CN1106743A - 热塑性聚氨酯弹性软管生产方法 - Google Patents
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Abstract
热塑性聚氨酯弹性软管生产方法包括(a)在加热
芯模圆周面上加压挤出热塑性聚氨酯弹性体,(b)拉
出芯模而得预成型管和(c)热拉伸预成型管而得要求
外径的软管,其中芯模温度和弹性体挤出压力落入已
预先按这两个参数确定的预成型管可热拉伸范围与
表面不出现气泡的范围重叠的区域。本发明方法可
得到热拉伸性良好且克服了因出现气泡或粒状结构
而导致的外观不良问题的TPU软管,而且可连续生
产稳定质量的TPU软管,因此其产率高。
Description
本发明涉及按所谓的加压法用热塑性聚氨酯弹性体(下称TPU)生产软管的改进方法。
通常将医用软管如套管,导管等插入血管(尤其是冠状动脉),气管,输卵管,尿道和各种器官中以注射液体,开通管道等。这些医用软管主要由TPU制成,其顶端经热拉伸成薄锥体以使其易于插入器官等。
包括这些医用软管在内的软管成形方法例子可举出将从模头挤出端挤出的TPU覆盖在芯模上的方法(下称制管法)。该制管法所用模头的部分剖面示于图3。在该制管法中,在模头内沿轴芯10a通过的芯模11沿箭头b的方向传送,而从挤出机(未示出)挤出的TPU 12则供入模头10,并如图3所示从口模13和嘴管14之间按规定厚度挤出。由于TPU 12的直径与有待被覆的的芯模11的直径大嘴管14的厚度,所以模头10的挤出端10b处TPU 12会脱落而覆盖在芯模11上。
但在该制管法中由于TPU 12在分离压力下覆盖在芯模11上,所以在TPU 12挤出成形体表面上会形成气泡。为了避免形成气泡,就需要降低TPU 12的挤出温度,而这又会导致TPU 12熔融不足,常会出现粒状结构(因TPU中反应而形成高分子量线性聚合物,从而在其表面上形成直径为几十至几百μm的球状突出物)。因此,制管法不可能消除因出现气泡或粒状结构而导致的外观不良现象。
制管方法的另一例子是在模头中用TPU挤出覆盖芯模的方法(下称加压法)。该加压法所用模头的部分剖面示于图2。在该加压法中,在模头1内沿轴芯1a通过的芯模2沿箭头a的方向传送,而从挤出机(未示出)挤出的TPU 3则供入模头1,并如图2所示使TPU 3在嘴管4的挤出端4a处与芯模2接触。芯模2进一步沿箭头a的方向传送,从而使TPU 3在芯模3和口模5之间按规定厚度覆盖芯模2后挤出。
在该加压法中,TPU 3加压覆盖在芯模2上,使其与上述制管法形成鲜明对照。因此,大大减少了气泡或粒状结构的出现并且软管外观良好。但该加压法得到的成形体热拉伸性差。也就是说,将该成形体顶端加热到不低于玻璃化温度(Tg)的温度后再热拉伸成薄锥体时,由于微型裂口或出现粒状结构,所以拉伸部位会发白,甚至断裂。
考虑到以上各种情况,本发明目的是提出TPU软管生产方法,其中包括在芯模圆周面上加压挤出TPU,将芯模拉出而形成预成形管并将所得预成形管热拉伸而得到具有要求外径的软管,该方法没有因出现气泡或粒状结构而致使其外观不良的问题并且所得TPU管的热拉伸性良好。
以下说明本发明。
热塑性聚氨酯弹性软管生产方法,其中包括
(a)在加热的芯模圆周面上加压挤出热塑性聚氨酯弹性体,
(b)将芯模拉出而形成预成形管,和
(c)将所得预成形管热拉伸而得到具有要求外径的软管,其中该芯模的温度和弹性体挤出压力落入可使预成形管进行热拉伸的范围与预成形管表面上不出现气泡的范围重叠的区域,所说两范围已预先以加热后芯模的温度和弹性体挤出压力作为参数确定下来。
图1表明了可进行热拉伸的范围(A、C)和软管表面不出现气泡的范围(B,C)这些范围已以下述实施例中芯模的温度和TPU挤出压力作为参数确定,其中Ti为芯模的初始温度。
图2为加压法中模头1的部分剖面图,其中1a为轴芯,2为芯模,而3为TPU。
图3为制管法中模头10的部分剖面图。
可用于本发明的挤出机并不受特别限制,只要能达到本发明目的即可,其例子包括螺杆挤出机(如单螺杆挤出机,多螺杆挤出机)及非螺杆挤出机(如弹性熔体挤出机,液压挤出机,柱塞式连续挤出机,滚压挤出机,齿轮挤出机),优选单螺杆挤出机。本发明中,挤出机不包括具有口模的模头。
本发明生产方法中TPU覆盖在模头轴芯内的芯模上。模头意指挤出机套筒端部设置的模具,例子可举出十字头模(包括角头模)和异型孔模。本文中模头轴芯意指有待覆盖TPU的芯模从模头经过的部分。芯模例子包括退火铜线,软SUS线和ETFE线。尽管芯模直径不受限制,但一般为约0.1-2.0mm。
