CN1109688A - 含有纤维素的稳定的模塑材料或纺丝液 - Google Patents

含有纤维素的稳定的模塑材料或纺丝液 Download PDF

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CN1109688A
CN1109688A CN94190266A CN94190266A CN1109688A CN 1109688 A CN1109688 A CN 1109688A CN 94190266 A CN94190266 A CN 94190266A CN 94190266 A CN94190266 A CN 94190266A CN 1109688 A CN1109688 A CN 1109688A
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glucosides
moulding material
spinning solution
acid
cellulose
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CN1039418C (zh
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W·卡尔特
J·曼纳
D·艾兴格
C·施伦姆夫
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Lenzing AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paper (AREA)
  • Multicomponent Fibers (AREA)
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Abstract

稳定的模塑材料或纺丝液，其含有纤维素、一种 叔胺氧化物，尤其是N-甲基吗啉-N-氧化物和需要 时的水及一种稳定剂，其特征是，用棓酸糖苷和m- 双棓酸糖苷混合物作稳定剂。本发明所用稳定剂在 长期稳定溶于叔胺氧化物中的纤维素方面超过了棓 酸丙酯。

Description

本发明涉及一种含有纤维素和一种含水的叔胺氧化物的稳定的模塑材料和纺丝液（Spinnmasse）。本发明还涉及将特殊稳定剂用于稳定溶于一种叔胺氧化物中的纤维素的用途。
由US-PS2179181已知叔胺氧化物能够溶解纤维素，且通过沉淀可由该溶液得到纤维素纤维。制备这类溶液的一种方法例如已由EP-A-0356419所公开。按照该公开，先配制一种纤维素在一种含水的叔胺氧化物中形成的悬浮液。该胺氧化物含有最多至40%（质量）的水。加热该含水的纤维素悬浮液，并在减压条件下蒸馏出水，直至纤维素进入溶液为止。
在溶解过程中和溶液在较高温度下放置期间出现纤维素和溶剂的分解。分解产物可使沉淀后得到的模制体例如纤维和薄膜明显变色，并在回收化学制品时只有花费巨额资金才能回收。而为了避免环境污染，必需对后者进行回收。
EP-A-0047929建议用棓酸丙酯（GPE）作为稳定剂。但事实证明，该化合物的稳定化作用仅能持续相对短的时间，因此必须快速处理已加热的纤维素溶液。此外，GPE价格昂贵，其溶解度使其难溶于极性溶剂如水中。
本发明的任务在于提供一种稳定剂，该稳定剂不具有上述缺点，并可在比GPE长的时间内稳定溶解的纤维素不分解。
本发明完成了所述任务，其解决方案是用棓酸糖苷和m-双棓酸糖苷混合物来稳定纤维素使其不分解。
本发明还涉及一种稳定的模塑材料或纺丝液，其含有纤维素、一种叔胺氧化物、尤其是N-甲基吗啉-N-氧化物，和需要时的水，以及一种稳定剂，其中用棓酸糖苷和m-双棓酸糖苷混合物作稳定剂。
本发明稳定的模塑材料或纺丝液的一种优选实施方式包括用丹宁酸作稳定剂。
根据药典记载，丹宁酸[CAS1401-55-4]定义为D（+）-葡糖与棓酸和m-双棓酸的酯类的一种混合物。优选物质中葡糖的所有醇OH基都被棓酸和m-双棓酸所酯化，其中m-双棓酸最好占棓酸和m-双棓酸总数的40%至90%。
丹宁酸也包含在同样可在本发明中用作稳定剂的所称的丹宁中。因此，本发明稳定的模塑材料或纺丝液的另一种优选实施方式包括用丹宁作稳定剂。
丹宁是以工业规模用来鞣皮革的产物。它分作植物物质和合成物质，其中植物产物由天然物质如木质和植物中提取得到。
本发明表明，不但植物丹宁而且丹宁酸本身都具有对叔胺氧化物中的纤维素有很好的稳定作用的特性。已确定，在溶液制备的常规条件下阻止了纤维素的分解，并可看到降低了叔胺氧化物的分解。
业已证明，本发明所用的稳定剂在最大为0.05%（质量）（以纤维素为基准）的浓度下就已经可以达到很好的效果。该浓度低于现有技术中对棓酸丙酯所建议的浓度。因此，以纤维素的质量计，本发明模塑材料或纺丝液的一种特别优选的实施方式含有最高0.05%（质量）浓度的稳定剂。
下面用实施例进一步解释本发明。
实施例
用含70%（质量）NMMO的水溶液来制备溶液。向该NMMO溶液掺入纤维素，在一台试验室搅拌机中于250毫巴压力和约95℃温度下蒸出水并使纤维素溶解。数量选择得使所得溶液含有10%（质量）纤维素、15%水和75%NMMO。
在纤维素溶解后30分钟和750分钟用一台Bohlin流变仪（测量温度：120℃）测定溶液的粘度。所得结果列于下表作为“对比”。
接着重复两次上述过程，但加入GPE（浓度：0.05%，以纤维素为基准）或丹宁酸（浓度：0.05%，以纤维素为基准;Aldrich Chemicals的丹宁酸）作稳定剂。所得结果同样列于下表中。
表
稳定剂  粘度(Pa·s)
30分钟后  750分钟后
对比(无稳定剂)  753  18
GPE  985  383
丹宁酸  985  755
由表可知，用GPE作稳定剂时溶液的粘度降至明显低于用丹宁酸时的值。这就是说，与GPE相比，丹宁酸在750分钟（＝12小时30分钟）时间期间可以更好地稳定纤维素使之不分解。
用棓酸糖苷和m-双棓酸糖苷的其它混合物也得到类似的良好结果。

