CN112220968B - 一种长期替代型组织工程半月板支架的光固化3d打印制备方法 - Google Patents
一种长期替代型组织工程半月板支架的光固化3d打印制备方法 Download PDFInfo
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Abstract
本发明公开了一种可长期替代型组织工程半月板支架的光固化3D打印制备方法。打印长期替代型半月板支架所用光敏树脂的原料组分按重量份数计含量如下:聚氨酯丙烯酸酯10~80份,丙烯酸酯单体20~80份,自由基型光引发剂0.5~5.0份,消泡剂0.001~0.5份。所述聚氨酯丙烯酸酯具有如式I的结构。式I中,R1具体可为异氟尔酮基、六亚甲基、二环己基甲烷基中的一种;R2具体可为乙基、丙基、正丁基中的一种或几种;R3具体可为氢或甲基的一种;n具体可为10~100。本发明提供的半月板支架具有良好的生物相容性和体内稳定性,其力学性能与天然半月板相近,而且光固化3D打印可以精确控制其三维结构和多孔结构。
Description
技术领域
本发明属于组织工程技术领域,具体涉及一种长期替代型组织工程半月板支架的光固化3D打印制备方法。
背景技术
半月板是覆盖在关节表面的一种白色透明软骨,其光滑的表面可以明显降低运动过程中关节面间的摩擦力。近年来半月板损伤发病率越来越高,但是该部位由于缺乏血液供应、神经支配及淋巴回流,损伤后自我修复能力很差。构建受损半月板的替代物,即组织工程半月板,可以取得良好的治疗效果。半月板支架材料应具有良好的生物相容性,合理的三维和多孔结构,可以实现营养物质的自由扩散,还应具有良好的力学性能,支架的力学性能应与天然半月板相近,压缩模量应在75-150 kPa范围内,拉伸模量在75-150 MPa范围内[Biomaterials, 126, 18-30, 2017]。
半月板支架材料可以分为替代型和降解型。其中替代型半月板移植物主要采用具有良好的生物相容性、体内稳定性和生物力学性能优异的聚乙烯醇水凝胶、聚碳酸酯型聚氨酯等材料。降解型半月板支架,根据材料来源不同,可分为胶原蛋白、丝素蛋白等天然材料和聚乳酸、聚己内酯等合成材料半月板支架。对于新陈代谢较慢的老年人,长期替代型半月板移植物具有较大的优势。
目前,制备半月板支架的合成材料主要包括具有良好生物相容性的聚氨酯、聚己内酯、聚乳酸等。其中,聚己内酯和聚乳酸韧性、弹性不足,与天然半月板的力学性能相差加大。分子结构可调、材料性能可控的聚氨酯材料是目前制备半月板支架的研究热点。英国Orteq公司制备的一种可降解型聚己内酯/聚氨酯半月板支架已经商业化 (商品名为Atifit®) [Biomaterials, 35, 3527-3540, 2014]。Song等人制备了具有生物活性表面的羟基磷灰石杂化聚氨酯型支架,通过控制其孔隙率调节其力学性能并将其用作半月板移植物 [Macromolecular Materials and Engineering, 304, 2019]。但是,上述材料都无法精确控制支架孔隙结构以及无法为患者定制特定三维形状的半月板支架,近年来3D打印技术的出现,使得人工半月板材料的成型加工和微细结构精确控制成为可能。目前,有一些采用3D打印制备的半月板支架的专利报道(中国专利CN 105013011A, CN 110478527A),但是制备的半月板支架力学性能与天然半月板相差较大,而且打印的精度较低。
