CN116120618A - 具有高强度、高恢复的双层润滑水凝胶的制备方法和应用 - Google Patents
具有高强度、高恢复的双层润滑水凝胶的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种具有高强度、高恢复的双层润滑水凝胶的制备方法,本发明通过三价铁离子与丙烯酸之间的金属络合作用增强了水凝胶的机械性能,得到具有较强力学性能的凝胶网络,再利用基于柠檬酸‑铁氧化还原机制,在Fe3+负载的水凝胶基质表面原位生成Fe2+催化剂,通过表面催化自由基聚合机理,引发单体溶液在固‑液界面生成新的润滑层水凝胶,得到了机械强度高,恢复速度快,且具有较好的润滑性能的双层润滑水凝胶,实现了高力学强度与低摩擦的平衡,解决了水凝胶强度差、耐疲劳性差以及表面润滑性不足的问题,可用于仿生关节软骨材料。
Description
技术领域
本发明涉及凝胶类仿生关节软骨材料制备技术领域,更具体地,涉及一种具有高强度、高恢复的双层润滑水凝胶及制备方法和应用。
背景技术
健康的关节软骨对人类的生命活动至关重要,其有效的润滑表面起主要作用。如果关节软骨受到损伤,其润滑功能将受到阻碍,关节软骨表面摩擦增加,导致软骨组织和软骨下骨的渐进结构和功能损伤,最终导致关节疼痛和残疾,引发如关节炎(OA)等疾病,我国骨关节炎发病率约10%,而55岁以上年龄段的发病率高达80%。在过去三十年里,人们对使用合成人工材料替代受损的天然软骨产生了相当大的兴趣。其中合成材料,如超高分子量聚乙烯(UHMWPE),钛合金,不锈钢和陶瓷,用于部分和全部关节置换。然而,这些材料通常较硬,在天然软骨滑动条件下,由于界面接触应力高,表面润滑不良,会导致严重磨损和关节变性。因此,减少表面接触应力和增加表面润滑是开发新型软骨替代材料的有效途径。
关节软骨主要由胶原纤维和蛋白聚糖组成,在较宽的接触动力学范围内可以实现高承载(3–18MPa),并提供抗拉强度和增强组织的压缩模量以抵抗剪切力。同时,软骨最表层附着透明质酸、润滑素、磷脂酰胆碱脂质等自组装成分,在摩擦过程中与关节腔内的滑膜液结合,在生理高压下,可通过其水合润滑作用将表面摩擦系数降低至0.001-0.1,减小磨损。水凝胶具有亲水聚合物网络、柔软的弹性和水化特征,较低摩擦以及可控的生物相容性,已经在人工关节软骨方面有广泛应用。在CN201610647658.0公开了一种可用于骨软骨修复的双层复合水凝胶材料,其骨修复层由海藻酸钠/镁黄长石/葡萄糖酸内酯复合水凝胶组成,软骨修复层由海藻酸钠/琼脂糖复合水凝胶组成。该专利还公开了该双层复合水凝胶的制备方法及应用,可模拟骨与软骨组织,双层复合水凝胶界面间连接紧密,可模拟骨软骨结合界面。该专利所述的双层复合水凝胶虽然能够在促进骨软骨组织再生的同时促进新生骨组织中的血管生成,从而促进骨组织与软骨组织的修复。但是由于该水凝胶的强度难以满足或达到关节软骨的高承载力,且该仿生关节软骨在承载受力后的恢复性能较差,难以满足人体一些经常承载受力的关节性能的要求。同时,该方法得到的仿生软骨无法提供表面润滑,容易在摩擦过程中受损,因而该双层复合水凝胶在软骨关节的应用中有了一定的限制。
发明内容
本发明要解决的技术问题是针对现有技术中制备的水凝胶强度差、耐疲劳性差以及表面润滑性的不足,提供一种具有高强度、高恢复的双层润滑水凝胶的制备方法。
本发明要解决的另一技术问题是提供该方法制备的高强度、高恢复的双层润滑水凝胶在关节软骨中的应用。
本发明的目的通过以下技术方案予以实现:
一种具有高强度、高恢复的双层润滑水凝胶的制备方法,制备步骤包括:
S1.将单体一、单体二和单体三按比例溶解于溶剂中,加入引发剂,搅拌均匀,聚合制备得到底层水凝胶材料;
S2.将S1中底层水凝胶材料浸泡在Fe3+溶液中,得到Fe3+交联的底层水凝胶材料;
S3.将Fe3+交联的底层水凝胶材料再浸泡至柠檬酸溶液中,通过紫外光照射,得到处理后的的底层水凝胶材料;
S4.将经过柠檬酸与紫外线处理后的底层水凝胶材料浸泡在含有引发剂的单体四溶液中,聚合顶部润滑层,得到具有高强度、高恢复的双层润滑水凝胶。
进一步地,S1中所述单体一为丙烯酸、丙烯酸羟乙酯、丙烯酸正丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸、丙烯腈中的一种或多种。
进一步地,S1中所述单体二和丙烯酰胺、N,N-异丙基丙烯酰胺、N,N-二甲基丙烯酰胺、甲基丙烯酰胺、N,N-二甲基甲酰胺中的一种
