CN1338950A - 一种由线型聚氨酯嵌段共聚物组成的医用薄膜及其生产方法 - Google Patents
一种由线型聚氨酯嵌段共聚物组成的医用薄膜及其生产方法 Download PDFInfo
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Abstract
本发明介绍一种由线型聚氨酯-脲嵌段共聚物组成的医用薄膜,该聚合物中含有可水解的酯基。这些酯基在碳链上必须按一定的间隔相互隔开,所述间隔要使其水解时产生的片段小到能从人体或哺乳动物的身体分泌出去的程度。该薄膜的特征在于它是多孔的,其平均孔径最多600μm。本发明还包括一种生产该薄膜的方法,该方法是将浓度为5-30%的成膜聚合物溶液涂在一表面上,形成薄层,然后使溶剂蒸发,和/或用沉淀聚合物试剂处理此薄层。
Description
技术领域
本发明介绍一种由线型聚氨酯-脲嵌段共聚物组成的医用薄膜,该聚合物中含有可水解的基团。本发明的薄膜是多孔的,并设计成人体或哺乳动物在手术或受损伤后临时用的植入物。本发明特别包括一种获得所要求的孔隙率的方法。
现有技术
手术或受损伤后活组织的治愈意味着涉及一系列不同细胞类型的复杂过程,大体地概括下列过程按以下顺序发生:首先形成纤维蛋白基质,然后上皮细胞开始分裂并封住伤口。在上皮层下,成纤维细胞开始构建由胶原和基本物质组成的结缔组织。这样,该结缔组织逐渐形成血管并聚集到伤疤组织中。
在另一种情况下,例如断骨的愈合,基质形成后是干细胞的生长,该细胞属于成软骨细胞范畴。这些细胞在断裂处形成由软骨组成的软骨痂。成纤维细胞迁移进软骨中,并形成胶原区带,然后成骨细胞进入并形成新的疏松骨。治愈的最后期包括转变为硬骨,以及恢复原有的结构。这些过程需要几年才能完成。技术问题
尽管治愈过程一般预后是良好的,但其复杂的进程使产生不良后果的可能性增加。例如,会受到微生物的侵袭,或是受伤面与错误的“相邻面”一起作用,并形成结合生长。常常发生成纤维细胞迅速生长的情况,这是形成有害结缔组织的根源。这种有害的结缔组织会妨碍骨组织或其他所需组织的重建。
问题的解决
因此,长久以来,人们就希望能辅助自我治愈过程,并克服上述问题。根据本发明,可生产一种由线型聚氨酯-脲嵌段共聚物组成的医用薄膜,该共聚物中含有可水解的酯基,这些酯基在碳链上按一定的间隔隔开,该间隔的大小要使其水解时生成的片段小到能从人体或哺乳动物体中分泌出去的程度,该薄膜的特征在于它是多孔的,其平均孔径最大600μm。
根据本发明,该薄膜的进一步特征在于横过薄膜厚度来看,其孔隙率可以不同。
根据本发明,横越薄膜厚度的孔隙度率可以是非对称的,即薄的外层孔隙率较低。
根据本发明,该薄膜与生物可降解的材料制成的筛网层叠压在一起常常是相宜的。
根据本发明,该薄膜可由涂于生物可降解筛网或其类似物的各纱线上的涂层组成。
本发明还包括一种生产医用薄膜的方法,该薄膜由含有可水解酯基的线型聚氨酯嵌段共聚物组成,此方法的特征是将浓度为5-30%的聚合物溶液涂在一表面上,形成薄层,然后使溶剂蒸发,和/或用沉淀聚合物试剂处理该薄层。
根据本发明,该沉淀剂最好选自包括水、甲醇和丙酮的一组溶剂。
根据本发明,薄膜的孔隙率可由聚合物的浓度、溶剂、温度和/或时间来调节,聚合物的浓度高、溶剂挥发性强、温度高时,所得薄膜的孔均小,蒸发时间或沉淀时间短,如果合适时,所得薄膜的孔也小。
根据本发明,可采用二种或二种以上挥发性不同的溶剂的混合物,使穿过薄膜厚度的孔隙率不同。
根据本发明,也可通过将已形成的薄膜加以调理,来调节该薄膜的孔隙率,其方法是将已形成的薄膜浸入溶剂或溶剂与非溶剂的混合物中,和/或对膜进行热处理。
多孔薄膜可在受伤面上起屏障作用,从而有助于防止不需要的细胞生长。此外,在移植软骨等情况下,多孔薄膜可用来修补或补充骨膜。膜的多孔性,使溶解的物质,例如代谢物和/或蛋白质可通过膜输送。如果孔的大小足够大,某些类型的细胞也可在膜上生长。孔很大的膜也能形成血管。对于上述各种不同的过程,其平均孔径的限定值如下:
<1μm,溶解组分的扩散和胶原的生长,
