CN102264786B - 靴形压带 - Google Patents
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Abstract
本发明涉及包括由含异氰酸酯基团的尿烷预聚物和扩链剂共混物制得的聚氨酯聚合物的靴形压带，该尿烷预聚物使用1，4-亚苯基二异氰酸酯(PPDI)制备且该扩链剂共混物包括甲基-双(3-氯-2，6-二乙基-苯胺)(MCDEA)。
Description
发明背景
本发明一般地涉及用于造纸工艺不同阶段的压带。更特别地，本发明涉及在纸板、纸张和纸浆机中的压制段的靴形压机中以及制造某类纸张时造纸砑光机的靴形压机中使用的靴形压带。
靴形压机通常用于纸浆、纸板和纸张机以使纤维网脱水。通过旋转的压辊将在这种靴形压机中高速运行的湿纤维网的一面压榨，同时通过由具有弹性弹性体的环带所包围的固定压力靴压榨该纤维网的另一面。该带以与纤维网近似相同的速率在压辊和压力靴之间运行。压毡之上的纤维网通过靴形压机驱动，压带的外表面与压毡直接接触且压带的内表面相对于压力靴滑动。典型地在该带与压力靴之间提供润滑油，以确保该带的自由运动。
现有技术的压带典型地含有弹性体材料如聚氨酯或橡胶，以及在该带内部由纱线制成的支撑结构。靴形压机的一个例子公开在FI20040166。
通常来说，在纤维网以高速率通过靴形压机运行时，靴形压带在压辊和压力靴之间经受循环的高弯曲力和压力。随着时间的推移，这些应力会在使用期间使压带材料产生裂纹，最终使压带损坏而不能使用。通常趋势是提高造纸机中的织物速率以改进制造效率。由于采用更高速率来针对与先前相同的干物质含量，必须提高压力。由此压榨步骤中使用的靴形压带也经受越来越高的负荷，由此要求压带具有多种性能以确保高性能。随着造纸机中织物速率增加，该带由于一方面增加的速率以及另一方面润滑油的升温而经受越来越高的热负荷。考虑到该带的使用寿命，该带的良好耐热性也是基本方面。
纸张、纸板和纸浆机中靴形压机的操作温度通常低于70℃。最近已发现，通过提高靴形压机的温度，也可以提高制造效率，更高的纤维网温度可以能实现更好的干物质含量，因为水粘度降低且水更有效地离开。例如，可以通过蒸汽、热辊或者通过升高物质温度来加热纤维网。在公知的脉冲干燥技术中，将温度升高到高到200℃以上。另外在公知的靴形砑光机中，热辊温度可以200℃以上。相同因素从外侧升高靴形压带的温度。提高压力负荷改进了干物质。但是同时摩擦产生的热量将润滑该靴形压带的油加热并在该靴形压带内部升高温度。这些因素一起增加了对于靴形压毡指出的耐热性要求。
由普通聚氨酯制成的靴形压带良好地抵抗低于70℃的温度。但是，在更高温度下聚氨酯的机械和动力学特性，以及相应地靴形压带的这些性能明显恶化。聚氨酯在高温下软化且该带的磨损增加。由于软化该带凹槽变得扁平，且不能恢复到它们原始形状，这样由于凹槽不再能够吸收足够的水而使损害脱水。在高温下，且特别是在造纸化学品残留物的存在下，在聚氨酯中开始发生热和化学氧化反应。由此，聚合物链断裂，这样反过来使聚氨酯性能恶化。这点随后显示为带磨损和抗破裂性削弱。使用时，靴形压带处于恒定动态压榨和拉伸负荷下。这就是为什么重要的是其动态性能在这些温度范围下保持良好的原因所在。
现有技术中大量地描述了适用于靴形压机的带。例如，EP 1338696A1公开了适用于造纸工艺中压榨步骤的带，如靴形压带，该带包括嵌入聚氨酯层内的增强基材。与支撑纤维网的压毡直接接触的、该带的外周表面是由尿烷预聚物和作为硬化剂的二甲基硫代甲苯二胺(DMTDA)形成的。该带目的在于减少或减缓任何裂纹，其通常特别是在带的外表面上发生，以及防止氧化剂和聚氨酯层之间的分层。
EP 877118 A2公开了具有基础层以及在其两侧上的树脂层的靴形压带。该树脂是由甲亚苯基二异氰酸酯聚醚型聚氨酯聚合物制成的，使用4，4’-亚甲基双(2-氯苯胺)(MOCA/MBOCA)作为扩链剂。提及该带提供了所需的耐磨性、挠曲疲劳强度和裂纹抑制。
