CN114456358A - 医用防粘连用可吸收柔性聚酯材料、制备方法及其应用 - Google Patents
医用防粘连用可吸收柔性聚酯材料、制备方法及其应用 Download PDFInfo
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Abstract
本发明提供一种医用防粘连用可吸收柔性聚酯材料及其应用,属于医用高分子材料领域。本发明中的材料为端氨基聚酯,其重均分子量为40000~200000,玻璃化转变温度在34℃~39℃,使用时将端氨基聚酯制成纤维膜,所述纤维膜的厚度为0.06mm~0.14mm,主要用于术后防粘连隔离材料。与现有技术相比,本发明从分子结构中引入聚己内酯和聚羟基乙酸结构,增加其柔顺性其纤维膜断裂伸长率达600%以上;在聚乳酸分子结构中引入氨基,由于本发明的材料在体内降解过程中会产生酸性物质,同时也会产生氨基碱性基团,氨基的碱性可以平衡酸性,使周围的降解环境维持一定范围内,使降解速度平稳,本发明材料具有优异的柔顺性、适宜的降解时间以及减少炎症的发生的优点。
Description
技术领域
本发明属于医用高分子材料领域,具体涉及一种医用防粘连用可吸收柔性聚酯材料、制备方法及其应用。
背景技术
粘连是外科手术中一种常见的并发症,给患者的生活带来了极大的痛苦。目前治疗粘连的主要方法是采用物理隔离,即在手术创面与其周围正常组织之间放入一个固体材料,设置一个物理屏障,从而在组织愈合的过程中起到隔离的作用,达到防粘连效果,有效的降低不良粘连的发生。常用材料有很多种,如透明质酸钠、壳聚糖、聚乙二醇、聚乳酸、聚乙醇酸等,由于聚乳酸具有良好的生物降解性、组织相容性和优良的力学性能等,目前市场常用材料之一,但是由于机械强度高,柔韧性有限,其降解可控性也较差,在降解过程中会产生酸性物质,导致机体炎症,影响组织的再生和康复,其临床使用效果也并不理想。国际专利W02006/100895公开了以丙交酯和己内酯共聚物为组成的医用膜,其具有很好的柔性和强度,但是材料本身的降解速率较慢,完全吸收需要6个月,有可能影响伤口愈合及组织修复功能。中国专利CN1305928C公开了乳酸与聚乙二醇共聚得到乳酸/聚乙二醇共聚物;中国专利CN103055354 B公开了丙交酯、乙交酯与聚乙二醇共聚得到聚乙二醇-聚丙交酯乙交酯嵌段共聚物。虽然两项专利将聚乙醇酸及聚乙二醇的引入可以加快聚乳酸的体内降解速率,但是在降解过程中产生酸性物质,影响周围环境pH值发生变化,影响隔膜降解速度,同时易引起炎症发生,从而限制了其在临床医用领域的广阔应用。
发明内容
为了解决上述技术不足,本发明的目的是提供一种医用防粘连用可吸收柔性聚酯材料、制备方法及其应用,该材料具有优异的柔顺性、适宜的降解时间以及减少炎症的发生。
为了实现上述目的,本发明的具体技术方案为:
一种医用防粘连用可吸收柔性聚酯材料及其应用,该材料为端氨基聚酯,其重均分子量为40000~200000,分子式为:
其中:-R-为(1)、(2)、(3)中的一种或多种,
-R1-为:
-R2-为:
其中w=(2~145);x=(0~576);y=(0~240);z=(0~92);
使用时将端氨基聚酯制成纤维膜,所述纤维膜的厚度为0.06 mm ~0.14mm。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,由丙交酯、乙交酯、己内酯聚合得到聚酯二醇,再通过脂肪族二异氰酸酯封端,经过二元胺扩链得到。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,制备方法如下:
a、聚合:将丙交酯:乙交酯:己内酯按质量比为(63~83):(8~28):(8~10.5)加入反应器中,然后加入引发剂和催化剂溶液,通入氮气-抽真空并反复多次,在130~180℃反应4h~48h,得到粗品聚酯二醇;
