CN102232099B - 一种塑料增强用麻纤维及其制备方法 - Google Patents
一种塑料增强用麻纤维及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种塑料增强用麻纤维及其制备方法。该麻纤维由以下按重量份计的组分组成：短切麻纤维100份，麻纤维处理剂0.1～100份，功能性聚烯烃1～10份，偶联剂0.1～10份和抗氧剂0.1～0.5份。该方法包括步骤：将短切麻纤维切断，置于氢氧化钠水溶液中浸泡并搅拌，冲洗干净，甩干水份，再浸泡在麻纤维处理剂水溶液中，烘干，得到经表面处理的短切麻纤维；将短切麻纤维、偶联剂、功能性聚烯烃和抗氧剂依次加入到预热的捏合机中，搅拌得到塑料增强用麻纤维。本发明制备的短切麻纤维色泽好，刚性和耐热性好，与塑料的相容性好，可用于制备高性能的短麻纤维\塑料复合材料，并在塑料基体中起到增强的作用。
Description
技术领域
本发明属于天然纤维复合材料及木塑复合材料技术领域，具体是指一种塑料增强用麻纤维及其制备方法
背景技术
近几年来，天然植物纤维复合材料及木塑复合材料方面的研究方兴未艾。一方面由于天然植物纤维的来源广泛，价格低廉；另一方面性能方面天然植物纤维增强塑料大有取代矿物纤维增强塑料的趋势。
多数天然植物纤维是以长纤维状或编制成纤维毡后再与热固性树脂热压成型，不能像玻纤一样直接加入到热塑性塑料中用于注塑成型；同时天然植物纤维一方面由于表面富含羟基，表现出强极性和亲水性，与非极性或弱极性的塑料相容性极差，制备的复合材料的性能差；另一方面由于植物纤维体积大、填充量大，纤维与塑料、纤维与设备及纤维之间的摩擦大使得植物纤维增强塑料难于加工，特别是用于注射成型。为了解决植物纤维与塑料界面相容的问题，目前主要的解决方法就是添加界面相容剂，一类是偶联剂类、如硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、稀土偶联剂、异氰酸酯偶联剂等，另一类是马来酸酐与聚烯烃的接枝或共聚物。偶联剂类多数为液体用量少且不容易均匀分散到植物纤维中，影响其偶联效果，工业应用需要特殊的设备来处理；马来酸酐与聚烯烃的接枝或共聚物多数是颗粒状容易分散到塑料和植物纤维中，但其接枝率低难于提高界面粘结力。尽管如此，填充大量的植物纤维和塑料的复合物也给加工带来困难，难于挤出或注射成型。为了解决植物纤维与塑料复合材料的加工问题，出现各种加工助剂，如烯烃蜡、酰胺蜡、硬脂酸、硬脂酸锌、硬脂酸钙等，但是过多的加工助剂的加入也会使得复合材料的性能下降。
发明内容
为克服上述现有技术中存在的不足，本发明的首要目的在于提供一种塑料增强用麻纤维。
本发明的另一目的在于提供上述塑料增强用麻纤维的制备方法。
为实现上述目的，本发明提供如下技术方案：一种塑料增强用麻纤维，该塑料增强用麻纤维由以下按重量份计的组分组成：
所述短切麻纤维为苎麻纤维、亚麻纤维、剑麻纤维、黄麻纤维和焦麻纤维中的一种以上。
所述麻纤维处理剂为尿素-甲醛树脂预聚体、三羟甲基三聚氰胺树脂或六羟甲基三聚氰胺树脂。
所述功能性聚烯烃为茂金属聚乙烯蜡、茂金属聚丙烯、茂金属聚烯烃、氧化茂金属聚烯烃蜡和茂金属聚烯烃蜡-马来酸酐接枝物中的一种以上。
所述偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、异氰酸酯偶联剂和稀土偶联剂中的一种以上。
所述抗氧剂是抗氧剂1010和抗氧剂168，两者的质量比为2∶1。
上述的一种塑料增强用麻纤维的制备方法，包括以下操作步骤：
(1)将麻纤维切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液中浸泡并搅拌1～20min后，用清水冲洗干净，甩干水份后晾干，再浸泡在温度为80～90℃的麻纤维处理剂水溶液中5min～30min，待麻纤维吸尽麻纤维处理剂水溶液后，烘干，得到经表面处理的短切麻纤维；
(2)将经表面处理的短切麻纤维、偶联剂、功能性聚烯烃和抗氧剂依次加入到预热至70～80℃的捏合机中，搅拌，得到塑料增强用麻纤维。
步骤(1)所述氢氧化钠水溶液的质量百分比浓度为1％～10％；所述麻纤维处理剂水溶液的质量百分比浓度为10％～50％；所述甩干水份是采用离心方式甩干水分；所述晾干是晾至质量含水率为8～15％(麻纤维的正常含水率)。
步骤(1)所述烘干是采用真空干燥进行烘干，烘干温度为90～150℃，烘干至麻纤维的质量含水率小于1％；所述用清水冲洗为冲洗至pH 7.0～9.0。
步骤(2)所述搅拌的时间为5～10min；所述搅拌的速度为每分钟50～300转。
