WO2023066269A1 - 一种邻苯二甲酸酐和环氧丙烷混合投料方法、设备及应用 - Google Patents

一种邻苯二甲酸酐和环氧丙烷混合投料方法、设备及应用 Download PDF

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WO2023066269A1
WO2023066269A1 PCT/CN2022/126045 CN2022126045W WO2023066269A1 WO 2023066269 A1 WO2023066269 A1 WO 2023066269A1 CN 2022126045 W CN2022126045 W CN 2022126045W WO 2023066269 A1 WO2023066269 A1 WO 2023066269A1
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propylene oxide
feeding
phthalic anhydride
mixing
liquid
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PCT/CN2022/126045
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English (en)
French (fr)
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李洪国
闫怡
董良
傅海
魏怀建
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山东联欣环保科技有限公司
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Publication of WO2023066269A1 publication Critical patent/WO2023066269A1/zh

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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
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • the invention relates to the field of C08L69/00 classified by IPC, in particular to a method, equipment and application for mixing and feeding phthalic anhydride and propylene oxide.
  • Biodegradable plastic refers to a type of plastic that can be degraded into environmentally harmless substances under natural environmental conditions after use. It is considered to be one of the effective ways to solve the problem of plastic pollution, and has gradually been encouraged and supported by the state and everyone's attention.
  • PPC-P is a new type of degradable plastic obtained by chemically modifying PPC with phthalic anhydride (phthalic anhydride, referred to as phthalic anhydride or PA).
  • phthalic anhydride referred to as phthalic anhydride or PA.
  • Diformic anhydride improves the rigidity of the polymer chain, significantly improves the mechanical and thermal properties of PPC, and can greatly increase the added value of PPC plastics.
  • Cikon patent CN202010337273.0 discloses a method for synthesizing carbon dioxide-based polyester-polycarbonate terpolymer (PPC-P) with phthalic anhydride, propylene oxide and CO as raw materials.
  • PPC-P polyester-polycarbonate terpolymer
  • the disadvantage is that the feeding method of phthalic anhydride and propylene oxide mentioned in the patent is added separately in sequence.
  • phthalic anhydride If phthalic anhydride is added in solid form, it takes a long time to dissolve and absorbs a lot of heat, prolonging the The reaction time increases energy consumption; if phthalic anhydride is added in liquid form, since the melting point of phthalic anhydride is 133°C, it is very easy to cause the local temperature of the reactor to be too high when adding, which will cause an increase in by-products and reduce the yield. Reduced, and the partial pressure of the reactor will be high.
  • the existing conventional process is to add solid phthalic anhydride and propylene oxide independently in batches.
  • the technical problems with this approach are more obvious.
  • the feeding of solid phthalic anhydride requires a lot of manual operation, which is inefficient; factors such as residue in the packaging bag and dust loss can easily cause the feeding to be unable to be accurately measured; during the feeding process, there is a lot of solid dust, which is harmful to the occupational health of the operators.
  • solid dust which is harmful to the occupational health of the operators.
  • the melting point of phthalic anhydride is relatively high. After being added to the reactor, a large amount of heat is required to melt it, which consumes a lot of energy, and the energy efficiency is relatively poor due to frequent cooling and heating; solid materials have absorption Moisture phenomenon, and the reaction is more sensitive to moisture, which has a greater impact on the experimental results; in the process of adding solid materials, it is often not evenly distributed, which requires high stirring and affects the stability of subsequent reactions.
  • the first aspect of the present invention provides a method for mixing and feeding phthalic anhydride and propylene oxide, the steps at least include the following steps: (1) metering of phthalic anhydride and propylene oxide; (2) Mixing and feeding; (3) Mixing and stirring; (4) Adding auxiliary materials; (5) Ventilation polymerization; (6) Filtering and drying.
  • the feeding and metering of the phthalic anhydride and propylene oxide is: the mass metering of liquid propylene oxide and liquid phthalic anhydride raw materials.
  • the molar ratio of the liquid propylene oxide to the liquid phthalic anhydride is 0.5-10:1.
  • the molar ratio of the liquid propylene oxide to the liquid phthalic anhydride is 5-8:1.
