CN1150952A - 可光降解的纤维素酯丝束 - Google Patents

可光降解的纤维素酯丝束 Download PDF

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CN1150952A
CN1150952A CN96105800A CN96105800A CN1150952A CN 1150952 A CN1150952 A CN 1150952A CN 96105800 A CN96105800 A CN 96105800A CN 96105800 A CN96105800 A CN 96105800A CN 1150952 A CN1150952 A CN 1150952A
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T·A·布罗多夫
J·B·霍普金斯
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Abstract

本发明涉及一种人造纤维，含有纤维素酯和0.05-5.0％(重量)平均粒径小于100纳米的二氧化钛。

Description

可光降解的纤维素酯丝束
本发明涉及一种可光降解的纤维素酯丝束。
纤维素酯丝束是已知的。见Kirk-Othmer著的《Encyclopediaof Chemical Technology》一书第4版第5卷第496-529页(由John Wiley & Sons出版，纽约，1993年)。醋酸纤维素丝束也是已知的，是Kirk-Othmer著的《Encyclopedia of ChemicalTechnology》一书第三版第5卷第89-117页(由John Wiley &Sons出版，1979，纽约)。掺杂用作去光剂的二氧化钛颜料如锐钛矿或金红石的醋酸纤维素丝束也是已知的，见Kirk-Othmer著的《Ibid》第3版第90页以及美国专利US4,022,632。理想的去光的二氧化钛颜料具有200-350nm(0.2-0.35微米)的粒径，见Kemira公司未标出出版日期的出版物“The Savannah Story”。这些颜料一般是被涂覆以阻止其光催化作用。见Rabek，J.F.，＂聚合物中的光致物理过程和光致化学反应的机理(Mechanisms ofPhotophysical Processes and Photochemical Reactions inPolymers)＂，John Wiley & Sons出版，纽约，1987，第585-587页。
已有人提出，锐钛矿型二氧化钛可用于加速纤维素酯丝束的光降解过程。见EP-A-597,478、WO93/24685和US5,242,880。这些可光降解纤维素酯丝束使用未涂覆的锐钛矿，见《Ibid》。作为可光降解的加速剂，锐钛矿型二氧化钛优于金红石型二氧化钛，见申请的权利要求21。在EP-A-597478中，纤维素丝束具有约0-5％(重量)的锐钛矿型二氧化钛，该二氧化钛的平均粒径为约300nm(0.3μm)，粒径分布为10-1000nm(0.01-1μm)，比表面积为3-30m2/g。在WO 93/24685中，参照48页表1中所列的例举的光活性锐钛矿二氧化钛，给出了平均粒径。其中公开了三种可商购的颜料。已知每种都具有约350nm(0.35μm)的平均粒径。在US5,242,880中，用光活性催化剂浸渍可氧化的聚合物如醋酸纤维素或聚丙烯以增加生物降解性。该光活性催化剂含有锐钛矿型二氧化钛，该二氧化钛含有盐或被盐涂覆。该盐占催化剂的2-30％(重量)。
细颗粒晶态二氧化钛(8-210nm或0.008-0.210μm)作为光降解剂用于塑料中是已知的，见Meldrum，B.J.，＂细颗粒TiO2-简介＂，SPE49th Annual Technical Conference Exhibits，，1991。其中，将未涂覆的细二氧化钛颗粒加到聚丙烯膜中，然后将其暴露于紫外线照射，以验证其光降解作用。
人们需要可光降解纤维素酯丝束，以减少由于在马路上丢弃具有纤维素酯丝束制成的过滤嘴的烟头而造成杂乱的问题。
本发明涉及一种人造纤维，它含有纤维素酯和0.05-5.0％(重量)的平均粒径小于100纳米(nm)的二氧化钛。
下面详述本发明。
本发明是一种人造纤维，它含有纤维素酯和0.05-5.0％(重量)的平均粒径小于100纳米的二氧化钛。当该纤维素酯是酯酸纤维素时，具有1.5-2.7的取代度，优选的二氧化钛重量范围为0.1-3.0％。这些人造纤维适于光降解。具有取代度为1.5-2.7的醋酸纤维素纤维在300小时或更短的时间内基本降解。测量＂基本降解＂的基准是下面详述的AATCC试验方法169-1990。优选地，基本降解是指在200小时时的强度小于或等于0.2克/旦。
纤维素酯是指有机酯。这种酯的例子包括：醋酸纤维素、丙酸纤维素、丁酸纤维素、乙酸-丙酸纤维素、乙酸-丁酸纤维素、丙酸-丁酸纤维素，等等，以及它们的结合物。用于本发明的纤维素酯可以用任何已知技术制备。见Kirk-Othmer著《Encyclopedia ofChemical Technology》一书第三版第5卷第89-129页(John Wiley& Sons出版，纽约，1979年)；和Libscomb，A.G.著的《乙酸纤维素：制备及应用》(Ernest Benn公司出版，英国伦敦，1933年)，这两本书均通过参考而引入本文。本发明的纤维素酯优选地具有至少2个葡糖酐环，而最好具有约2个至5000个葡糖酐环。还有，这类聚合物典型地具有约0.2-3.0分升/克的比浓对数粘度(IV)，最优选地为约1-1.6，在25℃由0.5克试样在100ml的60/40(重量)苯酚/四氯乙烷中的溶液测得。另外，用于本文纤维素酯的DS/AGU(每个葡糖酐单元的取代度)为约1.5-2.7。特别优选的是具有DS/AGU为1.7-2.6的乙酸纤维素。最优选的乙酸纤维素具有DS/AGU为1.8-2.2及IV为1.3-1.5。
