CN106715503A - 自润滑聚合物组合物 - Google Patents
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Abstract
公开了一种包含化学连接的润滑剂结构的聚合物树脂组合物,其用于制备自润滑医疗设备,由此不需要目前所需的可用于医疗和外科设备中的二次润滑步骤。
Description
技术领域
本发明涉及一种包含化学连接的润滑剂结构的聚合物树脂组合物,其可用于制造自润滑医疗设备,由此不需要目前所需的二次润滑步骤。
背景
输注治疗产品具有多种需要润滑的组件,包括插管、导管、楔子、尖头和血液控制致动器。在这些组件的生产期间,目前在二次基于溶剂的工艺中施加润滑剂。二次润滑施加工艺期间所用的溶剂一直受到监管机构的仔细审查。生产商一直致力于升级其生产工艺以利用可接受的溶剂,从而确保符合持续变化的监管标准。然而,对生产商而言,持续改变和升级生产工艺以符合持续变化的监管标准(例如从使用HCFC溶剂转换至VOC可燃溶剂)会是资金和资源密集的。因此,消除二次基于溶剂的润滑步骤将导致极大的节约,这不仅是因为消除了溶剂,而且还因为就资本设备、时间和资源而言的二次工艺本身的成本。消除二次基于溶剂的润滑步骤还导致显著的环境益处,且因为消除生产工艺中的溶剂而提高工作场所的安全性。
作为涂层施加或者混入塑料本身中的润滑剂可沥滤出,从而进入病人的血流中。同时监管机构目前允许一定受控量的基于硅氧烷(或其它)润滑剂进入病人中。因此,消除潜在的沥滤会导致病人安全性的提高。
因此,需要一种自润滑聚合物组合物,其不需要二次基于溶剂的润滑步骤,同时允许可调性而不需要添加剂或额外的涂层。还需要一种自润滑聚合物组合物,其还由于润滑剂与树脂化学结合而导致一致的涂层厚度和量,由此减轻对由于工艺变化所导致的润滑性能变化的担忧。还需要一种官能化的润滑剂,其消除了对润滑剂进入血流中的迁移担忧。
发明内容
一个方面涉及一种自润滑聚氨酯组合物,其包含二异氰酸酯与包含短链二元醇、长链聚醚或聚酯二元醇和润滑剂的二元醇混合物的反应产物。在一个或多个实施方案中,所述聚氨酯具有化学连接在该聚氨酯树脂中的润滑剂。在一个实施方案中,将所述润滑剂并入所述聚氨酯树脂的主链中。在一个或多个实施方案中,所述二异氰酸酯选自脂族二异氰酸酯、脂环族二异氰酸酯和芳族二异氰酸酯。在更具体的实施方案中,所述二异氰酸酯选自4,4-二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)和亚甲基双(4-环己基异氰酸酯)(HMDI)。在一个或多个实施方案中,所述短链二元醇选自乙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇,和具有至多10个碳原子的脂环族二醇。在一个或多个实施方案中,所述聚酯二元醇为聚亚烷基二醇。在一个实施方案中,所述聚亚烷基二醇为聚(四亚甲基醚)二醇。在一个或多个实施方案中,所述润滑剂为非硅氧烷二元醇、硅氧烷二元醇或氟化润滑剂。在一个实施方案中,所述硅氧烷二元醇为聚二甲基硅氧烷二元醇。在一个具体实施方案中,所述聚二甲基硅氧烷以所述聚氨酯组合物的约3-10重量%的量存在。在一个或多个实施方案中,所述自润滑聚氨酯组合物包含与所述自润滑聚氨酯共价连接的抗微生物结构部分。在一个或多个实施方案中,所述自润滑聚氨酯组合物包含与自润滑聚氨酯共价连接的抗血栓形成结构部分。在一个或多个实施方案中,所述润滑剂可以以所述聚氨酯组合物的约1-10重量%的量存在。在一个或多个实施方案中,将所述润滑剂并入由所述二异氰酸酯和二元醇混合物形成的主链中。
在一个或多个实施方案中,反应进一步包含选自如下组的催化剂:二月桂酸二丁基锡、叔胺和金属化合物。在一个具体实施方案中,所述叔胺为1,4-二氮杂二环[2.2.2]辛烷。在一个具体实施方案中,所述金属化合物为二月桂酸二丁基锡或辛酸铋。
另一方面涉及式I的聚氨酯:
其中m重复单元为5-2000;n重复单元为1-40,且所述聚氨酯树脂的总分子量为15,000-130,000g/mol。
另一方面涉及一种由本文所公开的自润滑聚氨酯组合物模制的制品。在一个或多个实施方案中,所述制品为插管、导管、楔子、尖头、血液控制致动器或注射器的组件。在一个具体实施方案中,所述制品为塞子。
具体实施方式
在描述本发明的若干示例性实施方案之前,应理解的是本发明不限于下文描述中所述的构造或工艺步骤的细节。本发明能呈其它实施方案形式,且以各种方式实践或实施。
