WO2020082589A1 - 一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法 - Google Patents

一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法 Download PDF

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WO2020082589A1
WO2020082589A1 PCT/CN2018/124472 CN2018124472W WO2020082589A1 WO 2020082589 A1 WO2020082589 A1 WO 2020082589A1 CN 2018124472 W CN2018124472 W CN 2018124472W WO 2020082589 A1 WO2020082589 A1 WO 2020082589A1
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performance
polymerization
neutralization
polyisophthaloyl
polymer
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French (fr)
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吕继平
宋西全
潘士东
高东
翟恩全
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烟台泰和新材料股份有限公司
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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
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides

Definitions

  • the present application relates to a method for preparing polyisophthaloyl isophthalamide spinning solution by low temperature solution polymerization, in particular to a continuous polymerization method for preparing high performance polyisophthaloyl metaphenylene diamine, meta-aromatic Nylon fiber and flame-retardant and high-temperature protective materials.
  • Poly-m-phenylene isophthalamide fiber that is, meta-aramid fiber, has excellent high temperature resistance and flame retardancy, as well as excellent electrical insulation, radiation resistance and chemical resistance, and is mainly used for flame retardant protection Clothing, high-temperature filtration and high-temperature insulation materials are important basic materials for the development of high-tech industries such as aerospace, energy industry, and environmental protection.
  • the preparation of high-quality, high-molecular-weight polyisophthaloyl metaphenylene diamine polymer solution is the guarantee for manufacturing high-performance meta-aramid fiber.
  • Interfacial polymerization m-phenylenediamine and m-phthaloyl chloride are reacted in a poor solvent of poly-m-phenylene m-phenylenediamine, and then mixed with an aqueous solution containing an acid absorbent, and polymer powder is formed after the reaction is completed Then, the polymer powder is filtered, dried, and dissolved in an amide solvent for spinning. When dissolving, chloride salt is added as a co-solvent.
  • Interfacial polymerization can be accomplished by continuous polymerization or batch polymerization.
  • the polymer is separated from the polymerization system and dissolved, resulting in poor stability of the spinning solution (such as patent US3640970), the performance of the fiber obtained by spinning is general, and the preparation process It is more complicated and not conducive to industrialization.
  • the one-step polymerization and one-step neutralization method are adopted, resulting in that all the salts generated by neutralizing hydrogen chloride are left in the polymer solution and the salt content reaches 10 %, Resulting in high salt content and halogen content in the final fiber.
  • Patent CN201210138473.9 mainly introduces a device and method for continuously preparing polyisophthaloyl metaphenylene diamine solution. It adopts a one-step polymerization and one-step neutralization process. In the polymerization stage, a two-stage screw reactor is connected in series. The reaction time is extended and the reaction heat can be discharged in time.
  • Patent CN201010227716.7 uses a continuous polymerization process and equipment to prepare poly-m-phenylene isophthalamide solution, which uses a one-step polymerization and one-step neutralization process, especially the calcium hydroxide neutralization method, the salt in the solution The content is close to 10%.
  • the patents CN106046364A and CN106076232A mainly introduce the method and device for continuously preparing poly-m-phenylene isophthalamide solution. It adopts a one-step polymerization and one-step neutralization process. In the polymerization stage, a screw reactor and a reaction tank are used. The polymerization device reduces equipment investment. However, the polymer solution prepared by the one-step method has a relatively low molecular weight of the polymer, which is not conducive to the preparation of high-performance fibers, and the halogen salt content is too high.
  • the purpose of this application is to overcome the shortcomings of the existing technology, to provide a continuous polymerization method for preparing high-performance polyisophthaloyl metaphenylene diamine, which combines a continuous polymerization process and a solution polymerization process, integrating two The characteristics of this process have better operability.
  • Another object of the present application is to provide a meta-aramid fiber with high strength and excellent performance.
  • Another object of the present application is to provide a flame-retardant and high-temperature resistant protective material, which can be flame-retardant, high-temperature resistant and high-strength, and can be used as flame-retardant protective clothing, high-temperature filtration and high-temperature insulating materials.
  • a continuous polymerization method for preparing high-performance polyisophthaloyl isophthalamide including prepolymerization, neutralization, polymerization, neutralization, and filtration processes, characterized in that the polymerization process and the neutralization process are two steps, Among them, ammonia gas is used for neutralization in the first step, and organic amine is used for neutralization in the second step. In the first step, ammonia gas is used for neutralization. After neutralization, the neutralized salt ammonium chloride particles are filtered and removed, which greatly reduces the viscosity and the salt content of the polymerization raw solution.
  • the salt content is controlled below 2.0%, which is conducive to preparing high High-molecular-weight polyisophthaloyl metaphenylene diamine polymer solution, and fibers made of polymers with low chloride content can meet international fiber and fabric standards with low halogen content.
  • the second step neutralizes the hydrogen chloride generated by the polymerization of the organic amine, and the generated chlorinated organic amine can be well dissolved in the polymer solution and contributes to the stability of the polymer solution.
