CN1073881A - 聚氨酯矫形绷带材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种用作骨科外固定的水固化型
聚氨酯矫形绷带材料及其制备方法,主要成分聚氨酯
预聚体中的稳定剂是马来酐,以及混合催化剂是α-
(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷和无水碳酸
钾。由于含有共轭双键的马来酐能吸附预聚体中微
量水分和水溶性碱性化合物并与异氰酸根生成的凝
胶基闭反应后呈酸性的马来酸衍生物,从而阻止了矫
形绷带材料在使用之前即贮存期间的早期固化现
象。
Description
本发明是涉及一种新的,不同以往的用作骨科矫正畸形固定折断的肢体和关节以及安静患部等塑形包扎的矫形绷带材料及其制备方法,该材料由稳定的水固化型聚氨酯予聚体涂复在网眼状合成纤维或玻璃纤维边链织物基材上制备而成,其特征在于聚氨酯予聚体中的稳定剂是马来酐,催化剂是α-(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷与无水碳酸钾的混合物。
近年来,美国专利4376438首先提出在织物上浸渍水固化型聚氨酯予聚体制成绷带材料以取代骨折治疗中的石膏绷带,这种绷带使用方法与石膏硼带相同,浸水后,即在病人肢体上包扎,水能使予聚体发生聚合即对病人起固化定形作用,由于,该绷带材料具有重量轻,强度大,透气性好,能抗水,X线能透过,使用方便等优点已被世界各国医疗卫生部门广泛应用。为了使绷带得到临床使用所要求在15分钟内迅速固化,必须在聚氨酯予聚体中掺入适当的催化剂。由于在予聚体中的催化剂存在以及绷带制备和包装过程中带入微量水份,导致绷带在使用之前,即贮存期间聚氨酯予聚体发生凝胶的付反应,而使绷带过早地固化以致不能使用。
为了阻止绷带材料早期固化现象,提高绷带的贮存稳定性,美国专利4433680和4644280、中国专利89103603,2提出在聚氨酯予聚体中掺入苯甲酰氯作为稳定剂,但是,苯甲酰氯是一种腐蚀性很大,又极易分解液体,即使加入量很少,也会使绷带材料带有刺激性气味,作为医用材料难以被医务人员接受。
美国专利4427002提出无机酸如磷酸为稳定剂,但是磷酸掺和在予聚体中极易分解呈红色磷酸盐,这样,就起不到稳定作用。
美国专利4574793,中国专利90102934,3,提出在聚氨酯予聚体中加入少量甲基磺酸作为稳定剂,然后,甲基磺酸是一种强酸,在制备聚氨酯予聚体过程,一旦混入即迅速与聚醚中的OH基团结合,而降低予聚体的稳定性。
PCT/GB8700716(WO88/02636)提出有机酸酐如丁二酸酐作为稳定剂,在制备聚氨酯予聚体过程中加入能起稳定作用。但是,丁二酸酐是以磨成(75μm细颗粒固体形式掺入予聚体中。由于,不能完全充分混和而影响了予聚体的稳定效果。
本发明提出含有共轭双键的马来酐作为稳定剂,因为,马来酐能吸附在予聚体中的微量水份和水溶性的碱性基团,并与予聚体中少量异氰酸根生成的凝胶基团相互反应后呈酸性的马来酸衍生物,予聚体材料在这样的酸性环境中,有效地阻止了矫形绷带材料使用之前,即贮存期间的早期固化现象,由于,马来酐能溶于丙酮、氯仿、乙醚等有机溶剂中,聚氨酯予聚体制备过程中,马来酐以溶液形式均匀分散在予聚体中,充分地显示对予聚体的稳定作用,克服了其它稳定剂存在的缺点,显著地提高了矫形绷带的贮存稳定性。
马来酐稳定剂的含量为聚氨酯予聚体的0.1-5.0%,推荐的含量为0.5-2.0%。
本发明所用的混合催化剂包括液相和固相二部分,其中液相催化剂是由二氯二乙氧基乙烷与吗啉合成制取的一种新的双吗啉结构化合物,即α-(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷,合成反应式如下:
分子式:G4H28N2O4
分子量:288
沸程:145-150℃/1-2mHg
性能:无色、无味、无毒,不挥发的透明粘稠液体,易溶于水和苯、甲苯、丙酮、氯仿、乙酸乙酯、乙醚等有机溶剂。
采用这一种双吗啉结构化合物作为聚氨酯予聚体的催化剂,由此而引起的付反应形成速率较以往所用其它叔胺类催化剂要低得多,在确保临床所需固化时间的前提下,绷带的贮存稳定性有明显的提高。
其含量为聚氨酯予聚体总重量的0.1-10.0%,推荐含量为0.5-2.0%。
其中固相催化剂是无水碳酸钾,并磨成小於100μm微细颗粒分散聚酯予聚体中。由于,该化合物不溶于聚氨酯予聚体,使用前在予聚体中十分稳定,使用时,绷带一旦遇水,碳酸钾立即溶于水中成为碱性催化溶液,使绷带迅速固化。
无水碳酸钾的含量为聚氨酯聚体总重量的1-10%,推荐含量为4-6%。
本发明的聚氨酯予聚体中的芳香族异氰酸酯可以是聚氨酯化学中阐述的任何一种芳香族异氰酸酯,例如Interscience出版社,1962年出版的《聚氨酯化学和工艺学》一书中阐述的化合物
芳香族异氰酸酯包括甲苯二异氰酸酯(TDI)、二苯甲烷二异氰酸酯(MDI)或含碳化二亚胺基团的改性液MDI。
本发明中的聚氨酯予聚体中的多羟基化合物为二羟基聚醚或二羟醚与三羟基聚醚的混合物,其分子量从500至1500。聚氨酯予聚体中的NCO∶OH为3∶1至9∶1,NCo含量在10~15%。
