WO2022183604A1 - 一种预聚-乳化全连续制备水性聚氨酯的方法 - Google Patents

一种预聚-乳化全连续制备水性聚氨酯的方法 Download PDF

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WO2022183604A1
WO2022183604A1 PCT/CN2021/095919 CN2021095919W WO2022183604A1 WO 2022183604 A1 WO2022183604 A1 WO 2022183604A1 CN 2021095919 W CN2021095919 W CN 2021095919W WO 2022183604 A1 WO2022183604 A1 WO 2022183604A1
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parts
stage
emulsification
chain extender
reaction
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French (fr)
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陈意
周帅
范浩军
颜俊
李成祥
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Sichuan University
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    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Definitions

  • the invention relates to a method for preparing water-based polyurethane by prepolymerization and emulsification, and belongs to the field of polymer materials.
  • Waterborne polyurethane was introduced in the 1960s, and it is a new type of polyurethane system that uses water instead of organic solvents as the dispersion medium. Compared with traditional solvent-based polyurethane, water-based polyurethane only volatilizes water into the atmosphere during use, which is environmentally friendly and meets the requirements of modern green chemical processes; at the same time, because the dispersion medium is water, water-based polyurethane is also non-toxic, non-flammable, and difficult It can replace traditional solvent-based polyurethane and is widely used in leather, synthetic leather, biomedical, furniture, automobile and aerospace and other fields. It is a new material developed by the country.
  • the most commonly used production process of water-based polyurethane is batch production, that is, a polyurethane prepolymer with a hydrophilic group in the main chain is first synthesized in a prepolymerization reactor, and then the material is transferred to a dispersion tank and emulsified with water.
  • This production process mainly has the following shortcomings: (1) the reaction time is long (6-8 hours), the production efficiency is low, and the production cost is high; (2) the production relies too much on labor, and the degree of automation is low; (3) the product quality is unstable, There is a large gap between batches; (4) In order to facilitate emulsification, a low-boiling organic solvent must be added to the prepolymer to reduce the viscosity, and after emulsification, the solvent is removed by vacuum distillation, resulting in increased energy consumption and waste of resources; (5) The product is solid The low content results in high drying and shipping costs.
  • Patents CN202011253943.7, CN201310255840.8, CN201711045576.X, CN201711049518.4, CN201210116805.3 all use twin-screw extruder as the reactor for water-based polyurethane synthesis, which can realize continuous production of water-based polyurethane. Since the twin-screw extruder is characterized by high production efficiency and short action time, the above patent can only shorten the reaction time by increasing the reaction temperature (the reaction temperature even exceeds 200°C).
  • the temperature of the polyurethane reaction is generally in the range of 70-90 °C, especially in the later stage of the reaction, if the temperature exceeds 90 °C, side reactions such as branching and cross-linking will be triggered, the ratio of raw materials will be destroyed, and the product structure will be out of control. Emulsification also affects product quality.