本发明涉及一种具有并入的润滑剂结构的聚氨酯树脂,其可用于制造自润滑医疗设备或医疗设备的组件。本发明的树脂不需要通常在许多医疗设备组件生产中所见的二次润滑步骤。由于并入的润滑剂的较低表面能,该并入的润滑剂具有在导管制造工艺期间和在制造后作为时间函数迁移至表面的倾向。
在本发明的一个或多个实施方案中,润滑剂与聚氨酯树脂化学连接。在一个或多个实施方案中,可使用现有的润滑剂,例如聚二甲基硅氧烷或氟化润滑剂。所述润滑剂发生化学反应,从而与所需且感兴趣的聚氨酯树脂连接或并入所需且感兴趣的聚氨酯树脂。在一个或多个实施方案中,所述润滑剂与树脂的主链结构共价连接或者并入树脂的主链结构。所述润滑剂可使用若干技术而与所需的聚氨酯树脂化学连接。一种将润滑剂与所需的聚氨酯化学连接的技术是在将氨基甲酸酯单体聚合成聚氨酯聚合物之前,对所述单体进行改性。在一个实施方案中,使异氰酸酯单体与多元醇反应,从而形成聚氨酯。可将所述异氰酸酯单体改性以包含润滑结构部分,且与多元醇的反应将继续,从而形成自润滑聚氨酯。
另一种将润滑剂与所需的聚氨酯化学连接的技术是使用受控化学(例如ATRP、官能团反应,或者对树脂表面进行等离子体改性,随后将润滑剂接枝到树脂表面上)将润滑剂接枝到现有树脂的树脂主链上。
另一种将润滑剂与所需的聚氨酯化学连接的技术是利用润滑化学品上的官能团来使其与单体共聚成共聚物,由此将润滑结构部分直接增加在聚合物主链中。例如,可使用醇或“OH”官能团来制备润滑剂如PDMS,这是聚氨酯合成的必要反应性基团。具有-OH官能团的PDMS的结构与异氰酸酯一起反应,从而将PDMS链并入聚氨酯中,由此形成自润滑聚合物。
预期将润滑剂官能化至树脂上的化学改性方法仍能使得该树脂适用于II级医疗设备中。
在医疗设备组件的制造方法期间和之后,润滑剂由于硅氧烷或氟化基团的较低表面能而起霜(bloom)至表面。由于润滑剂与本体材料的聚合物链的化学连接,不需要额外的润滑工艺步骤来获得所需的润滑性能。
在本发明的另一方面中,合成技术还可用来将抗微生物化学品或抗血栓形成化学品并入本发明的包含润滑剂结构的聚合物树脂组合物中。
本发明的树脂可用于需要润滑的基于聚合物的医疗设备中,例如注射器筒和/或塞子。本发明的树脂还可用于预先充有将润滑剂由注射器筒表面溶出且将其带入病人血流中的盐水或其它溶液的注射器中。
实施例1—PDMS-聚氨酯(自润滑氨基甲酸酯):
制备了下述的一系列式I聚氨酯树脂:
其中m重复单元为5-2000。n重复单元为1-40。所述聚氨酯树脂的总分子量为15,000-130,000g/mol。
式I的聚氨酯树脂由以下制备:400-77,000g/mol的硅氧烷流体如Gelest DMS-S31、多元醇如DuPont Tetrathane T-1000、4,4-二苯基甲烷二异氰酸酯(MDI)和1,4-丁二醇(BDO)。将二元醇即DMS-S31、Tetrathane T-1000和BDO混合,加热至65±3℃。然后添加MDI,将混合物搅拌以防止液体混合物发生相分离。在约1-3分钟以后,将温度升至约80℃。然后,将所述液体混合物倾入内衬有聚四氟乙烯的盘中,并加热至100℃过夜以完成聚合。在冷却至环境温度之后,将树脂破碎并挤出成膜以测量物理性能。结果示于表1中。作为对照,制备样品#1“0%PDMS”,其中不添加DMS-S31流体且用相同量的多元醇代替。结果也包括在表1中。
表1.分子量
表2.拉伸性能
平均断裂拉伸(Psi) | 标准偏差 | |
0%PDMS | 5887 | 1951 |
1%PDMS | 5684 | 965 |
2%PDMS | 6565 | 1645 |
3%PDMS | 6396 | 800 |
4%PDMS | 3574 | 457 |
5%PDMS | 2650 | 582 |
6%PDMS | N/A | N/A |
7%PDMS | 2157 | 582 |
10%PDMS | 1538 | 417 |
表3.摩擦系数(CoF)
表4.热分析
Tc(℃) | Tc焓(J/g) | Td(℃) | |
0%PDMS | 161.5 | 16.7 | 305 |
1%PDMS | ND | ND | 309 |
2%PDMS | ND | ND | 308 |
3%PDMS | ND | ND | 308 |
4%PDMS | ND | ND | 306 |
5%PDMS | ND | ND | 304 |
6%PDMS | ND | ND | 307 |
7%PDMS | ND | ND | 301 |
10%PDMS | ND | ND | 309 |
ND定义为“未检测” |
