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CN105816909A - Method for preparing high-elasticity high-absorbency hemostatic and bacteriostatic expansive sponge - Google Patents

Method for preparing high-elasticity high-absorbency hemostatic and bacteriostatic expansive sponge Download PDF

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CN105816909A
CN105816909A CN201610306067.7A CN201610306067A CN105816909A CN 105816909 A CN105816909 A CN 105816909A CN 201610306067 A CN201610306067 A CN 201610306067A CN 105816909 A CN105816909 A CN 105816909A
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sodium alginate
polyvinyl alcohol
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郑裕东
王岩森
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Beijing Zhongjie Rcomm Technology Development LLC
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University of Science and Technology Beijing USTB
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Abstract

一种高弹性高吸液性止血抑菌膨胀海绵及制备方法,属于医用材料领域。本发明将聚乙烯醇在去离子水中搅拌形成溶液,并向溶液中加入表面活性剂和海藻酸钠,通过搅拌使得海藻酸钠混合均匀,再加入催化剂、交联剂及抑菌剂,高速搅拌后倒入模具进行交联反应。将模具放入烘箱中成型,然后将样品浸泡在抑菌剂溶液或溶胶中,制成为海藻酸钠复合聚乙烯醇缩醛化膨胀海绵;或是向聚乙烯醇海藻酸钠混合溶液中加入银氨溶液,然后通过银镜反应生成银,合成海藻酸钠‑纳米银复合聚乙烯醇缩醛化膨胀海绵。本发明质轻、导热系数小、生物相容性好、干态润湿速率快、强度高、吸液倍率高、膨胀速率,可用作医用止血、抑菌敷料以及骨科或鼻腔手术填充材料。

The invention discloses a highly elastic and highly liquid-absorbing hemostatic and antibacterial expansion sponge and a preparation method thereof, which belong to the field of medical materials. In the present invention, polyvinyl alcohol is stirred in deionized water to form a solution, and surfactants and sodium alginate are added to the solution, and the sodium alginate is mixed evenly by stirring, then catalyst, crosslinking agent and bacteriostatic agent are added, and the mixture is stirred at high speed Then pour into the mold for cross-linking reaction. Put the mold into an oven to shape, and then soak the sample in the antibacterial agent solution or sol to make a sodium alginate composite polyvinyl acetalized expansion sponge; or add silver to the polyvinyl alcohol sodium alginate mixed solution Ammonia solution, and then generate silver through silver mirror reaction, and synthesize sodium alginate-nano-silver composite polyvinyl acetalization expansion sponge. The invention is light in weight, small in thermal conductivity, good in biocompatibility, fast in dry state wetting rate, high in strength, high in liquid absorption rate and expansion rate, and can be used as medical hemostasis, antibacterial dressing and orthopedic or nasal surgery filling material.

Description

一种高弹性高吸液性止血抑菌膨胀海绵的制备方法A kind of preparation method of high elasticity and high liquid absorption hemostatic antibacterial expansion sponge

技术领域technical field

本发明涉及应用于医用止血,生物抑菌,伤口快速愈合,骨填充物,鼻腔、牙龈等手术填充物等诸多领域的聚乙烯醇缩醛化膨胀海绵,尤其涉及一种生物相容性好、吸液速率快、吸液膨胀速率快的局部止血、医药载体及抑菌、降低创口感染率的聚乙烯醇缩醛化膨胀海绵及其制备方法。The present invention relates to a polyvinyl acetalized expansion sponge used in many fields such as medical hemostasis, biological antibacterial, rapid wound healing, bone filling, nasal cavity, gum and other surgical fillings, especially relates to a kind of good biocompatibility, A polyvinyl acetalized swelling sponge with fast liquid absorption rate and fast liquid absorption expansion rate, a medical carrier, antibacterial, and reduced wound infection rate, and a preparation method thereof.

背景技术Background technique

聚乙烯醇缩醛类海绵,特别是在一定缩醛度范围内的具有发泡结构的聚乙烯醇缩醛化海绵具有超强的吸液能力,其吸液倍数可达到自身重量的几倍至几十倍。另外,其具有高的吸液速率,吸液后具有良好的湿弹性,干速快,因而被广泛应用于医学领域,与传统明胶类、棉类、纱布类止血材料相比,其止血、膨胀、拉伸收缩性能等具有明显优势,发展前景好。Polyvinyl acetal sponges, especially polyvinyl acetalized sponges with a foaming structure within a certain range of acetalization, have super strong liquid absorption capacity, and their liquid absorption times can reach several times their own weight. Dozens of times. In addition, it has a high liquid absorption rate, good wet elasticity after absorbing liquid, and fast drying speed, so it is widely used in the medical field. Compared with traditional gelatin, cotton, and gauze hemostatic materials, its hemostatic, swelling , stretching and shrinkage properties have obvious advantages, and the development prospect is good.

海藻酸钠(SA)是从褐藻或细菌中提取出的天然多糖,可作为支架材料用于医学用途,并具备良好的生物相容性。通过离子交联形成的海藻酸钙纤维贴敷与出血创面可以吸收自重l5~20倍血液形成藻酸油凝胶发挥止血作用,并且已被广泛的运用于外科手术的止血中。Sodium alginate (SA) is a natural polysaccharide extracted from brown algae or bacteria, which can be used as a scaffold material for medical purposes and has good biocompatibility. Calcium alginate fibers formed by ionic cross-linking can absorb 15-20 times its own weight of blood to form alginate oil gel to play a hemostatic effect on bleeding wounds, and it has been widely used in surgical hemostasis.

在医用方面,传统医用材料纱布、棉球等会在使用过程中粘着创面,更换时造成机械性损伤,此外还会有细小纤维脱落、通透性差等缺点。海绵类材料一方面由于一体化成型,使用过程中不会有海绵碎屑脱落,另一方面又具备的多孔结构和较好的弹性,在吸收手术过程中渗出液的同时,能够及时通过压迫伤口方式止血。In terms of medical use, traditional medical materials such as gauze and cotton balls will stick to the wound during use and cause mechanical damage when replaced. In addition, there will be shortcomings such as shedding of fine fibers and poor permeability. On the one hand, due to the integrated molding of the sponge material, there will be no sponge debris falling off during use; Wound means hemostasis.

