CN114560995A - 一种涤纶混杂纤维制备聚氨酯的方法及聚氨酯的应用 - Google Patents
一种涤纶混杂纤维制备聚氨酯的方法及聚氨酯的应用 Download PDFInfo
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Abstract
本发明所述的涤纶混杂纤维制备聚氨酯的方法，包括步骤：聚氨酯多元醇前驱体的制备：将涤纶混杂纤维与醇解剂混合，在金属锡类催化剂作用下及惰性气体保护下，加热反应得聚氨酯多元醇前驱体；聚氨酯的制备：将聚氨酯多元醇前驱体与聚醚多元醇按比例混合，加热反应后冷却，再加入异氰酸酯，反应后经熟化得到含有纤维增强颗粒的、具有弹性的聚氨酯。本发明中采用涤纶为主的混杂纤维作为原料，包含醇解后带羟基的化合物、及具有酰胺结构的化合物，羟基和酰胺基中均具有活泼氢，可在后续的反应中形成氢键交联，提高产品聚氨酯的力学性能。未被醇解的混杂纤维如丙纶可起到纤维增强的效果，使聚氨酯不仅具备很高的力学性能，同时具有耐磨性能及回弹性。
Description
技术领域
本发明涉及废弃涤纶混杂纤维再利用领域，更具体地，涉及一种涤纶混杂纤维制备聚氨酯的方法及聚氨酯的应用。
背景技术
通常，涤纶纤维材料具有优良的抗皱性、尺寸稳定性和弹性，同时良好的绝缘性和耐老化特性使其成为化纤产品中产量最大的品种。随着涤纶纤维用量在纺织、服装中的占比增加，涤纶纤维固废的数量也日渐增多，对社会造成了极大的环境和资源压力。针对废旧涤纶再资源化的方法很多，其中经济效益较好的是利用废旧涤纶进行降解制备再生化合物。如CN110156932A公开了一种以涤纶纤维为原料制备不饱和树脂的方法；CN111647147A公开了一种以涤纶纺纤维为原料制备纤维源不饱和树脂的方法，该发明将含聚酯纤维(≥80％)的废旧涤纶纺纤维作为主要原料，经醇解过程，将分离出来的未醇解的纤维作为其它用途纤维增强材料。分离的液体部分经缩聚反应制备高粘结强度的纤维源不饱和树脂用于人造石材和户外砖等绿色建材的粘结剂材料。华南理工大学利用PET醇解多元醇用于聚氨酯弹性体的合成(卢晓玲，黄承亚，赵冉.废PET醇解产物及在聚氨酯弹性体合成中的应用，聚氨酯工业，2011)。
上述的技术主要针对较高纯度涤纶纤维的化学回收方法，而在实际生产中，涤纶纤维往往混杂锦纶、丙纶和氨纶等废料，导致对涤纶为主混杂纤维固废的回收利用往往需要预先分离地步骤。然而，复杂繁琐的分离操作大大增加了聚酯混纺纤维纺织品回收利用的难度。
发明内容
本发明的首要目的在于针对上述缺陷和不足，解决现有技术中废弃涤纶混杂纤维回收再利用过程繁杂、难度大的技术问题，通过对60～80％涤纶含量的混杂纤维进行醇解获得部分带有端羟基的聚酯多元醇前驱体作为原料并进一步制备聚氨酯弹性体，为涤纶为主混杂纤维固废的高值资源化应用提供新途径。
本发明的另一个目的在于，提供一种制备得到的聚氨酯的应用。
为了实现上述目的，本发明采用的具体技术方案为：
本发明所述的涤纶混杂纤维制备聚氨酯的方法，包括以下步骤：
1)聚氨酯多元醇前驱体的制备：
将涤纶混杂纤维与醇解剂按质量比1:2～6混合，在质量份数为涤纶混杂纤维0.2％～0.75％的金属锡类催化剂作用下，及惰性气体保护下，加热并冷凝回流反应得聚氨酯多元醇前驱体；
2)聚氨酯的制备：
将步骤1得到的聚氨酯多元醇前驱体与聚醚多元醇按质量比例1:3～8混合均匀，升温并真空脱水、降温，再按异氰酸酯基与羟基摩尔比1～1.5加入异氰酸酯，升温进行活泼氢原位交联反应，反应后经熟化得到含有纤维增强颗粒的、具有弹性的聚氨酯。
优选地，所述涤纶混杂纤维包括质量分数为60～80％的涤纶，其余为混杂物；该混杂物包括丙纶、氨纶、或锦纶中的一种或多种。
优选地，所述聚氨酯多元醇前驱体羟值为232～380，数均分子量为500～1500。
优选地，所述醇解剂为一缩二乙二醇。
优选地，所述步骤1中加热反应条件包括加热温度210～220℃，反应时间3～5h。