任何已知的常规的添加到纤维素酯丝束中的添加剂也可以结合到本发明丝束中。例如，去光剂(如二氧化钛)和纺丝油剂可以加入，这是公知的。
用于本文的二氧化钛是指平均粒径小于100纳米的任何二氧化钛原料。这些二氧化钛也可具有大于50m2/g的比表面积。这种原料可由下列公司购得：萨特勒本化学股份有限公司(SachtlebenChemie GmbH，德国杜伊斯堡，商标名为“HOMBIFINE N”)；可米拉集团(Kemira Group，芬兰波里，商标名为“UV-Titan”)；衣施哈拉公司(Ishihara Corporation，美国加利弗尼亚旧金山，商品名为TIPAQUER二氧化钛TTO-55和TTO-51系列)；氧化钛化学有限公司(Tioxide Chemicals Itd.，英国克利夫兰郡比灵汉姆(Billingham)，注册商标为“UF”)。
优选地，该二氧化钛是平均粒径为小于10纳米和比表面积约为250m2/g的未涂覆锐钛矿。未涂覆是指不存在用于阻止各种商购二氧化钛光催化作用的无机材料涂层。见Rabek，J.著《Ibid》第257-259页，该书结合入本文供参考。这种无机涂层包括(并不限于此)：氧化铝、二氧化硅、氧化锌、乙酸锰、乙酸银、乙酸亚铊、  乙酸镓、乙酸铁、乙酸铅、乙酸铷、乙酸锶、乙酸铝、乙酸镧、乙酸锆、乙酸双氧铀、乙酸钾、乙酸钐、乙酸镨、乙酸铌、乙酸钕、乙酸铜、乙酸镁、乙酸钡、乙酸钇、乙酸钠、乙酸锂、乙酸铬、乙酸锡、乙酸钕镨、乙酸镍、乙酸钙、乙酸铈、乙酸锌、乙酸钴以及乙酸锰。
在挤塑进入丝束之前，该二氧化钛加到＂纺丝原液(dope)＂(即：已溶剂化的纤维素酯)中。可以在挤塑之前任何方便的时候加入该二氧化钛。除了要保证该细颗粒的聚集为最小或最低以使该细颗粒所具有的光活性最大这一点之外，对二氧化钛的制备没有什么特别限制。可以用常规公知方法进行丝束的挤塑。见Browne，C.L.著的《香烟的设计》一书第59-64页(Hoechst Celanese Corporation出版，Charlotle，NC，1990)，该书也引入本文供参考。
本文所指的香烟是任何公知的香烟，它包括烟草杆和过滤嘴，这些是工业上常用的术语。见Browne，C.L.著的《香因的设计》一书(Hoechst Celanese Corporation 出版，Charlotle，NC，1990)，该书引入本文供参考。
                        实施例
所有的纱线均以常规方法制备。见《纤维素化学及其应用》一书(Ellis Harwood Ltd.出版，Chichester，England，1985，P474-476)，该书引入本文供参考。将乙酸纤维素聚合物溶于96％丙酮和4％水的溶剂中。在所有情况下，制备的100磅总溶液均含有溶于73磅的96％/4％丙酮/水溶剂中的27磅乙酸纤维素聚合物。如果加入二氧化钛，它在聚合物溶于该溶剂之后进行。该混合物进行搅拌直到均匀，并过滤。过滤后，通过孔径为52μm的190孔喷丝板挤塑出纱。这得到具有2.9旦/单丝的纤维。
根据美国纺织化学师和着色师协会(AATCC)的程序对纱线进行评估。使用AATCC试验方法169-1990＂织物耐气候性：氙灯照射＂，方案1。制备纱以进行评估，它根据AATCC试验方法177-1993＂在升高温度和湿度下对光的颜色固着性：水冷氙灯装置＂的方法进行。
将纱缠绕在纸卡上并置于金属夹持器中，将带有纱的金属夹持器置于Atlas C65型Weatherometer(老化测试机)中，并经受交替的氙光照射和喷水环境。已经将环境(方案1)预设为相当于南佛罗里达州的周围环境。每隔100小时将纱移走，这大概相当于室外暴露1个月，将环境改为室内环境，然后测量断裂强度。实施例1
如上所述制备纱，加入了0.135磅平均直径为420nm的KemiraO-310颜料级的TiO2(锐钛矿)。实施例2
如上所述制备不添加TiO2的纱。实施例3
如上所述制备纱，加入了0.135磅Kemira 0-310 TiO2(锐钛矿)及0.135磅的初级粒径小于10nm的Hombifine N超细研磨的TiO2(锐钛矿)。实施例4
如上所述制备加入了0.135磅Hombifine N TiO2的纱。实施例5
如上所述制备加入了0.27磅Hombifine N TiO2的纱。
如表1所示，用超细TiO2制备的纱(实施例3、4和5)的分解(即断裂强度＝0克/旦)要比用颜料等级TiO2(实施例1)或完全不用TiO2(实施例2)制备的纱的分解快。即使实施例3和4两者均含有相同量的超细研磨TiO2，还含有颜料等级TiO2的实施例3的分解比只含有超细研磨TiO2实施例4的分解要慢。这是由于颜料等级TiO2的光反射性造成的。
                               表1
                   暴露在老化试验机中的各种乙酸
                       纤维素纱的强度(克/旦)
 0小时 100小时 200小时 300小时
试样
实施例10.5％颜料等级TiO2 1.06 0.79 0.54 0.15
实施例20.0％TiO2 1.14 0.68 0.53 0.14
实施例30.5％超细TiO20.5％颜料等级TiO2 1.06 0.46 0.14 0
实施例40.5％超细TiO2 1.08 0.55 0.06 0
实施例51.0％超细TiO2 1.05 0.28 0 0

