CN112359603A - 一种具有抗紫外性能的水性超支化聚氨酯上浆剂及其制备方法 - Google Patents

一种具有抗紫外性能的水性超支化聚氨酯上浆剂及其制备方法 Download PDF

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CN112359603A
CN112359603A CN202011400225.8A CN202011400225A CN112359603A CN 112359603 A CN112359603 A CN 112359603A CN 202011400225 A CN202011400225 A CN 202011400225A CN 112359603 A CN112359603 A CN 112359603A
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hyperbranched polyurethane
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aqueous
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敖玉辉
方岚清
刘浏
庄海林
宁臣
孔令强
鄢飞
尚垒
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Changchun University of Technology
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Abstract

本发明提供一种具有抗紫外性能的水性超支化聚氨酯上浆剂及其制备方法，属于上浆剂技术领域。该上浆剂按照重量份数计，包括：超支化聚氨酯1‑5份，中和剂0.5‑10份，去离子水90‑98.5份；所述的超支化聚氨酯的结构式如式1所示。本发明还提供一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，该方法先制备具有抗紫外性能的扩链剂，然后制备超支化聚氨酯，最后制备具有抗紫外性能的水性超支化聚氨酯上浆剂。该上浆剂不仅可以有效提高碳纤维聚酰胺基树脂复合材料的界面结合能力，还具有优异的抗紫外性能。