医用海绵多为聚氨酯海绵,生产程序相对较为复杂。聚氨酯海绵弹性差,质地较硬,不适用于手术伤口的吸液止血,只能用于术前消毒等。此外,废弃的聚氨酯海绵燃烧会生成大量含有氰基的有毒气体,难以处理。改性PVA海绵在一定程度上改善了聚氨酯海绵的弹性差与质地较硬的缺点,但由于其只具备单一的吸收液体性能,不具备及时快速止血的功能,不能满足手术或开放性创伤的治疗需要。Most medical sponges are polyurethane sponges, and the production procedures are relatively complicated. Polyurethane sponge has poor elasticity and hard texture, so it is not suitable for absorbing liquid to stop bleeding in surgical wounds, and can only be used for preoperative disinfection. In addition, the burning of waste polyurethane sponge will generate a large amount of toxic gas containing cyano groups, which is difficult to deal with. Modified PVA sponge has improved the disadvantages of poor elasticity and hard texture of polyurethane sponge to a certain extent, but because it only has a single liquid absorption performance, it does not have the function of timely and rapid hemostasis, and cannot meet the treatment of surgery or open wounds. need.

常用的可吸收止血海绵有壳聚糖、明胶海绵等,它们的作用机理和使用方法不尽相同,止血效果也有差别。壳聚糖(chitosans)是一种天然高分子材料,有良好的生物相容性,但仅由壳聚糖制备的止血海绵在较大的出血创面效果并不理想。明胶海绵是从动物皮肤中提取并经纯化得到的明胶制备的,用于外科手术和急救中,但明胶海绵的粘附性较差,易脱落,并且增加了伤口感染的可能性。Commonly used absorbable hemostatic sponges include chitosan, gelatin sponge, etc. Their mechanisms of action and methods of use are different, and their hemostatic effects are also different. Chitosan (chitosans) is a natural polymer material with good biocompatibility, but the hemostatic sponge prepared only from chitosan is not ideal for large bleeding wounds. Gelatin sponge is prepared from gelatin extracted and purified from animal skin, and is used in surgery and first aid, but gelatin sponge has poor adhesion, is easy to fall off, and increases the possibility of wound infection.

目前公开的专利中存在以下问题:采用淀粉等作为发泡剂制备医用改性PVA快速吸液海绵,但残留的发泡剂接触到伤口,容易引发基体的排异反应,发泡剂清洗与污染问题也制约其生产应用;采用碳酸氢钠作为发泡剂,制备了高吸水发泡聚乙烯醇海绵,产品泡孔不均匀,大小不一,工艺较难控制,产品成品率低;以聚乙烯醇、壳聚糖为原料,甲醛为交联剂,硫酸为催化剂,使用表面活性剂制备了具有抗菌性能的聚乙烯醇缩甲醛海绵,引入了壳聚糖,降低了材料的吸水性和柔和度,使复合材料不具备吸水时迅速膨胀的特点。另外在医用方面,急需高弹性、高吸液、柔性、生物相容性好并且抑菌、抗感染的医用敷料。The following problems exist in the currently disclosed patents: starch and the like are used as foaming agents to prepare medical modified PVA fast liquid-absorbing sponges, but the residual foaming agent contacts the wound, which is likely to cause rejection of the matrix, foaming agent cleaning and pollution Problems also restrict its production and application; using sodium bicarbonate as a foaming agent, a highly water-absorbing foamed polyvinyl alcohol sponge is prepared, the product cells are not uniform, the size is different, the process is difficult to control, and the product yield is low; Alcohol and chitosan are used as raw materials, formaldehyde is used as a crosslinking agent, sulfuric acid is used as a catalyst, and a surfactant is used to prepare a polyvinyl formal sponge with antibacterial properties. Chitosan is introduced to reduce the water absorption and softness of the material , so that the composite material does not have the characteristics of rapid expansion when absorbing water. In addition, medical dressings with high elasticity, high liquid absorption, flexibility, good biocompatibility, bacteriostasis and anti-infection are urgently needed.

本发明基于以上需要,为了克服以上制备方法存在的缺陷,解决传统生产方式导致的成品率低、质变、气泡不均,为了解决当前医用海绵不能满足实际需求的问题,需要开发一种具备高吸液、快速膨胀的性能,生物相容性好且质地柔软的膨胀海绵,并使其具备止血、抗菌能力。The present invention is based on the above needs, in order to overcome the defects of the above preparation methods, solve the low yield, qualitative change, and uneven bubbles caused by traditional production methods, and solve the problem that current medical sponges cannot meet actual needs, it is necessary to develop a sponge with high absorption capacity. Liquid, rapid swelling performance, good biocompatibility and soft texture swelling sponge, and make it have hemostatic and antibacterial ability.

发明内容Contents of the invention

本发明提供一种原料种类少、制备工艺简单、生产成本低廉的吸液止血、抑菌、具有良好生物相容性的聚乙烯醇缩醛化膨胀海绵,较高的孔隙率和开孔结构赋予材料高吸收液体和快膨胀能力。所用海藻酸盐为天然多糖碳水化合物,能够加速血凝过程,使海绵可以应用于外科手术中清理渗出液并凝血止血。发明制备出的多糖修饰聚乙烯醇缩醛化膨胀海绵质地柔软,回弹性接近100%,适合做鼻腔手术的填充海绵,起到止血支撑作用,也可作为医用敷料,起到抗菌、止血作用。本发明还可在较宽的范围内调节膨胀海绵孔径大小、弹性、强度、吸水速率及吸水倍率等物理性能指标,满足不同应用领域对产品性能的不同要求。The invention provides a polyvinyl acetalized expansion sponge with few types of raw materials, simple preparation process and low production cost, which is liquid-absorbing, hemostatic, antibacterial, and has good biocompatibility. It has high porosity and open-pore structure. Material high liquid absorption and fast swelling capacity. The alginate used is a natural polysaccharide carbohydrate, which can accelerate the blood coagulation process, so that the sponge can be used in surgical operations to clean up exudate and coagulate to stop bleeding. The polysaccharide-modified polyvinyl alcohol acetalized expansion sponge prepared by the invention is soft in texture and has a resilience close to 100%. It is suitable as a filling sponge for nasal surgery, plays a role of hemostatic support, and can also be used as a medical dressing to play antibacterial and hemostatic effects. The present invention can also adjust physical performance indicators such as the pore size, elasticity, strength, water absorption rate and water absorption ratio of the expanded sponge within a wide range, so as to meet the different requirements of different application fields for product performance.