  • the toughness and molecular weight uniformity of PPC-P are effectively improved by limiting the molar ratio of liquid propylene oxide and liquid phthalic anhydride.
  • the mixing and feeding is as follows: liquid propylene oxide and liquid phthalic anhydride are mixed and put into a preparation container for heating and stirring; anhydride.
  • the feed temperature of liquid propylene oxide is 0-40°C; the feed temperature of liquid phthalic anhydride is 120-160°C.
  • the feed temperature of liquid propylene oxide is 15-30°C; the feed temperature of liquid phthalic anhydride is 130-150°C.
  • the mixing and stirring is as follows: the liquid propylene oxide and liquid phthalic anhydride after feeding are set at a set temperature, the stirring speed is fixed, and the stirring time is fixed, so as to achieve a high degree of mixing of the two raw materials.
  • the stirring temperature of the preparation container is 30-120° C.; the stirring speed of the preparation container is 30-200 r/min; the preparation and mixing time is 20-60 min.
  • the stirring temperature of the preparation container is 50-90° C.; the stirring speed of the preparation container is 60-120 r/min; the preparation and mixing time is 40-50 min.
  • the propylene oxide and phthalic anhydride adopted in the application are fed separately with propylene oxide and phthalic anhydride in the prior art in the form of a liquid mixture, and phthalic anhydride directly Compared with the solid feeding method, it has the characteristics of more uniform material mixing and flexible feeding method, and the preferentially added propylene oxide can be effectively used as a benign dispersion medium of phthalic anhydride, so that propylene oxide and phthalic anhydride
  • the molecular doping of acid anhydride is more uniform; and the method of mixing liquid raw materials for feeding effectively avoids the feeding method of solid phthalic anhydride and propylene oxide, so it takes a certain time for phthalic anhydride to mix evenly in the reactor, prolonging the The problem of reaction
  • the auxiliary material is at least one of an inorganic base catalyst, a metal salt catalyst, an organic catalyst, and an ionic liquid catalyst.
  • the auxiliary material is zinc glutarate.
  • the ventilation polymerization is as follows: after the liquid propylene oxide and liquid phthalic anhydride are mixed and put into the reaction vessel, the reaction vessel is filled with carbon dioxide gas with a fixed pressure, reacted at high temperature for a period of time, and the reaction ends Then release carbon dioxide.
  • the weight ratio of the liquid propylene oxide to carbon dioxide is 3.8-4.2:0.6-0.8.
  • the weight ratio of the liquid propylene oxide to carbon dioxide is 3.8:0.692.
  • the reaction rate of polymerization is effectively increased, and the reaction stability is further improved.
  • the applicant speculates that: when the weight ratio of liquid propylene oxide to carbon dioxide is 3.8:0.692, while liquid propylene oxide can serve as a dispersion medium for mixing and feeding in the system, the degree of contact between the mixture and carbon dioxide can be fully improved.
  • the mixture is not limited to the surface layer of the mixture during the polymerization process, but can be effectively driven to the entire part of the column-type mixing system with a certain content of propylene oxide, thereby increasing the reaction rate. On the basis of maintaining good reaction stability, the product yield is obviously improved.
  • the mass ratio of carbon dioxide to auxiliary materials is 9-11:1.
  • the mass ratio of carbon dioxide to auxiliary materials is 9.6-9.8:1.
  • the fixed pressure is 2-3 MPa.
  • the fixed pressure is 2.1 MPa.
  • the aerated polymerization reaction time is 8-12 hours.
  • the aerated polymerization reaction time is 10 h.
  • the polymerization reaction temperature during the ventilation polymerization process is 50-90°C.
  • the polymerization reaction temperature during the ventilation polymerization process is 60-80°C.
  • the structure of the feeding equipment mainly includes a metering tank, a preparation tank 5 and a reaction tank 6 .
  • the metering tank includes a phthalic anhydride metering tank 4 and a propylene oxide metering tank 3; Or a heat medium or a refrigerant is passed into the coil 7 to control the temperature in the kettle; the preparation kettle 5 is equipped with a stirring paddle 5-1, which can make the temperature of the materials evenly mixed.