Description

一种具有抗紫外性能的水性超支化聚氨酯上浆剂及其制备 方法
技术领域
本发明属于上浆剂技术领域，具体涉及一种具有抗紫外性能的水性超支化聚氨酯上浆剂及其制备方法。
背景技术
碳纤维因其综合性能优异，是增强聚合物基复合材料的理想材料。在当今世界高速工业化的大背景下，碳纤维用途正趋向多样化。碳纤维复合材料已在军事及民用工业的各个领域取得广泛应用。从航天、航空、汽车、电子、机械、化工、轻纺等民用工业到运动器材和休闲用品等。碳纤维增强的复合材料可以应用于飞机制造等军工领域、风力发电叶片等工业领域、电磁屏蔽除电材料、人工韧带等身体代用材料以及用于制造火箭外壳、机动船、工业机器人、汽车板簧和驱动轴等。
碳纤维表面呈现惰性，并且纤维表面光滑，因此形成的复合材料的界面结合性能较差，其增强复合材料的力学性能与理论值相去甚远。通过碳纤维表面改性的方法可以改善纤维与树脂基体的界面粘结强度，从而改善复合材料的综合力学性能。上浆法不仅操作简单，还能避免碳纤维表面受到污染，保护表面基团的活性，提高纤维集束性，还能浸润碳纤维，减小碳纤维与基体树脂间的表面张力，增强碳纤维与基体树脂间的界面粘结程度，提髙复合材料力学性能。
超支化聚合物因其低粘度，官能团数量多而被广泛研究。超支化聚氨酯由于相似相容性能与尼龙基体有良好的相容性，并且在碳纤维表面上浆聚氨酯后能在碳纤维和尼龙之间形成良好的界面层，有效提高碳纤维/尼龙复合材料的力学性能。但由于聚氨酯具有光不稳定性，在长期光照环境下易分解，从而影响复合材料使用寿命。专利CN 105088798 A公开了一种水性聚氨酯上浆剂，该上浆剂的主要成分为线性聚氨酯，长期光照条件下易黄边老化，应用可能会受到限制。专利CN 109321119 A公开了一种稳定性好的水性聚氨酯涂料，通过制备改性剂改性聚氨酯以制得稳定乳液，操作过程较为复杂，耗时长，反应步骤较多。综上所述，开发适用于聚酰胺树脂的抗紫外、环保的水性热塑性上浆剂对碳纤维行业的发展具有重要意义。同时，水性上浆剂处理后的碳纤维在水中具有良好的分散性，可用于多种领域，如：炭纸、耐摩擦材料、体育器材的制备。
发明内容
本发明的目的是提供一种具有抗紫外性能的水性超支化聚氨酯上浆剂及其制备方法，该上浆剂不仅可以有效提高碳纤维聚酰胺基树脂复合材料的界面结合能力，还具有优异的抗紫外性能。
本发明首先提供一种具有抗紫外性能的水性超支化聚氨酯上浆剂，按照重量份数计，包括：
超支化聚氨酯1-5份，中和剂0.5-10份，去离子水90-98.5份；
所述的超支化聚氨酯的结构式如式1所示：
Figure BDA0002816702710000021
式1中，n的取值范围为20～80。
优选的是，所述的中和剂为三乙胺。
本发明还提供一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，包括以下步骤：
步骤一：具有抗紫外性能的扩链剂的制备
取纳米氧化物和二羟甲基丙酸溶于溶剂中，升温至70℃-90℃，在氮气保护下反应12-16小时，得到具有抗紫外性能的扩链剂；
步骤二：超支化聚氨酯的制备
取低聚物多元醇、二异氰酸酯和催化剂溶于溶剂，通氮气，在80℃-90℃条件下反应2-4小时，得到支化聚氨酯预聚体，然后加入步骤一的扩链剂，反应4-8小时，旋转蒸发除去溶剂，干燥，得到超支化聚氨酯；
步骤三：具有抗紫外性能的水性超支化聚氨酯上浆剂的制备
将步骤二得到的超支化聚氨酯粉末在高速搅拌作用下分散在水中，滴加中和剂反应，得到具有抗紫外性能的水性超支化聚氨酯上浆剂。
优选的是，所述的纳米金属氧化物选自纳米二氧化钛、纳米氧化锌或纳米二氧化硅中的一种。
优选的是，所述的纳米氧化物和二羟甲基丙酸的摩尔比为(10-15)：(20-40)。
优选的是，所述的低聚物多元醇选自没食子酸或绿原酸中的一种。
优选的是，所述的二异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯或二环己基甲烷二异氰酸酯中的一种。
优选的是，所述的催化剂选自二月桂酸二丁基锡、辛酸亚锡或辛酸锡中的一种。
优选的是，所述的步骤二的溶剂选自N，N-二甲基甲酰胺或四氢呋喃中的一种。
优选的是，所述的低聚物多元醇、二异氰酸酯和扩链剂的摩尔比为(1-3)：(3-10)：(3-10)。
与现有技术方案相比，本发明的有益效果如下：
本发明提供一种具有抗紫外性能的水性超支化聚氨酯上浆剂及其制备方法，该上浆剂按照重量份数计，包括超支化聚氨酯1-5份，中和剂0.5-10份，去离子水90-98.5份；本发明中的超支化聚氨酯具有低粘度，官能团密度大的特点，有利于在碳纤维表面形成均匀且官能团密度大的涂层，使碳纤维复合材料表现出更好的力学性能，同时由于纳米金属氧化物具有良好的紫外吸收性能，能保护超支化聚氨酯不在紫外光下降解，能在长期的紫外光照射环境下稳定存在。
附图说明
图1为本发明实施例中超支化聚氨酯的红外光谱图。
具体实施方式
本发明首先提供一种具有抗紫外性能的水性超支化聚氨酯上浆剂，按照重量份数计，包括：
超支化聚氨酯1-5份，中和剂0.5-10份，去离子水90-98.5份；
所述的超支化聚氨酯的结构式如式1所示：
Figure BDA0002816702710000041
式1中，n的取值范围为20～80。
按照本发明，所述的中和剂优选为三乙胺。
本发明还提供一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，包括以下步骤：
步骤一：具有抗紫外性能的扩链剂的制备：
取纳米氧化物和二羟甲基丙酸溶于溶剂中，所述的溶剂优选为异丙醇，然后在反应之前优选进行超生处理，所述的超生处理的时间优选为5-10分钟，再升温至70℃-90℃，在氮气保护下反应12-16小时，优选经过10000rpm离心10分钟，除去上清液，将沉淀溶于甲醇再次10000rpm离心10分钟，得到下层沉淀，60℃干燥12小时，得到具有抗紫外性能的扩链剂；所述的纳米金属氧化物优选选自纳米二氧化钛、纳米氧化锌或纳米二氧化硅中的一种。所述的纳米氧化物和二羟甲基丙酸的摩尔比优选为(10-15)：(20-40)。
步骤二：超支化聚氨酯的制备
取低聚物多元醇、二异氰酸酯和催化剂溶于溶剂，通氮气，在80℃-90℃条件下反应2-4小时，得到支化聚氨酯预聚体，然后加入步骤一的扩链剂，反应4-8小时，旋转蒸发除去溶剂，优选120℃干燥12小时，得到超支化聚氨酯；
所述的低聚物多元醇优选选自没食子酸或绿原酸中的一种。
所述的二异氰酸酯优选选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯或二环己基甲烷二异氰酸酯中的一种。