  • m-phenylenediamine is mixed with a polar solvent, 80-95% of m-phthaloyl chloride is added to the total amount of phthaloyl chloride, and then ammonia gas is added for neutralization , Get the prepolymer, filter and remove the ammonium chloride formed by the neutralization of the prepolymer; then add the remaining 5-20% of the melted isophthaloyl chloride to the prepolymer, after the polymerization is completed, use organic amine Neutralize hydrogen chloride produced by polymerization.
  • the viscosity of the polymer is adjusted to 40-80 Pa ⁇ S by adding isophthaloyl chloride.
  • m-phenylenediamine and m-phthaloyl chloride are both measured and added in the molten state.
  • the concentration of m-phenylenediamine is 9-11%.
  • the melted m-phenylenediamine is added to the mixing tank containing the polar solvent, and the concentration is controlled at 9-11 %%.
  • the concentration is controlled at 9-11 %%.
  • enter the prepolymerization reactor and then add the melted isophthaloyl chloride to the prepolymerization reactor in stages.
  • the amount of isophthaloyl chloride added accounts for 80-95% of its total amount;
  • Ammonia gas is introduced into the reactor to carry out the neutralization reaction.
  • the completed prepolymer enters the buffer tank and circulates and filters the ammonium chloride particles formed by the neutralization until the prepolymer is clear and transparent;
  • the prepolymer in the buffer tank into the polymerization reactor, and add the remaining 5-20% of the melted isophthaloyl chloride to complete the polymerization reaction in the polymerization reactor; after the polymerization is completed, neutralize the polymerization with organic amine
  • the generated hydrogen chloride, the organic amine is ethylamine or triethylamine, the generated chlorinated organic amine is dissolved in the polymer solution without removing; the polymer then enters the storage tank, and the viscosity is tested, according to the needs and target control to decide whether Add a very small amount of isophthaloyl chloride to fine-tune the viscosity to meet the spinning needs.
  • the polymer solution is finally used for spinning after filtering, defoaming and other processes.
  • the prepolymerization, the two-step neutralization process and the second-step polymerization process are all completed under low temperature conditions, using a refrigerant to lower the temperature, and the temperature is controlled at -10 to 0 ° C.
  • the reaction of the two monomers can be carried out smoothly, the occurrence of side reactions can be reduced, and the preparation of high-performance polymer stock solution can be realized.
  • the prepolymerization, two-step neutralization process is completed in a dynamic pipeline reactor, and the second-step polymerization process is completed in a twin-screw reactor.
  • the length-diameter ratio of the twin-screw reactor is as large as possible, such as 40-60: 1, and the rotation speed of the screw is designed to be 200-300 rpm.
  • twin-screw power module must be used for mixing, shearing, and kneading to achieve full reaction and uniform mixing of the polymer.
  • the pipeline reactor and twin-screw reactor are used. It has the characteristics of fast and uniform reaction speed and no dead angle of stirring.
  • the organic amine includes one or more of ethylamine, ethylenediamine, triethylamine, and diethylamine.
  • the polar solvent includes dimethylacetamide, dimethylformamide, and the like.
  • a meta-aramid fiber is produced by spinning a polyisophthaloyl metaphenylene diamine polymer polymerized by the above-mentioned continuous polymerization method of high performance polyisophthaloyl isophthalamide.
  • a flame-retardant and heat-resistant protective material which is made of the above meta-aramid fiber.
  • This application provides a continuous low-temperature solution polymerization process. Compared with the two-step batch polymerization, it has the advantages of simple process, compact polymerization equipment, stable polymerization conditions, low energy consumption, low investment, large operation flexibility, and high polymer quality. , To improve the uniformity of the polymer, is an important basis for the preparation and production of high-quality fiber products.
  • Figure 1 is a schematic diagram of the application process.
  • the prepolymer directly enters the dynamic pipeline reactor for neutralization reaction, and ammonia gas is used for neutralization.
  • the amount of ammonia gas added is 70kg, and the pH of the prepolymer after the neutralization is controlled to 5.0.
  • the prepolymer enters the buffer tank, and the ammonium chloride particles formed by neutralization are circulated and filtered in the buffer tank until the prepolymer is clear and transparent.
  • the filtered and transparent prepolymer is metered into the screw reactor using a gear metering pump.
  • the ratio of the length and diameter of the screw reactor is 40: 1, and the rotation speed is 200 rpm.
  • the melted state is added
  • the addition amount of isophthaloyl chloride is 112kg (accounting for 20% of the total), and the polymerization reaction is basically completed after passing through the screw reactor.
  • the hydrogen chloride generated by the polymerization process is neutralized with ethylamine, and the generated chlorinated organic amine is well soluble in the polymer solution and contributes to the stability of the polymer solution; at this time, the salt in the polymer solution The content is about 3%, the polymer enters the storage tank again, and its viscosity is automatically detected.
  • the viscosity requirement is generally 30-100Pa ⁇ S, and the polymer solution is directly used for spinning after filtration, defoaming and other processes to obtain meta-aramid fiber.
  • the molecular weight of the polymer is 180,000-200,000, which is higher than the molecular weight of the common meta-aramid polymer.
