CN112267167B - 一种自愈性发光有机水凝胶纤维的制备方法 - Google Patents
一种自愈性发光有机水凝胶纤维的制备方法 Download PDFInfo
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- CN112267167B CN112267167B CN202011096095.3A CN202011096095A CN112267167B CN 112267167 B CN112267167 B CN 112267167B CN 202011096095 A CN202011096095 A CN 202011096095A CN 112267167 B CN112267167 B CN 112267167B
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- solution
- carboxymethyl cellulose
- fiber
- hydroxyethyl
- hydrogel
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 83
- 239000000835 fiber Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 hydroxyethyl carboxymethyl Chemical group 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 45
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 44
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 44
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 44
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 21
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 21
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 21
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
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- 239000000243 solution Substances 0.000 claims description 78
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- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
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- 238000002791 soaking Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 238000000502 dialysis Methods 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
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- ZFGMDIBRIDKWMY-PASTXAENSA-N heparin Chemical compound CC(O)=N[C@@H]1[C@@H](O)[C@H](O)[C@@H](COS(O)(=O)=O)O[C@@H]1O[C@@H]1[C@@H](C(O)=O)O[C@@H](O[C@H]2[C@@H]([C@@H](OS(O)(=O)=O)[C@@H](O[C@@H]3[C@@H](OC(O)[C@H](OS(O)(=O)=O)[C@H]3O)C(O)=O)O[C@@H]2O)CS(O)(=O)=O)[C@H](O)[C@H]1O ZFGMDIBRIDKWMY-PASTXAENSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