b、提纯:将步骤a中得到的粗品聚酯二醇在溶剂A中完全溶解后,缓慢滴加溶剂B,使聚酯二醇慢慢析出,最后在40℃~60℃下真空干燥12h以上。
c、封端:将步骤b中得到的聚酯二醇用5~10倍重量的N,N-二甲基甲酰胺溶解,缓慢滴加脂肪族二异氰酸酯溶液,其用量为NCO:OH为(2.1~2.2):1,加入二月桂酸二丁基锡,二月桂酸二丁基锡的量为加入聚酯二醇和脂肪族二异氰酸酯总质量的0.001wt%~0.01wt%,反应温度为60℃~85℃,反应时间4 h ~24h。
d、扩链:在步骤c反应后的溶液中滴加二元胺单体,其用量NH2:NCO为(1.1~1.5):1,加入溶剂B析出,然后进行真空干燥,得到端氨基聚酯。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,所述步骤b中的提纯后的聚酯二醇的重均分子量为20000~100000。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,步骤a中所用的引发剂、丙交酯、乙交酯和己内酯单体在使用前均进行干燥处理,其含水量在200ppm以下。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,步骤a中的所述引发剂为乙二醇、1,4-丁二醇,聚乙二醇400、聚乙二醇1000或聚乙二醇2000中的一种,所述引发剂的用量为丙交酯、乙交酯和己内酯的投入总量的0.07wt%~7.5wt%。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,步骤a中的所述催化剂溶液中的溶剂为二氯甲烷,浓度为0.1wt%~10wt%,催化剂用量为丙交酯、乙交酯和己内酯的总质量的0.00015wt%~0.001wt%,所用催化剂为异丙醇铝、二乙烯基锌、氯化亚锡或辛酸亚锡中的一种或多种。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,步骤b中的所述溶剂A为二氯甲烷、三氯甲烷或丙酮中的一种或多种,其用量为聚酯二醇的5~15倍;溶剂B为无水甲醇、无水乙醇、正己烷、***或异丙醚中一种或多种。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,所述脂肪族二异氰酸酯溶液为脂肪族二异氰酸酯/N,N-二甲基甲酰胺溶液,浓度为1wt%~10wt%,所用脂肪族二异氰酸酯为六亚甲基二异氰酸酯(HDI)、1,4-环己烷二异氰酸酯(BDI)、L-赖氨酸二异氰酸酯(LDI)其中一种或多种。
上述医用防粘连用可吸收柔性聚酯材料的制备方法,所述二元胺单体为乙二胺;所述引发剂优选聚乙二醇400;所用催化剂优选为辛酸亚锡;所用脂肪族二异氰酸酯优选六亚甲基二异氰酸酯。
与现有技术相比,本发明从分子结构中引入聚己内酯和聚羟基乙酸结构,增加其柔顺性其纤维膜断裂伸长率达600%以上,玻璃化转变温度在34℃~39℃,接近人体温度,植入患者体内具有很好地贴服性舒适感;在聚乳酸分子结构中引入氨基,由于本发明的材料在体内降解过程中产生酸性物质,同时也会产生氨基碱性基团,氨基的碱性可以平衡酸性,使周围的降解环境的PH值呈中性,使降解速度平稳,玻璃化转变温度在34℃~39℃,接近人体温度,植入患者体内具有很好地贴服性舒适感。采用本发明公开的聚酯材料制备的防粘连纤维膜,具有优异的柔软度、顺应性,能适应贴合组织部位避免缝合固定的操作且减少刺激,降解时间在6~9周。
具体实施方式
本发明的医用防粘连用可吸收柔性聚酯材料的制备方法,由丙交酯、乙交酯、己内酯聚合得到聚酯二醇,再通过脂肪族二异氰酸酯封端,经过二元胺扩链得到。
