CN111926411A - 一种低摩擦系数聚氨酯弹性纤维及其制备方法 - Google Patents

一种低摩擦系数聚氨酯弹性纤维及其制备方法 Download PDF

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CN111926411A
CN111926411A CN202010854578.9A CN202010854578A CN111926411A CN 111926411 A CN111926411 A CN 111926411A CN 202010854578 A CN202010854578 A CN 202010854578A CN 111926411 A CN111926411 A CN 111926411A
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elastic fiber
polyurethane elastic
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周志伟
刘亚辉
陈铃
杨晓印
许图远
王靖
袁昆山
谢作形
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Abstract

本发明是一种低摩擦系数聚氨酯弹性纤维及其制备方法，该聚氨酯弹性纤维以聚氨酯脲原液A为芯材，聚氨酯脲原液B为皮材通过干法纺丝制得，制备方法为：以PTMEG、MDI为主原料，二胺作为扩链剂，DMAC为溶剂，并加入抗氧剂、抗紫外剂、防黄剂的助剂制备聚氨酯脲原液A；以PTMEG、双端羟基聚二甲基硅氧烷、MDI为主原料，二胺作为扩链剂，DMAC为溶剂，并加入硅酮粉、抗氧剂、抗紫外剂、防黄剂的助剂制备聚氨酯脲原液B；以原液A为芯材，原液B为皮材，通过喷丝板组合件，采用干法纺丝技术制备具有皮芯结构的纤维；纤维通过高温甬道挥发其中的DMAc，再经过上油罗拉涂覆油剂，即可制得具有低摩擦系数的聚氨酯弹性纤维。

Description

一种低摩擦系数聚氨酯弹性纤维及其制备方法
技术领域
本发明涉及一种低摩擦系数聚氨酯弹性纤维及其制备方法，属于聚氨酯弹性纤维制备的技术领域。
背景技术
聚氨酯弹性纤维是一种具有高弹性回复率、高断裂伸长率的特种化学纤维，广泛的应用在纺织服装品中。聚氨酯弹性纤维在后道应用时主要通过圆机、包纱机、一体机等与其它纤维混织，织造过程中纤维需要在高速退绕的状态下与金属、陶瓷、塑料等材料接触，会产生一定的摩擦力而出现断丝现象，影响下游客户的织造效率。因此，开发一种具有低摩擦系数的聚氨酯弹性纤维，可以有效解决纤维后道应用时的摩擦断丝问题。
目前，关于低摩擦系数聚氨酯弹性纤维制备方面的专利及文献报道较少，针对聚氨酯弹性纤维断丝的改善的专利则有一些报道，专利CN100338300C通过在油剂添加二价硬脂酸盐作为防粘助剂来改善纤维的退绕性，该方法对比不添加硬脂酸镁的油剂确实可以起到一定的润滑作用，降低纤维底部发粘断丝的几率，但是对其摩擦系数改善很小，因此，摩擦断丝的改善效果并不明显。专利CN201911225804通过在聚氨酯原液中添加高分子耐磨剂来降低断丝率，该法虽然也可以一定程度的降低断丝率，但是通过耐磨剂的作用，对聚氨酯弹性纤维本身的一个摩擦系数并没有降低，而且该法加入的高分子耐磨剂不易在聚氨酯原液中分散，容易团聚，影响纤维的均一性。本发明针对上述问题，开发了一种生产低摩擦系数聚氨酯弹性纤维的新技术，纤维为皮芯结构，结合在皮层以及在它所涂覆的油剂中添加一定量的润滑降磨助剂，赋予纤维表层极低的摩擦系数，可极大的降低聚氨酯弹性纤维在后道使用时的断丝率，而且不会影响聚氨酯原液的稳定性及纤维的性能。