TPU优选为主要由组成软段(不含氢键的橡胶基质部分)的多元醇,组成硬段(含氨酯和脲键的氢键部分)的增链剂和二异氰酸酯构成的嵌段共聚物。
作为多元醇,可用分子中具有至少两个活性氢原子,优选含羟基的多元醇。这种多元醇例子包括用脂族胺,芳族胺等作为引发剂将环氧烷加到多元醇如二醇和三醇上而得到的聚亚氧乙基多元醇;酸和醇缩合而得到的聚酯多元醇,聚丁二醇,聚丁二烯多元醇,聚丙二醇,聚1,4-丁二醇已二酸酯,聚乙二醇已二酸酯,聚丁二醇,聚乙二醇和双酚A与环氧丙烷的加聚物,优选双酚A与环氧丙烷的加聚物。该多元醇的优选重均分子量为约200-2000。该多元醇可单独或组合应用。
增链剂例子包括二醇如乙二醇,1,4-丁二醇和二乙二醇,胺如二乙醇胺,三乙醇胺,甲苯二胺和已二胺,多异氰酸酯如三羟甲基丙烷的TDI(甲苯二异氰酸酯)加合物和三苯基甲烷三异氰酸酯,双(2-羟乙基)氢醌,双酚A与环氧乙烷的反应产物和双酚A与环氧丙烷的反应产物,这些化合物可单独或组合应用。特别优选1,4-丁二醇。
二异氰酸酯并不特别受限制,可用常用于是聚氨酯的二异氰酸酯。其例子包括2,4-或2,6-甲苯二异氰酸酯,4,4’-二苯基甲烷二异氰酸酯,已二异氰酸酯,间或对苯二异氰酸酯和异氟尔酮二异氰酸酯,这些化合物可单独或组合应用。特别优选4,4’-二苯基甲烷二异氰酸酯。
多元醇,增链剂和二异氰酸酯mol比为1:0.5-2:1.5-3,优选1:0.8-1.5:1.8-2.5,更优选为1:0.9-1.2:1.9-2.2。
TPU数均分子量优选为30000-300000,更优选为50000-150000。
必要时可用催化剂促进TPU合成反应。催化剂例子包括叔胺如三乙胺,四甲基已二胺和甲苯二胺以及以锡催化剂为代表的金属催化剂如辛酸亚锡,油酸亚锡和二丁基二月桂酸锡,这些化合物可单独或组合应用。
可用上述多元醇,增链剂和二异氰酸酯及必要时用催化剂合成TPU。合成方法已见于例如未审查日本专利申请公开Nos 293214/1986和244341/1988。适当变化多元醇,增链剂和二异氰酸酯中的每一组分,可任选改变玻璃化温度(Tg)。
本发明中可用的TPU的Tg优选为-30-60℃,更优选为25-50℃。
当TPU中水含量高时,容易因发泡而形成气泡。TPU的吸水性要求减少其水含量。因此,TPU优选应在约80℃下进行不少于5小时的干燥后才加入挤出机。
在本发明中加热的芯模温度指该芯模在送入模头前接近模头入口时的温度,而TPU的挤出压力为模头入口(将TPU供入模头的套筒出料端)处TPU的压力。
预成形管为从覆盖芯模外圆周面的TPU挤出成形体内除去芯模而得到的空心TPU成形体,而可进行预成形体热拉伸的范围为以加热后芯模温度和TPU挤出压力作为参数确定的范围并且指不低于TPU玻璃化温度(Tg)的温度下可拉伸150%或以上的范围。预成形管表面上不出现气泡的范围亦为以加热后芯模的温度和TPU的挤出压力为参数确定的范围并且指该预成形管表面上基本上不存在可目视气泡或粒状结构的范围。这些范围根据初始TPU原料,其组成比,预定预成形管厚度等变化,尤其取决于TPU的假交联部分(硬段)。
根据本发明,将芯模加热到落入上述两范围重叠区域的温度,而TPU覆盖在挤出机的芯模上并将其挤出而得覆盖芯模的挤出产品。在冷却槽等中将该挤出成形体冷却。芯模的导出速度应尽可能高,只要不影响成形产品的厚度即可,其中考虑到在从挤出到冷却的工艺时间太长时可能因TPU中溶存空气发泡而形成气泡。以这种方式,可得到预成形管。
尽管软管厚度不受特别限制,但一般为约0.05-0.4mm。
本发明软管优选用作医用软管。本文中医用软管指可插入动物包括人体内而用于进行试验,观察,诊断,治疗和预防及其它目的的管状医疗器械(如导管,套管,冲洗管,探条等)。也就是说,根据应用部位如循环系统,呼吸系统,消化系统,泌尿系统,生殖系统等及其使用目的和功能,该管可包括各种类型,其例子可举出具有液体注射和排出,体温测定,血压测定和血液检查,化学分析或内部探视等功能的软管以及装有激光纤维或气球的软管。因此,这些软管可用于包括人在内的哺乳动物(如牛,兔,马,羊,猴,狗,猫)。