具体的制备方法如下:
a、聚合:将丙交酯:乙交酯:己内酯按质量比为(63~83):(8~28):(8~10.5)加入反应器中,然后加入引发剂和催化剂溶液,通入氮气-抽真空并反复多次,在130℃~180℃反应4h~48h,得到粗品聚酯二醇;
b、提纯:将步骤a中得到的粗品聚酯二醇在溶剂A中完全溶解后,缓慢滴加溶剂B,使聚酯二醇慢慢析出,最后,在40℃~60℃下真空干燥12h以上。提纯后的聚酯二醇的重均分子量为20000~100000。
c、封端:将步骤b中得到的聚酯二醇用5~10倍重量的N,N-二甲基甲酰胺溶解,缓慢滴加脂肪族二异氰酸酯溶液,其用量为NCO:OH为(2.1~2.2):1,加入二月桂酸二丁基锡,用量为聚酯二醇和脂肪族二异氰酸酯总质量的0.001wt%~0.01wt%,反应温度为60℃~85℃,反应时间4h~24h。
d、扩链:在步骤c反应后的溶液中滴加二元胺单体,其用量NH2:NCO为(1.1~1.5):1,加入溶剂B析出,然后进行真空干燥,得到端氨基聚酯,该端氨基聚酯的重均分子量为40000~200000。
使用时,利用静电纺丝技术,将端氨基聚酯制成防粘连聚酯纤维膜,所述防粘连聚酯纤维膜的厚度为0.06 mm ~0.14mm。
步骤a中所用的引发剂、丙交酯、乙交酯和己内酯单体在使用前均进行干燥处理,其含水量在200ppm以下。
步骤a中的所述引发剂为乙二醇、1,4-丁二醇,聚乙二醇400、聚乙二醇1000或聚乙二醇2000中的一种,所述引发剂的用量为丙交酯、乙交酯和己内酯投入总量的0.07wt%~7.5wt%。
步骤a中的所述催化剂溶液中的溶剂为二氯甲烷,浓度为0.1wt%~10wt%,催化剂用量为所用单体总质量的0.00015wt%~0.001wt%,所用催化剂为异丙醇铝、二乙烯基锌、氯化亚锡或辛酸亚锡中的一种或多种。
步骤a中的所述溶剂A为二氯甲烷、三氯甲烷或丙酮中的一种或多种,其用量为聚酯二醇的5~15倍;溶剂B为无水甲醇、无水乙醇、正己烷、***或异丙醚中一种或多种。
所述脂肪族二异氰酸酯溶液为脂肪族二异氰酸酯/N,N-二甲基甲酰胺溶液,浓度为1wt%~10wt%,所用脂肪族二异氰酸酯为六亚甲基二异氰酸酯(HDI)、1,4-环己烷二异氰酸酯(BDI)、L-赖氨酸二异氰酸酯(LDI)其中一种或多种。
所述二元胺单体为乙二胺;所述引发剂优选聚乙二醇400;所用催化剂优选为辛酸亚锡;所用脂肪族二异氰酸酯优选六亚甲基二异氰酸酯。
以下实施例用于说明本发明。
实施例1
将所需单体经过实验室常规干燥方法进行,控制水含量在200ppm以下。
将丙交酯70g、己内酯10.5g、乙交酯19.5g单体加入反应器中,3%辛酸亚锡/二氯甲烷溶液0.5g,聚酯二醇(400)1.5g、通氮气-抽真空反复操作3次,在真空下封管,145℃油浴中反应24h,得到粗品聚酯二醇,
用1000g二氯甲烷溶解,然后缓慢滴加无水乙醇,使聚酯二醇慢慢析出,50℃下真空干燥12h,得到聚酯二醇,分子量50000;
另取一个四口瓶中加入800gN,N-二甲基甲酰胺,80g聚酯二醇,完全溶解后缓慢滴加浓度为1wt%的六亚甲基二异氰酸酯(HDI)/N,N-二甲基甲酰胺溶液56.52g,加入0.0008g二月桂酸二丁基锡,80℃下反应时间24h。
然后加入0.32g乙二胺进行扩链,最后加入无水乙醇,真空干燥得到端氨基聚酯,其分子量为100000,玻璃化转变温度为37.5℃,总溶剂残留0.15%以下,锡含量27ppm。
利用静电纺丝技术,将端氨基聚酯的制备成防粘连聚酯纤维膜,膜厚0.120mm,断裂伸长率在658%,降解时间8~9周,该膜具有很好的柔顺性和适宜的降解时间。
实施例2
将所需单体经过实验室常规干燥方法进行,控制水含量在200ppm以下。