<5μm,纤维组织不生长
<15μm,纤维组织生长较少
40-200μm,纤维组织生长并形成血管
>600μm,细胞生长减少和组织坏死
用于生产薄膜的聚合物可降解为无害的物质,然后通过分泌或代谢清除出体外。根据本发明,降解的时间不会太短,这样可避免体内存有局部高浓度的降解产物。聚合物的降解速度是不同的,这也是为了适应于不同用途的需要。
对薄膜机械性能的要求取决于其应用的场合。在很多应用场合,撕裂强度尤为重要,例如,在薄膜需要用别针等固定,或是要牢固地缝住时。需要时,弹性模量、撕裂强度等可通过以下方法来改进,即将薄膜层压在生物可降解纤维的筛网上。另一种方法是,将筛网浸透,或涂布聚合物溶液或分散液,然后将溶剂除去。发明详述聚合物
目前已可证实,具有所需性能的多孔薄膜或片材可由线型聚氨酯-脲嵌段共聚物类聚合物来生产。适合的聚合物可按照已知具体成分所用的方法,用二异氰酸酯、二醇和碳链延伸剂来生产。为了能成膜,聚合物的分子量应>10,000道尔顿,优选>100,000道尔顿。
一种生产该聚合物的方便的技术是采用所谓的预聚合技术,亦即先生产带异氰酸酯端基的预聚物,然后用二胺延伸其碳链,从而获得所需分子量的聚合物。反应式如下: (1) (2)其中至少R1、R2和R3之一其碳链上必须含有1个或1个以上的酯基团,以满足其降解成小片段的要求。也可以采用几种预聚物的混合物,以达到特定的效果,例如,引进一些基团,这些基团在聚合之后能起反应而在聚合物中引入有生理活性的基团。此外,也可加入少量的碳链终止剂以限制其分子量的上限。
可用的二异氰酸酯是二苯基甲烷-4,4’-二异氰酸酯(MDI)、二环己基甲烷-4,4’-二异氰酸酯、环己基-1,4-二异氰酸酯、甲代亚苯基二异氰酸酯和很多市售的二异氰酸酯,以及实验室生产的品种,例如以氨基酸为基础的品种,如1-赖氨酸甲基酯二异氰酸酯。
所用的二烯属可以是简单的脂肪族化合物,例如乙二醇、二甘醇或更高级的低聚物、四氢呋喃二醇或更高级的低聚物;二醇酯例如低聚已内酯二醇、低聚乙二醇己二酸二醇、低聚二甘醇己二酸酯、二羟甲基丙酸、二羟甲基丙酸甲酯、三羟甲基丙烷单烯丙基醚以及其他很多种二烯属化合物。
碳链增量剂可以是简单的二胺,例如乙二胺1,3-丙二胺或1,2-丙二胺。上述二胺类化合物在碳链上也可含有酯基团,以便可通过水解降。也可采用碳链增量剂的混合物,而且往往是有利的。
伯或仲单胺可用作链终止剂,例如二乙胺、吗啉或丙胺。同样,采用混合物也是可取的。
上述反应式中的反应1可在升温下进行本体聚合反应,对于MDI为70-80℃,对于二环己基甲烷二异氰酸酯为100-110℃。在有催化剂时,反应可在大大降低的温度下进行。然而,反应2,即碳链延伸的反应,由于反应速度高以及所形成的聚合物的胶化趋势,该反应宜在溶液中进行。生成的聚合物溶液可以直接或稀释后用于薄膜或片材生产。在某些溶剂中,例如丙酮,所生成的聚合物是沉淀形式,此时可将其滤出,然后再溶于溶剂中用于薄膜或片材生产,例如可溶于二甲基甲酰胺、二甲基亚砜、二甲基乙酰胺中。薄膜
该薄膜由溶液制成,将溶液在一平坦的表面上涂成薄层,然后使溶剂蒸发和/或用沉淀剂处理该薄膜。为了获得多孔的薄膜,聚合物的浓度必须为5-30%,优选为10-20%。在涂布后,溶剂可以全部或部分蒸发,或是加入反溶剂将溶剂除去。反溶剂的例子为水、甲醇和丙酮。
达到多孔性的前题是聚合物溶液在除去溶剂过程的某一阶段形成凝胶,亦即凝结物。通过相分离和氢键键合作用,嵌段聚物间发生强烈的相互作用,而使本发明的聚合物有明显的凝结趋势。其他有利于形成凝胶的重要因素是高的聚合物浓度和高的分子量。
孔的大小和孔径的分布可通过浓度、沉淀的条件,连同反溶剂的加入来调节。另一种方法是,用溶剂、溶剂和反溶剂的混合物、和/或热处理对预先生产的膜进行调理。调理的方法是将预先生产的薄膜浸入随后要蒸发的溶剂中,或是将薄膜加热,使其膨胀起来。这样便可将孔的大小及其分布调节至所要求之值。
