CN103405802A

CN103405802A - Preparation method of polyurethane bandage with functions of sterilization and itch relief and bandage manufactured by method

Info

Publication number: CN103405802A
Application number: CN2012102404960A
Authority: CN
Inventors: 王栋; 陆莹; 沈博强; 胡修元; 张新强
Original assignee: SHAOXING LIDE BIOTECHNOLOGY Co Ltd
Current assignee: Zhejiang Stange Sports Medical Technology Co ltd
Priority date: 2012-07-12
Filing date: 2012-07-12
Publication date: 2013-11-27
Anticipated expiration: 2032-07-12
Also published as: CN103405802B

Abstract

一种具有杀菌止痒的医用聚氨酯绷带的制备方法，包括如下步骤：先制备聚氨酯预聚体和具有杀菌止痒功能的壳聚糖微球或壳聚糖季铵盐，再将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下进行涂覆壳聚糖微球或壳聚糖季铵盐。利用该方法制得的绷带包括基材、涂覆在基材上的聚氨酯预聚体、包含杀菌止痒功能的壳聚糖微球或壳聚糖季铵盐，所以相比于传统的固定绷带，具有塑形性好、强度高，同时又具有重量轻、价廉美观等优点，而且可以有效杀灭皮肤表面的细菌，防止皮肤红肿瘙痒，为患者提供干燥舒适的康复环境。A preparation method of a medical polyurethane bandage with bactericidal and antipruritic properties, comprising the following steps: first preparing a polyurethane prepolymer and chitosan microspheres or chitosan quaternary ammonium salts with bactericidal and antipruritic functions, and then making the polyurethane prepolymer Evenly coated on the base cloth, the base cloth coated with polyurethane prepolymer is then coated with chitosan microspheres or chitosan quaternary ammonium salt under the guidance of the guide cylinder. The bandage prepared by this method includes a base material, a polyurethane prepolymer coated on the base material, chitosan microspheres or chitosan quaternary ammonium salts containing bactericidal and antipruritic functions, so compared with traditional fixed bandages , has the advantages of good shaping, high strength, light weight, low price and beautiful appearance, and can effectively kill bacteria on the skin surface, prevent skin redness, swelling and itching, and provide patients with a dry and comfortable rehabilitation environment.

Description

Preparation method of bactericidal and antipruritic polyurethane bandage and bandage prepared by the method

技术领域 technical field

本发明涉及医疗卫生用品技术领域，尤其是涉及一种具有杀菌止痒功能的水扩链的医用聚氨酯绷带的制备方法，及利用该方法制得的绷带。The invention relates to the technical field of medical and sanitary products, in particular to a method for preparing a water chain-extended medical polyurethane bandage with the function of sterilizing and relieving itching, and the bandage prepared by the method.

背景技术 Background technique

八十年代初，Bayer公司首先提出在网眼织物上涂覆聚氨酯预聚体制成绷带，这在骨科治疗领域中格式一个重大的发展。这种绷带的使用方法就是将绷带先与室温下的水接触，然后缠绕到患者的患部，涂覆在基布上的聚氨酯预聚体会与水反应由最初柔软的塑性绷带逐渐变硬，一定时间后形成刚性材料固定住患者患部，此时绷带具有很高的强度其形状也不能再改变。由于该绷带具有重量轻、强度高、X射线透过性好等优点，已在许多医疗卫生部门广泛应用。In the early 1980s, Bayer first proposed coating polyurethane prepolymers on mesh fabrics to make bandages, which was a major development in the field of orthopedic treatment. The method of using this bandage is to contact the bandage with water at room temperature first, and then wrap it around the affected part of the patient. The polyurethane prepolymer coated on the base cloth will react with water and gradually harden from the initially soft plastic bandage. Finally, a rigid material is formed to fix the patient's affected part. At this time, the bandage has a high strength and its shape cannot be changed. Because the bandage has the advantages of light weight, high strength, and good X-ray permeability, it has been widely used in many medical and health departments.

但在实际应用中我们发现国内外的聚氨酯绷带产品易导致皮肤红肿瘙痒等过敏现象，由于聚氨酯绷带一般使用层数为5-8层，虽然透气性比严实的石膏绷带好，但在炎热的夏天或者对于皮肤敏感者，患者皮肤就会因绷带透气性不够好而有瘙痒红肿的现象发生；再者现有的聚氨酯绷带的原材料昂贵，生产成本较高。However, in practical applications, we found that polyurethane bandage products at home and abroad can easily cause skin redness, swelling, itching and other allergic phenomena. Since polyurethane bandages generally use 5-8 layers, although the air permeability is better than that of tight plaster bandages, it is not suitable for use in hot summer. Or for those with sensitive skin, the patient's skin will have the phenomenon of itching, redness and swelling because of the poor air permeability of the bandage; moreover, the raw materials of the existing polyurethane bandage are expensive, and the production cost is relatively high.

发明内容 Contents of the invention

本发明为了克服现有技术的不足，提供一种具有杀菌止痒功能的绷带的制备方法，本发明的制备方法制造成本低廉，制备出的聚氨酯绷带能缓释杀菌止痒的药物，解决患者因皮肤敏感的带来的红肿瘙痒等困扰。In order to overcome the deficiencies of the prior art, the present invention provides a preparation method of a bandage with bactericidal and antipruritic functions. The preparation method of the present invention has low manufacturing cost, and the prepared polyurethane bandage can slowly release the bactericidal and antipruritic medicine, which solves the problem of patients with Redness, swelling, itching and other troubles caused by sensitive skin.

为了实现上述目的，本发明采用以下技术方案：一种具有杀菌止痒的医用聚氨酯绷带的制备方法，包括如下步骤：In order to achieve the above object, the present invention adopts the following technical solutions: a preparation method of a medical polyurethane bandage with sterilization and antipruritic, comprising the steps of:

1)聚氨酯预聚体的制备1) Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入芳香族二异氰酸酯100份、稳定剂0.1-5份和有机硅消泡剂0.5-5份，在25-50℃下搅拌30min后，缓慢加入15-70份的成分A，继续加热搅拌30-120min后逐滴加入10-55份的成分B，反应1-3h后加入催化剂1-8份，润滑剂3-10份，继续加热搅拌10-90min；所述成分A为分子量为800-1100的聚醚二元醇或分子量为300-600聚醚三元醇，所述成分B为分子量为1800-2200的聚醚二元醇；Add 100 parts of aromatic diisocyanate, 0.1-5 parts of stabilizer and 0.5-5 parts of silicone defoamer in a four-port reaction kettle with agitator and thermometer, and feed it with high-purity nitrogen. After stirring for 30 minutes, slowly add 15-70 parts of component A, continue heating and stirring for 30-120 minutes, then add 10-55 parts of component B dropwise, react for 1-3 hours, add 1-8 parts of catalyst, 3-10 parts of lubricant part, continue heating and stirring for 10-90min; the component A is a polyether diol with a molecular weight of 800-1100 or a polyether triol with a molecular weight of 300-600, and the component B is a polyether polyol with a molecular weight of 1800-2200 dihydric alcohol;

2）具有杀菌止痒功能的壳聚糖微球或壳聚糖季铵盐的制备2) Preparation of chitosan microspheres or chitosan quaternary ammonium salt with bactericidal and antipruritic functions

具有杀菌止痒药物的壳聚糖微球的制备：Preparation of chitosan microspheres with bactericidal and antipruritic drugs:

a.将壳聚糖50份溶解于质量分数为0.5-15%醋酸溶液中,搅拌至壳聚糖完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；a. Dissolve 50 parts of chitosan in 0.5-15% acetic acid solution with a mass fraction of 0.5-15%, stir until the chitosan is completely dissolved, and centrifuge to coagulate the chitosan solution; after standing for 36 hours, filter under reduced pressure, and use anhydrous After washing with ethanol to neutrality, dry in a constant temperature drying oven to obtain chitosan microspheres;

b.称取上述制备的壳聚糖微球1-5份，用10-50份质量分数为0.1-10%醋酸溶液搅拌溶解,形成A液；b. Take 1-5 parts of chitosan microspheres prepared above, stir and dissolve with 10-50 parts of mass fraction of 0.1-10% acetic acid solution to form A solution;

c.取杀菌止痒药物0.5-2份，用5-20份无水乙醇搅拌溶解,形成B液；c. Take 0.5-2 parts of antibacterial and antipruritic drugs, stir and dissolve with 5-20 parts of absolute ethanol to form B liquid;

d.取c步骤中的B液1-5份，缓慢匀速滴入10-20份的A液中,剧烈搅拌10min,形成C液；在C液中滴加质量分数为10-50%戊二醛水溶液5-10份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥，即得具有杀菌止痒功能的壳聚糖微球；d. Take 1-5 parts of liquid B in step c, drop slowly and uniformly into 10-20 parts of liquid A, stir vigorously for 10 minutes to form liquid C; add 10-50% pentadiol dropwise to liquid C 5-10 parts of aldehyde aqueous solution, cross-linked and solidified for 12 hours, then centrifugally settled, and the precipitate was washed and dried again to obtain chitosan microspheres with bactericidal and antipruritic functions;