将丙交酯63g,己内酯9g、乙交酯28g单体加入反应器中,3%辛酸亚锡/二氯甲烷溶液0.5g,聚酯二醇(2000)3.5g、通氮气-抽真空反复操作3次,在真空下封管,130℃反应4h,得到粗品聚酯二醇,
用1500g二氯甲烷溶解,然后缓慢滴加无水乙醇,使聚酯二醇慢慢析出,50℃下真空干燥12h,得到聚酯二醇,分子量100000;
另取一个四口瓶中加入800gN,N-二甲基甲酰胺,80g聚酯二醇,完全溶解后缓慢滴加浓度为10wt%的L-赖氨酸二异氰酸酯(LDI)/N,N-二甲基甲酰胺溶液3.98g,加入0.0040g二月桂酸二丁基锡,65℃下反应时间24h,
然后加入0.159g乙二胺进行扩链,最后加入无水乙醇,真空干燥得到端氨基聚酯,其各项性能如下,其分子量为200000,玻璃化转变温度35℃,总溶剂残留0.45%,锡含量36ppm。
利用静电纺丝技术,将端氨基聚酯的制备成防粘连聚酯纤维膜,膜厚0.050mm,断裂伸长率在612%,降解时间8~9周,该膜具有很好的柔顺性和适宜的降解时间。
实施例3
将所需单体经过实验室常规干燥方法进行,控制水含量在200ppm以下。
将丙交酯83g,己内酯9g、乙交酯8 g单体加入反应器中,3%辛酸亚锡/二氯甲烷溶液0.5g,聚酯二醇(400)1.0g、通氮气-抽真空反复操作3次,在真空下封管,180℃油浴中反应48h,得到粗品聚酯二醇,
用1500g二氯甲烷溶解,然后缓慢滴加无水乙醇,使聚酯二醇慢慢析出,50℃下真空干燥12h,得到聚酯二醇,分子量50000;
另取一个四口瓶中加入800gN,N-二甲基甲酰胺,80g聚酯二醇,完全溶解后缓慢滴加浓度为5wt%的1,4-环己烷二异氰酸酯(BDI)/N,N-二甲基甲酰胺溶液11.7g,加入0.0061g二月桂酸二丁基锡,80℃下反应时间12h,
然后加入0.27g乙二胺进行扩链,最后加入无水乙醇,真空干燥得到端氨基聚酯,其分子量为100000,玻璃化转变温度39℃,总溶剂残留0.24%,锡含量含量42ppm。
利用静电纺丝技术,将端氨基聚酯的制备成防粘连聚酯纤维膜,膜厚0.120mm,断裂伸长率在620%,降解时间7~8周,该膜具有很好的柔顺性和适宜的降解时间。
实施例4
将所需单体经过实验室常规干燥方法进行,控制水含量在200ppm以下。
将丙交酯66g,己内酯8g、乙交酯26g单体加入反应器中,3%辛酸亚锡/二氯甲烷溶液0.5g,聚酯二醇(1000)3.75g、通氮气-抽真空反复操作3次,在真空下封管,130℃油浴中反应4h,得到粗品聚酯二醇,
用500g二氯甲烷溶解,然后缓慢滴加无水乙醇,使聚酯二醇慢慢析出,50℃下真空干燥12h,得到聚酯二醇,分子量20000;
另取一个四口瓶中加入400gN,N-二甲基甲酰胺,80g聚酯二醇,完全溶解后缓慢滴加浓度为10 wt%的L-赖氨酸二异氰酸酯(LDI)/N,N-二甲基甲酰胺溶液19g,加入0.0082g二月桂酸二丁基锡,65℃下反应时间24h。
然后加入0.76g乙二胺进行扩链,最后加入无水乙醇,真空干燥得到端氨基聚酯,其分子量为50000,玻璃化转变温度34℃,总溶剂残留0.15%,锡含量45ppm。
利用静电纺丝技术,将端氨基聚酯的制备成防粘连聚酯纤维膜,膜厚0.080mm,断裂伸长率在650%,降解时间6周~7周,该膜具有很好的柔顺性和适宜的降解时间。
本发明的聚酯结构中存在酯基和氨酯基,酯基在降解过程中产生酸性物质(如乳酸、乳酸低聚物、乙醇酸、乙醇酸低聚物以及COOH的低聚物等等),氨酯基降解过程中产生胺类物质(含氨基低聚物),所述酸性物质与胺类物质和聚酯分子链两端的氨基发生中和反应。从而平衡降解产物的PH值,避免炎症和不适。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。
Claims (10)