如表1-4所示,测试了各种聚氨酯/聚硅氧烷树脂的各种特性如数均分子量、重均分子量、多分散性、平均断裂拉伸、摩擦系数和热分析,结果示于表1-4中。
如表3的结果所示,在聚氨酯合成中添加3重量%共聚物PDMS获得了与现有润滑聚氨酯材料相同(如果不低于)的摩擦系数。聚氨酯的现有润滑需要额外的添加有5重量%PDMS的涂层。这种将润滑官能团共聚至聚氨酯中的方法在获得比简单涂覆额外PDMS层更低的摩擦系数方面更有效。
如表4所示,将PDMS共聚至树脂主链中破坏了硬段的结晶,而不影响拉伸性能。
硅氧烷二元醇(例如美国专利4,647,643中所公开的那些)是可通过本领域所报告的合成方法制备的已知产品,其可用作本发明的润滑剂。非硅氧烷二元醇,例如氟化二元醇如以“Krytox”二元醇由Dupont商购获得的那些可用作本发明的润滑剂。
就合成而言,本领域技术人员知晓所述硅氧烷二元醇可包含R官能团的混合物,例如亚乙基和亚丁基的组合。
用于本发明中的本发明优选的硅氧烷二元醇为具有400-139,000g/mol分子量的聚二甲基硅氧烷二元醇。
通常,本发明的聚氨酯通过以下容易地制备:形成包含短链二元醇、长链聚醚或聚酯二元醇和式的硅氧烷二元醇的二元醇混合物,在所述二元醇混合物中添加二异氰酸酯。可使用通常用于合成聚氨酯的催化剂,例如二月桂酸二丁基锡、叔胺(即1,4-二氮杂二环[2.2.2]辛烷)和金属化合物(即二月桂酸二丁基锡或辛酸铋)。
可用于本发明中的聚醚二元醇包括聚亚烷基二醇。本发明优选用于本发明中的两种聚醚二元醇为具有650-约2000分子量的聚(四亚甲基醚)二醇。该类多元醇可作为Polymeg 1000(Quaker Oats Co.,化学部门)和Terathane T-1000(DuPont)商购获得。
本发明聚氨酯树脂中所包含的二元醇可包括乙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇等。可使用的其它二元醇为具有至多10个碳原子的脂环族二元醇,例如1,4-环己二醇、1,4-二甲醇环己烷等。
可用于本发明中的代表性二异氰酸酯包括芳族和脂环族二异氰酸酯,例如4,4-二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、亚甲基双(4-环己基异氰酸酯)(HMDI)等。在这些中,本发明优选MDI和HMDI。
所述二异氰酸酯和二元醇以产物的1-10重量%的量包含。在一个或多个实施方案中,所述二异氰酸酯为40-75重量%。在一个或多个实施方案中,硅氧烷二元醇可以以1-10重量%的量添加。通常,OH与异氰酸酯官能团之比为约1:1比。
所述长链聚醚二元醇或长链聚醚二元醇或两种二元醇的混合物构成了所述聚氨酯树脂的余量。
本发明的聚氨酯树脂可通过常规热塑性塑料制造技术(包括溶液浇铸、挤出模制等)制成膜、管或其它形式。需要的话,所述树脂可在其中引入常规稳定剂和其它添加剂。这些物质的量根据所述聚氨酯的应用而变化,但通常以所述聚合物的约0.2-50重量%的量存在。
所述聚氨酯-聚硅氧烷可包含聚二甲基硅氧烷(PDMS)。
在一个或多个实施方案中,设想可使抗微生物化学品或抗血栓形成化学品与所述树脂共价结合。
本发明还允许使用一次模制来注射模制导管而不牺牲光学透明性的能力。
本说明书通篇中的措辞“一个实施方案”、“某些实施方案”、“一个或多个实施方案”或“实施方案”意指就该实施方案所述的具体特征、结构、物质或特性包括在本发明的至少一个实施方案中。因此,本说明书通篇各处出现的短语如“在一个或多个实施方案中”、“在某些实施方案中”、“在一个实施方案中”或“在实施方案中”并非必然指代本发明的同一实施方案。此外,所述具体特征、结构、物质或特性可在一个或多个实施方案中以任何合适的方式组合。
尽管此处已参照具体实施方案描述了本发明,然而应理解的是这些实施方案仅仅是示意本发明的原理和应用。本领域技术人员清楚可对本发明的方法和装置进行各种改进和改变而不偏离本发明的主旨和范围。因此,本发明意欲包括落入所附权利要求及其等同方案范围内的改进和改变。
Claims (20)
1.自润滑聚氨酯,其包含二异氰酸酯与包含短链二元醇、长链聚醚或聚酯二元醇和润滑剂的二元醇混合物的反应产物。
2.根据权利要求1所述的自润滑聚氨酯,其中所述二异氰酸酯选自脂族二异氰酸酯、脂环族二异氰酸酯和芳族二异氰酸酯。
3.根据权利要求2所述的自润滑聚氨酯,其中所述二异氰酸酯选自4,4-二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)和亚甲基双(4-环己基异氰酸酯)(HMDI)。