WO 2005/090429 A1公开了适用于靴形压机的带，该带包括基于尿烷、含有纳米颗粒的涂层。在涂层中添加纳米颗粒的目的在于，例如，改进该带抗挠曲疲劳性和抗裂纹扩散性，且提供该带硬度和磨损特性。
EP 0939162 A2公开了包括两个由甲亚苯基二异氰酸酯聚醚型聚氨酯聚合物制成的树脂层的靴形压带，其中使用3，3’-二氯-4，4’-二氨基二苯基甲烷(MOCA/MBOCA)作为增强基材。目的在于获得同时在机械方面和横跨机器方面上的强度的带，以及防止树脂从带中分层。
上述靴形压带存在的问题是，它们的耐热性在纸板、纸张、和纸浆机中为了最大化制造效率而越来越优选的生产速率下并不足够。
EP 1136618 A2中公开的方案是，鉴于压带操作期间温度升高而使用绝缘填料剂。同样，DE 19702138 A1提出，通过在弹性体基质中使用导热填料颗粒来改进压带的耐热性。在DE 19651557 A1中在压带上提供了保护在下面的弹性体免受化学品和热量影响的涂层。
但是，上述基于使用填料剂或涂层的这类方案，可能在带中产生其它问题。聚合物材料可能变脆，或者由于填料剂而与增强基材分层。特别是长时间使用时，在涂层与带材料的粘合力方面也可能产生问题。
由此期望，以仍更简单的方式，获得具有良好耐热性且不存在现有技术问题，且在更宽的操作温度范围下和特别是更高温度下保持它们的良好动力学和机械性能的靴形压带。
发明概述
本发明的目的是提供满足现代纸板、纸张和纸浆机设定的关于良好耐热性的特别要求的靴形压带。这通过具有独立权利要求中所述特征的靴形压带得以实现。
令人吃惊地发现，在用于靴形压带的聚氨酯制备中使用特定类型的原材料，即特定异氰酸酯单体和特定扩链剂，能改进该带的耐热性。该带耐热性改进的一种标志是，其保持其抗断裂性。同时，特定原材料也改进了聚氨酯带的其它特性，如耐磨性和压缩回弹性。
本发明靴形压带的一种优点在于，良好耐热性根本上延长了带的使用寿命。
发明详述
本发明提供了新的靴形压带，其包括由含异氰酸酯基团的尿烷预聚物和扩链剂共混物制得的聚氨酯聚合物，该尿烷预聚物是用1，4-亚苯基二异氰酸酯(PPDI)制备，且该扩链剂共混物包括甲基-双(3-氯-2，6-二乙基苯胺)(MCDEA)。MCDEA在本领域也公知为4，4’-亚甲基-双(3-氯-2，6-二乙基苯胺)。
本发明靴形压带中使用的聚氨酯聚合物以本身已知的方式来制备。该聚氨酯可以是可倾倒的或是可挤出的，且其可以采用本领域中已知的预聚技术来制备，此时该预聚可以部分地(公知为半预聚物技术)或是完全地(公知为全预聚物技术)进行。本发明中，通过将尿烷预聚物胺基团(NH2-)(在其末端具有异氰酸酯基团)与扩链剂混和来制备聚氨酯。该扩链剂通过将长的预聚物链一起结合而使预聚物链扩大，由此形成尿烷或尿键，并获得现象聚氨酯结构，其可以进一步反应以形成具有缩二尿、尿基甲酸酯和氢键的网络结构。
本发明的上下文中，尿烷聚合物表示由所述1，4-亚苯基二异氰酸酯(PPDI)和多元醇之间的反应形成的产物。
聚氨酯制备中使用PPDI是众所周知的。依据研究，PPDI可以用于制备其中游离异氰酸酯(NCO)基团比例小于之前的预聚物。使用含有更少游离NCO基团的预聚物能够减少暴露于惰性、即游离异氰酸酯单体产生的挥发性和有毒气体。
已发现，由PPDI制得的聚氨酯相比由2，2’-二苯基甲烷-二异氰酸酯(MDI)制得的聚氨酯具有更好特性。依据研究，更好的性能是因为PPDI的平面结构(Yang等，Polymer 44(2003)，第3251-3258页)。PPDI和MDI的空间结构如下所示。
由于PPDI单体的对称结构，在聚氨酯弹性体中观察到形成了由硬和软块构成的线性且牢固的多相结构。硬和软块之间的相分离认为是PPDI聚氨酯弹性体优异性能、且特别是动态性能改进的最重要原因。