具有杀菌止痒功能的壳聚糖季铵盐的制备：Preparation of chitosan quaternary ammonium salt with bactericidal and antipruritic functions:

a.在10-50份乙醇、丙酮或异丙醇介质中，加入1-15份质量分数为10-30%的氢氧化钠或碳酸钠作为缚酸剂，加入季铵化试剂环氧丙烷或溴丙烷2-15份，壳聚糖5-40份进行接枝改性，得到壳聚糖季铵盐物料；a. In 10-50 parts of ethanol, acetone or isopropanol medium, add 1-15 parts of sodium hydroxide or sodium carbonate with a mass fraction of 10-30% as an acid-binding agent, and add quaternization reagent propylene oxide or 2-15 parts of bromopropane and 5-40 parts of chitosan are grafted and modified to obtain chitosan quaternary ammonium salt material;

b.将上述壳聚糖季铵盐物料，用甲醇及/或乙醇水溶液洗涤，从而得到部分除盐的含季铵化壳聚糖的固体物料后，用去离子水或蒸馏水溶解，再置于透析袋中于蒸馏水中进行透析除盐；b. the above-mentioned chitosan quaternary ammonium salt material is washed with methanol and/or ethanol aqueous solution to obtain a partially desalinated solid material containing quaternized chitosan, dissolved in deionized water or distilled water, and placed in Dialysis in distilled water to remove salt in the dialysis bag;

c.透析除盐后减压浓缩或常压直接浓缩以生成含壳聚糖季铵盐30%-80%的浓溶液，再用无水乙醇及/或丙酮沉淀出壳聚糖季铵盐湿物料，最后用无水乙醇及/或丙酮洗涤壳聚糖季铵盐湿物料,干燥后即可得到壳聚糖季铵盐产品；c. After dialysis and desalination, concentrate under reduced pressure or directly concentrate under normal pressure to generate a concentrated solution containing 30%-80% of chitosan quaternary ammonium salt, and then use absolute ethanol and/or acetone to precipitate chitosan quaternary ammonium salt. Material, finally wash the wet material of chitosan quaternary ammonium salt with absolute ethanol and/or acetone, after drying, the chitosan quaternary ammonium salt product can be obtained;

3)含有杀菌止痒药物的聚氨酯绷带的制备3) Preparation of polyurethane bandage containing bactericidal and antipruritic drugs

将步骤1中制得的聚氨酯预聚体升温到55℃，在空气湿含量低于10%的氮气保护环境下，采用带加温的双槽盛液，分别为盛装聚氨酯预聚体的A槽和盛装含有杀菌止痒功能壳聚糖微球或者壳聚糖季铵盐的B槽，基布先经过A槽将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下经过B槽，对涂有聚氨酯预聚体的基布进行功能化处理，均匀粘附具有杀菌止痒功能的壳聚糖微球或壳聚糖季铵盐，再在送布、辊压等工艺处理后进行收卷、剪切再用铝塑复合袋包装。Raise the temperature of the polyurethane prepolymer prepared in step 1 to 55°C, and in a nitrogen protection environment with an air moisture content lower than 10%, use a heated double tank to hold the liquid, which is the tank A for the polyurethane prepolymer And tank B containing chitosan microspheres or chitosan quaternary ammonium salts with bactericidal and antipruritic functions. The base cloth first passes through tank A to evenly coat the polyurethane prepolymer on the base cloth. Under the guidance of the guide cylinder, the base fabric passes through the B groove, and the base fabric coated with polyurethane prepolymer is functionalized, and the chitosan microspheres or chitosan quaternary ammonium salt with bactericidal and antipruritic functions are evenly adhered. After processing such as cloth feeding and rolling, it is rewound, cut and packed in aluminum-plastic composite bags.

作为优选，所述催化剂选自二甲基乙醇胺，有机锡催化剂，三亚乙基二胺，二甲基苄胺，双(2，2-吗啉乙基)醚，二甲基氨基乙醇，四甲基二丙稀三胺，二甲基二乙醇胺，二甲胺基丙胺二异丙醇中的一种。As preferably, the catalyst is selected from dimethylethanolamine, organotin catalyst, triethylenediamine, dimethylbenzylamine, bis(2,2-morpholine ethyl) ether, dimethylaminoethanol, tetramethyl One of dipropylene triamine, dimethyldiethanolamine, dimethylaminopropylamine diisopropanol.

作为优选，所述稳定剂选自丙酰氯、苯甲酰氯、甲基磺酸、马来酸酐中的一种；所述润滑剂为硅油润滑剂或者聚氧化乙烯。Preferably, the stabilizer is selected from one of propionyl chloride, benzoyl chloride, methanesulfonic acid, and maleic anhydride; the lubricant is silicone oil lubricant or polyethylene oxide.

作为优选，所述芳香族二异氰酸酯选自4，4'-二苯基甲烷二异氰酸酯、2，4'-二苯基甲烷二异氰酸酯、2，2'-二苯基甲烷二异氰酸酯、甲苯-2,4-二异氰酸酯中的一种。Preferably, the aromatic diisocyanate is selected from 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, toluene-2 , One of the 4-diisocyanates.

作为优选，所述聚醚二元醇为聚丙二醇或聚四氢呋喃二醇。Preferably, the polyether diol is polypropylene glycol or polytetrahydrofuran diol.

作为优选，所述成分A为分子量为800-1100的聚醚二元醇,所述成分B为分子量为1800-2200的聚醚二元醇，成分A与成分B的质量比为1：0.57。Preferably, the component A is polyether diol with a molecular weight of 800-1100, the component B is polyether diol with a molecular weight of 1800-2200, and the mass ratio of component A to component B is 1:0.57.

作为优选，所述成分A为63份。Preferably, the component A is 63 parts.

作为优选，所述杀菌止痒药物选自氯己定、阿莫西林、四环素、桉叶油、复方吲哚美辛酊、水杨酸甲酯、丙酸倍氯米松中的一种或多种的组合。Preferably, the bactericidal and antipruritic drug is selected from one or more of chlorhexidine, amoxicillin, tetracycline, eucalyptus oil, compound indomethacin tincture, methyl salicylate, and beclomethasone dipropionate The combination.

本发明还提供另一技术方案：一种采用上述制备方法制得的绷带，所述绷带包括基材、涂覆在基材上的聚氨酯预聚体、包含杀菌止痒功能的壳聚糖微球或壳聚糖季铵盐。The present invention also provides another technical solution: a bandage prepared by the above-mentioned preparation method, the bandage includes a base material, a polyurethane prepolymer coated on the base material, and chitosan microspheres containing bactericidal and antipruritic functions Or chitosan quaternary ammonium salt.

作为优选，所述绷带的单位重量为95-110g/m²，横向伸长率为2.7-3.5%，纵向伸长率为10-20%。Preferably, the bandage has a unit weight of 95-110 g/m ² , a transverse elongation of 2.7-3.5%, and a longitudinal elongation of 10-20%.

本发明所述芳香族二异氰酸酯中的“芳香族”可以是任何带有苯环的芳香族基团，由于芳香族二异氰酸酯主要用于聚氨酯预聚体，而本发明中聚氨酯预聚体是一种赋形剂（“excipient”）,又称为辅剂。带有苯环的芳香族基团可以使芳香族二异氰酸酯具有较强的物理结构，进而提高聚氨酯预聚体的物理结构强度和硬度。The "aromatic" in the aromatic diisocyanate of the present invention can be any aromatic group with a benzene ring, because the aromatic diisocyanate is mainly used in polyurethane prepolymers, and polyurethane prepolymers in the present invention are a An excipient ("excipient"), also known as an adjuvant. The aromatic group with benzene ring can make the aromatic diisocyanate have a stronger physical structure, thereby improving the physical structure strength and hardness of the polyurethane prepolymer.

本发明的有益效果：Beneficial effects of the present invention:

1.本发明的绷带制备方法，工艺简单，制造成本低廉，其聚醚采用分子量为1800-2200的二羟基聚醚或分子量为300-600的三羟基聚醚，与分子量为800-100的二羟基聚醚组合，其均为市面上易获得药品，制造方便，适合产量化生产。1. preparation method of bandage of the present invention, technique is simple, and manufacturing cost is cheap, and its polyether adopts the dihydroxy polyether that molecular weight is 1800-2200 or the trihydroxy polyether that molecular weight is 300-600, and the dihydroxy polyether that molecular weight is 800-100 Hydroxypolyether combination, all of which are readily available drugs on the market, are easy to manufacture, and are suitable for mass production.

2.利用该方法制备的绷带能提供给患者舒适骨科治疗条件，其中添加含壳聚糖季铵盐或带杀菌止痒药物的壳聚糖微球，绷带缠绕到患者患部后，壳聚糖季铵盐或从微球中缓慢释放出来的杀菌止痒药物能有效杀灭皮肤表面的细菌，防止皮肤红肿瘙痒，为患者提供干燥舒适的康复环境。该方法中壳聚糖季铵盐由于含有-N⁺-带正电荷，而细菌表面是带负电荷的，在聚氨酯绷带表面的壳聚糖季铵盐能有效的吸引细菌，同时烃基基团穿透细菌，达到有效杀菌的效果。2. The bandage prepared by this method can provide patients with comfortable orthopedic treatment conditions, wherein chitosan microspheres containing chitosan quaternary ammonium salt or band bactericidal and antipruritic drugs are added, and after the bandage is wrapped around the affected part of the patient, the chitosan quaternary Ammonium salts or bactericidal and antipruritic drugs slowly released from the microspheres can effectively kill bacteria on the skin surface, prevent skin redness, swelling and itching, and provide patients with a dry and comfortable recovery environment. In this method, the chitosan quaternary ammonium salt is positively charged due to the -N ⁺ -, and the surface of the bacteria is negatively charged. The chitosan quaternary ammonium salt on the surface of the polyurethane bandage can effectively attract bacteria, and at the same time, the hydrocarbon group wears Penetrate bacteria to achieve effective sterilization effect.

3.本方法制备的绷带由于遇水前能保持基布的柔韧性，遇水交联固化后又具有高强度，所以相比于传统的固定绷带，具有塑形性好、强度高，同时又具有重量轻、价廉美观等优点。3. The bandage prepared by this method can maintain the flexibility of the base cloth before encountering water, and has high strength after cross-linking and curing when encountering water. Therefore, compared with traditional fixed bandages, it has good plasticity, high strength, and at the same time It has the advantages of light weight, low price and beautiful appearance.

