CN1193987A - 用磷化合物阻燃整理的再生纤维素 - Google Patents
用磷化合物阻燃整理的再生纤维素 Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 claims abstract description 39
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- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
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- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
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Abstract
本发明涉及阻燃整理的再生纤维素,它含有化学式(Ⅰ)的至少一种化合物。本发明还涉及化学式(Ⅰ)化合物作为专门用作再生纤维素的阻燃剂和再生纤维素的阻燃整理的用途,这是以化学式(Ⅰ)化合物的掺入或含有这些化合物的分散液的掺入为特征的。
Description
本发明主题是含有选出的磷化合物作阻燃剂的再生纤维素。
本发明特别涉及阻燃整理的再生纤维素,此纤维素含有化学式I的至少一个化合物,其中R1,R2相互独立,是未取代或取代的C1-12-烷基-,C5-7-环烷基-,C7-12芳烷基-或C6-12芳基和X是氧或硫。
在化学式I中R1和R2优选是异丁基,和X优选是氧。
化学式I的化合物是已知的和可用专业人员已知的方法制备,例如按USP 4855507所描述的方法。
它们作为阻燃剂在全合成的聚合物,特别是聚烯烃,耐冲击韧性改性的聚苯乙烯,聚酰胺,聚苯醚,用耐冲击韧性改性聚苯乙烯改性的聚苯醚,聚对苯二甲酸乙二酯和聚氨酯的应用同样是已知的。惊奇地发现,化学式I的化合物也可以适用于再生纤维素的阻燃整理。因此本发明的主题是化学式I的化合物作为阻燃剂应用于再生纤维素和通过添加化学式I的化合物或含有这些化合物的分散液对纤维素进行阻燃整理的方法。
“再生-或水合纤维素”是一众所周知的表达。再生纤维素一般是通过以下方法制造,即将纤维素按已知方法溶解。通过将纤维素溶解于适当的有机溶剂中,如胺氧化物,特别是N-甲基吗啉氧化物(“Lyocell方法”)或将纤维素转化成可溶解的纤维素衍生物,如黄原酸酯(“粘胶法”)或可溶解的四胺铜(II)-氢氧化物-络合物(Tetraminkupfer(II)-hydroxid-Komplexe)(“Glanzstoff方法”)。化学式I的化合物可直接或分散在适当的介质中加入到纤维素溶液中。加料按已知方法可连续或不连续进行,例如间断加料,要进行强烈搅拌,以使化学式I化合物或其分散液均匀地分布在纤维素溶液中。将再生纤维素从上述含化学式I化合物的纤维素溶液中按已知方法凝固出来,例如将此溶液挤压通过细喷丝孔或长缝制造纤维或薄膜。再生纤维素的主要工艺性能由于加入本发明的式I阻燃剂仅受到非本质轻微的影响。
优选的是本发明的阻燃再生纤维素从胺氧化物的纤维素溶液中,特别是从N-甲基吗啉氧化物(NMMO)的纤维素溶液中凝固出来。
一般而言,纤维素可极好地溶于含水的叔胺氧化物,特别是含水的N-甲基吗啉氧化物(NMMO)中。从纤维素在胺氧化物的这种溶液中制造纤维素产品可按已知的方法进行,溶液通过成型模具挤出和通过空气间隙在牵引下将其引入一个含水的沉降浴中,使纤维素从溶液中凝固出来。
事实表明,化学式(I)的化合物,和这里特别是在化学式(I)中R1和R2是异丁基和X是氧的化合物,它与当前技术水平的商业化产品的区别在于对此工艺的条件极为稳定和从而可用经济的方法获得耐燃的纤维素产品。
阻燃的纤维素可按成型的方法形成例如纤维或薄膜。
按本发明阻燃整理的再生纤维素含有化学式(I)的化合物的量为以100%(重量)纯的再生纤维素为基础的5-35%(重量),优选为10至25%(重量),特别是25%(重量)。相应量的化学式(I)的化合物在成型之前加入纤维素溶液中。
在采用Lyocell-方法时化学式(I)的化合物也可以加入纤维素在叔胺氧化物的含水悬浮液中,后者用作制备溶液。
按本发明的分散液的制备可用普通已知的方法进行,例如由分散剂,分散介质和化学式(I)的化合物形成的浓的混合物通过研磨,例如在球磨机,砂磨机,玻璃球-或粒状石英-磨机中研磨至不溶解粒子大小平均为0.5-5μm,优选为1μm,和必要时通过加入分散介质,该介质优选为水来调节所需的浓度。
通常按本发明的分散液中含有10至60%(重量),优选15至50%(重量),特别是20至40%(重量)化学式(I)的一个化合物或化学式(I)的多个化合物的混合物;4-50%(重量),优选5-45%(重量)和特别是6-35%(重量)的分散剂,以化学式(I)化合物的重量为基础计算;其余是分散介质,优选为水。