本发明所涉及的聚氨酯矫形绷带的制备方法是在一严格控制的低湿度干燥N2环境中,系统中含水量小于100PPm,经过送布、涂复、收卷、剪切、封口等工序,在适当温度下,定量的聚氨酯予聚体涂复在基材上。然后,在N2保护下密封于铝-塑复合袋内,予聚体涂复量,如:4″宽绷带16~20克/米2,低湿度干燥N2系统包括:空气压缩机,深冷分离器,干燥塔,再生塔等以及成套自动仪表,监测仪器等,将空气深压缩分离为含量为99.999%纯N2,再经深度干燥后N2中含水量达到100PPm以下。
本发明的矫形绷带材料采用具有良好透气性的基材为含有气孔的合成纤维或玻璃纤维网眼状边链织物,采用边链衬纬1×3编织法,宽度为2″(5.0公分)、3″(7.5分公)4″(10.0公分)、5″(12.5公分)4种,每平方厘米含网眼孔15~30个,厚度为0.01~0.05厘米。
绷带的包装材料直接影响其贮存稳定性问题,本发明的矫形绷带材料使用PET/AL/LDPE.EVA多层共挤铝塑复合三边封软包装袋,这种复合包装袋具有金属容器保藏长久的特点,它同时具有构成复合材料的各层薄膜优点,如:气密性高,防潮性和耐腐性良好,还能耐高温、高压,特别适用矫形绷带材料长期贮存的包装袋。
矫形绷带的贮存期是反映聚氨酯予聚体稳定性的重要指标,它的稳定性通常依赖于其化学结构和链的离解能,由于,聚氨酯予聚体不是单一的均聚物,所以,提高贮存温度实际上是提高链的离解能,促进热反应加速固化,热老化快速试验方法是评定聚氨酯材料的稳定性,使用期和贮存期的有效评定方法,但是,至今国际上尚未有一个统一的标准试验方法,所以试验温度和条件相差甚大,通常选择试验温度比实际工作温度高出20~40℃,本发明的聚氨酯绷带热老化试验温度选在40℃,在这一温度条件下存放124天不固化,相当于室温20℃中,可贮存二年。
下面给出本发明的实施例:
一、聚氨酯予聚体的制备:
配方:
二羟基聚醚Pluracol 710,OH=150,6410克
液体MDI Lupranate MM-103,3580克
MCO=OH=4.2∶1
消泡硅油 20克
马来酐 100克
α-(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷80克
无水碳酸钾 500克
在分别装有温度计,搅拌器,加液器和N2进口的10立升反应器中,按配方先加入二羟基聚醚、消泡硅油和马来酐丙酮溶液予混均匀,然后加热升温至55℃,在30分钟内滴加液体MD1,控制温度在60℃,反应1.5小时后,加入混合催化剂α-(吗啉代乙氧基-乙氧基-β-吗啉代乙烷和<100μm的无水碳酸钾,充分搅拌混和10分钟,冷却至40℃在N2保护下出料放入容器内待用,予聚体的特性粘度50℃时为2500厘泊,NCO含量13.9%。
二、聚氨酯矫形绷带的制备:
取5000克上述制备的聚氨酯予聚体加热至50℃,在含水量50PPm低湿度干燥N2环境下,采用双辊筒涂复法,经过送布、涂复、收卷、剪切、封口等工序,将予聚体涂复在网眼涤纶基材上,然后热封装入铝塑复合袋内,每卷4英寸宽,3.6米长,涂复量18克/米,透气率:8层绷带:510公升/公尺/秒,压缩强度:Instron 1122型试验机,试验机速度:100mm/min,8层绷带:160N,绷带在室温20℃的水中浸五天后强度不变,开封后启用的绷带在25℃水中浸15秒后,缠绕在病人患部,固化时间为8分钟。绷带材料放入40℃条件下加速热老化试验,贮存192天仍未固化,相当于在室温20℃中,可贮存三年以上。
Claims (8)
1、一种用作骨科矫正畸形固定折断的肢体和关节以及安静患部等塑形包扎的聚氨酯矫形绷带材料,由稳定的水固化型聚氨酯予聚体涂复在网眼状合成纤维或玻璃纤维边链织物基材上制备而成,其特征在于聚氨酯予聚体中的稳定剂是马来酐,催化剂是α-(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷与无水碳酸钾的混合物。
4、根据权利要求一所述的聚氨酯矫形绷带材料,其特征在于含有马来酐稳定剂的聚氨酯予聚体中所述的芳香族异氰酸酯是含碳化二亚胺的二苯基甲烷二异氰酸酯,所述的多羟基化合物是二羟基聚醚或二羟基聚醚与三羟基聚醚的混合物,NCO和OH之当量比为3∶1至6∶1。
5、一种聚氨酯矫形绷带材料的制备方法,其特征在于是在含有气孔的网眼合成纤维或玻璃纤维边链织物基材上涂复含有马来酐稳定剂与α-(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷和无水碳酸钾混合催化剂的聚氨酯予聚体而成。
6、根据权利要求五所述的聚氨酯矫形绷带材料制备方法其特征在于在一严格控制的低湿度(含水量 小於100PPm)干燥N2环境中经过送布、涂复、收卷、剪切、封口等工序制备而成。
7、根据权利要求五所述的聚氨酯矫形绷带材料制备方法,其特征在于矫形绷带基材为合成纤维或玻璃纤维网眼状边链织物,每平方厘米含网眼15~30个,厚度为0.01~0.05厘米。
8、根据权利要求五所述的聚氨酯矫形绷带材料制备方法,其特征在于制成的绷带材料装入充有干燥N2密封防潮的由多层共挤塑料薄膜与铝泊复合制成的三边封软包装袋内。
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CN92108533A CN1051717C (zh) | 1992-08-14 | 1992-08-14 | 聚氨酯矫形绷带材料 |
