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CN101280048B - Transparent aquagel having antibacterial action and preparation thereof - Google Patents

Transparent aquagel having antibacterial action and preparation thereof Download PDF

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CN101280048B
CN101280048B CN2008101124843A CN200810112484A CN101280048B CN 101280048 B CN101280048 B CN 101280048B CN 2008101124843 A CN2008101124843 A CN 2008101124843A CN 200810112484 A CN200810112484 A CN 200810112484A CN 101280048 B CN101280048 B CN 101280048B
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chitosan
superabsorbent resin
acrylamide
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polyacrylic acid
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CN101280048A (en
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马榴强
刘薇
姜紫鹏
何江川
程艳玲
谢飞
李若慧
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Beijing Union University
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Abstract

一种具有抗菌作用的透明水凝胶及其制备方法。该水凝胶为壳聚糖接枝到聚丙烯酸和/或丙烯酰胺系高吸水性树脂上的共聚物,其中,壳聚糖的含量为水凝胶总重量的3%~5%。其制备方法:具(1)合成聚丙烯酸和/或丙烯酰胺系高吸水性树脂;(2)将硝酸铈铵溶解于壳聚糖水溶液中;(3)将聚丙烯酸和/或丙烯酰胺系高吸水性树脂浸入壳聚糖溶液;(4)在30~95℃条件下,将吸附了含有硝酸铈铵之壳聚糖溶液的聚丙烯酸和/或丙烯酰胺系高吸水性树脂置于红外辐射箱中引发聚合,得到共聚物;(5)将共聚物用去离子水和三氯甲烷淋洗,即为具有抗菌作用的透明生物水凝胶。其该水凝胶具有很好保水的性能,并具有一定的抗菌性。作为软性接触眼镜将有良好发展前景。

Figure 200810112484

A transparent hydrogel with antibacterial effect and its preparation method. The hydrogel is a copolymer of chitosan grafted on polyacrylic acid and/or acrylamide superabsorbent resin, wherein the content of chitosan is 3%-5% of the total weight of the hydrogel. Its preparation method: (1) synthesizing polyacrylic acid and/or acrylamide superabsorbent resin; (2) dissolving cerium ammonium nitrate in chitosan aqueous solution; (3) polyacrylic acid and/or acrylamide superabsorbent resin The water-absorbent resin is immersed in the chitosan solution; (4) under the condition of 30-95°C, the polyacrylic acid and/or acrylamide superabsorbent resin that has absorbed the chitosan solution containing ammonium cerium nitrate is placed in an infrared radiation box (5) The copolymer is rinsed with deionized water and chloroform to form a transparent biohydrogel with antibacterial effect. The hydrogel has good water retention performance and certain antibacterial properties. It will have a good development prospect as a soft contact lens.

Figure 200810112484

Description

具有抗菌作用的透明水凝胶及其制备方法 Transparent hydrogel with antibacterial effect and preparation method thereof

技术领域technical field

本发明涉及一种具有抗菌作用的透明水凝胶及其制备方法,属于新材料、生物材料领域。The invention relates to a transparent hydrogel with antibacterial effect and a preparation method thereof, belonging to the fields of new materials and biological materials.

背景技术Background technique

壳聚糖是自然界存在的第二大类多糖-甲壳素(Chitin)的最重要的衍生物,是一类由2-氨基-2-脱氧葡萄糖通过β-1,4-糖苷键连接而成的带正电荷的直链多糖,可通过碱水解法脱去甲壳素的乙酰基而制得。壳聚糖所具有的独特的生物特性和理化性质使其在许多方面有着潜在的广阔的应用价值。Chitosan is the most important derivative of the second largest polysaccharide in nature - chitin (Chitin). Positively charged linear polysaccharides can be prepared by deacetylating chitin by alkaline hydrolysis. The unique biological characteristics and physical and chemical properties of chitosan make it have potential broad application value in many aspects.

作为外用药物,壳聚糖具有抗菌性,可促进皮肤组织愈合,对破损的人体表皮组织有修复、止血等作用,可应用于治疗外伤、创伤,治疗烧伤、烫伤,治疗溃疡,治疗褥疮等。As a medicine for external use, chitosan has antibacterial properties, can promote the healing of skin tissue, and has the effects of repairing and hemostasis on damaged human epidermal tissue.

壳聚糖可以制成生物材料,应用于人体,如磷酸钙骨水泥/壳聚糖骨填充修复材料、羟基磷灰石/壳聚糖骨填充修复材料、磷酸钙/壳聚糖多孔骨组织工程材料、有机物/壳聚糖复合骨修复材料、活性生长因子/壳聚糖骨组织工程材料、壳聚糖软组织工程材料等。Chitosan can be made into biomaterials and applied to the human body, such as calcium phosphate bone cement/chitosan bone filling repair materials, hydroxyapatite/chitosan bone filling repair materials, calcium phosphate/chitosan porous bone tissue engineering materials, organic/chitosan composite bone repair materials, active growth factors/chitosan bone tissue engineering materials, chitosan soft tissue engineering materials, etc.

在眼科方面,壳聚糖可应用于人工泪液、医用黏弹剂、青光眼手术植入物、眼用药物长效缓释制剂。壳聚糖还可用作眼科敷料,在动物实验中发现壳聚糖与动物眼膜相容性良好,而且能够生成较多的成胶原和成纤细胞,有利于眼疾治疗。In ophthalmology, chitosan can be used in artificial tears, medical viscoelastics, implants for glaucoma surgery, and long-acting sustained-release preparations of ophthalmic drugs. Chitosan can also be used as an ophthalmic dressing. In animal experiments, it was found that chitosan has good compatibility with animal eye membranes, and can generate more collagen and fibroblasts, which is beneficial to the treatment of eye diseases.

本发明利用壳聚糖的抗菌性和保水性,使之在引发剂和红外射线加热的作用下接枝改性丙烯酸系聚合物,从而得到具有一定抗菌作用的透明水凝胶;作为生物材料,此种水凝胶可用于制作软接触透镜及角膜接触透镜。The invention utilizes the antibacterial properties and water retention properties of chitosan to graft and modify the acrylic polymer under the action of initiator and infrared ray heating, thereby obtaining a transparent hydrogel with a certain antibacterial effect; as a biological material, The hydrogel can be used to make soft contact lenses and corneal contact lenses.

