CN106589336B - 一种完全生物可降解聚酯及其制备方法 - Google Patents
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Abstract
本发明属于高分子材料技术领域,具体为一种完全生物可降解共聚物的制备方法。本发明的PTMC‑LLA‑GA共聚物是在催化剂作用下,利用三亚甲基碳酸酯(TMC)开环聚合制备不同分子量的PTMC大分子预聚物,PTMC再与左旋丙交酯(LLA)、乙交酯(GA)在一定的条件下无规共聚而成。本发明制得的共聚物是一种半结晶性聚合物,具有强度高,韧性好,降解速度可控的特点,可在组织工程支架、介入性医疗器械等生物医学领域取得应用。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种生物可降解聚酯及其制备方法。
背景技术
聚左旋乳酸(PLLA)是一种具有优良生物相容性的可降解聚酯,已在组织工程支架、介入性医疗器械等医用材料领域取得应用。但是,PLLA的脆性高,延伸率一般低于10%。同时,PLLA的结晶及其降解后的酸性产物已被临床证实会引起病灶炎症反应。研究发现在PLLA链中引入柔性TMC可以使材料韧性大为提升,减弱材料降解酸性,改善医疗效果。针对LLA链产生的不良效果,通过在PTMC-LLA中引入具有较高反应活性的GA单元,使可结晶的LLA链段规整度和结晶度降低,可以提升材料韧性,加快降解速率,实现对材料综合性能的调控和优化。
本发明提出了一种由聚三亚甲基碳酸酯引发丙交酯/乙交酯无规共聚物及其制备方法。该发明不仅可以满足生物医用材料力学性能和医疗构建恢复期匹配的要求,而且从分子结构设计上更符合医用材料对生物相容性与降解性能的要求。
发明内容
本发明的目的在于提供一种完全生物可降解聚酯及其制备方法,以实现材料力学性能优化和降解速率可控。
该共聚物在韧性上得到了极大地提升,而依然保持足够的拉伸强度。同时,结晶度降低,可望克服后期炎症反应和降解速度太慢的问题。特别适合应用于生物医用材料。
本发明提供的完全生物可降解聚酯,由聚三甲基碳酸酯引发丙交酯/乙交酯无规共聚合成,其分子链结构如下式所示:
其中,n,p,q分别为TMC,LLA,GA的链节数;n的范围为100~500,p的范围为1000~10000,q的范围为100~500。
该共聚物中TMC单元的摩尔含量为10.0~30.0%;LLA单元的摩尔含量为60.0~90.0%;GA单元的摩尔含量为1.0~10.0%。
该PTMC大分子预聚物的数均分子量为1.0×104~5.0×104g/mol,分子量分布系数为1.2~1.6,共聚物的数均分子量为5.0×104~3.0×105g/mol,分子量分布系数为1.3~2.0。
本发明还提供所述的完全生物可降解聚酯的制备方法,具体步骤为:
(1)将干燥的TMC单体以及催化剂加入聚合管中,催化剂的加入量为单体总质量的1/5000~1/500;在N2或Ar惰性气体的保护下加热融化;然后,冷却至凝固态后,持续抽真空;
(2)待真空度不高于100Pa后,将聚合管熔断,使物料处于真空状态之下;
(3)将聚合管置于恒温反应箱中,反应温度为100~130℃,反应时间为4~24h,然后取出;
(4)将聚合管中的PTMC产物用溶剂溶出,接着用沉淀剂析出,充分干燥;
(5)将干燥的PTMC及LLA和GA单体以及催化剂加入聚合管中,催化剂的加入量为单体总质量的1/5000~1/500;在N2或Ar惰性气体的保护下加热融化;然后,冷却至凝固态后,持续抽真空;
(6)待真空度不高于100Pa后,将聚合管熔断,使物料处于真空状态之下;
(7)将聚合管置于恒温反应箱中,反应温度为120~160℃,反应时间为72~144h,然后取出;
(8)将聚合管中的产物用溶剂溶出,然后用沉淀剂析出,干燥充分后置于干燥器中低温保存。
步骤(1)和(5)中,所述的催化剂为辛酸亚锡或低毒的锌盐。优选辛酸亚锡。催化剂的加入量为单体总质量的1/5000~1/500,优选1/5000~1/1000。
步骤(5)中,所述的LLA的光学纯度为90~100%ee,优选97~100%ee。