下列实例中如无其它指定的话,其份量为计重份量,百分比为重量百分比。实施例I.按本发明分散液的制备实例1
25份的化学式(I)化合物和6.25份以萘磺酸钠为基础的分散剂进行混合和在68.75份的水中搅拌。然后将此混合物放在型号为DynoKDL-Pilot的球磨机中用1100ml的粒状石英研磨。在第一行程的研磨后将此混合物进行68小时的循环研磨。然后将此分散液进行过滤。II.按本发明再生纤维素的制备实例2
将15份按实例1制备的分散液在搅拌下加入到由18份α-纤维素制备的200份的黄原酸酯的溶液中。此溶液通过常规纺丝装置的喷丝板挤压在凝固浴中,此凝固浴中每立升含有125g硫酸(H2SO4),240g无水硫酸钠(Na2SO4)和12g无水硫酸锌(ZnSO4)。将这样得到的纤维进行彻底洗涤,干燥和加工成针织品。此针织品按Fenimore和Martin(Modern Plastics,November 1966)的方法测试阻燃性能,在此测定LOI-值(极限氧指数)。
按本发明阻燃整理的纤维素针织品之间进行比较表明,由于化合物(I)的存在明显降低了可燃性。
-LOI-值(按本发明处理的纤维素针织品): 27
-LOI-值(未经处理的纤维素针织品): 19实例3
将含有来自实例1的10%(重量)化学式(I)化合物和3%(重量)的表面活性剂Hypermer PS 2(ICI制造)的含水分散液放在球磨机中研磨,直至在显微镜下判断,看不到大于5μm的阻燃剂粒子为止。
在一捏合机HKD-T 0.6(IKA-实验室技术工厂制造)中将233g的50%含水NMMO,14.5g纤维素Buckeye V5和45g上述的分散液蒸发去过量的水制得组成为9.0%纤维素/3%化合物(1)/76%NMMO/12%H2O的纺丝原液。
作为纺丝设备采用在塑料加工中通用的熔融指数仪(Davenpot制造)。此仪器由一加热的温度调节园筒组成的,在其中装填纺丝原液。借助于一个在原来仪器中用一活塞加载的活塞(在采用的改造过的样机中活塞推进是通过步进马达)将纺丝原液通过在园筒下面安装的喷丝板挤压出。
纺丝原液在温度为100℃和吐出量为0.025g/孔/分钟通过1-孔/100μ的喷丝板挤压出和在通过60mm的空气间隙后进入一个水浴中,此水浴温度为23℃,长度为20cm,在此纤维素凝固出来。
所采用的纺丝方法称为干/湿纺丝法。在将长丝纤维中残余的NMMO洗涤15分钟后将纤维在70℃进行干燥。
得到以下的纤维:方法:
纺织测试按BISFA-规程“测试粘胶,莫代尔(modal)铜氨纤维,Lyocell,醋酯纤维,三醋酸酯短纤维和毛条的国际通过的方法”(Internationally agreed methods for testing viscose,modal,cupro,lyocell,acetate,triacetate staple fibres and tows”1993年出版。磷含量:
将纤维用H2SO4/H2O2进行分解,用钼酸铵进行颜色反应后做比色测定。数据:
纤度(dtex) | 1.74 |
磷含量 | 3.98 |
最高拉伸强力(空调)(cN/tex) | 23.3 |
断裂伸长(空调)(%) | 9.4 |
最高拉伸强力(湿)(cN/tex:) | 18.0 |
断裂伸长(湿)(%) | 11.9 |
BISFA-模量(cN/tex,5%) | 7.4 |
勾结强度(cN/tex) | 15.6 |
勾结伸长(%) | 4.7 |
结节强度(cN/tex) | 20.6 |
纤维的磷含量相当于纺丝掺入量的86%,与100%之差包含材料损失,这是由于阻燃剂粘附在磨的玻璃珠上。丝条显示出与火焰接触后自熄的性能。实施例4
将含有10%(重量)按实例1的化学式(1)化合物和1%(重量)表面活性剂Hypermer PS2(ICI生产的)的含水分散液在球磨机里研磨,直至在显微镜下判断看不到大于5μm的阻燃剂粒子为止。
在一搅拌釜中由3036g 75%含水的NMMO,360g纤维素BuckeyeV5(Buckeye,Memphis美国制造)和900g上述分散液借助于蒸发除去过量的水制备纺丝原液,它的组成为12%纤维素/3.0%化合物(1)/73.4% NMMO/11.6%水。
纺丝原液在温度为120℃,吐出量为0.025g/孔/分钟通过200-孔/100μ喷丝板挤压出,在30mm长的空气间隙牵伸和在含水的纺丝浴中纤维素凝固出。所采用的纺丝方法称为干/湿法。在30分钟洗净纤维中残余量的NMMO后,将纤维在70℃干燥。
得到以下的纤维:
方法:
纺织测试和磷含量:如同实例3
极限氧指数(LOI值):
20g梳理纤维网在180℃和200bar 1小时压缩成面积重为76g/m2,厚度为0.15mm的测试样品。将此测试样置于由氮气和氧气组成的气流,将其中氧气的份额逐步提高。LOI-值是测试样品在点着后刚刚还能继续燃烧的氧浓度。数据:
纤度(dtex) | 1.55 |
磷含量(%) | 2.68 |
最高拉伸强力(空调)(cN/tex) | 35.6 |
断裂伸长(空调)(%) | 9.4 |
最高拉伸强力(湿)(cN/tex ) | 30.2 |
断裂伸长(湿)(%) | 13.4 |
BISFA-模量(cN/tex,5%) | 11.6 |
勾结强度(cN/tex) | 14.0 |
勾结伸长(%) | 1.9 |
结节强度(cN/tex ) | 22.5 |
极限氧指数(%) | 24 |
Claims (14)
1.再生纤维素,该再生纤维素含有化学式I化合物至少一种
其中
R1,R2相互独立地是未取代的或取代的C1-12-烷基,C5-7环烷基,C7-12芳烷基或C6-12芳基和
X是氧或硫。
2.按权利要求1的再生纤维素,其特征是,R1和R2是异-丁基和X是氧。
3.按权利要求1或2的再生纤维素,其特征是,它以纯的再生纤维素为基础含有化学式I化合物的量为5-35%(重量),优选为10-25%(重量),特别优选为25%(重量)。
4.按权利要求1至3之一的再生纤维素,其特征是,纤维素通过由胺氧化物溶液,优选为N-甲基吗啉氧化物溶液凝固出来而获得。
5.按权利要求4的再生纤维素,其特征是,纤维素可作为纤维或薄膜存在。
6.再生纤维素阻燃整理的方法,其特征是,按已知方法,将至少一种按权利要求1的化学式I化合物加入到纤维素溶液中,加入量以纯纤维素为基础计为5-35%(重量),并进行混合和再生纤维素按已知方法从纤维素溶液中凝固出来。
7.按权利要求6的方法,其特征是,将化学式I的一种化合物以纯的再生纤维素为基础计为10-25%(重量),优选为25%(重量)的量加入。
8.按权利要求6和7的方法,其特征是,纤维素溶液是在胺氧化物,优选是在N-甲基吗啉氧化物中的溶液。
9.按权利要求8的方法,其特征是,将纤维素溶液加工成纤维或薄膜。
10.化学式I的化合物在再生纤维素中用作阻燃剂的应用。
11.按权利要求10的应用,用于通过纤维素从在胺氧化物,优选在N-甲基吗啉氧化物的溶液中凝固而制造纤维素成型品的过程。
12.用于阻燃整理再生纤维素的分散液,该分散液包括至少一种按权利要求1的化学式I化合物,一种分散介质和至少一种在此领域常用的分散剂和必要时一种分散稳定剂或分散稳定剂混合物。
13.按权利要求12的分散液,其特征是,它含有10-60%(重量),优选为15至50%(重量),特别优选为20-40%(重量)的至少一种化学式I的化合物和4-50%(重量),优选为5-45%(重量),特别优选为6-35%(重量)的至少一种分散剂,它是以化学式I化合物的重量为基础计。
14.按权利要求12或13的分散液,其特征是,分散介质是水。
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JP (1) | JP3881694B2 (zh) |
CN (1) | CN1085993C (zh) |
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DE (1) | DE59609756D1 (zh) |
ES (1) | ES2184879T3 (zh) |
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AT404846B (de) * | 1997-06-16 | 1999-03-25 | Chemiefaser Lenzing Ag | Zusammensetzung enthaltend feine feststoffteilchen |
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Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1464545A (en) * | 1974-05-21 | 1977-02-16 | Courtaulds Ltd | Flame-retardant regenerated cellulose filaments |
IT1039783B (it) * | 1975-07-11 | 1979-12-10 | Snia Viscosa | Metodo perfezionato per la produzione di fibre cellulosiche ad alta resistenza alla combustio ne e fibre e prodotti tessili otenuti secondo il detto metodo |
