CN103797042B - 用于制备亲水性纤维的热塑性聚氨酯 - Google Patents
用于制备亲水性纤维的热塑性聚氨酯 Download PDFInfo
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- CN103797042B CN103797042B CN201280045341.XA CN201280045341A CN103797042B CN 103797042 B CN103797042 B CN 103797042B CN 201280045341 A CN201280045341 A CN 201280045341A CN 103797042 B CN103797042 B CN 103797042B
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- isocyanates
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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- 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
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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Abstract
本发明涉及通过使至少下面的组分反应可获得的热塑性聚氨酯:具有两个异氰酸酯基团的异氰酸酯;结构(HO‑(CH2‑CH2‑O)x‑H)的第一聚(乙二醇)聚醚二醇,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn为≥6000且≤16000 g/mol;结构(HO‑(CH2‑CH2‑O)x‑H)的第二聚(乙二醇)聚醚二醇,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn等于所述第一聚(乙二醇)聚醚二醇B1)的数均分子量Mn的最多80%;扩链剂,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn为≥60且<600g/mol;任选的催化剂和任选的助剂和添加剂,其中所述异氰酸酯A)与所述聚(乙二醇)聚醚二醇B1)和B2)的当量比为1.5:1.0‑10.0:1.0并且NCO指数为90‑105,所述指数由异氰酸酯基团与对异氰酸酯呈反应活性的基团的总数的当量比之商乘以100而形成。本发明进一步涉及一种制备根据本发明的热塑性聚氨酯的方法和涉及按照本发明的方法可得到的热塑性聚氨酯。
Description
本发明涉及特别是可用于制备亲水性纤维的热塑性聚氨酯。本发明进一步提供了制备本发明的热塑性聚氨酯的方法以及通过本发明的方法可获得的热塑性聚氨酯。
热塑性聚氨酯(TPU)由于其良好的弹性性能和热塑性可加工性而具有重要的技术和工业意义。例如Kunststoff Handbuch [G. Becker, D. Braun], 卷7 "Polyurethanes", Munich, Vienna, Carl Hanser Verlag, 1983中对TPU制备、性能和应用进行了综述。
TPU通常由线性多元醇(大分子二醇),如聚酯二醇、聚醚二醇或聚碳酸酯二醇,有机二异氰酸酯和短链的、通常是二官能的醇(扩链剂)构成。它们可以以连续的方式或以间歇的方式制成。最为人所知的制备方法是带式法(GB-A 1 057 018)和挤出机法(DE-A 1964 834)。
热塑性可加工的聚氨酯弹性体可以分步(预聚体加料法)或通过所有组分在一个阶段中同时反应(一步加料法)构成。
WO 2004/044028A公开了含有聚乙二醇作为结构单元的热塑性聚氨酯。所述文献还描述了使用这些热塑性聚氨酯制备纤维。这些特征在于高的水蒸气通透性,但是不能吸收水。相反,它们构成对液体水的屏障,这在该申请中也另外明确描述为要解决的问题。
为了制造伤口敷料,纤维必须能够吸水而溶胀并由此形成凝胶。这样不仅能够从伤口除去过量的流体而且能够产生对伤口恢复有利的潮湿的伤口环境。这里一个重要的要求是所述纤维在发生吸水之后应当保留足够的机械稳定性,因为否则的话例如部分所述纤维可能遗留在伤口中。