步骤(4)和步骤(8)中,所述的溶剂为酮类、苯类以及氯代烃类溶剂中的一种或多种,包括丙酮、环己酮、二氯甲烷、三氯甲烷、1,2-二氯乙烷、四氯化碳、二氯苯、氯苯、四氢呋喃中的一种或多种。优选二氯甲烷、三氯甲烷。所述的沉淀剂为水、甲醇或乙醇中的一种或多种。优选甲醇或乙醇。
步骤(6)中,所述的真空度不高于100Pa,优选不高于1Pa。
步骤(7)中,所述的反应温度为120~160℃,优选120~150℃;反应时间为72~144h,优选72~96h。
本发明还提供了所述的完全生物可降解共聚物的应用,其可广泛用于生物医学领域,如手术缝合线、心血管支架和骨修复材料等。
本发明的原料和试剂皆市售可得。
本发明先利用TMC开环聚合制备相对柔性的PTMC大分子预聚物,再与LLA,GA进行开环无规聚合,制备主链是以相对柔性非晶态的PTMC均聚链段键接LLA-GA二元无规共聚链段的三元共聚物,其中LLA链段中无规分布的GA单元不仅能够调控材料的降解速率,而且链段规整度的破坏也降低LLA链段的结晶能力。从结构上看,优化的PTMC-LLA-GA材料具有强度高、韧性好和降解速度理想的性能,是一种新型生物可降解聚合物材料。
本发明制备的共聚物数均分子量高于5.0×104g/mol,拉伸强度为32.4~52.3MPa,延伸率为50~400%,结晶度较低。与聚左旋乳酸(PLLA)相比,本发明制得的共聚物在韧性上得到了极大地提升,而依然保持较高的拉伸强度。TMC单元的引入,使得该共聚物的降解产物的酸性降低;同时,通过加入不同含量的GA单元可以调控共聚物的体内降解速度。因此,本发明制得的共聚物具有优异的力学性能、良好的生物相容性以及可控的降解速度,在生物医学领域具有广阔的应用前景。
附图说明
图1为 PTMC-LLA-GA共聚物的红外谱图。
图2为PTMC-LLA-GA共聚物的1H NMR谱图。
图3为PTMC-LLA-GA的DSC谱图:样品从室温开始以50℃/min升温至200℃,等温1min以消除热历史;然后以150℃/min降温至30℃,再以10℃/min升温至200℃。结果取自第二遍升温曲线。
具体实施方式
下面用实施例来进一步说明本发明,但本发明并不受其限制,实施例中的原料均为常规市售产品,其中:
本发明制备的完全生物可降解共聚物,通过凝胶渗透色谱仪(GPC)测定其分子量及其分布,傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H NMR)确定其化学组成,差示扫描量热法(DSC)测定其热性能,万能拉力试验机测定其力学性能。
实施例1
(1) 将三亚甲基碳酸酯19.85g、辛酸亚锡60.1mg加入到聚合管中。充氮赶氧,抽真空,重复三次。然后持续抽真空,控制聚合管中的真空度不高于1Pa。将聚合管置于120℃的恒温烘箱中,反应24h,得到PTMC大分子预聚物。将所得产物纯化,测定其数均分子量为3.3×104g/mol,分散系数为1.2。将干燥的PTMC 2.0g、左旋丙交酯11.08g、乙交酯0.35g、辛酸亚锡40.5mg加入到聚合管中,充氮赶氧,抽真空,重复三次。然后持续抽真空,控制聚合管中的真空度不高于1Pa。将聚合管置于140℃的恒温烘箱中,反应72h,即得到完全生物可降解PTMC-LLA-GA共聚物。所得产物经纯化,测定其数均分子量为2.2×105g/mol,分散系数为1.4。其中左旋丙交酯的光学纯度为98.5%ee;
(2)图1为PTMC-LLA-GA共聚物的红外谱图。图中2998、2947、1459和1387 cm-1处的吸收峰归属于LA链段的-CH3,1423cm-1归属于GA链段的-CH2。1756cm-1处的强吸收峰归属于LA、TMC和GA单元上C=O的伸缩振动,1085、1133、1183和1215 cm-1处的吸收峰归属于LA、TMC和GA链段上C-O-C的伸缩振动。说明该共聚物含有LLA、TMC、GA链段单元。同时,单个羰基的出现,说明共聚物没有发生相分离,为均相体系;