一种高弹性高吸液性止血抑菌膨胀海绵,其特征在于,所述材料包括聚乙烯醇、海藻酸钠、抑菌剂或银氨溶液、交联剂、催化剂、表面活性剂;其中,聚乙烯醇的醇解度在80%~90%之间,平均聚合度在1000~2000之间;各物料用量按重量计为:聚乙烯醇5%~10%,海藻酸钠1%~5%,抑菌剂6%~8%,交联剂7%~9%,催化剂1~3%,表面活性剂0.25%~0.45%,余量水余量水50%~60%,银氨溶液5%~10%。止血抑菌膨胀海绵吸水倍数为9~25倍,体积膨胀倍率为10~15倍。A highly elastic and highly liquid-absorbent hemostatic and antibacterial expansion sponge, characterized in that the material includes polyvinyl alcohol, sodium alginate, bacteriostatic agent or silver ammonia solution, crosslinking agent, catalyst, and surfactant; wherein, The degree of alcoholysis of polyvinyl alcohol is between 80% and 90%, and the average degree of polymerization is between 1000 and 2000; the amount of each material is calculated by weight: polyvinyl alcohol 5% to 10%, sodium alginate 1% to 5 %, bacteriostatic agent 6%~8%, crosslinking agent 7%~9%, catalyst 1~3%, surfactant 0.25%~0.45%, balance water, balance water 50%~60%, silver ammonia solution 5% to 10%. The hemostatic and antibacterial expansion sponge has a water absorption ratio of 9 to 25 times and a volume expansion ratio of 10 to 15 times.

如上所述抑菌剂为无机抑菌剂、有机抑菌剂及光催化抑菌剂中的一种或多种;交联剂为醛溶液,是甲醛、戊二醛,脂肪醛中的一种或多种;所述催化剂为盐酸、硫酸中的一种或多种;所述表面活性剂为十二烷基磺酸钠、十二烷基硫酸铵、十二烷基苯磺酸钠中的一种或多种。As mentioned above, the bacteriostatic agent is one or more of inorganic bacteriostatic agents, organic bacteriostatic agents and photocatalytic bacteriostatic agents; the crosslinking agent is an aldehyde solution, which is one of formaldehyde, glutaraldehyde, and fatty aldehyde or more; the catalyst is one or more of hydrochloric acid, sulfuric acid; the surfactant is sodium dodecylsulfonate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate one or more.

所述止血抑菌膨胀海绵的制备分2种方法,复合抑菌剂法和银氨溶液反应合成法。The preparation of the hemostatic and antibacterial expansion sponge is divided into two methods, the compound antibacterial agent method and the silver ammonia solution reaction synthesis method.

1、复合抑菌剂法具体制备工艺为:1. The specific preparation process of compound antibacterial agent method is:

步骤一、聚乙烯醇与海藻酸钠的溶解,Step 1, the dissolution of polyvinyl alcohol and sodium alginate,

按质量比为1:5~1:9称取聚乙烯醇与蒸馏水混合,将其在85℃~95℃恒温水浴锅内低速搅拌溶解至溶液澄清透明;Weigh polyvinyl alcohol and distilled water at a mass ratio of 1:5 to 1:9, mix it with distilled water, stir and dissolve it in a constant temperature water bath at 85°C to 95°C until the solution is clear and transparent;

将恒温水浴锅温度调至50~70℃,按聚乙烯醇与海藻酸钠质量比为1:0.1~1:1称取海藻酸钠,加入到上述聚乙烯醇溶液中,继续搅拌至海藻酸钠溶解均匀;Adjust the temperature of the constant temperature water bath to 50-70°C, weigh the sodium alginate according to the mass ratio of polyvinyl alcohol to sodium alginate at 1:0.1-1:1, add it to the above polyvinyl alcohol solution, and continue stirring until the alginic acid Sodium dissolves evenly;

步骤二、表面活性剂与催化剂的添加方案,Step 2, the addition scheme of surfactant and catalyst,

在聚乙烯醇海藻酸钠混合溶液中加入表面活性剂与催化剂混合溶液,低速搅拌2~5min,使表面活性剂与催化剂能够均匀分散到溶液中;Add the mixed solution of surfactant and catalyst to the mixed solution of polyvinyl alcohol sodium alginate, and stir at a low speed for 2 to 5 minutes, so that the surfactant and catalyst can be uniformly dispersed in the solution;

步骤三、交联剂的加入Step 3, the addition of cross-linking agent

按缩醛反应聚乙烯醇与醛的摩尔比例称取一定质量醛溶液,加入到步骤二中所得的混合溶液中,迅速调高搅拌转速,搅拌6~15min.;Weigh a certain amount of aldehyde solution according to the molar ratio of polyvinyl alcohol and aldehyde in the acetal reaction, add it to the mixed solution obtained in step 2, quickly increase the stirring speed, and stir for 6-15 minutes.;

步骤四、聚乙烯醇缩醛化膨胀海绵成型,Step 4: Polyvinyl acetalization expansion sponge molding,

把步骤三中得到混合液体注入模具中,将模具放入烘箱,调节温度至50~75℃,使交联继续进行,待6~8h后取出模具,将膨胀海绵从模具中取出,用去离子水冲洗2~5次,裁剪成合适的形状,将裁剪后的产品浸泡在含有过氧化氢的溶液中,或浸泡在超声清洗槽中进行超声清洗;Inject the mixed liquid obtained in step 3 into the mold, put the mold into an oven, adjust the temperature to 50-75°C to continue the cross-linking, take out the mold after 6-8 hours, take the expanded sponge out of the mold, and use deionized Rinse with water for 2 to 5 times, cut into a suitable shape, soak the cut product in a solution containing hydrogen peroxide, or soak in an ultrasonic cleaning tank for ultrasonic cleaning;

步骤五、抑菌剂复合Step five, antibacterial compound

将经过深度清洗的样品浸泡在占体系总质量为6%~8%的抑菌剂的溶液或溶胶中,使样品全部浸没,10~15h后取出样品,得到高弹性高吸液性止血抑菌聚乙烯醇缩醛化膨胀海绵成品。Soak the deeply cleaned sample in the solution or sol of bacteriostatic agent accounting for 6% to 8% of the total mass of the system, so that the sample is completely submerged, and take out the sample after 10 to 15 hours to obtain a highly elastic, highly liquid-absorbent hemostatic and antibacterial agent Polyvinyl acetalized expanded sponge finished product.