  • the phthalic anhydride metering tank 4 and the propylene oxide metering tank 3 are fixedly connected to the upper pipeline of the preparation kettle 5, and the pipeline is used for the transmission of liquid phthalic anhydride and propylene oxide.
  • the front end parts of the phthalic anhydride metering tank 4 and the propylene oxide metering tank 3 are respectively fixedly connected with a phthalic anhydride feed port 2 and a propylene oxide feed port 1, with With the import of raw materials.
  • the preparation kettle and the reaction kettle are fixedly connected through pipelines, and the pipelines are used for the transmission of liquid phthalic anhydride and propylene oxide mixture.
  • the second aspect of the present invention provides an application of the above method for mixing and feeding phthalic anhydride and propylene oxide, including the application of the method in the preparation process of synthetic biodegradable plastics.
  • the present invention intends to improve the raw material feeding process of a biodegradable carbon dioxide polyester-polycarbonate terpolymer disclosed in patent CN202010337273.0, further improve the conversion rate of raw materials and the yield of products, and reduce production costs.
  • the mixing and feeding process provided in this application can effectively realize the staged feeding, so as to effectively realize the composition control of the molecular chain of the product, realize the block design of the chain segment, and finally endow the polymer with various performance.
  • a mixed feeding process provided in this application can effectively realize the comprehensive utilization of energy consumption of thermal phthalic anhydride, make full use of the characteristics of high melting point of phthalic anhydride, add polymerization kettle at high temperature, can effectively Provide the reaction temperature for the polymerization process, thus effectively reducing the heat energy supply of the reaction process.
  • Fig. 1 is the structural representation of the mixing feeding equipment of the present application
  • Embodiment 1 The first aspect provides a kind of phthalic anhydride and propylene oxide mixed feeding method, and step comprises the following several steps: (1) the feeding metering of phthalic anhydride and propylene oxide; (2) mixed feeding (3) mixing and stirring; (4) adding auxiliary materials; (5) aerated polymerization; (6) filtering and drying.
  • the second aspect of this embodiment provides a mixing and feeding equipment as shown in FIG. 1 , the structure mainly includes a metering tank, a preparation tank and a reaction tank.
  • the metering tank includes a phthalic anhydride metering tank and a propylene oxide metering tank; the outer layer of the preparation kettle and the reaction kettle has a jacket, and heat medium and refrigerant are passed into the jacket to control the temperature inside the kettle; the preparation kettle has a stirring The paddle can make the material temperature mix evenly.
  • the phthalic anhydride metering tank and the propylene oxide metering tank are fixedly connected with the upper pipeline of the preparation kettle, and the pipelines are used for the transmission of liquid phthalic anhydride and propylene oxide.
  • the preparation kettle and the reaction kettle are fixedly connected through pipelines, and the pipelines are used for the transmission of liquid phthalic anhydride and propylene oxide mixture.
  • preparation work the preparation kettle and the reaction kettle are selected from a 1m3 high-pressure reaction kettle, and nitrogen is replaced three times; (1) use a metering tank to measure and weigh 380Kg liquid propylene oxide and 172Kg liquid phthalic anhydride; (2 ) put the above-mentioned raw materials into the preparation kettle in turn, control the feeding temperature of liquid propylene oxide to be 25°C, and control the feeding temperature of liquid phthalic anhydride to be 140°C; (3) control the temperature in the preparation kettle to 70°C, and the stirring speed is 90r/ min, after mixing and stirring for 30min, propylene oxide and phthalic anhydride were evenly mixed to obtain a mixed solution; (4) the mixed solution was passed into a reactor, and 7.2Kg zinc glutarate catalyst was added to the mixed solution; (5) the mixed solution was filled with Add 69.2KG of 2.1MPa carbon dioxide, and react at 80°C for 10h.
  • the propylene oxide was purchased from Shandong Sanyue Chemical Co., Ltd., an excellent grade of propylene oxide.
  • phthalic anhydride was purchased from Shandong Hongxin Chemical Co., Ltd., a superior product of phthalic anhydride.
  • the specific implementation of the present embodiment is the same as Example 1, and the difference is that the add-on of liquid propylene oxide is 392Kg, the add-on of solid phthalic anhydride is 161Kg, the add-on of catalyst is 6.9Kg, and the amount of carbon dioxide introduced is 72.6Kg; the measured mass of the final polymer is 494.6Kg, and the calculated polymer yield is 79.06%.