具体实施方式 Detailed ways

为了使本技术领域的人员更好的理解本发明方案，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。In order to enable those skilled in the art to better understand the solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below in conjunction with the embodiment of the present invention. Obviously, the described embodiment is only the embodiment of the present invention. Some, but not all, embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

实施例1Example 1

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4'-二苯基甲烷二异氰酸酯100份、苯甲酰氯稳定剂0.5份和有机硅消泡剂2.5份，在45℃下搅拌30min后，缓慢加入分子量为800-1100的聚丙二醇20份，继续加热搅拌60min后逐滴加入分子量为1800-2200的聚丙二醇35份，反应2h后加入催化剂二甲基乙醇胺3份，润滑剂硅油5份，继续加热搅拌15min后，即得聚氨酯预聚体。Add 100 parts of 4,4'-diphenylmethane diisocyanate, 0.5 parts of benzoyl chloride stabilizer and 2.5 parts of silicone defoamer After stirring at 45°C for 30 minutes, slowly add 20 parts of polypropylene glycol with a molecular weight of 800-1100, continue heating and stirring for 60 minutes, then add 35 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, and add the catalyst dimethylethanolamine after 2 hours of reaction 3 parts, lubricant silicone oil 5 parts, continue heating and stirring for 15 minutes to obtain polyurethane prepolymer.

②具有杀菌止痒药物的壳聚糖微球的制备②Preparation of chitosan microspheres with bactericidal and antipruritic drugs

将壳聚糖50份溶解于质量分数为5%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；称取上述制备的壳聚糖微球5份，用30份质量分数为0.1%醋酸溶液搅拌溶解,形成A液；取杀菌止痒药物阿莫西林1份，用10份无水乙醇搅拌溶解,形成B液；取B液2份，缓慢匀速滴入12份的A液中,剧烈搅拌10min,形成C液；在C液中滴加质量分数为10%戊二醛水溶液5份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥，即得具有杀菌止痒功能的壳聚糖微球；Dissolve 50 parts of chitosan in 5% acetic acid solution with a mass fraction of 5%, stir until completely dissolved, centrifuge and coagulate to obtain the chitosan solution; after standing for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral Dry in a constant temperature drying oven to obtain chitosan microspheres; weigh 5 parts of chitosan microspheres prepared above, stir and dissolve with 30 parts of 0.1% acetic acid solution with a mass fraction to form A liquid; 1 part of moxicillin was stirred and dissolved with 10 parts of absolute ethanol to form liquid B; 2 parts of liquid B was slowly and uniformly dropped into 12 parts of liquid A, and vigorously stirred for 10 minutes to form liquid C; The fraction is 5 parts of 10% glutaraldehyde aqueous solution, cross-linked and solidified for 12 hours, centrifuged and settled, and the sediment was washed and dried again to obtain chitosan microspheres with bactericidal and antipruritic functions;

③含有杀菌止痒药物壳聚糖微球的水扩链聚氨酯绷带的制备③Preparation of water chain-extended polyurethane bandage containing chitosan microspheres, a bactericidal and antipruritic drug

将①中制得的聚氨酯预聚体升温到55℃，在空气湿含量低于10%的氮气保护环境下，采用带加温的双槽盛液，分别为盛装聚氨酯预聚体的A槽和盛装含有杀菌止痒药物壳聚糖微球的B槽，涤纶纱线制成的基布先经过A槽将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下经过B槽，对涂有聚氨酯预聚体的基布进行功能化处理，均匀粘附具有杀菌止痒功能的壳聚糖微球，再在送布、辊压等工艺处理后进行收卷、剪切再用铝塑复合袋包装。Raise the temperature of the polyurethane prepolymer prepared in ① to 55°C, and in a nitrogen protection environment with an air moisture content lower than 10%, use a double tank with heating to hold the liquid, which is the tank A and the tank containing the polyurethane prepolymer respectively. Tank B containing chitosan microspheres, a bactericidal and antipruritic drug. The base fabric made of polyester yarn first passes through slot A to evenly coat the polyurethane prepolymer on the base fabric, and the base fabric coated with polyurethane prepolymer Then, under the guidance of the guide cylinder, it passes through the B groove, and the base cloth coated with polyurethane prepolymer is functionalized, and the chitosan microspheres with the function of sterilizing and antipruritic are evenly adhered, and then in the cloth feeding, rolling and other processes After treatment, it is rolled, cut and packed in aluminum-plastic composite bags.

实施例2Example 2

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入2，4'-二苯基甲烷二异氰酸酯100份、苯甲酰氯1.8份和有机硅消泡剂3.2份，在30℃下搅拌30min后，缓慢加入分子量为800-1100的聚四氢呋喃二醇18份，继续加热搅拌90min后逐滴加入分子量为1800-2200的聚丙二醇40份，反应2.5h后加入催化剂三亚乙基二胺1-8份，硅油润滑剂3-10份，继续加热搅拌50min后，即得聚氨酯预聚体。In a four-port reactor with a stirrer and a thermometer that feeds high-purity nitrogen, add 100 parts of 2,4'-diphenylmethane diisocyanate, 1.8 parts of benzoyl chloride and 3.2 parts of silicone defoamer. After stirring at 30°C for 30 minutes, slowly add 18 parts of polytetrahydrofuran diol with a molecular weight of 800-1100, continue heating and stirring for 90 minutes, then add 40 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, and add the catalyst triethylene glycol after 2.5 hours of reaction. 1-8 parts of diamine, 3-10 parts of silicone oil lubricant, and continue heating and stirring for 50 minutes to obtain a polyurethane prepolymer.

②具有杀菌止痒功能的壳聚糖季铵盐的制备②Preparation of chitosan quaternary ammonium salt with bactericidal and antipruritic functions

在10份丙酮介质中，加入5份质量分数为30%氢氧化钠作为缚酸剂，加入季铵化试剂环氧丙烷5份，壳聚糖20份进行接枝改性，得到壳聚糖季铵盐物料。将该物料用质量分数为10%的甲醇水溶液洗涤以部分除去物料中的盐分，从而得到部分除盐的含季铵化壳聚糖的固体物料后，用蒸馏水溶解，再置于透析袋中于蒸馏水中进行透析除盐。透析除盐后常压直接浓缩以生成含壳聚糖季铵盐的浓溶液，再用足量丙酮沉淀，将沉淀物用无水乙醇洗涤得壳聚糖季铵盐湿物料，再经干燥即可得到壳聚糖季铵盐产品。In 10 parts of acetone medium, add 5 parts of mass fraction of 30% sodium hydroxide as an acid-binding agent, add 5 parts of quaternizing agent propylene oxide, and 20 parts of chitosan for graft modification to obtain chitosan quaternary Ammonium salt material. The material is washed with 10% methanol aqueous solution to partially remove the salinity in the material, so as to obtain a partially desalinated solid material containing quaternized chitosan, dissolve it with distilled water, and then place it in a dialysis bag. Distilled water for dialysis to remove salt. After dialysis and desalination, concentrate directly under normal pressure to generate a concentrated solution containing chitosan quaternary ammonium salt, then precipitate with a sufficient amount of acetone, wash the precipitate with absolute ethanol to obtain chitosan quaternary ammonium salt wet material, and then dry it. Chitosan quaternary ammonium salt products can be obtained.

③含有杀菌止痒功能的壳聚糖季铵盐的水扩链聚氨酯绷带的制备③Preparation of water chain-extended polyurethane bandage containing chitosan quaternary ammonium salt with bactericidal and antipruritic functions

将①中制得的聚氨酯预聚体升温到55℃，在空气湿含量低于10%的氮气保护环境下，采用带加温的双槽盛液，分别为盛装聚氨酯预聚体的A槽和盛装含有杀菌止痒功能的壳聚糖季铵盐的B槽，涤纶纱线基布先经过A槽将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下经过B槽，对涂有聚氨酯预聚体的基布进行功能化处理，均匀粘附具有杀菌止痒功能的壳聚糖季铵盐，再在送布、辊压等工艺处理后进行收卷、剪切再用铝塑复合袋包装。Raise the temperature of the polyurethane prepolymer prepared in ① to 55°C, and in a nitrogen protection environment with an air moisture content lower than 10%, use a double tank with heating to hold the liquid, which is the tank A and the tank containing the polyurethane prepolymer respectively. Tank B containing chitosan quaternary ammonium salt with bactericidal and antipruritic functions, the polyester yarn base fabric first passes through tank A to evenly coat the polyurethane prepolymer on the base fabric, and then the base fabric coated with polyurethane prepolymer Under the guidance of the guide cylinder, it passes through the B groove, and the base cloth coated with polyurethane prepolymer is functionalized, and the chitosan quaternary ammonium salt with the function of sterilizing and antipruritic is evenly adhered, and then in the cloth feeding, rolling and other processes After treatment, it is rolled, cut and packed in aluminum-plastic composite bags.

实施例3Example 3

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4'-二苯基甲烷二异氰酸酯100份、丙酰氯4.2份和有机硅消泡剂3.5份，在20℃下搅拌30min后，缓慢加入分子量为300-600聚醚三元醇30份，继续加热搅拌70min后逐滴加入分子量为1800-2200的聚四氢呋喃二醇10份，反应1.5h后加入有机锡催化剂中的二丁基锡二月桂酸酯3份，硅油润滑剂5份，继续加热搅拌45min，即得聚氨酯预聚体。In a four-port reactor with a stirrer and a thermometer that is fed with high-purity nitrogen, add 100 parts of 4,4'-diphenylmethane diisocyanate, 4.2 parts of propionyl chloride and 3.5 parts of silicone defoamer. After stirring at ℃ for 30 minutes, slowly add 30 parts of polyether triol with a molecular weight of 300-600, continue heating and stirring for 70 minutes, then add 10 parts of polytetrahydrofuran diol with a molecular weight of 1800-2200 dropwise, react for 1.5 hours, and then add an organotin catalyst 3 parts of dibutyltin dilaurate and 5 parts of silicone oil lubricant in the mixture, and continue heating and stirring for 45 minutes to obtain a polyurethane prepolymer.