医用软管的具体例子可包括静脉导管,心脏导管,血管造影导管,血管扩张导管,除去血栓的导管,胆管导管,支气管导管,胃管软管,硬膜外导管,食道探条,中心静脉导管,排尿软管,胰管软管,子宫颈管留置导管,内视镜导管,排尿导管,经鼻氧气导管,吸引导管,套针导管,ED(肠内饮食)导管和输液软管等。
按本发明挤出成形制管方法,没有因气泡或粒状结构引起的外观不良问题并且具有良好热拉伸性的软管可通过将芯模加热到预定温度并在特定挤出压力下将TPU挤出成形而得到,其中确定的温度和压力落入可进行预成形管热拉伸的范围和不出现预成形体表面气泡的范围的重叠区域,其中所说的两范围已预先以加热后芯模的温度和TPU挤出压力为参数确定。
换句话说,加热到该特定范围内的温度下的芯模,即使在模头内熔融的TPU与芯模接触时,也不会将TPU硬段固定下来(形成假交联部分)。而且,由于TPU在特定范围内的挤出压力下从模头中挤出,所以假交联部分不会在TPU挤出后立即形成。再进一步,TPU进行拉伸时应力缓解,逐渐形成假交联部分。以这种方式,在应力缓解完了之后,假交联部分和非晶形部分(软段)才固定下来。因此,在所得成形体加热到不低于其玻璃化温度(Tg)的温度时,TPU的软段得以脱离,这样就可进行拉伸。尽管在TPU中的溶存空气一般可通过加热芯模或降低TPU的挤出压力而以气泡形式放出,但本发明成形方法中通过将芯模温度和TPU挤出压力限制在特定范围内而阻止了成形体表面出现气泡。
按照常规加压方法,在模头中熔融的TPU与芯模接触并且残留应力增大时,会形成假交联部分,从而提高了这部分的粘度。因此,在假交联部分的维持固定状态下拉伸TPU,同时拔出芯模,应力缓解明显受阻。此外,由于非晶形部分仍保持拉伸,所以将所得成形体加热到不低于玻璃化温度(Tg)的温度会使TPU的软段脱离,而由于已进行过拉伸,所以再进行拉伸就几乎不可能。相比之下,假交联部分(硬段)表现出形状记忆特性,在形成假交联部分时(即在熔融TPU接触芯模时),该假交联部分倾向于恢复到其原始状态。因此,因出现微裂纹或粒状结构而会使被拉伸部分发白,甚至会因热拉伸性差而使被 拉伸部分断裂。
以下实施例和比较例详述本发明,但并不限制本发明。
实施例1-6和比较例1-7
玻璃化温度约45℃的TPU(商标MM4510,由Mitsubishi Jukogyo Kabushiki Kaisha制造)约80℃下干燥不少于5小时。该TPU在以下挤出条件下挤出后覆盖在退火铜线芯模上并拉出芯模。按此方式,得到50种模制TPU软管。
模口径 1.3mm
嘴管直径 1.02mm
挤出机(双螺杆挤出机)温度 130-225℃
模头(十字模头)温度 205-215℃
口模温度 195-210℃
加热的芯模温度 室温-120℃
用热空气加热器加热十字模头前30cm部分,在十字模头入口前用接触型温度计测定这部分的温度以进行温度控制。
TPU挤出压力 35-234kg/cm
芯模导出速度 1.6-11.9m/min
适当调整芯模引出速度以便TPU软管厚度达到约0.35mm。
检测每一TPU软管热拉伸性和外观并以芯模温度和挤出压力为参数作图(图1)。将软管拉伸,同时用热空气(85℃)加热,以评价热拉伸性,并且按可能出现的粒状结构或气泡评价外观,再用4倍放大器证实。在图1中,粗线X为不低于TPU的Tg的温度下可拉伸150%或更多时的区域与不能进行这种拉伸的区域的分界线,而线X以上的区域为前者(可拉伸150%或更多),该线以下的区域为后者(不可拉伸150%或更多)。细线Y为表明不出现表面气泡的范围的分界线,界定出不良和良好外观,其中线Y以下的区域表明良好外观范围,而该线以上的区域表明不良外观范围。
如图1所示,由粗线X,细线Y和表明Ti的线Z界定出4个区域A-D。也就是说,区域A表明可拉伸150%或更多,但外观不良的范围;区域B表明不能拉伸150%或更多,但外观良好的范围;区域C表明可拉伸150%或更多且外观良好的范围;而区域D表明不能拉伸150%或更多并且外观亦不良的范围。
在表1所列温度(℃)和挤出压力(kg/cm)下制成TPU软管并如上述检测热拉伸性和外观。结果列在表1中,其中热拉伸项下的○指可以拉伸到150%或更多,而×指不可拉伸到150%或更多;外观项下的○指良好,而×指不良。除芯模温度和挤出压力之外的条件如上述。
从上述实施例可以清楚地看出,在落入可进行热拉伸的范围(A和C)及不会出现表面气泡的范围(B和C)重叠的区域(C)内的设定芯模温度和挤出压力下通过加压式挤出成形方法得到的TPU软管热拉伸性和外观均优异,其中所说范围已预先以芯模温度和TPU挤出压力为参数确定下来。