  • the specific implementation of the present embodiment is the same as that of Example 1, except that the addition of liquid propylene oxide is 408Kg, and the addition of solid phthalic anhydride is 166Kg, and the addition of propylene oxide and phthalic anhydride solid does not
  • the stirring and mixing step in the preparation kettle was carried out, directly placed in the reaction kettle, 7.5Kg of catalyst was added, and the amount of carbon dioxide introduced was 75.6Kg; the mass of the final polymer was measured to be 445.7Kg, and the calculated polymer yield was 68.61%.
  • the specific implementation of the present embodiment is the same as Example 1, and the difference is that: the add-on of liquid propylene oxide is 400Kg, the add-on of liquid phthalic anhydride is 165Kg, and the amount of carbon dioxide introduced is 68.6Kg; The mass of the product was 614.8Kg, and the calculated polymer yield was 97.03%.
  • Example 1 It can be known from Examples 1 to 4 that a kind of mixed feeding method of phthalic anhydride and propylene oxide provided by the present invention, as well as equipment and application, the technology in this application has good energy consumption control ability, and can realize Segmented feeding, so as to effectively control the length of the reactive molecular chain of the polymer and block design, is suitable for promotion in the field of plastic manufacturing and processing, and has broad development prospects.
  • Example 1 obtained the best product purity and yield under factors such as having the best preparation raw material proportioning and preparation technology.

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Abstract

本发明涉及一种邻苯二甲酸酐和环氧丙烷混合投料方法，设备及应用。本申请中的投料方法步骤至少包含以下几步：（1）邻苯二甲酸酐和环氧丙烷的投料计量；（2）混合投料；（3）混合搅拌；（4）加入辅料；（5）通气聚合；（6）过滤干燥。设备主要结构包括计量罐，配制釜和反应釜。本申请中的工艺具有良好的能耗控制能力，能够实现分段式加料，从而有效地控制聚合物的反应分子链的长度以及嵌段设计，适宜在塑料制造加工领域推广，具有广阔的发展前景。