接触透镜分为硬接触透镜、软接触透镜和高透氧半硬性接触透镜等。硬接触透镜的透光性好,但含水量小使得其配戴不舒适;而软接触透镜的含水量大、抗菌效果差,给细菌的滋生创造了环境条件,而且作为透镜它的矫正角膜散光、镜片保养、镜片强度情况均不够理想;而高透氧半硬性接触透镜也存在抗菌性差等问题。Contact lenses are divided into hard contact lenses, soft contact lenses and high oxygen permeability semi-rigid contact lenses. Hard contact lenses have good light transmission, but the small water content makes them uncomfortable to wear; while soft contact lenses have high water content and poor antibacterial effect, which creates environmental conditions for the growth of bacteria, and as a lens, it corrects corneal astigmatism , lens maintenance, and lens strength are not ideal; and high oxygen permeability semi-rigid contact lenses also have problems such as poor antibacterial properties.

用于制造接触透镜的制备方法有很多种,有关这方面的专利也非常丰富,如CN87104122、CN1045270、CN1048521、CN1055542、CN1175701、CN1234522。上述这些专利技术大多数采用聚合工艺,即聚合单体在引发剂、稳定剂存在下按不同的方式进行聚合。所采用的聚合方法主要有悬浮聚合、微悬浮聚合、乳液聚合、反相聚合、分散聚合等方法。There are many preparation methods for making contact lenses, and the patents related to this aspect are also very abundant, such as CN87104122, CN1045270, CN1048521, CN1055542, CN1175701, CN1234522. Most of the above-mentioned patented technologies adopt a polymerization process, that is, the polymerized monomers are polymerized in different ways in the presence of initiators and stabilizers. The polymerization methods used mainly include suspension polymerization, microsuspension polymerization, emulsion polymerization, reverse phase polymerization, dispersion polymerization and other methods.

还有一些专利是关于对接触透镜性能的改进,如CN1537249、CN1902527、CN1914028、CN1436261、CN1254103、CN1255068、CN1321258、CN1294697。这些专利注重的则是高吸水性树脂的透氧性、多焦点功能、整体着色功能、透镜的稳定性、降低配戴透镜引起的眼睛敏感、配戴的美观等。Also some patents are about the improvement to the contact lens performance, as CN1537249, CN1902527, CN1914028, CN1436261, CN1254103, CN1255068, CN1321258, CN1294697. These patents focus on the oxygen permeability of superabsorbent resin, multi-focus function, overall coloring function, lens stability, reducing eye sensitivity caused by wearing lenses, and wearing aesthetics.

上述专利很少关注接触透镜的自身杀菌问题。有些方法虽有所涉及,但采用辐射本体聚合的方法,对一般实验室或企业较难实现。The aforementioned patents pay little attention to self-sterilizing contact lenses. Although some methods are involved, it is difficult for general laboratories or enterprises to realize the method of radiation body polymerization.

发明内容Contents of the invention

本发明的目的在于提供一种具有抗菌作用的透明水凝胶,该透明性水凝胶可应用于诸如接触眼镜等许多方面,该透明性水凝胶制造成本低廉、使用安全。The object of the present invention is to provide a transparent hydrogel with antibacterial effect, which can be applied to many aspects such as contact lenses, and which is cheap to manufacture and safe to use.

本发明的另一个目的在于提供一种其制具有抗菌作用的透明水凝胶的方法。Another object of the present invention is to provide a method for preparing a transparent hydrogel with antibacterial effect.

为实现上述目的,本发明采取以下技术方案:To achieve the above object, the present invention takes the following technical solutions:

一种具有抗菌作用的透明水凝胶,所述的水凝胶为壳聚糖接枝到聚丙烯酸和/或丙烯酰胺系高吸水性树脂上的共聚物,其中,壳聚糖的含量为水凝胶总重量的3%~5%。A kind of transparent hydrogel with antibacterial effect, described hydrogel is the copolymer that chitosan is grafted on polyacrylic acid and/or acrylamide series superabsorbent resin, wherein, the content of chitosan is water 3% to 5% of the total weight of the gel.

在本发明的具有抗菌作用的透明水凝胶中,所述的聚丙烯酸和/或丙烯酰胺系高吸水性树脂为包括丙烯酸和/或丙烯酰胺单体共聚组成的聚合物。In the antibacterial transparent hydrogel of the present invention, the polyacrylic acid and/or acrylamide superabsorbent resin is a polymer composed of acrylic acid and/or acrylamide monomers.

在上述的丙烯酸和/或丙烯酰胺单体中,可以有以下三种组合,包括有丙烯酸一种单体;包括有丙烯酰胺一种单体;包括丙烯酸和丙烯酰胺两种单体,其中,丙烯酸和丙烯酰胺之间的重量比例是任意的。Among the above-mentioned acrylic acid and/or acrylamide monomers, there may be the following three combinations, including one monomer of acrylic acid; one monomer of acrylamide; two monomers of acrylic acid and acrylamide, wherein, acrylic acid The weight ratio between acrylamide and acrylamide is arbitrary.

在共聚组成所述的聚丙烯酸和/或丙烯酰胺系高吸水性树脂的单体中,还可以包括丙烯酸酯、丙烯酸羟基酯中的一种或几种的共聚单体,和/或可以包括双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体。In the monomers for the copolymerization of the polyacrylic acid and/or acrylamide superabsorbent resin, one or more comonomers of acrylate and hydroxyacrylate may also be included, and/or may include bis One or more cross-linking monomers selected from ethylene glycol acrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, and N,N-methylenebisacrylamide.

在共聚组成所述的聚丙烯酸和/或丙烯酰胺系高吸水性树脂的单体中,丙烯酸和/或丙烯酰胺单体的含量为80wt%-100wt%;丙烯酸酯、丙烯酸羟基酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体含量为0-20wt%。In the monomers of the polyacrylic acid and/or acrylamide superabsorbent resin copolymerized to form the above, the content of acrylic acid and/or acrylamide monomers is 80wt%-100wt%; one of acrylate and hydroxyacrylate or several comonomers, and/or one or several of ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, N,N-methylenebisacrylamide The cross-linking monomer content of the species is 0-20wt%.