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- 229910021538 borax Inorganic materials 0.000 claims description 8
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000047 product Substances 0.000 claims description 8
- 239000004328 sodium tetraborate Substances 0.000 claims description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 7
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- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
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- 239000004332 silver Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
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- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
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- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
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Abstract
本发明涉及高分子材料领域,公开了一种自愈性发光有机水凝胶纤维的制备方法,本方法首先以羟乙基纤维素为原料,采用均相反应制备羟乙基羧甲基纤维素;然后以羟乙基羧甲基纤维素为第一网络,聚甲基丙烯酸为第二网络,碳载银纳米粒子为发光体,建立一种连续的水凝胶纤维纺丝工艺;采用铁离子双交联法增强羟乙基羧甲基纤维素/聚甲基丙烯酸复合双网络水凝胶,并用甘油代替水凝胶纤维中部分水,得到有机水凝胶纤维;最后将硼酸交联聚乙烯醇包覆在纤维表面,抑制应用过程中Fe3+的流失。本发明所得有机水凝胶纤维具有良好的自愈性、粘弹性和光响应性,优良的保水性和低温性能,在生物检测,智能传感,柔性可穿戴设备等领域有良好的应用前景。
Description
技术领域
本发明涉及高分子材料领域,尤其涉及一种自愈性发光有机水凝胶纤维的制备方法。
背景技术
水凝胶是一类包含大量水分的具有三维网络结构的高分子材料,在组织工程、药物控释载体、电子皮肤、软体机器人等领域具有重要的应用前景,近年来引起了研究人员的极大关注。但常规水凝胶的高含水量特性,导致其柔软易脆,机械强度低,对环境敏感,耐候性差,水的蒸发和冻结都会导致功能障碍,失去柔韧性,影响正常使用。
羧甲基纤维素(CMC)作为离子型聚合物在其电离时由于同种电荷的电离基团间的静电排斥,导致大分子链伸展,粘度上升,因此常用于食品增粘剂,但它的抗盐能力差,不适用于高盐溶液中。羟乙基纤维素(HEC)是一种水溶性的非离子型醚,它具有与广泛范围的水溶性聚合物、表面活性剂及盐的相容性和没有凝胶点也没有沉淀点的特性,以及其杰出的增稠、悬浮、分散和保失水等性能,因此HEC被广泛地用于医药卫生、食品、油田采油等领域。羟乙基羧甲基纤维素(HECMC)在纤维素分子链上同时含有羧甲基离子和羟乙基非离子的纤维素混合醚,它结合了CMC和HEC的优点,从而有广阔的应用前景。