  • the present invention provides a method for preparing water-based polyurethane by pre-polymerization-emulsification, characterized in that the process steps and conditions of the method are as follows, and the parts of materials used are all parts by weight number:
  • the material enters the second stage ultrasonic treatment zone, the ultrasonic intensity is 200-300W/cm 2 , the frequency is 25-30kHz, the reaction temperature is controlled at 70-80 °C, and the reaction time is 3-6min;
  • the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 200-400r/min, the number of cycles is 30-50 times, and the emulsification time is 20-40min, and water-based polyurethane is obtained after emulsification;
  • the ratio of the length L to the diameter D of the twin-screw reactor screw is 15 ⁇ L/D ⁇ 30, and the rotational speed is 200-300rmp;
  • the diisocyanate described in step (1) is one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate and hexamethylene diisocyanate. one or more;
  • the dihydric alcohol described in step (1) is polybutylene adipate diol, polyethylene adipate diol, polypropylene glycol, polyethylene glycol, polycarbonate with a number-average molecular weight of 500-8000 One or more of ethylene glycol and polypropylene carbonate glycol;
  • the small molecule chain extender described in step (1) is one or more of 1,4-butanediol, 1,3-propanediol, ethylene glycol, ethylenediamine, and 1,4-butanediamine;
  • the hydrophilic chain extender described in step (1) is dimethylol propionic acid, dimethylol butyric acid, methyldiethanolamine, sodium ethylenediaminoethanesulfonate, 1,4-butanediol-2 - one or more of sodium sulfonate;
  • the catalyst described in step (1) is one or more of dibutyltin dilaurate, bismuth isooctanoate, bismuth laurate, and bismuth neodecanoate;
  • the neutralizing agent described in the step (4) refers to a compound that neutralizes the hydrophilic group in the hydrophilic chain extender into an ionic group;
  • Chain agent, neutralizer is one or more of triethylamine, dimethylethanolamine, for methyldiethanolamine hydrophilic chain extender, neutralizer is one or more of formic acid, acetic acid, for Sodium ethylenediamine ethanesulfonate, 1,4-butanediol-2-sodium sulfonate hydrophilic chain extender, no neutralizer is needed;
  • the post-chain extender described in step (5) is one or more of ethylenediamine, hexamethylenediamine, hydrazine hydrate, and p-phenylenediamine.
  • the reaction degree of the water-based polyurethane is about 15-20% after the pre-reaction for 2-4 minutes under the conditions of step (1) in the claims (100-150° C.), although the temperature is relatively high in this stage. , but with few side effects.
  • step (1) the conditions of step (1) in the claims (100-150° C.)
  • step (2) under the cavitation of ultrasonic, the reactivity of isocyanate group with hydroxyl and amino groups in the material will be greatly improved;
  • the whole reaction can be completed by reacting in the twin-screw reactor for 5-8min. Since the reaction temperature in the later stage is the same as that of the traditional batch process, the problems of increased by-products and uncontrolled product structure caused by high temperature in the later stage are avoided.
  • the addition timing and conditions of the ultrasonic treatment zone must be strictly limited.
  • the reaction activity of the material is not improved enough, and the low temperature of the third stage at 70-80 °C cannot promote the reaction to 100% in a short time; if the second stage ultrasonic treatment is too late, the material If the reactivity is increased excessively, a large number of side reactions will occur in the third stage, the viscosity of the product will increase sharply, and even normal emulsification will not be possible.
  • the time, intensity, frequency and temperature of the second ultrasonic treatment must also be strictly limited to the conditions described in step (2) of the claims, otherwise the improvement of the reactivity of the material will be insufficient or excessive.
  • the process method involved in the present invention does not use any organic solvent, has no selectivity to raw materials, and is suitable for the synthesis of any type of water-based polyurethane.