本发明的原理是：本发明通过稀碱液洗去纤维表面的杂质，再用尿素-甲醛树脂预聚体、三羟甲基三聚氰胺树脂或六羟甲基三聚氰胺树脂等处理剂的水溶液处理，纤维表面的羟基与处理剂的羟甲基发生反应，在纤维表面包覆上一层脲醛树脂或三聚氰胺树脂，降低了麻纤维的表面极性，减低麻纤维的吸水率，同时提高了麻纤维的刚性和耐热性；再通过偶联剂提高麻纤维与塑料的相容性，及通过功能性聚烯烃改善纤维内部的润滑性和分散性。
与现有技术相比，本发明具有如下的有益效果：本发明制备的短切麻纤维色泽好，刚性和耐热性好，可以直接像短玻纤一样加入到塑料基体中，与塑料的相容性好，可用于制备高性能的短麻纤维\塑料复合材料，并在塑料基体中起到增强的作用。
具体实施方式
下面结合实施例对本发明做进一步详细的描述，但本发明的实施方式不限于此。
实施例1
(1)将100重量份苎麻纤维切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液(质量百分比浓度为1％)中浸泡并搅拌20min后，用清水冲洗至pH 7.0，离心甩干水份，再浸泡在温度为80℃的麻纤维处理剂(80重量份尿素-甲醛树脂预聚体)水溶液(质量百分比浓度为30％)中处理30min，待麻纤维吸尽麻纤维处理剂水溶液后采用温度110℃真空干燥至麻纤维质量含水率小于1％，得到经表面处理的短切麻纤维；
(2)将经表面处理的短切麻纤维、2重量份硅烷偶联剂、9重量份功能性聚烯烃(5重量份茂金属聚乙烯蜡和4重量份茂金属聚烯烃蜡-马来酸酐接枝物混合)和0.4重量份抗氧剂(抗氧剂1010和抗氧剂168，两者的质量比为2∶1)依次加入到预热至70℃的捏合机中，以每分钟100转的速度搅拌5min，得到塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。
实施例2
(1)将100重量份亚麻纤维切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液(质量百分比浓度为10％)中浸泡并搅拌2min后，用清水冲洗至pH 9.0，离心甩干水份，再浸泡在温度为90℃的麻纤维处理剂(90重量份三羟甲基三聚氰胺树脂)水溶液(质量百分比浓度为20％)中30min，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度150℃真空干燥至麻纤维含水率小于1％，得到经表面处理的短切麻纤维；
(2)将经表面处理的短切麻纤维、8重量份偶联剂(4重量份钛酸酯偶联剂和4重量份稀土偶联剂混合)、4重量份功能性聚烯烃(2重量份茂金属聚丙烯和2重量份茂金属聚烯烃混合)和0.5重量份抗氧剂(抗氧剂1010和抗氧剂168，两者的质量比为2∶1)依次加入到预热至80℃的捏合机中，以每分钟50转的速度搅拌10min，得到塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。
实施例3
(1)将100重量份剑麻纤维切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液(质量百分比浓度为5％)中浸泡并搅拌5min后，用清水冲洗至pH 8.0，离心甩干水份，再浸泡在温度为85℃的麻纤维处理剂(100重量份六羟甲基三聚氰胺树脂)水溶液(质量百分比浓度为10％)中处理20min，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度120℃真空干燥至麻纤维质量含水率小于1％，得到经表面处理的短切麻纤维；
(2)将经表面处理的短切麻纤维、7重量份偶联剂(5重量份铝酸酯偶联剂和2重量份异氰酸酯偶联剂)、7重量份功能性聚烯烃(5重量份茂金属聚烯烃和2重量份氧化茂金属聚烯烃蜡混合)和0.4重量份抗氧剂(抗氧剂1010和抗氧剂168，两者的质量比为2∶1)依次加入到预热至75℃的捏合机中，以每分钟300转的速度搅拌5min，得到塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。
实施例4
(1)将100重量份黄麻纤维切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液(质量百分比浓度为3％)中浸泡并搅拌1min后，用清水冲洗至pH 7.5，离心甩干水份，再浸泡在温度为88℃的麻纤维处理剂(50重量份尿素-甲醛树脂预聚体)水溶液(质量百分比浓度为30％)中处理25min，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度100℃真空干燥至麻纤维质量含水率小于1％，得到经表面处理的短切麻纤维；
(2)将经表面处理的短切麻纤维、8重量份偶联剂(5重量份异氰酸酯偶联剂和3重量份稀土偶联剂混合)、1重量份氧化茂金属聚烯烃蜡和0.3重量份抗氧剂(抗氧剂1010和抗氧剂168，两者的质量比为2∶1)依次加入到预热至78℃的捏合机中，以每分钟150转的速度搅拌8min，得到塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。