其中,抑菌剂也可以在步骤三中与交联剂一同加入。Wherein, the antibacterial agent can also be added together with the crosslinking agent in step three.

所述聚乙烯醇缩醛化膨胀海绵,具有三维网状开孔结构,平均孔径大小在The polyvinyl acetalized expansion sponge has a three-dimensional network open-pore structure, and the average pore size is between

10μm~1500μm之间,开孔率在30%~60%之间,孔隙率在60%~90%之Between 10μm and 1500μm, the porosity is between 30% and 60%, and the porosity is between 60% and 90%.

间,缩醛度在50%~85%之间。Between, the degree of acetalization is between 50% and 85%.

2、银氨溶液反应合成法具体制备工艺为:2. The specific preparation process of silver ammonia solution reaction synthesis method is:

步骤一、聚乙烯醇与海藻酸钠的溶解;Step 1, the dissolution of polyvinyl alcohol and sodium alginate;

按质量比为1:5~1:9称取聚乙烯醇与蒸馏水混合,将其在85℃~95℃恒温水浴锅内低速搅拌溶解至溶液澄清透明;Weigh polyvinyl alcohol and distilled water at a mass ratio of 1:5 to 1:9, mix it with distilled water, stir and dissolve it in a constant temperature water bath at 85°C to 95°C until the solution is clear and transparent;

将恒温水浴锅温度调至50~70℃,按聚乙烯醇与海藻酸钠质量比为1:0.1~1:1称取海藻酸钠,加入到上述聚乙烯醇溶液中,继续搅拌至海藻酸钠溶解均匀;Adjust the temperature of the constant temperature water bath to 50-70°C, weigh the sodium alginate according to the mass ratio of polyvinyl alcohol to sodium alginate at 1:0.1-1:1, add it to the above polyvinyl alcohol solution, and continue stirring until the alginic acid Sodium dissolves evenly;

步骤二、表面活性剂与催化剂的添加方案,Step 2, the addition scheme of surfactant and catalyst,

在聚乙烯醇海藻酸钠混合溶液中加入表面活性剂与催化剂混合溶液,低转速搅拌2~5min,使表面活性剂与催化剂能够均匀分散到溶液中;Add the mixed solution of surfactant and catalyst into the mixed solution of polyvinyl alcohol sodium alginate, stir at low speed for 2-5 minutes, so that the surfactant and catalyst can be evenly dispersed in the solution;

步骤三、银氨溶液的加入,Step 3, the addition of silver ammonia solution,

将配置好的银氨溶液,用滴液漏斗缓慢滴入聚乙烯醇海藻酸钠混合溶液中,滴完后静置2~3min,使银氨溶液分散均匀;Slowly drop the prepared silver ammonia solution into the polyvinyl alcohol sodium alginate mixed solution with a dropping funnel, and let it stand for 2 to 3 minutes after dropping to make the silver ammonia solution evenly dispersed;

步骤四、交联剂的加入及银镜反应,Step 4, the addition of cross-linking agent and silver mirror reaction,

按缩醛反应聚乙烯醇与醛的摩尔比例称取一定质量醛溶液,将醛溶液加入到步骤二中所得的混合溶液中,迅速调高搅拌转速,发生银镜反应:以甲醛为例(NH4)2CO3:HCHO+4[Ag(NH3)2]OH=(NH4)2CO3+4Ag↓+6NH3+2H2O,Weigh a certain amount of aldehyde solution according to the molar ratio of polyvinyl alcohol and aldehyde in the acetal reaction, add the aldehyde solution to the mixed solution obtained in step 2, quickly increase the stirring speed, and a silver mirror reaction occurs: take formaldehyde as an example (NH 4 ) 2 CO 3 : HCHO+4[Ag(NH 3 ) 2 ]OH=(NH 4 ) 2 CO 3 +4Ag↓+6NH 3 +2H 2 O,

有黑棕色Ag生成,搅拌6~15min;Black-brown Ag is formed, stir for 6-15 minutes;

步骤五、高弹性高吸液性止血抑菌聚乙烯醇缩醛化膨胀海绵成型,Step 5. High elasticity, high fluid absorption, hemostatic and antibacterial polyvinyl acetalization expansion sponge molding,

把步骤四中得到混合液体注入模具中,将模具放入烘箱,调节温度至50~75℃,使交联继续进行,待6~8h后取出模具,将膨胀海绵从模具中取出,用去离子水充分清洗,裁剪成合适的形状,将裁剪后的产品浸泡在超声清洗槽中进行超声清洗,最终得到高弹性高吸液性止血抑菌聚乙烯醇缩醛化膨胀海绵成品。Inject the mixed liquid obtained in step 4 into the mold, put the mold into an oven, adjust the temperature to 50-75°C, and continue the cross-linking, take out the mold after 6-8 hours, take the expanded sponge out of the mold, and use deionized Fully wash with water, cut into a suitable shape, soak the cut product in an ultrasonic cleaning tank for ultrasonic cleaning, and finally obtain a finished product of high elasticity, high liquid absorption, hemostatic and antibacterial polyvinyl acetalized expansion sponge.

