CN101817986A - 纤维素/树脂复合体及其制造方法 - Google Patents
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Abstract
本发明提供：纤维素在树脂中均匀分散的纤维素/树脂复合体及其制造方法。含有采用溶解了纤维素的离子性液体，在极性溶剂中使纤维素再析出而形成的纤维素结晶，上述纤维素结晶的纤维素I型结晶成分的比率、纤维素II型结晶成分的比率、与纤维素非结晶成分的比率之和为1，上述纤维素I型结晶成分的比率在0.4以上，上述纤维素II型结晶成分的比率在0.1以上。
Description
技术领域
本发明涉及纤维素/树脂复合体及其制造方法。
背景技术
在建设可持续发展社会时，强烈要求从原来的大量生产、大量消费、大量废弃型向循环型的转变。特别是原来采用石油等枯竭资源作材料所形成的工业制品必需转变为采用生物质(biomass)资源。在这种情况下，希望作为木质材料主成分的纤维素得到有效利用。在这里，原来采用来自石油的树脂所形成的材料与纤维素进行复合化已经完成。其中，通过具有I型结晶结构的纤维素与树脂的复合化，可以谋求树脂的低热膨张化及强度的增加等。
具有I型结晶结构的纤维素可以作为纸、木质材料及衣料而利用，然而，天然纤维素多数为纤维状，难以以任意形状与树脂均匀分散。
树脂与其他化合物复合化，使树脂本来具有的特性提高的纤维强化树脂，即：微原纤维化的纤维素纤维构成的无纺布浸渍树脂而形成的纳米纤维片等已为人知。另外，细菌纤维素构成的集合体，浸渍纤维形成纤维强化复合体的方法已为人知(参照非专利文献1、2)。任何一种公知之例也是具有I型的纤维素结晶的纤维素构成的纤维素集合体浸渍树脂，由此形成与树脂的复合体。该方法由于是使纤维浸渍树脂形成复合体，故对具有复杂形状的材料，或具有厚度的材料，或熔融粘度高的热塑性树脂等的成型、加工困难。
[现有技术文献]
[非专利文献]
[非专利文献1]App1.Phys.A2005，A80，155
[非专利文献2]App1.Phys.Lett.2005，87，243110
发明内容
发明要解决的课题
本发明的目的是提供：在树脂中均匀分散了纤维素的纤维素/树脂复合体，及其制造方法。
用于解决课题的手段
即，本发明的纤维素/树脂复合体，其特征在于含有纤维素结晶，该纤维素结晶是采用溶解了纤维素的离子性液体，在极性溶剂中使纤维素再析出而形成的；上述纤维素结晶的纤维素I型结晶成分的比率、纤维素II型结晶成分的比率、与纤维素非结晶成分的比率之和为1，纤维素I型结晶成分的比率在0.4以上，上述纤维素II型结晶成分的比率在0.1以上。
另外，纤维素/树脂复合体的制造方法，其特征在于，该方法包括：在离子性液体中溶解纤维素的工序；在分散了树脂微粒的极性溶剂中，添加溶解了上述纤维素的离子性液体，使纤维素再析出的工序；上述树脂微粒发生分散，对纤维素再析出的溶液加以过滤、洗涤，形成纤维素/树脂粉体的工序；以及，对上述纤维素/树脂粉体进行加热、加压，使树脂熔融，形成纤维素/树脂复合体的工序。
发明效果
按照本发明，可将纤维素在树脂中均匀分散。
具体实施方式
下面详细地说明本发明。
本发明，通过使在离子性液体中可溶化的纤维素再析出时，与树脂微粒混合后，加热树脂，可以得到纤维素在树脂中均匀分散了的纤维素/树脂复合体。
具体的是，通过下述(1)～(3)工序形成：(1)使树脂微粒在溶解了纤维素的离子性液体中分散，往醇或水溶液中滴加离子性液体，得到纤维素与树脂的分散液的工序，或把溶解了纤维素的离子性液体，滴加至树脂微粒分散了的醇或水溶液中，得到纤维素与树脂微粒的分散液的工序；(2)把纤维素与树脂微粒的分散液加以过滤、干燥，得到纤维素与树脂微粒的粉体的工序；(3)把纤维素与树脂微粒的粉体进行加热、加压，使树脂微粒熔融，得到树脂与纤维素的复合体的工序。