  • hydrophilic chain extender methyldiethanolamine
  • the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 200W/cm 2 , the frequency is 25kHz, the reaction temperature is controlled at 70°C, and the reaction time is 6min;
  • the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 200r/min, the number of cycles is 35 times, and the emulsification time is 40min, and water-based polyurethane is obtained after emulsification;
  • hydrophilic chain extender dimethylol propionic acid
  • post-chain extender hydrazine hydrate
  • the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 300W/cm 2 , the frequency is 30kHz, the reaction temperature is controlled at 72°C, and the reaction time is 4min;
  • the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 300r/min, the number of cycles is 40 times, and the emulsification time is 30min, and water-based polyurethane is obtained after emulsification;
  • hydrophilic chain extender sodium 1,4-butanediol-2-sulfonate
  • the material enters the second-stage ultrasonic treatment zone, the ultrasonic intensity is 250W/cm 2 , the frequency is 25kHz, the reaction temperature is controlled at 78°C, and the reaction time is 3min;
  • reaction products 400 parts of reaction products, 400 parts of deionized water, 2 parts of post-chain extender (p-phenylenediamine) are simultaneously injected into the fifth-stage static mixer for pre-emulsification;
  • post-chain extender p-phenylenediamine
  • the material enters the sixth-stage tubular emulsifier, the circulating flow rate is 400r/min, the number of cycles is 40 times, and the emulsification time is 35min, and water-based polyurethane is obtained after emulsification;
  • Example Example 1 Example 2 Example 3 solid content 31% 45% 56% Emulsion viscosity (20°C) 245cP 420cP 580cP Modulus at 100% stretch 1.3 1.9 4.2 Tensile strength (MPa) 9 26 38 Elongation at break 840 930 1150

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明公开了一种预聚-乳化全连续制备水性聚氨酯的工艺方法。该方法以声化学强化的双螺杆挤出机作为水性聚氨酯预聚、中和反应器，以静态混合器、管式乳化器作为预聚体乳化装置，预聚、乳化全连续进行，生产效率高、成本低、产品质量稳定，尤其适用于高固含水性聚氨酯生产。更为重要的是，在双螺杆挤出机的特定区域，加装特殊超声发生器，对预聚中间体进行声化学处理，可显著提升物料反应活性，使预聚反应后期可在70-80℃低温条件下快速完成，生产工艺节能环保，也避免了后期高温导致的支化、交联、降解等副反应发生，获得的水性聚氨酯结构可控、品质稳定。上述工艺方法不使用任何有机溶剂，对原料无选择性，适用于任何类型水性聚氨酯的合成。