步骤五、高弹性高吸液性止血抑菌聚乙烯醇缩醛化膨胀海绵成型Step 5. High elasticity, high liquid absorption, hemostatic and antibacterial polyvinyl acetalization expansion sponge molding

把步骤四中得到混合液体注入模具中,将模具放入烘箱,调节温度至50~75℃,使交联继续进行,待6~8h后取出模具,将膨胀海绵从模具中取出,用去离子水充分清洗,裁剪成合适的形状,将裁剪后的产品浸泡在超声清洗槽中进行超声清洗,最终得到高弹性高吸液性止血抑菌聚乙烯醇缩醛化膨胀海绵成品。Inject the mixed liquid obtained in step 4 into the mold, put the mold into an oven, adjust the temperature to 50-75°C, and continue the cross-linking, take out the mold after 6-8 hours, take the expanded sponge out of the mold, and use deionized Fully wash with water, cut into a suitable shape, soak the cut product in an ultrasonic cleaning tank for ultrasonic cleaning, and finally obtain a finished product of high elasticity, high liquid absorption, hemostatic and antibacterial polyvinyl acetalized expansion sponge.

与现有技术相比,本发明具有如下优点和有益效果Compared with the prior art, the present invention has the following advantages and beneficial effects

1、本发明所获得的高弹性高吸液性止血抑菌聚乙烯醇缩醛化膨胀海绵,回弹性接近100%,且拉伸强度好,不会有碎屑脱落,克服了现有医用纱布在手术过程中会有细小纤维脱落、吸收组织液或血液效果差、效率低的问题,并且具有优异的生物相容性和细胞亲和性,可以在手术过程中迅速吸收伤口流出的大量组织液和血液,能够有效降低流出液体对手术的干扰且不会残留碎屑。1. The polyvinyl acetalized expansion sponge with high elasticity, high liquid absorption, hemostatic antibacterial and antibacterial properties obtained by the present invention has a resilience close to 100%, and has good tensile strength, and no debris will fall off, which overcomes the existing medical gauze During the operation, there will be problems such as shedding of fine fibers, poor absorption of tissue fluid or blood, and low efficiency. It has excellent biocompatibility and cell affinity, and can quickly absorb a large amount of tissue fluid and blood from the wound during the operation. , can effectively reduce the interference of the outflow fluid to the operation and will not leave debris.

2、本发明所获得的高弹性高吸液性止血抑菌聚乙烯醇缩醛化膨胀海绵,具有较为优异的吸液性能,能吸收10~20倍自身重量的生理盐水,吸液后体积膨胀可达10~15倍,较之普通海绵有较大提升。2. The polyvinyl acetalized expansion sponge with high elasticity and high liquid absorption, hemostasis and antibacterial properties obtained in the present invention has relatively excellent liquid absorption performance, can absorb 10 to 20 times its own weight of normal saline, and expands in volume after absorbing liquid It can reach 10-15 times, which is a big improvement compared with ordinary sponges.

3、本发明所获得的高弹性高吸液性止血抑菌聚乙烯醇缩醛化膨胀海绵,具有较好的抑菌能力,对多种细菌均有良好的抑菌效果,可针对不同的抑菌环境,在膨胀海绵上复合合适的抑菌剂。3. The polyvinyl acetalized expansion sponge with high elasticity, high liquid absorption, hemostasis and antibacterial properties obtained in the present invention has good antibacterial ability, and has good antibacterial effect on various bacteria, and can be used for different antibacterial Bacterial environment, compound the appropriate antibacterial agent on the expansion sponge.

4、本发明的制备过程简单,工艺成熟,生产效率高,产品生产周期短;所采用原料成本低,易得,易合成;节约了生产用水,降低了生产能耗,减少了生产排放。利用表面活性剂,并采用机械搅拌的方法气泡,孔径大小可控,孔隙率可控,产品泡孔均匀。4. The preparation process of the present invention is simple, the process is mature, the production efficiency is high, and the product production cycle is short; the raw materials used are low in cost, easy to obtain, and easy to synthesize; production water is saved, production energy consumption is reduced, and production discharge is reduced. Using surfactants and adopting the method of mechanical stirring to make air bubbles, the pore size and porosity are controllable, and the product cells are uniform.

附图说明Description of drawings

图1为缩醛反应化学结构示意图Figure 1 is a schematic diagram of the chemical structure of the acetal reaction

图2(a)(b)为海藻酸钠复合聚乙烯醇缩醛化膨胀海绵的光学显微镜及扫描电镜图Figure 2(a)(b) is the optical microscope and scanning electron microscope images of sodium alginate composite polyvinyl acetalized expanded sponge

图3为纳米银/藻酸钠复合聚乙烯醇缩醛化膨胀海绵的扫描电镜图。Fig. 3 is a scanning electron micrograph of nano-silver/sodium alginate composite polyvinyl acetalized swelling sponge.

具体实施方式detailed description

以下结合具体实施案例进一步阐述本发明。应理解为,这些实施案例仅仅用于说明本发明而不是用于限制本发明的范围。此外应理解,本领域的技术人员在阅读了本发明讲授的内容之后,对本发明所做各种等价形式之改动,同样落入本申请权利要求书所要求的范围之内。The present invention will be further described below in conjunction with specific examples of implementation. It should be understood that these embodiments are only used to illustrate the present invention rather than limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various equivalent changes to the present invention, which also fall within the scope required by the claims of the present application.

实施例1Example 1

步骤一、去一定质量的PVA,按PVA与去离子水质量比为1:5的要求加入一定量的去离子水。在95℃的水浴锅中加热搅拌1h,让PVA颗粒充分溶解。将恒温水浴锅温度调至60℃,按聚乙烯醇与海藻酸钠质量比为1:0.2称取海藻酸钠,加入到上述聚乙烯醇溶液中,继续搅拌至海藻酸钠溶解均匀,静置0.5h,除去气泡并保温。Step 1: remove a certain amount of PVA, and add a certain amount of deionized water according to the requirement that the mass ratio of PVA to deionized water is 1:5. Heat and stir in a water bath at 95°C for 1 hour to fully dissolve the PVA particles. Adjust the temperature of the constant temperature water bath to 60°C, weigh the sodium alginate according to the mass ratio of polyvinyl alcohol to sodium alginate as 1:0.2, add it to the above polyvinyl alcohol solution, continue to stir until the sodium alginate dissolves evenly, and let stand 0.5h, remove air bubbles and keep warm.