实施例5
(1)将100重量份焦麻纤维切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液(质量百分比浓度为8％)中浸泡并搅拌15min后，用清水冲洗至pH 8.5，离心甩干水份，再浸泡在温度为80℃的麻纤维处理剂(20重量份三羟甲基三聚氰胺树脂)水溶液(质量百分比浓度为50％)中处理15min，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度90℃真空干燥至麻纤维质量含水率小于1％，得到经表面处理的短切麻纤维；
(2)将经表面处理的短切麻纤维、0.1重量份异氰酸酯偶联剂、5重量份功能性聚烯烃(1重量份茂金属聚乙烯蜡、2重量份茂金属聚丙烯和3重量份茂金属聚烯烃蜡-马来酸酐接枝物混合)和0.1重量份抗氧剂(抗氧剂1010和抗氧剂168，两者的质量比为2∶1)依次加入到预热至76℃的捏合机中，以每分钟250转的速度搅拌8min，得到塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。
实施例6
(1)将100重量份麻纤维(苎麻纤维和焦麻纤维混合)以上切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液(质量百分比浓度为6％)中浸泡并搅拌12min后，用清水冲洗至pH 7.5，离心甩干水份，再浸泡在温度为90℃的麻纤维处理剂(50重量份六羟甲基三聚氰胺树脂)水溶液(质量百分比浓度为30％)中处理5min，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度150℃真空干燥至麻纤维质量含水率小于1％，得到经表面处理的短切麻纤维；
(2)将经表面处理的短切麻纤维、10重量份偶联剂(2重量份硅烷偶联剂、5重量份铝酸酯偶联剂和3重量份稀土偶联剂混合)、10重量份功能性聚烯烃(2重量份茂金属聚乙烯蜡、3重量份茂金属聚丙烯、2重量份茂金属聚烯烃和3重量份氧化茂金属聚烯烃蜡)和0.5重量份抗氧剂(抗氧剂1010和抗氧剂168，两者的质量比为2∶1)依次加入到预热至72℃的捏合机中，以每分钟280转的速度搅拌7min，得到塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种塑料增强用麻纤维，其特征在于：该塑料增强用麻纤维由以下按重量份计的组分组成：
2.根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述短切麻纤维为苎麻纤维、亚麻纤维、剑麻纤维、黄麻纤维和焦麻纤维中的一种以上。
3.根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述麻纤维处理剂为尿素-甲醛树脂预聚体、三羟甲基三聚氰胺树脂或六羟甲基三聚氰胺树脂。
4.根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述功能性聚烯烃为茂金属聚乙烯蜡、茂金属聚丙烯、茂金属聚烯烃、氧化茂金属聚烯烃蜡和茂金属聚烯烃蜡-马来酸酐接枝物中的一种以上。
5.根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、异氰酸酯偶联剂和稀土偶联剂中的一种以上。
6.根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述抗氧剂是抗氧剂1010和抗氧剂168，两者的质量比为2∶1。
7.根据权利要求1所述的一种塑料增强用麻纤维的制备方法，其特征在于包括以下操作步骤：
(1)将麻纤维切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液中浸泡并搅拌1～20min后，用清水冲洗，甩干水份后晾干，再浸泡在温度为80～90℃的麻纤维处理剂水溶液中5min～30min，待麻纤维吸尽麻纤维处理剂水溶液后烘干，得到经表面处理的短切麻纤维；
(2)将经表面处理的短切麻纤维、偶联剂、功能性聚烯烃和抗氧剂依次加入到预热至70～80℃的捏合机中，搅拌，得到塑料增强用麻纤维。
8.根据权利要求7所述的制备方法，其特征在于：步骤(1)所述氢氧化钠水溶液的质量百分比浓度为1％～10％；所述麻纤维处理剂水溶液的质量百分比浓度为10％～50％；所述甩干水份是采用离心方式甩干水分；所述晾干是晾至质量含水率为8～15％。
9.根据权利要求7所述的制备方法，其特征在于：步骤(1)所述烘干是采用真空干燥进行烘干，烘干温度为90～150℃，烘干至质量含水率小于1％；所述用清水冲洗为冲洗至pH 7.0～9.0。