Claims (5)

1.一种人造纤维，它含有：
纤维素酯，和
约0.05-5.0％(重量)平均粒径小于100纳米的二氧化钛。
2.一种人造纤维，它含有：
取代度为1.5-2.7的乙酸纤维素，
约0.05-5.0％(重量)平均粒径小于100纳米的二氧化钛，按AATCC试验方法169-1990测量，它可在300小时或更短时间内被基本上降解。
3.权利要求2的纤维，其中所述二氧化钛在乙酸纤维素中的含量为约1.0-3.0％(重量)。
4.权利要求2的纤维，其中的基本降解意指在200小时时的强度小于或等于0.2克/旦。
5.一种香烟，它含有：
烟草杆，和
含有权利要求1-4所述纤维的过滤嘴。
CNB961058005A 1995-03-14 1996-03-13 可光降解的纤维素酯丝束 Expired - Fee Related CN1135273C (zh)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1099438C (zh) * 1998-03-31 2003-01-22 日本烟草产业株式会社 生物分解性醋酸纤维素成形制品及吸烟物品用的过滤芯
CN108103604A (zh) * 2017-12-20 2018-06-01 南通大学 降解醋酸纤维的复合光敏添加剂及其制备方法和用途
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CN110613163A (zh) * 2017-12-20 2019-12-27 南通大学 含有复合光敏添加剂的降解醋酸纤维在烟滤嘴中的应用
CN110904681A (zh) * 2019-12-02 2020-03-24 江苏龙汇纳米科技有限公司 一种基于高分子纳米复合材料制备的预处理工艺
CN115005497A (zh) * 2022-07-20 2022-09-06 湖北中烟工业有限责任公司 一种可降解香烟滤棒母料和可降解香烟滤棒

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JPH08260231A (ja) 1996-10-08
ATE173305T1 (de) 1998-11-15
EP0732432B1 (en) 1998-11-11
US5647383A (en) 1997-07-15
DE69600936D1 (de) 1998-12-17
US5491024A (en) 1996-02-13

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