步骤二、在聚乙烯醇海藻酸钠混合溶液中加入表面活性剂与催化剂混合溶液,以低速搅拌2~5min,使表面活性剂与催化剂能够均匀分散到溶液中,使表面活性剂与催化剂能够均匀分散到溶液中。Step 2: Add the mixed solution of surfactant and catalyst to the mixed solution of polyvinyl alcohol sodium alginate, and stir at a low speed for 2 to 5 minutes, so that the surfactant and catalyst can be uniformly dispersed in the solution, so that the surfactant and catalyst can be uniformly dispersed. dispersed into the solution.

步骤三、按聚乙烯醇与甲醛溶液质量比为1:1称取甲醛溶液,将甲醛溶液加入到混合溶液中,迅速调高搅拌转速,搅拌约6~8min。Step 3: Weigh the formaldehyde solution according to the mass ratio of polyvinyl alcohol and formaldehyde solution at 1:1, add the formaldehyde solution into the mixed solution, quickly increase the stirring speed, and stir for about 6-8 minutes.

步骤四、把混合液体注入模具中,将模具放入烘箱,调节温度至60℃,使交联继续进行,待6~8h后取出模具,将膨胀海绵从模具中取出,用去离子水冲洗2~5次,裁剪成合适的形状,将裁剪后的产品浸泡在超声清洗槽中进行超声清洗。Step 4: Inject the mixed liquid into the mold, put the mold into an oven, adjust the temperature to 60°C to continue the crosslinking, take out the mold after 6-8 hours, take the expansion sponge out of the mold, and rinse with deionized water for 2 ~5 times, cut into a suitable shape, soak the cut product in an ultrasonic cleaning tank for ultrasonic cleaning.

步骤五、将经过深度清洗的样品浸泡在占体系总质量8%季铵盐溶液中,使样品全部浸没,12h后取出样品,得到季铵盐-海藻酸钠复合聚乙烯醇缩醛化膨胀海绵成品。Step 5. Soak the deep-cleaned sample in 8% quaternary ammonium salt solution accounting for the total mass of the system, so that the sample is completely submerged, and take out the sample after 12 hours to obtain a quaternary ammonium salt-sodium alginate composite polyvinyl acetalized expansion sponge finished product.

实施例2Example 2

步骤一、去一定质量的PVA,按PVA与去离子水质量比为1:7的要求加入一定量的去离子水。在95℃的水浴锅中加热搅拌1h,让PVA颗粒充分溶解。将恒温水浴锅温度调至60℃,按聚乙烯醇与海藻酸钠质量比为1:0.6称取海藻酸钠,加入到上述聚乙烯醇溶液中,继续搅拌至海藻酸钠溶解均匀,静置0.5h,除去气泡并保温。Step 1. Remove a certain amount of PVA, and add a certain amount of deionized water according to the requirement that the mass ratio of PVA to deionized water is 1:7. Heat and stir in a water bath at 95°C for 1 hour to fully dissolve the PVA particles. Adjust the temperature of the constant temperature water bath to 60°C, weigh the sodium alginate according to the mass ratio of polyvinyl alcohol to sodium alginate as 1:0.6, add it to the above polyvinyl alcohol solution, continue to stir until the sodium alginate dissolves evenly, and let stand 0.5h, remove air bubbles and keep warm.

步骤二、在聚乙烯醇海藻酸钠混合溶液中加入表面活性剂与催化剂混合溶液,低速搅拌2~5min,使表面活性剂与催化剂能够均匀分散到溶液中。Step 2: Add the mixed solution of surfactant and catalyst into the mixed solution of polyvinyl alcohol sodium alginate, and stir at a low speed for 2-5 minutes, so that the surfactant and catalyst can be uniformly dispersed in the solution.

步骤三、按聚乙烯醇与戊二醛溶液质量比为1:1.5称取戊二醛溶液,加入到混合溶液中,同时加入占体系总质量6%的TiO2颗粒,迅速调高搅拌转速,搅拌约6~8min。Step 3, take the glutaraldehyde solution by weighing the glutaraldehyde solution as 1:1.5 according to the mass ratio of polyvinyl alcohol to the glutaraldehyde solution, add it to the mixed solution, add TiO particles accounting for 6% of the total mass of the system at the same time, and quickly increase the stirring speed, Stir for about 6-8 minutes.

步骤四、把混合液体注入模具中,将模具放入烘箱,调节温度至60℃,使交联继续进行,待6~8h后取出模具,将膨胀海绵从模具中取出,用去离子水冲洗2~5次,裁剪成合适的形状,将裁剪后的产品浸泡在超声清洗槽中进行超声清洗,得到复合聚乙烯醇缩醛化膨胀海绵成品。Step 4: Inject the mixed liquid into the mold, put the mold into an oven, adjust the temperature to 60°C to continue the crosslinking, take out the mold after 6-8 hours, take the expansion sponge out of the mold, and rinse with deionized water for 2 ~5 times, cut into a suitable shape, soak the cut product in an ultrasonic cleaning tank for ultrasonic cleaning, and obtain a finished composite polyvinyl acetalized expansion sponge.

实施例3Example 3

步骤一、去一定质量的PVA,按PVA与去离子水质量比为1:8的要求加入一定量的去离子水。在95℃的水浴锅中加热搅拌1h,让PVA颗粒充分溶解。将恒温水浴锅温度调至60℃,按聚乙烯醇与海藻酸钠质量比为1:1称取海藻酸钠,加入到上述聚乙烯醇溶液中,继续搅拌至海藻酸钠溶解均匀,静置0.5h,除去气泡并保温。Step 1: remove a certain amount of PVA, and add a certain amount of deionized water according to the requirement that the mass ratio of PVA to deionized water is 1:8. Heat and stir in a water bath at 95°C for 1 hour to fully dissolve the PVA particles. Adjust the temperature of the constant temperature water bath to 60°C, weigh the sodium alginate according to the mass ratio of polyvinyl alcohol to sodium alginate as 1:1, add it to the above polyvinyl alcohol solution, continue to stir until the sodium alginate dissolves evenly, and let stand 0.5h, remove air bubbles and keep warm.