10.根据权利要求7所述的制备方法，其特征在于：步骤(2)所述搅拌的时间为5～10min；所述搅拌的速度为每分钟50～300转。
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| KR101715317B1 (ko) * | 2015-10-05 | 2017-03-22 | 주식회사 서연이화 | 발포체 조성물 및 그 제조방법 |
| CN106079723B (zh) * | 2016-06-24 | 2018-08-31 | 浙江大学宁波理工学院 | 阻燃改性苎麻织物/苯并噁嗪树脂层压板及其制备方法 |
| CN107012587A (zh) * | 2017-05-15 | 2017-08-04 | 吉林大学 | 一种天然环保型麻纤维增强可降解聚合物基毡材及其复合板材与制备方法 |
| CN110219163B (zh) * | 2019-04-30 | 2021-12-21 | 江阴芗菲纺织科技有限公司 | 一种碱-尿素预处理纯亚麻纱线的方法 |
| CN114015122A (zh) * | 2021-11-23 | 2022-02-08 | 广东富强科技股份有限公司 | 一种汽车顶棚基材及其制备方法 |
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| WO2006052421A2 (en) * | 2004-11-05 | 2006-05-18 | Owens-Corning Fiberglass Technology Ii, Llc | Fiber size, sized reinforcements, and articles reinforced with such reinforcements |
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| WO2005080514A1 (en) * | 2004-02-12 | 2005-09-01 | Virtic, Llc | Security ink |
| PL1812634T3 (pl) * | 2004-10-22 | 2011-12-30 | Dow Global Technologies Llc | Ulepszone materiały poliolefinowe do kompozytów z tworzyw sztucznych |
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| DE102007036792A1 (de) * | 2007-08-03 | 2009-02-05 | Clariant International Limited | Hochkristalline Polypropylenwachse |
| CN100564023C (zh) * | 2008-02-15 | 2009-12-02 | 南京林业大学 | 一种麻塑复合材料板材及其制备方法 |
| US7846295B1 (en) * | 2008-04-30 | 2010-12-07 | Xyleco, Inc. | Cellulosic and lignocellulosic structural materials and methods and systems for manufacturing such materials |
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| CN1688428A (zh) * | 2002-10-15 | 2005-10-26 | 陶氏环球技术公司 | 含有纤维增强的热塑性聚合物组合物的制品 |
| WO2006052421A2 (en) * | 2004-11-05 | 2006-05-18 | Owens-Corning Fiberglass Technology Ii, Llc | Fiber size, sized reinforcements, and articles reinforced with such reinforcements |
| CA2621336A1 (en) * | 2005-09-16 | 2007-03-29 | University Of Maine System Board Of Trustees | Thermoplastic composites containing lignocellulosic materials and methods of making the same |
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