进一步地,S1中所述单体三为丙烯酰胺、N,N-异丙基丙烯酰胺、N,N-二甲基丙烯酰胺、甲基丙烯酰胺、N,N-二甲基甲酰胺中的一种,且单体三与单体二的单体物质不同。
进一步地,S21中所述单体一、单体二和单体三的质量比为1~5:5:1。
进一步地,所述引发剂为过硫酸铵、过硫酸钾、戊二醛、偶氮二异丁腈中的一种或多种。
进一步地,所述引发剂的添加量为单体的总摩尔浓度的0.5~2mol%。
进一步地,所述Fe3+溶液浓度为0.1~0.8M,浸泡时间为8~24h。
进一步地,所述柠檬酸处理时间为2.5~20min,紫外光照射时间为2.5~20min。
进一步地,所述单体四为2-丙烯酰胺-2-甲基丙磺酸(AMPS)、3-磺酸丙基甲基丙烯酸钾(SPMA)、(2-(甲基丙烯酰氧基)乙基)二甲基(3-磺酸丙基)氢氧化铵(SBMA)、二甲基二烯丙基氯化铵(DADMAC)、丙烯酰氧乙基三甲基氯化铵(DAC)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)中的一种。
进一步地,所述具有高强度、高恢复的双层润滑水凝胶的制备方法制备的水凝胶用于仿生关节软骨材料。
与现有技术相比,有益效果是:
本发明以Fe3+与丙烯酸之间的金属络合作用增强了水凝胶的机械性能,得到具有较强力学性能的凝胶网络,再经过柠檬酸处理、紫外照射,在Fe3+负载的水凝胶基质表面原位生成Fe2+催化剂,通过表面催化自由基聚合机理,引发单体溶液在固-液界面生成新的润滑层水凝胶,从而实现了高力学强度、高恢复与低摩擦的平衡。本发明所述方法操作简单,制备的双层水凝胶材料机械强度高,恢复速度快,且具有较好的润滑性能,可用于仿生关节软骨材料。
附图说明
图1为实施例1中制备的双层润滑水凝胶材料SEM图像;
图2为实施例1-5中不同丙烯酸浓度制备的双层润滑水凝胶材料在的压缩力学性能:(a)压缩应力-应变曲线;(b)抗压强度与弹性模量;
图3为实施例1和6-9中在不同Fe3+浓度制备的双层润滑水凝胶材料的压缩力学性能:(a)压缩应力-应变曲线;(b)抗压强度与弹性模量;
图4为实施例1中制备的双层润滑水凝胶材料压缩加载-卸载10次后的应力-应变曲线;
图5为实施例1中制备的双层润滑水凝胶材料加载-卸载后分别休息30s、1min、2min、3min后的;(a)压缩应力-应变曲线;(b)耗散能、弹性模量、以及峰值应力的恢复率;
图6为实施例1中制备的双层润滑水凝胶材料与底层水凝胶在不同摩擦速率和载荷的摩擦系数。
图7为实施例1中制备的双层润滑水凝胶材料与底层水凝胶材料摩擦后的磨损情况(摩擦条件:载荷30N,滑动速率1mm/s)。
具体实施方式
下面结合实施例进一步解释和阐明,但具体实施例并不对本发明有任何形式的限定。若未特别指明,实施例中所用的方法和设备为本领域常规方法和设备,所用原料均为常规市售原料。
实施例1
本实施例提供具有高强度、高恢复的双层润滑水凝胶的制备方法,步骤包括:
S1.将丙烯酸、N,N-二甲基丙烯酰胺和甲基丙烯酰胺按(2.5:5:1)溶解于去离子水中,加入0.5mol%的过硫酸钾作为热引发剂,搅拌均匀,在60℃反应1h聚合制备得到底层水凝胶材料。
S2.将S1中底层水凝胶材料浸泡在0.4M的Fe3+溶液中12h,得到Fe3+交联的底层水凝胶材料;
S3.将Fe3+交联的底层水凝胶材料再浸泡至pH值为3的柠檬酸溶液中15min,通过紫外光照射10min,得到表面氧化还原的底层水凝胶材料;
S4.将表面氧化还原的底层水凝胶材料浸泡在含有1mol%的过硫酸钾引发剂的3-磺酸丙基甲基丙烯酸钾溶液中,反应15min聚合顶部润滑层,得到具有高强度、高恢复的双层润滑水凝胶。
实施例2-5
本实施例根据实施例1所述方法,分别采用不同的原料比例制备得到具有高强度、高恢复的双层润滑水凝胶,原料丙烯酸、N,N-二甲基丙烯酰胺和甲基丙烯酰胺的比例分别如下表1所示:
表1
丙烯酸∶N,N-二甲基丙烯酰胺∶甲基丙烯酰胺 | |
实施例2 | 1.5:5:1 |
实施例3 | 2:5:1 |
实施例4 | 3:5:1 |
实施例5 | 3.5:5:1 |
如图1制备的双层润滑水凝胶,从图2检测的不同丙烯酸浓度制备的双层润滑水凝胶材料在的压缩力学性能可知,实施例1-5中所制备的水凝胶,其力学性能随着丙烯酸浓度的增加呈现先增加后减少的趋势,在丙烯酸浓度为10wt.%时,水凝胶的压缩强度和压缩模量达到了最高,因此可以确定丙烯酸、N,N-二甲基丙烯酰胺和甲基丙烯酰胺各原料的最佳配比为2.5:5:1。