2.一种医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,由丙交酯、乙交酯、己内酯聚合得到聚酯二醇,再通过脂肪族二异氰酸酯封端,经过二元胺扩链得到。
3.如权利要求2所述的医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,制备方法如下:
聚合:将丙交酯:乙交酯:己内酯按质量比为(63~83):(8~28):(8~10.5)加入反应器中,然后加入引发剂和催化剂溶液,通入氮气-抽真空并反复多次,在130℃~180℃反应4 h ~48h,得到粗品聚酯二醇;
提纯:将步骤a中得到的粗品聚酯二醇在溶剂A中完全溶解后,缓慢滴加溶剂B,使聚酯二醇慢慢析出,最后,在40℃~60℃下真空干燥12h以上;
封端:将步骤b中得到的聚酯二醇用5~10倍重量的N,N-二甲基甲酰胺溶解,缓慢滴加脂肪族二异氰酸酯溶液,其用量为NCO:OH为(2.1~2.2):1,加入二月桂酸二丁基锡,二月桂酸二丁基锡的量为加入聚酯二醇和脂肪族二异氰酸酯总质量的0.001wt%~0.01wt%,反应温度为60℃~85℃,反应时间4 h ~24h;
扩链:在步骤c反应后的溶液中滴加二元胺单体,其用量NH2:NCO为(1.1~1.5):1,加入溶剂B析出,然后进行真空干燥。
4.如权利要求3所述的医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,所述步骤b中的提纯后的聚酯二醇的重均分子量为20000~100000。
5.如权利要求4所述的医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,步骤a中所用的引发剂、丙交酯、乙交酯和己内酯单体在使用前均进行干燥处理,其含水量在200ppm以下。
6.如权利要求5所述的医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,步骤a中的所述引发剂为乙二醇、1,4-丁二醇,聚乙二醇400、聚乙二醇1000或聚乙二醇2000中的一种,所述引发剂的用量为丙交酯、乙交酯和己内酯投入总量的0.07wt%~7.5wt%。
7.如权利要求6所述的医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,步骤a中的所述催化剂溶液中的溶剂为二氯甲烷,浓度为0.1wt%~10wt%,催化剂用量为所用单体总质量的0.00015wt%~0.001wt%,所用催化剂为异丙醇铝、二乙烯基锌、氯化亚锡或辛酸亚锡中的一种或多种。
8.如权利要求7所述的医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,步骤b中的所述溶剂A为二氯甲烷、三氯甲烷或丙酮中的一种或多种,其用量为聚酯二醇的5~15倍;溶剂B为无水甲醇、无水乙醇、正己烷、***或异丙醚中一种或多种。
9.如权利要求8所述的医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,所述步骤c中脂肪族二异氰酸酯溶液为脂肪族二异氰酸酯/N,N-二甲基甲酰胺溶液,浓度为1wt%~10wt%,所用脂肪族二异氰酸酯为六亚甲基二异氰酸酯(HDI)、1,4-环己烷二异氰酸酯(BDI)、L-赖氨酸二异氰酸酯(LDI)其中一种或多种。
10.如权利要求9所述的医用防粘连用可吸收柔性聚酯材料的制备方法,其特征在于,所述二元胺单体为乙二胺;所述引发剂优选聚乙二醇400;所用催化剂优选为辛酸亚锡;所用脂肪族二异氰酸酯优选六亚甲基二异氰酸酯。
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