Description

一种预聚-乳化全连续制备水性聚氨酯的方法 技术领域
本发明涉及一种预聚-乳化全连续制备水性聚氨酯的方法，属于高分子材料领域。
背景技术
水性聚氨酯于上世纪60年代问世，是以水代替有机溶剂作为分散介质的新型聚氨酯体系。与传统溶剂型聚氨酯相比，水性聚氨酯在使用过程中仅有水挥发进入大气，环境友好，满足现代绿色化工过程要求；同时，由于分散介质为水，水性聚氨酯还具有无毒、不易燃、不易爆等特性，可取代传统溶剂型聚氨酯，广泛应用于皮革、合成革、生物医疗、家具、汽车及航空航天等领域，属国家重点发展的新材料。
目前，水性聚氨酯最常用的生产工艺为间歇式生产，即先在预聚反应釜中合成主链含亲水基团的聚氨酯预聚体，再将物料转移到分散釜中和并加水乳化。这种生产工艺主要存在如下缺点：(1)反应时间长(6-8小时)，生产效率低，生产成本高；(2)生产过度依赖人工，自动化程度低；(3)产品质量不稳定，各批次间差距较大；(4)为便于乳化，预聚体中须添加低沸点有机溶剂降低粘度，乳化后再减压蒸馏去除溶剂，造成能耗增加与资源浪费；(5)产品固含量低，导致干燥和运输费用成本高。
连续化生产可解决传统间歇式生产存在的瓶颈问题。专利 CN202011253943.7、CN201310255840.8、CN201711045576.X、CN201711049518.4、CN201210116805.3均采用双螺杆挤出机作为水性聚氨酯合成的反应器，可实现水性聚氨酯连续化生产。由于双螺杆挤出机的特点是生产效率高、作用时间短，上述专利只能通过提高反应温度(反应温度甚至超过了200℃)缩短反应时间。然而，聚氨酯反应的温度一般在70-90℃范围内，尤其是在反应后期，如温度超过90℃，会引发支化、交联等副反应，破坏原料配比，导致产品结构失控，既难于乳化，也影响产品品质。
发明内容
本发明是为了克服现有技术存在的缺点和不足，提供一种预聚-乳化全连续制备水性聚氨酯的方法，其特征在于该方法的工艺步骤和条件如下，所用物料的份数均为重量份数：
(1)将二异氰酸酯50-180份、二元醇80-300份、小分子扩链剂1-10份、亲水扩链剂5-20份、催化剂0.055-0.24份混合均匀，再预热至100-150℃，连续注入第一段双螺杆反应器，反应温度控制在100-150℃，反应时间2-4min；
(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为200-300W/cm 2，频率为25-30kHz，反应温度控制在70-80℃，反应时间3-6min；
(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在70-80℃，反应时间5-8min；
(4)第三段反应完毕后，物料与中和剂0-15份进入第四段双螺杆反 应器，反应温度控制在30-40℃，反应时间1-2min，获得中和产物；
(5)将中和产物、去离子水300-1100份、后扩链剂0-3份同时注入第五段静态混合器进行预乳化；
(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为200-400r/min，循环次数为30-50次，乳化时间为20-40min，乳化后得到水性聚氨酯；
步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为15≤L/D≤30，转速200-300rmp；
步骤(1)中所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、氢化甲苯二异氰酸酯、氢化二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种；
步骤(1)中所述二元醇为数均分子量在500-8000的聚己二酸丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚丙二醇、聚乙二醇、聚碳酸亚乙酯二醇、聚碳酸亚丙酯二醇中的一种或多种；
步骤(1)中所述小分子扩链剂为1,4-丁二醇、1,3-丙二醇、乙二醇、乙二胺、1,4-丁二胺中的一种或多种；
步骤(1)中所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、甲基二乙醇胺、乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠中一种或多种；
步骤(1)中所述催化剂为二月桂酸二丁基锡、异辛酸铋、月桂酸铋、新癸酸铋中的一种或多种；
步骤(4)中所述中和剂是指将亲水扩链剂中的亲水基团中和成 离子基团的化合物；对于二羟甲基丙酸、二羟甲基丁酸亲水扩链剂，中和剂为三乙胺、二甲基乙醇胺中的一种或多种，对于甲基二乙醇胺亲水扩链剂，中和剂为甲酸、乙酸中的一种或多种，对于乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠亲水扩链剂，则无需中和剂；
步骤(5)中所述后扩链剂为乙二胺、己二胺、水合肼、对苯二胺中的一种或多种。
本发明所涉及的方法的原理是：