常规加压法和制管方法的优化条件狭窄并且重现性差。因此,各条件如芯模的导出速度及挤出压力的变化会导致热拉伸性不良或TPU软管外观不良,难于获得满足这两项要求的TPU软管。如上述实施例所示,与常规方法获得的区域相比,重叠区域(区域C)更大。而且,根据本发明,重现性更好,可连续生产具有稳定质量的成形产品并且该成形产品的产率得以提高。
按本发明的挤出成形方法生产软管可解决因出现气泡或粒状结构而带来的外观不良的问题并且可得到具有良好热拉伸性的TPU软管。本发明的优点还在于,重现性或重复性优异,可连续生产具有稳定质量的成形产品并且该成形产品产率高。
表
试验项目 | 评价项目 | |||
加热温度 | 挤出压力 | 热拉伸 | 外观 | |
实施例1 | 85 | 166 | ○ | ○ |
实施例2 | 90 | 186 | ○ | ○ |
实施例3 | 95 | 220 | ○ | ○ |
实施例4 | 110 | 215 | ○ | ○ |
实施例5 | 130 | 200 | ○ | ○ |
实施例6 | 140 | 200 | ○ | ○ |
比较例1 | 70 | 75 | ○ | × |
比较例2 | 110 | 131 | ○ | × |
比较例3 | 120 | 143 | ○ | × |
比较例4 | 40 | 135 | × | ○ |
比较例5 | 50 | 145 | × | ○ |
比较例6 | 70 | 140 | × | ○ |
比较例7 | 50 | 110 | × | × |
Claims (3)
1、热塑性聚氨酯弹性软管生产方法,其中包括
(a)在加热的芯模圆周面上加压挤出热塑性聚氨酯弹性体,
(b)将芯模拉出而形成预成形管,和
(c)将所得预成形管热拉伸而得到具有要求外径的软管,其中该芯模的温度和弹性体挤出压力落入可使预成形管进行热拉伸的范围与预成形管表面上不出现气泡的范围重叠的区域,所说两范围已预先以加热后芯模的温度和弹性体挤出压力作为参数确定下来。
2、权利要求1的方法,其中热塑性聚氨酯弹性体包括多元醇,增链剂和二异氰酸酯,其mol比为1:0.5-2:1.5-3。
3、权利要求2的方法,其中该mol比为1:0.8-1.5:1.8-2.5。
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FR2569114B1 (fr) * | 1984-08-20 | 1988-11-18 | Biotrol Sa Lab | Sonde d'injection a haut debit de produit de contraste pour examens radiologiques et son procede d'obtention |
DE3504671A1 (de) * | 1985-02-12 | 1986-08-14 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung matter, nichtblockender, duennwandiger formkoerper aus linearen, thermoplastischen, polyaddukt-haltigen polyurethanelastomeren und ihre verwendung |
JPS6253363A (ja) * | 1985-08-31 | 1987-03-09 | Toyoda Gosei Co Ltd | 燃料系ホ−ス |
US4898702A (en) * | 1988-04-04 | 1990-02-06 | Cordis Corporation | Method and apparatus for removal of a wire mandrel from a catheter |
JP2528943B2 (ja) * | 1988-07-01 | 1996-08-28 | 三井石油化学工業株式会社 | ゴムチュ―ブの製造方法およびそれに用いる樹脂被覆装置 |
JPH02198564A (ja) * | 1989-01-30 | 1990-08-07 | Ube Nitto Kasei Co Ltd | 医療用ポリウレンタンチューブ |
JP2671047B2 (ja) * | 1989-11-13 | 1997-10-29 | 横浜ゴム株式会社 | ホースの製造方法 |