因此本发明解决的问题是提供热塑性聚氨酯,所述聚氨酯适合于制备亲水性纤维,所述纤维吸水可溶胀且即使在溶胀状态也具有足够的机械稳定性。
这个问题通过使至少下面的组分反应可获得的热塑性聚氨酯得以解决:
A) 具有两个异氰酸酯基团的异氰酸酯,
B1) 结构(HO-(CH2-CH2-O)x-H)的第一聚(乙二醇)聚醚二醇,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn为≥ 6000且≤ 16000 g/mol,
B2) 结构(HO-(CH2-CH2-O)x-H)的第二聚(乙二醇)聚醚二醇,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn等于所述第一聚(乙二醇)聚醚二醇B1)的数均分子量Mn的10-80%,
C) 扩链剂,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn为≥ 60且< 600 g/mol,
D) 任选的催化剂,和
E) 任选的助剂和添加剂,
其特征在于:所述扩链剂C)是至少一种选自下组的化合物:乙二醇、1,6-己二醇、1,4-丁二醇、1,12-十二烷二醇、异佛尔酮二胺、乙二胺、1,2-丙二胺、1,3-丙二胺、N-甲基丙-1,3-二胺、N,N'-二甲基乙二胺、对苯二甲酸-双乙二醇、对苯二甲酸-双-1,4-丁二醇、1,4-二(-羟乙基)氢醌,优选乙二醇、1,6-己二醇、1,4-丁二醇、1,12-十二烷二醇和更优选1,4-丁二醇,并且
其中所述异氰酸酯A)与所述聚(乙二醇)聚醚二醇B1)和B2)的当量比为1.5:1.0-10.0:1.0并且NCO指数为90-105,所述指数由异氰酸酯基团与对异氰酸酯呈反应活性的基团的总数的当量比之商乘以100而形成。
已经清楚的是本发明的所述热塑性聚氨酯可用于制备亲水性纤维,所述纤维能够通过胶凝作用吸水并且在溶胀状态具有足够的机械稳定性。
本文中对异氰酸酯呈反应活性的基团特别是羟基和伯/仲氨基。
在本发明优选的实施方案中,NCO指数为92-104,优选为95-102,并更优选为97-100。
发明内容
异氰酸酯A)
作为异氰酸酯A)可以使用例如脂族、环脂族、芳脂族、杂环和芳族二异氰酸酯,例如如Justus Liebigs Annalen der Chemie, 562, 75-136页中所描述。
异氰酸酯A)的实例是二异氰酸亚乙酯,1,4-四亚甲基二异氰酸酯,1,12-十二烷二异氰酸酯,1,6-六亚甲基二异氰酸酯;环脂族二异氰酸酯,如异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、1-甲基-2,4- 和2,6-环己烷二异氰酸酯以及相应的异构体混合物,4,4'-、2,4'-和2,2'-二环己基甲烷二异氰酸酯以及相应的异构体混合物和芳族二异氰酸酯,如2,4'-甲苯二异氰酸酯、2,4-和2,6-甲苯二异氰酸酯的混合物,4,4'-二苯基甲烷二异氰酸酯,2,4-二苯基甲烷二异氰酸酯和2,2'-二苯基甲烷二异氰酸酯,2,4'-二苯基甲烷二异氰酸酯和4,4'-二苯基甲烷二异氰酸酯的混合物;氨基甲酸酯改性的液体4,4'-二苯基甲烷二异氰酸酯和/或2,4'-二苯基甲烷二异氰酸酯,4,4'-二异氰酸根合二苯基-乙烷-1,2和1,5-亚萘基二异氰酸酯。
然而,使用脂族和/或环脂族二异氰酸酯是优选的。
因此特别优选使用选自下组的一种或多种化合物作为异氰酸酯A):1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和二环己基甲烷二异氰酸酯。
然而非常特别优选仅仅使用1,6-六亚甲基二异氰酸酯。
聚乙二醇B1)和B2)
聚(乙二醇)聚醚二醇 B1)和B2)是以常规的方式通过用环氧乙烷将适合的二官能起始分子烷氧基化可获得的化合物(例如Ullmanns Encyclopädie der technischenChemie, 第4版,第19卷,Verlag Chemie, Weinheim 第31-38页中所描述)。除了环氧乙烷,还可使用另外的环氧化物例如环氧丙烷或环氧丁烷用于制备聚(乙二醇)聚醚二醇,在该情况下这些组分的质量分数基于各自的聚乙二醇计优选小于30重量%,更优选小于15重量%并更优选小于5重量%。在非常特别优选的实施方案中,除了环氧乙烷之外不使用另外的环氧化物。作为起始分子可以使用二醇例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇、新戊二醇、1,4-双羟甲基环己烷、2-甲基-1,3-丙二醇、2,2,4-三甲基戊烷-1,3-二醇、二-、三-或四乙二醇、双丙二醇、二丁二醇、聚丁二醇或双酚A。