4.根据权利要求1所述的自润滑聚氨酯,其中所述短链二元醇选自乙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇,和具有至多10个碳原子的脂环族二元醇。
5.根据权利要求1所述的自润滑聚氨酯,其中所述聚酯二元醇为聚亚烷基二醇。
6.根据权利要求5所述的自润滑聚氨酯,其中所述聚亚烷基二醇为聚(四亚甲基醚)二醇。
7.根据权利要求1所述的自润滑聚氨酯,其中所述润滑剂为非硅氧烷二元醇、硅氧烷二元醇或氟化润滑剂。
8.根据权利要求7所述的自润滑聚氨酯,其中所述硅氧烷二元醇为聚二甲基硅氧烷二元醇。
9.根据权利要求8所述的自润滑聚氨酯,其中所述聚二甲基硅氧烷二元醇以所述聚氨酯组合物的约3-10重量%的量存在。
10.由权利要求1所述的自润滑聚氨酯组合物模制的医疗制品。
11.根据权利要求10所述的医疗制品,其中所述医疗制品为插管、导管、楔子、尖头、血液控制致动器、塞子或注射器的组件。
12.根据权利要求1所述的自润滑聚氨酯组合物,进一步包含与所述自润滑聚氨酯共价连接的抗微生物结构部分。
13.根据权利要求1所述的自润滑聚氨酯组合物,进一步包含与所述自润滑聚氨酯共价连接的抗血栓形成结构部分。
14.根据权利要求1所述的自润滑聚氨酯组合物,其中所述润滑剂以所述聚氨酯组合物的约1-10重量%的量存在。
15.根据权利要求1所述的自润滑聚氨酯,其中反应进一步包含催化剂。
16.根据权利要求15所述的自润滑聚氨酯,其中所述催化剂选自二月桂酸二丁基锡、叔胺和金属化合物。
17.根据权利要求16所述的自润滑聚氨酯,其中所述叔胺为1,4-二氮杂二环[2.2.2]辛烷)。
18.根据权利要求16所述的自润滑聚氨酯,其中所述金属化合物为二月桂酸二丁基锡或辛酸铋。
19.根据权利要求1所述的自润滑聚氨酯,其中将所述润滑剂并入由所述二异氰酸酯和二元醇混合物形成的主链中。
20.式I的聚氨酯树脂:
其中m重复单元为5-2000;n重复单元为1-40;且所述聚氨酯树脂的总分子量为15,000-130,000g/mol。
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CN112041362A (zh) * | 2018-04-12 | 2020-12-04 | 巴斯夫欧洲公司 | 电活性聚合物 |
CN112041362B (zh) * | 2018-04-12 | 2022-12-13 | 巴斯夫欧洲公司 | 电活性聚合物 |
CN112739391A (zh) * | 2018-09-24 | 2021-04-30 | 贝克顿·迪金森公司 | 自润滑医疗制品 |
CN113164657A (zh) * | 2018-09-24 | 2021-07-23 | 贝克顿·迪金森公司 | 自润滑医疗制品 |
CN113164657B (zh) * | 2018-09-24 | 2024-02-09 | 贝克顿·迪金森公司 | 自润滑医疗制品 |
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EP3172255A1 (en) | 2017-05-31 |
JP2017530207A (ja) | 2017-10-12 |
JP7004567B2 (ja) | 2022-01-21 |
SG11201700510XA (en) | 2017-02-27 |
CA2955996C (en) | 2022-11-01 |
WO2016014755A1 (en) | 2016-01-28 |
BR112017001396B1 (pt) | 2022-03-29 |
BR112017001396A2 (pt) | 2017-11-21 |
US10995299B2 (en) | 2021-05-04 |
AU2015292555B2 (en) | 2018-03-01 |
CN106715503B (zh) | 2020-01-14 |
CA2955996A1 (en) | 2016-01-28 |
US20180237721A1 (en) | 2018-08-23 |
US20160024419A1 (en) | 2016-01-28 |
AU2015292555A1 (en) | 2017-02-16 |
US10995298B2 (en) | 2021-05-04 |
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