CN115025282A - 一种木质素/纳米羟基磷灰石基复合材料及其制备方法 - Google Patents
一种木质素/纳米羟基磷灰石基复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种木质素/纳米羟基磷灰石基复合材料及其制备方法。该木质素/纳米羟基磷灰石基复合材料是指将木质素溶解于10%的NaOH溶液，然后将制备纳米羟基磷灰石的可溶性磷盐和钙盐制备原料在60~80℃下缓慢滴加后，保持pH值大于10，搅拌反应3~5小时，室温下陈化24 h后用蒸馏水洗涤到中性，烘干研磨成粉末即可得复合材料。同时该复合材料制备方法简单易行，所用原料来源丰富，且在加工成型时可直接添加β‑磷酸三钙或二氧化硅无机粒子对复合材料增强，也可在溶解的木质素溶液中可添加适量竹纤维、剑麻纤维、或木质纤维对其增强改性，从而使该复合材料力学性能优良，降解速度合适及生物相容性良好，有望用于新型骨修复材料的研制。
Description
技术领域
本发明涉及一种木质素/纳米羟基磷灰石基复合材料及其制备方法，属于生物医用材料领域。
背景技术
近年来，模仿自然骨组织的组分，将纳米羟基磷灰石与高聚物复合，充分结合二者的优异性，是目前骨修复材料关注的重点。目前常用的高分子包括聚乳酸、聚酰胺、聚碳酸酯、聚乙烯等合成高分子，及壳聚糖、丝素蛋白、胶原、明胶等天然高分子。随着人们对天然高分子的研究深入，采用天然可降解高分子与纳米羟基磷灰石复合制备骨修材料材备受关注。
木质素(lignin，又称木素)是第二大丰富的天然生物质资源，仅次于纤维素，其结构单元为苯丙烷型非结晶性的三维高分子网状酚类高分子聚合物，是典型的天然两亲性大分子。木质素具有热塑性、阻燃性和耐热性、防老化性、防紫外辐射、成核性、生物降解以及无毒等优点。因此，其应用越来越受到国内外研究人员的重视。将木质素修饰纳米SiO2后与高密度聚乙烯共混，可改善纳米SiO2的分散性且提高塑料的力学性能。将木质素通过电子束辐射后在异氰尿酸三烯丙酯存在下可以与聚乳酸有良好的界面结合，以致提高聚乳酸的力学性能及水解性能。木质素还有抗氧化、抗菌、抗突变等优异的生物学性能，如作为药品片剂添加剂、抗菌水凝胶或涂层、3D打印抗氧化绷带以及载药纳米粒子，在健康领域用途广泛。木质素与其它高分子共聚后可以与DNA形成配合物，作为基因载体具有较高的传染率及较低的细胞毒性。尽管以上文献表明木质素是优良的绿色环保型化工原料，且对生物体是无毒的，但至今未见将其应用于骨科方面的报道。
基于此，若采用溶液沉淀法，使纳米羟基磷灰石在木质素上有序生长，则有望获得类似于纳米羟基磷灰石在胶原纤维上有序组装的仿生骨结构，以致在骨修复材料领域展现良好的功能性。
发明内容
针对上述情况，本发明的目的在于提供一种木质素/纳米羟基磷灰石基复合材料及其制备方法。
本发明的木质素/纳米磷灰石基复合材料是由木质素和纳米磷灰石构成的复
合材料，也可是添加其他无机粒子增强或纤维增强的木质素/纳米磷灰石复材料。
本发明所说的木质素，其特征是可为碱木质素，也可为磺酸木质素；
本发明所说的木质素/纳米磷灰石基复合材料，其特征是指保持纳米磷灰石
质量在复合材料中占60%~90%；
本发明所说的添加其他无机粒子，其特征是指添加质量比为3%~8%的β-磷酸三钙或二氧化硅。
本发明所说的添加纤维，其特征是指添加质量比5%~50%的竹纤维、剑麻纤维或木质纤维，纤维可以是改性或不改性，其直径为0.05mm，长度为1 mm。
本发明的木质素/纳米磷灰石基复合材料的制备方法，其特征是指：
（1）复合材料的制备：将木质素溶于10%的NaOH溶液，根据Ca/P=1.67称
取Na3PO4·12H2O和Ca(NO3)2· 4H2O粉末并分别溶于蒸馏水中，然后将Ca(NO3)2·4H2O溶液缓慢滴加到碱木素溶液中，30 min后将Na3PO4·12H2O溶液缓慢滴加到混合液中，保持pH值大于10，在60~80 ℃下搅拌反应3~5小时后，室温下陈化24 h，用蒸馏水洗涤到中性，80℃烘干研磨成粉末。
（2）纤维增强的木质素/纳米磷灰石复合材料的制备：将纤维用超声波破碎仪均匀分散到蒸馏水中，然后将木质素溶解在氢氧化钠溶液中并逐滴加入其中，随后按照上述复合材料制备的步骤。