将壳聚糖50份溶解于15%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结。静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干即得壳聚糖微球。称取上述制备的壳聚糖微球2份，用25份质量分数为0.8%的醋酸溶液搅拌溶解,形成A液。取杀菌止痒药物四环素1.5份，用20份无水乙醇搅拌溶解,形成B液。将4份B液缓慢匀速滴入15份A液中,剧烈搅拌10min,形成C液。在C液中滴加20%戊二醛水溶液7份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥即得具有杀菌止痒功能的壳聚糖微球。Dissolve 50 parts of chitosan in 15% acetic acid solution, stir until completely dissolved, obtain chitosan solution, and centrifuge to coagulate. After standing still for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral, and then dry in a constant temperature drying oven to obtain chitosan microspheres. Weigh 2 parts of chitosan microspheres prepared above, stir and dissolve with 25 parts of 0.8% acetic acid solution by mass fraction to form A solution. Take 1.5 parts of tetracycline, a bactericidal and antipruritic drug, stir and dissolve with 20 parts of absolute ethanol to form liquid B. Slowly and uniformly drop 4 parts of liquid B into 15 parts of liquid A, and stir vigorously for 10 minutes to form liquid C. Add 7 parts of 20% glutaraldehyde aqueous solution dropwise to liquid C, centrifuge and settle after 12 hours of cross-linking and solidification, wash and dry the precipitate again to obtain chitosan microspheres with bactericidal and antipruritic functions.

将①中制得的聚氨酯预聚体升温到55℃，在空气湿含量低于10%的氮气保护环境下，采用带加温的双槽盛液，分别为盛装聚氨酯预聚体的A槽和盛装含有杀菌止痒药物壳聚糖微球的B槽，基布先经过A槽将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下经过B槽，对涂有聚氨酯预聚体的基布进行功能化处理，均匀粘附具有杀菌止痒功能的壳聚糖微球，再在送布、辊压等工艺处理后进行收卷、剪切再用铝塑复合袋包装。Raise the temperature of the polyurethane prepolymer prepared in ① to 55°C, and in a nitrogen protection environment with an air moisture content lower than 10%, use a double tank with heating to hold the liquid, which is the tank A and the tank containing the polyurethane prepolymer respectively. Tank B containing chitosan microspheres, a bactericidal and antipruritic drug, the base fabric first passes through tank A to evenly coat the polyurethane prepolymer on the base fabric, and then the base fabric coated with polyurethane prepolymer is guided by the guide cylinder After passing through the B tank, the base cloth coated with polyurethane prepolymer is functionalized, and the chitosan microspheres with the function of sterilizing and antipruritic are evenly adhered, and then the winding, Cut and pack in aluminum-plastic composite bags.

实施例4Example 4

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4'-二苯基甲烷二异氰酸酯100份、甲基磺酸3.8份和有机硅消泡剂0.9份，在40℃下搅拌80min后，缓慢加入分子量为300-600聚醚三元醇45份，继续加热搅拌30min后逐滴加入分子量为1800-2200的聚丙二醇25份，反应3h后加入催化剂二甲基苄胺3.5份，润硅油滑剂6份，继续加热搅拌65min，即得聚氨酯预聚体。Add 100 parts of 4,4'-diphenylmethane diisocyanate, 3.8 parts of methanesulfonic acid and 0.9 parts of organosilicon defoamer into a four-port reaction kettle with agitator and thermometer which is fed with high-purity nitrogen, After stirring at 40°C for 80 minutes, slowly add 45 parts of polyether trihydric alcohol with a molecular weight of 300-600, continue heating and stirring for 30 minutes, then add 25 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, react for 3 hours and then add the catalyst dimethyl 3.5 parts of benzylamine, 6 parts of silicone lubricant, and continue heating and stirring for 65 minutes to obtain a polyurethane prepolymer.

将壳聚糖50份溶解于质量分数为9%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；称取壳聚糖微球3份，用40份质量分数为1%醋酸溶液搅拌溶解,形成A液；Dissolve 50 parts of chitosan in 9% acetic acid solution by mass fraction, stir until completely dissolved, centrifuge and coagulate to obtain the chitosan solution; after standing for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral Dry in a constant temperature drying oven to obtain chitosan microspheres; weigh 3 parts of chitosan microspheres, stir and dissolve with 40 parts of 1% acetic acid solution with a mass fraction to form A liquid;

取杀菌止痒药物桉叶油1.5份，用18份无水乙醇搅拌溶解,形成B液；取B液3份，缓慢匀速滴入15份的A液中,剧烈搅拌10min,形成C液；在C液中滴加质量分数为20%戊二醛水溶液7份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥，即得具有杀菌止痒功能的壳聚糖微球。Take 1.5 parts of eucalyptus oil, a bactericidal and antipruritic drug, and stir and dissolve it with 18 parts of absolute ethanol to form liquid B; take 3 parts of liquid B, slowly and uniformly drop it into 15 parts of liquid A, stir vigorously for 10 minutes, and form liquid C; Add 7 parts of 20% glutaraldehyde aqueous solution dropwise to liquid C, centrifuge and settle after 12 hours of cross-linking and curing, and re-wash and dry the precipitate to obtain chitosan microspheres with bactericidal and antipruritic functions.

实施例5Example 5

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入2，4'-二苯基甲烷二异氰酸酯100份、甲基磺酸0.7份和有机硅消泡剂4份，在45℃下搅拌30min后，缓慢加入分子量为800-1100的聚四氢呋喃二醇63份，继续加热搅拌30min后逐滴加入分子量为1800-2200的聚丙二醇35.91份，反应1h45min后加入催化剂双(2，2-吗啉乙基)醚5份，硅油润滑剂6份，继续加热搅拌10min，即得聚氨酯预聚体。Add 100 parts of 2,4'-diphenylmethane diisocyanate, 0.7 parts of methanesulfonic acid and 4 parts of organosilicon defoamer into a four-port reaction kettle with agitator and thermometer that is fed with high-purity nitrogen, After stirring at 45°C for 30 minutes, slowly add 63 parts of polytetrahydrofuran diol with a molecular weight of 800-1100, continue heating and stirring for 30 minutes, then add 35.91 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, and add catalyst bis(2 , 5 parts of 2-morpholine ethyl) ether, 6 parts of silicone oil lubricant, and continue heating and stirring for 10 minutes to obtain a polyurethane prepolymer.

将壳聚糖50份溶解于质量分数为0.5%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；称取壳聚糖微球4.5份，用18份质量分数为0.9%醋酸溶液搅拌溶解,形成A液；Dissolve 50 parts of chitosan in 0.5% acetic acid solution with a mass fraction of 0.5%, stir until completely dissolved, and centrifuge to coagulate the chitosan solution; after standing for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral Dry in a constant temperature drying oven to obtain chitosan microspheres; weigh 4.5 parts of chitosan microspheres, stir and dissolve with 18 parts of 0.9% acetic acid solution with a mass fraction to form A liquid;

取杀菌止痒药物复方吲哚美辛酊2份，用15份无水乙醇搅拌溶解,形成B液；取B液3份，缓慢匀速滴入15份的A液中,剧烈搅拌10min,形成C液；在C液中滴加质量分数为23%戊二醛水溶液6.5份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥，即得具有杀菌止痒功能的壳聚糖微球。Take 2 parts of compound indomethacin tincture, a bactericidal and antipruritic drug, stir and dissolve with 15 parts of absolute ethanol to form liquid B; take 3 parts of liquid B, drop them into 15 parts of liquid A slowly and at a uniform speed, and stir vigorously for 10 minutes to form liquid C. solution; 6.5 parts of 23% glutaraldehyde aqueous solution was added dropwise in the C solution, cross-linked and solidified for 12 hours, centrifuged and settled, and the precipitate was washed and dried again to obtain chitosan microspheres with bactericidal and antipruritic functions.

实施例6Example 6

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入2，2'-二苯基甲烷二异氰酸酯100份、马来酸酐0.1-5份和有机硅消泡剂0.5-5份，在25-50℃下搅拌30min后，缓慢加入分子量为800-1100的聚丙二醇55份，继续加热搅拌30min后逐滴加入分子量为1800-2200的聚四氢呋喃二醇35份，反应1h45min后加入催化剂二甲基氨基乙醇5份，聚氧化乙烯3份，继续加热搅拌15min，即得聚氨酯预聚体。In a four-port reactor equipped with a stirrer and a thermometer that is fed with high-purity nitrogen, add 100 parts of 2,2'-diphenylmethane diisocyanate, 0.1-5 parts of maleic anhydride and 0.5- 5 parts, after stirring at 25-50°C for 30 minutes, slowly add 55 parts of polypropylene glycol with a molecular weight of 800-1100, continue heating and stirring for 30 minutes, then add 35 parts of polytetrahydrofuran diol with a molecular weight of 1800-2200 dropwise, and react for 1h45min Add 5 parts of catalyst dimethylaminoethanol and 3 parts of polyethylene oxide, and continue heating and stirring for 15 minutes to obtain a polyurethane prepolymer.

将壳聚糖50份溶解于质量分数为0.5%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；称取壳聚糖微球3.5份，用40份质量分数为0.2%醋酸溶液搅拌溶解,形成A液；Dissolve 50 parts of chitosan in 0.5% acetic acid solution with a mass fraction of 0.5%, stir until completely dissolved, and centrifuge to coagulate the chitosan solution; after standing for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral Dry in a constant temperature drying oven to obtain chitosan microspheres; weigh 3.5 parts of chitosan microspheres, stir and dissolve with 40 parts of 0.2% acetic acid solution with a mass fraction to form A liquid;

取杀菌止痒药物水杨酸甲酯0.8份和桉叶油0.5份，用18份无水乙醇搅拌溶解,形成B液；取B液5份，缓慢匀速滴入18份的A液中,剧烈搅拌10min,形成C液；在C液中滴加质量分数为23%戊二醛水溶液10份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥，即得具有杀菌止痒功能的壳聚糖微球。Take 0.8 parts of bactericidal and antipruritic drug methyl salicylate and 0.5 parts of eucalyptus oil, stir and dissolve with 18 parts of absolute ethanol to form B liquid; take 5 parts of B liquid, slowly and uniformly drop into 18 parts of A liquid, vigorously Stir for 10 minutes to form liquid C; add 10 parts of glutaraldehyde aqueous solution with a mass fraction of 23% dropwise in liquid C, centrifuge and settle after 12 hours of cross-linking and solidification, and re-wash and dry the precipitate to obtain chitosan with bactericidal and antipruritic functions. sugar microspheres.