本发明中可以使用的纤维素，只要是在离子性液体中可溶解的即可。可以举出从木材及棉花、海草等植物纤维分离的纤维素，从海鞘的被囊等动物纤维分离的纤维素，以及细菌纤维素等，优选从植物分离的纤维素。可以采用把纸浆、棉花及木材制成粉状，除去木质素等的木粉等。还有，这些纤维素既可单独使用1种，也可2种以上混合使用。
本发明中可以使用的树脂微粒，只要是本发明中使用的树脂成分为热塑性树脂即可而未作特别限定，例如，可以采用聚乙烯、聚丙烯、聚苯乙烯、氯乙烯树脂、聚对苯二甲酸乙二醇酯、醋酸乙烯树脂、ABS树脂、丙烯酸树脂、氟树脂、聚酰胺树脂、聚氨酯、乙缩醛树脂、聚碳酸酯、纤维素塑料、聚乳酸、聚乙醇酸、聚谷氨酸、聚赖氨酸、聚乙烯醇、聚乙二醇等聚醚、聚-3-羟基丁酸酯、聚-4-羟基丁酸酯、聚羟基戊酸酯、聚己二酸乙二醇酯、聚己内酰胺、聚丙内酰胺等聚酯等热塑性树脂。树脂微粒的平均粒径优选在1mm以下。当处于1mm以上时，通过树脂熔融与纤维素复合时，发生纤维素凝聚。
本发明提供的纤维素与树脂的复合体，优选纤维素纤维的重量比率小于60重量％。当纤维素纤维的重量比率处于60重量％以上时，发生熔融粘度增加等成型性问题。
纤维素在离子性液体中可溶已为人知，通过把在离子性液体中可溶化的纤维素添加至能溶解醇及水等离子性液体的极性液体中，离子性液体溶于极性溶剂的同时，在醇及水等液体中不溶的纤维素发生再析出已为人知(US2003/0157351，J.Am.Chem.2002，124，4974-4975，Macromolecules 2005，38，8272-8277)。
作为可以使用的极性溶剂，只要是纤维素成分不溶，能溶解离子性液体的溶剂即可而未作特别限定。例如，可以采用水、甲醇及乙醇等醇类，乙腈、呋喃及二噁烷等醚，丙酮等酮，另外，这些也可2种以上并用。优选的是乙醇、甲醇等醇类。
纤维素通过溶于离子性液体的纤维素与极性溶剂混合，能够得到纤维素。所得到的纤维素，通过与管、纤维、粒子等混合时的处理，能够得到任意形状的纤维素。
溶于离子性液体的纤维素，在极性溶剂中再析出时，边在溶剂中使树脂微粒分散，边使纤维素再析出，析出的纤维素，边与树脂微粒进行均匀混合，边过滤、纯化、干燥，由此可以得到树脂微粒在纤维素中均匀分散的纤维素与树脂的粉体。所得到的纤维素与树脂的粉体通过加热至树脂微粒的熔点以上，使树脂微粒熔融，压缩，由此可以得到纤维素均匀分散在树脂中的纤维素与树脂的复合体。
本发明使用的离子性液体，即使在室温下也保持液态，主要是在室温下溶解的盐或盐的混合物。这种盐或混合物，为含阳离子及阴离子的化合物。作为阳离子，可以混合咪唑鎓离子等环状脒离子，吡啶鎓离子，铵离子，锍离子，鏻离子等有机阳离子以一种或二种以上使用。作为阴离子，可以混合卤素、NO2 -、NO3 -、SO4 -、SbF6 -、AsF6 -、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、CH3COO-、CF3COO-、CF3SO3 -、(CF3SO2)2N-、(CF3SO2)3C-等以一种或二种以上使用。
本发明的混合物及混合材料中使用的纤维素，纤维素I型结晶成分的比率、纤维素II型结晶成分的比率、与纤维素非结晶成分的比率之和为1，该纤维素I型结晶成分的比率在0.4以上，该纤维素II型结晶成分的比率在0.1以上。通过溶解于离子性液体的纤维素与极性溶剂混合得到纤维素时，溶解于离子性液体的纤维素长时间保存后与极性溶剂混合，由此而得到纤维素，所得到的纤维素的结晶性恶化，非结晶成分增多，在与树脂形成复合体时，所形成的复合体的线膨胀系数不能充分降低。
本发明的纤维素I型结晶与II型结晶的结晶比率，是指把干燥的纤维素试样粉碎至粉状，成型为片剂，用Cu-Kα作为X线源，在用反射法得到的广角X线衍射图中，从各自的结晶峰求出的值。即，纤维素I型结晶的结晶比率(XI)是指，从纤维素I型结晶的(110)面峰的2θ＝15.0°的绝对峰强度h0以及从该面间隔中的基线的峰强度h1，按照式(1)求出的值。同样，纤维素II型结晶的结晶比率(XII)是指，从纤维素II型结晶的(110)面峰的2θ＝12.6°的绝对峰强度h0 *以及从该面间隔中的基线的峰强度h1 *，按照式(2)求出的值。