步骤二、在聚乙烯醇海藻酸钠混合溶液中加入表面活性剂与催化剂混合溶液,低转速搅拌2~5min,使表面活性剂与催化剂能够均匀分散到溶液中。Step 2: Add the mixed solution of surfactant and catalyst into the mixed solution of polyvinyl alcohol sodium alginate, and stir at a low speed for 2-5 minutes, so that the surfactant and catalyst can be uniformly dispersed in the solution.

步骤三、按聚乙烯醇与脂肪醛质量比为1:1称取脂肪醛溶液,加入到混合溶液中,迅速调高搅拌转速,搅拌约6~8min。Step 3: Weigh the fatty aldehyde solution according to the mass ratio of polyvinyl alcohol and fatty aldehyde to 1:1, add it into the mixed solution, quickly increase the stirring speed, and stir for about 6-8 minutes.

步骤四、把混合液体注入模具中,将模具放入烘箱,调节温度至60℃,使交联继续进行,待6~8h后取出模具,将膨胀海绵从模具中取出,用去离子水冲洗2~5次,裁剪成合适的形状,将裁剪后的产品浸泡在超声清洗槽中进行超声清洗。Step 4: Inject the mixed liquid into the mold, put the mold into an oven, adjust the temperature to 60°C to continue the crosslinking, take out the mold after 6-8 hours, take the expansion sponge out of the mold, and rinse with deionized water for 2 ~5 times, cut into a suitable shape, soak the cut product in an ultrasonic cleaning tank for ultrasonic cleaning.

步骤五、将经过深度清洗的样品浸泡在150ml质量分数为0.15mol/L的纳米银溶液中,使样品全部浸没于溶液中12h后取出样品,得到复合聚乙烯醇缩醛化膨胀海绵成品。Step 5. Soak the deep-cleaned sample in 150ml of nano-silver solution with a mass fraction of 0.15mol/L, immerse the sample completely in the solution for 12 hours, and then take out the sample to obtain a finished composite polyvinyl acetalized expanded sponge.

实施例4Example 4

步骤一、去一定质量的PVA,按PVA与去离子水质量比为1:6的要求加入一定量的去离子水。在95℃的水浴锅中加热搅拌1h,让PVA颗粒充分溶解。将恒温水浴锅温度调至60℃,按聚乙烯醇与海藻酸钠质量比为1:0.6称取海藻酸钠,加入到上述聚乙烯醇溶液中,继续搅拌至海藻酸钠溶解均匀,静置0.5h,除去气泡并保温。Step 1. Remove a certain amount of PVA, and add a certain amount of deionized water according to the requirement that the mass ratio of PVA to deionized water is 1:6. Heat and stir in a water bath at 95°C for 1 hour to fully dissolve the PVA particles. Adjust the temperature of the constant temperature water bath to 60°C, weigh the sodium alginate according to the mass ratio of polyvinyl alcohol to sodium alginate as 1:0.6, add it to the above polyvinyl alcohol solution, continue to stir until the sodium alginate dissolves evenly, and let stand 0.5h, remove air bubbles and keep warm.

步骤二、将配置好的0.1mol/L银氨溶液,用滴液漏斗滴入聚乙烯醇海藻酸钠混合溶液中,滴完后静置2~3min,使银氨溶液分散均匀。Step 2. Drop the prepared 0.1mol/L silver ammonia solution into the polyvinyl alcohol sodium alginate mixed solution with a dropping funnel, and let it stand for 2-3 minutes after dropping to make the silver ammonia solution evenly dispersed.

步骤三、在聚乙烯醇海藻酸钠混合溶液中加入表面活性剂与催化剂混合溶液,低转速搅拌2~5min,使表面活性剂与催化剂能够均匀分散到溶液中。Step 3: Add the mixed solution of surfactant and catalyst into the mixed solution of polyvinyl alcohol sodium alginate, and stir at a low speed for 2-5 minutes, so that the surfactant and catalyst can be uniformly dispersed in the solution.

步骤四、按聚乙烯醇与乙醇醛物质的量比为1:1乙醇醛溶液,加入到混合溶液中,迅速调高搅拌转速,待有黑棕色Ag生成,搅拌6~15min。Step 4: According to the ratio of polyvinyl alcohol and glycolaldehyde to 1:1 glycolaldehyde solution, add it to the mixed solution, quickly increase the stirring speed, and stir for 6-15 minutes when black-brown Ag is formed.

步骤五、把混合液体注入模具中,将模具放入烘箱,调节温度至60℃,使交联继续进行,待6~8h后取出模具,将膨胀海绵从模具中取出,用去离子水冲洗2~5次,裁剪成合适的形状,将裁剪后的产品浸泡在超声清洗槽中进行超声清洗,最终得到复合聚乙烯醇缩醛化膨胀海绵成品。Step 5. Inject the mixed liquid into the mold, put the mold into an oven, adjust the temperature to 60°C, and continue the cross-linking. After 6-8 hours, take out the mold, take out the expansion sponge from the mold, and rinse with deionized water for 2 ~5 times, cut into a suitable shape, soak the cut product in an ultrasonic cleaning tank for ultrasonic cleaning, and finally obtain a composite polyvinyl acetalized expansion sponge product.