  • the prepolymer directly enters the dynamic pipeline reactor for neutralization reaction, and ammonia gas is used for neutralization.
  • the amount of ammonia gas added is 80 kg, and the pH of the prepolymer after the neutralization is controlled to 5.0.
  • the prepolymer enters the buffer tank, and the ammonium chloride particles formed by neutralization are circulated and filtered in the buffer tank until the prepolymer is clear and transparent.
  • the filtered and transparent prepolymer is metered into the screw reactor using a gear metering pump.
  • the ratio of the length and diameter of the screw reactor is 50: 1, and the rotation speed is 300 rpm.
  • the addition amount of isophthaloyl chloride is 56kg (accounting for 10% of the total), and the polymerization reaction is basically completed after passing through the screw reactor.
  • the hydrogen chloride generated by the polymerization process is neutralized with ethylamine, and the generated chlorinated organic amine is well soluble in the polymer solution and contributes to the stability of the polymer solution; at this time, the salt in the polymer solution The content is about 2%, the polymer enters the storage tank again, and its viscosity is automatically detected.
  • the viscosity requirement is generally 30-100Pa ⁇ S, and the polymer solution is directly used for spinning after filtration, defoaming and other processes to obtain meta-aramid fiber.
  • the molecular weight of the polymer is 180,000-200,000, which is higher than the molecular weight of the common meta-aramid polymer.
  • the prepolymer directly enters the dynamic pipeline reactor for neutralization reaction, and ammonia gas is used for neutralization.
  • the amount of ammonia gas added is 80kg, and the pH of the prepolymer after the neutralization is controlled to 4.0.
  • the prepolymer enters the buffer tank, and the ammonium chloride particles formed by neutralization are circulated and filtered in the buffer tank until the prepolymer is clear and transparent.
  • the filtered and transparent prepolymer is metered into the screw reactor using a gear metering pump.
  • the ratio of the length and diameter of the screw reactor is 45: 1, and its rotation speed is 250 rpm.
  • the melted state is added
  • the addition amount of isophthaloyl chloride is 28kg (accounting for 5% of the total), and the polymerization reaction is basically completed after passing through the screw reactor.
  • the hydrogen chloride generated by the polymerization process is neutralized with ethylenediamine, and the generated chlorinated organic amine can be well dissolved in the polymer solution and contribute to the stability of the polymer solution; at this time, the polymer solution
  • the salt content is about 1.5%
  • the polymer enters the storage tank again, and its viscosity is automatically detected.
  • the apparent viscosity of the polymer is about 90Pa ⁇ S.
  • the polymer solution is directly used for spinning after filtration, defoaming and other processes. Obtain meta-aramid fiber.
  • the molecular weight of the polymer is 200,000, which is higher than the molecular weight of the common meta-aramid polymer.
  • the prepolymer directly enters the dynamic pipeline reactor for neutralization reaction, and ammonia gas is used for neutralization.
  • the added amount of ammonia gas is 85kg, and the pH of the prepolymer after the neutralization is controlled to 4.8.
  • the prepolymer enters the buffer tank, and the ammonium chloride particles formed by neutralization are circulated and filtered in the buffer tank until the prepolymer is clear and transparent.
  • the filtered and transparent prepolymer was metered into the screw reactor using a gear metering pump.
  • the ratio of the length and diameter of the screw reactor was 55: 1, and its rotation speed was 260 rpm / min.
  • the addition amount of isophthaloyl chloride is 28kg (accounting for 5% of the total), and the polymerization reaction is basically completed after passing through the screw reactor.
  • the hydrogen chloride generated by the polymerization process is neutralized with diethylamine, and the generated chlorinated organic amine can be well dissolved in the polymer solution and contribute to the stability of the polymer solution; at this time, the polymer solution
  • the salt content is about 1.5%
  • the polymer enters the storage tank again, and its viscosity is automatically detected.
  • the apparent viscosity of the polymer is about 80Pa ⁇ S.
  • the polymer solution is directly used for spinning after filtration, defoaming and other processes. Obtain meta-aramid fiber.
  • the molecular weight of the polymer is 190,000, which is higher than the molecular weight of the common meta-aramid polymer.
  • the prepolymer directly enters the dynamic pipeline reactor for neutralization reaction, and ammonia gas is used for neutralization.
  • the amount of ammonia gas added is 85kg, and the pH of the prepolymer is controlled to 5 after neutralization.
  • the prepolymer enters the buffer tank, and the ammonium chloride particles formed by neutralization are circulated and filtered in the buffer tank until the prepolymer is clear and transparent.
  • the filtered and transparent prepolymer is metered into the screw reactor using a gear metering pump.
  • the ratio of the length and diameter of the screw reactor is 60: 1, and the rotation speed is 300 rpm.
  • the melted state is added
  • the addition amount of isophthaloyl chloride is 83kg (accounting for 14.7% of the total), and the polymerization reaction is basically completed after passing through the screw reactor.
  • the hydrogen chloride generated by the polymerization process is neutralized with triethylamine, and the generated chlorinated organic amine can be well dissolved in the polymer solution and contribute to the stability of the polymer solution; at this time, the polymer solution
  • the salt content is about 2.5%
  • the polymer enters the storage tank again, and its viscosity is automatically detected.