在另外的有利实施方案中,所述第一聚(乙二醇)聚醚二醇B1)具有的数均分子量Mn为6000-12000 g/mol,优选6000-10000 g/mol,更优选6000-8000 g/mol和最优选8000g/mol。
在另外的有利实施方案中,所述第二聚(乙二醇)聚醚二醇B2)具有的数均分子量Mn为600-4000 g/mol,优选1000-3000 g/mol,更优选1800-2200 g/mol和最优选2000 g/mol。
在同样优选的实施方案中,所述第二聚(乙二醇)聚醚二醇B2)的数均分子量Mn等于所述第一聚(乙二醇)聚醚二醇B1)的数均分子量Mn的10-70%,优选15-50%和更优选15-33%。
在类似地有利的实施方案中,所述第一聚(乙二醇)聚醚二醇B1)与所述第二聚(乙二醇)聚醚二醇B2)的重量比为 1-30,优选5-25和最优选为10-20。
除B)之外还存在的具有的数均分子量Mn为600-16000 g/mol的二醇的含量为低于20重量%,优选低于10重量%并最优选低于5重量%,基于总的聚氨酯质量计。
在特别优选的实施方案中,除所述聚(乙二醇)聚醚二醇B1)和B2)之外没有数均分子量Mn≥ 600且≤ 16000 g/mol的另外的二醇共反应。
在优选的实施方案中,在反应前,例如在减压下,例如在1-800mbar下,和升高的温度,例如在70-150℃下干燥所述聚(乙二醇)聚醚二醇B1)和B2);这样达到了减少痕量存在的水。
扩链剂C)
作为扩链剂C)特别可以使用脂族二醇或(环)脂族二胺。适合的脂族二醇的实例是具有2-14个碳原子的脂族二醇如乙二醇、1,6-己二醇、1,12-十二烷二醇和特别是1,4-丁二醇。所述(环)脂族二胺可以特别地是异佛尔酮二胺、乙二胺、1,2-丙二胺、1,3-丙二胺、N-甲基-丙-1,3-二胺、N,N'-二甲基乙二胺。也可以使用上面提到的扩链剂的混合物。除此之外也可以添加少量三醇。
然而,所述扩链剂C)优选为至少一种选自下组的化合物:乙二醇、1,6-己二醇、1,4-丁二醇、1,12-十二烷二醇、异佛尔酮二胺、乙二胺、1,2-丙二胺、1,3-丙二胺、N-甲基-丙-1,3-二胺、N,N'-二甲基乙二胺,更优选乙二醇、1,6-己二醇、1,12-十二烷二醇或1,4-丁二醇并最优选1,4-丁二醇。
然而,在非常特别优选的实施方案中,只使用1,4-丁二醇作为组分C)。
尤其对于具有相当低的光稳定性要求的应用也可使用芳族二醇和二胺。适合的芳族二醇的实例是对苯二甲酸与具有2-4个碳原子的二醇的二酯,例如对苯二甲酸-双乙二醇或对苯二甲酸-双-1,4-丁二醇、氢醌的羟基亚烷基醚,例如1,4-二(-羟乙基)氢醌和乙氧基化的双酚类。适合的芳族二胺的实例是2,4-甲苯二胺和2,6-甲苯二胺、3,5-二乙基-2,4-甲苯二胺和3,5-二乙基-2,6-甲苯二胺和主要是单-、二-、三-或四烷基-取代的4,4'-二氨基二苯基甲烷。
催化剂D)
适合的催化剂D)是现有技术中已知的和常用的叔胺,例如三乙胺、二甲基环己胺、N-甲基吗啉、N,N'-二甲基哌嗪、2-(二甲基氨基乙氧基)乙醇、二氮杂双环[2.2.2]辛烷等,以及特定的有机金属化合物如钛酸酯、铁化合物或锡化合物如二乙酸锡、二辛酸锡、二月桂酸锡或脂族羧酸的二烷基锡盐如二乙酸二丁基锡或二月桂酸二丁基锡等。优选的催化剂是有机金属化合物,特别是钛酸酯和铁、锡、锆和铋化合物。
本发明的TPU中的催化剂总量基于TPU的总量计优选为0-5重量%,更优选为0-2重量%和甚至更优选为0.01-0.5重量%。也可添加酸组分以调节催化效应和用于稳定作用。
助剂和添加剂E)
可以存在TPU化学中常用的助剂和添加剂E)。典型的助剂和添加剂是润滑剂和脱模剂,如脂肪酸酯、它们的金属皂、脂肪酸酰胺、脂肪酸酯酰胺和硅酮化合物,增塑剂,防粘连剂,抑制剂,抵抗水解、热和褪色的稳定剂,染料,颜料,杀生物活性物质以及无机和/有机填料和它们的混合物。
在技术文献,例如J. H. Saunders, K. C. Frisch: “High Polymers”, 卷XVI,Polyurethanes,部分1和2, Interscience Publishers 1962和1964中分别可找到关于所述助剂和添加剂的进一步说明。