(3)图2为PTMC-LLA-GA共聚物的1H NMR谱图。图中1号峰(5.0~5.2ppm)为LLA单元中-CH上的H,4号峰(1.4~1.7ppm)为乳酸单元中-CH3上的H;2号峰(4.24ppm)为TMC单元中O-CH2上的H,3号峰(2.03ppm)为TMC单元中心-CH2上的H;5号峰(4.6-5.0ppm)为GA单元中-CH2上的H。从图中可以看出,乳酸单元中-CH上的H明显区分为两个化学位移区间。其中,5.2ppm左右的峰为长链段LLA的特征峰,而5.0ppm左右的峰是与TMC或GA相连接的LLA的特征峰。同时,GA上-CH2的特征峰分裂为多重峰,这是因为GA单元的化学位移受到了相邻LLA和TMC单元的明显影响,体现了GA单元较高的反应活性。1H NMR结果证实PTMC-LLA-GA共聚物已经成功合成,由各个峰的积分面积可以求出共聚物中TMC、LLA、GA的摩尔比为20/77/3,与投料比一致;
(4)图3为PTMC-LLA-GA共聚物的DSC谱图。该样品的玻璃化转变温度(T g)为49.5℃,在163.2℃处有熔融峰,焓值为20.1J/g。较低的结晶度在原理上将很大程度降低后期炎症反应风险;
(5)PTMC-LLA-GA共聚物的机械性能按照GB/T 528-1998实施,试样制成2-型哑铃状样条,长度20mm,宽度4mm。每个样品测试5根平行样条。得到试样的拉伸强度为45.4MPa,杨氏模量为1074.5MPa,延伸率为115.2%。所有实施例的力学性能测试结果见表1。
实施例2
将实施例1中步骤(1)得到的PTMC 2.0g、左旋丙交酯11.15g、乙交酯0.11g、辛酸亚锡40.8mg加入到聚合管中。其中左旋丙交酯的光学纯度为98.5%ee。合成过程如实施例1中步骤(1)所述。所得产物经纯化,测定其数均分子量为2.1×105g/mol,分散系数为1.5。TMC、LLA、GA三种单体的摩尔比为20/79/1。玻璃化转变温度为46.8℃,熔点为166.3℃,焓值为30.1J/g。拉伸强度为48.6MPa,杨氏模量为1198.2MPa,延伸率为80.8%。
实施例3
将实施例1中步骤(1)得到的PTMC 2.0g、左旋丙交酯10.6g、乙交酯0.55g、辛酸亚锡40.7mg加入到聚合管中。其中左旋丙交酯的光学纯度为98.5%ee。合成过程如实施例1中步骤(1)所述。所得产物经纯化,测定其数均分子量为2.0×105g/mol,分散系数为1.6。TMC、LLA、GA三种单体的摩尔比为20/75/5。玻璃化转变温度为46.3℃,熔点为160.3℃,,焓值为10.1J/g。拉伸强度为41.5MPa,杨氏模量为967.8MPa,延伸率为136.7%。
实施例4
将实施例1中步骤(1)得到的PTMC 2.0g、左旋丙交酯10.31g、乙交酯0.8g、辛酸亚锡40.0mg加入到聚合管中。其中左旋丙交酯的光学纯度为98.5%ee。合成过程如实施例1中步骤(1)所述。所得产物经纯化,测定其数均分子量为2.0×105g/mol,分散系数为1.5。TMC、LLA、GA三种单体的摩尔比为20/73/7。玻璃化转变温度为44.3℃,无结晶行为。拉伸强度为36.7MPa,杨氏模量为851.3MPa,延伸率为331.5%。
实施例5
将实施例1中步骤(1)得到的PTMC 2.0g、左旋丙交酯9.9g、乙交酯1.14g、辛酸亚锡40.6mg加入到聚合管中。其中左旋丙交酯的光学纯度为98.5%ee。合成过程如实施例1中步骤(1)所述。所得产物经纯化,测定其数均分子量为1.9×105g/mol,分散系数为1.6。TMC、LLA、GA三种单体的摩尔比为20/70/10。玻璃化转变温度为44.8℃,无结晶行为。拉伸强度为32.4MPa,杨氏模量为843.6MPa,延伸率为356.7%。
为了能够更好理解PTMC-LLA-GA共聚物中,GA单元分别对材料热性能、力学性能所起到的作用,特进行以下对比实施例。
实施例6
将实施例1中步骤(1)得到的PTMC 2.0g、左旋丙交酯11.3g、辛酸亚锡40.2mg加入到聚合管中。其中左旋丙交酯的光学纯度为98.5%ee。合成过程如实施例1中步骤(1)所述。所得产物经纯化,测定其数均分子量为2.0×105g/mol,分散系数为1.6。TMC、LLA两种单体的摩尔比为20/80。玻璃化转变温度为47.5℃,熔点为166.2℃,焓值为33.6J/g。拉伸强度为52.3MPa,杨氏模量为1262.3MPa,延伸率为60.4%。其力学性能测试结果亦列于表1中。