在聚丙烯酸和/或丙烯酰胺系高吸水性树脂中所称的高吸水性树脂也称超强吸水性聚合物(Super absorbent Polymers),简写为SAP。它是一种含有羧基、羟基等强亲水性基团并具有一定交联度的水溶胀型的高分子聚合物,不溶于水也不溶于有机溶剂,能够吸收自身重量的几百倍甚至上千倍的水,且吸水膨胀后生成的凝胶具有良好的保水性和耐候性,一旦吸水膨胀成水凝胶,即使加压也难以将水分离出来。The super absorbent resin referred to in polyacrylic acid and/or acrylamide super absorbent resin is also called super absorbent polymer (Super absorbent Polymers), abbreviated as SAP. It is a water-swellable polymer containing strong hydrophilic groups such as carboxyl and hydroxyl groups and has a certain degree of crosslinking. It is insoluble in water and organic solvents, and can absorb hundreds of times its own weight or even Thousand times of water, and the gel formed after absorbing water and swelling has good water retention and weather resistance. Once it absorbs water and expands into a hydrogel, it is difficult to separate the water even if it is pressurized.

一般高吸水性树脂与吸水性树脂的概念是等同,因此,也可以将聚丙烯酸和/或丙烯酰胺系高吸水性树脂称为聚丙烯酸和/或丙烯酰胺系吸水性树脂。但高吸水性树脂更强调树脂的吸水性,是一种吸水能力特别强的功能高分子材料,一般的吸水倍数在几百倍甚至上千倍以上。;高吸水性树脂的吸水率已从上世纪80年代的百倍提高到目前的四五千倍。目前世界上占主导地位的是聚丙烯酸盐类高吸水性树脂。Generally, the concepts of superabsorbent resin and water absorbent resin are equivalent, therefore, polyacrylic acid and/or acrylamide-based superabsorbent resin can also be called polyacrylic acid and/or acrylamide-based water-absorbent resin. However, superabsorbent resin places more emphasis on the water absorption of the resin. It is a functional polymer material with a particularly strong water absorption capacity. The general water absorption multiple is hundreds or even thousands of times. ; The water absorption rate of superabsorbent resin has increased from a hundred times in the 1980s to four or five thousand times at present. At present, polyacrylate superabsorbent resin is dominant in the world.

一种具有抗菌作用的透明水凝胶的生产方法,该方法包括以下的步骤:A kind of production method of the transparent hydrogel with antibacterial effect, this method comprises the following steps:

(1)首先合成聚丙烯酸和/或丙烯酰胺系高吸水性树脂,并干燥;(1) first synthesize polyacrylic acid and/or acrylamide superabsorbent resin, and dry;

(2)将硝酸铈铵溶解于壳聚糖水溶液中,其中,壳聚糖水溶液的浓度为4wt%~6wt%,硝酸铈铵的加入量为相对于壳聚糖水溶液的0.5%~1.5wt%;(2) dissolving ammonium cerium nitrate in the chitosan aqueous solution, wherein the concentration of the chitosan aqueous solution is 4wt%~6wt%, and the addition of ceric ammonium nitrate is 0.5%~1.5wt% relative to the chitosan aqueous solution ;

(3)将已干燥的(1)中所述及的聚丙烯酸和/或丙烯酰胺系高吸水性树脂浸入(2)中所述及的壳聚糖水溶液,浸入的时间为24h~30h;(3) Immerse the dried polyacrylic acid and/or acrylamide superabsorbent resin mentioned in (1) into the chitosan aqueous solution mentioned in (2), and the immersion time is 24h~30h;

(4)在30~95℃条件下,将(3)中吸附了含有硝酸铈铵之壳聚糖水溶液的聚丙烯酸和/或丙烯酰胺系高吸水性树脂置于红外辐射箱中引发聚合,得到共聚物;(4) Under the condition of 30~95 DEG C, the polyacrylic acid and/or acrylamide series superabsorbent resin which has adsorbed the chitosan aqueous solution containing ammonium cerium nitrate in (3) is placed in an infrared radiation box to initiate polymerization to obtain copolymer;

(5)将(4)中反应后的共聚物用去离子水和三氯甲烷淋洗,即为具有抗菌作用的透明生物水凝胶。(5) Rinse the reacted copolymer in (4) with deionized water and chloroform to form a transparent biological hydrogel with antibacterial effect.

在本发明的的具有抗菌作用的透明水凝胶的生产方法中,将(4)中反应后的共聚物干燥后继续浸入(2)中所述及的壳聚糖水溶液,浸入的时间为24h~30h;并重复(4)、(5)步骤。In the production method of the transparent hydrogel with antibacterial effect of the present invention, continue to immerse the chitosan aqueous solution mentioned in (2) after the copolymer after the reaction in (4) is dried, the time of immersion is 24h ~30h; and repeat (4), (5) steps.

在本发明的具有抗菌作用的透明水凝胶的生产方法中,在所述步骤(1)中,单体中有没有丙烯酸,就涉及到滴加不滴加NaOH水溶液的问题。单体采用丙烯酸,或采用以丙烯酸单体为主,或采用以丙烯酸、丙烯酰胺单体为主,就必须滴加NaOH水溶液,就是下述的滴加NaOH水溶液,制备聚丙烯酸系(或者聚丙烯酸和丙烯酰胺系)高吸水性树脂的方法。单体不采用丙烯酸,而是采用丙烯酰胺,或采用以丙烯酰胺单体为主、又不采用丙烯酸,就不用滴加NaOH水溶液,就是下述的不用滴加NaOH水溶液,制备聚丙烯酰胺系高吸水性树脂的方法。In the production method of the transparent hydrogel with antibacterial effect of the present invention, in the step (1), whether or not there is acrylic acid in the monomer involves the problem of whether or not to add NaOH aqueous solution. The monomer adopts acrylic acid, or mainly adopts acrylic acid monomer, or adopts mainly acrylic acid and acrylamide monomer, and NaOH aqueous solution must be added dropwise, which is the following dropwise NaOH aqueous solution to prepare polyacrylic acid (or polyacrylic acid) and acrylamide-based) superabsorbent resin method. The monomer does not use acrylic acid, but uses acrylamide, or uses acrylamide as the main monomer without using acrylic acid, so there is no need to add NaOH aqueous solution dropwise, that is, the following method does not need to add NaOH aqueous solution to prepare polyacrylamide-based high-grade The method of water-absorbent resin.