  • the apparent viscosity of the polymer is about 70Pa ⁇ S.
  • the polymer solution is directly used for spinning after filtration, defoaming and other processes. Obtain meta-aramid fiber.
  • the molecular weight of the polymer is 180,000, which is higher than the molecular weight of the common meta-aramid polymer.
  • Comparative Example 1 Preparation using the polymerization method mentioned in patent CN201210138473.9;
  • Comparative Example 2 The polymerization method mentioned in patent CN201010227716.7 was used for preparation;
  • Comparative Example 4 The ammonia in the first step of the neutralization process in Example 1 was replaced with an organic amine;
  • Comparative Example 5 The organic amine in the second step of the neutralization process in Example 1 was replaced with ammonia water;
  • Comparative Example 6 The first-step neutralization reaction in Example 1 was carried out at 20 ° C;
  • Comparative Example 7 The second-step neutralization reaction in Example 1 was carried out at 20 ° C.
  • isophthaloyl and meta-phenylenediamine were sequentially subjected to the first polymerization reaction, the first neutralization reaction, the second polymerization reaction, and the second neutralization reaction, and
  • the neutralizing agents used to control the first neutralization reaction and the second neutralization reaction are different. They are ammonia gas and organic amine. After ammonia gas is neutralized, the neutralized ammonium chloride particles can be discharged by circulating filtration. Reduce the viscosity and salt content of the polymerization stock solution, which is conducive to the preparation of high-concentration and high-molecular-weight polyisophthaloyl metaphenylene diamine polymer solution.
  • Organic amines are well soluble in polymer solutions and contribute to the stability of polymer solutions. Compared with the two-step batch polymerization, it has the advantages of simple process, compact polymerization equipment, stable polymerization conditions, low energy consumption, low investment, large operation flexibility, high polymer quality, etc., which improves the uniformity of the polymer. An important foundation for producing high-quality fiber products.
  • the continuous polymerization method for preparing high-performance polyisophthaloyl m-phenylenediamine provided in this example has a simple process, compact polymerization equipment, stable polymerization conditions, low energy consumption, and low investment