Description

一种邻苯二甲酸酐和环氧丙烷混合投料方法、设备及应用
本申请要求于2021年10月19日提交中国专利局、申请号为CN202111213851.0、发明名称为“一种邻苯二甲酸酐和环氧丙烷混合投料工艺，设备及应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及IPC分类的C08L69/00领域，尤其涉及一种邻苯二甲酸酐和环氧丙烷混合投料方法、设备及应用。
背景技术
随着塑料制品的大量使用，塑料“白色污染”问题受到人们的广泛关注。生物可降解塑料是指使用后可在自然环境条件下降解成对环境无害物质的一类塑料，被认为是解决塑料污染问题的有效途径之一，逐渐受到国家的鼓励支持以及大家的瞩目。
PPC-P作为一种新型生物可降解塑料，是用邻苯二甲酸酐(邻苯二甲酸酐，简称苯酐或PA)化学改性PPC得到的新型降解塑料，通过在PPC主链上引入邻苯二甲酸酐，提高了高分子链的刚性，使PPC的力学和热学性能得到显著改善，可大幅提高PPC塑料的附加值。
中国专利CN202010337273.0中公开了一种以邻苯二甲酸酐、环氧丙烷和CO 2为原料合成二氧化碳基聚酯-聚碳酸酯三元共聚物(PPC-P)的方法，将一定质量的邻苯二甲酸酐、环氧丙烷、催化剂加入到高压反应釜中，充入1.0-3.0MPa CO 2，在60～100℃下反应12h，反应结束后淬火反应，产物经溶解、沉淀、干燥得到产品。不足的是专利中提到的邻苯二甲酸酐和环氧丙烷的加料方式为依次单独加入，若邻苯二甲酸酐以固态形式加入，因溶解需较长时间，且吸收大量热量，延长了反应时间，增加了能耗；若邻苯二甲酸酐以液态形式加入，由于邻苯二甲酸酐熔点为133℃，加入时极易造成反应釜局部温度过高，会造成副产物增多，产率降低，且会使反应釜局部压力偏高。
因此，亟需一种能够有效地抑制副反应的产生，提高产率且能够提高邻苯二甲酸酐的转化率和产品选择性的混合投料工艺及其设备。
现有常规工艺为固体邻苯二甲酸酐、环氧丙烷分批独立加入。此方法的技术问题较为明显。首先，固体邻苯二甲酸酐加料，需大量人工操作，效率低下；包装袋中残留、粉尘损耗等因素，易造成投料无法精确计量；投料过程中，固体粉尘较多，对操作人员的职业健康有一定的危害，车间卫生也难以保证；加料过程中，釜内原有的物料，多为易燃易爆有毒物质，沸点较低的物料外溢，既危害操作人员的健康，又易发生安全事故。
实际操作过程中，根据物料特性，邻苯二甲酸酐的熔点较高，加入反应釜后，需大量的热量进行融化，耗能较高，且频繁的降温升温，能效比较差；固体物料存在吸潮现象，而该反应对水分较为敏感，对实验效果有较大影响；固体料加入的过程中，往往不能均匀的分布，对搅拌有较高的要求，且影响后续的反应稳定性。
发明内容
为了解决上述问题，本发明第一方面提供了一种邻苯二甲酸酐和环氧丙烷混合投料方法，步骤至少包含以下几步：(1)邻苯二甲酸酐和环氧丙烷的投料计量；(2)混合投料；(3)混合搅拌；(4)加入辅料；(5)通气聚合；(6)过滤干燥。
作为一种优选的方案，所述邻苯二甲酸酐和环氧丙烷的投料计量为：液体环氧丙烷和液体邻苯二甲酸酐原料的质量计量。
作为一种优选的方案，所述液体环氧丙烷与液体邻苯二甲酸酐的摩尔比为0.5～10：1。
作为一种优选的方案，所述液体环氧丙烷与液体邻苯二甲酸酐的摩尔比为5～8：1。
本申请中，通过限定液体环氧丙烷和液体邻苯二甲酸酐的投料混合摩尔比有效地提高了PPC-P的韧性和分子量均匀性。本申请人推测为：本申请中当液体环氧丙烷与液体邻苯二甲酸酐的摩尔比为5～8:1时，协同两者的液体混合投料，能够有效实现不同原料之间的分子链接触程度，从而在混合投料时就形成均一且稳定的硬段-软段-硬段的嵌段式结构，有效控制产物的分子链组成，形成具有较强韧性的分子链结构。
作为一种优选的方案，所述混合投料为：将液体环氧丙烷与液体邻苯二甲酸酐混合投入配制容器进行升温搅拌；投入顺序为先加入液体环氧丙 烷，后加入液体邻苯二甲酸酐。
作为一种优选的方案，所述混合投料时，液体环氧丙烷的进料温度为0～40℃；液体邻苯二甲酸酐的进料温度为120～160℃。
作为一种更优选的方案，所述混合投料时，液体环氧丙烷的进料温度为15～30℃；液体邻苯二甲酸酐的进料温度为130～150℃。
作为一种优选的方案，所述混合搅拌为：将投料后的液体环氧丙烷和液体邻苯二甲酸酐在设置温度下，固定搅拌转速，搅拌固定时间，以达到两种原料的高度混合。