XI＝h1/h0… (1)
XII＝h1 */h0 *… (2)
可采用ビスコ-ス法(C.F.Cross，E.T.Bevan and C.Beadle，Ber.，26，1090-1097(1893))，铜氨法，有机溶剂法(C.F.Cross，E.T.Bevanand C.Beadle，Ber.，26，1090-1097(1893))等得到的、所谓再生纤维素，大部分由纤维素II型结晶构成，与本发明的纤维素不同，本发明的特征为，纤维素I型结晶成分的比率、纤维素II型结晶成分的比率、与纤维素非结晶成分的比率之和为1，该纤维素I型结晶成分的比率在0.4以上，该纤维素II型结晶成分的比率在0.1以上。
实施例
下面对本发明的实施例加以说明。
实施例1
把ダイセル制造的湿润セリツシユKY-100G进行脱水、干燥。把离子性液体(1-丁基-3-甲基咪唑鎓氯化物)用油浴加热至100℃，使熔融。向熔融了的离子性液体中添加100℃干燥的原样セリツシユKY-100G，使达到10重量％。用磁力搅拌机搅拌3小时，使セリツシユKY-100G溶解于离子性液体中。把得到的纤维素-离子性液体边用磁力搅拌机搅拌，边向分散了平均粒径110μm的树脂微粒(高强度聚乙烯)HDPE(商品名サンフアイン，アサヒケミカルズ社制造)的乙醇中滴加以使再析出纤维素达到30重量％。滴加后，用超声波均化机(商品名VC-130，SONIC and MATERIALS社制造)搅拌5分钟，使纤维素在乙醇中再析出。然后，过滤，进行用乙醇的洗涤，得到纤维素/树脂粉体。测定得到的纤维素/树脂粉体中的纤维素结晶性的结果为：纤维素I型结晶成分的比率为0.5、纤维素II型结晶成分的比率为0.3。
把得到的纤维素/树脂粉体于200℃进行真空热压，得到含纤维素30重量％的0.3mm的树脂/纤维素复合体膜。所得到的纤维素/树脂的复合体膜的线膨胀系数，用热机械试验机(商品名：TM 9300，真空理工社制造)测定的结果为0.8×10-5(1/K)(试验片：25×3(mm)，测定范围：25℃～110℃)。线膨胀系数比纤维素和树脂微粒混合所形成的复合体(比较例3)还低。
形成复合体膜时的纤维素与树脂的复合体的量增加，得到厚度2mm纤维素与树脂的复合体片。把得到的树脂与纤维素的复合体片切成颗粒状、进行加工后，把得到的颗粒用注射成型机，在圆筒体温度205℃、模具温度80℃进行成型加工，由此得到弯曲强度试验用成型体。弯曲强度试验按JIS K7171的3点弯曲试验来进行。所得到的复合体的弯曲强度为70MPa。强度比纤维素与树脂微粒混合所形成的复合体(比较例3)还高。
实施例2
树脂微粒采用平均粒径105μm的聚丙烯微粒(商品名サンアロマ-PM900A，サンアロマ-社制造)。采用与实施例1同样的方法，得到含纤维素30重量％的树脂与纤维素的复合体膜及片。所得到的膜的线膨胀系数为3.2×10-5(1/K)(试验片：25×3(mm)，测定范围：-40℃～110℃)。
所得到的树脂与纤维素的复合体片，与实施例1同样成型，得到弯曲强度试验用成型体。所得到的复合体的弯曲强度为120MPa。
另外，把得到的颗粒用注射成型机，在注射成型机圆筒体温度205℃、模具温度80℃进行成型加工，得到能够用于马达用壳体的成型体。
比较例1
树脂微粒采用(高强度聚乙烯)HDPE(商品名サンフアイン，アサヒケミカルズ社制造)，不添加纤维素，采用与实施例1同样的方法，得到树脂膜及片。所得到的膜的线膨胀系数为2.8×10-5(1/K)。另外，所得到的树脂与纤维素的复合体片，与实施例1同样成型，得到弯曲强度试验用成型体。所得到的成型体的弯曲强度为20MPa。