实施例6-9
本实施例根据实施例1所述方法,分别采用不同的浓度的Fe3+溶液浸泡底层水凝胶材料,制备得到具有高强度、高恢复的双层润滑水凝胶,Fe3+溶液如下表2所示:
表2
<![CDATA[Fe<sup>3+</sup>溶液浓度(M)]]> | |
实施例6 | 0.2 |
实施例7 | 0.3 |
实施例8 | 0.5 |
实施例9 | 0.6 |
如图3所示,实施例1和实施例6-9不同Fe3+溶液浓度所制备的水凝胶的力学性能随着Fe3+浓度的增加呈现先增加后减少的趋势,最佳Fe3+浓度为0.4M。
将实施例1所得到的双层润滑水凝胶制备高度为4mm、直径为8mm的圆柱形试样。在电子万能试验机上进行力学测试,对圆柱形试样在压缩速率为5mm/min进行压缩,检测水凝胶的压缩强度和压缩模量,检测结果如下表3所示:
表3
压缩应变 | 20% | 30% | 50% | 80% |
压缩强度 | 0.39MPa | 0.75MPa | 2.18MPa | 18.55MPa |
压缩模量 | 1.69MPa | 1.68MPa | 1.72MPa | 1.71MPa |
用实施例1所得到的双层润滑水凝胶制备高度为4mm、直径为8mm的圆柱形试样。在电子万能试验机上进行力学测试,对圆柱形试样在压缩应变保持为30%时,以5mm/min的压缩速率进行多次循环压缩,检测其力学保留率如下表4所示
表4
循环次数 | 10 | 50 | 100 | 500 | 1000 |
压缩强度 | 98% | 95% | 92% | 87% | 80% |
压缩模量 | 97% | 93% | 88% | 78% | 75% |
由表3、表4和图4所示,实施例1所得到的双层润滑水凝胶的压缩形变量在80%,其压缩强度达到了18MPa,能够实现高承载。并且经过多次的压缩循环,仍能保持较好的力学性能。
用实施例1所得到的双层润滑水凝胶制备高度为4mm、直径为8mm的圆柱形试样。在电子万能试验机上进行力学测试,对圆柱形试样在压缩应变保持为30%时,第一次加载-卸载实验后分别休息30s、1min、2min、3min后的力学性能重新进行测试。
如图5所示,实施例1所得到的双层润滑水凝胶在进行加载后,经过3min的休息后,其力学性能能恢复到原来的99%。
用实施例1所得到的双层润滑水凝胶制备厚度4mm、边长15mm的长方体试样。在多功能微摩擦试验机上对摩擦系数进行测定,试验采用直径为10mm的不锈钢钢球作为摩擦副,与下部水凝胶进行来回滑动,在37℃去离子水中进行,载荷为5~30N,往复速度为0.1~1mm/s和行程长度5mm,检测其在不同摩擦速率和载荷的摩擦系数以及摩擦后的磨损情况。
相较于单层的无润滑层的水凝胶,如图6-7所示,实施例1所得到的双层润滑水凝胶的摩擦系数大大降低,平均摩擦系数降低约88%,并且其摩擦后的磨损也急剧减少,最大磨损深度降低约91%,具有良好的润滑防磨损效果。
实施例10
本实施例提供具有高强度、高恢复的双层润滑水凝胶的制备方法,步骤包括:
S1.将丙烯腈、丙烯酰胺和N,N-异丙基丙烯酰胺以按比例溶解于去离子水中,加入0.8mol%的过硫酸钾作为热引发剂,搅拌均匀,在30℃反应1h聚合制备得到底层水凝胶材料。
S2.将S1中底层水凝胶材料浸泡在0.2M的Fe3+溶液中12h,得到Fe3+交联的底层水凝胶材料;
S3.将Fe3+交联的底层水凝胶材料再浸泡至pH为3的柠檬酸溶液中10min,通过紫外光照射10min,得到表面氧化还原的底层水凝胶材料;
S4.将表面氧化还原的底层水凝胶材料浸泡在含有1.8mol%的过硫酸钾引发剂的3-磺酸丙基甲基丙烯酸钾溶液中,反应15min聚合顶部润滑层,得到具有高强度、高恢复的双层润滑水凝胶。
实施例11
本实施例提供具有高强度、高恢复的双层润滑水凝胶的制备方法,步骤包括:
S1.将丙烯酸正酯、N,N-二甲基丙烯酰胺和甲基丙烯酰胺按比例溶解于去离子水中,加入1mol%的过硫酸钾作为热引发剂,搅拌均匀,在40℃反应2h聚合制备得到底层水凝胶材料。
S2.将S1中底层水凝胶材料浸泡在0.5M的Fe3+溶液中14h,得到Fe3+交联的底层水凝胶材料;
S3.将Fe3+交联的底层水凝胶材料再浸泡至pH为4的柠檬酸溶液中10min,通过紫外光照射15min,得到表面氧化还原的底层水凝胶材料;
