
进行终缩聚，制得色相品质良好的环保PET聚酯；终缩聚反应的温度为279℃，压力为60Pa。The final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 279 ° C, and the pressure is 60 Pa.
最终制得的色相品质良好的环保PET聚酯的色相指标b值为2.8，色相指标L值为86.9，特性粘度为0.648dL/g。The finally obtained environmentally friendly PET polyester with good hue quality has a hue index b value of 2.8, a hue index L value of 86.9, and an intrinsic viscosity of 0.648 dL/g.
实施例5Example 5
在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，连续聚合装置为五釜连续聚合装置，包括酯化釜I、酯化釜II、预缩聚釜I、预缩聚釜II和终缩聚釜，具体步骤如下：A method for preparing environmentally friendly PET polyester with good hue and quality on a continuous polymerization device. The continuous polymerization device is a five-pot continuous polymerization device, including esterification kettle I, esterification kettle II, precondensation kettle I, precondensation kettle II and final polycondensation kettle, the specific steps are as follows:
(1)原料的准备：(1) Preparation of raw materials:
二元酸：对苯二甲酸；Dibasic acid: terephthalic acid;
二元醇：乙二醇；Diol: ethylene glycol;
钛系催化剂：钛酸四丁酯；Titanium catalyst: tetrabutyl titanate;
(2)酯化；(2) Esterification;
将二元酸和二元醇以1:1.2的摩尔比混合后进行酯化反应；酯化反应的温度为235℃，压力为0.2MPa；其中，酯化反应之后，向酯化釜II中添加钛系催化剂，加入的钛系催化剂的钛元素相对于PET总量的重量占比为3ppm；Mix the dibasic acid and the dibasic alcohol in a molar ratio of 1:1.2 to carry out the esterification reaction; the temperature of the esterification reaction is 235°C, and the pressure is 0.2MPa; wherein, after the esterification reaction, add Titanium series catalyst, the weight proportion of the titanium element of the added titanium series catalyst relative to the PET total amount is 3ppm;
(3)预缩聚；(3) Precondensation;
将步骤(2)的产物进行预缩聚；预缩聚反应的温度为262℃，压力为500Pa；从预缩聚釜II中抽取出部分PET聚酯低聚物物料a，将钛系催化剂与PET聚酯低聚物物料a在全混搅拌釜内混合，将混合物加入到预缩聚釜II与终缩聚釜之间的物流管道中，其中，PET聚酯低聚物物料a为预缩聚得到的全部PET聚酯低聚物物料b总质量的1/17，钛系催化剂的钛元素相对于PET总量的重量占比为2ppm，混合的温度与物流管道的温度相同；The product of step (2) is pre-condensed; the temperature of the pre-condensation reaction is 262 ° C, and the pressure is 500 Pa; a part of the PET polyester oligomer material a is extracted from the pre-condensation kettle II, and the titanium-based catalyst and the PET polyester The oligomer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank II and the final polycondensation tank, wherein, the PET polyester oligomer material a is all the PET polymer obtained by pre-condensation 1/17 of the total mass of the ester oligomer material b, the weight ratio of the titanium element of the titanium series catalyst to the total amount of PET is 2ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
(4)终缩聚；(4) final polycondensation;
进行终缩聚，制得色相品质良好的环保PET聚酯；终缩聚反应的温度为270℃，压力为20Pa。The final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 270°C, and the pressure is 20Pa.
最终制得的色相品质良好的环保PET聚酯的色相指标b值为1.6，色相指标L值为88，特性粘度为0.647dL/g。The finally obtained environmentally friendly PET polyester with good hue quality has a hue index b value of 1.6, a hue index L value of 88, and an intrinsic viscosity of 0.647dL/g.
