CN108059706A - 生物可降解聚氨酯及其制备方法 - Google Patents

生物可降解聚氨酯及其制备方法 Download PDF

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CN108059706A
CN108059706A CN201711362702.4A CN201711362702A CN108059706A CN 108059706 A CN108059706 A CN 108059706A CN 201711362702 A CN201711362702 A CN 201711362702A CN 108059706 A CN108059706 A CN 108059706A
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amino acids
biodegradable polyurethane
diisocyanate
polyurethane
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周建
颜玉荣
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Suzhou Hao Yang Pu Technology Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

本发明公开了一种生物可降解聚氨酯及其制备方法，该聚氨酯由软段和硬段构成，所述软段为聚己内酯，硬段为降解无毒的氨基酸类二异氰酸酯。制备方法包括步骤：(1)将聚己内酯和扩链剂溶于有机溶剂，在催化剂条件下，回流反应20‑26h，得到预聚物；(2)向步骤(1)中得到的预聚物滴加氨基酸类二异氰酸酯，在100‑105℃下反应1‑3h，得到所述生物可降解聚氨酯。本发明的聚氨酯具有良好的生物安全性和生物相容性，具有可控的降解性，能满足生物医学功能需要的可加工、易保存性能；制备方法简单、易操作，条件温和。

Description

生物可降解聚氨酯及其制备方法
技术领域
本发明涉及聚氨酯领域，尤其涉及一种生物可降解的聚氨酯及其制备方法。
背景技术
随着医疗技术的不断发展，有关生物医用材料的研究越来越受到人们的广泛关注，尤其是生物可降解医用高分子材料在作为组织工程材料、伤口敷料、外科手术缝合线、药物控制释放载体等方面表现出巨大的应用潜力。理想的生物降解医用高分子材料应具有良好的生物安全性和生物相容性、可控的降解性以及能满足生物医学功能需要的可加工、易保存性能，已开发的生物降解医用高分子材料主要分为天然降解和合成降解高分子材料、天然生物降解高分子材料有纤维素、多糖、蛋白质与多肽等合成。这类合成成本较高，且不易保存。
发明内容
发明目的：本发明提供了一种生物可降解的聚氨酯及其制备方法，该聚氨酯解决了医用对生物降解高分子材料的需求，同时解决了现有技术中生物降解高分子材料合成成本较高，且不易保存的问题，该制备方法简单易实现。
技术方案：本发明的生物可降解聚氨酯，该聚氨酯由软段和硬段构成，所述软段为聚己内酯，硬段为降解无毒的氨基酸类二异氰酸酯。
其中，氨基酸类二异氰酸酯为赖氨酸二异氰酸酯和/或L-赖氨酸二异氰酸酯。
聚氨酯是一类由软硬段交替排列的多嵌段聚合物，分子结构的设计自由度大可以通过选择特定的单体，调节软硬段的比例，进而设计合成出具有独特化学结构和优异综合性能的高分子合成材料，生物可降解聚氨酯由于其优良的可降解性和安全性，可望在药物释放载体和组织工程等领域有广阔的应用前景。
上述生物可降解聚氨酯的制备方法，包括以下步骤：
(1)将聚己内酯和扩链剂溶于有机溶剂，在催化剂条件下，回流反应20-26h，得到预聚物；
(2)向步骤(1)中得到的预聚物滴加氨基酸类二异氰酸酯，在100-105℃下反应1-3h，得到所述生物可降解聚氨酯。
步骤(1)中，扩链剂为丁二胺、丁二醇、丙二醇和乙二醇中的一种或几种。
所述催化剂为辛酸亚锡。
所述聚己内酯的浓度为0.5-0.8mol/L，聚己内酯与扩链剂、氨基酸类二异氰酸酯的摩尔比为3-5:1:1。
所述有机溶剂为DMF和DMSO中的一种或两种。
有益效果：1、本发明的生物可降解聚氨酯能够满足医用高分子材料的需求；2、具有良好的生物安全性和生物相容性；3、具有可控的降解性；4、能满足生物医学功能需要的可加工、易保存性能；5、成本低；6、制备方法简单、易操作，条件温和。
具体实施方式
实施例1
生物可降解聚氨酯的制备方法，包括以下步骤：
(1)将0.3mol聚己内酯和0.1mol丁二胺溶于600ml DMSO中，在催化剂辛酸亚锡条件下，回流反应20h，得到预聚物；
(2)向步骤(1)中得到的预聚物滴加0.1mol赖氨酸二异氰酸酯，在105℃下反应1h，得到所述生物可降解聚氨酯。
实施例2
生物可降解聚氨酯的制备方法，包括以下步骤：
(1)将0.4mol聚己内酯和0.1mol丙二醇溶于667ml DMF中，在催化剂辛酸亚锡条件下，回流反应23h，得到预聚物；
(2)向步骤(1)中得到的预聚物滴加0.1mol L-赖氨酸二异氰酸酯，在103℃下反应2h，得到所述生物可降解聚氨酯。
实施例3
生物可降解聚氨酯的制备方法，包括以下步骤：
(1)将0.5mol聚己内酯和0.1mol乙二醇溶于625ml DMF中，在催化剂辛酸亚锡条件下，回流反应26h，得到预聚物；
(2)向步骤(1)中得到的预聚物滴加0.1mol氨基酸类二异氰酸酯，在100℃下反应3h，得到所述生物可降解聚氨酯。