滴加NaOH水溶液,制备聚丙烯酸系高吸水性树脂的方法:The method for preparing polyacrylic acid superabsorbent resin by adding NaOH aqueous solution dropwise:

在所述步骤(1)中,是采用包括丙烯酸单体合成聚丙烯酸系(或者聚丙烯酸和丙烯酰胺系)高吸水性树脂,在上述单体中滴加NaOH水溶液进行中和,中和度为75%,然后在上述单体中加入过硫酸铵,其中,上述单体的重量份数和过硫酸铵的重量份数比为100∶1,混合均匀后开始升温至50℃-90℃,反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应,合成得到聚丙烯酸系(或者聚丙烯酸和丙烯酰胺系)高吸水性树脂。In the step (1), the polyacrylic acid series (or polyacrylic acid and acrylamide series) superabsorbent resin is synthesized by using acrylic acid monomers, and NaOH aqueous solution is added dropwise to the above monomers for neutralization, and the degree of neutralization is 75%, and then add ammonium persulfate to the above-mentioned monomers, wherein the ratio of the parts by weight of the above-mentioned monomers to the number of parts by weight of ammonium persulfate is 100:1. When the mixture changes from a white turbid gel to a transparent gel, the reaction is stopped, and a polyacrylic (or polyacrylic and acrylamide) superabsorbent resin is synthesized.

其中,NaOH水溶液的浓度范围在10wt%-40wt%。Wherein, the concentration range of the NaOH aqueous solution is 10wt%-40wt%.

在所述步骤(1)中,在上述采用包括丙烯酸单体合成聚丙烯酸系高吸水性树脂中,所采用的单体还包括丙烯酰胺、丙烯酸羟基酯、丙烯酸酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体。其中,丙烯酸(在单体中没有丙烯酰胺的情况下),或者丙烯酸和丙烯酰胺(在单体中有丙烯酰胺的情况下)占总的单体含量的80wt%-100wt%;丙烯酸酯、丙烯酸羟基酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体占总的单体含量的0-20wt%。也就是说,若为一种单体,则必须为丙烯酸;若包括其他的上述单体,也是以丙烯酸单体为主,或以丙烯酸和丙烯酰胺为主。In the step (1), in the above-mentioned synthesis of polyacrylic superabsorbent resin using acrylic acid monomers, the monomers used also include one or more of acrylamide, acrylate hydroxyl ester, and acrylate Comonomer, and/or cross-linking of one or more of ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, N,N-methylenebisacrylamide monomer. Among them, acrylic acid (in the case of no acrylamide in the monomer), or acrylic acid and acrylamide (in the case of acrylamide in the monomer) accounts for 80wt%-100wt% of the total monomer content; acrylate, acrylic acid One or more comonomers of hydroxy esters, and/or ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, N,N-methylenebisacrylamide One or more of the cross-linking monomers account for 0-20wt% of the total monomer content. That is to say, if it is a monomer, it must be acrylic acid; if other above-mentioned monomers are included, it is mainly acrylic acid monomer, or acrylic acid and acrylamide.

不用滴加NaOH水溶液,制备聚丙烯酰胺系高吸水性树脂的方法:Method for preparing polyacrylamide-based superabsorbent resin without adding NaOH aqueous solution dropwise:

在所述步骤(1)中,是采用包括丙烯酰胺合成聚丙烯酰胺系高吸水性树脂,然后在上述单体中加入过硫酸铵,其中,上述单体的重量份数和过硫酸铵的重量份数比为100∶1,混合均匀后开始升温至50℃-90℃,反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应,合成得到聚丙烯酰胺系高吸水性树脂。In the step (1), acrylamide is used to synthesize polyacrylamide-based superabsorbent resin, and then ammonium persulfate is added to the above-mentioned monomers, wherein the parts by weight of the above-mentioned monomers and the weight of ammonium persulfate The ratio of parts is 100:1. After mixing evenly, the temperature starts to rise to 50°C-90°C. When the reaction mixture changes from white turbid gel to transparent gel, the reaction is stopped, and polyacrylamide superabsorbent resin is synthesized.

在所述步骤(1)中,合成聚丙烯酰胺系高吸水性树脂的单体中,还包括丙烯酸羟基酯、丙烯酸酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体。其中,丙烯酰胺占总的单体含量的80wt%-100wt%;丙烯酸酯、丙烯酸羟基酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体占总的单体含量的0-20wt%。也就是说,若为一种单体,则必须为丙烯酰胺;若包括其他的上述单体,也是以丙烯酰胺单体为主,而不包括丙烯酸。In the step (1), the monomers for synthesizing polyacrylamide-based superabsorbent resins also include one or more comonomers of hydroxyl acrylate and acrylate, and/or ethylene diacrylate Alcohol ester, butylene glycol diacrylate, trimethylolpropane triacrylate, N, N-methylene bisacrylamide or one or more crosslinking monomers. Among them, acrylamide accounts for 80wt%-100wt% of the total monomer content; one or more comonomers in acrylate, hydroxyacrylate, and/or ethylene glycol diacrylate, butylene glycol diacrylate One or more cross-linking monomers of ester, trimethylolpropane triacrylate, N,N-methylenebisacrylamide account for 0-20wt% of the total monomer content. That is to say, if it is a monomer, it must be acrylamide; if it includes other above-mentioned monomers, it is mainly acrylamide monomer, excluding acrylic acid.

在单体和过硫酸铵反应中,是在反应器中将单体和过硫酸铵混合均匀后,加热反应物料至50℃-90℃。此反应为放热反应,当反应开始放热时,注意控制反应温度在50℃-90℃之间。In the reaction of the monomer and ammonium persulfate, after mixing the monomer and ammonium persulfate uniformly in the reactor, the reaction material is heated to 50°C-90°C. This reaction is an exothermic reaction. When the reaction starts to exotherm, pay attention to controlling the reaction temperature between 50°C and 90°C.

本发明的优点是:The advantages of the present invention are:

发明的优点和积极效果:Advantages and positive effects of the invention:

在本发明的具有抗菌作用的透明水凝胶中,聚丙烯酸和/或丙烯酰胺系高分子由于其骨架上含有大量亲水基团,因而具有亲水性。具有不同交联度的交联型聚丙烯酸系树脂,吸水后不会溶解,而是溶胀成水凝胶,具有迅速吸收及并保持大量水分而又不溶于水的优越性能。将水溶性的壳聚糖接枝到聚丙烯酸和/或丙烯酰胺系高吸水性树脂上之后,产物为透明状凝胶。其不仅具有很好保水的性能,同时具有一定的抗菌性。在生物医用材料领域,此聚合物可具有与生理组织相近的水分含量,且具有良好的生物相容性,若作为软性接触眼镜将有良好发展前景。In the transparent hydrogel with antibacterial effect of the present invention, polyacrylic acid and/or acrylamide-based macromolecules are hydrophilic due to the large amount of hydrophilic groups contained in their skeletons. Cross-linked polyacrylic resins with different degrees of cross-linking will not dissolve after absorbing water, but will swell into a hydrogel, which has the superior performance of rapidly absorbing and retaining a large amount of water while being insoluble in water. After the water-soluble chitosan is grafted onto the polyacrylic acid and/or acrylamide superabsorbent resin, the product is a transparent gel. It not only has good water retention performance, but also has certain antibacterial properties. In the field of biomedical materials, this polymer can have a moisture content close to that of physiological tissues, and has good biocompatibility. It will have a good development prospect as a soft contact lens.