（3）复合材料的加工及力学性能的测试：将一定量的复合材料研磨成粉末状后，也可加入其它用于增强的无机粒子，混合均匀后用少量5~8%的壳聚糖溶液中调和成糊状，注入自制的医用注射器中成型得直径为6 mm，高度为12 mm的圆柱状样品，置于烘箱中烘干。采用万能材料试验机（DWD-20）对样品按照GB/T1042-92标准测试压缩性能，每个样品测3个平行样取平均值。
本发明所获得的复合材料与现有的骨修复材料相比，具有以下优势：
（1）在复合材料的选材上，本发明选用的木质素是一种天然高聚物，具有抗氧化、抗菌、抗突变等优异的生物学性能，因而是优良的天然医用高分子材料。另外木质素具有一定的亲水性，可与亲水性的无机纳米磷灰石粒子很好地复合，将获得力学性能、骨传导性及降解性能都优良的骨修复材料。
（2）该复合材料制备方法简单，反应条件温和，加工过程方便，且可通过调节木质素、纳米羟基磷灰石及其他无机粒子或纤维含量调控复合材料的力学性能、降解性能及骨传导性，以获得满足不同部位骨缺损修复要求的各种复合材料；同时还可添加不同药物或其他生长因子得到性能更好的骨修复材料。
附图说明
图1 为复合材料的加工成型的样品及SEM照片。
具体实施方式
实施例1：取1.0 g碱木质素，搅拌溶解于50 ml 10%的NaOH溶液中，取5.48 g Ca(NO3)2·4H2O溶于100 ml去离子水中，搅拌下缓慢滴加于木质素溶液中，反应30 min后，取5.29 g Na3PO4·12H2O溶解于100 ml溶液中，缓慢滴加于上述混合溶液，保持pH值大于10，70 ℃下反应4小时，室温下陈化24 h后用蒸馏水洗涤到中性，80℃烘干研磨成粉末。取1.0g粉末加8%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为46.5 MPa。
实施例2：取1.0 g磺酸木质素，搅拌溶解于50 ml 10%的NaOH溶液中，取3.53 g Ca(NO3)2·4H2O溶于100 ml去离子水中，搅拌下缓慢滴加于木质素溶液中，反应30 min后，取3.40 g Na3PO4·12H2O溶解于100 ml溶液中，缓慢滴加于上述混合溶液，保持pH值大于10，60 ℃下反应3小时，室温下陈化24 h后用蒸馏水洗涤到中性，80℃烘干研磨成粉末。取1.0g粉末和0.05 g二氧化硅加8%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为52.8 MPa。
实施例3：取1.0 g碱木质素，搅拌溶解于50 ml 10%的NaOH溶液中，取9.41 g Ca(NO3)2·4H2O溶于150 ml去离子水中，搅拌下缓慢滴加于木质素溶液中，反应30 min后，取9.07 g Na3PO4·12H2O溶解于150 ml溶液中，缓慢滴加于上述混合溶液，保持pH值大于10，80 ℃下反应4小时，室温下陈化24 h后用蒸馏水洗涤到中性，80℃烘干研磨成粉末。取1.0g粉末和0.08 gβ-磷酸三钙加5%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为63.9 MPa。
实施例4：取1.0 g磺酸木质素，搅拌溶解于50 ml 10%的NaOH溶液中，取21.6 g Ca(NO3)2·4H2O溶于200 ml去离子水中，搅拌下缓慢滴加于木质素溶液中，反应30 min后，取20.8 g Na3PO4·12H2O溶解于200 ml溶液中，缓慢滴加于上述混合溶液，保持pH值大于10，80 ℃下反应4小时，室温下陈化24 h后用蒸馏水洗涤到中性，80℃烘干研磨成粉末。取1.0g粉末和0.1 g二氧化硅加5%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为61.6 MPa。
实施例5：取0.75 g竹纤维分散于150 ml去离子水中，另取1.0 g碱木质素，搅拌溶解于50 ml 10%的NaOH溶液中，缓慢滴加于上述溶液中，再取9.41 g Ca(NO3)2·4H2O溶于150 ml去离子水中，搅拌下缓慢滴加于竹纤维和木质素混合溶液中，反应30 min后，再取9.07 g Na3PO4·12H2O溶解于150 ml溶液中，缓慢滴加于上述混合溶液，保持pH值大于10，70 ℃下反应5小时，室温下陈化24 h后用蒸馏水洗涤到中性，80℃烘干研磨成粉末。取1.0g粉末加8%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为68.8 MPa。