实施例7
将三亚甲基碳酸酯2.0g、左旋丙交酯10.9g、乙交酯0.34g、辛酸亚锡38.6mg加入到聚合管中。其中左旋丙交酯的光学纯度为98.5%ee。充氮赶氧,抽真空,重复三次。然后持续抽真空,控制聚合管中的真空度不高于1Pa。将聚合管置于130℃的恒温烘箱中,反应72h,即得到PLLA-TMC-GA无规共聚物。所得产物经纯化,测定其数均分子量为2.3×105g/mol,分散系数为1.7。TMC、LLA、GA三种单体的摩尔比为20/77/3。玻璃化转变温度为51.0℃,无结晶行为。拉伸强度为30.5MPa,杨氏模量为756.7MPa,延伸率为98.8%。其力学性能测试结果亦列于表1中。
从上述实施例可以看出,利用TMC开环聚合制备PTMC大分子预聚物,再与左旋丙交酯(LLA)、乙交酯(GA)进行无规开环聚合,得到PTMC均聚链段键接降解速率理想的LLA-GA无规共聚链段构造的三元共聚物。通过加入不同含量的GA单元,可以人为调控其降解速率。并且与无规共聚物相比,该共聚物具有一定的结晶度,强度得到明显提高。因此,PTMC-LLA-GA共聚物结构新颖、力学性能优良、降解速率可控,是一种理想的生物医用材料。
表1
Claims (6)
2.如权利要求1所述的完全生物可降解聚酯,其特征在于,PTMC大分子预聚物的数均分子量为1.0×104~5.0×104g/mol,分子量分布系数为1.2~1.6,共聚物的数均分子量为5.0×104~3.0×105g/mol,分子量分布系数为1.3~2.0。
3.一种如权利要求1或2所述的完全生物可降解聚酯的制备方法,其特征在于,具体步骤为:
(1)将干燥的TMC单体以及催化剂辛酸亚锡加入聚合管中,催化剂的加入量为单体总质量的1/5000~1/500;在N2或Ar惰性气体的保护下加热融化;然后,冷却至凝固态后,持续抽真空;
(2)待真空度不高于100Pa后,将聚合管熔断,使物料处于真空状态之下;
(3)将聚合管置于恒温反应箱中,反应温度为120℃,反应时间为24h,然后取出;
(4)将聚合管中的PTMC产物用溶剂溶出,接着用沉淀剂析出,充分干燥;
(5)将干燥的PTMC及LLA和GA单体以及催化剂辛酸亚锡加入聚合管中,催化剂的加入量为单体总质量的1/5000~1/500;在N2或Ar惰性气体的保护下加热融化;然后,冷却至凝固态后,持续抽真空;
(6)待真空度不高于100Pa后,将聚合管熔断,使物料处于真空状态之下;
(7)将聚合管置于恒温反应箱中,反应温度为140℃,反应时间为72h,然后取出;
(8)将聚合管中的产物用溶剂溶出,接着用沉淀剂析出,充分干燥。
4.如权利要求3所述的制备方法,其特征在于,步骤(5)所述的LLA的光学纯度为90~100%ee。
5.如权利要求3所述的制备方法,其特征在于,步骤(4)和(8)中所述的溶剂选自丙酮、环己酮、二氯甲烷、三氯甲烷、1,2-二氯乙烷、四氯化碳、二氯苯、氯苯、四氢呋喃中的一种或多种;所述的沉淀剂为水、甲醇或乙醇中的一种或多种。
6.一种如权利要求1所述的完全生物可降解聚酯作为生物医用材料的应用。
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (2)
Title |
---|
"Bioresorbable terpolymers based on L-lactide,glycolide and trimethylene carbonate with shape memory behaviour";A.Smola et. al.;《Polymer Chemistry》;20131216;第5卷;第2442-2452页 * |
"Scaffolds with shape memory behavior for the treatment of large bone defects";Piotr Rychter et.al.;《Society For Biomaterials》;20150522;第103A卷(第11期);第3503-3515页 * |
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