为了制备本发明中的尿烷预聚物，将PPDI与多元醇反应。该多元醇可以是聚氨酯制备中通常使用的任意多元醇。由此该多元醇可以是聚醚多元醇、聚酯多元醇、聚醚碳酸酯多元醇、聚碳酸酯多元醇或聚己内酰胺多元醇。聚醚多元醇包括、但不限于聚四亚甲基醚二醇(PTMEG)、聚丙二醇(PPG)、聚乙二醇(PEG)、聚六亚甲基醚二醇；聚酯多元醇包括单乙二醇的聚己二酸酯和聚己内酯；聚醚碳酸酯多元醇可以是例如形式H[O-(CH2)6]n-O-CO-O-[(CH2)6-O]n-(CH2)6-O-CO-O-…-OH的，但是它们并不限定于此；聚碳酸酯多元醇可以是例如形式HO-[(CH2)6-O-CO-O]n-(CH2)6-OH的，但是它们并不限定于此。依据本发明的实施方案，采用PTMEG作为多元醇来制备尿烷预聚物。依据本发明的另一实施方案，采用聚醚碳酸酯多元醇作为多元醇。
依据本发明，通过将在末端具有异氰酸酯基团的尿烷聚合物与包括含有胺基团的甲基-双(3-氯-2，6-二乙基-苯胺)(MCDEA)的扩链剂共混物混和，制备聚氨酯聚合物，由此获得具有尿和尿烷键的长聚氨酯链。
依据本发明，已发现，在聚氨酯制备中除了对称的PPDI之外还使用包括对称的MCDEA的扩链剂共混物时，提供了由这种具有优异耐热性品质的聚氨酯制得的靴形压带。下式中可以看出MCDEA的对称结构。并不受限于任意特定理论，可以推断，选择所述对称的原材料导致具有优选、极佳的硬和软相的组织化相结构的聚氨酯弹性体，其赋予了该材料特别好的耐热性。下面的结果令人吃惊地显示，随时间推移，热量并不会削弱材料的强度，甚至有所改进。这意味着材料中存在由热量冲击造成的不断提高的组织结构的趋势。
依据本发明的实施方案，扩链剂共混物包括至少10wt％的MCDEA。依据本发明的另一实施方案，扩链剂共混物包括25wt％以上、特别地至少50wt％的MCDEA。
本发明的靴形压带适用于所有类型靴形压机。FI申请20055556中公开了一种类型的靴形压机。
本发明的支撑结构可以典型地包括由例如聚酰胺、聚丙烯、聚乙烯、聚酯、聚乙烯醇或耐高温纤维材料如聚芳酰胺、聚苯硫醚或聚醚醚酮制成的单丝或多丝纱线。
本发明的靴形压带可以以本身已知的方式来制造。例如，可以采用公知的离心筒浇铸来制造，其中在横跨机器和机器方向上首先将增强纱线置于浇铸筒的内表面上，并随着筒循环，将聚氨酯材料均匀地分散在纱线四周和它们之上。这种带制造技术公开于例如US 5609811。
本发明的靴形压带也可以通过将带浇铸到浇铸筒上来制备。这种方法公开于例如US 5134010。该方法开始于机械方向，将增强纱线连接到浇铸筒上，随后在筒旋转时将弹性体材料浇铸到其上，并同时将四周增强纱线缠绕到机器方向纱线上。
制造本发明靴形压带的仍另一种可能性是，将基础织物在圆柱形模具中用聚氨酯浸渍，将挤出织物置于外壳和心轴之间。使该模具经受吸气以产生负压，并随后将聚氨酯材料注入该模具内。由此聚氨酯材料均匀地吸收到基础织物上。这种方法描述于例如US 5833898。
本发明的靴形压带也可以通过用聚合物在两侧上浸渍和/或通过涂布无端编织的、褶叠的或层压的增强结构来制造。这类方法公开于例如US 6465074。
本发明靴形压带的优异耐热性在收集于下表1的结果中举例说明。样品1代表本发明的靴形压带，其中聚氨酯是由PPDI和PTMEG形成的预聚物与含有MCDEA的扩链剂制成的。MCDEA的比例是该扩链剂共混物的50％。在66℃的加工温度下制备该聚氨酯。在120℃下炉中进行带的后处理16小时。预聚物中异氰酸酯基团的比例为5.52％。
样品2是对照带，其中聚氨酯是由2，2’-二苯基甲烷二异氰酸酯(MDI)和PTMEG多元醇形成的预聚物与含有MOCA的扩链剂制成的。扩链剂共混物中MOCA的比例为25％。在45℃的加工温度下制备该聚氨酯。在80℃下炉中进行带的后处理24小时。预聚物中异氰酸酯基团的比例为13.15％。