发明内容
技术问题：本发明拟解决的技术问题是设计一种低摩擦系数的聚氨酯弹性纤维及其制备方法。该制备方法的实施过程稳定，制备的纤维具有极低的摩擦系数，与金属、陶瓷、塑料等材料接触时摩擦力显著降低，可极大的降低聚氨酯弹性纤维的摩擦断丝率。本发明制备工艺技术先进，设备常规，可以产业化实施。
技术方案：本发明的一种低摩擦系数聚氨酯弹性纤维以聚氨酯脲原液A为芯材，聚氨酯脲原液B为皮材通过干法纺丝制得，所述的原液A与原液B的质量比在9:1～7:3之间；
其中聚氨酯脲原液A包括如下质量百分比组分：
聚四亚甲基醚二醇PTMEG 75～85％
4,4-二苯基甲烷二异氰酸酯MDI 10～22％
扩链剂 1.5～5％；
聚氨酯脲原液B包括如下质量百分比组分：
Figure BDA0002645950440000021
其中，
所述的聚氨酯脲原液A还包括链终止剂和/或作为助剂的抗氧剂、抗紫外剂、防黄剂；
基于聚氨酯脲原液A总质量的质量组分为：
Figure BDA0002645950440000022
所述的聚氨酯脲原液B还包括链终止剂和/或作为助剂的抗氧剂、抗紫外剂、防黄剂，
基于聚氨酯脲原液B总质量的质量组分为：
Figure BDA0002645950440000023
Figure BDA0002645950440000031
所述的双端羟基聚二甲基硅氧烷的分子量在2000～3500之间。
所述的硅酮粉中硅氧烷与二氧化硅的质量比在2:1～4:3之间，硅酮粉的初始粒径＜20um。
本发明的低摩擦系数聚氨酯弹性纤维的制备方法包括以下步骤：
以PTMEG、MDI为主原料，二元胺作为扩链剂，一元胺作为链终止剂，DMAC为溶剂，并加入抗氧剂、抗紫外剂、防黄剂的助剂制备聚氨酯脲原液A；
以PTMEG、双端羟基聚二甲基硅氧烷、MDI为主原料，二元胺作为扩链剂，一元胺作为链终止剂，DMAC为溶剂，并加入硅酮粉、抗氧剂、抗紫外剂、防黄剂的助剂制备聚氨酯脲原液B；
以原液A为芯材，原液B为皮材，通过喷丝板组合件，采用干法纺丝技术制备具有皮芯结构的纤维；
纤维通过高温甬道挥发其中的DMAc，再经过上油罗拉涂覆油剂，即可制得具有低摩擦系数的聚氨酯弹性纤维。
其中，
所述的聚氨酯弹性纤维通过上油罗拉涂覆的油剂涂覆量占聚氨酯弹性纤维质量百分比的3.0％～5.0％之间。
所述的聚氨酯弹性纤维通过上油罗拉涂覆的油剂的质量百分比配方为：
Figure BDA0002645950440000032
所述的改性硅油为苯甲基硅油或长链烷基改性硅油，粘度在350～3000cst之间；苯甲基硅油具有如下结构式：其中m≥3，n≥3
Figure BDA0002645950440000041
长链烷基改性硅油具有如下结构式：其中m≥3，n≥3，x≥7
Figure BDA0002645950440000042
。
所述的二元胺为乙二胺、丙二胺、丁二胺、戊二胺、己二胺及其异构体中的一种及以上；一元胺为二乙胺、二丙胺、环己胺、乙醇胺中的一种及以上。
有益效果：与现有技术相比，本发明的优点为：
(1)本发明通过在皮层聚氨酯链段中引入低表面张力的聚二甲基硅氧烷结构，同时加入可明显降低摩擦系数的润滑剂硅酮粉，可降低聚氨酯弹性纤维摩擦系数；
(2)利用独特的纺丝工艺，制备具有皮芯结构的聚氨酯弹性纤维，聚二甲基硅氧烷以及硅酮粉都添加在纤维的皮层中，可最大限度的发挥它们润滑降磨的作用，而且不影响聚氨酯弹性纤维的整体性能。
(3)在纤维表面涂覆的特定的油剂进一步降低聚氨酯弹性纤维摩擦系数。通过结合(1)和(3)的双重协同作用，该法制备的纤维具有极低的摩擦系数，与金属、陶瓷、塑料等介质接触时摩擦力低，可极大的降低聚氨酯弹性纤维后道使用时的断丝率。