实施例7Example 7

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4'-二苯基甲烷二异氰酸酯100份、马来酸酐5份和有机硅消泡剂2份，在40℃下搅拌30min后，缓慢加入分子量为800-1100的聚丙二醇50份，继续加热搅拌40min后逐滴加入分子量为1800-2200的聚四氢呋喃二醇10份，反应1h15min后加入催化剂四甲基二丙稀三胺7份，硅油润滑剂10份，继续加热搅拌35min。In a four-port reactor with a stirrer and a thermometer that feeds high-purity nitrogen, add 100 parts of 4,4'-diphenylmethane diisocyanate, 5 parts of maleic anhydride and 2 parts of silicone defoamer. After stirring at 40°C for 30 minutes, slowly add 50 parts of polypropylene glycol with a molecular weight of 800-1100, continue heating and stirring for 40 minutes, then add 10 parts of polytetrahydrofuran diol with a molecular weight of 1800-2200 dropwise, react for 1 hour and 15 minutes, and then add the catalyst tetramethyl di 7 parts of propylene triamine, 10 parts of silicone oil lubricant, continue heating and stirring for 35 minutes.

在20份异丙醇介质中，加入8份质量分数为30%碳酸钠作为缚酸剂，季铵化试剂溴丙烷10份，壳聚糖15份进行接枝改性，得到壳聚糖季铵盐物料。将该物料用质量分数为20%的甲醇水溶液洗涤以部分除去物料中的盐分，从而得到部分除盐的含季铵化壳聚糖的固体物料后，用去离子水溶解，再置于透析袋中于蒸馏水中进行透析除盐。透析除盐后减压浓缩以生成含壳聚糖季铵盐的浓溶液，再用足量无水乙醇沉淀，将沉淀物用无水乙醇洗涤得壳聚糖季铵盐湿物料，再经干燥即可得到壳聚糖季铵盐产品;In 20 parts of isopropanol medium, add 8 parts of mass fraction of 30% sodium carbonate as an acid-binding agent, 10 parts of quaternizing agent bromopropane, and 15 parts of chitosan for graft modification to obtain chitosan quaternary ammonium salt material. Wash the material with 20% methanol aqueous solution to partially remove the salt in the material, so as to obtain a partially desalted solid material containing quaternized chitosan, dissolve it with deionized water, and then place it in a dialysis bag Dialyze in distilled water to remove salt. After dialysis and desalination, concentrate under reduced pressure to generate a concentrated solution containing chitosan quaternary ammonium salt, then precipitate with sufficient amount of absolute ethanol, wash the precipitate with absolute ethanol to obtain chitosan quaternary ammonium salt wet material, and then dry Chitosan quaternary ammonium salt product can be obtained;

将①中制得的聚氨酯预聚体升温到55℃，在空气湿含量低于10%的氮气保护环境下，采用带加温的双槽盛液，分别为盛装聚氨酯预聚体的A槽和盛装含有杀菌止痒功能的壳聚糖季铵盐的B槽，基布先经过A槽将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下经过B槽，对涂有聚氨酯预聚体的基布进行功能化处理，均匀粘附具有杀菌止痒功能的壳聚糖季铵盐，再在送布、辊压等工艺处理后进行收卷、剪切再用铝塑复合袋包装。Raise the temperature of the polyurethane prepolymer prepared in ① to 55°C, and in a nitrogen protection environment with an air moisture content lower than 10%, use a double tank with heating to hold the liquid, which is the tank A and the tank containing the polyurethane prepolymer respectively. Tank B containing chitosan quaternary ammonium salt with bactericidal and antipruritic functions, the base fabric first passes through tank A to evenly coat the polyurethane prepolymer on the base fabric, and the base fabric coated with polyurethane prepolymer is then placed on the guide cylinder Under the guidance of the guide, the base cloth coated with polyurethane prepolymer is functionalized through the B tank, and the chitosan quaternary ammonium salt with the function of sterilizing and antipruritic is evenly adhered, and then processed after cloth feeding, rolling and other processes. Rewinding, cutting and packaging in aluminum-plastic composite bags.

实施例8Example 8

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入2，4'-二苯基甲烷二异氰酸酯100份、马来酸酐1.8份和有机硅消泡剂3.8份，在35℃下搅拌30min后，缓慢加入分子量为800-1100的聚四氢呋喃二醇60份，继续加热搅拌120min后逐滴加入分子量为1800-2200的聚丙二醇25份，反应2.5h后加入催化剂二甲基二乙醇胺4份，聚氧化乙烯7份，继续加热搅拌15min。In a four-port reactor with a stirrer and a thermometer that feeds high-purity nitrogen, add 100 parts of 2,4'-diphenylmethane diisocyanate, 1.8 parts of maleic anhydride and 3.8 parts of silicone defoamer. After stirring at 35°C for 30 minutes, slowly add 60 parts of polytetrahydrofuran diol with a molecular weight of 800-1100, continue heating and stirring for 120 minutes, then add 25 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, react for 2.5 hours and then add the catalyst dimethyl 4 parts of diethanolamine, 7 parts of polyethylene oxide, continue heating and stirring for 15 minutes.

将壳聚糖50份溶解于质量分数为13%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；称取上述制备的壳聚糖微球2份，用25份质量分数为8%醋酸溶液搅拌溶解,形成A液；Dissolve 50 parts of chitosan in 13% acetic acid solution with a mass fraction of 13%, stir until completely dissolved, and centrifuge to coagulate the chitosan solution; after standing for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral Dry in a constant temperature drying oven to obtain chitosan microspheres; weigh 2 parts of chitosan microspheres prepared above, stir and dissolve with 25 parts of 8% acetic acid solution with a mass fraction to form A liquid;

取杀菌止痒药物氯己定1.5份，用10份无水乙醇搅拌溶解,形成B液；取B液2份，缓慢匀速滴入10份的A液中,剧烈搅拌10min,形成C液；在C液中滴加质量分数为15%戊二醛水溶液10份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥，即得具有杀菌止痒功能的壳聚糖微球。Take 1.5 parts of the bactericidal and antipruritic drug chlorhexidine, stir and dissolve with 10 parts of absolute ethanol to form liquid B; take 2 parts of liquid B, slowly and uniformly drop into 10 parts of liquid A, stir vigorously for 10 minutes, and form liquid C; 10 parts of 15% glutaraldehyde aqueous solution was added dropwise to liquid C, cross-linked and solidified for 12 hours, then centrifugally settled, and the precipitate was washed and dried again to obtain chitosan microspheres with bactericidal and antipruritic functions.

实施例9Example 9

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入2，2'-二苯基甲烷二异氰酸酯100份、苯甲酰氯稳定剂3份和有机硅消泡剂5份，在45℃下搅拌30min后，缓慢加入分子量为300-600聚醚三元醇55份，继续加热搅拌90min后逐滴加入分子量为1800-2200的聚四氢呋喃二醇45份，反应2h后加入催化剂二甲胺基丙胺二异丙醇7份，聚氧化乙烯10份，继续加热搅拌85min。Add 100 parts of 2,2'-diphenylmethane diisocyanate, 3 parts of benzoyl chloride stabilizer and 5 parts of silicone defoamer After stirring at 45°C for 30 minutes, slowly add 55 parts of polyether triol with a molecular weight of 300-600, continue heating and stirring for 90 minutes, then add 45 parts of polytetrahydrofuran diol with a molecular weight of 1800-2200 dropwise, and add the catalyst after 2 hours of reaction 7 parts of dimethylaminopropylamine diisopropanol, 10 parts of polyethylene oxide, continue heating and stirring for 85 minutes.

将壳聚糖50份溶解于质量分数为5%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；称取上述制备的壳聚糖微球5份，用30份质量分数为0.1%醋酸溶液搅拌溶解,形成A液；Dissolve 50 parts of chitosan in 5% acetic acid solution with a mass fraction of 5%, stir until completely dissolved, centrifuge and coagulate to obtain the chitosan solution; after standing for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral Dry in a constant temperature drying oven to obtain chitosan microspheres; weigh 5 parts of chitosan microspheres prepared above, stir and dissolve with 30 parts of 0.1% acetic acid solution with a mass fraction to form A liquid;

取杀菌止痒药物阿莫西林1份，用10份无水乙醇搅拌溶解,形成B液；取B液2份，缓慢匀速滴入12份的A液中,剧烈搅拌10min,形成C液；在C液中滴加质量分数为10%戊二醛水溶液5-10份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥，即得具有杀菌止痒功能的壳聚糖微球。Take 1 part of the bactericidal and antipruritic drug amoxicillin, stir and dissolve it with 10 parts of absolute ethanol to form liquid B; take 2 parts of liquid B, slowly and uniformly drop it into 12 parts of liquid A, stir vigorously for 10 minutes, and form liquid C; Add 5-10 parts of 10% glutaraldehyde aqueous solution dropwise to liquid C, centrifuge and settle after 12 hours of cross-linking and solidification, and re-wash and dry the precipitate to obtain chitosan microspheres with bactericidal and antipruritic functions.