碳量子点(CDs)自2004年发现以来,由于其优异的物理化学性质引起了人们的广泛关注。与传统的半导体量子点及有机染料相比,碳量子点不仅具有原料来源廉价、制备方法简单等特点,还具有低毒、生物相容性好、光学性质稳定、激发和发射波长可调以及表面易于功能化修饰等独特的优势,已经在光催化、生物成像、照明器件、荧光探针和生物传感等领域具有广泛的应用。
材料的自修复能力大致可分为两类,外援性自修复和本征自修复,外援性自修复是借助材料包裹的可修复单体或粘合剂来实现自修复,修复性能有限。所以我们逐渐将目光移向本征自修复材料。希望自修复材料能够通过自身的特殊作用自我修复自身受到的损伤。
发明内容
为了解决上述技术问题,本发明提供了一种自愈性发光有机水凝胶纤维的制备方法。本发明首先以羟乙基纤维素为原料,采用均相反应制备羟乙基羧甲基纤维素,纤维素分子链上同时含有羧甲基离子和羟乙基非离子,有大量的反应活性位点。然后以羟乙基羧甲基纤维素为第一网络,聚甲基丙烯酸为第二网络,碳载银纳米粒子为发光体,建立一种连续的水凝胶纤维纺丝工艺。采用铁离子双交联法增强羟乙基羧甲基纤维素/聚甲基丙烯酸复合双网络水凝胶,Fe3+与来自羟乙基羧甲基纤维素和聚甲基丙烯酸两种分子链上的羧基均发生离子交联,以形成相互贯穿的超分子网络,同时碳载银纳米粒子上丰富的羟基、氨基和羧基可以与水凝胶基体形成大量的氢键,可逆的金属离子配位键和氢键作用,赋予水凝胶良好的自修复性能。用甘油代替水凝胶纤维中的一部分水,得到有机水凝胶纤维,通过简单的一步溶剂替换,可极大地提高水凝胶的保水性和低温性能。最后将硼酸交联聚乙烯醇包覆在纤维表面,抑制应用过程中Fe3+的流失。本发明制备的有机水凝胶纤维不仅具有良好的自愈性、粘弹性和光响应性,还有优良的保水性和低温性能,有很高的实际应用价值。
本发明的具体技术方案为:一种自愈性发光有机水凝胶纤维的制备方法,包括如下步骤:
步骤1)羟乙基羧甲基纤维素的制备:将羟乙基纤维素和四硼酸钠混合后,浸泡于异丙醇溶液中;加入与羟乙基纤维素等摩尔量的一氯乙酸,加入35-45wt% 的NaOH溶液,反应0.5-1.5h,熟化1-2h,固体物用冰醋酸中和至pH=6.5-7.5时,用水将产物溶解,再用甲醇重结晶,并用甲醇洗涤,抽滤,真空干燥制得羟乙基羧甲基纤维素。
由于羟乙基纤维素为水溶性纤维素醚,因此由羟乙基纤维素制备羟乙基羧甲基纤维素的反应是在异丙醇溶液体系中进行的均相反应。这一反应需要给予体系一定的能量,使一氯乙酸钠离解出高能正离子,与HEC发生亲核取代反应生成产物。但太高的温度一方面造成羟乙基纤维素的降解,另一方面使开始的羧甲基化速度过快,在反应体系中的纤维素的衍生物容易形成凝胶,所以温度的控制至关重要。
四硼酸钠在水溶液中水解后能与多糖分子中的羟基形成一个四配合体的阴离子。羟乙基纤维素分子链中存在许多- OH,它们与硼酸形成配合体后使羟乙基纤维素分子在水溶液中稳定不易聚集,从而可以提高产物的取代均匀度。
步骤2):取步骤1)制得的羟乙基羧甲基纤维素,加入去离子水搅拌溶解,获得羟乙基羧甲基纤维素溶液,待用。
步骤3)碳纳米点的制备:称取肝素钠置于容器中,加入去离子水,超声震荡至完全溶解,将所得混合溶液倒入水热反应釜中加热反应;反应后将混合液冷却至室温,然后离心处理,取上清液,用0.22μm微孔过滤膜重复过滤数次;将过滤所得液体装入透析膜内进行透析;将透析所得液体真空干燥,得到固体的碳纳米点。
以肝素钠为原料,采用水热法制备的碳纳米粒子粒径分布较均匀,平均粒径小,粒径形貌及结晶程度较好,且表面含有大量的羟基、氨基、羰基、羧基基团,具有较好的水溶性及稳定性。
步骤4)碳载银纳米粒子的制备:取0.008-0.012 g步骤1)所得碳纳米点置于容器中,加入8-12mL去离子水,水浴超声使碳纳米点均匀分散,然后加入硝酸银溶液;将所得混合溶液置于紫外光下照射,当混合溶液从黄色变成深棕色时,获得碳载银纳米粒子溶液。
碳纳米粒子表面具有丰富的官能团,在紫外光激发下,碳纳米粒子的电子转移可以使Ag+还原成银纳米粒子。并且由于碳纳米点的亲水性,制备的纳米粒子在溶剂中可以单分散,即使不添加任何其他物质,在溶剂中的分散体也具有良好的稳定性。