Claims (7)

1. a high resiliency high liquid-absorbing hemostatic bacteriostatic expandable sponges, it is characterised in that described material includes gathering Vinyl alcohol, sodium alginate, antibacterial or silver ammino solution, cross-linking agent, catalyst, surfactant;Wherein, The alcoholysis degree of polyvinyl alcohol is between 80%~90%, and average degree of polymerization is between 1000~2000;Each material Consumption is by weight: polyvinyl alcohol 5%~10%, sodium alginate 1%~5%, antibacterial 6%~8%, Cross-linking agent 7%~9%, catalyst 1~3%, surfactant 0.25%~0.45%, excess water 50%~60%, Silver ammino solution 5%~10%.
A kind of high resiliency high liquid-absorbing hemostatic bacteriostatic expandable sponges the most according to claim 1, its feature Being, described antibacterial is one or more in inorganic antibacterial, organic antibacterial and photocatalysis antibacterial; Cross-linking agent is aldehyde solution, is formaldehyde, glutaraldehyde, one or more in fatty aldehyde;Described catalyst be hydrochloric acid, One or more in sulphuric acid;Described surfactant be dodecyl sodium sulfate, ammonium lauryl sulfate, ten One or more in dialkyl benzene sulfonic acids sodium.
A kind of high resiliency high liquid-absorbing hemostatic bacteriostatic expandable sponges the most according to claim 1, its feature Being, sponge sucks in water, and multiple is 9~25 times, and volume expansion ratio is 10~15 times.
4. the preparation of an a kind of high resiliency high liquid-absorbing hemostatic bacteriostatic expandable sponges according to claim 1 Method, it is characterised in that the preparation of hemostatic bacteriostatic expandable sponges uses compound preservative legal system, and it specifically prepares work Skill is:
Step one, polyvinyl alcohol and the dissolving of sodium alginate,
It is that 1:5~1:9 weighing polyvinyl alcohol mixes with distilled water in mass ratio, by it at 85 DEG C~95 DEG C of constant temperature In water-bath, stirring at low speed is dissolved to solution clear;
Water bath with thermostatic control pot temperature is adjusted to 50~70 DEG C, is 1:0.1~1:1 by polyvinyl alcohol and sodium alginate mass ratio Weigh sodium alginate, join in above-mentioned poly-vinyl alcohol solution, continue stirring to sodium alginate and be uniformly dissolved;
Step 2, surfactant and the interpolation scheme of catalyst,
Adding surfactant and catalyst mixed solution in polyvinyl alcohol mixed solution of sodium alginate, low speed stirs Mix 2~5min, enable surfactant and catalyst to evenly spread in solution;
Step 3, the addition of cross-linking agent
Weigh certain mass aldehyde solution by the molar ratio of aldolisation polyvinyl alcohol Yu aldehyde, join in step 2 In the mixed solution of gained, heighten rapidly speed of agitator, stir 6~15min.;
Step 4, Polyvinyl acetal expandable sponges molding,
Inject in mould step 3 obtains mixing liquid, mould put into baking oven, adjust the temperature to 50~ 75 DEG C, make crosslinking proceed, behind 6~8h, take out mould, expandable sponges is removed from the molds, spends Ionized water rinses 2~5 times, is cut into suitable shape, is immersed in the product after cutting containing hydrogen peroxide Solution in, or be immersed in ultrasonic cleaning tank and carry out ultrasonic cleaning;
Step 5, antibacterial are compound
The sample cleaned through the degree of depth is immersed in the solution or molten of the antibacterial that the system gross mass of accounting for is 6%~8% In glue, make the whole submergence of sample, after 10~15h, take out sample, obtain high resiliency high liquid-absorbing hemostatic bacteriostatic and gather Vinyl acetal expandable sponges finished product.
The preparation side of a kind of high resiliency high liquid-absorbing hemostatic bacteriostatic expandable sponges the most according to claim 4 Method, it is characterised in that antibacterial is together to add with cross-linking agent in step 3.
The preparation side of a kind of high resiliency high liquid-absorbing hemostatic bacteriostatic expandable sponges the most according to claim 4 Method, it is characterised in that described Polyvinyl acetal expandable sponges, has three-dimensional netted open-celled structure, Mean pore size between 10 μm~1500 μm, percent opening between 30%~60%, porosity Between 60%~90%, acetalizing degree is between 50%~85%.
The preparation side of a kind of high resiliency high liquid-absorbing hemostatic bacteriostatic expandable sponges the most according to claim 1 Method, it is characterised in that the preparation of hemostatic bacteriostatic expandable sponges uses silver ammino solution reaction synthesis method,
Concrete preparation technology is:
Step one, polyvinyl alcohol and the dissolving of sodium alginate;
It is that 1:5~1:9 weighing polyvinyl alcohol mixes with distilled water in mass ratio, by it at 85 DEG C~95 DEG C of constant temperature In water-bath, stirring at low speed is dissolved to solution clear;
Water bath with thermostatic control pot temperature is adjusted to 50~70 DEG C, is 1:0.1~1:1 by polyvinyl alcohol and sodium alginate mass ratio Weigh sodium alginate, join in above-mentioned poly-vinyl alcohol solution, continue stirring to sodium alginate and be uniformly dissolved;
Step 2, surfactant and the interpolation scheme of catalyst,
Surfactant and catalyst mixed solution, the slow-speed of revolution is added in polyvinyl alcohol mixed solution of sodium alginate Stirring 2~5min, enables surfactant and catalyst to evenly spread in solution;
Step 3, the addition of silver ammino solution,
The silver ammino solution that will have configured, is slowly dropped in polyvinyl alcohol mixed solution of sodium alginate with Dropping funnel, Stand 2~3min after dripping off, make silver ammino solution be uniformly dispersed;
Step 4, the addition of cross-linking agent and silver mirror reaction,
Weigh certain mass aldehyde solution by the molar ratio of aldolisation polyvinyl alcohol Yu aldehyde, aldehyde solution is joined In step 2 in the mixed solution of gained, heighten rapidly speed of agitator, silver mirror reaction occurs: have dark brown Ag Generate, stir 6~15min;
Step 5, high resiliency high liquid-absorbing hemostatic bacteriostatic Polyvinyl acetal expandable sponges molding,
Inject in mould step 4 obtains mixing liquid, mould put into baking oven, adjust the temperature to 50~ 75 DEG C, make crosslinking proceed, behind 6~8h, take out mould, expandable sponges is removed from the molds, spends Ionized water fully cleans, and is cut into suitable shape, is immersed in ultrasonic cleaning tank by the product after cutting and carries out Ultrasonic cleaning, finally gives high resiliency high liquid-absorbing hemostatic bacteriostatic Polyvinyl acetal expandable sponges finished product.
CN201610306067.7A 2016-05-10 2016-05-10 Method for preparing high-elasticity high-absorbency hemostatic and bacteriostatic expansive sponge Pending CN105816909A (en)

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