CN110128807A - 一种新型尼龙6/聚氨酯复合材料及其制备方法 - Google Patents

一种新型尼龙6/聚氨酯复合材料及其制备方法 Download PDF

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CN110128807A
CN110128807A CN201910520132.XA CN201910520132A CN110128807A CN 110128807 A CN110128807 A CN 110128807A CN 201910520132 A CN201910520132 A CN 201910520132A CN 110128807 A CN110128807 A CN 110128807A
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李悦
汪济奎
张世平
严辉
赵忠华
周佳
肖俊
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East China University of Science and Technology
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Abstract

本发明涉及一种新型尼龙6/聚氨酯复合材料及其制备方法,其组分的重量百分比为:己内酰胺81%‑84%,聚丙二醇13‑16%,聚二甲基硅氧烷1%‑2%,改性活化剂1%‑1.5%,阴离子聚合引发剂0.15%‑0.2%。以己内酰胺为反应溶剂,加入聚丙二醇、聚二甲基硅氧烷和活化剂在70‑85℃反应3小时后,升高温度至130‑145℃减压蒸馏1小时除去混合液中的水分。然后加入阴离子聚合引发剂,减压蒸馏30分钟,与活化剂混合后浇铸170℃模具中成型得到尼龙6/聚氨酯复合材料。这种复合材料具有高强高韧、耐水性强等优点,且生产工艺简单,适于大规模生产。