优选地，所述异氰酸酯为二苯基甲烷二异氰酸酯(MDI)。
优选地，所述步骤2中加热真空脱水的温度不低于120℃，经真空脱水后冷却至不超过80℃。
优选地，所述步骤2中熟化温度不低于85℃时间不少于10h。
本发明所述的应用为聚氨酯在环保型塑胶跑道的应用，也可以根据应用的需要添加助剂使用，添加的助剂包括增塑剂、填料、颜料等。
本发明与现有技术相比，具有以下有益效果：
本发明中采用涤纶为主混杂纤维作为原料，包含的混杂纤维包括但丙纶、氨纶或锦纶中的一种或多种，在催化剂的作用下，氨纶醇解为带羟的化合物；锦纶的结构中含有酰胺结构，羟基和酰胺基中均具有活泼氢，可在后续的聚氨酯原位交联聚合中与异氰酸酯的分子链形成氢键交联，提高产品聚氨酯的拉伸强度、断裂伸长率等力学性能。未被醇解的混杂纤维如丙纶可起到纤维增强的效果，使聚氨酯不仅具备很高的力学性能，同时显示出优异的耐磨性能及回弹性。
下面结合附图对本发明作进一步的说明。
附图说明
图1为本发明优选实施方式中聚氨酯制备流程示意图。
具体实施方式
下面通过具体实施方式对本发明做进一步的解释及说明，应当理解下面的实施方式的目的是为了使本发明的技术方案更加清楚、易于理解，并不限制权利要求的保护范围。
实施例1
(1)将洗净、烘干的涤纶混杂纤维(涤纶60份，氨纶20份，锦纶10份，丙纶10份)、200份一缩二乙二醇加入反应釜，加入0.2份金属锡类催化剂，通入干燥氮气置换出反应体系内的空气，将反应体系的温度升高至210℃，反应3h，醇解反应结束后，得到聚氨酯多元醇前驱体混合物。
(2)将步骤(1)得到的聚氨酯多元醇前驱体100份与200份聚醚多元醇混合均匀，升温至120℃，真空脱水1h，停止抽真空，将体系温度降至80℃，按nNCO:nOH＝1.0加入二苯基甲烷二异氰酸酯，反应30min后抽气泡，再继续反应2h，倒入模具于85℃熟化10h，得到含有纤维增强颗粒的聚氨酯弹性体。
实施例2
(1)将洗净、烘干的涤纶混杂纤维(涤纶70份，氨纶20份，锦纶5份，丙纶5份)、400份一缩二乙二醇加入反应釜，加入0.3份金属锡类催化剂，通入干燥氮气置换出反应体系内的空气，将反应体系的温度升高至215℃，反应5h，醇解反应结束后得到聚氨酯多元醇前驱体。
(2)将步骤(1)得到的聚氨酯多元醇前驱体100份与400份聚醚多元醇混合均匀，升温至120℃，真空脱水1h，停止抽真空，将体系温度降至80℃，按nNCO:nOH＝1.2加入二苯基甲烷二异氰酸酯，反应30min后抽气泡，再继续反应2h，倒入模具于85℃熟化10h，得到含有纤维增强颗粒的聚氨酯弹性体。
实施例3
(1)将洗净、烘干的涤纶混杂纤维(涤纶75份，氨纶10份，锦纶10份，丙纶5份)、300份一缩二乙二醇加入反应釜，加入0.5份金属锡类催化剂，通入干燥氮气置换出反应体系内的空气，将反应体系的温度升高至220℃，反应4h，醇解反应结束后得到聚氨酯多元醇前驱体。
(2)将步骤(1)得到的聚氨酯多元醇前驱体100份与800份聚醚多元醇混合均匀，升温至120℃，真空脱水1h，停止抽真空，将体系温度降至80℃，按nNCO:nOH＝1.4依次加入二苯基甲烷二异氰酸酯，反应30min后抽气泡，再继续反应2h，倒入模具于85℃熟化10h，得到含有纤维增强颗粒的聚氨酯弹性体。
实施例4
(1)将洗净、烘干涤纶混杂纤维(涤纶80份，氨纶5份，锦纶10份，丙纶5份)、600份一缩二乙二醇加入反应釜，加入0.75份金属锡类催化剂，通入干燥氮气置换出反应体系内的空气，将反应体系的温度升高至220℃，反应5h，醇解反应结束后得到聚氨酯多元醇前驱体。
(2)将步骤(1)得到的聚氨酯多元醇前驱体100份与600份聚醚多元醇混合均匀，升温至120℃，真空脱水1h，停止抽真空，将体系温度降至80℃，按nNCO:nOH＝1.5依次加入二苯基甲烷二异氰酸酯，反应30min后抽气泡，再继续反应2h，倒入模具于85℃熟化10h，得到含有纤维增强颗粒的聚氨酯弹性体。
对比例1