作为一种优选的方案，所述配制容器的搅拌温度为30～120℃；所述配制容器的搅拌转速为30～200r/min；所述配制混合时间为20～60min。
作为一种更优选的方案，所述配制容器的搅拌温度为50～90℃；所述配制容器的搅拌转速为60～120r/min；所述配制混合时间为40～50min。
本申请中，通过液体环氧丙烷和液体邻苯二甲酸酐的混合投料，以及对于投料温度的限定设置，有效地提高了邻苯二甲酸酐的转化率，从而提高整体产物的产率和纯度。本申请人推测为：本申请中采用的环氧丙烷和邻苯二甲酸酐以液体混合物投料的形式，与现有技术中环氧丙烷、邻苯二甲酸酐单独投料，邻苯二甲酸酐直接投固体的投料方式相比，具有物料混合更均匀和投料方式灵活的特点，且优先加入的环氧丙烷能够有效地作为邻苯二甲酸酐良性分散介质，从而使得环氧丙烷与邻苯二甲酸酐的分子掺杂更加均匀；并且混合液体原料投料的方法有效避免了采用固体邻苯二甲酸酐和环氧丙烷的投料方式，则邻苯二甲酸酐在反应釜内需一定时间来混合均匀，延长了反应时间的问题，并且同时避免了液体邻苯二甲酸酐和环氧丙烷单独投料时，邻苯二甲酸酐在投入反应釜后由于温度在130℃以上会导致副反应的增加，降低产品PPC-P的选择性，还会导致反应釜局部压力过高，形成安全隐患的技术问题。
作为一种优选的方案，所述辅料为无机碱催化剂、金属盐催化剂、有机催化剂、离子液体催化剂中的至少一种。
作为一种优选的方案，所述辅料为戊二酸锌。
作为一种优选的方案，所述通气聚合为：液体环氧丙烷与液体邻苯二甲酸酐的混合投入反应容器中后，向反应容器充入固定压强的二氧化碳气 体，高温反应一段时间，反应结束后释放二氧化碳。
作为一种优选的方案，所述液体环氧丙烷与二氧化碳的重量比为3.8～4.2：0.6～0.8。
作为一种更优选的方案，所述液体环氧丙烷与二氧化碳的重量比为3.8：0.692。
本申请中，通过控制环氧丙烷与通入的二氧化碳气体的质量复配比，有效地提高了聚合的反应速率，并且进一步的提高了反应稳定性。本申请人推测为：当液体环氧丙烷与二氧化碳的重量比为3.8：0.692时，液体环氧丙烷能够在体系中充当混合投料的分散介质的同时，充分的提高混合料与二氧化碳的接触程度在合适的范围之内，从而使得混合料在聚合过程不仅局限于混合料的表层部分，能够有效的随着一定含量的环氧丙烷的带动至柱型混合体系的整体部分，从而在提高反应速率的基础上保持良好的反应稳定性，明显提高产物收率。
作为一种优选的方案，所述二氧化碳与辅料的质量比为9～11：1。
作为一种更优选的方案，所述二氧化碳与辅料的质量比为9.6～9.8：1。
作为一种优选的方案，所述固定压强为2～3MPa。
作为一种更优选的方案，所述固定压强为2.1MPa。
作为一种优选的方案，所述通气聚合反应时间为8～12h。
作为一种更优选的方案，所述通气聚合反应时间为10h。
作为一种优选的方案，所述通气聚合过程中聚合反应温度为50～90℃。
作为一种更优选的方案，所述通气聚合过程中聚合反应温度为60～80℃。
作为一种优选的方案，投料设备的结构主要包括计量罐，配制釜5和反应釜6。
作为一种优选的方案，所述计量罐包括邻苯二甲酸酐计量罐4和环氧丙烷计量罐3；所述配制釜5和反应釜6外层带有夹套或盘管7，夹套或盘管7中通入热媒或冷媒以控制釜内温度；所述配制釜5带有搅拌桨5-1，可以使物料温度混合均匀。
作为一种优选的方案，所述邻苯二甲酸酐计量罐4和环氧丙烷计量罐3与配制釜5的上部管道固定连接，管道用以液体邻苯二甲酸酐和环氧丙烷的传输。
作为一种优选的方案，所述邻苯二甲酸酐计量罐4和环氧丙烷计量罐3的前端部分分别固定连接有邻苯二甲酸酐进料口2和环氧丙烷进料口1，用以原料的导入。
作为一种优选的方案，所述配制釜与反应釜通过管道固定连接，管道用以液体邻苯二甲酸酐和环氧丙烷混合液的传输。
本发明第二方面提供了一种上述邻苯二甲酸酐和环氧丙烷混合投料方法的应用，包括该方法在合成生物可降解塑料制备工艺中的应用。
本发明意在对专利CN202010337273.0公开的一种生物可降解二氧化碳聚酯-聚碳酸酯三元共聚物的原料投料工艺进行改进，进一步提高原料的转化率和产物的收率，降低生产成本。
有益效果：
1、本申请中提供的一种混合投料工艺，能够有效地实现分阶段加料，从而能够有效地实现对于产物的分子链的组成控制，实现对于链段的嵌段设计，最终赋予聚合物多种性能。