具体实施方式
本发明涉及这样的一种低摩擦系数聚氨酯弹性纤维及其制备方法：借助于在聚氨酯弹性纤维表层中引入低表面张力的双端羟基聚二甲基硅氧烷以及润滑剂硅酮粉，结合在纺丝油剂中加入高效润滑剂改性硅油和硅酮粉，从而使纤维表层具有极低的摩擦系数，与金属、陶瓷等材料接触时摩擦力低，极大的降低了聚氨酯弹性纤维的断丝率。
下面实施例用来详细描述本发明及其生产过程，但这些实施例不得理解为任何意义上的对本发明的限制。此外应理解，在阅读了本发明讲述的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
油剂的制备：
将48％重量份的二甲基硅油(25℃时的运动粘度为10mPa.s)，30％重量份的白油(40℃时的运动粘度为10mPa.s)，15％重量份的长链烷基改性硅油，5％重量份司盘80,2％重量份的硅酮粉依次加入到高速机械搅拌分散装置中，于70℃的温度下以200r/min的转速搅拌2h得到淡黄色透明的自制油剂A。
将40％重量份的二甲基硅油(25℃时的运动粘度为10mPa.s)，35％重量份的白油(40℃时的运动粘度为10mPa.s)，18％重量份的苯甲基硅油，5％重量份司盘-80,2％重量份的硅酮粉依次加入到高速机械搅拌分散装置中，于70℃的温度下以200r/min的转速搅拌2h得到淡黄色透明的自制油剂B。
油剂C为中纺海天购买的RZ-3209F油剂，该油剂主要成分为二甲基硅油、白油、硬脂酸镁以及一定量的表面活性剂混合物。不含自制油剂中添加的长链烷基改性硅油、苯甲基硅油以及硅酮粉。
实施例1
将195kg溶剂二甲基乙酰胺(DMAC)加入到反应釜(RA1)，开启搅拌，再向RA1中加入288kg聚四氢呋喃醚二醇和70.5kg二苯基甲烷二异氰酸酯，在45℃下反应2h得预聚体PPS，将PPS移送进入扩链反应釜(RA2)中。向RA1中加入375kg清洗DMAC，将清洗DMAC移送进入RA2，开启搅拌，待RA2温度冷却到10℃左右时，向RA2中滴加含有5.76kg乙二胺和1.2kg二乙胺的混合胺溶液进行扩链反应和链终止反应，其中混合胺溶液质量浓度为5.45％。反应完成后，将所得聚合物移送进入D-FETK。向D-FETK中加入723g抗氧化剂CY，1.086kg抗紫外剂UTP，543g防黄变剂UDT，反应熟化20h，得聚合纺丝原液A。
将40kg溶剂二甲基乙酰胺(DMAC)加入到反应釜(RA1)，开启搅拌，再向RA1中加入23.6kg聚四氢呋喃醚二醇、24.5kg双端羟基聚二甲基硅氧烷和12.5kg二苯基甲烷二异氰酸酯，在60℃下反应3h得预聚体PPS，将PPS移送进入扩链反应釜(RA2)中。向RA1中加入50kg清洗DMAC，将清洗DMAC移送进入RA2，开启搅拌，待RA2温度冷却到10℃左右时，向RA2中滴加含有1.59kg乙二胺和0.30kg二乙胺的混合胺溶液进行扩链反应和链终止反应，其中混合胺溶液质量浓度为5.45％。反应完成后，将所得聚合物移送进入D-FETK。向D-FETK中加入2.63kg硅酮粉、197.5g抗氧化剂CY，325g抗紫外剂UTP，325g防黄变剂UDT，反应熟化20h，得聚合纺丝原液B。
以述原液A为芯层，原液B为皮层，通过复合喷丝板组合件进行干法纺丝，通过上油罗拉涂覆质量分数4.0％的自制油剂A，得到聚氨酯弹性纤维1。
以述原液A为芯层，原液B为皮层，通过复合喷丝板组合件进行干法纺丝，通过上油罗拉涂覆质量分数4.0％的自制油剂B，得到聚氨酯弹性纤维2。
实施例2