所述的催化剂优选选自二月桂酸二丁基锡、辛酸亚锡或辛酸锡中的一种。
所述的的溶剂优选选自N，N-二甲基甲酰胺或四氢呋喃中的一种。
所述的低聚物多元醇、二异氰酸酯、催化剂和扩链剂的摩尔比为(1-3)：(3-10)：(0.3-1.5)：(3-10)。
步骤三：具有抗紫外性能的水性超支化聚氨酯上浆剂的制备
将步骤二得到的超支化聚氨酯粉末在高速搅拌作用下分散在水中，所述的搅拌速度优选为300rpm，缓慢滴加中和剂反应，所述的的中和剂优选为三乙胺，所述的反应时间优选为20-30分钟，得到具有抗紫外性能的水性超支化聚氨酯上浆剂。
下面结合具体实施例对本发明做进一步详细的说明，实施例中涉及到的原料均为商购。
对比例1
将未处理的碳纤维切短为5mm每段，以10％的含量与聚酰胺6在260℃，60rpm条件下混合15min，出料切粒，得复合材料。拉伸测试及弯曲测试样条通过注塑制得，经万能试验机测试得拉伸强度为87.64MPa，弯曲强度为125.13MPa。具体如表1所示。
实施例1
超支化聚氨酯水性上浆剂的制备方法，包括以下步骤：
(1)将35g二羟甲基丙酸溶于异丙醇中，加入8g纳米二氧化钛，超声处理10分钟，升温至90℃，在氮气保护下反应12小时，10000rpm离心十分钟，沉淀甲醇洗三次，60℃干燥12小时，得到纳米二氧化钛接枝的二羟甲基丙酸。
(2)称取没食子酸13g，溶于N，N-二甲基甲酰胺中，加入异佛尔酮二异氰酸酯48ml，二月桂酸二丁基锡5ml，通氮气，升温至90℃反应2小时，得到超支化聚氨酯预聚体，加入步骤(1)中所得的48g纳米二氧化钛接枝二羟甲基丙酸，反应4小时，旋转蒸发除去溶剂，120℃干燥12小时，得到超支化聚氨酯。得到的超支化聚氨酯红外光谱如图1所示。
(3)取步骤(2)中得到的超支化聚氨酯粉末50g，在300rpm转速的高速搅拌作用下分散于水中，缓慢滴加三乙胺2ml，反应30分钟，得到具有抗紫外性能的水性超支化聚氨酯上浆剂。
将碳纤维在实施例1制备得到的上浆剂中浸渍走丝，速度为15m/min，在100℃下干燥后将碳纤维切短为5mm每段，以10％的含量与聚酰胺6在260℃，60rpm条件下混合15min，出料切粒，得复合材料。拉伸测试及弯曲测试样条通过注塑制得，经万能试验机测试得拉伸强度为111.93MPa，弯曲强度为142.56MPa，具体如表1所示。结果表明机械性能与未上浆碳纤维/尼龙6复合材料相比有明显提升。
实施例2
超支化聚氨酯水性上浆剂的制备方法，包括以下步骤：
(1)将270g二羟甲基丙酸溶于异丙醇中，加入80g纳米二氧化钛，超声处理五分钟，升温至85℃，在氮气保护下反应12小时，10000rpm离心十分钟，沉淀甲醇洗三次，60℃干燥12小时，得到纳米二氧化钛接枝的二羟甲基丙酸。
(2)称取没食子酸170g，溶于N，N-二甲基甲酰胺中，加入甲苯二异氰酸酯540g，二月桂酸二丁基锡50ml，通氮气，升温至80℃反应3小时，得到超支化聚氨酯预聚体，加入步骤(1)中所得的540g二氧化钛接枝的二羟甲基丙酸，反应6小时，减压蒸馏除去溶剂，120℃干燥12小时，得到超支化聚氨酯。
(3)取步骤(2)中制得的超支化聚氨酯200g，在300rpm转速的高速搅拌作用下分散于水中，缓慢滴加三乙胺30ml，反应30分钟，得到具有抗紫外性能的水性超支化聚氨酯上浆剂。
将碳纤维在实施例2制备得到的上浆剂中浸渍走丝，速度为15m/min，在100℃下干燥后将碳纤维切短为5mm每段，以10％的含量与聚酰胺6在260℃，60rpm条件下混合15min，出料切粒，得复合材料。拉伸测试及弯曲测试样条通过注塑制得，经万能试验机测试得拉伸强度为121.23MPa，弯曲强度为153.44MPa，具体如表1所示。结果表明机械性能与未上浆碳纤维/尼龙6复合材料相比有明显提升。
实施例3
超支化聚氨酯水性上浆剂的制备方法，包括以下步骤：
(1)将27g二羟甲基丙酸溶于异丙醇中，加入4g纳米氧化锌，超声处理五分钟，升温至85℃，在氮气保护下反应15小时，10000rpm离心十分钟，沉淀甲醇洗三次，60℃干燥12小时，得到纳米氧化锌接枝的二羟甲基丙酸。
(2)称取绿原酸35.5g，溶于N，N-二甲基甲酰胺中，加入六亚甲基二异氰酸酯84g，二月桂酸二丁基锡8ml，通氮气，升温至80℃反应4小时，得到超支化聚氨酯预聚体。加入步骤(1)中所得的110g氧化锌接枝的二羟甲基丙酸，反应8小时，减压蒸馏除去溶剂，120℃干燥12小时，得到超支化聚氨酯。
(3)取步骤(2)中制得的超支化聚氨酯100g，在300rpm转速的高速搅拌作用下分散于水中，缓慢滴加三乙胺10ml，反应30分钟，得到具有抗紫外性能的水性超支化聚氨酯上浆剂。
将碳纤维在实施例3制备得到的上浆剂中浸渍走丝，速度为15m/min，在100℃下干燥后将碳纤维切短为5mm每段，以10％的含量与聚酰胺6在260℃，60rpm条件下混合15min，出料切粒，得复合材料。拉伸测试及弯曲测试样条通过注塑制得，经万能试验机测试得拉伸强度为117.46MPa，弯曲强度为146.37MPa，具体如表1所示。结果表明机械性能与未上浆碳纤维复合材料相比有明显提升。
表1为对比例1和本发明实施例1-3提供的水性超支化聚氨酯上浆剂上浆碳纤维后，制备复合材料测试拉伸强度和弯曲强度的结果。
表1
实施例1 实施例2 实施例3 对比例1
拉伸强度(MPa) 111.93 121.23 117.46 87.64
弯曲强度(MPa) 142.56 153.44 146.37 125.13
表1的结果说明：用本发明的上浆剂制备得到的复合材料的机械性能与未上浆碳纤维复合材料相比有明显提升。
表2为对比例1和本发明实施例1-3提供的水性超支化聚氨酯上浆剂上浆碳纤维后，制备复合材料，对复合材料进行为期一周的氙灯照射紫外老化试验后，测试拉伸强度和弯曲强度的结果。
表2
实施例1 实施例2 实施例3 对比例1
拉伸强度(MPa) 108.75 120.10 115.56 80.95
弯曲强度(MPa) 140.87 151.24 144.69 108.65
表3为对比例1和本发明实施例1-3提供的水性超支化聚氨酯上浆剂上浆碳纤维后，制备复合材料，对复合材料进行为期一周的氙灯照射紫外老化试验后，拉伸强度及弯曲强度保留率的结果。
表3
实施例1 实施例2 实施例3 对比例1
拉伸强度保留率(％) 97.16 98.99 98.38 92.37
弯曲强度保留率(％) 98.81 98.57 98.85 86.83
表2和表3说明，用本发明的上浆剂制备得到的复合材料具有优异的抗紫外性能。