Description

一种新型尼龙6/聚氨酯复合材料及其制备方法
技术领域
本发明涉及一种尼龙6/聚氨酯复合材料及其制备方法,具有高强高韧和耐水等特性,属于高分子材料技术领域。
背景技术
尼龙6由于其强度高、质量轻、耐磨损、抗老化以及良好的力学性能和耐化学稳定性,但也普遍具备着低温韧性差、耐热性差、耐水性差等缺点,这严重限制了其应用的宽度与广度。
由聚丙二醇与过量的改性活化剂反应制得-NCO 封端的聚氨酯预聚体,再与具有良好疏水性和耐候性的羟基封端聚二甲基硅氧烷(PDMS-OH)反应,合成有机硅改性聚氨酯(PDMS-PU),控制 n(-NCO) / n(-OH)﹥1,将其加入尼龙中制备PA6/PDMS-PU共聚物。随着硅氧键成分在聚氨酯分子主链中的加入,使改性后的聚氨酯有足够的伸缩性和弹性来保证它在使用过程中的理化和力学性能优异,并且PDMS在充当混合软段的同时可提高材料的疏水性和耐候性,对聚氨酯材料的热稳定性也有一定的贡献。
发明内容
针对尼龙的缺点,本发明加入有机硅改性聚氨酯,通过原位聚合反应制备了尼龙6/聚氨酯复合材料,提高了尼龙6与聚氨酯的相容性,实现了两种材料的优势互补。与传统的制备方法相比,本发明制备的尼龙6/聚氨酯复合材料的相容性和分散性更加优异,具有更强的机械性能、耐热性能、耐候性等。本发明是一种新颖的改性尼龙的方法,生产工艺简单,方便大规模生产。
本发明是通过以下技术方案实现的:
一种新型尼龙6/聚氨酯复合材料,其特征在于:以己内酰胺、聚丙二醇、聚二甲基硅氧烷、改性活化剂、阴离子聚合引发剂为原料,其各组分的占比如下:
己内酰胺 81%-84%
聚丙二醇 13-16%
聚二甲基硅氧烷 1%-2%
改性活化剂 1%-1.5%
阴离子聚合引发剂 0.15%-0.2%
其总重量满足100%,
所述的聚丙二醇的分子量为3000克/摩尔,
所述的聚二甲基硅氧烷为羟丙基聚二甲基硅氧烷,分子量为2000克/摩尔,
所述的改性活化剂为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或两种,
所述的阴离子聚合引发剂为氢氧化钠。
本发明的另一目的是为了提供一种新型尼龙6/聚氨酯复合材料的制备方法。
一种新型的尼龙6/聚氨酯复合材料的制备方法,其特征在于,所述的方法包括以下步骤:
(1)向烧瓶A中加入己内酰胺单体,在130-145℃熔融,减压蒸馏30分钟,将温度降至70-85℃并通氮气保护;
(2)将步骤(1)中熔融的己内酰胺作为反应溶剂,向其中加入聚丙二醇、聚二甲基硅氧烷搅拌1小时,再加入改性活化剂在氮气保护下反应2小时得到己内酰胺/聚氨酯混合液;
(3)向烧瓶B中加入与步骤(1)相同质量的己内酰胺单体,在130-145℃熔融,加入阴离子聚合引发剂,减压蒸馏30分钟;
(4)将烧瓶A与烧瓶B中的液体混合,高速搅拌混合均匀后,浇铸入170℃模具中成型1小时得到尼龙6/聚氨酯复合材料。
本发明采用原位聚合法,以己内酰胺为反应溶剂和阴离子聚合的反应单体,聚丙二醇、聚二甲基硅氧烷和改性活化剂在其中进行反应,生成了有机硅改性聚氨酯作为大分子活化剂,引发了己内酰胺的阴离子聚合。与现有技术相比,本发明所制得的尼龙6/聚氨酯复合材料具有高强高韧、强耐水性、强热稳定性等优点。
具体实施方式
通过下列实施例描述本发明,在不违反本发明的宗旨下,本发明应不限于以下实施例具体明示的内容。
实施例、对比例所用原料如下
己内酰胺,中国石化巴陵有限责任公司;
聚丙二醇,上海麦克林生化科技有限公司;
聚二甲基硅氧烷,上海四里工贸有限公司;
改性活化剂,甲苯二异氰酸酯,萨恩化学技术(上海)有限公司;
阴离子聚合引发剂,氢氧化钠,上海泰坦科技股份有限公司;
对比例1
准确称量80g己内酰胺,在130℃熔融后减压蒸馏30min后加入0.18g氢氧化钠,减压蒸馏30min以除去反应过程中生成的水,然后加入1.22g甲苯二异氰酸酯,混合均匀后立即浇入170℃预热模具中成型1小时后取出。将样品制成标准样条后在90℃下干燥24小时后进行性能测试,测得样条的缺口冲击强度为4.23kJ/m2,拉伸强度为73.25MPa,吸水率为4.7%,接触角为49.63°。
对比例2
准确称量80g己内酰胺,在130℃熔融后减压蒸馏30min后加入0.18g氢氧化钠,减压蒸馏30min以除去反应过程中生成的水,然后加入12g聚氨酯后升温至180℃,待聚氨酯溶解后与己内酰胺混合均匀,然后加入1.22g甲苯二异氰酸酯,混合均匀后立即浇入170℃预热模具中成型1小时后取出。将样品制成标准样条后在90℃下干燥24小时后进行性能测试,测得样条的缺口冲击强度为14.45 kJ/m2,拉伸强度为42.89MPa,吸水率为4.0%,接触角为61.12°。对比例2相比对比例1,冲击强度大幅提升,说明聚氨酯可以提高尼龙的韧性,吸水率和接触角有小幅提升,但拉伸强度下降幅度较大。
对比例3
准确称量40g己内酰胺,在130熔融后减压蒸馏30分钟,将温度降至70-85℃并通氮气保护,然后向其中加入12g聚丙二醇搅拌1小时,再加入1.22g甲苯二异氰酸酯在氮气保护下反应2小时得到己内酰胺/聚氨酯混合液升温至130℃,减压蒸馏30min除去混合液中残留的小分子和水。再准确称量40g己内酰胺,在130℃熔融后减压蒸馏30分钟后加入0.18g氢氧化钠,减压蒸馏30分钟以除去反应过程中生成的水。将烧瓶A与烧瓶B中的液体混合,混合均匀后立即浇入170℃预热模具中成型1小时后取出。将样品制成标准样条后在90℃下干燥24小时后进行性能测试,测得样条的缺口冲击强度为18.73 kJ/m2,拉伸强度为47.56MPa,吸水率为3.7%,接触角为65.31°。对比例3相比对比例2,冲击强度和拉伸强度同时提高,接触角提升,吸水率下降,说明经过共聚改性得到的尼龙6/聚氨酯复合材料的性能更加良好。
实施例1
准确称量40g己内酰胺,在130熔融后减压蒸馏30分钟,将温度降至70-85℃并通氮气保护,然后向其中加入12g聚丙二醇、1.2g聚二甲基硅氧烷搅拌1小时,再加入1.22g甲苯二异氰酸酯在氮气保护下反应2小时得到己内酰胺/聚氨酯混合液升温至130℃,减压蒸馏30min除去混合液中残留的小分子和水。再准确称量40g己内酰胺,在130℃熔融后减压蒸馏30分钟后加入0.18g氢氧化钠,减压蒸馏30分钟以除去反应过程中生成的水。将烧瓶A与烧瓶B中的液体混合,混合均匀后立即浇入170℃预热模具中成型1小时后取出。将样品制成标准样条后在90℃下干燥24小时后进行性能测试,测得样条的缺口冲击强度为19.12kJ/m2,拉伸强度48.12MPa,吸水率为3.1%,接触角为87.74°。实施例1相比对比例3,冲击强度和拉伸强度同时提高,接触角提升,吸水率下降,这说明经过聚二甲基硅氧烷改性可提升尼龙6/聚氨酯复合材料的强度的耐水性。
实施例2
准确称量40g己内酰胺,在130熔融后减压蒸馏30分钟,将温度降至70-85℃并通氮气保护,然后向其中加入12g聚丙二醇、1.8g聚二甲基硅氧烷搅拌1小时,再加入1.22g甲苯二异氰酸酯在氮气保护下反应2小时得到己内酰胺/聚氨酯混合液升温至130℃,减压蒸馏30min除去混合液中残留的小分子和水。再准确称量40g己内酰胺,在130℃熔融后减压蒸馏30分钟后加入0.18g氢氧化钠,减压蒸馏30分钟以除去反应过程中生成的水。将烧瓶A与烧瓶B中的液体混合,混合均匀后立即浇入170℃预热模具中成型1小时后取出。将样品制成标准样条后在90℃下干燥24小时后进行性能测试,测得样条的缺口冲击强度为19.31kJ/m2,拉伸强度为50.83MPa,吸水率为2.9%,接触角为95.52°。实施例2相比实施例1,说明提高聚二甲基硅氧烷含量可使尼龙6/聚氨酯复合材料的力学强度和耐水性进一步增强。