(1)将经洗净、烘干后的涤纶100份，一缩二乙二醇200份加入反应釜，加入0.3份金属锡类催化剂，通入干燥氮气置换出反应体系内的空气，将反应体系的温度升高至215℃，反应5h，醇解反应结束后得到聚氨酯多元醇前驱体。
(2)将步骤(1)得到的聚氨酯多元醇前驱体100份与400份聚醚多元醇混合均匀，升温至120℃，真空脱水1h，停止抽真空，将体系温度降至80℃，按nNCO:nOH＝1.2依次加入二苯基甲烷二异氰酸酯，反应30min后抽气泡，再继续反应2h，倒入模具于85℃熟化10h，得到含有纤维增强颗粒的聚氨酯弹性体。
实施例1-4为涤纶为主混杂纤维制备聚氨酯弹性体，为了对比，对比例1采用纯的涤纶纤维进行如实施例1～4的醇解制备聚氨酯弹性体；将实施例1-4和对比例1得到的产物羟值进行分析，羟值采用乙酸酐/高氯酸/乙酸乙酯常温酰化法进行测试：所用乙酰化试剂为乙酸酐-乙酸乙酯溶液，用0.5mol/L的KOH甲醇溶液滴定，指示剂为质量分数为10％的酚酞吡啶溶液；测试结果分别为380，321，254，232，367；聚氨酯弹性体按照测试标准进行制样测试，其中，拉伸性能按GB/T 528-1998标准进行；回弹性按GB/T 1618进行测试；邵尔A硬度按照GB/T531-1999进行测试，测试结果见表1。由表1的数据可见，实施例1-4制备的聚氨酯弹性体均显示出较高的拉伸强度、伸长率、邵A硬度。证明涤纶为主混杂纤维醇解制备的聚氨酯弹性体具有比纯涤纶纤维醇解制备的聚氨酯更好的力学性能；实施例4得到的聚氨酯回弹性最优，高于纯涤纶醇解产物制备的聚氨酯(对比例1)，显示出优异的回弹性特征。综上所述，采用涤纶为主混杂纤维醇解制备得到的聚氨酯弹性体具有比纯涤纶醇解制备聚氨酯更好的力学性能及回弹性，解决了混杂纤维难处置的环境问题，具有很好的经济性和环保性。
表1实施例1-4所得聚氨酯弹性体的力学性能
本发明是通过实施例来描述的，但并不对本发明构成限制，参照本发明的描述，所公开的实施例的其他变化，如对于本领域的专业人士是容易想到的，这样的变化应该属于本发明权利要求限定的范围之内。
Claims (9)
1.一种涤纶混杂纤维制备聚氨酯的方法，其特征在于：
包括以下步骤：
1)聚氨酯多元醇前驱体的制备：
将涤纶混杂纤维与醇解剂按质量比1:2～6混合，
在质量份数为涤纶混杂纤维0.2％～0.75％的金属锡类催化剂作用下，及惰性气体保护下，
加热并冷凝回流反应得聚氨酯多元醇前驱体；
2)聚氨酯的制备：
将步骤1得到的聚氨酯多元醇前驱体与聚醚多元醇按质量比例1:3～8混合均匀，升温并真空脱水、降温，
再按异氰酸酯基与羟基摩尔比1～1.5加入异氰酸酯，升温，
反应后经熟化得到含有纤维增强颗粒的、具有弹性的聚氨酯。
2.根据权利要求1所述的涤纶混杂纤维制备聚氨酯的方法，其特征在于：
所述涤纶混杂纤维包括质量分数为60～80％的涤纶，其余为混杂物；
该混杂物包括丙纶、氨纶、或锦纶中的一种或多种。
3.根据权利要求1所述的涤纶混杂纤维制备聚氨酯的方法，其特征在于：
所述聚氨酯多元醇前驱体羟值为232～380，数均分子量为500～1500。
4.根据权利要求1所述的涤纶混杂纤维制备聚氨酯的方法，其特征在于：
所述醇解剂为一缩二乙二醇。
5.根据权利要求1所述的涤纶混杂纤维制备聚氨酯的方法，其特征在于：
所述步骤(1)中加热反应条件为加热温度210～220℃，反应时间3～5h。
6.根据权利要求1所述的涤纶混杂纤维制备聚氨酯的方法，其特征在于：
所述异氰酸酯为二苯基甲烷二异氰酸酯。
7.根据权利要求1所述的涤纶混杂纤维制备聚氨酯的方法，其特征在于：
所述步骤(2)中升温并真空脱水时的温度不低于120℃，经真空脱水后冷却至不超过80℃。
8.根据权利要求1所述的涤纶混杂纤维制备聚氨酯的方法，其特征在于：
所述步骤2中熟化包括温度不低于85℃时间不少于10h于模具的过程。
9.一种如权利要求1～8任一项制备的聚氨酯在环保型塑胶跑道的应用。
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