Ag+的光还原进程受紫外光照射时间影响,紫外照射时间越长,Ag+的还原数量越多,银纳米粒子的粒径越大,荧光特性也会随之改变。因此选择合适的光照时间对银纳米粒子的性能影响尤其重要。
步骤5)湿法纺丝:将单体甲基丙烯酸和光引发剂1173,碳载银纳米粒子溶液加入步骤2)制得的羟乙基羧甲基纤维素溶液中混合均匀,缓慢搅拌以除去混合溶液中的气泡,即得到纺丝液;将纺丝液转移至注射器中,采用湿法纺丝工艺,在紫外光的凝固浴中引发纤维的光聚合,将纤维在Fe3+凝固浴中浸泡2-4h,使Fe3+和羧基配位发生铁离子双交联,最后浸泡在去离子水中平衡40-50 h,除掉未反应的单体和双网络中多余的铁离子,得到水凝胶纤维。
羟乙基羧甲基纤维素分子链和聚甲基丙烯酸共聚物链上的羧基同时与 Fe3+交联,当交联的金属离子为单价金属离子时,一个金属离子最多只能与一个羧基形成交联点,交联网络比较疏松;当交联的金属离子为二价金属离子时,一个金属离子最多能与两个羧基形成交联点,其交联网络较单价金属离子的交联网络紧密;当交联的金属离子为三价金属离子时,一个金属离子最多可与三个羧基形成交联点,从而使得交联网络进一步紧密。因此本发明选取三价的铁离子作为交联剂,得到高强韧的双网络水凝胶。
双网络水凝胶是在一层网络结构的基础上增加了一层网络结构。双网络水凝胶在受到外力作用时,一个水凝胶的网络断裂会形成许多网络碎片存在于第二层网络中,以“碎片”的形式成为第二层网络的缠结点,防止水凝胶发生宏观的破坏,进而可增加水凝胶的力学强度。
步骤6)溶剂替换:将步骤5)得到的水凝胶纤维浸泡在甘油和FeCl3溶液按质量比0.8-1.2:1组成的混合溶剂中15-25 h,得到有机水凝胶纤维。
通过溶剂替换法将水凝胶中的一部分水替换成甘油,可有效解决水凝胶易干和低温下易结冰问题,提高水凝胶的保水性和低温性能。
步骤7):将聚乙烯醇加入去离子水中,水浴加热至70-80℃并搅拌溶解,然后静置至聚乙烯醇完全溶解后,得到聚乙烯醇溶液;将步骤6)得到的有机水凝胶纤维浸泡在聚乙烯醇溶液中,0.5-1.5h后取出,并于硼酸溶液中浸没25-35 s,取出自然风干,即得到自愈性发光有机水凝胶纤维。
在纤维表面引入硼酸交联聚乙烯醇包覆层,可以有效抑制铁离子的流失,进而提高纤维的自修复性能。
作为优选,步骤1)中,四硼酸钠的加入量为羟乙基羧甲基纤维素的0.4-0.6wt%,NaOH与一氯乙酸的摩尔比为1.4-2.0 : 1,反应温度为45-55 ℃。
作为优选,步骤3)中,所述混合溶液中肝素钠水溶液的浓度为0.02-0.03 g/mL,反应温度为130-150 ℃,反应时间为10-15h。
作为优选,步骤3)中,离心转速为8000-12000 r/min,离心时间为5-15min;所述透析膜的规格为1000 Da,透析时间为40-50 h;真空干燥温度为35-45℃,真空干燥时间为40-50 h。
作为优选,步骤4)中,超声时间为20-40分钟,硝酸银溶液的浓度为0.008-0.012mol/L,紫外光波长为360-370 nm,光照时间为70-90分钟。
作为优选,步骤5)中,单体甲基丙烯酸的添加量为羟乙基羧甲基纤维素溶液的3-7wt%,光引发剂1173的添加量为羟乙基羧甲基纤维素溶液的0.08-0.12wt%;紫外光波长为360-370 nm,凝固浴为0.04-0.08mol/L的FeCl3溶液。
作为优选,步骤6)中,FeCl3溶液的浓度为0.02-0/04 mol/L。
作为优选,步骤7)中,聚乙烯醇溶液的浓度为0.03-0.05%,搅拌时间2-3 h,硼酸溶液的浓度为2.6-3.0 g/100 mL。
作为优选,步骤2)中,羟乙基羧甲基纤维素溶液的浓度为1-3wt%。
与现有技术对比,本发明的有益效果是:
(1)以羟乙基纤维素为原料,采用均相反应制备羟乙基羧甲基纤维素,所制产品在水中速溶,且粘度稳定性好,并首次将羟乙基羧甲基纤维素引入智能水凝胶领域。
(2)以肝素钠为原料,采用水热法制备性能优良的碳纳米点,成本低,合成简单,原材料极易获得。
(3)提出了一种以碳纳米点为还原剂,在紫外光照射下快速、简便、绿色合成银纳米粒子的方法。该方法制得的碳载银纳米粒子,具有良好的光学性能和较低的光致发光阈值。同时由于碳纳米点的亲水性,制备的纳米粒子在溶剂中可以单分散,即使不添加任何其他物质,在溶剂中的分散体也具有良好的稳定性。