实施例6：取1.0 g改性木质素纤维分散于150 ml去离子水中，另取1.0 g碱木质素，搅拌溶解于50 ml 10%的NaOH溶液中，缓慢滴加于上述溶液中，再取9.41 g Ca(NO3)2·4H2O溶于150 ml去离子水中，搅拌下缓慢滴加于竹纤维和木质素混合溶液中，反应30 min后，再取9.07 g Na3PO4·12H2O溶解于150 ml溶液中，缓慢滴加于上述混合溶液，保持pH值大于10，70 ℃下反应5小时，室温下陈化24 h后用蒸馏水洗涤到中性，80℃烘干研磨成粉末。取1.0 g粉末加8%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为64.5 MPa。
实施例7：取1.0 g改性剑麻纤维分散于150 ml去离子水中，另取1.0 g磺酸木质素，搅拌溶解于50 ml 10%的NaOH溶液中，缓慢滴加于上述溶液中，再取3.53 g Ca(NO3)2·4H2O溶于100 ml去离子水中，搅拌下缓慢滴加于竹纤维和木质素混合溶液中，反应30 min后，再取3.40 g Na3PO4·12H2O溶解于100 ml溶液中，缓慢滴加于上述混合溶液，保持pH值大于10，70 ℃下反应3小时，室温下陈化24 h后用蒸馏水洗涤到中性，80℃烘干研磨成粉末。取1.0 g粉末加5%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为57.5 MPa。
实施例8：取0.75 g改性竹纤维分散于100 ml去离子水中，另取1.0 g碱木质素，搅拌溶解于50 ml 10%的NaOH溶液中，缓慢滴加于上述溶液中，再取9.41 g Ca(NO3)2·4H2O溶于150 ml去离子水中，搅拌下缓慢滴加于竹纤维和木质素混合溶液中，反应30 min后，再取9.07 g Na3PO4·12H2O溶解于150 ml溶液中，缓慢滴加于上述混合溶液，保持pH值大于10，70 ℃下反应3小时，室温下陈化24 h后用蒸馏水洗涤到中性，80℃烘干研磨成粉末。取1.0g粉末加5%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为60.8 MPa。
对比实施：取2.77 g Na3PO4·12H2O及2.35 g Ca(NO3)2·4H2O分别溶于50 ml去离子水中，在搅拌条件下将Ca(NO3)2溶液逐滴加入Na3PO4溶液，滴加完后用10% NaOH溶液调pH大于10，保持温度为60 ℃，反应5小时，静置48小时后，用去离子水洗涤至中性，烘干研磨成粉。取1.0 g粉末加5%壳聚糖溶液调和成糊状后用注射器自制加工成型，测得抗压强度为17.8 MPa。
以上样品的测试都是在温度25±0.2 ℃，湿度60%±5 ℃环境下进行，使用圆柱状直径为6 mm，高度为12 mm的圆柱状样品在电子万能材料试验机上以5±0.2 mm/min标准试验速度测试，压缩比设置为50% 得到。
Claims (3)
1.一种木质素/纳米磷灰石基复合材料的制备方法，其特征是指将碱木质素或磺酸木质素溶解于10%的NaOH溶液，然后添加不同比例的纳米羟基磷灰石的制备原料，使纳米羟基磷灰石的含量在复合材料中质量比为60 %~90 %，在60~80 ℃下搅拌反应3~5小时，室温下陈化24 h后用蒸馏水洗涤到中性，烘干研磨成粉末。
2.根据权利要求1所说的木质素/纳米羟基磷灰石基复合材料，其特征是指在加
工成型时可添加质量比为3%~8%的β-磷酸三钙或二氧化硅无机粒子。
3.根据权利要求1所说的木质素/纳米磷灰石基复合材料，其特征是指在溶解的
木质素溶液中可添加质量比5%~50%的改性或不改性的竹纤维、剑麻纤维、
或木质纤维。
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