优选使用的抗氧化剂是具有酚结构单元的常见添加剂,如例如R. Gächter, H. Müller (Ed.): Taschenbuch der Kunststoff-Additive, 第3版,Hanser Verlag, Munich1989中所描述。
作为可能的光稳定剂可以使用UV稳定剂、抗氧化剂和/或HALS化合物。在例如H.Zweifel, Plastics Additives Handbook, 2001, 5th Ed., Carl Hanser Verlag,Munich中可找到进一步说明。
典型地,基于TPU的总量计加入最多10重量%的常用助剂和添加剂E)。
本发明进一步提供了一种制备根据本发明的热塑性聚氨酯的方法,其中制备所述聚(乙二醇)聚醚二醇B1)、B2)与所述扩链剂C)的混合物I)并将所述混合物I)与所述异氰酸酯A)充分混合。
在根据本发明的方法的优选实施方案中,所述混合物I)与所述异氰酸酯A)在最多5秒内均匀地混合,其中所述混合物I)的温度和所述异氰酸酯A)的温度在所述混合之前为≥ 60且≤ 150℃并且温差≤ 50℃并优选≤ 20℃。
在同样优选的实施方案中,所述混合物I)与所述异氰酸酯A)在具有的长/径比为8:1-16:1的静态混合机中混合。
得到的热塑性聚氨酯也可任选地在另外的步骤中造粒。
本发明进一步提供了一种连续制备根据本发明的热塑性聚氨酯的方法,所述方法特征在于以连续方式混合所述混合物I)和扩链剂C),然后使其与异氰酸酯A)反应,反应在排料容器中完成并将产物任选地造粒。此形式的方法是特别优选的。
本发明的热塑性聚氨酯也可通过预聚物法获得,在所述情况下在开始步骤中异氰酸酯A)与聚(乙二醇)聚醚二醇B1)和B2)反应形成预聚物并在第二步中将此预聚物与扩链剂C)混合和反应。
本发明的TPU可以用于制备纤维或成形体,用于制备挤出体(例如膜片)和注塑部件。优选纤维的制备,所述纤维可以进一步加工成纺织物、编织物或粘结和未粘结的非织造织物。每种制备和加工的方法与技术是本领域技术人员已知的。
现在通过实施例进一步描述本发明。
实施例
除非另外说明,所有的用量、比例和百分比都是基于重量和总量计或者基于组合物的总重量计。
除非另外说明,所有的分析测量值都是在23℃的温度下的测量值。
用具有单螺杆(18 x 520 mm)的挤出机测试可纺性,所述螺杆带有混合区和具有2-24个孔的喷丝头。调节挤出速率使得在挤出机中的停留时间为大约10分钟,并且第一恒温区的温度为85℃和喷丝头的上游区域的温度为120-210℃。所述纤维用卷绕机收起。
方法:
除非另外明确提到,NCO含量根据DIN-EN ISO 11909体积法测定。
对游离NCO基团的检查用IR光谱(在2260 cm-1谱带处)进行。
数均分子量Mn通过凝胶渗透色谱法以聚苯乙烯为标准在四氢呋喃中在23℃下测定。
材料:
使用的异氰酸酯来自于德国 Leverkusen的Bayer MaterialScience AG。
除非另外说明,另外的化学品来自德国Taufkirchen的Sigma-Aldrich ChemieGmbH。
溶液A
将8.298 g氯化钠和0.368 g氯化钙溶解在1升去离子水中。
聚(乙二醇)聚醚二醇
PEG 8000:聚乙二醇,数均分子量Mn 8000 g/mol
PEG 6000:聚乙二醇,数均分子量Mn 6000 g/mol
PEG 4000:聚乙二醇,数均分子量Mn 4000 g/mol
PEG 2000:聚乙二醇,数均分子量Mn 2000 g/mol
PEG 1000:聚乙二醇,数均分子量Mn 1000 g/mol。
热塑性聚氨酯的制备
实施例1(本发明实施例):
547 g PEG 8000和34.7 g PEG 2000的混合物在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与0.34 g磷酸二丁酯和9.6 g1,12-十二烷二醇混合。加热到120℃之后,加入34.9 g 亚甲基双(4-环己基异氰酸酯)和0.34 g 乙基己酸锡(II)并加热容器直到温度已达到196℃(大约20分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
实施例2(本发明实施例):