本发明经过大量实验后发现，在权力要求书步骤(1)条件(100-150℃)下预反应2-4min后，水性聚氨酯的反应程度约为15-20％，这一阶段虽温度较高，但副反应很少。在这一阶段后，如物料经过步骤(2)所述超声处理，在超声的空化作用下，物料中异氰酸酯基团与羟基、氨基的反应活性将大幅提升；后期只需在70-80℃的双螺杆反应器中反应5-8min，就可以完成全部反应。由于后期反应温度与传统间歇式工艺无异，避免了后期高温导致的副产物增多、产品结构失控问题。
需要指出的是，超声处理区的添加时机和条件须严格限制。实验发现，如第二段超声处理过早，对物料反应活性提升不够，第三段70-80℃低温无法在短时间内将反应推进至100％；如第二段超声处理过晚，对物料反应活性提升过度，在第三段会出现大量副反应，产物粘度暴增，甚至无法正常乳化。与此同时，第二段超声处理的时间、强度、频率、温度也须严格限定为权力要求书步骤(2)中所述条件，否者对物料反应活性的提升也会出现不足或过度。
与现有技术相比，本发明所涉及的方法的有益效果为：
(1)在第一、三段双螺杆反应器之间添加一超声处理区，严格限制超声处理的时间、强度、温度、频率，可显著提升水性聚氨酯预聚中间体的反应活性，使反应后期可在70-80℃低温条件下进行，同时反应时间不会大幅延长，保持了双螺杆挤出反应的高效性，生产方法节能环保，反应副反应少，产品结构可控；
(2)本发明的整个预聚、乳化过程全连续进行，生产效率高，自动化程度高，生产成本低，产品质量稳定，尤其适用于高固含水性聚氨酯生产；
(3)本发明涉及的工艺方法不使用任何有机溶剂，对原料无选择性，适用于任何类型水性聚氨酯的合成。
具体实施方式
下面通过实施例对本发明进行具体的描述，只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限定，该领域的技术工程师可根据上述发明的内容对本发明作出一些非本质的改进和调整。
实施例1：
配方：(重量份数)
80份聚合物二元醇：聚碳酸亚乙酯二醇(Mn＝3000)
50份二异氰酸酯：异佛尔酮二异氰酸酯
2份小分子扩链剂：1,3-丙二醇
5份亲水扩链剂：甲基二乙醇胺
0.055份催化剂：二月桂酸二丁基锡
300份去离子水
1.93份中和剂：甲酸
2份后扩链剂：乙二胺
制备方法：
(1)将异佛尔酮二异氰酸酯50份、聚碳酸亚乙酯二醇(Mn＝3000)80份、小分子扩链剂(1,3-丙二醇)2份、亲水扩链剂(甲基二乙醇胺)5份、催化剂(二月桂酸二丁基锡)0.055份混合均匀，再预热至100℃，连续注入第一段双螺杆反应器，反应温度控制在120℃，反应时间3min；
(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为200W/cm 2，频率为25kHz，反应温度控制在70℃，反应时间6min；
(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在70℃，反应时间8min；
(4)第三段反应完毕后，物料与1.93份中和剂(甲酸)进入第四段双螺杆反应器，反应温度控制在30℃，反应时间2min，获得中和产物；
(5)将中和产物、去离子水300份、后扩链剂(乙二胺)2份同时注入第五段静态混合器进行预乳化；
(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为200r/min，循环次数为35次，乳化时间为40min，乳化后得到水性聚氨酯；
步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为L/D＝20，转速200rmp。
实施例2：
配方：(重量份数)
200份聚合物二元醇：聚碳酸亚乙酯二醇(Mn＝2000)
100份二异氰酸酯：甲苯二异氰酸酯
6份小分子扩链剂：1,4-丁二醇
15份亲水扩链剂：二羟甲基丙酸
0.15份催化剂：异辛酸铋
400份去离子水
10份中和剂：二甲基乙醇胺
2.5份后扩链剂：水合肼
制备方法：
(1)将甲苯二异氰酸酯100份、聚碳酸亚乙酯二醇(Mn＝2000)200份、小分子扩链剂(1,4-丁二醇)6份、亲水扩链剂(二羟甲基丙酸)15份、催化剂(异辛酸铋)0.15份混合均匀，再预热至120℃，连续注入第一段双螺杆反应器，反应温度控制在130℃，反应时间3min；
(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为300W/cm 2，频率为30kHz，反应温度控制在72℃，反应时间4min；
(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在75℃，反应时间6min；
(4)第三段反应完毕后，物料与10份中和剂(二甲基乙醇胺)进入第四段双螺杆反应器，反应温度控制在35℃，反应时间1.5min，获得中和产物；
(5)将中和产物、去离子水400份、后扩链剂(水合肼)2.5份同时注入第五段静态混合器进行预乳化；
(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为300r/min，循环次数为40次，乳化时间为30min，乳化后得到水性聚氨酯；
步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为L/D＝25，转速250rmp。
实施例3：