JP5201507A JPH08154966A (ja) | 1992-08-14 | 1993-08-13 | ポリウレタン整形用包帯材料およびその調製方法 |
FR9310101A FR2694695B1 (fr) | 1992-08-14 | 1993-08-13 | Matière de bandage orthopédique en polyuréthane et son procédé de préparation. |
US08/106,337 US5455294A (en) | 1992-08-14 | 1993-08-13 | Polyurethane orthopedic cast material and the method of its preparation |
DE4327498A DE4327498A1 (de) | 1992-08-14 | 1993-08-16 | Orthopädisches Polyurethan-Verbandsmaterial und sein Herstellungsverfahren |
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CN92108533A CN1051717C (zh) | 1992-08-14 | 1992-08-14 | 聚氨酯矫形绷带材料 |
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CN1051717C CN1051717C (zh) | 2000-04-26 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1065440C (zh) * | 1996-01-22 | 2001-05-09 | 益多实业股份有限公司 | 水固化聚氨酯矫形绷带 |
CN1310993C (zh) * | 2002-04-09 | 2007-04-18 | 拉克西米·C·古普塔 | 水可固化聚氨酯组合物及其用途 |
CN108245295A (zh) * | 2016-12-28 | 2018-07-06 | 北京航空航天大学 | 拇外翻术后矫形固定护具 |
CN112626873A (zh) * | 2020-11-12 | 2021-04-09 | 南京伯纳德防护用品有限公司 | 一种玻璃纤维经编医用绷带 |
CN115369564A (zh) * | 2022-08-29 | 2022-11-22 | 江苏华宜医用新材料有限公司 | 一种玻璃纤维经编医用绷带 |
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JPH07163649A (ja) * | 1993-11-10 | 1995-06-27 | Arukea Kk | 水硬化性固定材 |
EP0735067B1 (en) * | 1995-03-31 | 2001-05-16 | Huntsman Corporation | Dimorpholinodiethylether having improved isocyanate stability |
DK0812866T3 (da) * | 1996-06-12 | 2004-02-23 | Sika Schweiz Ag | Lagerstabil fugtighedshærdende klæbestofmasse |
US5894032A (en) * | 1997-05-20 | 1999-04-13 | Green; Richard | Process for the manufacture of printed orthopedic casting tape |
DE19905799A1 (de) * | 1999-02-12 | 2000-08-17 | Lohmann Gmbh & Co Kg | Reaktionsmaterial und Verfahren zum Verhindern einer vollständigen Aushärtung von mit Polyurethanprepolymer imprägniertem Bindenmaterial sowie dessen Verwendung |
DE10033210B4 (de) * | 2000-07-07 | 2013-03-07 | Lohmann & Rauscher Gmbh & Co. Kg | Material zur Herstellung eines Stützverbandes und Verfahren zur Herstellung des Materials |
US6695801B1 (en) | 2001-12-14 | 2004-02-24 | Russ Toronto | Form-in-place foam orthopedic splint system |
US7718442B2 (en) * | 2002-11-22 | 2010-05-18 | Genvault Corporation | Sealed sample storage element system and method |