530.5 g PEG 8000和33.6 g PEG 2000的混合物在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与0.66 g磷酸二丁酯和6.27 g 1,4-丁二醇混合。加热到120℃之后,加入41.1 g 亚甲基双(4-环己基异氰酸酯)和0.34 g Borchikat 24 (OMG Borchers GmbH, Langenfeld/德国)并加热容器直到温度已达到196℃(大约15分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
实施例3(本发明实施例):
526.1 g PEG 8000、33.4 g PEG 2000和16.74 g氢醌双(2-羟乙基)醚的混合物在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与0.3 g磷酸二丁酯混合。加热到110℃之后,加入26.9 g 1,6-六亚甲基二异氰酸酯和0.34 g 乙基己酸锡(II)并加热容器直到温度已达到180℃(大约5分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
实施例4(本发明实施例):
549.7 g PEG 8000和34.8 g PEG 2000的混合物在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与1.88 g磷酸二丁酯和6.5g 1,4-丁二醇混合。加热到165℃之后,加入38.08 g 4,4-二苯基甲烷二异氰酸酯并加热容器直到温度已达到196℃(大约5分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
实施例5(本发明实施例):
549.7 g PEG 8000和44.7 g PEG 1000的混合物在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与0.30 g磷酸二丁酯和15.2 g 1,4-丁二醇以及0.30 g 乙基己酸锡(II)混合。加热到110℃之后,加入45.8 g 1,6-六亚甲基二异氰酸酯并加热容器直到温度已达到160℃(大约4分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
实施例6(对比例):
575.4 g PEG 8000在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与0.30 g磷酸二丁酯和12.4 g 1,4-丁二醇以及0.30g 乙基己酸锡(II)混合。加热到110℃之后,加入35.1 g 1,6-六亚甲基二异氰酸酯并加热容器直到温度已达到160℃(大约6分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
实施例7(对比例):
528.0 g PEG 2000在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与0.38 g磷酸二丁酯和24.1 g 1,4-丁二醇以及0.38g 乙基己酸锡(II)混合。加热到110℃之后,加入87.0 g 1,6-六亚甲基二异氰酸酯并加热容器直到温度已达到160℃(大约3分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
实施例8(对比例):
538.5 g PEG 2000在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与0.30 g磷酸二丁酯和11.4 g 1,4-丁二醇以及0.30g 乙基己酸锡(II)混合。加热到110℃之后,加入68.7 g 1,6-六亚甲基二异氰酸酯并加热容器直到温度已达到160℃(大约2分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
实施例9(对比例):
528.0 g PEG 4000在100℃下通过搅拌在容器中(大约20 mbar的真空)干燥2小时。接着在氮气下搅拌所述混合物并与0.38 g磷酸二丁酯和12.4 g 1,4-丁二醇以及0.30g 乙基己酸锡(II)混合。加热到110℃之后,加入45.8 g 1,6-六亚甲基二异氰酸酯并加热容器直到温度已达到160℃(大约4分钟)。随后将所得聚合物倒入盘中并在105℃进一步储存1小时。