将195kg溶剂二甲基乙酰胺(DMAC)加入到反应釜(RA1)，开启搅拌，再向RA1中加入288kg聚四氢呋喃醚二醇和70.5kg二苯基甲烷二异氰酸酯，在45℃下反应2h得预聚体PPS，将PPS移送进入扩链反应釜(RA2)中。向RA1中加入375kg清洗DMAC，将清洗DMAC移送进入RA2，开启搅拌，待RA2温度冷却到10℃左右时，向RA2中滴加含有5.76kg乙二胺和1.2kg二乙胺的混合胺溶液进行扩链反应和链终止反应，其中混合胺溶液质量浓度为5.45％。反应完成后，将所得聚合物移送进入D-FETK。向D-FETK中加入723g抗氧化剂CY，1.086kg抗紫外剂UTP，543g防黄变剂UDT，反应熟化20h，得聚合纺丝原液C。
将40kg溶剂二甲基乙酰胺(DMAC)加入到反应釜(RA1)，开启搅拌，再向RA1中加入18.5kg聚四氢呋喃醚二醇、31.6kg双端羟基聚二甲基硅氧烷和10.8kg二苯基甲烷二异氰酸酯，在60℃下反应3h得预聚体PPS，将PPS移送进入扩链反应釜(RA2)中。向RA1中加入50kg清洗DMAC，将清洗DMAC移送进入RA2，开启搅拌，待RA2温度冷却到10℃左右时，向RA2中滴加含有1.32kg乙二胺和0.28kg二乙胺的混合胺溶液进行扩链反应和链终止反应，其中混合胺溶液质量浓度为5.45％。反应完成后，将所得聚合物移送进入D-FETK。向D-FETK中加入1.32kg硅酮粉、197.5g抗氧化剂CY，325g抗紫外剂UTP，325g防黄变剂UDT，反应熟化20h，得聚合纺丝原液D。
以述原液C为芯层，原液D为皮层，通过复合喷丝板组合件进行干法纺丝，通过上油罗拉涂覆质量分数4.0％的自制油剂A，得到聚氨酯弹性纤维3。
以述原液A为芯层，原液B为皮层，通过复合喷丝板组合件进行干法纺丝，通过上油罗拉涂覆质量分数4.0％的自制油剂B，得到聚氨酯弹性纤维4。
对比样1：以实施例1中的原液A通过干法纺丝得到不含皮芯结构常规聚氨酯弹性纤维，涂覆的油剂为4％的中纺海天RZ-3209F油剂。
对比样2：以实施例1中的原液A为芯层，实施例2中的原液C为皮层，其中，皮层结构没有添加双端羟基聚二甲基硅氧烷和硅酮粉，通过复合喷丝板组合件进行干法纺丝得到含有皮芯结构的聚氨酯弹性纤维，涂覆的油剂为4％的中纺海天RZ-3209F油剂。
对比样3：以实施例1中的原液A为芯层，实施例2中的原液C为皮层，其中，皮层结构没有添加双端羟基聚二甲基硅氧烷和硅酮粉，通过复合喷丝板组合件进行干法纺丝得到含有皮芯结构的聚氨酯弹性纤维，涂覆的油剂为4％的自制油剂A。
对比样4：以实施例1原液A为芯层，原液B为皮层，通过复合喷丝板组合件进行干法纺丝得到含有皮芯结构的聚氨酯弹性纤维，涂覆的油剂为4％的中纺海天RZ-3209F油剂。
聚氨酯弹性纤维摩擦系数测试方法(罗得氏法)如下：使用Y151型纤维摩擦系数测定仪，将纤维以一定的角度包围在摩擦辊上，在纤维两端施加相等张力，当减少丝一端张力或转动摩擦辊时，由于纤维与摩擦辊表面存在摩擦力，纤维一端张力会变小，借助测力装置测得该张力变化。根据欧拉公式，即可算得纤维的静摩擦系数和动摩擦系数。采用上述方法对实施例和对比例聚氨酯弹性纤维进行静摩擦和动摩擦测试，测试结果如表1所示：
表1：不同聚氨酯弹性纤维摩擦系数测试数据
Figure BDA0002645950440000071
从表1可以明显看出，本发明实施例1-4的聚氨酯弹性纤维产品，通过摩擦测试表明，无论是静摩擦系数还是动摩擦系数的数值都明显优异于对比例1-4的产品。此外，在实际后道使用过程中，本发明产品基本不出现断丝率现象且回弹性、力学等综合性能优良。

Claims (10)

1.一种低摩擦系数聚氨酯弹性纤维，其特征在于该聚氨酯弹性纤维以聚氨酯脲原液A为芯材，聚氨酯脲原液B为皮材通过干法纺丝制得，所述的原液A与原液B的质量比在9:1～7:3之间；
其中聚氨酯脲原液A包括如下质量百分比组分：