US7148287B2 (en) * | 2003-05-15 | 2006-12-12 | Gupta Laxmi C | Water curable polyurethane compositions with improved viscosity characteristics |
US7179242B2 (en) | 2003-08-01 | 2007-02-20 | Belzidsky Hugues C | Method of treating deep vein thrombosis |
WO2013074072A1 (en) | 2011-11-14 | 2013-05-23 | Empire Technology Development Llc | Composite and methods of making and using the same |
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US4427002A (en) * | 1981-11-18 | 1984-01-24 | Hexcel Corporation | Cold water curable orthopedic cast |
US4433680A (en) * | 1982-02-10 | 1984-02-28 | Johnson & Johnson Products, Inc. | Polyurethane casting material |
US4574793A (en) * | 1984-08-21 | 1986-03-11 | Hexcel Corporation | Stabilized, catalyzed water activated polyurethane systems |
US4644280A (en) * | 1984-09-20 | 1987-02-17 | Elscint Ltd. | Magnetic resonance image zooming |
US4968542A (en) * | 1986-09-03 | 1990-11-06 | Minnesota Mining And Manufacturing Company | Curable material for semi-rigid resilient orthopedic support |
US4888225A (en) * | 1985-10-04 | 1989-12-19 | Minnesota Mining And Manufacturing Company | Resin-impregnated foam materials and methods |
US5042464A (en) * | 1985-10-04 | 1991-08-27 | Minnesota Mining And Manufacturing Company | Off-the shelf custom knee brace |
US4705840A (en) * | 1985-10-04 | 1987-11-10 | Minnesota Mining And Manufacturing Company | Catalysts for the curing of a water-curable isocyanate-functional prepolymer |
US4683877A (en) * | 1985-10-04 | 1987-08-04 | Minnesota Mining And Manufacturing Company | Orthopedic casting article and method |
US4655208A (en) * | 1986-03-12 | 1987-04-07 | Johnson & Johnson Products Inc. | Fast-setting casting tape |
US5007418A (en) * | 1986-09-03 | 1991-04-16 | Minnesota Mining And Manufacturing Company | Resilient semi-rigid orthopedic support devices |
US4893617A (en) * | 1986-09-03 | 1990-01-16 | Minnesota Mining And Manufacturing Company | Resilient semi-rigid orthopedic support devices |
GB8624645D0 (en) * | 1986-10-14 | 1986-11-19 | Smith & Nephew Ass | Bandages |
US5005566A (en) * | 1987-01-15 | 1991-04-09 | Carapace, Incorporated | Water-activated orthopedic cast composition having colorant |
US4841958A (en) * | 1987-05-05 | 1989-06-27 | Minnesota Mining And Manufacturing Company | Nonwoven orthopedic casting materials with apertures |