加工和应用试验
将根据实施例1-9获得的热塑性聚氨酯冷却到室温,造粒和在气流中干燥。然后将粒料各自通过温度可调节的带有喷头的挤出机加工成纤维。将所得纤维卷绕在转动的辊上。评价纤维的制备容易性(判定标准:良好的材料流动、罕有纤维断裂、少数凝胶颗粒)和进一步加工的容易性(判定标准:良好的缠绕和解缠绕、机械强度、低粘性)。
使粒料和纤维也在“溶液A”中经历溶胀试验。这里所希望的是高吸收(在过量“溶液A”中10分钟后的质量增加)。同时,纤维应当不溶解。应当形成致密、透明和稳定的凝胶,所述凝胶基于未溶胀的聚合物的质量计吸收了至少20倍质量的溶液A。
每次试验的评价
分级标度:1-非常好至5-非常差或不可操作:
试验编号 | 可纺性 | 纤维的机械性能 | 凝胶性能 | 10分钟后重量增加/1g聚合物,以g计 |
1)* | 2 | 1 | 1 | 29 |
2)* | 1 | 2 | 2 | 29 |
3)* | 2 | 2 | 3 | 25 |
4)* | 2 | 2 | 2 | 25 |
5)* | 1 | 1 | 2 | 23 |
6) | 5 | 3-4 | 5 (溶解) | 不能被测定(因为溶解) |
7) | 4 | 4 | 4 | 10 |
8) | 4 | 4 | 4 | 6 |
9) | 3 | 2 | 4 (部分溶解) | 18 |
*本发明的实施例。
在本发明的实施例中在所有产生纤维的步骤中的可加工性为良好并且纤维性能为良好。本发明的纤维吸收大量的溶液A同时形成凝胶,其中溶胀的纤维具有足够的机械稳定性。相反,对比例的热塑性聚氨酯仅仅产生质量上明显次等的纤维,另外所述纤维只能吸收较少的溶液A。另外,这些纤维缺乏机械稳定性。
Claims (24)
1.包含热塑性聚氨酯的聚合物纤维,该热塑性聚氨酯能够通过使至少下面的组分反应获得:
A) 具有两个异氰酸酯基团的异氰酸酯,
B1) 结构(HO-(CH2-CH2-O)x-H)的第一聚(乙二醇)聚醚二醇,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn为≥ 6000且≤ 16000 g/mol,
B2) 结构(HO-(CH2-CH2-O)x-H)的第二聚(乙二醇)聚醚二醇,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn等于所述第一聚(乙二醇)聚醚二醇B1)的数均分子量Mn的10-80%,
C) 扩链剂,其具有两个对异氰酸酯呈反应活性的基团且数均分子量Mn为≥ 60且< 600g/mol,
D) 任选的催化剂,和
E) 任选的助剂和添加剂,
其特征在于:所述扩链剂C)是至少一种选自下组的化合物:乙二醇、1,6-己二醇、1,4-丁二醇、1,12-十二烷二醇、异佛尔酮二胺、乙二胺、1,2-丙二胺、1,3-丙二胺、N-甲基丙-1,3-二胺、N,N'-二甲基乙二胺、对苯二甲酸-双乙二醇、对苯二甲酸-双-1,4-丁二醇、1,4-二(-羟乙基)氢醌,并且
其中所述异氰酸酯A)与所述聚(乙二醇)聚醚二醇B1)和B2)的当量比为1.5:1.0-10.0:1.0并且NCO指数为90-105,所述指数由异氰酸酯基团与对异氰酸酯呈反应活性的基团的总数的当量比之商乘以100而形成。
2.如权利要求1所述的聚合物纤维,其特征在于:除所述聚(乙二醇)聚醚二醇B1)和B2)之外没有数均分子量Mn≥ 600且≤ 16000 g/mol的另外的二醇共反应。
3.如权利要求1或2之一所述的聚合物纤维,其特征在于:所述第一聚(乙二醇)聚醚二醇B1)与所述第二聚(乙二醇)聚醚二醇B2)的重量比为 1-30。
4.如权利要求1或2所述的聚合物纤维,其特征在于:所述异氰酸酯包含一种或多种选自六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯的化合物。
5.如权利要求1或2所述的聚合物纤维,其特征在于:所述第二聚(乙二醇)聚醚二醇B2)具有的数均分子量Mn为600-4000 g/mol。
6.如权利要求1或2所述的聚合物纤维,其特征在于:所述第二聚(乙二醇)聚醚二醇B2)的数均分子量Mn等于所述第一聚(乙二醇)聚醚二醇B1)的数均分子量Mn的10-70%。