发明内容
本发明的目的在于提供一种长期替代型聚氨酯组织工程半月板支架的光固化3D打印制备方法。本发明制备的组织工程半月板具有良好的生物相容性,体内实验证明其具有良好的体内稳定性,而且制备的半月板支架具有与天然半月板相近的力学性能。此外,本发明采用打印精度最高的光固化3D打印,制备的半月板支架表面光滑,可以定制特定三维结构和多孔结构的半月板支架。
本发明所提供的可长期替代型组织工程半月板支架的光固化3D打印制备方法,包括下述步骤:
1)制备光敏树脂,所述光敏树脂的原料组分按重量份数计含量如下:
式I所示聚氨酯丙烯酸酯 10~80份
丙烯酸酯单体 20~80份
自由基型光引发剂 0.5~5.0份
消泡剂 0.001~0.5份;
2)将步骤1)所述光敏树脂进行3D打印,得到半月板模型坯体;
3)将所述半月板模型坯体进行清洗、后固化,得到可长期替代型组织工程半月板支架。
上述方法步骤1)中,聚氨酯丙烯酸酯具有如式I所示的结构:
式I
式I中,R1具体可为异氟尔酮基、六亚甲基、二环己基甲烷基中的任一种。
R2具体可为乙基、丙基、正丁基中的一种或几种。
R3具体可为氢或甲基。
n具体可为10~100的自然数。
式I所示的聚氨酯丙烯酸酯可按照如下步骤的方法制备得到:
S1:在催化剂存在下,使二异氰酸酯与聚醚二醇发生缩聚反应,得到异氰酸酯基封端的聚氨酯类树脂;所述二异氰酸酯的结构式如式II所示:式II,其中R1的定义同式I,所述聚醚二醇的结构式如式III所示:式III,其中R2、n的定义同式I;所述催化剂可为叔胺类或有机金属类催化剂,如三亚乙基二胺、三甲基羟乙基丙二胺、二月桂酸二丁基锡、辛酸亚锡等中的一种或几种的组合物;所述反应的反应温度可为20~100℃,反应时间可为2~14 h;
S2:将上述制备的异氰酸酯基封端的聚氨酯类树脂与甲基丙烯酸羟乙酯或丙烯酸羟乙酯反应,期间加入阻聚剂对苯二酚,得到甲基丙烯酸酯或丙烯酸酯封端的聚氨酯类树脂(式I);所述反应的反应温度可为50~100 ℃,反应时间可为2~8 h。
上述方法步骤1)中,所述丙烯酸酯单体为丙烯酸羟乙酯、丙烯酸异冰片酯、二乙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、(乙氧基化)三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯的一种或几种的组合物。
上述方法步骤1)中,所述自由基型光引发剂可为苯偶酰衍生物、α-羟烷基苯酮类或酰基磷氧化合物等裂解型光引发剂中的一种或几种的组合物。
其中,苯偶酰衍生物具体如DMPA (α,α-二甲氧基-α-苯基苯乙酮),α-羟烷基苯酮类,具体如1173( 2-羟基-2-甲基-1-苯基丙酮)或184( 1-羟基环己基苯基甲酮),酰基磷氧化合物具体如TPO(2,4,6-三甲基苯甲酰二苯基氧化磷)。
上述方法步骤1)中,所述的消泡剂采用BYK-053N、BYK-055、BYK-057、BYK-061中的一种或几种的组合物。
上述方法步骤1)中,优选的所述光敏树脂的原料组分按重量份数计含量如下:
式I所示聚氨酯丙烯酸酯 50~60份
丙烯酸酯单体 35~50份
自由基型光引发剂 0.5~5份(优选1~3份)
消泡剂 0.001~0.5份(优选0.01-0.1份)。
根据本发明的一个实施例,所述光敏树脂的原料组分按重量份数计含量如下:
聚氨酯丙烯酸酯PU-1 60份,丙烯酸羟乙酯 34份,三羟甲基丙烷三丙烯酸酯 5份,
2-羟基-2-甲基-1-苯基丙酮 1份,BYK-057 0.01份。
根据本发明的再一个实施例,所述光敏树脂的原料组分按重量份数计含量如下:
聚氨酯丙烯酸酯PU-2 55份,丙烯酸羟乙酯 34份,三羟甲基丙烷三丙烯酸酯 9份,
2-羟基-2-甲基-1-苯基丙酮 2份,BYK-061 0.05份。
根据本发明的再一个实施例,所述光敏树脂的原料组分按重量份数计含量如下:
聚氨酯丙烯酸酯PU-3 50份,丙烯酸异冰片酯20份,丙烯酸羟乙酯18份,三羟基丙烯酸三丙烯酸酯10份,2,4,6-三甲基苯甲酰二苯基氧化磷 2份,BYK-055 0.1份。
上述方法步骤1)中所述光敏树脂的制备方法如下:
a)按照比例称取聚氨酯丙烯酸酯、丙烯酸酯单体、自由基型光引发剂、消泡剂;
b)将所述聚氨酯丙烯酸酯、丙烯酸酯单体、自由基型光引发剂、消泡剂依次倒入搅拌器中,低速搅拌混匀得到透明的光敏树脂;其中,低速搅拌的转速为400 r/min,搅拌时间为2~4 h。
上述方法步骤3)中,所述清洗可用乙醇或异丙醇对半月板模型坯体进行清洗,具体可为:将半月板模型坯体放入乙醇或异丙醇中,超声清洗10 min。
上述方法步骤3)中,所述后固化过程为:在紫外箱中采用紫外光后固化30 min,然后放入60-100 ºC烘箱后固化0.5-3 h。
所述方法还进一步包括对得到的可长期替代型组织工程半月板支架进行消毒的步骤。
上述方法制备得到的可长期替代型组织工程半月板支架也属于本发明的保护范围。
此外,上述提供的光敏树脂也属于本发明的保护范围。
与现有技术相比,本发明具有如下优点:
(1)本发明提供的半月板支架具有良好的生物相容性、体内稳定性;
(2)本发明提供的半月板支架具有与天然半月板相近的力学性能;
(3)本发明制备半月板支架采用光固化3D打印的方式,打印精度高,可以精确控制其三维结构和多孔结构。
附图说明
图1显示的是本发明通过数字光处理(DLP)3D打印制作的半月板支架模型。
图2显示的是实施例8中打印制作的半月板支架的力学拉伸曲线。
图3显示的是实施例8中打印制作的半月板支架的拉伸模量与天然半月板拉伸模量的对比图。
图4显示的是激光共聚焦显微镜观察细胞核心骨架染色的照片;
图5显示的是将本申请的聚氨酯半月板植入家兔膝关节,术后3个月核磁共振T2像检查照片;
图6显示的是植入家兔体内术后3个月解剖照片。
图7显示的是支架周围关节滑膜组织病理HE染色照片。
具体实施方式
下面通过具体实施例对本发明进行说明,但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
实施例1、式I所示的聚氨酯丙烯酸酯(R1=六亚甲基;R2=乙基、正丁基;R3=氢)的合成
在装配有机械搅拌、氮气导入管、温度计和滴液漏斗的250 mL 圆底烧瓶中,加入16.8 g 六亚甲基二异氰酸酯(HDI),然后将40.0 g聚乙二醇二醇(分子量2000)和90.0 g聚四氢呋喃二醇(分子量为3000)的混合物逐滴滴加到三口烧瓶中,此时保持瓶内反应体系温度60 °C。滴加完毕后,混合物继续反应5 h。向体系中加入催化剂辛酸亚锡(反应物质量的600 ppm),促使反应充分发生。反应程度通过傅里叶红外监测,当异氰酸酯基红外特征吸收峰不再减小时,再将0.1 g对苯二酚和13.9 g丙烯酸羟乙酯的混合物逐滴加入体系中,期间保持体系温度50 °C。滴加完成后,继续反应,直至红外谱图中异氰酸酯基团的特征吸收峰完全消失,即得到聚氨酯丙烯酸酯,设计数均分子量为2179,命名为PU-1。