  • the advantages of high operating elasticity and high polymer quality improve the uniformity of the polymer and are an important basis for the preparation and production of high-quality fiber products.

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Abstract

一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，包括预聚、中和、聚合、中和、过滤过程，所述聚合过程和中和过程均为两步，其中第一步中和采用氨气，第二步中和采用有机胺。具体采用连续式低温溶液聚合工艺，相比两步法的间歇式聚合，具有流程简单、聚合设备紧凑，聚合条件稳定、能耗小、投资小、操作弹性大、聚合物质量高等优点，提高了聚合物的均匀性，是制备和生产高品质纤维产品的重要基础。由该方法制备的一种间位芳纶纤维以及由该间位芳纶纤维制备而成的阻燃耐高温防护材料强度高，性能优异。

Description

一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法
相关申请的交叉引用
本申请要求于2018年10月24日提交中国专利局的申请号为201811245040.7、名称为“一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法”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
本申请涉及一种低温溶液聚合制备聚间苯二甲酰间苯二胺纺丝液的方法，特别涉及一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法、间位芳纶纤维以及阻燃耐高温防护材料。
背景技术
聚间苯二甲酰间苯二胺纤维即间位芳纶纤维，具有优异的耐高温性和阻燃性，以及优良的电绝缘性、耐辐射和耐化学腐蚀性能，主要用于阻燃防护服装、高温过滤及高温绝缘材料等，是航空航天、能源工业、环境保护等高技术产业发展的重要基础材料。
高品质高分子量的聚间苯二甲酰间苯二胺聚合体溶液的制备，是制造高性能间位芳纶纤维的保证。
聚间苯二甲酰间苯二胺的制备反应：
现有的制备聚间苯二甲酰间苯二胺聚合物的方法通常有：
1)界面聚合：间苯二胺与间苯二甲酰氯在聚间苯二甲酰间苯二胺的不良溶剂中进行反应，然后与含有酸吸收剂的水溶液混合，反应完成后生成聚合物粉末，然后将聚合物粉末滤出、干燥，将其溶解于酰胺溶剂中进行纺丝，溶解时需添加氯化盐作为助溶剂。
界面聚合可以采用连续聚合或间歇聚合方式来完成，聚合物从聚合体系中分离出来再溶解，得到的纺丝溶液稳定性较差(如专利US3640970)，纺丝所得纤维的性能一般，而且制备流程较为复杂，不利于产业化。
2)溶液聚合：间苯二胺和间苯二甲酰氯在极性酰胺类溶剂中聚合得到聚间苯二甲酰间苯二胺，然后中和副产物氯化氢，中和生成可溶于聚合体系的氯化盐，该聚合物溶液可直接用于干法纺丝，专利US3063966采用了此方法，得到的纤维性能优良。但是专利US3063966和其他相关专利均未涉及是采用间歇聚合或连续聚合，同时其采用的一步聚合一步中和法，导致中和氯化氢所产生的盐分全部留在聚合物溶液中，其盐分含量达到10％， 导致最终的纤维中盐含量和卤素含量也很高。
国内的主要间位芳纶生产厂家采用的多是间歇的低温溶液聚合，导致聚合物批次之间的差异大，不利于纤维产品的稳定，不利于制备高端间位芳纶产品。
现有主要研究情况如下：
专利CN201210138473.9主要介绍了连续制备聚间苯二甲酰间苯二胺溶液的装置和方法，其采用的是一步聚合一步中和工艺，在聚合阶段采用了2级螺杆反应器串联的装置，加长了反应时间并能够及时排出反应热。
专利CN201010227716.7中采用了连续聚合工艺和设备制备聚间苯二甲酰间苯二胺溶液，其采用的是一步聚合一步中和工艺，尤其是采用氢氧化钙中和法，溶液中的盐含量接近10％。
专利CN106046364A和CN106076232A主要介绍了连续制备聚间苯二甲酰间苯二胺溶液的方法和装置，其采用的是一步聚合一步中和工艺，在聚合阶段采用了螺杆反应器和反应罐相结合的聚合装置，降低了设备投资。但一步法制备的聚合物溶液其聚合物分子量较低，不利于制备高性能纤维，而且卤素盐含量过高。
发明内容
本申请的目的在于克服现有技术存在的不足之处，提供一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，将连续聚合工艺和溶液聚合工艺相结合，综合了两种工艺的特点，具有更好的可操作性。
本申请的另一目的在于提供一种间位芳纶纤维，其强度高，性能优异。
本申请的又一目的在于提供一种阻燃耐高温防护材料，其能够阻燃、耐高温，强度高，可作为阻燃防护服装、高温过滤及高温绝缘材料。
为实现上述至少一个目的，本申请采取的技术方案如下：