7.如权利要求1或2所述的聚合物纤维,其特征在于:所述扩链剂C)是脂族二醇、脂族二胺或环脂族二胺。
8.如权利要求1或2所述的聚合物纤维,其特征在于: NCO指数为92-104。
9.如权利要求1所述的聚合物纤维,其特征在于:所述扩链剂C)是至少一种选自下组的化合物:乙二醇、1,6-己二醇、1,4-丁二醇、1,12-十二烷二醇。
10.如权利要求1所述的聚合物纤维,其特征在于:所述扩链剂C)是1,4-丁二醇。
11.如权利要求1或2所述的聚合物纤维,其特征在于:所述第一聚(乙二醇)聚醚二醇B1)与所述第二聚(乙二醇)聚醚二醇B2)的重量比为5-25。
12.如权利要求1或2所述的聚合物纤维,其特征在于:所述第一聚(乙二醇)聚醚二醇B1)与所述第二聚(乙二醇)聚醚二醇B2)的重量比为 10-20。
13.如权利要求1或2所述的聚合物纤维,其特征在于:所述第二聚(乙二醇)聚醚二醇B2)具有的数均分子量Mn为1000-3000 g/mol。
14.如权利要求1或2所述的聚合物纤维,其特征在于:所述第二聚(乙二醇)聚醚二醇B2)具有的数均分子量Mn为1800-2200 g/mol。
15.如权利要求1或2所述的聚合物纤维,其特征在于:所述第二聚(乙二醇)聚醚二醇B2)具有的数均分子量Mn为2000 g/mol。
16.如权利要求1或2所述的聚合物纤维,其特征在于:所述第二聚(乙二醇)聚醚二醇B2)的数均分子量Mn等于所述第一聚(乙二醇)聚醚二醇B1)的数均分子量Mn的15-50%。
17.如权利要求1或2所述的聚合物纤维,其特征在于:所述第二聚(乙二醇)聚醚二醇B2)的数均分子量Mn等于所述第一聚(乙二醇)聚醚二醇B1)的数均分子量Mn的15-33%。
18.如权利要求1或2所述的聚合物纤维,其特征在于: NCO指数为95-102。
19.如权利要求1或2所述的聚合物纤维,其特征在于: NCO指数为97-100。
20.制备如权利要求1-19任一项所述的包含热塑性聚氨酯的聚合物纤维的方法,其特征在于:制备所述聚(乙二醇)聚醚二醇B1)、B2)与所述扩链剂C)的混合物I)并将所述混合物I)与所述异氰酸酯A)充分混合。
21.如权利要求20所述的方法,其特征在于:所述混合物I)与所述异氰酸酯A)在最多5秒内均匀地混合,其中所述混合物I)的温度和所述异氰酸酯A)的温度在所述混合之前为≥60且≤ 150℃并且温差≤ 50℃。
22.如权利要求20或21之一所述的方法,其特征在于:所述混合物I)与所述异氰酸酯A)在具有的长/径比为8:1-16:1的静态混合机中混合。
23.如权利要求20所述的方法,其特征在于:所述混合物I)与所述异氰酸酯A)在最多5秒内均匀地混合,其中所述混合物I)的温度和所述异氰酸酯A)的温度在所述混合之前为≥60且≤ 150℃并且温差≤ 20℃。
24.聚合物纤维,其能够通过如权利要求20-23中任一项所述的方法获得。
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- 2012-09-17 WO PCT/EP2012/068202 patent/WO2013041471A2/de active Application Filing
- 2012-09-17 EP EP12759712.8A patent/EP2758444B1/de not_active Not-in-force
- 2012-09-17 CN CN201280045341.XA patent/CN103797042B/zh not_active Expired - Fee Related
- 2012-09-17 US US14/345,412 patent/US20140350206A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
CN103797042A (zh) | 2014-05-14 |
WO2013041471A2 (de) | 2013-03-28 |
EP2758444B1 (de) | 2018-01-24 |
WO2013041471A3 (de) | 2013-06-27 |
EP2758444A2 (de) | 2014-07-30 |
US20140350206A1 (en) | 2014-11-27 |
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