实施例2、式I所示的聚氨酯丙烯酸酯(R1=六亚甲基;R2=异丙基、正丁基;R3=氢)的合成
在装配有机械搅拌、氮气导入管、温度计和滴液漏斗的250 mL 圆底烧瓶中,加入16.8 g 六亚甲基二异氰酸酯(HDI),然后将30.0 g聚丙二醇二醇(分子量1000)和60.0 g聚四氢呋喃二醇(分子量为2000)的混合物逐滴滴加到三口烧瓶中,此时保持瓶内反应体系温度90 °C。滴加完毕后,混合物继续反应2 h。向体系中加入催化剂辛酸亚锡(反应物质量的600 ppm),促使反应充分发生。反应程度通过傅里叶红外监测,当异氰酸酯基红外特征吸收峰不再减小时,再将0.1 g对苯二酚和9.2 g丙烯酸羟乙酯的混合物逐滴加入体系中,期间保持体系温度60 °C。滴加完成后,继续反应,直至红外谱图中异氰酸酯基团的特征吸收峰完全消失,即得到聚氨酯丙烯酸酯,设计数均分子量为2902,命名为PU-2。
实施例3、式I所示的聚氨酯丙烯酸酯(R1=异弗尔酮基;R2=乙基、正丁基;R3=甲基)的合成
在装配有机械搅拌、氮气导入管、温度计和滴液漏斗的250 mL 圆底烧瓶中,加入22.2 g 异弗尔酮二异氰酸酯(IPDI),然后将60.0 g聚乙二醇二醇(分子量2000)和60.0 g聚四氢呋喃二醇(分子量为2000)的混合物逐滴滴加到三口烧瓶中,此时保持瓶内反应体系温度100 °C。滴加完毕后,混合物继续反应2 h。向体系中加入催化剂辛酸亚锡(反应物质量的600 ppm),促使反应充分发生。反应程度通过傅里叶红外监测,当异氰酸酯基红外特征吸收峰不再减小时,再将0.1 g对苯二酚和10.4 g甲基丙烯酸羟乙酯的混合物逐滴加入体系中,期间保持体系温度70 °C。滴加完成后,继续反应,直至红外谱图中异氰酸酯基团的特征吸收峰完全消失,即得到聚氨酯丙烯酸酯,设计数均分子量为3815,命名为PU-3。
实施例4、光敏树脂的制备
首先,按照配方比例称取原材料:光敏树脂的原料组分计按重量份数计含量如下:
聚氨酯丙烯酸酯PU-1 60份
丙烯酸羟乙酯 34份
三羟甲基丙烷三丙烯酸酯 5份
2-羟基-2-甲基-1-苯基丙酮 1份
BYK-057 0.01份
然后,将各组分依次倒入搅拌器中,低速搅拌混匀得到透明的光敏树脂,搅拌的转速为400 r/min,搅拌时间为4 h。
实施例5、光敏树脂的制备
首先,按照配方比例称取原材料:光敏树脂的原料组分计按重量份数计含量如下:
聚氨酯丙烯酸酯PU-2 55份
丙烯酸羟乙酯 34份
三羟甲基丙烷三丙烯酸酯 9份
2-羟基-2-甲基-1-苯基丙酮 2份
BYK-061 0.05份
然后,将各组分依次倒入搅拌器中,低速搅拌混匀得到透明的光敏树脂,搅拌的转速为400 r/min,搅拌时间为4 h。
实施例6、光敏树脂的制备
首先,按照配方比例称取原材料:光敏树脂的原料组分计按重量份数计含量如下:
聚氨酯丙烯酸酯PU-3 50份
丙烯酸异冰片酯 20份
丙烯酸羟乙酯 18份
三羟基丙烯酸三丙烯酸酯 10份
2,4,6-三甲基苯甲酰二苯基氧化磷 2份
BYK-055 0.1份
然后,将各组分依次倒入搅拌器中,低速搅拌混匀得到透明的光敏树脂,搅拌的转速为400 r/min,搅拌时间为3 h。
实施例7~9、半月板支架的打印