US5063018A (en) * | 1990-06-04 | 1991-11-05 | Cordis Corporation | Extrusion method |
US5100379A (en) * | 1990-11-19 | 1992-03-31 | The Kendall Company | Microcatheter having improved tensile strength |
US5061424A (en) * | 1991-01-22 | 1991-10-29 | Becton, Dickinson And Company | Method for applying a lubricious coating to an article |
CA2107539A1 (en) * | 1992-10-02 | 1994-04-03 | Vas-Cath Incorporated | Catheters and method of manufacture |
-
1994
- 1994-11-18 TW TW83110712A patent/TW267971B/zh active
- 1994-11-19 EP EP19940118253 patent/EP0654284A1/en not_active Withdrawn
- 1994-11-21 CA CA 2136291 patent/CA2136291A1/en not_active Abandoned
- 1994-11-21 US US08/345,740 patent/US5498377A/en not_active Expired - Fee Related
- 1994-11-22 CN CN94113845A patent/CN1106743A/zh active Pending
- 1994-11-22 KR KR1019940030703A patent/KR950013700A/ko active IP Right Grant
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107636215A (zh) * | 2015-05-20 | 2018-01-26 | 巴斯夫欧洲公司 | 由tpu制得的非常细的管及其制备方法 |
CN107636215B (zh) * | 2015-05-20 | 2020-06-26 | 巴斯夫欧洲公司 | 由tpu制得的非常细的管及其制备方法 |
CN109954197A (zh) * | 2017-12-25 | 2019-07-02 | 先健科技(深圳)有限公司 | 球囊导管及其制备方法 |
CN109954197B (zh) * | 2017-12-25 | 2021-08-03 | 元心科技(深圳)有限公司 | 球囊导管及其制备方法 |
CN114025941A (zh) * | 2019-02-28 | 2022-02-08 | 爱彼爱彼欧创新公司 | 用于形成包含形状记忆聚合物的装置的方法和预制件 |
US12011869B2 (en) | 2019-02-28 | 2024-06-18 | Ip2Ipo Innovations Limited | Method and preform for forming a device comprising a shape memory polymer |
CN114025941B (zh) * | 2019-02-28 | 2024-07-30 | 爱彼爱彼欧创新公司 | 用于形成包含形状记忆聚合物的装置的方法和预制件 |
Also Published As
Publication number | Publication date |
---|---|
KR950013700A (ko) | 1995-06-15 |
CA2136291A1 (en) | 1995-05-23 |
TW267971B (zh) | 1996-01-11 |
EP0654284A1 (en) | 1995-05-24 |
US5498377A (en) | 1996-03-12 |
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