本发明的合成方法简单,在硝酸铈铵作用下,利用红外线加热可以使水溶性的壳聚糖与水溶性的丙烯酸及丙烯酸酯发生接枝聚合反应,也可使水溶性的壳聚糖与非水溶性的丙烯酸酯发生接枝聚合反应,从而可以使产品中具有两种化合物的性能。The synthesis method of the present invention is simple. Under the action of cerium ammonium nitrate, the water-soluble chitosan can be grafted and polymerized with water-soluble acrylic acid and acrylic acid ester by infrared heating, and the water-soluble chitosan can be combined with non- Water-soluble acrylate undergoes graft polymerization, so that the product can have the properties of two compounds.

附图说明Description of drawings

图1为实施例1中使用的聚丙烯酸和丙烯酰胺系高吸水性树脂的红外光谱图。FIG. 1 is an infrared spectrogram of polyacrylic acid and acrylamide-based superabsorbent resin used in Example 1.

图2为壳聚糖的红外光谱图。Fig. 2 is the infrared spectrogram of chitosan.

图3为实施例1所制备的接枝了壳聚糖的聚丙烯酸和丙烯酰胺系高吸水性树脂(即实施例1所制备的具有抗菌作用的透明水凝胶)的红外光谱图。Fig. 3 is the infrared spectrogram of the polyacrylic acid and acrylamide superabsorbent resin grafted with chitosan prepared in Example 1 (that is, the transparent hydrogel with antibacterial effect prepared in Example 1).

具体实施方式Detailed ways

制备具有一定抗菌作用的透明水凝胶的技术方案包括以下步骤:The technical scheme for preparing a transparent hydrogel with a certain antibacterial effect comprises the following steps:

1)在反应器中加入丙烯酸、丙烯酸酯、丙烯酸羟基酯、丙烯酰胺中的一种或几种的共聚单体(但必须包含丙烯酸和/或丙烯酰胺)及双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺的一种或几种的交联单体共100重量份。在上述共聚单体中如果含有丙烯酸,需要滴加NaOH水溶液进行中和,中和度为75%;在上述共聚单体中如果没有丙烯酸,直接进行步骤2)。1) Add one or more comonomers of acrylic acid, acrylate, hydroxy acrylate, acrylamide (but must contain acrylic acid and/or acrylamide) and ethylene glycol diacrylate, diacrylic acid to the reactor A total of 100 parts by weight of one or more cross-linking monomers of butanediol ester, trimethylolpropane triacrylate, and N,N-methylenebisacrylamide. If there is acrylic acid in the above-mentioned comonomers, NaOH aqueous solution needs to be added dropwise for neutralization, and the degree of neutralization is 75%; if there is no acrylic acid in the above-mentioned comonomers, step 2) is directly carried out.

2)然后加入1重量份的过硫酸铵,混合均匀后开始升温,反应温度在50℃-90℃之间。2) Then add 1 part by weight of ammonium persulfate, and start to heat up after mixing evenly, and the reaction temperature is between 50°C and 90°C.

3)升温反应至反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应。3) When the temperature is raised and the reaction mixture changes from a white turbid gel to a transparent gel, the reaction is stopped.

4)将凝胶取出,置于表面皿,切碎置于烘箱中干燥。4) Take out the gel, put it on a watch glass, chop it up and put it in an oven to dry.

5)配制不同浓度的壳聚糖水溶液,同时将硝酸铈铵溶解于壳聚糖水溶液中。5) Prepare chitosan aqueous solutions with different concentrations, and dissolve cerium ammonium nitrate in the chitosan aqueous solution simultaneously.

6)将步骤4)干燥后的聚合物浸入步骤5)的壳聚糖水溶液中,放置24h。6) Immerse the dried polymer in step 4) in the chitosan aqueous solution in step 5), and place it for 24 hours.

7)将步骤6)的凝胶置于红外烘箱中,在30-95℃下接枝聚合8h。7) Put the gel in step 6) in an infrared oven, and perform graft polymerization at 30-95° C. for 8 hours.

8)将接枝聚后的聚合物用去离子水和三氯甲烷反复淋洗处理掉为反应的单体,即可获得含有壳聚糖的透明水凝胶。8) The polymer after grafting is rinsed repeatedly with deionized water and chloroform to remove unreacted monomers, and a transparent hydrogel containing chitosan can be obtained.

在下述实施例中,所得的水凝胶中壳聚糖的含量是采用重量法进行测试的,即在物质总量一定的情况下,通过水和溶剂的抽提,去除未反应的壳聚糖的质量,获得壳聚糖的质量、接枝共聚物的质量,从而进行计算出水凝胶中壳聚糖的含量。In the following examples, the content of chitosan in the resulting hydrogel is tested by gravimetric method, that is, under the condition of a certain total amount of substances, unreacted chitosan is removed by extraction with water and solvent The quality of the obtained chitosan quality, the quality of the graft copolymer, so as to calculate the content of chitosan in the hydrogel.

实施例1Example 1

在反应器中加入100重量份的丙烯酸及丙烯酰胺,开动电磁搅拌;滴加NaOH水溶液进行中和,中和度为75%。其中,NaOH水溶液的浓度为20wt%。Add 100 parts by weight of acrylic acid and acrylamide into the reactor, start electromagnetic stirring; add NaOH aqueous solution dropwise for neutralization, and the neutralization degree is 75%. Wherein, the concentration of NaOH aqueous solution is 20wt%.

需要说明的是,在100重量份的丙烯酸及丙烯酰胺中,丙烯酸和丙烯酰胺之间的重量比例是任意的,在本实施例1中,丙烯酸和丙烯酰胺的重量比例为1∶1。It should be noted that, in 100 parts by weight of acrylic acid and acrylamide, the weight ratio between acrylic acid and acrylamide is arbitrary. In Example 1, the weight ratio of acrylic acid and acrylamide is 1:1.