Claims (2)

1.一种尼龙6/聚氨酯复合材料,其特征在于,所述的复合材料中各组分的占比如下:
己内酰胺 81%-84%
聚丙二醇 13-16%
聚二甲基硅氧烷 1%-2%
改性活化剂 1%-1.5%
阴离子聚合引发剂 0.15%-0.2%
其总重量满足100%,
所述的聚丙二醇的分子量为3000克/摩尔,
所述的聚二甲基硅氧烷为羟丙基聚二甲基硅氧烷,分子量为2000克/摩尔,
所述的改性活化剂为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或两种,
所述的阴离子聚合引发剂为氢氧化钠。
2.如权利要求1所述的一种尼龙6/聚氨酯复合材料的制备方法,其特征在于,所述的方法包括以下步骤:
(1)向烧瓶A中加入己内酰胺单体,在130-145℃熔融,减压蒸馏30分钟,将温度降至70-85℃并通氮气保护;
(2)将步骤(1)中熔融的己内酰胺作为反应溶剂,向其中加入聚丙二醇、聚二甲基硅氧烷搅拌1小时,再加入改性活化剂在氮气保护下反应2小时得到己内酰胺/聚氨酯混合液;
(3)向烧瓶B中加入与步骤(1)相同质量的己内酰胺单体,在130-145℃熔融,加入阴离子聚合引发剂,减压蒸馏30分钟;
(4)将烧瓶A与烧瓶B中的液体混合,高速搅拌混合均匀后,浇铸入170℃模具中成型1小时得到尼龙6/聚氨酯复合材料。
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CN111285993A (zh) * 2020-03-09 2020-06-16 江苏科技大学 一种高流动聚酰胺6弹性体的制备方法
CN111690131A (zh) * 2020-02-16 2020-09-22 武汉纺织大学 力致变色高韧性尼龙6及其制备方法
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CN114621584A (zh) * 2022-04-25 2022-06-14 福建工程学院 一种连续纤维增强热塑性聚酰胺弹性体复合材料及其制备方法

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CN111690131A (zh) * 2020-02-16 2020-09-22 武汉纺织大学 力致变色高韧性尼龙6及其制备方法
CN111690131B (zh) * 2020-02-16 2022-04-26 武汉纺织大学 力致变色高韧性尼龙6及其制备方法
CN111285993A (zh) * 2020-03-09 2020-06-16 江苏科技大学 一种高流动聚酰胺6弹性体的制备方法
CN111285993B (zh) * 2020-03-09 2022-01-28 江苏科技大学 一种高流动聚酰胺6弹性体的制备方法
CN112250861A (zh) * 2020-09-21 2021-01-22 扬州倍尔特新材料有限公司 一种浇铸尼龙6聚二甲基硅氧烷共聚物的制备方法
CN114621584A (zh) * 2022-04-25 2022-06-14 福建工程学院 一种连续纤维增强热塑性聚酰胺弹性体复合材料及其制备方法
CN114621584B (zh) * 2022-04-25 2023-12-19 福建工程学院 一种连续纤维增强热塑性聚酰胺弹性体复合材料及其制备方法

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Application publication date: 20190816