一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，包括预聚、中和、聚合、中和、过滤过程，其特征在于：聚合过程和中和过程均为两步，其中第一步中和采用氨气，第二步中和采用有机胺。第一步中和采用的是氨气，中和后将中和盐氯化铵微粒过滤除去，极大的降低了聚合原液的粘度和盐分含量，盐含量控制在2.0％以下，有利于制备高浓度高分子量的聚间苯二甲酰间苯二胺聚合物溶液，同时低氯化物含量的聚合物制备的纤维可以达到低卤素含量的国际纤维和织物标准。第二步中和以有机胺中和聚合生成的氯化氢，产生的氯化有机胺可很好的溶于聚合物溶液中，并且有助于聚合物溶液的稳定性。
进一步地，在本申请的其他实施方式中，将间苯二胺与极性溶剂混合，加入占苯二甲酰氯总量的80-95％的间苯二甲酰氯，接着加入氨气进行中和，得到预聚物，过滤去 除预聚物中的中和形成的氯化铵；接着向预聚物中加入剩余的5-20％的融化态间苯二甲酰氯，聚合完成后，以有机胺中和聚合生成的氯化氢。
进一步地，在本申请的其他实施方式中，用有机胺中和聚合生成的氯化氢时，还包括对聚合物进行粘度调制，聚合物的粘度通过加入间苯二甲酰氯调整至30-100Pa·S。
进一步地，在本申请的其他实施方式中，聚合物的粘度通过加入间苯二甲酰氯调整至40-80Pa·S。
进一步地，在本申请的其他实施方式中，间苯二胺和间苯二甲酰氯均以融化态计量并加入。
进一步地，在本申请的其他实施方式中，将间苯二胺加入至极性溶剂中时，间苯二胺的浓度为9-11％。
具体地，首先将融化态间苯二胺加入到含有极性溶剂的调配罐中，浓度控制在9-11％％。经混合后，进入预聚合反应器中，然后向预聚合反应器中分段加入融化态间苯二甲酰氯，间苯二甲酰氯的添加量占其总量的80-95％；然后在中和反应器中通入氨气进行中和反应，完成后的预聚物进入缓冲罐并对中和形成的氯化铵微粒进行循环过滤，直至预聚物澄清透明；
将缓冲罐中的预聚物打入聚合反应器，同时添加剩余的5-20％的融化态间苯二甲酰氯，在聚合反应器中完成聚合反应；聚合完成后，以有机胺中和聚合生成的氯化氢，有机胺为乙胺或三乙胺，生成的氯化有机胺溶于聚合物溶液中无须去除；聚合物再进入储罐，并对其粘度进行检测，根据需求和目标控制决定是否添加极少量的间苯二甲酰氯进行粘度微调以满足纺丝需求，聚合物溶液最后经过过滤、脱泡等工序后直接用于纺丝。
进一步地，预聚、两步中和过程及第二步聚合过程均在低温条件下完成，采用冷媒降温，温度控制在-10～0℃。低温条件下可以实现两种单体反应的顺利进行，减少副反应的发生，实现高性能聚合物原液的制备。
进一步地，预聚、两步中和过程在动态管道反应器中完成，第二步聚合过程在双螺杆反应器完成。双螺杆反应器的长径比尽可能大一点，如40-60:1，螺杆的转速设计200-300转/分。
因为在第二步聚合反应时，聚合物粘度较高，必须利用双螺杆的强力模块进行混合、剪切、捏合来实现聚合物的充分反应和混合均匀，采用的管道反应器和双螺杆反应器具有反应速度快、均匀，没有搅拌死角的特点。
进一步地，在本申请的其他实施方式中，有机胺包括乙胺、乙二胺、三乙胺和二乙胺中的一种或几种。
进一步地，在本申请的其他实施方式中，极性溶剂包括二甲基乙酰胺、二甲基甲酰胺 等。
一种间位芳纶纤维，其是由上述高性能聚间苯二甲酰间苯二胺的连续聚合方法聚合而成的聚间苯二甲酰间苯二胺聚合物经纺丝而成。
一种阻燃耐高温防护材料，其是由上述间位芳纶纤维制成。
本申请提供的是连续式低温溶液聚合工艺，相比两步法的间歇式聚合，具有流程简单、聚合设备紧凑，聚合条件稳定、能耗小、投资小、操作弹性大、聚合物质量高等优点，提高了聚合物的均匀性，是制备和生产高品质纤维产品的重要基础。
附图说明
图1为本申请的流程示意图。
具体实施方式
实施例1
请参阅图1，首先将融化态间苯二胺300kg加入到极性溶剂二甲基乙酰胺3000kg中，浓度为9.1％。经降温冷却，温度达到-10℃后，经计量进入管道反应器中，然后分2次加入融化态间苯二甲酰氯，预聚合过程中间苯二甲酰氯的添加量为451kg，占总量的80％。
然后预聚物直接进入动态管道反应器中进行中和反应，使用氨气进行中和，氨气的添加量为70kg，控制中和后预聚物的pH为5.0。完成后预聚物进入缓冲罐，在缓冲罐对中和形成的氯化铵微粒进行循环过滤，直至预聚物澄清透明。
第二步聚合时将过滤透明的预聚物采用齿轮计量泵计量打入螺杆反应器，螺杆反应器的长度和直径的比值为40:1，其转动速度为200转/min；同时添加融化态间苯二甲酰氯，添加量为112kg(占总量的20％)，经过螺杆反应器后基本完成了聚合反应。
聚合完成后，以乙胺中和聚合过程生成的氯化氢，产生的氯化有机胺可很好的溶于聚合物溶液中，并且有助于聚合物溶液的稳定性；此时聚合物溶液中盐分含量约为3％，聚合物再进入储罐，并对其粘度进行自动检测，根据需求和目标控制，决定是否进行粘度微调，即添加极少量的间苯二甲酰氯调节粘度，湿法纺丝的粘度要求一般在30-100Pa·S，聚合物溶液经过过滤、脱泡等工序后直接用于纺丝，获得间位芳纶纤维。
经GPC检测分析，聚合物的分子量为18-20万，高于目前常见间位芳纶聚合物分子量。
实施例2
首先将融化态间苯二胺300kg加入到极性溶剂二甲基乙酰胺2500kg中，经降温冷却，温度达到-10℃后，经计量进入管道反应器中，然后分2次加入融化态间苯二甲酰氯，预聚 合过程中间苯二甲酰氯的添加量为507kg，占总量的90％。
然后预聚物直接进入动态管道反应器中进行中和反应，使用氨气进行中和，氨气的添加量为80kg，控制中和后预聚物的pH为5.0。完成后预聚物进入缓冲罐，在缓冲罐对中和形成的氯化铵微粒进行循环过滤，直至预聚物澄清透明。
第二步聚合时将过滤透明的预聚物采用齿轮计量泵计量打入螺杆反应器，螺杆反应器的长度和直径的比值为50:1，其转动速度为300转/min；同时添加融化态间苯二甲酰氯，添加量为56kg(占总量的10％)，经过螺杆反应器后基本完成了聚合反应。