DE3807030A1 (de) * | 1988-03-04 | 1989-09-14 | Pfersee Chem Fab | Waessriges textilbehandlungsmittel und verfahren zum knitterfestmachen von textilmaterial |
CA1311496C (en) * | 1988-03-28 | 1992-12-15 | Allan James Robertson | 1,4-disubstituted-2,3,5,6-tetrahydroxy-1, 4-diphosphorinanes and their oxides or sulfides |
WO1989009649A1 (en) * | 1988-04-05 | 1989-10-19 | Shinkohjinkasei Co., Ltd. | Highly functional regenerated cellulose composition |
GB9126841D0 (en) * | 1991-12-18 | 1992-02-19 | Courtaulds Plc | Heterocyclic compounds |
DE4308524C1 (de) * | 1992-06-16 | 1994-09-22 | Thueringisches Inst Textil | Verfahren zur Herstellung von Cellulosefasern und -filamenten nach dem Trocken-Naßextrusionsverfahren |
GB9305969D0 (en) * | 1993-03-23 | 1993-05-12 | Courtaulds Plc | Phosphorus-containing flame retardants |
GB9309617D0 (en) * | 1993-05-11 | 1993-06-23 | Courtaulds Fibres Ltd | Fibre production process |
-
1996
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- 1996-07-04 US US08/973,611 patent/US6130327A/en not_active Expired - Lifetime
- 1996-07-04 WO PCT/EP1996/002945 patent/WO1997002315A1/de active IP Right Grant
- 1996-07-04 EP EP96922909A patent/EP0836634B1/de not_active Expired - Lifetime
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- 1996-07-04 AU AU63609/96A patent/AU720168B2/en not_active Ceased
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Also Published As
Publication number | Publication date |
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JPH11511185A (ja) | 1999-09-28 |
CA2225943A1 (en) | 1997-01-23 |
ATE225379T1 (de) | 2002-10-15 |
AU6360996A (en) | 1997-02-05 |
CA2225943C (en) | 2008-01-15 |
US6130327A (en) | 2000-10-10 |
PT836634E (pt) | 2003-02-28 |
CN1085993C (zh) | 2002-06-05 |
BR9609652A (pt) | 1999-02-23 |
NO316726B1 (no) | 2004-04-19 |
EP0836634B1 (de) | 2002-10-02 |
DE59609756D1 (de) | 2002-11-07 |
NO980011L (no) | 1998-01-02 |
AU720168B2 (en) | 2000-05-25 |
EP0836634A1 (de) | 1998-04-22 |
ES2184879T3 (es) | 2003-04-16 |
WO1997002315A1 (de) | 1997-01-23 |
JP3881694B2 (ja) | 2007-02-14 |
NO980011D0 (no) | 1998-01-02 |
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