(4)采用铁离子双交联法增强羟乙基羧甲基纤维素/聚甲基丙烯酸复合双网络水凝胶,Fe3+与羟乙基羧甲基纤维素和聚甲基丙烯酸两种分子链上的羧基均发生离子交联,形成了相互贯穿的超分子网络,同时碳载银纳米粒子上丰富的羟基、氨基和羧基可以与水凝胶基体形成大量的氢键,可逆的金属离子配位键和氢键作用,赋予水凝胶良好的自修复性能。
(5)通过溶剂替换法将水凝胶中的一部分水替换成甘油,有效地解决了水凝胶易干和低温下易结冰问题,提高了水凝胶的保水性和低温性能。
(6)在有机水凝胶纤维表面引入了硼酸交联聚乙烯醇包覆层,可以有效抑制铁离子的流失,进而提高纤维的自修复性能。
具体实施方式
下面结合实施例对本发明作进一步的描述。
实施例1
一种自愈性发光有机水凝胶纤维的制备方法,包括如下制备步骤:
步骤1)羟乙基羧甲基纤维素的制备:将1 g羟乙基纤维素和5 mg四硼酸钠混合后,浸泡于异丙醇溶液中。然后加入1.43 g一氯乙酸和2.58 g 40% NaOH溶液,在50 ℃下反应1h,熟化1.5 h,固体物用冰醋酸中和至pH= 7时,用少量水将产物溶解,再用甲醇重结晶,并用甲醇洗涤三次,抽滤,放入真空箱中干燥制得羟乙基羧甲基纤维素。
步骤2):取0.1 g步骤1)制得的羟乙基羧甲基纤维素,加入适量去离子水搅拌溶解,配成质量分数1%的纤维素溶液,待用。
步骤3):碳纳米点的制备:称取0.55 g肝素钠置于烧杯中,加入20 mL去离子水,超声震荡至完全溶解。将混合溶液倒入50 mL聚四氟乙烯内衬的水热反应釜中,140 ℃下加热反应12 h。反应后的混合液冷却至室温,然后置于离心管离心10 min,转速为10000 r/min。取上清液,用0.22 μm的微孔过滤膜重复过滤3次。将过滤后的液体装入1000 Da的透析膜内透析,于超纯水中透析48 h。将透析后的液体置于真空干燥箱内,40℃条件下干燥48 h,得到碳纳米点固体。
步骤4)碳载银纳米粒子的制备:取0.01 g步骤1)制得的碳纳米点置于烧杯中,加入10mL去离子水在超声水浴锅中超声30 min,使碳纳米点均匀分散,然后加入0.01 mol/L的硝酸银溶液;将混合溶液置于365 nm紫外光下照射80 min,当混合溶液从黄色变成深棕色时,表明银离子转化为银纳米粒子。
步骤5)湿法纺丝:将0.5 g甲基丙烯酸和0.01 g光引发剂1173,碳载银纳米粒子加入步骤2)制得的羟乙基羧甲基纤维素溶液中混合均匀,缓慢搅拌以除去混合溶液中的气泡,即得到纺丝液。将纺丝液转移至注射器中,采用湿法纺丝工艺,在紫外光的凝固浴中引发纤维的光聚合,将纤维在0.06 mol/L FeCl3溶液凝固浴中浸泡3 h,使Fe3+和羧基配位发生铁离子双交联,最后浸泡在去离子水中平衡48 h,除掉未反应的单体和双网络中多余的铁离子。
步骤6)溶剂替换:将步骤5)得到的水凝胶纤维浸泡在甘油和0.03 mol/L FeCl3溶液1:1组成的混合溶剂中20 h,即得到保水性良好的有机水凝胶纤维。
步骤7):将聚乙烯醇加入去离子水中,水浴加热至75℃,通过剧烈搅拌使聚乙烯醇溶解,然后静置待聚乙烯醇完全溶解,配制成0.04%聚乙烯醇溶液;将步骤6)得到的有机水凝胶纤维浸泡在聚乙烯醇溶液中,1 h后将纤维取出,并于硼酸溶液(2.8 g/100 mL)中浸没30 s,取出自然风干,即得到硼酸交联聚乙烯醇包覆的有机水凝胶纤维。
本实施例制得的自愈性发光有机水凝胶纤维断裂拉伸强度为0.75 MPa,断裂伸长率为543.2%;将水凝胶纤维切成两段,当两个半体接触并在室温下保持约6 h不受干扰时,水凝胶纤维会自行愈合。愈合后,交界处没有明显的物理损伤痕迹,并且自修复过程是可重复的,即使在-70℃仍具有柔韧性和自愈性。将水凝胶和有机水凝胶纤维置于20℃,45%湿度的相同环境中,4 h后水凝胶几乎失去全部水分,而有机水凝胶纤维在22 h内保持了超过85%的重量。
实施例2
一种自愈性发光有机水凝胶纤维的制备方法,包括如下制备步骤:
步骤1):羟乙基羧甲基纤维素的制备:将1 g羟乙基纤维素和5 mg四硼酸钠混合后,浸泡于异丙醇溶液中。然后加入1.43 g一氯乙酸和2.58 g 40% NaOH溶液,在50 ℃下反应1 h,熟化1.5 h,固体物用冰醋酸中和至pH= 7时,用少量水将产物溶解,再用甲醇重结晶,并用甲醇洗涤三次,抽滤,放入真空箱中干燥制得羟乙基羧甲基纤维素。