2、本申请中提供的一种混合投料工艺，能够有效地实现热邻苯二甲酸酐的能耗综合利用，充分利用邻苯二甲酸酐熔点高的特点，在高温时加入聚合釜，能够有效的为聚合过程提供反应温度，从而有效减少了反应过程的热能供应。
3、本申请中提供的一种混合投料工艺，邻苯二甲酸酐的预溶解，除了能够有效地实现气、液反应完全，反应更容易引发，可操控性更强，搅拌更加均匀，同时还能够实现全程邻苯二甲酸酐的聚合反应，实现产物更均匀的分子量分布。
说明书附图
图1为本申请混合投料设备结构示意图；
图中：1环氧丙烷进料口、2邻苯二甲酸酐进料口、3环氧丙烷计量罐、4邻苯二甲酸酐计量罐、5配制釜、5-1搅拌桨、6反应釜、7夹套或盘管。
具体实施方式
实施例1
实施例1第一方面提供了一种邻苯二甲酸酐和环氧丙烷混合投料方法，步骤包含以下几步：(1)邻苯二甲酸酐和环氧丙烷的投料计量；(2)混合投料；(3)混合搅拌；(4)加入辅料；(5)通气聚合；(6)过滤干燥。
本实施例第二方面提供了一种如图1所示的混合投料设备，结构主要包括计量罐，配制釜和反应釜。
其中计量罐包括邻苯二甲酸酐计量罐和环氧丙烷计量罐；配制釜和反应釜外层带有夹套，夹套中通入热媒和冷媒以控制釜内温度；配制釜带有搅拌桨，可以使物料温度混合均匀。
邻苯二甲酸酐计量罐和环氧丙烷计量罐与配制釜的上部管道固定连接，管道用以液体邻苯二甲酸酐和环氧丙烷的传输。
配制釜与反应釜通过管道固定连接，管道用以液体邻苯二甲酸酐和环氧丙烷混合液的传输。
实际的操作过程：准备工作：配制釜和反应釜选用1m 3高压反应釜，氮气置换三次；(1)使用计量罐分别计量称取380Kg液体环氧丙烷和172Kg液体邻苯二甲酸酐；(2)将上述原料依次投入配制釜，控制液体环氧丙烷的投料温度为25℃，控制液体邻苯二甲酸酐的投料温度为140℃；(3)控制配制釜内温度70℃，搅拌转速90r/min，混合搅拌30min后环氧丙烷和邻苯二甲酸酐混合均匀，得混合液；(4)将混合液通入反应釜，并且向混合液加入7.2Kg戊二酸锌催化剂；(5)充入2.1MPa二氧化碳69.2KG，在80℃下反应10h，反应结束后用无水乙醇溶解产物直至全部溶解，结束反应，沉淀后得到聚合物；(6)聚合物于真空干燥箱80℃干燥60h，测量聚合物的质量为602.3Kg，计算聚合物收率为96.96％。
本实施例中，环氧丙烷购买自山东三岳化工有限公司优等品级环氧丙烷。
本实施例中，邻苯二甲酸酐购买自山东宏信化工有限公司优级品邻苯二甲酸酐。
实施例2
本实施例的具体实施方式同实施例1，不同之处在于：液体环氧丙烷 的加入量为392Kg，固体邻苯二甲酸酐加入量为161Kg，催化剂加入量为6.9Kg，二氧化碳通入量为72.6Kg；测得最终聚合物的质量为494.6Kg，计算聚合物收率为79.06％。
实施例3
本实施例的具体实施方式同实施例1，不同之处在于：液体环氧丙烷的加入量为408Kg，固体邻苯二甲酸酐加入量为166Kg，且环氧丙烷和邻苯二甲酸酐固体不进行配制釜内的搅拌混合步骤，直接置入反应釜内，加入7.5Kg催化剂，二氧化碳通入量为75.6Kg；测得最终聚合物的质量为445.7Kg，计算聚合物收率为68.61％。
实施例4
本实施例的具体实施方式同实施例1，不同之处在于：液体环氧丙烷的加入量为400Kg，液体邻苯二甲酸酐加入量为165Kg，二氧化碳通入量为68.6Kg；测得最终聚合物的质量为614.8Kg，计算聚合物收率为97.03％。
通过实施例1～4可以得知，本发明提供的一种邻苯二甲酸酐和环氧丙烷的混合投料方法，以及设备和应用，本申请中的工艺具有良好的能耗控制能力，能够实现分段式加料，从而有效地控制聚合物的反应分子链的长度以及嵌段设计，适宜在塑料制造加工领域推广，具有广阔的发展前景。其中实施例1在具有最佳的制备原料配比和制备工艺等因素下获得了最佳产品纯度和收率。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (19)

  1. 一种邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：步骤至少包含以下几步：(1)邻苯二甲酸酐和环氧丙烷的投料计量；(2)混合投料；(3)混合搅拌；(4)加入辅料；(5)通气聚合；(6)过滤干燥。
  2. 根据权利要求1所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述邻苯二甲酸酐和环氧丙烷的投料计量为：液体环氧丙烷和液体邻苯二甲酸酐原料的质量计量。