实施例6Example 6
在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，连续聚合装置为五釜连续聚合装置，包括酯化釜I、酯化釜II、预缩聚釜I、预缩聚釜II和终缩聚釜，具体步骤如下：A method for preparing environmentally friendly PET polyester with good hue and quality on a continuous polymerization device. The continuous polymerization device is a five-pot continuous polymerization device, including esterification kettle I, esterification kettle II, precondensation kettle I, precondensation kettle II and final polycondensation kettle, the specific steps are as follows:
(1)原料的准备：(1) Preparation of raw materials:
二元酸：对苯二甲酸；Dibasic acid: terephthalic acid;
二元醇：乙二醇；Diol: ethylene glycol;
钛系催化剂：乙二醇钛；Titanium catalyst: titanium ethylene glycol;
(2)酯化；(2) Esterification;
将二元酸和二元醇以1:1.1的摩尔比混合后进行酯化反应；酯化反应的温度为230℃，压力为0.27MPa；其中，酯化反应之后，向酯化釜II中添加钛系催化剂，加入的钛系催化剂的钛元素相对于PET总量的重量占比为2ppm；Mix the dibasic acid and the dibasic alcohol in a molar ratio of 1:1.1 to carry out the esterification reaction; the temperature of the esterification reaction is 230°C, and the pressure is 0.27MPa; wherein, after the esterification reaction, add Titanium series catalyst, the weight proportion of the titanium element of the added titanium series catalyst relative to the PET total amount is 2ppm;
(3)预缩聚；(3) Precondensation;
将步骤(2)的产物进行预缩聚；预缩聚反应的温度为260℃，压力为300Pa；从预缩聚釜II中抽取出部分PET聚酯低聚物物料a，将钛系催化剂与PET聚酯低聚物物料a在全混搅拌釜内混合，将混合物加入到预缩聚釜II与终缩聚釜之间的物流管道中，其中，PET聚酯低聚物物料a为预缩聚得到的全部PET聚酯低聚物物料b总质量的1/20，钛系催化剂的钛元素相对于PET总量的重量占比为2ppm，混合的温度与物流管道的温度相同；The product of step (2) is pre-condensed; the temperature of the pre-condensation reaction is 260 ° C, and the pressure is 300 Pa; a part of the PET polyester oligomer material a is extracted from the pre-condensation kettle II, and the titanium-based catalyst and the PET polyester The oligomer material a is mixed in the fully mixed stirring tank, and the mixture is added to the logistics pipeline between the pre-condensation tank II and the final polycondensation tank, wherein, the PET polyester oligomer material a is all the PET polymer obtained by pre-condensation 1/20 of the total mass of the ester oligomer material b, the weight ratio of the titanium element of the titanium series catalyst to the total amount of PET is 2ppm, and the mixing temperature is the same as the temperature of the logistics pipeline;
(4)终缩聚；(4) final polycondensation;
进行终缩聚，制得色相品质良好的环保PET聚酯；终缩聚反应的温度为280℃，压力为30Pa。The final polycondensation is carried out to obtain environmentally friendly PET polyester with good color quality; the temperature of the final polycondensation reaction is 280 ° C, and the pressure is 30 Pa.
最终制得的色相品质良好的环保PET聚酯的色相指标b值为2.2，色相指标L值为86.8，特性粘度为0.650dL/g。The finally obtained environmentally friendly PET polyester with good hue quality has a hue index b value of 2.2, a hue index L value of 86.8, and an intrinsic viscosity of 0.650 dL/g.

Claims (9)

  1. 在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，原料由二元酸、二元醇和钛系催化剂组成；The method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device is characterized in that the raw materials are composed of dibasic acid, dibasic alcohol and titanium series catalyst;
    钛系催化剂在连续聚合装置中分2次加入；第1次加入的时机为预缩聚反应之前，第2次加入的时机为预缩聚反应之后、终缩聚反应之前；The titanium-based catalyst is added in two times in the continuous polymerization device; the timing of the first addition is before the pre-condensation reaction, and the timing of the second addition is after the pre-condensation reaction and before the final polycondensation reaction;
    第1次加入的钛系催化剂的钛元素相对于PET总量的重量占比为2～6ppm，第2次加入的钛系催化剂的钛元素相对于PET总量的重量占比为1～4ppm；The weight ratio of the titanium element of the titanium-based catalyst added for the first time relative to the total amount of PET is 2-6ppm, and the weight ratio of the titanium element of the titanium-based catalyst added for the second time relative to the total amount of PET is 1-4ppm;
    色相品质良好的环保PET聚酯的色相指标b值小于等于6，色相指标L值大于等于86。Environmentally friendly PET polyester with good hue quality has a hue index b value less than or equal to 6, and a hue index L value greater than or equal to 86.