步骤2):取0.2 g步骤1)制得的羟乙基羧甲基纤维素,加入适量去离子水搅拌溶解,配成质量分数2%的纤维素溶液,待用。
步骤3)碳纳米点的制备:称取0.55 g肝素钠置于烧杯中,加入20 mL去离子水,超声震荡至完全溶解。将混合溶液倒入50 mL聚四氟乙烯内衬的水热反应釜中,140 ℃下加热反应12 h。反应后的混合液冷却至室温,然后置于离心管离心10 min,转速为10000 r/min。取上清液,用0.22 μm的微孔过滤膜重复过滤3次。将过滤后的液体装入1000 Da的透析膜内透析,于超纯水中透析48 h。将透析后的液体置于真空干燥箱内,40℃条件下干燥48 h,得到碳纳米点固体。
步骤4)碳载银纳米粒子的制备:取0.01 g步骤1)制得的碳纳米点置于烧杯中,加入10mL去离子水在超声水浴锅中超声30 min,使碳纳米点均匀分散,然后加入0.01 mol/L的硝酸银溶液;将混合溶液置于365 nm紫外光下照射80 min,当混合溶液从黄色变成深棕色时,表明银离子转化为银纳米粒子。
步骤5)湿法纺丝:将0.5 g甲基丙烯酸和0.01 g光引发剂1173,碳载银纳米粒子加入步骤2)制得的羟乙基羧甲基纤维素溶液中混合均匀,缓慢搅拌以除去混合溶液中的气泡,即得到纺丝液。将纺丝液转移至注射器中,采用湿法纺丝工艺,在紫外光的凝固浴中引发纤维的光聚合,将纤维在0.06 mol/L FeCl3溶液凝固浴中浸泡3 h,使Fe3+和羧基配位发生铁离子双交联,最后浸泡在去离子水中平衡48 h,除掉未反应的单体和双网络中多余的铁离子。
步骤6)溶剂替换:将步骤5)得到的水凝胶纤维浸泡在甘油和0.03 mol/L FeCl3溶液1:1组成的混合溶剂中20 h,即得到保水性良好的有机水凝胶纤维。
步骤7):将聚乙烯醇加入去离子水中,水浴加热至75℃,通过剧烈搅拌使聚乙烯醇溶解,然后静置待聚乙烯醇完全溶解,配制成0.04%聚乙烯醇溶液;将步骤6)得到的有机水凝胶纤维浸泡在聚乙烯醇溶液中,1 h后将纤维取出,并于硼酸溶液(2.8 g/100 mL)中浸没30 s,取出自然风干,即得到硼酸交联聚乙烯醇包覆的有机水凝胶纤维。
本实施例制得的自愈性发光有机水凝胶纤维断裂拉伸强度为1.24 MPa,断裂伸长率为674.3%;将水凝胶纤维切成两段,当两个半体接触并在室温下保持约6 h不受干扰时,水凝胶纤维会自行愈合。愈合后,交界处没有明显的物理损伤痕迹,并且自修复过程是可重复的,即使在-70℃仍具有柔韧性和自愈性。将水凝胶和有机水凝胶纤维置于20℃,45%湿度的相同环境中,4 h后水凝胶几乎失去全部水分,而有机水凝胶纤维在22 h内保持了超过85%的重量。
实施例3
一种自愈性发光有机水凝胶纤维的制备方法,包括如下制备步骤:
步骤1)羟乙基羧甲基纤维素的制备:将1 g羟乙基纤维素和5 mg四硼酸钠混合后,浸泡于异丙醇溶液中。然后加入1.43 g一氯乙酸和2.58 g 40% NaOH溶液,在50 ℃下反应1h,熟化1.5 h,固体物用冰醋酸中和至pH= 7时,用少量水将产物溶解,再用甲醇重结晶,并用甲醇洗涤三次,抽滤,放入真空箱中干燥制得羟乙基羧甲基纤维素。
步骤2):取0.3 g步骤1)制得的羟乙基羧甲基纤维素,加入适量去离子水搅拌溶解,配成质量分数3%的纤维素溶液,待用。
步骤3)碳纳米点的制备:称取0.55 g肝素钠置于烧杯中,加入20 mL去离子水,超声震荡至完全溶解。将混合溶液倒入50 mL聚四氟乙烯内衬的水热反应釜中,140 ℃下加热反应12 h。反应后的混合液冷却至室温,然后置于离心管离心10 min,转速为10000 r/min。取上清液,用0.22 μm的微孔过滤膜重复过滤3次。将过滤后的液体装入1000 Da的透析膜内透析,于超纯水中透析48 h。将透析后的液体置于真空干燥箱内,40℃条件下干燥48 h,得到碳纳米点固体。
步骤4)碳载银纳米粒子的制备:取0.01 g步骤1)制得的碳纳米点置于烧杯中,加入10mL去离子水在超声水浴锅中超声30 min,使碳纳米点均匀分散,然后加入0.01 mol/L的硝酸银溶液;将混合溶液置于365 nm紫外光下照射80 min,当混合溶液从黄色变成深棕色时,表明银离子转化为银纳米粒子。