在反应器中加入1重量份的过硫酸铵,混合均匀后开始升温反应,控制反应温度在50℃-90℃之间。当反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应。将凝胶取出,置于烘箱中干燥,得到聚丙烯酸和丙烯酰胺系高吸水性树脂。聚丙烯酸和丙烯酰胺系高吸水性树脂的红外光谱图如图1所示。Add 1 part by weight of ammonium persulfate into the reactor, mix uniformly and start the temperature rise reaction, and control the reaction temperature between 50°C and 90°C. The reaction was stopped when the reaction mixture changed from a white turbid gel to a transparent gel. The gel is taken out and dried in an oven to obtain polyacrylic acid and acrylamide-based superabsorbent resin. The infrared spectrograms of polyacrylic acid and acrylamide superabsorbent resin are shown in Figure 1.

配置浓度为5wt%的壳聚糖水溶液,所采用的壳聚糖的红外光谱如图2所示。并同时加入相对于壳聚糖水溶液的1wt%的硝酸铈铵。将称量过的干燥的聚丙烯酸和丙烯酰胺系高吸水性树脂浸入浓度为5wt%的壳聚糖水溶液中放置24h。Configuration concentration is the chitosan aqueous solution of 5wt%, and the infrared spectrum of the chitosan adopted is as shown in Figure 2. And at the same time, 1 wt% ammonium cerium nitrate relative to the chitosan aqueous solution was added. The weighed dry polyacrylic acid and acrylamide-based superabsorbent resin were immersed in an aqueous chitosan solution with a concentration of 5 wt % and placed for 24 hours.

将凝胶取出,置于红外烤箱中,在95℃下接枝聚合。The gel was taken out, placed in an infrared oven, and grafted and polymerized at 95°C.

将接枝后的聚合物置于去离子水中反复淋洗,以除去未反应的水溶性壳聚糖及丙烯酸、丙烯酰胺单体,即制成本发明的具有抗菌作用的透明水凝胶,该水凝胶的红外光谱图如图3所示。在图3中,波数1549左右的谱带可归属羧酸盐的羰基振动;波数3408及1084左右的谱带可分别归属于羟基的O-H伸缩和C-OH变形振动;表明壳聚糖的存在。The grafted polymer is placed in deionized water and repeatedly rinsed to remove unreacted water-soluble chitosan and acrylic acid and acrylamide monomers, and the transparent hydrogel with antibacterial effect of the present invention is made. The infrared spectrum of the gel is shown in Figure 3. In Figure 3, the bands with wavenumbers around 1549 can be attributed to the carbonyl vibration of carboxylate; the bands with wavenumbers around 3408 and 1084 can be attributed to the O-H stretching and C-OH deformation vibrations of hydroxyl groups, indicating the presence of chitosan.

此水凝胶中壳聚糖的含量可达3%,可抑制霉菌滋生。The content of chitosan in the hydrogel can reach 3%, which can inhibit the growth of mold.

实施例2Example 2

在反应器中加入85重量份的丙烯酸,10重量份的甲基丙烯酸甲酯,5重量份的N,N-亚甲基双丙烯酰胺,开动电磁搅拌;滴加NaOH水溶液进行中和,中和度为75%。其中,NaOH水溶液的浓度为20wt%。Add 85 parts by weight of acrylic acid, 10 parts by weight of methyl methacrylate, and 5 parts by weight of N,N-methylene bisacrylamide into the reactor, start electromagnetic stirring; add NaOH aqueous solution dropwise for neutralization, neutralization The degree is 75%. Wherein, the concentration of NaOH aqueous solution is 20wt%.

在反应器中加入1重量份的过硫酸铵,混合均匀后开始升温反应,控制反应温度在50℃-90℃之间。当反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应。将凝胶取出,置于烘箱中干燥。Add 1 part by weight of ammonium persulfate into the reactor, mix uniformly and start the temperature rise reaction, and control the reaction temperature between 50°C and 90°C. The reaction was stopped when the reaction mixture changed from a white turbid gel to a transparent gel. The gel was taken out and placed in an oven to dry.

配置浓度为5wt%的壳聚糖水溶液,同时加入相对于壳聚糖水溶液的1wt%的硝酸铈铵。将称量过的干燥的聚丙烯酸系高吸水性树脂浸入浓度为5wt%的壳聚糖水溶液中放置24h。A chitosan aqueous solution with a concentration of 5 wt % is prepared, and 1 wt % cerium ammonium nitrate relative to the chitosan aqueous solution is added at the same time. The weighed dry polyacrylic acid-based superabsorbent resin was immersed in an aqueous chitosan solution with a concentration of 5 wt % and placed for 24 hours.

将凝胶取出,置于红外烤箱中,在95℃下接枝聚合。The gel was taken out, placed in an infrared oven, and grafted and polymerized at 95°C.

将接枝后的聚合物置于去离子水中反复淋洗,以除去未反应的水溶性壳聚糖及丙烯酸、甲基丙烯酸甲酯、N,N-亚甲基双丙烯酰胺单体,即制成本发明的具有抗菌作用的透明水凝胶。The grafted polymer is placed in deionized water and rinsed repeatedly to remove unreacted water-soluble chitosan and acrylic acid, methyl methacrylate, N, N-methylenebisacrylamide monomers, and then the The transparent hydrogel with antibacterial effect of the present invention.

此水凝胶中壳聚糖的含量可达3%,可抑制霉菌滋生。The content of chitosan in the hydrogel can reach 3%, which can inhibit the growth of mold.

实施例3Example 3

在反应器中加入85重量份的丙烯酸,10重量份的丙烯酸羟乙酯,5重量份的双丙烯酸乙二醇酯,开动电磁搅拌;滴加NaOH水溶液进行中和,中和度为75%。其中,NaOH水溶液的浓度为20wt%。Add 85 parts by weight of acrylic acid, 10 parts by weight of hydroxyethyl acrylate, and 5 parts by weight of ethylene glycol diacrylate into the reactor, start electromagnetic stirring; dropwise add NaOH aqueous solution for neutralization, and the degree of neutralization is 75%. Wherein, the concentration of NaOH aqueous solution is 20wt%.

在反应器中加入1重量份的过硫酸铵,混合均匀后开始升温反应,控制反应温度在50℃-90℃之间。当反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应。将凝胶取出,置于烘箱中干燥。Add 1 part by weight of ammonium persulfate into the reactor, mix uniformly and start the temperature rise reaction, and control the reaction temperature between 50°C and 90°C. The reaction was stopped when the reaction mixture changed from a white turbid gel to a transparent gel. The gel was taken out and placed in an oven to dry.