实施例10Example 10

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入甲苯-2,4-二异氰酸酯100份、丙酰氯稳定剂1.8份和有机硅消泡剂3.2份，在30℃下搅拌30min后，缓慢加入分子量为800-1100的聚丙二醇18份，继续加热搅拌110min后逐滴加入分子量为1800-2200的聚四氢呋喃二醇40份，反应1.5h后加入催化剂三亚乙基二胺1-8份，硅油润滑剂3-10份，继续加热搅拌90min。Add 100 parts of toluene-2,4-diisocyanate, 1.8 parts of propionyl chloride stabilizer and 3.2 parts of organosilicon defoamer to a four-port reactor with stirrer and thermometer, and feed it with high-purity nitrogen. After stirring for 30 minutes, slowly add 18 parts of polypropylene glycol with a molecular weight of 800-1100, continue heating and stirring for 110 minutes, then add 40 parts of polytetrahydrofuran diol with a molecular weight of 1800-2200 dropwise, and add the catalyst triethylenediamine after 1.5 hours of reaction 1-8 parts, silicone oil lubricant 3-10 parts, continue heating and stirring for 90 minutes.

实施例11Example 11

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4'-二苯基甲烷二异氰酸酯100份、芳香族苯甲酰氯稳定剂4.2份和有机硅消泡剂3.5份，在20℃下搅拌30min后，缓慢加入分子量为300-600聚醚三元醇30份，继续加热搅拌100min后逐滴加入分子量为1800-2200的聚丙二醇10份，反应1h后加入有机锡催化剂如二丁基锡二月桂酸酯3份，聚氧化乙烯5份，继续加热搅拌90min。Add 100 parts of 4,4'-diphenylmethane diisocyanate, 4.2 parts of aromatic benzoyl chloride stabilizer and silicone defoamer 3.5 parts, after stirring at 20°C for 30 minutes, slowly add 30 parts of polyether triols with a molecular weight of 300-600, continue heating and stirring for 100 minutes, then add 10 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, react for 1 hour, then add organic Tin catalyst such as 3 parts of dibutyltin dilaurate, 5 parts of polyethylene oxide, continue heating and stirring for 90 minutes.

将壳聚糖50份溶解于15%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结。静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干即得壳聚糖微球。称取上述制备的壳聚糖微球2份，用25份质量分数为0.8%的醋酸溶液搅拌溶解,形成A液。Dissolve 50 parts of chitosan in 15% acetic acid solution, stir until completely dissolved, obtain chitosan solution, and centrifuge to coagulate. After standing still for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral, and then dry in a constant temperature drying oven to obtain chitosan microspheres. Weigh 2 parts of chitosan microspheres prepared above, stir and dissolve with 25 parts of 0.8% acetic acid solution by mass fraction to form A solution.

取杀菌止痒药物四环素1.5份，用用20份无水乙醇搅拌溶解,形成B液。将4份B液缓慢匀速滴入15份A液中,剧烈搅拌10min,形成C液。在C液中滴加20%戊二醛水溶液7份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥即得具有杀菌止痒功能的壳聚糖微球。Take 1.5 parts of tetracycline, a bactericidal and antipruritic drug, and dissolve it with stirring with 20 parts of absolute ethanol to form liquid B. Slowly and uniformly drop 4 parts of liquid B into 15 parts of liquid A, and stir vigorously for 10 minutes to form liquid C. Add 7 parts of 20% glutaraldehyde aqueous solution dropwise to liquid C, centrifuge and settle after 12 hours of cross-linking and solidification, wash and dry the precipitate again to obtain chitosan microspheres with bactericidal and antipruritic functions.

将①中制得的聚氨酯预聚体升温到55℃，在空气湿含量低于10%的氮气保护环境下，采用带加温的双槽盛液，分别为盛装聚氨酯预聚体的A槽和盛装含有杀菌止痒药物壳聚糖微球的B槽，基布先经过A槽将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下经过B槽，对涂有聚氨酯预聚体的基布进行功能化处理，均匀粘附具有杀菌止痒功能的壳聚糖微球，再在送布、辊压等工艺处理后进行收卷、剪切再用铝塑复合袋包装。Raise the temperature of the polyurethane prepolymer prepared in ① to 55°C, and in a nitrogen protection environment with an air moisture content lower than 10%, use a double tank with heating to hold the liquid, which is the tank A and the tank containing the polyurethane prepolymer respectively. Tank B containing chitosan microspheres, a bactericidal and antipruritic drug, the base cloth first passes through slot A to evenly coat the polyurethane prepolymer on the base cloth, and then the base cloth coated with polyurethane prepolymer is guided by the guide cylinder. After passing through the B tank, the base cloth coated with polyurethane prepolymer is functionalized, and the chitosan microspheres with the function of sterilizing and antipruritic are evenly adhered. Cut and pack in aluminum-plastic composite bags.

实施例12Example 12

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4'-二苯基甲烷二异氰酸酯MDI100份、芳香族苯甲酰氯稳定剂3.8份和有机硅消泡剂0.9份，在40℃下搅拌30min后，缓慢加入分子量为300-600聚丙二醇45份，继续加热搅拌90min后逐滴加入分子量为1800-2200的聚丙二醇25份，反应1h45min后加入催化剂二甲基苄胺3.5份，润硅油滑剂6份，继续加热搅拌45min。Add 100 parts of 4,4'-diphenylmethane diisocyanate MDI, 3.8 parts of aromatic benzoyl chloride stabilizer and silicone defoamer 0.9 parts, after stirring at 40°C for 30 minutes, slowly add 45 parts of polypropylene glycol with a molecular weight of 300-600, continue heating and stirring for 90 minutes, then add 25 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, react for 1h45min, then add the catalyst dimethyl 3.5 parts of benzylamine, 6 parts of silicone lubricant, continue heating and stirring for 45 minutes.

将壳聚糖50份溶解于质量分数为9%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；称取壳聚糖微球3份，用40份质量分数为1%醋酸溶液搅拌溶解,形成A液；Dissolve 50 parts of chitosan in 9% acetic acid solution with a mass fraction of 9%, stir until completely dissolved, and centrifuge to coagulate the chitosan solution; after standing for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral Dry in a constant temperature drying oven to obtain chitosan microspheres; weigh 3 parts of chitosan microspheres, stir and dissolve with 40 parts of 1% acetic acid solution with a mass fraction to form A liquid;

实施例13Example 13

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4'-二苯基甲烷二异氰酸酯100份、丙酰氯1份和有机硅消泡剂3份，在40℃下搅拌30min后，缓慢加入分子量为800-1100的聚丙二醇50份，继续加热搅拌45min后逐滴加入分子量为1800-2200的聚四氢呋喃二醇10份，反应1h15min后加入催化剂双(2，2-吗啉乙基)醚7份，硅油润滑剂10份，继续加热搅拌30min。Add 100 parts of 4,4'-diphenylmethane diisocyanate, 1 part of propionyl chloride and 3 parts of organosilicon defoamer in a four-port reaction kettle with a stirrer and a thermometer fed with high-purity nitrogen. After stirring at ℃ for 30 minutes, slowly add 50 parts of polypropylene glycol with a molecular weight of 800-1100, continue heating and stirring for 45 minutes, then add 10 parts of polytetrahydrofuran diol with a molecular weight of 1800-2200 dropwise, and add catalyst bis(2,2 - 7 parts of morpholine ethyl) ether, 10 parts of silicone oil lubricant, continue heating and stirring for 30min.

将壳聚糖50份溶解于质量分数为2%醋酸溶液中,搅拌至完全溶解,得壳聚糖溶液后离心凝结；静置36h后减压抽滤,用无水乙醇洗涤至中性后置恒温干燥箱烘干，即得壳聚糖微球；称取壳聚糖微球3份，用15份质量分数为1.5%醋酸溶液搅拌溶解,形成A液；Dissolve 50 parts of chitosan in 2% acetic acid solution by mass fraction, stir until completely dissolved, centrifuge and coagulate to obtain the chitosan solution; after standing for 36 hours, filter under reduced pressure, wash with absolute ethanol until neutral Dry in a constant temperature drying oven to obtain chitosan microspheres; weigh 3 parts of chitosan microspheres, stir and dissolve with 15 parts of 1.5% acetic acid solution by mass fraction to form A liquid;

取杀菌止痒药物丙酸倍氯米松2份和氯己定1份，用20份无水乙醇搅拌溶解,形成B液；取B液5份，缓慢匀速滴入20份的A液中,剧烈搅拌10min,形成C液；在C液中滴加质量分数为50%戊二醛水溶液10份,交联固化12h后离心沉降，将沉淀物重新洗涤干燥，即得具有杀菌止痒功能的壳聚糖微球。Take 2 parts of bactericidal and antipruritic drugs beclomethasone dipropionate and 1 part of chlorhexidine, stir and dissolve with 20 parts of absolute ethanol to form B liquid; take 5 parts of B liquid, slowly and uniformly drop into 20 parts of A liquid, vigorously Stir for 10 minutes to form liquid C; dropwise add 10 parts of glutaraldehyde aqueous solution with a mass fraction of 50% in liquid C, centrifuge and settle after 12 hours of cross-linking and solidification, and re-wash and dry the precipitate to obtain chitosan with bactericidal and antipruritic functions. sugar microspheres.

实施例14Example 14

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入2，4'-二苯基甲烷二异氰酸酯100份、马来酸酐1.8份和有机硅消泡剂4.8份，在35℃下搅拌30min后，缓慢加入分子量为800-1100的聚四氢呋喃二醇60份，继续加热搅拌120min后逐滴加入分子量为1800-2200的聚丙二醇25份，反应2.5h后加入催化剂马来酸酐4份，聚氧化乙烯7份，继续加热搅拌10min。In a four-port reactor with a stirrer and a thermometer that feeds high-purity nitrogen, add 100 parts of 2,4'-diphenylmethane diisocyanate, 1.8 parts of maleic anhydride and 4.8 parts of silicone defoamer. After stirring at 35°C for 30 minutes, slowly add 60 parts of polytetrahydrofuran diol with a molecular weight of 800-1100, continue heating and stirring for 120 minutes, then add 25 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, and add catalyst maleic anhydride after 2.5 hours of reaction 4 parts, 7 parts of polyethylene oxide, continue to heat and stir for 10 minutes.