本发明的薄膜可由聚合物溶液用几种方法来生产。最简单的方法是在一表面上,例如一块玻璃平板上逐片生产,用涂抹器在玻璃平板上涂一层规定厚度的聚合物溶液,然后在仔细控制的条件下,通过蒸发或沉淀除去溶剂。连续生产按下法进行:将聚合物溶液涂在移动带上,移动带将此材料运送至沉淀区,然后再运送至一个或多个区作后处理,最后移动带回至原处时,将薄膜从带上取下。
通过拉伸可增加薄膜的强度。拉伸引起聚合物分子的定向并改变了孔的大小和形式。结果,沿拉伸方向其强度增加。双轴方向拉伸时,其强度沿二个方向均增加。
根据瑞典专利NO:505703的描述另一种增加薄膜强度的方法是将薄膜与可降解的纤维,例如聚氨酯-脲纤维筛网结合在一起。该专利介绍,此筛网可部分地与先前制备的膜层压在一起,或者将筛网用聚合物溶液浸渍或强化,然后按上述方法,使溶剂蒸发和/或沉淀。
在弯曲的表面上生产多孔薄膜的方法是浸渍法。将一模型,例如一端封闭的管,浸入聚合物溶液中,然后取出模型,通过溶剂的蒸发或用反溶剂凝结,使聚合物转变为固态。该步骤可反复进行,直至膜的厚度达到要求为止,然后将膜从模型剥下。
实施例
实施例1:二苯基甲烷二异氰酸酯(MDI)与聚己内酯二醇(分子量为530)按摩尔比2∶1,在70-80℃下反应2小时,制成预聚物。32.35g生成的预聚物溶于138g二甲基甲酰胺(DMF)中,并用溶于59g DMF的2.35g1,3-二氨基丙烷和0.08g二丁基胺在0℃下使碳链伸长。将反应后的溶液以12.5%比例释释,加入1%LiCl降低其粘度。
用涂抹器将部分所生成的聚合物溶液在玻璃平板上涂开,厚度为300μm。在通风橱内,20℃下处理20分钟以上,使部分溶剂蒸发。处理后的薄膜变白,明显地发生相分离。用水洗涤除去剩余的溶剂。用扫描电子显微镜(SEM)检测所形成薄膜,呈现的通孔平均孔径为2μm。
实施例2:将实施例1所得的部分聚合物溶液涂在玻璃板上,在通风橱内,20℃下使溶剂蒸发14小时。用水洗去残留的DMF。所生成的薄膜具有通孔结构,孔径为2-7μm。
实施例3:将实施例1所得的部分聚合物溶液涂在玻璃板上,并浸入丙酮中10分钟,由此聚合物分离出来。用水洗去丙酮和残留的DMF。所生成的薄膜具有通孔结构,孔径约1μm左右。
实施例4:将实施例1所得的部分聚合物溶液涂在玻璃板上。在2分钟之内将玻璃板加热至100℃,使部分溶剂蒸发。剩余的溶剂在通风橱内,20℃下,在1小时内蒸发。用水洗涤所生成的薄膜以除去剩余的DMF。所生成的薄膜具有通孔结构,孔的径为2-7μm。
实施例5:12.3g由实施例1所得的预聚物溶于52.5g二甲基甲酰胺(DMF)中,并用溶于22.5gDMF的0.9g1,3-二-氨基丙烷和0.06g二丁基胺在20℃下使链延长。
用涂抹器将部分所得的聚合物溶液涂在玻璃板上,厚度为500μm。在通风厨内,20℃下,使溶剂蒸发14小时。用水洗去残留的DMF。
实施例6:二环己烷甲烷二异氰酸酯(H12MDI)与聚己内酯二醇(分子量为530)按摩尔比2∶1,在100-110℃下反应4小时,制成预聚物。另外,将H12MDI与二羟甲基丙酸按摩尔比2∶1,在二甲基甲亚砜(DMSO)中,75-80℃下反应1小时,生成预聚物。26g预聚物1和8.7g预聚物2+DMSO溶于66g DMSO中,并用溶于20g DMSO的2.12g1,3-二氨基丙烷在20℃下使链延长。
用涂抹器将部分所生成的聚合物溶液涂在玻璃板上,厚度为300μm。在通风橱内,20℃下使溶剂蒸发14小时。用水洗去残留的DMF。
实施例7:二苯基甲烷二异氰酸酯(MDI)与聚二甘醇己二酸(分子量为550)按摩尔比2∶1,在70-80℃下反应2小时,制成预聚物。将13.2g所生成的预聚物溶于34g二甲基甲酰胺(DMF)中,并用溶于22g DMF中的0.68g1,3-二氨基丙烷和0.05g二丁基胺在20℃下使链延长。
用涂抹器将部分所生成的聚合物溶液涂在玻璃板上,厚度为500μm。在通风橱内,20℃下使溶剂蒸发14小时。用水洗去残留的DMF。
实施例8:二苯基甲烷二异氰酸酯(MDI)与3-烯丙氧基-1,2-丙二醇按摩尔比2∶1,在70-80℃下反应2小时,制成预聚物。将6.12g所生成的预聚物与17.62g实施例7中制备的预聚物溶于65g二甲基亚砜(DMSO)中,并用溶于3.5g丙酮和30g DMSO的2.17g1,2-二氨基丙烷加上0.07g乙胺,在20℃下使链延长。