配置浓度为5wt%的壳聚糖水溶液,同时加入相对于壳聚糖水溶液的1wt%的硝酸铈铵。将称量过的干燥的聚丙烯酸系高吸水性树脂浸入浓度为5wt%的壳聚糖水溶液中放置24h。A chitosan aqueous solution with a concentration of 5 wt % is prepared, and 1 wt % cerium ammonium nitrate relative to the chitosan aqueous solution is added at the same time. The weighed dry polyacrylic acid-based superabsorbent resin was immersed in an aqueous chitosan solution with a concentration of 5 wt % and placed for 24 hours.

将凝胶取出,置于红外烤箱中,在95℃下接枝聚合。The gel was taken out, placed in an infrared oven, and grafted and polymerized at 95°C.

将接枝后的聚合物置于去离子水中反复淋洗,以除去未反应的水溶性壳聚糖及丙烯酸、丙烯酸羟乙酯、双丙烯酸乙二醇酯单体,即制成本发明的具有抗菌作用的透明水凝胶。The grafted polymer is placed in deionized water and repeatedly rinsed to remove unreacted water-soluble chitosan and acrylic acid, hydroxyethyl acrylate, and ethylene glycol diacrylate monomers, and the antibacterial antibacterial agent of the present invention is made. transparent hydrogel.

此水凝胶中壳聚糖的含量可达3%,可抑制霉菌滋生。The content of chitosan in the hydrogel can reach 3%, which can inhibit the growth of mold.

实施例4Example 4

在反应器中加入丙烯酰胺及N,N-亚甲基双丙烯酰胺共100重量份,其中,丙烯酰胺为85重量份,N,N-亚甲基双丙烯酰胺为15重量份;再加入1重量份的过硫酸铵,混合均匀后开始升温反应,控制反应温度在50℃-90℃之间。当反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应。将凝胶取出,置于烘箱中干燥。A total of 100 parts by weight of acrylamide and N, N-methylenebisacrylamide were added into the reactor, wherein, acrylamide was 85 parts by weight, and N, N-methylenebisacrylamide was 15 parts by weight; After the ammonium persulfate in parts by weight is uniformly mixed, the temperature rise reaction is started, and the reaction temperature is controlled between 50°C and 90°C. The reaction was stopped when the reaction mixture changed from a white turbid gel to a transparent gel. The gel was taken out and placed in an oven to dry.

配置浓度为5wt%的壳聚糖水溶液,同时加入相对于壳聚糖水溶液的1wt%的硝酸铈铵。将称量过的干燥的聚丙烯酰胺系高吸水性树脂浸入浓度为5wt%的壳聚糖水溶液中放置24h。A chitosan aqueous solution with a concentration of 5 wt % is prepared, and 1 wt % cerium ammonium nitrate relative to the chitosan aqueous solution is added at the same time. The weighed dry polyacrylamide-based superabsorbent resin was immersed in an aqueous chitosan solution with a concentration of 5 wt % and placed for 24 hours.

将凝胶取出,置于红外烤箱中,在40℃下接枝聚合。The gel was taken out, placed in an infrared oven, and grafted and polymerized at 40°C.

将接枝后的聚合物置于去离子水中反复淋洗,以除去未反应的水溶性壳聚糖及丙烯酰胺、N,N-亚甲基双丙烯酰胺单体,即制成本发明的具有抗菌作用的透明水凝胶。The grafted polymer is placed in deionized water and rinsed repeatedly to remove unreacted water-soluble chitosan and acrylamide, N, N-methylenebisacrylamide monomer, which is to make the antibacterial transparent hydrogel.

此水凝胶中壳聚糖的含量可达3%,可抑制霉菌滋生。The content of chitosan in the hydrogel can reach 3%, which can inhibit the growth of mold.

实施例5Example 5

在反应器中加入85重量份的丙烯酰胺,10重量份的丙烯酸羟乙酯,5重量份的三羟甲基丙烷三丙烯酸酯,1重量份的过硫酸铵,混合均匀后开始升温反应,控制反应温度在50℃-90℃之间。当反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应。将凝胶取出,置于烘箱中干燥。In the reactor, add 85 parts by weight of acrylamide, 10 parts by weight of hydroxyethyl acrylate, 5 parts by weight of trimethylolpropane triacrylate, and 1 part by weight of ammonium persulfate, start the temperature rise reaction after mixing, control The reaction temperature is between 50°C and 90°C. The reaction was stopped when the reaction mixture changed from a white turbid gel to a transparent gel. The gel was taken out and placed in an oven to dry.

配置浓度为5wt%的壳聚糖水溶液,同时加入相对于壳聚糖水溶液的1wt%的硝酸铈铵。将称量过的干燥的聚丙烯酰胺系高吸水性树脂浸入浓度为5wt%的壳聚糖水溶液中放置24h。A chitosan aqueous solution with a concentration of 5 wt % is prepared, and 1 wt % cerium ammonium nitrate relative to the chitosan aqueous solution is added at the same time. The weighed dry polyacrylamide-based superabsorbent resin was immersed in a chitosan aqueous solution with a concentration of 5 wt % and placed for 24 hours.

将凝胶取出,置于红外烤箱中,在40℃下接枝聚合。The gel was taken out, placed in an infrared oven, and grafted and polymerized at 40°C.

将接枝后的聚合物置于去离子水中反复淋洗,以除去未反应的水溶性壳聚糖及丙烯酰胺、丙烯酸羟乙酯、三羟甲基丙烷三丙烯酸酯单体,即制成本发明的具有抗菌作用的透明水凝胶。The grafted polymer is placed in deionized water and rinsed repeatedly to remove unreacted water-soluble chitosan and acrylamide, hydroxyethyl acrylate, and trimethylolpropane triacrylate monomers, which are made into the present invention. transparent hydrogel with antibacterial properties.

此水凝胶中壳聚糖的含量可达3%,可抑制霉菌滋生。The content of chitosan in the hydrogel can reach 3%, which can inhibit the growth of mold.