③在40份乙醇介质中，加入15份质量分数为20%的氢氧化钠作为缚酸剂，加入季铵化试剂溴丙烷10份，壳聚糖30份进行接枝改性，得到壳聚糖季铵盐物料。将该物料用质量分数为5%的甲醇水溶液洗涤以部分除去物料中的盐分，从而得到部分除盐的含季铵化壳聚糖的固体物料后，用去离子水或蒸馏水溶解，再置于透析袋中于蒸馏水中进行透析除盐。透析除盐后减压浓缩以生成含壳聚糖季铵盐的浓溶液，再用足量无水乙醇沉淀，将沉淀物用无水乙醇洗涤得壳聚糖季铵盐湿物料，再经干燥即可得到壳聚糖季铵盐产品。③In 40 parts of ethanol medium, add 15 parts of sodium hydroxide with a mass fraction of 20% as an acid-binding agent, add 10 parts of quaternizing agent bromopropane, and 30 parts of chitosan for graft modification to obtain chitosan Quaternary ammonium salt material. The material is washed with 5% methanol aqueous solution to partially remove the salt in the material, so as to obtain a partially desalinated solid material containing quaternized chitosan, dissolve it with deionized water or distilled water, and then place Dialysis was carried out in distilled water to remove salt in the dialysis bag. After dialysis and desalination, concentrate under reduced pressure to generate a concentrated solution containing chitosan quaternary ammonium salt, then precipitate with sufficient amount of absolute ethanol, wash the precipitate with absolute ethanol to obtain chitosan quaternary ammonium salt wet material, and then dry The chitosan quaternary ammonium salt product can be obtained.

④含有杀菌止痒功能的壳聚糖季铵盐的水扩链聚氨酯绷带的制备④Preparation of water chain-extended polyurethane bandage containing chitosan quaternary ammonium salt with bactericidal and antipruritic functions

将①中制得的聚氨酯预聚体升温到55℃，在空气湿含量低于10%的氮气保护环境下，采用带加温的双槽盛液，分别为盛装聚氨酯预聚体的A槽和盛装含有杀菌止痒功能壳聚糖季铵盐的B槽，基布先经过A槽将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下经过B槽，对涂有聚氨酯预聚体的基布进行功能化处理，均匀粘附具有杀菌止痒功能的壳聚糖季铵盐，再在送布、辊压等工艺处理后进行收卷、剪切再用铝塑复合袋包装。Raise the temperature of the polyurethane prepolymer prepared in ① to 55°C, and in a nitrogen protection environment with an air moisture content lower than 10%, use a double tank with heating to hold the liquid, which is the tank A and the tank containing the polyurethane prepolymer respectively. Tank B containing chitosan quaternary ammonium salt with bactericidal and antipruritic functions, the base cloth first passes through tank A to evenly coat the polyurethane prepolymer on the base cloth, and then the base cloth coated with polyurethane prepolymer is placed on the guide cylinder Under the guidance of the B tank, the base cloth coated with polyurethane prepolymer is functionalized, and the chitosan quaternary ammonium salt with the function of sterilizing and antipruritic is evenly adhered, and then it is collected after cloth feeding, rolling and other processes. Rolled, cut and packed in aluminum-plastic composite bag.

实施例15Example 15

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4′-二苯基甲烷二异氰酸酯100份、苯甲酰氯稳定剂3份和有机硅消泡剂5份，在45℃下搅拌30min后，缓慢加入分子量为300-600聚醚三元醇55份，继续加热搅拌90min后逐滴加入分子量为1800-2200的聚丙二醇45份，反应2h后加入催化剂二甲胺基丙胺二异丙醇5份，聚氧化乙烯10份，继续加热搅拌80min。Add 100 parts of 4,4'-diphenylmethane diisocyanate, 3 parts of benzoyl chloride stabilizer and 5 parts of silicone defoamer , after stirring at 45°C for 30 minutes, slowly add 55 parts of polyether triol with a molecular weight of 300-600, continue heating and stirring for 90 minutes, then add 45 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, react for 2 hours, and then add the catalyst dimethyl 5 parts of aminopropylamine diisopropanol, 10 parts of polyethylene oxide, continue heating and stirring for 80 minutes.

在35份丙酮介质中，加入15份质量分数为25%的氢氧化钠作为缚酸剂，加入季铵化试剂溴丙烷10份，壳聚糖30份进行接枝改性，得到壳聚糖季铵盐物料。将该物料用质量分数为5%的甲醇水溶液洗涤以部分除去物料中的盐分，从而得到部分除盐的含季铵化壳聚糖的固体物料后，用去离子水或蒸馏水溶解，再置于透析袋中于蒸馏水中进行透析除盐。透析除盐后减压浓缩以生成含壳聚糖季铵盐的浓溶液，再用足量无水乙醇沉淀，将沉淀物用无水乙醇洗涤得壳聚糖季铵盐湿物料，再经干燥即可得到壳聚糖季铵盐产品。In 35 parts of acetone medium, add 15 parts of sodium hydroxide with a mass fraction of 25% as an acid-binding agent, add 10 parts of quaternizing agent bromopropane, and 30 parts of chitosan for graft modification to obtain chitosan quaternary Ammonium salt material. The material is washed with 5% methanol aqueous solution to partially remove the salt in the material, so as to obtain a partially desalinated solid material containing quaternized chitosan, dissolve it with deionized water or distilled water, and then place Dialysis was carried out in distilled water to remove salt in the dialysis bag. After dialysis and desalination, concentrate under reduced pressure to generate a concentrated solution containing chitosan quaternary ammonium salt, then precipitate with sufficient amount of absolute ethanol, wash the precipitate with absolute ethanol to obtain chitosan quaternary ammonium salt wet material, and then dry The chitosan quaternary ammonium salt product can be obtained.

③含有杀菌止痒功能壳聚糖季铵盐的水扩链聚氨酯绷带的制备③Preparation of water chain-extended polyurethane bandage containing chitosan quaternary ammonium salt with bactericidal and antipruritic functions

实施例16Example 16

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入2，4'-二苯基甲烷二异氰酸酯100份、苯甲酰氯1.8份和有机硅消泡剂3.2份，在30℃下搅拌30min后，缓慢加入分子量为800-1100的聚四氢呋喃二醇18份，继续加热搅拌100min后逐滴加入分子量为1800-2200的聚丙二醇40份，反应2.5h后加入催化剂三亚乙基二胺1-8份，硅油润滑剂3-10份，继续加热搅拌50min。In a four-port reactor with a stirrer and a thermometer that feeds high-purity nitrogen, add 100 parts of 2,4'-diphenylmethane diisocyanate, 1.8 parts of benzoyl chloride and 3.2 parts of silicone defoamer. After stirring at 30°C for 30 minutes, slowly add 18 parts of polytetrahydrofuran diol with a molecular weight of 800-1100, continue heating and stirring for 100 minutes, then add 40 parts of polypropylene glycol with a molecular weight of 1800-2200 dropwise, and add catalyst triethylene glycol after 2.5 hours of reaction. 1-8 parts of diamine, 3-10 parts of silicone oil lubricant, continue heating and stirring for 50 minutes.

在10份丙酮介质中，加入8份质量分数为30%碳酸钠作为缚酸剂，加入季铵化试剂环氧丙烷5份，壳聚糖20份进行接枝改性，得到壳聚糖季铵盐物料。将该物料用质量分数为10%的甲醇水溶液洗涤以部分除去物料中的盐分，从而得到部分除盐的含季铵化壳聚糖的固体物料后，用蒸馏水溶解，再置于透析袋中于蒸馏水中进行透析除盐。透析除盐后常压直接浓缩以生成含壳聚糖季铵盐的浓溶液，再用足量丙酮沉淀，将沉淀物用丙酮洗涤得壳聚糖季铵盐湿物料，再经干燥即可得到壳聚糖季铵盐产品。In 10 parts of acetone medium, add 8 parts of mass fraction of 30% sodium carbonate as an acid-binding agent, add 5 parts of quaternizing agent propylene oxide, and 20 parts of chitosan for graft modification to obtain chitosan quaternary ammonium salt material. The material is washed with 10% methanol aqueous solution to partially remove the salinity in the material, so as to obtain a partially desalinated solid material containing quaternized chitosan, dissolve it with distilled water, and then place it in a dialysis bag. Distilled water for dialysis to remove salt. After dialysis and desalination, concentrate directly under normal pressure to form a concentrated solution containing chitosan quaternary ammonium salt, then precipitate with a sufficient amount of acetone, wash the precipitate with acetone to obtain chitosan quaternary ammonium salt wet material, and then dry it to obtain Chitosan quaternary ammonium salt products.

将①中制得的聚氨酯预聚体升温到55℃，在空气湿含量低于10%的氮气保护环境下，采用带加温的双槽盛液，分别为盛装聚氨酯预聚体的A槽和盛装含有杀菌止痒药物壳聚糖微球的B槽，基布先经过A槽将聚氨酯预聚体均匀涂覆在基布上，涂覆有聚氨酯预聚体的基布再在导筒的引导下经过B槽，对涂有聚氨酯预聚体的基布进行功能化处理，均匀粘附具有杀菌止痒功能的壳聚糖微球或壳聚糖季铵盐，再在送布、辊压等工艺处理后进行收卷、剪切再用铝塑复合袋包装。Raise the temperature of the polyurethane prepolymer prepared in ① to 55°C, and in a nitrogen protection environment with an air moisture content lower than 10%, use a double tank with heating to hold the liquid, which is the tank A and the tank containing the polyurethane prepolymer respectively. Tank B containing chitosan microspheres, a bactericidal and antipruritic drug, the base fabric first passes through tank A to evenly coat the polyurethane prepolymer on the base fabric, and then the base fabric coated with polyurethane prepolymer is guided by the guide cylinder After passing through tank B, the base fabric coated with polyurethane prepolymer is functionalized, and chitosan microspheres or chitosan quaternary ammonium salts with bactericidal and antipruritic functions are evenly adhered, and then the cloth is fed, rolled, etc. After the process is processed, it is rolled, cut and then packed in aluminum-plastic composite bags.