配方：(重量份数)
300份聚合物二元醇：聚乙二醇(Mn＝2000)
180份二异氰酸酯：六亚甲基二异氰酸酯
8份小分子扩链剂：乙二醇
20份亲水扩链剂：1,4-丁二醇-2-磺酸钠
0.22份催化剂：月桂酸铋
400份去离子水
2份后扩链剂：对苯二胺
(1)将六亚甲基二异氰酸酯180份、聚乙二醇(Mn＝2000)300份、小分子扩链剂(乙二醇)8份、亲水扩链剂(1,4-丁二醇-2-磺酸钠)20份、催化剂(月桂酸铋)0.22份混合均匀，再预热至120℃，连续注入第一段双螺杆反应器，反应温度控制在140℃，反应时间2min；
(2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为250W/cm 2，频率为25kHz，反应温度控制在78℃，反应时间3min；
(3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在80℃，反应时间5min；
(4)第三段反应完毕后，物料直接进入第四段双螺杆反应器，反应温度控制在40℃，反应时间1min，获得反应产物；
(5)将反应产物、去离子水400份、后扩链剂(对苯二胺)2份同时注入第五段静态混合器进行预乳化；
(6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为400r/min，循环次数为40次，乳化时间为35min，乳化后得到水性聚氨酯；
步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为L/D＝20，转速300rmp。
实施例1-3所制得的水性聚氨酯的物性如下：
实施例 实施例1 实施例2 实施例3
固含量 31％ 45％ 56％
乳液粘度(20℃) 245cP 420cP 580cP
拉伸100％时模量 1.3 1.9 4.2
拉伸强度(MPa) 9 26 38
断裂伸长率 840 930 1150

Claims (1)

  1. 一种预聚-乳化全连续制备水性聚氨酯的方法，其特征在于该方法的工艺步骤和条件如下，所用物料的份数均为重量份数：
    (1)将二异氰酸酯50-180份、二元醇80-300份、小分子扩链剂1-10份、亲水扩链剂5-20份、催化剂0.055-0.24份混合均匀，再预热至100-150℃，连续注入第一段双螺杆反应器，反应温度控制在100-150℃，反应时间2-4min；
    (2)第一段反应完毕后，物料进入第二段超声处理区，超声强度为200-300W/cm 2，频率为25-30kHz，反应温度控制在70-80℃，反应时间3-6min；
    (3)第二段反应完毕后，物料进入第三段双螺杆反应器，反应温度控制在70-80℃，反应时间5-8min；
    (4)第三段反应完毕后，物料与中和剂0-15份进入第四段双螺杆反应器，反应温度控制在30-40℃，反应时间1-2min，获得中和产物；
    (5)将中和产物、去离子水300-1100份、后扩链剂0-3份同时注入第五段静态混合器进行预乳化；
    (6)预乳化完毕后，物料进入第六段管式乳化器，循环流速为200-400r/min，循环次数为30-50次，乳化时间为20-40min，乳化后得到水性聚氨酯；
    步骤(1)、(3)、(4)中所述双螺杆反应器螺杆的长度L与直径D比为15≤L/D≤30，转速200-300rmp；
    步骤(1)中所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异 氰酸酯、二苯基甲烷二异氰酸酯、氢化甲苯二异氰酸酯、氢化二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种；
    步骤(1)中所述二元醇为数均分子量在500-8000的聚己二酸丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚丙二醇、聚乙二醇、聚碳酸亚乙酯二醇、聚碳酸亚丙酯二醇中的一种或多种；
    步骤(1)中所述小分子扩链剂为1,4-丁二醇、1,3-丙二醇、乙二醇、乙二胺、1,4-丁二胺中的一种或多种；
    步骤(1)中所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、甲基二乙醇胺、乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠中一种或多种；
    步骤(1)中所述催化剂为二月桂酸二丁基锡、异辛酸铋、月桂酸铋、新癸酸铋中的一种或多种；
    步骤(4)中所述中和剂是指将亲水扩链剂中的亲水基团中和成离子基团的化合物；对于二羟甲基丙酸、二羟甲基丁酸亲水扩链剂，中和剂为三乙胺、二甲基乙醇胺中的一种或多种，对于甲基二乙醇胺亲水扩链剂，中和剂为甲酸、乙酸中的一种或多种，对于乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠亲水扩链剂，则无需中和剂；
    步骤(5)中所述后扩链剂为乙二胺、己二胺、水合肼、对苯二胺中的一种或多种。
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