用涂抹器将部分生成的聚合物溶液涂在玻璃板上,厚度为500μm。在通风橱内,20℃下使溶剂蒸发14小时。用水洗去残留的DMSO。
本发明不限于上述的制备实例,因为这些实施例可在专利权利要求范围内,以数种方式加以改变。
Claims (10)
1.由含有可水解酯基的线型聚氨酯-脲嵌段共聚物组成的医用薄膜,该酯基在碳链上按一定的间隔隔开,所述间隔要使其水解时产生的片段小到能从人体或哺乳动物体分泌出去的程度,其特征在于该薄膜是多孔的,其平均孔径最大600μm。
2.权利要求1的薄膜,其特征在于从横过该薄膜厚度来看,其孔隙率可以不同。
3.权利要求2的薄膜,其特征在于该薄膜厚度内的孔隙率是非对称的。
4.权利要求1-3中任何一项的薄膜,其特征在于该薄膜与生物可降解材料的筛网层压在一起。
5.权利要求1-3中任何一项的薄膜,其特征在于该薄膜在生物可降解的织物或类似物的各纱线上形成涂层。
6.生产医用薄膜的方法,该薄膜由含有可水解酯基的线型聚氨酯-脲嵌段共聚物组成,其特征在于将浓度为5-30%,优选10-20%的聚合物溶液在一表面上涂成薄层,然后使溶剂蒸发,和/或用沉淀聚合物试剂处理该薄层。
7.权利要求6的方法,其特征在于沉淀剂选自水、甲醇和丙酮。
8.权利要求6或7中任一项的方法,其特征在于薄膜的孔隙率可由聚合物的浓度、溶剂、温度和/或时间来调节,聚合物的浓度高、溶剂的挥发性强、温度高时、和/或蒸发或沉淀的时间适当短些,所得薄膜的孔均小。
9.权利要求6-8中任一项的方法,其特征在于采用二种或二种以上挥发性不同的溶剂的混合物,使所得薄膜穿越其厚度来看,其孔隙率不同。
10.权利要求6-9中任一项的方法,其特征在于通过将预先生产的薄膜加以调理来调节薄膜内孔之孔径,调理的方法是将预先生产的薄膜浸入溶剂,或溶剂与反溶剂的混合物中,和/或对薄膜作热处理。
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CN114634641A (zh) * | 2022-03-31 | 2022-06-17 | 重庆大学 | 具有规则孔隙的多孔聚合物薄膜用于制备防粘连膜的用途 |
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- 2000-01-18 PL PL00350052A patent/PL350052A1/xx not_active Application Discontinuation
- 2000-01-18 IL IL14428600A patent/IL144286A0/xx unknown
- 2000-01-18 CN CNB008033196A patent/CN1222326C/zh not_active Expired - Fee Related
- 2000-01-18 BR BR0007926-0A patent/BR0007926A/pt not_active Application Discontinuation
- 2000-01-18 CZ CZ20012590A patent/CZ20012590A3/cs unknown
- 2000-01-18 US US09/890,291 patent/US6627258B1/en not_active Expired - Fee Related
- 2000-01-26 AR ARP000100339A patent/AR022431A1/es unknown
-
2001
- 2001-07-11 NO NO20013448A patent/NO20013448L/no not_active Application Discontinuation
- 2001-07-13 ZA ZA200105804A patent/ZA200105804B/en unknown