步骤5)湿法纺丝:将0.5 g甲基丙烯酸和0.01 g光引发剂1173,碳载银纳米粒子加入步骤2)制得的羟乙基羧甲基纤维素溶液中混合均匀,缓慢搅拌以除去混合溶液中的气泡,即得到纺丝液。将纺丝液转移至注射器中,采用湿法纺丝工艺,在紫外光的凝固浴中引发纤维的光聚合,将纤维在0.06 mol/L FeCl3溶液凝固浴中浸泡3 h,使Fe3+和羧基配位发生铁离子双交联,最后浸泡在去离子水中平衡48 h,除掉未反应的单体和双网络中多余的铁离子。
步骤6)溶剂替换:将步骤5)得到的水凝胶纤维浸泡在甘油和0.03 mol/L FeCl3溶液1:1组成的混合溶剂中20 h,即得到保水性良好的有机水凝胶纤维。
步骤7):将聚乙烯醇加入去离子水中,水浴加热至75℃,通过剧烈搅拌使聚乙烯醇溶解,然后静置待聚乙烯醇完全溶解,配制成0.04%聚乙烯醇溶液;将步骤6)得到的有机水凝胶纤维浸泡在聚乙烯醇溶液中,1 h后将纤维取出,并于硼酸溶液(2.8 g/100 mL)中浸没30 s,取出自然风干,即得到硼酸交联聚乙烯醇包覆的有机水凝胶纤维。
本实施例制得的自愈性发光有机水凝胶纤维断裂拉伸强度为1.84 MPa,断裂伸长率为804.5%;将水凝胶纤维切成两段,当两个半体接触并在室温下保持约6 h不受干扰时,水凝胶纤维会自行愈合。愈合后,交界处没有明显的物理损伤痕迹,并且自修复过程是可重复的,即使在-70℃仍具有柔韧性和自愈性。将水凝胶和有机水凝胶纤维置于20℃,45%湿度的相同环境中,4 h后水凝胶几乎失去全部水分,而有机水凝胶纤维在22 h内保持了超过85%的重量。
本发明中所用原料、设备,若无特别说明,均为本领域的常用原料、设备;本发明中所用方法,若无特别说明,均为本领域的常规方法。
以上所述,仅是本发明的较佳实施例,并非对本发明作任何限制,凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换,均仍属于本发明技术方案的保护范围。
Claims (9)
1.一种自愈性发光有机水凝胶纤维的制备方法,其特征在于包括如下步骤:
步骤1)羟乙基羧甲基纤维素的制备:将羟乙基纤维素和四硼酸钠混合后,浸泡于异丙醇溶液中;加入与羟乙基纤维素等摩尔量的一氯乙酸,加入35-45wt% 的NaOH溶液,反应0.5-1.5h,熟化1-2h,固体物用冰醋酸中和至pH=6.5-7.5时,用水将产物溶解,再用甲醇重结晶,并用甲醇洗涤,抽滤,真空干燥制得羟乙基羧甲基纤维素;
步骤2):取步骤1)制得的羟乙基羧甲基纤维素,加入去离子水搅拌溶解,获得羟乙基羧甲基纤维素溶液,待用;
步骤3)碳纳米点的制备:称取肝素钠置于容器中,加入去离子水,超声震荡至完全溶解,将所得混合溶液倒入水热反应釜中加热反应;反应后将混合液冷却至室温,然后离心处理,取上清液,用0.22μm微孔过滤膜重复过滤数次;将过滤所得液体装入透析膜内进行透析;将透析所得液体真空干燥,得到固体的碳纳米点;
步骤4)碳载银纳米粒子的制备:取0.008-0.012 g步骤1)所得碳纳米点置于容器中,加入8-12mL去离子水,水浴超声使碳纳米点均匀分散,然后加入硝酸银溶液;将所得混合溶液置于紫外光下照射,当混合溶液从黄色变成深棕色时,获得碳载银纳米粒子溶液;
步骤5)湿法纺丝:将单体甲基丙烯酸和光引发剂1173,碳载银纳米粒子溶液加入步骤2)制得的羟乙基羧甲基纤维素溶液中混合均匀,缓慢搅拌以除去混合溶液中的气泡,即得到纺丝液;将纺丝液转移至注射器中,采用湿法纺丝工艺,在紫外光的凝固浴中引发纤维的光聚合,将纤维在Fe3+凝固浴中浸泡2-4h,使Fe3+和羧基配位发生铁离子双交联,最后浸泡在去离子水中平衡40-50 h,除掉未反应的单体和双网络中多余的铁离子,得到水凝胶纤维;
步骤6)溶剂替换:将步骤5)得到的水凝胶纤维浸泡在甘油和FeCl3溶液按质量比0.8-1.2:1组成的混合溶剂中15-25 h,得到有机水凝胶纤维;