  3. 根据权利要求2所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述液体环氧丙烷与液体邻苯二甲酸酐的摩尔比为0.5～10：1。
  4. 根据权利要求3所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述液体环氧丙烷与液体邻苯二甲酸酐的摩尔比为5～8：1。
  5. 根据权利要求1～4任一项所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述混合投料为：将液体环氧丙烷与液体邻苯二甲酸酐混合投入配制容器进行升温搅拌；投入顺序为先加入液体环氧丙烷，后加入液体邻苯二甲酸酐。
  6. 根据权利要求5所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述混合投料时，液体环氧丙烷的进料温度为0～40℃；液体邻苯二甲酸酐的进料温度为120～160℃。
  7. 根据权利要求6所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述混合投料时，液体环氧丙烷的进料温度为15～30℃；液体邻苯二甲酸酐的进料温度为130～150℃。
  8. 根据权利要求5所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述配制容器的搅拌温度为30～120℃；所述配制容器的搅拌转速为30～200r/min；所述配制容器的搅拌时间为20～60min。
  9. 根据权利要求8所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述配制容器的搅拌温度为50～90℃；所述配制容器的搅拌转速为60～120r/min；所述配制容器的搅拌时间为40～50min。
  10. 根据权利要求1所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述辅料为无机碱催化剂、金属盐催化剂、有机催化剂和离子液体催化剂中的至少一种。
  11. 根据权利要求10所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述辅料为戊二酸锌。
  12. 根据权利要求1所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述通气聚合为：液体环氧丙烷与液体邻苯二甲酸酐混合投入反应容器中后，向反应容器充入固定压强的二氧化碳气体，高温反应一段时间，反应结束后释放二氧化碳。
  13. 根据权利要求12所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述液体环氧丙烷与二氧化碳的重量比为3.8～4.2：0.6～0.8；所述二氧化碳与辅料的质量比为9～11：1。
  14. 根据权利要求12所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述固定压强为2～3MPa。
  15. 根据权利要求1或12所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述通气聚合的过程中聚合反应温度为50～90℃。
  16. 根据权利要求15所述的邻苯二甲酸酐和环氧丙烷混合投料方法，其特征在于：所述通气聚合的反应时间为8～12h。
  17. 一种用于权利要求1～16任一项所述的邻苯二甲酸酐和环氧丙烷混合投料方法的投料设备，其特征在于：所述投料设备的结构主要包括计量罐，配制釜和反应釜。
  18. 根据权利要求17所述的用于邻苯二甲酸酐和环氧丙烷混合投料方法的投料设备，其特征在于：所述计量罐包括邻苯二甲酸酐计量罐和环氧丙烷计量罐；所述配制釜和反应釜外层带有夹套或盘管，所述夹套或盘管中通入热媒或冷媒以控制釜内温度；所述配制釜带有搅拌桨，使物料温度混合均匀。
  19. 一种权利要求1～16任一项所述的邻苯二甲酸酐和环氧丙烷混合投料方法的应用，其特征在于：包括所述方法在合成生物可降解塑料制备工艺中的应用。
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