比较例2
树脂微粒采用聚丙烯，不添加纤维素，采用与实施例1同样的方法，得到树脂膜及片。所得到的膜的线膨胀系数为10.2×10-5(1/K)。另外，所得到的树脂与纤维素的复合体片，与实施例1同样成型，得到弯曲强度试验用成型体。所得到的成型体的弯曲强度为50MPa。
比较例3
把ダイセル制造的湿润セリツシユKY-100G，边用磁力搅拌机搅拌，边使平均粒径110μm的树脂微粒(高强度聚乙烯)分散，以使纤维素达到30重量％。用超声波均化机搅拌5分钟，然后，过滤，进行用乙醇的洗涤，得到纤维素/树脂粉体。测定得到的纤维素/树脂粉体中的纤维素结晶性，结果为：纤维素I型结晶成分的比率为0.7、该纤维素II型结晶成分的比率为0.1。
得到的纤维素/树脂粉体于200℃进行真空热压，由此得到含纤维素30重量％的复合体膜及片。所得到的膜的线膨胀系数为1.4×10-5(1/K)。与实施例1同样成型，得到弯曲强度试验用成型体。所得到的复合体的弯曲强度为50MPa。
比较例4
采用与比较例3同样的方法，采用平均粒径105μm树脂微粒(聚丙烯)，得到含纤维素30重量％的复合体膜及片。所得到的膜的线膨胀系数为4.8×10-5(1/K)。与实施例1同样成型，得到弯曲强度试验用成型体。所得到的复合体的弯曲强度为80MPa。
Claims (4)
1.纤维素/树脂复合体，其特征在于含有纤维素结晶，该纤维素结晶是采用溶解了纤维素的离子性液体，在极性溶剂中使纤维素再析出而形成的；上述纤维素结晶的纤维素I型结晶成分的比率、纤维素II型结晶成分的比率、与纤维素非结晶成分的比率之和为1，上述纤维素I型结晶成分的比率在0.4以上，上述纤维素II型结晶成分的比率在0.1以上。
2.按照权利要求1中所述的纤维素/树脂复合体，其特征在于，该复合体为膜状。
3.马达用壳体，其特征在于，采用权利要求1或2中所述的纤维素/树脂复合体。
4.纤维素/树脂复合体的制造方法，其特征在于，该方法具有：在离子性液体中溶解纤维素的工序；在分散了树脂微粒的极性溶剂中，添加溶解了上述纤维素的离子性液体，使纤维素再析出的工序；对上述树脂微粒发生分散、纤维素再析出的溶液加以过滤、洗涤，形成纤维素/树脂粉体的工序；以及，上述纤维素/树脂粉体进行加热、加压，使树脂融解，形成纤维素/树脂复合体的工序。
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| CN107474343B (zh) * | 2017-07-31 | 2020-02-18 | 华南理工大学 | 一锅法制备海鞘纳米微晶纤维素/橡胶纳米复合材料的方法 |
| CN109401021A (zh) * | 2018-11-08 | 2019-03-01 | 中国科学院过程工程研究所 | 一种离子液体改性的生物基复合材料及其制备方法 |
| CN109401021B (zh) * | 2018-11-08 | 2021-02-09 | 中国科学院过程工程研究所 | 一种离子液体改性的生物基复合材料及其制备方法 |
| CN118406316A (zh) * | 2024-07-02 | 2024-07-30 | 安徽正合雅聚新材料科技有限公司 | 一种亲肤抗菌聚丙烯材料 |
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| JP5055314B2 (ja) | 2012-10-24 |
| JP2010195996A (ja) | 2010-09-09 |
| US20100222460A1 (en) | 2010-09-02 |
| CN101817986B (zh) | 2012-10-03 |
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