  2. 根据权利要求1所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，钛系催化剂第1次加入的时机为酯化反应之前，或者为酯化反应过程中，或者为酯化反应之后、预缩聚反应之前。The method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device according to claim 1, wherein the timing of adding the titanium-based catalyst for the first time is before the esterification reaction, or during the esterification reaction , or after the esterification reaction and before the precondensation reaction.
  3. 根据权利要求1所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，钛系催化剂第2次加入在将预缩聚得到的PET聚酯输送至终缩聚釜的物流管道中。According to the method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device according to claim 1, it is characterized in that the titanium-based catalyst is added for the second time when the PET polyester obtained by pre-condensation is transported to the final polycondensation tank. in the logistics pipeline.
  4. 根据权利要求3所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，将钛系催化剂加入到物流管道中之前，从终缩聚釜前面的釜中抽取出来部分预缩聚得到的PET聚酯低聚物物料a，将待加入的钛系催化剂与PET聚酯低聚物物料a混合，混合的温度与所述物流管道的温度相同。The method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device according to claim 3, characterized in that, before the titanium series catalyst is added to the logistics pipeline, the part is extracted from the kettle in front of the final polycondensation kettle For the PET polyester oligomer material a obtained by precondensation, the titanium-based catalyst to be added is mixed with the PET polyester oligomer material a, and the mixing temperature is the same as the temperature of the logistics pipeline.
  5. 根据权利要求4所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，混合在全混搅拌釜或动态混合器内进行。The method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device according to claim 4, wherein the mixing is carried out in a fully mixed stirring tank or a dynamic mixer.
  6. 根据权利要求4所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，部分预缩聚得到的PET聚酯低聚物物料a的质量为预缩聚得到的全部PET聚酯低聚物物料b总质量的1/10～1/20。The method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device according to claim 4, wherein the quality of the PET polyester oligomer material a obtained by partial precondensation is the whole PET obtained by precondensation 1/10-1/20 of the total mass of the polyester oligomer material b.
  7. 根据权利要求1所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，钛系催化剂为钛酸酯类、乙二醇钛、钛硅复合催化剂或氯化钛水解络合物。The method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device according to claim 1, wherein the titanium-based catalyst is titanate, titanium glycol, titanium-silicon composite catalyst or titanium chloride Hydrolysis complex.
  8. 根据权利要求1所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，连续聚合装置为三釜连续聚合装置、四釜连续聚合装置或五釜连续聚合装置。The method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device according to claim 1, wherein the continuous polymerization device is a three-pot continuous polymerization device, a four-pot continuous polymerization device or a five-pot continuous polymerization device.
  9. 根据权利要求1所述的在连续聚合装置上制备色相品质良好的环保PET聚酯的方法，其特征在于，二元酸为对苯二甲酸，二元醇为乙二醇；酯化反应的温度为220～250℃，压力为0.15～0.35MPa，时间为1～5h；预缩聚反应的温度为260～270℃，压力为300～1000Pa，时间为0.5～2h；终缩聚反应的温度为270～285℃，压力为20～100Pa，时间为0.5～3h。The method for preparing environmentally friendly PET polyester with good hue quality on a continuous polymerization device according to claim 1, wherein the dibasic acid is terephthalic acid, and the dibasic alcohol is ethylene glycol; the temperature of the esterification reaction The temperature is 220-250°C, the pressure is 0.15-0.35MPa, and the time is 1-5h; the temperature of the pre-condensation reaction is 260-270°C, the pressure is 300-1000Pa, and the time is 0.5-2h; the temperature of the final polycondensation reaction is 270- 285°C, the pressure is 20-100Pa, and the time is 0.5-3h.
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