S4.将表面氧化还原的底层水凝胶材料浸泡在含有1mol%的过硫酸钾引发剂的3-磺酸丙基甲基丙烯酸钾溶液中,反应5min聚合顶部润滑层,得到具有高强度、高恢复的双层润滑水凝胶。
实施例12
本实施例提供具有高强度、高恢复的双层润滑水凝胶的制备方法,步骤包括:
S1.将丙烯酸羟乙酯、丙烯酰胺和N,N-二甲基丙烯酰胺按比例溶解于去离子水中,加入0.5mol%的过硫酸钾作为热引发剂,搅拌均匀,在40℃反应2h聚合制备得到底层水凝胶材料。
S2.将S1中底层水凝胶材料浸泡在0.3M的Fe3+溶液中12h,得到Fe3+交联的底层水凝胶材料;
S3.将Fe3+交联的底层水凝胶材料再浸泡至pH为2的柠檬酸溶液中10min,通过紫外光照射10min,得到表面氧化还原的底层水凝胶材料;
S4.将表面氧化还原的底层水凝胶材料浸泡在含有1.5mol%的过硫酸钾引发剂的3-磺酸丙基甲基丙烯酸钾溶液中,反应10min聚合顶部润滑层,得到具有高强度、高恢复的双层润滑水凝胶。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (10)
1.一种具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,制备步骤包括:
S1.将单体一、单体二和单体三按比例溶解于溶剂中,加入引发剂,搅拌均匀,聚合制备得到底层水凝胶材料;
S2.将S1中底层水凝胶材料浸泡在Fe3+溶液中,得到Fe3+交联的底层水凝胶材料;
S3.将Fe3+交联的底层水凝胶材料再浸泡至柠檬酸溶液中,通过紫外光照射,得到表面氧化还原的底层水凝胶材料;
S4.将表面氧化还原的底层水凝胶材料浸泡在含有引发剂的单体四溶液中,聚合顶部润滑层,得到具有高强度、高恢复的双层润滑水凝胶。
2.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,S1中所述单体一为丙烯酸、丙烯酸羟乙酯、丙烯酸正丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸、丙烯腈中的一种或多种。
3.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,S1中所述单体二和单体三分别为丙烯酰胺、N,N-异丙基丙烯酰胺、N,N-二甲基丙烯酰胺、甲基丙烯酰胺、N,N-二甲基甲酰胺中的一种,且单体二和单体三的单体物质不同。
4.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,S21中所述单体一、单体二和单体三的质量比为1~5:5:1。
5.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,所述引发剂为过硫酸铵、过硫酸钾、戊二醛、偶氮二异丁腈中的一种或多种。
6.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,所述引发剂的添加量为单体的总摩尔浓度的0.5~2mol%。
7.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,所述Fe3+溶液浓度为0.1~0.8M,浸泡时间为8~24h。
8.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,所述柠檬酸处理时间为2.5~20min,紫外光照射时间为2.5~20min。
9.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法,其特征在于,所述单体四为2-丙烯酰胺-2-甲基丙磺酸(AMPS)、3-磺酸丙基甲基丙烯酸钾(SPMA)、(2-(甲基丙烯酰氧基)乙基)二甲基(3-磺丙基)氢氧化铵(SBMA)、二甲基二烯丙基氯化铵(DADMAC)、丙烯酰氧乙基三甲基氯化铵(DAC)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)中的一种。
10.根据权利要求1所述具有高强度、高恢复的双层润滑水凝胶的制备方法制备的水凝胶用于仿生关节软骨材料。
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