步骤7):将聚乙烯醇加入去离子水中,水浴加热至70-80℃并搅拌溶解,然后静置至聚乙烯醇完全溶解后,得到聚乙烯醇溶液;将步骤6)得到的有机水凝胶纤维浸泡在聚乙烯醇溶液中,0.5-1.5h后取出,并于硼酸溶液中浸没25-35 s,取出自然风干,即得到自愈性发光有机水凝胶纤维。
2.如权利要求1所述的制备方法,其特征在于:步骤1)中,四硼酸钠的加入量为羟乙基羧甲基纤维素的0.4-0.6wt%,NaOH与一氯乙酸的摩尔比为1.4-2.0 : 1,反应温度为45-55℃。
3.如权利要求1所述的制备方法,其特征在于:步骤3)中,所述混合溶液中肝素钠水溶液的浓度为0.02-0.03 g/mL,反应温度为130-150 ℃,反应时间为10-15h。
4.如权利要求1所述的制备方法,其特征在于:步骤3)中,离心转速为8000-12000 r/min,离心时间为5-15min;所述透析膜的规格为1000 Da,透析时间为40-50 h;真空干燥温度为35-45℃,真空干燥时间为40-50 h。
5.如权利要求1所述的制备方法,其特征在于:步骤4)中,超声时间为20-40分钟,硝酸银溶液的浓度为0.008-0.012 mol/L,紫外光波长为360-370 nm,光照时间为70-90分钟。
6.如权利要求1所述的制备方法,其特征在于:步骤5)中,单体甲基丙烯酸的添加量为羟乙基羧甲基纤维素溶液的3-7wt%,光引发剂1173的添加量为羟乙基羧甲基纤维素溶液的0.08-0.12wt%;紫外光波长为360-370 nm,凝固浴为0.04-0.08mol/L的FeCl3溶液。
7.如权利要求1所述的制备方法,其特征在于:步骤6)中,FeCl3溶液的浓度为0.02-0/04mol/L。
8.如权利要求1所述的制备方法,其特征在于:步骤7)中,聚乙烯醇溶液的浓度为0.03-0.05%,搅拌时间2-3 h,硼酸溶液的浓度为2.6-3.0 g/100 mL。
9.如权利要求1所述的制备方法,其特征在于:步骤2)中,羟乙基羧甲基纤维素溶液的浓度为1-3wt%。
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2009072232A1 (ja) * | 2007-12-07 | 2009-06-11 | Sanyo Chemical Industries, Ltd. | 耐光性に優れた保水剤及び吸水ゲル組成物 |
JP2013049782A (ja) * | 2011-08-31 | 2013-03-14 | Mitsubishi Rayon Co Ltd | ゲルおよびその製造方法 |
CN106362202A (zh) * | 2016-11-16 | 2017-02-01 | 广东省生物工程研究所(广州甘蔗糖业研究所) | 一种具有微电流和药物缓释作用的水凝胶及制备方法与应用 |
WO2019167013A1 (en) * | 2018-03-02 | 2019-09-06 | Materias S.R.L. | Process for preparing a superabsorbent aerogel |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009072232A1 (ja) * | 2007-12-07 | 2009-06-11 | Sanyo Chemical Industries, Ltd. | 耐光性に優れた保水剤及び吸水ゲル組成物 |
JP2013049782A (ja) * | 2011-08-31 | 2013-03-14 | Mitsubishi Rayon Co Ltd | ゲルおよびその製造方法 |
CN106362202A (zh) * | 2016-11-16 | 2017-02-01 | 广东省生物工程研究所(广州甘蔗糖业研究所) | 一种具有微电流和药物缓释作用的水凝胶及制备方法与应用 |
WO2019167013A1 (en) * | 2018-03-02 | 2019-09-06 | Materias S.R.L. | Process for preparing a superabsorbent aerogel |
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