Claims (4)

1.具有抗菌作用的透明水凝胶的生产方法,其特征在于,该方法包括以下的步骤:1. the production method of the transparent hydrogel with antibacterial effect is characterized in that, the method comprises the following steps: (1)首先合成聚丙烯酸系高吸水性树脂和/或聚丙烯酰胺系高吸水性树脂,并干燥;(1) first synthesize polyacrylic acid superabsorbent resin and/or polyacrylamide superabsorbent resin, and dry; (2)将硝酸铈铵溶解于壳聚糖水溶液中,其中,壳聚糖水溶液的浓度为4wt%~6wt%,硝酸铈铵的加入量为相对于壳聚糖水溶液的0.5%~1.5wt%;(2) dissolving ammonium cerium nitrate in the chitosan aqueous solution, wherein the concentration of the chitosan aqueous solution is 4wt%~6wt%, and the addition of ceric ammonium nitrate is 0.5%~1.5wt% relative to the chitosan aqueous solution ; (3)将已干燥的(1)中所述及的聚丙烯酸和/或丙烯酰胺系高吸水性树脂浸入(2)中所述及的壳聚糖水溶液,浸入的时间为24h~30h;(3) Immerse the dried polyacrylic acid and/or acrylamide superabsorbent resin mentioned in (1) into the chitosan aqueous solution mentioned in (2), and the immersion time is 24h~30h; (4)在30~95℃条件下,将(3)中吸附了含有硝酸铈铵之壳聚糖溶液的聚丙烯酸系高吸水性树脂和/或聚丙烯酰胺系高吸水性树脂置于红外辐射箱中引发聚合,得到共聚物;(4) Under the condition of 30-95°C, place the polyacrylic acid superabsorbent resin and/or the polyacrylamide superabsorbent resin that has absorbed the chitosan solution containing ammonium cerium nitrate in (3) under infrared radiation Initiate polymerization in the box to obtain a copolymer; (5)将(4)中反应后的共聚物用去离子水和三氯甲烷淋洗,即为具有抗菌作用的透明生物水凝胶;(5) The copolymer reacted in (4) is rinsed with deionized water and chloroform, which is a transparent biological hydrogel with antibacterial effect; 其中:in: 在所述步骤(1)中,是采用包括丙烯酸的单体合成聚丙烯酸系高吸水性树脂,在上述单体中滴加NaOH水溶液进行中和,中和度为75%,然后在上述单体中加入过硫酸铵,其中,上述单体的重量份数和过硫酸铵的重量份数比为100∶1,混合均匀后开始升温至50℃-90℃,反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应,合成得到聚丙烯酸系高吸水性树脂;In the step (1), a polyacrylic acid-based superabsorbent resin is synthesized by using monomers including acrylic acid, and NaOH aqueous solution is added dropwise to the above-mentioned monomers for neutralization, and the degree of neutralization is 75%, and then the above-mentioned monomers Ammonium persulfate was added to the mixture, wherein the ratio of the parts by weight of the above-mentioned monomers to the parts by weight of ammonium persulfate was 100:1, and after mixing evenly, the temperature was raised to 50°C-90°C, and the reaction mixture changed from a white turbid gel to a When the gel is transparent, stop the reaction and synthesize polyacrylic acid superabsorbent resin; 或者,在所述步骤(1)中,是采用包括丙烯酰胺的单体合成聚丙烯酰胺系高吸水性树脂,然后在上述单体中加入过硫酸铵,其中,上述单体的重量份数和过硫酸铵的重量份数比为100∶1,混合均匀后开始升温至50℃-90℃,反应混合物由白色浑浊凝胶变为透明凝胶时,停止反应,合成得到聚丙烯酰胺系高吸水性树脂。Alternatively, in the step (1), a polyacrylamide-based superabsorbent resin is synthesized using monomers including acrylamide, and then ammonium persulfate is added to the monomers, wherein the parts by weight of the monomers and The weight ratio of ammonium persulfate is 100:1. After mixing evenly, the temperature starts to rise to 50°C-90°C. When the reaction mixture changes from a white turbid gel to a transparent gel, stop the reaction and synthesize a polyacrylamide-based superabsorbent Sexual resin. 2.根据权利要求1所述的具有抗菌作用的透明水凝胶的生产方法,其特征在于,将(4)中反应后的共聚物干燥后继续浸入(2)中所述及的壳聚糖水溶液,浸入的时间为24h~30h;并重复(4)、(5)步骤。2. the production method of the transparent hydrogel with antibacterial effect according to claim 1 is characterized in that, after the copolymer after the reaction in (4) is dried, continue to immerse the chitosan described in (2) Aqueous solution, immersion time is 24h~30h; And repeat (4), (5) steps. 3.根据权利要求1所述的具有抗菌作用的透明水凝胶的生产方法,其特征在于,在所述步骤(1)中,合成聚丙烯酸系高吸水性树脂的单体中,还包括丙烯酰胺、丙烯酸羟基酯、丙烯酸酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体,其中,丙烯酸,或者丙烯酸和丙烯酰胺占总的单体含量的80wt%-100wt%;丙烯酸酯、丙烯酸羟基酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体占总的单体含量的0-20wt%。3. the production method of the transparent hydrogel with antibacterial effect according to claim 1, is characterized in that, in described step (1), in the monomer of synthesizing polyacrylic acid superabsorbent resin, also comprise propylene One or more comonomers of amide, hydroxy acrylate, acrylate, and/or ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, N,N- One or more cross-linking monomers in methylene bisacrylamide, wherein acrylic acid, or acrylic acid and acrylamide account for 80wt%-100wt% of the total monomer content; one of acrylate and hydroxyacrylate One or more comonomers, and/or one or more of ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, N,N-methylenebisacrylamide Several crosslinking monomers account for 0-20 wt% of the total monomer content. 4.根据权利要求1所述的具有抗菌作用的透明水凝胶的生产方法,其特征在于,在所述步骤(1)中,合成聚丙烯酰胺系高吸水性树脂的单体中,还包括丙烯酸羟基酯、丙烯酸酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体;其中,丙烯酰胺占总的单体含量的80wt%-100wt%;丙烯酸酯、丙烯酸羟基酯中的一种或几种的共聚单体,和/或双丙烯酸乙二醇酯、双丙烯酸丁二醇酯、三羟甲基丙烷三丙烯酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种的交联单体占总的单体含量的0-20wt%。4. the production method of the transparent hydrogel with antibacterial effect according to claim 1, is characterized in that, in described step (1), in the monomer of synthesizing polyacrylamide superabsorbent resin, also include One or several comonomers of hydroxy acrylate and acrylate, and/or ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, N,N-methylene One or more cross-linking monomers of bisacrylamide; among them, acrylamide accounts for 80wt%-100wt% of the total monomer content; one or more copolymerization monomers of acrylate and hydroxy acrylate body, and/or one or more cross-linking monomers of ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, N,N-methylenebisacrylamide Accounting for 0-20wt% of the total monomer content.
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