US4856502A (en) * | 1987-05-05 | 1989-08-15 | Minnesota Mining And Manufacturing Company | Curable resin coated sheets having reduced tack |
JP2606803B2 (ja) * | 1988-09-07 | 1997-05-07 | アルケア株式会社 | 整形外科用キヤステイングテープ |
JPH02202215A (ja) * | 1989-01-31 | 1990-08-10 | Suzuki Motor Co Ltd | ラジオ受信機 |
US5027873A (en) * | 1989-03-09 | 1991-07-02 | Anselm Kenneth R | Balancing of tooling for a wood lathe |
JPH02255551A (ja) * | 1989-03-30 | 1990-10-16 | Hitachi Cable Ltd | 紫外線硬化樹脂被覆光ファイバの製造方法 |
US5052380A (en) * | 1989-07-07 | 1991-10-01 | Minnesota Mining And Manufacturing Company | Colored orthopedic resins and orthopedic casting materials incorporating same |
WO1991009909A1 (en) * | 1989-12-27 | 1991-07-11 | Polysar Financial Services S.A. | Polymeric composition having orthopedic utility |
CN1053891A (zh) * | 1990-09-15 | 1991-08-21 | 李海晟 | 稳定催化水活性聚氨酯绷带 |
US5342291A (en) * | 1991-08-29 | 1994-08-30 | Minnesota Mining And Manufacturing Company | Printed woven fiber materials and method |
-
1992
- 1992-08-14 CN CN92108533A patent/CN1051717C/zh not_active Expired - Fee Related
-
1993
- 1993-08-13 FR FR9310101A patent/FR2694695B1/fr not_active Expired - Fee Related
- 1993-08-13 US US08/106,337 patent/US5455294A/en not_active Expired - Fee Related
- 1993-08-13 JP JP5201507A patent/JPH08154966A/ja active Pending
- 1993-08-16 DE DE4327498A patent/DE4327498A1/de not_active Withdrawn
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1065440C (zh) * | 1996-01-22 | 2001-05-09 | 益多实业股份有限公司 | 水固化聚氨酯矫形绷带 |
CN1310993C (zh) * | 2002-04-09 | 2007-04-18 | 拉克西米·C·古普塔 | 水可固化聚氨酯组合物及其用途 |
CN108245295A (zh) * | 2016-12-28 | 2018-07-06 | 北京航空航天大学 | 拇外翻术后矫形固定护具 |
CN108245295B (zh) * | 2016-12-28 | 2021-01-01 | 北京航空航天大学 | 拇外翻术后矫形固定护具 |
CN112626873A (zh) * | 2020-11-12 | 2021-04-09 | 南京伯纳德防护用品有限公司 | 一种玻璃纤维经编医用绷带 |
CN115369564A (zh) * | 2022-08-29 | 2022-11-22 | 江苏华宜医用新材料有限公司 | 一种玻璃纤维经编医用绷带 |
Also Published As
Publication number | Publication date |
---|---|
CN1051717C (zh) | 2000-04-26 |
FR2694695A1 (fr) | 1994-02-18 |
US5455294A (en) | 1995-10-03 |
FR2694695B1 (fr) | 1995-04-14 |
JPH08154966A (ja) | 1996-06-18 |
DE4327498A1 (de) | 1994-02-24 |
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