Claims (7)

1.一种生物可降解聚氨酯，其特征在于：该聚氨酯由软段和硬段构成，所述软段为聚己内酯，硬段为降解无毒的氨基酸类二异氰酸酯。
2.根据权利要求1所述的生物可降解聚氨酯，其特征在于：所述氨基酸类二异氰酸酯为赖氨酸二异氰酸酯和/或L-赖氨酸二异氰酸酯。
3.如权利要求1-2所述的生物可降解聚氨酯的制备方法，其特征在于，包括以下步骤：
(1)将聚己内酯和扩链剂溶于有机溶剂，在催化剂条件下，回流反应20-26h，得到预聚物；
(2)向步骤(1)中得到的预聚物滴加氨基酸类二异氰酸酯，在100-105℃下反应1-3h，得到所述生物可降解聚氨酯。
4.根据权利要求3所述的制备方法，其特征在于：步骤(1)中，扩链剂为丁二胺、丁二醇、丙二醇和乙二醇中的一种或几种。
5.根据权利要求3所述的制备方法，其特征在于：所述催化剂为辛酸亚锡。
6.根据权利要求3所述的制备方法，其特征在于：所述聚己内酯的浓度为0.5-0.8mol/L，聚己内酯与扩链剂、氨基酸类二异氰酸酯的摩尔比为3-5:1:1。
7.根据权利要求3所述的制备方法，其特征在于：所述有机溶剂为DMF和DMSO中的一种或两种。
CN201711362702.4A 2017-12-18 2017-12-18 生物可降解聚氨酯及其制备方法 Withdrawn CN108059706A (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138632A (zh) * 2019-12-19 2020-05-12 福建成杰高分子材料有限公司 一种生物基无溶剂聚氨酯的生产方法
CN111499827A (zh) * 2020-04-15 2020-08-07 贵州大学 一种超韧性生物基聚氨酯复合材料的制备方法
CN115011301A (zh) * 2022-06-13 2022-09-06 烟台德邦科技股份有限公司 一种可穿戴低敏可降解型uv湿气双固化胶黏剂

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1995086A (zh) * 2006-12-30 2007-07-11 四川大学 水性无毒可降解聚氨酯弹性体的制备方法
CN101654508A (zh) * 2009-09-25 2010-02-24 北京理工大学 一种可降解无毒医用聚氨酯材料及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1995086A (zh) * 2006-12-30 2007-07-11 四川大学 水性无毒可降解聚氨酯弹性体的制备方法
CN101654508A (zh) * 2009-09-25 2010-02-24 北京理工大学 一种可降解无毒医用聚氨酯材料及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138632A (zh) * 2019-12-19 2020-05-12 福建成杰高分子材料有限公司 一种生物基无溶剂聚氨酯的生产方法
CN111499827A (zh) * 2020-04-15 2020-08-07 贵州大学 一种超韧性生物基聚氨酯复合材料的制备方法
CN115011301A (zh) * 2022-06-13 2022-09-06 烟台德邦科技股份有限公司 一种可穿戴低敏可降解型uv湿气双固化胶黏剂

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Application publication date: 20180522