在0-4天内测量带的残留强度、磨损和残留压缩。依据SFS标准2983测量残留强度，依据DIN 53516测量磨损，且依据SFS2564/ISO815-1972测量残留压缩。带的暴露温度为130℃。
结果显示，样品1的强度在热量暴露下并未削弱，但是相反地趋于增强。然后样品2的强度在1天温度暴露下再次变得实质上更弱。样品1的耐磨性和压缩回弹性在温度暴露下并未降低。相比于样品2，样品1在温度暴露之前已具有实质上更好的耐磨性和压缩回弹性。
本领域技术人员将发现显然的是，随着技术发展，可以以各种方式来实施本发明的基本观点。由此，本发明及其实施方案并不限定于上述实施例，而是可以在权利要求的范围内变化。
Claims (5)
1.一种靴形压带，其包括由含异氰酸酯基团的尿烷预聚物和扩链剂共混物制得的聚氨酯聚合物，该尿烷预聚物是用1，4-亚苯基二异氰酸酯(PPDI)制备，且该扩链剂共混物包括甲基-双(3-氯-2，6-二乙基-苯胺)(MCDEA)。
2.权利要求1的靴形压带，其中该扩链剂包括至少10wt％的MCDEA。
3.权利要求1的靴形压带，其中该扩链剂包括25wt％以上的MCDEA。
4.权利要求1的靴形压带，其中该尿烷预聚物由1，4-亚苯基二异氰酸酯和聚四亚甲基醚二醇(PTMEG)制得。
5.权利要求1的靴形压带，其中该尿烷预聚物由1，4-亚苯基二异氰酸酯和聚醚碳酸酯多元醇制得。
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| US8871059B2 (en) * | 2012-02-16 | 2014-10-28 | International Paper Company | Methods and apparatus for forming fluff pulp sheets |
| WO2015086555A1 (de) * | 2013-12-13 | 2015-06-18 | Voith Patent Gmbh | Pressband und dessen verwendung sowie presswalze und schuhpresse |
| JP6501537B2 (ja) * | 2015-01-16 | 2019-04-17 | イチカワ株式会社 | シュープレスベルト及びその製造方法 |
| JP6674698B2 (ja) | 2015-04-07 | 2020-04-01 | ヤマウチ株式会社 | シュープレス用ベルト |
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| DE102017115591A1 (de) * | 2017-07-12 | 2019-01-17 | Voith Patent Gmbh | Pressmantel, Schuhpresse und Verwendung eines solchen |
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| AU2009326935B2 (en) | 2014-04-24 |
| WO2010066950A3 (en) | 2010-12-23 |
| BRPI0923330A2 (pt) | 2016-01-12 |
| FI20086190A0 (fi) | 2008-12-12 |
| ES2581659T3 (es) | 2016-09-06 |
| BRPI0923330B1 (pt) | 2023-10-31 |
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| EP2367980A2 (en) | 2011-09-28 |
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