聚四亚甲基醚二醇PTMEG 75～85％
4,4-二苯基甲烷二异氰酸酯MDI 10～22％
扩链剂 1.5～5％；
聚氨酯脲原液B包括如下质量百分比组分：
Figure FDA0002645950430000011
2.根据权利要求1所述的低摩擦系数聚氨酯弹性纤维，其特征在于，所述的聚氨酯脲原液A还包括链终止剂和/或作为助剂的抗氧剂、抗紫外剂、防黄剂；
基于聚氨酯脲原液A总质量的质量组分为：
Figure FDA0002645950430000012
3.根据权利要求1所述的低摩擦系数聚氨酯弹性纤维，其特征在于，所述的聚氨酯脲原液B还包括链终止剂和/或作为助剂的抗氧剂、抗紫外剂、防黄剂，
基于聚氨酯脲原液B总质量的质量组分为：
Figure FDA0002645950430000013
Figure FDA0002645950430000021
4.根据权利要求3所述的低摩擦系数聚氨酯弹性纤维，其特征在于，所述的双端羟基聚二甲基硅氧烷的分子量在2000～3500之间。
5.根据权利要求3所述的低摩擦系数聚氨酯弹性纤维，其特征在于，所述的硅酮粉中硅氧烷与二氧化硅的质量比在2:1～4:3之间，硅酮粉的初始粒径＜20um。
6.一种如权利要求1所述的低摩擦系数聚氨酯弹性纤维的制备方法，其特征在于，所述的低摩擦系数聚氨酯弹性纤维的制备方法包括以下步骤：
以PTMEG、MDI为主原料，二元胺作为扩链剂，一元胺作为链终止剂，DMAC为溶剂，并加入抗氧剂、抗紫外剂、防黄剂的助剂制备聚氨酯脲原液A；
以PTMEG、双端羟基聚二甲基硅氧烷、MDI为主原料，二元胺作为扩链剂，一元胺作为链终止剂，DMAC为溶剂，并加入硅酮粉、抗氧剂、抗紫外剂、防黄剂的助剂制备聚氨酯脲原液B；
以原液A为芯材，原液B为皮材，通过喷丝板组合件，采用干法纺丝技术制备具有皮芯结构的纤维；
纤维通过高温甬道挥发其中的DMAc，再经过上油罗拉涂覆油剂，即可制得具有低摩擦系数的聚氨酯弹性纤维。
7.根据权利要求6所述的低摩擦系数聚氨酯弹性纤维，其特征在于，所述的聚氨酯弹性纤维通过上油罗拉涂覆的油剂涂覆量占聚氨酯弹性纤维质量百分比的3.0％～5.0％之间。
8.根据权利要求6或7所述的低摩擦系数聚氨酯弹性纤维，其特征在于，所述的聚氨酯弹性纤维通过上油罗拉涂覆的油剂的质量百分比配方为：
Figure FDA0002645950430000022
Figure FDA0002645950430000031
9.根据权利要求8所述的低摩擦系数聚氨酯弹性纤维，其特征在于，所述的改性硅油为苯甲基硅油或长链烷基改性硅油，粘度在350～3000cst之间；苯甲基硅油具有如下结构式：其中m≥3，n≥3
Figure FDA0002645950430000032
长链烷基改性硅油具有如下结构式：其中m≥3，n≥3，x≥7
Figure FDA0002645950430000033
10.根据权利要求6所述的低摩擦系数聚氨酯弹性纤维，其特征在于，所述的二元胺为乙二胺、丙二胺、丁二胺、戊二胺、己二胺及其异构体中的一种及以上；一元胺为二乙胺、二丙胺、环己胺、乙醇胺中的一种及以上。
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Address after: No. 1788, Development Zone Avenue, Ruian Dongshan Economic Development Zone, Wenzhou City, Zhejiang Province, 325200

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