聚合完成后，以乙胺中和聚合过程生成的氯化氢，产生的氯化有机胺可很好的溶于聚合物溶液中，并且有助于聚合物溶液的稳定性；此时聚合物溶液中盐分含量约为2％，聚合物再进入储罐，并对其粘度进行自动检测，根据需求和目标控制，决定是否进行粘度微调，即添加极少量的间苯二甲酰氯调节粘度，湿法纺丝的粘度要求一般在30-100Pa·S，聚合物溶液经过过滤、脱泡等工序后直接用于纺丝，获得间位芳纶纤维。
经GPC检测分析，聚合物的分子量为18-20万，高于目前常见间位芳纶聚合物分子量。
实施例3
首先将融化态间苯二胺300kg加入到极性溶剂二甲基乙酰胺2600kg中，经降温冷却，温度达到-10℃后，经计量进入管道反应器中，然后分2次加入融化态间苯二甲酰氯，预聚合过程中间苯二甲酰氯的添加量为535kg，占总量的95％。
然后预聚物直接进入动态管道反应器中进行中和反应，使用氨气进行中和，氨气的添加量为80kg，控制中和后预聚物的pH为4.0。完成后预聚物进入缓冲罐，在缓冲罐对中和形成的氯化铵微粒进行循环过滤，直至预聚物澄清透明。
第二步聚合时将过滤透明的预聚物采用齿轮计量泵计量打入螺杆反应器，螺杆反应器的长度和直径的比值为45:1，其转动速度为250转/min；同时添加融化态间苯二甲酰氯，添加量为28kg(占总量的5％)，经过螺杆反应器后基本完成了聚合反应。
聚合完成后，以乙二胺中和聚合过程生成的氯化氢，产生的氯化有机胺可很好的溶于聚合物溶液中，并且有助于聚合物溶液的稳定性；此时聚合物溶液中盐分含量约为1.5％，聚合物再进入储罐，并对其粘度进行自动检测，聚合物表观粘度约为90Pa·S，聚合物溶液经过过滤、脱泡等工序后直接用于纺丝，获得间位芳纶纤维。
经GPC检测分析，聚合物的分子量为20万，高于目前常见间位芳纶聚合物分子量。
实施例4
首先将融化态间苯二胺300kg加入到极性溶剂二甲基乙酰胺2600kg中，经降温冷却， 温度达到-10℃后，经计量进入管道反应器中，然后分2次加入融化态间苯二甲酰氯，预聚合过程中间苯二甲酰氯的添加量为535kg，占总量的95％。
然后预聚物直接进入动态管道反应器中进行中和反应，使用氨气进行中和，氨气的添加量为85kg，控制中和后预聚物的pH为4.8。完成后预聚物进入缓冲罐，在缓冲罐对中和形成的氯化铵微粒进行循环过滤，直至预聚物澄清透明。
第二步聚合时将过滤透明的预聚物采用齿轮计量泵计量打入螺杆反应器，螺杆反应器的长度和直径的比值为55:1，其转动速度为260转/min；同时添加融化态间苯二甲酰氯，添加量为28kg(占总量的5％)，经过螺杆反应器后基本完成了聚合反应。
聚合完成后，以二乙胺中和聚合过程生成的氯化氢，产生的氯化有机胺可很好的溶于聚合物溶液中，并且有助于聚合物溶液的稳定性；此时聚合物溶液中盐分含量约为1.5％，聚合物再进入储罐，并对其粘度进行自动检测，聚合物表观粘度约为80Pa·S，聚合物溶液经过过滤、脱泡等工序后直接用于纺丝，获得间位芳纶纤维。
经GPC检测分析，聚合物的分子量为19万，高于目前常见间位芳纶聚合物分子量。
实施例5
首先将融化态间苯二胺300kg加入到极性溶剂二甲基甲酰胺2800kg中，经降温冷却，温度达到-3℃后，经计量进入管道反应器中，然后分2次加入融化态间苯二甲酰氯，预聚合过程中间苯二甲酰氯的添加量为480kg，占总量的85.3％。
然后预聚物直接进入动态管道反应器中进行中和反应，使用氨气进行中和，氨气的添加量为85kg，控制中和后预聚物的pH为5。完成后预聚物进入缓冲罐，在缓冲罐对中和形成的氯化铵微粒进行循环过滤，直至预聚物澄清透明。
第二步聚合时将过滤透明的预聚物采用齿轮计量泵计量打入螺杆反应器，螺杆反应器的长度和直径的比值为60:1，其转动速度为300转/min；同时添加融化态间苯二甲酰氯，添加量为83kg(占总量的14.7％)，经过螺杆反应器后基本完成了聚合反应。
聚合完成后，以三乙胺中和聚合过程生成的氯化氢，产生的氯化有机胺可很好的溶于聚合物溶液中，并且有助于聚合物溶液的稳定性；此时聚合物溶液中盐分含量约为2.5％，聚合物再进入储罐，并对其粘度进行自动检测，聚合物表观粘度约为70Pa·S，聚合物溶液经过过滤、脱泡等工序后直接用于纺丝，获得间位芳纶纤维。
经GPC检测分析，聚合物的分子量为18万，高于目前常见间位芳纶聚合物分子量。
对比实验
对比例1：采用专利CN201210138473.9中提及的聚合方法进行制备；
对比例2：采用专利CN201010227716.7中提及的聚合方法进行制备；
对比例3：采用专利CN106046364A中提及的聚合方法进行制备；
对比例4：将实施例1中的第一步中和过程中的氨水替换为有机胺；
对比例5：将实施例1中的第二步中和过程中的有机胺替换为氨水；
对比例6：将实施例1中的第一步中和反应在20℃下进行；
对比例7：将实施例1中的第二步中和反应在20℃下进行。
将实施例1-5以及对比例1-7获得的聚合物经纺丝形成的间位芳纶纤维进行性能检测，检测结果请参阅下表：
Figure PCTCN2018124472-appb-000001
从上表可以看出，实施例1-5获得的综合性能明显由于对比例1-7，其中，对比例1-4的盐分含量明显高于实施例1-5，并且分子量低，而对比例5-7的稳定性不佳，其综合性能仍然差于实施例1-5。
综上所述，本实施例中通过将间苯二甲酰和间苯二胺依次进行第一次聚合反应、第一次中和反应、第二次聚合反应以及第二次中和反应，并且控制第一次中和反应和第二次中和反应所用的中和剂不同，分别为氨气和有机胺，经过氨气中和后，可通过循环过滤排出中和后的氯化铵微粒，降低聚合原液的粘度和盐分含量，有利于制备高浓度高分子量的聚 间苯二甲酰间苯二胺聚合物溶液，第二步中和以有机胺中和聚合生成的氯化氢，产生的氯化有机胺可很好的溶于聚合物溶液中，并且有助于聚合物溶液的稳定性。相比两步法的间歇式聚合，具有流程简单、聚合设备紧凑，聚合条件稳定、能耗小、投资小、操作弹性大、聚合物质量高等优点，提高了聚合物的均匀性，是制备和生产高品质纤维产品的重要基础。