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2002
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101703811B (zh) * | 2009-11-10 | 2014-06-25 | 成都迈狄美科技有限公司 | 医用可降解聚酯非对称膜及其制备方法 |
CN104312140A (zh) * | 2014-10-22 | 2015-01-28 | 四川大学华西医院 | 一种聚氨酯/小肠粘膜下层复合材料及用途 |
CN104312140B (zh) * | 2014-10-22 | 2017-02-15 | 四川大学华西医院 | 一种聚氨酯/小肠粘膜下层复合材料及用途 |
CN112745471A (zh) * | 2020-12-29 | 2021-05-04 | 南京理工大学 | 室温本征自修复玻璃态聚合物材料及其制备方法 |
CN112745471B (zh) * | 2020-12-29 | 2022-08-09 | 南京理工大学 | 室温本征自修复玻璃态聚合物材料及其制备方法 |
CN114634641A (zh) * | 2022-03-31 | 2022-06-17 | 重庆大学 | 具有规则孔隙的多孔聚合物薄膜用于制备防粘连膜的用途 |
CN114656678A (zh) * | 2022-03-31 | 2022-06-24 | 重庆大学 | 具有规则孔隙的多孔聚合物薄膜用于制备人工骨膜的用途 |
WO2023184852A1 (zh) * | 2022-03-31 | 2023-10-05 | 重庆大学 | 一种形状记忆聚氨酯及其制成的自增强规则孔隙聚合物薄膜 |
Also Published As
Publication number | Publication date |
---|---|
PL350052A1 (en) | 2002-10-21 |
HUP0104965A2 (en) | 2002-06-29 |
BR0007926A (pt) | 2001-11-06 |
SE9900345D0 (sv) | 1999-02-02 |
EP1148896A1 (en) | 2001-10-31 |
TR200102199T2 (tr) | 2002-01-21 |
AR022431A1 (es) | 2002-09-04 |
IL144286A0 (en) | 2002-05-23 |
SE9900345L (sv) | 2000-08-03 |
JP2002536461A (ja) | 2002-10-29 |
EE200100400A (et) | 2002-10-15 |
SE514064C2 (sv) | 2000-12-18 |
YU53201A (sh) | 2003-08-29 |
KR20010101930A (ko) | 2001-11-15 |
US6627258B1 (en) | 2003-09-30 |
CA2361439A1 (en) | 2000-08-10 |
NO20013448D0 (no) | 2001-07-11 |
ID29174A (id) | 2001-08-09 |
HK1044491A1 (zh) | 2002-10-25 |
CZ20012590A3 (cs) | 2001-11-14 |
NO20013448L (no) | 2001-08-07 |
AU2836400A (en) | 2000-08-25 |
SK10682001A3 (sk) | 2001-12-03 |
CN1222326C (zh) | 2005-10-12 |
WO2000045869A1 (en) | 2000-08-10 |
AU767426B2 (en) | 2003-11-13 |
ZA200105804B (en) | 2002-10-30 |
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