步骤1,用DLP 3D打印设备对上述实施例4~6制得的光敏树脂进行模型打印,模型表面光滑且精细度高;3D打印机的打印参数根据需要进行设定,在本申请的实施例7~9中,3D打印机的打印参数相同。
步骤2,将样件坯体去除支撑,并放入乙醇中超声10 min,之后放入紫外箱后固化15 min,最后放入80 ºC烘箱后固化1 h,最终得到半月板支架。
半月板支架的力学性能评价。
按照GB/T2567-2008测试标准对打印的半月板支架进行力学性能评价包括拉伸强度、断裂伸长率及拉伸模量。
实施例7 | 实施例8 | 实施例9 | |
拉伸强度 (MPa) | 23.5 | 26.2 | 24.2 |
断裂伸长率 | 274.4% | 297.1% | 280.0% |
拉伸模量 (MPa) | 79.8 | 96.2 | 85.8 |
图1为通过数字光处理(DLP)3D打印制作的半月板支架模型。
图2为实施例8中打印制作的半月板支架的力学拉伸曲线。
图3为本发明中实施例8中打印制作的半月板支架的拉伸模量与天然半月板拉伸模量的对比图,显示与天然半月板力学拉伸模量相近。
图4为将体外细胞(兔脂肪间充质干细胞)种植于实施例8提供的半月板支架上,通过激光共聚焦显微镜观察细胞核心骨架染色检测,观察到细胞在本发明提供的材料表面贴附良好,细胞骨架在材料表面充分伸展。
图5显示为将实施例8的聚氨酯半月板植入家兔膝关节,术后3个月核磁共振T2像检查照片,图中显示(箭头所示)半月板支架在关节间隙中结构完整,关节软骨未见明显破坏,支架周围有自体组织长入。
图6为植入家兔体内术后3个月解剖照片,术后3个月内侧股骨髁软骨及内侧胫骨平台软骨未见明显骨性关节炎,关节软骨状态良好,说明本发明半月板支架起到了良好保护关节软骨的作用。
图7为支架周围关节滑膜组织病理HE染色照片,结果显示滑膜状态良好,无明显炎症反应。
本发明制备的组织工程半月板具有良好的生物相容性和体内稳定性,其力学性能与天然半月板相近,而且打印精度高,可以定制特定三维结构和多孔结构的半月板支架。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变形,本发明的范围由所附权利要求极其等同限定。
Claims (6)
1.一种用于制备可长期替代型组织工程半月板支架的光敏树脂,所述光敏树脂的原料组分按重量份数计含量如下:
式I所示聚氨酯丙烯酸酯 50~60份
丙烯酸酯单体 35~50份
自由基型光引发剂 0.5~5份
消泡剂 0.001~0.5份
式I
式I中,R1为异佛尔酮基、六亚甲基中的任一种;
R2为亚乙基、亚异丙基、亚正丁基中的一种或几种;
R3为氢或甲基;
n为10-100的自然数;
所述丙烯酸酯单体为丙烯酸羟乙酯、丙烯酸异冰片酯、三羟甲基丙烷三丙烯酸酯的一种或几种的组合物;
所述自由基型光引发剂为苯偶酰衍生物、α-羟烷基苯酮类或酰基磷氧化合物中的一种或几种的组合物;
所述的消泡剂采用BYK-053N、BYK-055、BYK-057、BYK-061中的一种或几种的组合物;
所述式I所示聚氨酯丙烯酸酯选自下述1)-3)中任一制备的聚氨酯丙烯酸酯:
1)在装配有机械搅拌、氮气导入管、温度计和滴液漏斗的250 mL 圆底烧瓶中,加入16.8 g 六亚甲基二异氰酸酯,然后将40.0 g分子量2000的聚乙二醇二醇和90.0 g分子量为3000聚四氢呋喃二醇的混合物逐滴滴加到三口烧瓶中,此时保持瓶内反应体系温度60 °C;滴加完毕后,混合物继续反应5 h;向体系中加入催化剂辛酸亚锡,促使反应充分发生;反应程度通过傅里叶红外监测,当异氰酸酯基红外特征吸收峰不再减小时,再将0.1 g对苯二酚和13.9 g丙烯酸羟乙酯的混合物逐滴加入体系中,期间保持体系温度50 °C;滴加完成后,继续反应,直至红外谱图中异氰酸酯基团的特征吸收峰完全消失,即得到聚氨酯丙烯酸酯,设计数均分子量为2179,命名为PU-1;
2)在装配有机械搅拌、氮气导入管、温度计和滴液漏斗的250 mL 圆底烧瓶中,加入16.8 g 六亚甲基二异氰酸酯,然后将30.0 g分子量1000的聚丙二醇二醇和60.0 g分子量为2000聚四氢呋喃二醇的混合物逐滴滴加到三口烧瓶中,此时保持瓶内反应体系温度90 °C;滴加完毕后,混合物继续反应2 h;向体系中加入催化剂辛酸亚锡,促使反应充分发生;反应程度通过傅里叶红外监测,当异氰酸酯基红外特征吸收峰不再减小时,再将0.1 g对苯二酚和9.2 g丙烯酸羟乙酯的混合物逐滴加入体系中,期间保持体系温度60 °C;滴加完成后,继续反应,直至红外谱图中异氰酸酯基团的特征吸收峰完全消失,即得到聚氨酯丙烯酸酯,设计数均分子量为2902,命名为PU-2;
3)在装配有机械搅拌、氮气导入管、温度计和滴液漏斗的250 mL 圆底烧瓶中,加入22.2 g 异佛尔酮二异氰酸酯,然后将60.0 g分子量2000的聚乙二醇二醇和60.0 g分子量为2000聚四氢呋喃二醇的混合物逐滴滴加到三口烧瓶中,此时保持瓶内反应体系温度100°C;滴加完毕后,混合物继续反应2 h;向体系中加入催化剂辛酸亚锡,促使反应充分发生;反应程度通过傅里叶红外监测,当异氰酸酯基红外特征吸收峰不再减小时,再将0.1 g对苯二酚和10.4 g甲基丙烯酸羟乙酯的混合物逐滴加入体系中,期间保持体系温度70 °C;滴加完成后,继续反应,直至红外谱图中异氰酸酯基团的特征吸收峰完全消失,即得到聚氨酯丙烯酸酯,设计数均分子量为3815,命名为PU-3。
2.权利要求1所述的光敏树脂在制备可长期替代型组织工程半月板支架中的应用。
3.一种可长期替代型组织工程半月板支架的光固化3D打印制备方法,包括下述步骤:
1)制备权利要求1所述的光敏树脂;
2)将步骤1)所述光敏树脂进行3D打印,得到半月板模型坯体;
3)将所述半月板模型坯体进行清洗、后固化,得到所述可长期替代型组织工程半月板支架;
所述步骤1)中,所述光敏树脂的制备方法如下:
a)按照比例称取聚氨酯丙烯酸酯、丙烯酸酯单体、自由基型光引发剂、消泡剂;
b)将所述聚氨酯丙烯酸酯、丙烯酸酯单体、自由基型光引发剂、消泡剂依次倒入搅拌器中,低速搅拌混匀得到透明的光敏树脂;其中,低速搅拌的转速为400 r/min,搅拌时间为2~4 h。
4.根据权利要求3所述的方法,其特征在于:所述步骤3)中,所述清洗用乙醇或异丙醇对半月板模型坯体进行清洗;具体清洗方法为:将半月板模型坯体放入乙醇或异丙醇中,超声清洗10 min。
5.根据权利要求3所述的方法,其特征在于:所述步骤3)中,所述后固化的过程为:在紫外箱中采用紫外光后固化30 min,然后放入60-100 ºC烘箱后固化0.5-3 h。
6.权利要求3-5中任一项所述方法制备得到的可长期替代型组织工程半月板支架。
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