工业实用性
本实施例提供的制备高性能聚间苯二甲酰间苯二胺的连续聚合方法相比两步法的间歇式聚合，具有流程简单、聚合设备紧凑，聚合条件稳定、能耗小、投资小、操作弹性大、聚合物质量高等优点，提高了聚合物的均匀性，是制备和生产高品质纤维产品的重要基础。

Claims (15)

  1. 一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于，包括预聚、中和、聚合、中和、过滤过程，其特征在于：所述聚合过程和中和过程均为两步，其中第一步中和采用氨气，第二步中和采用有机胺。
  2. 根据权利要求1所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于，将间苯二胺与极性溶剂混合，加入占苯二甲酰氯总量的80-95％的间苯二甲酰氯，接着加入氨气进行中和，得到预聚物，过滤去除所述预聚物中的中和形成的氯化铵；接着向所述预聚物中加入剩余的5-20％的融化态间苯二甲酰氯，聚合完成后，以有机胺中和聚合生成的氯化氢。
  3. 根据权利要求2所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于，用所述有机胺中和聚合生成的氯化氢之后，还包括对聚合物进行粘度调制，所述聚合物的粘度通过加入间苯二甲酰氯调整至30-100Pa·S。
  4. 根据权利要求3所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于，所述聚合物的粘度通过加入间苯二甲酰氯调整至40-80Pa·S。
  5. 根据权利要求2所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于，所述间苯二胺和所述间苯二甲酰氯均以融化态计量并加入。
  6. 根据权利要求2所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于，将所述间苯二胺加入至所述极性溶剂中时，所述间苯二胺的浓度为9-11％。
  7. 根据权利要求2所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于：所述极性溶剂包括二甲基乙酰胺和二甲基甲酰胺中的一种或两种。
  8. 根据权利要求1所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于：
    首先将融化态间苯二胺加入到含有极性溶剂的调配罐中，浓度控制在9-11％；经混合后，进入预聚合反应器中，然后向预聚合反应器中分段加入融化态间苯二甲酰氯，间苯二甲酰氯的添加量占其总量的80-95％；然后在中和反应器中通入氨气进行中和反应，完成后的预聚物进入缓冲罐并对中和形成的氯化铵微粒进行循环过滤，直至预聚物澄清透明；
    将缓冲罐中的预聚物打入聚合反应器，同时添加剩余的5-20％的融化态间苯二甲酰氯，在聚合反应器中完成聚合反应；聚合完成后，以有机胺中和聚合生成的氯化氢，所述有机胺为乙胺或三乙胺，生成的氯化有机胺溶于聚合物溶液中无须去除；此时，聚合物中盐含量低于2％；
    聚合物再进入储罐，并对其粘度进行检测，根据需求和目标控制决定是否添加极少量的间苯二甲酰氯进行粘度微调以满足纺丝需求；间位芳纶湿法纺丝的聚合物粘度一般控制在40-80Pa·S，聚合物溶液经过过滤、脱泡等工序后能够直接用于纺丝。
  9. 根据权利要求1所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于：预聚、两步中和过程及第二步聚合过程均在低温条件下完成，采用冷媒降温，温度控制在-10～0℃。
  10. 根据权利要求1所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于：预聚、两步中和过程在动态管道反应器中完成，第二步聚合过程在双螺杆反应器完成。
  11. 根据权利要求10所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于：所述双螺杆反应器的长度和直径的比例为40-60:1。
  12. 根据权利要求10所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于：所述双螺杆反应器的转速为200-300转/分。
  13. 根据权利要求1所述一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法，其特征在于：所述有机胺包括乙胺、乙二胺、三乙胺和二乙胺中的一种或几种。
  14. 一种间位芳纶纤维，其特征在于，其是由如权利要求1-13任一项所述的高性能聚间苯二甲酰间苯二胺的连续聚合方法聚合而成的聚间苯二甲酰间苯二胺聚合物经纺丝而成。
  15. 一种阻燃耐高温防护材料，其特征在于，其是由如权利要求14所述的间位芳纶纤维制成。
PCT/CN2018/124472 2018-10-24 2018-12-27 一种制备高性能聚间苯二甲酰间苯二胺的连续聚合方法 WO2020082589A1 (zh)

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