实施例17Example 17

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在30份异丙醇介质中，加入10份质量分数为25%的氢氧化钠作为缚酸剂，加入季铵化试剂环氧丙烷10份，壳聚糖30份进行接枝改性，得到壳聚糖季铵盐物料。将该物料用质量分数为5%的甲醇水溶液洗涤以部分除去物料中的盐分，从而得到部分除盐的含季铵化壳聚糖的固体物料后，用去离子水或蒸馏水溶解，再置于透析袋中于蒸馏水中进行透析除盐。透析除盐后减压浓缩以生成含壳聚糖季铵盐的浓溶液，再用足量丙酮沉淀，将沉淀物用丙酮洗涤得壳聚糖季铵盐湿物料，再经干燥即可得到壳聚糖季铵盐产品。In 30 parts of isopropanol medium, add 10 parts of sodium hydroxide with a mass fraction of 25% as an acid-binding agent, add 10 parts of quaternizing agent propylene oxide, and 30 parts of chitosan for graft modification to obtain shell Polysaccharide quaternary ammonium salt material. The material is washed with 5% methanol aqueous solution to partially remove the salt in the material, so as to obtain a partially desalinated solid material containing quaternized chitosan, dissolve it with deionized water or distilled water, and then place Dialysis was carried out in distilled water to remove salt in the dialysis bag. After dialysis and desalination, concentrate under reduced pressure to generate a concentrated solution containing chitosan quaternary ammonium salt, then precipitate with a sufficient amount of acetone, wash the precipitate with acetone to obtain chitosan quaternary ammonium salt wet material, and then dry to obtain shell Polysaccharide quaternary ammonium salt products.

实施例18Example 18

①聚氨酯预聚体的制备① Preparation of polyurethane prepolymer

在带有搅拌器、温度计的通入高纯氮的四口反应釜中，加入4，4′-二苯基甲烷二异氰酸酯100份、丙酰氯1份和有机硅消泡剂3份，在40℃下搅拌30min后，缓慢加入分子量为800-1100的聚丙二醇50份，继续加热搅拌45min后逐滴加入分子量为1800-2200的聚四氢呋喃二醇10份，反应1h15min后加入催化剂双(2，2-吗啉乙基)醚7份，硅油润滑剂10份，继续加热搅拌30min。Add 100 parts of 4,4'-diphenylmethane diisocyanate, 1 part of propionyl chloride and 3 parts of organosilicon defoamer in a four-port reaction kettle with a stirrer and a thermometer fed with high-purity nitrogen. After stirring at ℃ for 30 minutes, slowly add 50 parts of polypropylene glycol with a molecular weight of 800-1100, continue heating and stirring for 45 minutes, then add 10 parts of polytetrahydrofuran diol with a molecular weight of 1800-2200 dropwise, and add catalyst bis(2,2 - 7 parts of morpholine ethyl) ether, 10 parts of silicone oil lubricant, continue heating and stirring for 30min.

在40份异丙醇介质中，加入15份质量分数为20%的碳酸钠作为缚酸剂，加入季铵化试剂环氧丙烷10份，壳聚糖35份进行接枝改性，得到壳聚糖季铵盐物料。将该物料用质量分数为5%的甲醇水溶液洗涤以部分除去物料中的盐分，从而得到部分除盐的含季铵化壳聚糖的固体物料后，用去离子水或蒸馏水溶解，再置于透析袋中于蒸馏水中进行透析除盐。透析除盐后减压浓缩以生成含壳聚糖季铵盐的浓溶液，再用足量无水乙醇沉淀，将沉淀物用无水乙醇洗涤得壳聚糖季铵盐湿物料，再经干燥即可得到壳聚糖季铵盐产品。In 40 parts of isopropanol medium, add 15 parts of sodium carbonate with a mass fraction of 20% as an acid-binding agent, add 10 parts of quaternization reagent propylene oxide, and 35 parts of chitosan for graft modification to obtain chitosan Sugar quaternary ammonium salt material. The material is washed with 5% methanol aqueous solution to partially remove the salt in the material, so as to obtain a partially desalinated solid material containing quaternized chitosan, dissolve it with deionized water or distilled water, and then place Dialysis was carried out in distilled water to remove salt in the dialysis bag. After dialysis and desalination, concentrate under reduced pressure to generate a concentrated solution containing chitosan quaternary ammonium salt, then precipitate with sufficient amount of absolute ethanol, wash the precipitate with absolute ethanol to obtain chitosan quaternary ammonium salt wet material, and then dry The chitosan quaternary ammonium salt product can be obtained.

Claims

1. the preparation method with medical polyurethane binder of sterilizing and itch-relieving function, is characterized in that: comprise the steps:

1) preparation of base polyurethane prepolymer for use as

In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 100 parts of aromatic diisocyanates, stabilizing agent 0.1-5 part and silicone defoaming agent 0.5-5 part, after under 25-50 ℃, stirring 30min, the composition A that slowly adds 15-70 part, continue the composition B that dropwise adds 10-55 part after heated and stirred 30-120min, after reaction 1-3h, add catalyst 1-8 part, lubricant 3-10 part, continue heated and stirred 10-90min; Described composition A is that molecular weight is that polyether Glycols or the molecular weight of 800-1100 is the 300-600 polyether-tribasic alcohol, and described composition B is that molecular weight is the polyether Glycols of 1800-2200;

2) has the preparation of chitosan microball or the chitosan quaternary ammonium salt of sterilizing and itch-relieving function

Preparation with chitosan microball of sterilizing and itch-relieving medicine:

A. 50 parts of chitosans being dissolved in to mass fraction is in the 0.5-15% acetum, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball;

B. taking chitosan microball 1-5 part of above-mentioned preparation, is 0.1-10% acetum stirring and dissolving with 10-50 part mass fraction, forms A liquid;

C. get sterilizing and itch-relieving medicine 0.5-2 part, dissolve by 5-20 part absolute ethyl alcohol and stirring, form B liquid;

D. get the B liquid 1-5 part in the c step, slowly at the uniform velocity splash in the A liquid of 10-20 part, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 10-50% glutaraldehyde water solution 5-10 part, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function; Preparation with chitosan quaternary ammonium salt of sterilizing and itch-relieving function:

A. in 10-50 part ethanol, acetone or isopropanol medium, adding 1-15 part mass fraction is that the sodium hydroxide of 10-30% or sodium carbonate are as acid binding agent, add quaternizing agent expoxy propane or N-Propyl Bromide 2-15 part, chitosan 5-40 part is carried out graft modification, obtains the chitosan quaternary ammonium salt material;

B. by above-mentioned chitosan quaternary ammonium salt material, with mass fraction, be methanol and/or the ethanol water washing of 5-30%, thereby after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, dissolve with deionized water or distilled water, then be placed in bag filter in the distilled water desalination of dialysing;

C. dialyse after desalination concentrating under reduced pressure or normal pressure is directly concentrated to generate the concentrated solution of chitosan-containing quaternary ammonium salt, with enough dehydrated alcohol and/or acetone precipitation, go out the chitosan quaternary ammonium salt wet stock again, finally use dehydrated alcohol and/or washing with acetone chitosan quaternary ammonium salt wet stock, can obtain the chitosan quaternary ammonium product salt after drying;

3) contain the preparation of the polyurethane bandage of sterilizing and itch-relieving function

The base polyurethane prepolymer for use as made in step 1 is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and chitosan microball that splendid attire contains the sterilizing and itch-relieving function or the B groove of chitosan quaternary ammonium salt, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to chitosan microball or the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.

2. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described catalyst is selected from dimethylethanolamine, organotin catalysts, triethylenediamine, dimethyl benzylamine, two (2,2-morpholine ethyl) ether, dimethylaminoethanol, the rare triamine of tetramethyl dipropyl, the dimethyl diethanolamine, a kind of in the DIMAPA diisopropanol.

3. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1 is characterized in that: described stabilizing agent is selected from a kind of in propionyl chloride, Benzenecarbonyl chloride., pyrovinic acid, maleic anhydride;

Described lubricant is silicone lubricant or polyethylene glycol oxide.

4. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described aromatic diisocyanate is selected from 4,4'-methyl diphenylene diisocyanate, 2,4'-methyl diphenylene diisocyanate, 2,2'-methyl diphenylene diisocyanate, Toluene-2,4-diisocyanate, a kind of in the 4-vulcabond.

5. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described polyether Glycols is polypropylene glycol or polytetrahydrofuran diol.

6. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described composition A is that molecular weight is the polyether Glycols of 800-1100, described composition B is that molecular weight is the polyether Glycols of 1800-2200, and the mass ratio of composition A and composition B is 1:0.57.

7. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described composition A is 63 parts.

8. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1 is characterized in that: described sterilizing and itch-relieving medicine is selected from one or more the combination in chlorhexidine, amoxicillin, tetracycline, eucalyptus oil, Co tinctura indomethacinum, methyl salicylate, beclometasone.

9. the binder made according to the described preparation method of any one in claim 1-8 is characterized in that: described binder comprises base material, is coated in the base polyurethane prepolymer for use as on base material, the chitosan microball that comprises the sterilizing and itch-relieving function or chitosan quaternary ammonium salt.

10. binder according to claim 9, it is characterized in that: the Unit Weight of described binder is 95-110g/m ², cross direction elongation is 2.7-3.5%, the longitudinal tensile strain rate is 10-20%.