Claims (10)

1.一种具有抗紫外性能的水性超支化聚氨酯上浆剂，其特征在于，按照重量份数计，包括：
超支化聚氨酯1-5份，中和剂0.5-10份，去离子水90-98.5份；
所述的超支化聚氨酯的结构式如式1所示：
Figure FDA0002816702700000011
式1中，n的取值范围为20～80。
2.根据权利要求1所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂，其特征在于，所述的中和剂为三乙胺。
3.根据权利要求1所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，其特征在于，包括以下步骤：
步骤一：具有抗紫外性能的扩链剂的制备
取纳米氧化物和二羟甲基丙酸溶于溶剂中，升温至70℃-90℃，在氮气保护下反应12-16小时，得到具有抗紫外性能的扩链剂；
步骤二：超支化聚氨酯的制备
取低聚物多元醇、二异氰酸酯和催化剂溶于溶剂，通氮气，在80℃-90℃条件下反应2-4小时，得到支化聚氨酯预聚体，然后加入步骤一的扩链剂，反应4-8小时，旋转蒸发除去溶剂，干燥，得到超支化聚氨酯；
步骤三：具有抗紫外性能的水性超支化聚氨酯上浆剂的制备
将步骤二得到的超支化聚氨酯粉末在高速搅拌作用下分散在水中，滴加中和剂反应，得到具有抗紫外性能的水性超支化聚氨酯上浆剂。
4.根据权利要求3所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，其特征在于，所述的纳米金属氧化物选自纳米二氧化钛、纳米氧化锌或纳米二氧化硅中的一种。
5.根据权利要求3所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，其特征在于，所述的纳米氧化物和二羟甲基丙酸的摩尔比为(10-15)：(20-40)。
6.根据权利要求3所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，其特征在于，所述的低聚物多元醇选自没食子酸或绿原酸中的一种。
7.根据权利要求3所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，其特征在于，所述的二异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯或二环己基甲烷二异氰酸酯中的一种。
8.根据权利要求3所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，其特征在于，所述的催化剂选自二月桂酸二丁基锡、辛酸亚锡或辛酸锡中的一种。
9.根据权利要求3所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，其特征在于，所述的步骤二的溶剂选自N，N-二甲基甲酰胺或四氢呋喃中的一种。
10.根据权利要求3所述的一种具有抗紫外性能的水性超支化聚氨酯上浆剂的制备方法，其特征在于，所述的低聚物多元醇、二异氰酸酯和扩链剂的摩尔比为(1-3)：(3-10)：(3-10)。
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