Claims (5)

1、稳定的模塑材料或纺丝液，其含有纤维素、一种叔胺氧化物、尤其是N-甲基吗啉-N-氧化物和一种稳定剂以及需要时的水，其特征在于，用棓酸糖苷和m-双棓酸糖苷的一种混合物作为稳定剂。
2、按照权利要求1所述的稳定的模塑材料或纺丝液，其特征在于，用丹宁酸作稳定剂。
3、按照权利要求1所述的稳定的模塑材料或纺丝液，其特征在于，用丹宁作稳定剂。
4、按照权利要求1至3中之一所述的稳定的模塑材料或纺丝液，其特征在于，以纤维素质量为基准，含有最高0.05%（质量）浓度的稳定剂。
5、棓酸糖苷和m-双棓酸糖苷混合物在稳定含纤维素和一种叔胺氧化物的模塑材料或纺丝液中的应用。
CN94190266A 1993-05-05 1994-04-29 含有稳定剂的用于模塑或纺丝液的材料 Expired - Fee Related CN1039418C (zh)

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ATA886/93 1993-05-05
AT0088693A AT399348B (de) 1993-05-05 1993-05-05 Form- bzw. spinnmasse enthaltend cellulose und verwendung bestimmter stoffe zu ihrer stabilisierung

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AT (2) AT399348B (zh)
AU (1) AU670873B2 (zh)
BG (1) BG61698B1 (zh)
BR (1) BR9405331A (zh)
CA (1) CA2137783A1 (zh)
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FI (1) FI945853A0 (zh)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1078890C (zh) * 1995-08-18 2002-02-06 连津格股份公司 制备胺氧化物水溶液的方法
CN1082102C (zh) * 1996-08-14 2002-04-03 坦塞尔有限公司 挤出制品的制造方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT403057B (de) * 1995-05-09 1997-11-25 Chemiefaser Lenzing Ag Verfahren zur herstellung cellulosischer formkörper
US6210801B1 (en) 1996-08-23 2001-04-03 Weyerhaeuser Company Lyocell fibers, and compositions for making same
US6471727B2 (en) 1996-08-23 2002-10-29 Weyerhaeuser Company Lyocell fibers, and compositions for making the same
US6306334B1 (en) 1996-08-23 2001-10-23 The Weyerhaeuser Company Process for melt blowing continuous lyocell fibers
US6331354B1 (en) 1996-08-23 2001-12-18 Weyerhaeuser Company Alkaline pulp having low average degree of polymerization values and method of producing the same
US5989605A (en) * 1996-10-31 1999-11-23 Teepak Investments, Inc. Sausage product and method for making
US6773648B2 (en) 1998-11-03 2004-08-10 Weyerhaeuser Company Meltblown process with mechanical attenuation
DE10035799A1 (de) * 2000-07-22 2002-01-31 Kalle Nalo Gmbh & Co Kg Nach dem Aminoxidverfahren hergestellte Nahrungsmittelhüllen auf Cellulosebasis
AT514137A1 (de) * 2013-04-05 2014-10-15 Lenzing Akiengesellschaft Polysaccharidfaser und Verfahren zu ihrer Herstellung
AT514136A1 (de) * 2013-04-05 2014-10-15 Lenzing Akiengesellschaft Polysaccharidfaser mit erhöhtem Fibrillationsvermögen und Verfahren zu ihrer Herstellung

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
JPS5156084A (ja) * 1974-11-12 1976-05-17 Kobe Steel Ltd Sokansetsudansochi
DE3034685C2 (de) * 1980-09-13 1984-07-05 Akzo Gmbh, 5600 Wuppertal Cellulose-Form- und Spinnmasse mit geringen Anteilen an niedermolekularen Abbauprodukten
DD158656A1 (de) * 1981-04-27 1983-01-26 Birgitte Lukanoff Verfahren zur verringerung des celluloseabbaus in aminoxidhaltigen celluloseloesungen
ATA92690A (de) * 1990-04-20 1992-06-15 Chemiefaser Lenzing Ag Verfahren zur herstellung einer loesung von cellulose in n-methylmorpholin-n-oxid und wasser
AT395246B (de) * 1990-07-16 1992-10-27 Chemiefaser Lenzing Ag Loesung von cellulose in wasser und n-methyl-morpholin-n-oxid
AT395724B (de) * 1990-12-07 1993-02-25 Chemiefaser Lenzing Ag Verfahren zur herstellung von celluloseformkoerpern

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1078890C (zh) * 1995-08-18 2002-02-06 连津格股份公司 制备胺氧化物水溶液的方法
CN1082102C (zh) * 1996-08-14 2002-04-03 坦塞尔有限公司 挤出制品的制造方法

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GB9424713D0 (en) 1995-03-01
ATA88693A (de) 1994-09-15
EP0649436A1 (de) 1995-04-26
GB2284207B (en) 1996-10-23
BG99273A (bg) 1996-06-28
NO944605D0 (no) 1994-11-30
RU94046417A (ru) 1996-10-27
AU6559994A (en) 1994-11-21
SI0649436T1 (zh) 1997-10-31
DK0649436T3 (da) 1996-05-20
GR3019220T3 (en) 1996-06-30
FI945853A (fi) 1994-12-13
CH685998A5 (de) 1995-11-30
JPH07509024A (ja) 1995-10-05
CN1039418C (zh) 1998-08-05
FI945853A0 (fi) 1994-12-13
LV11329B (en) 1996-10-20
DE59400095D1 (de) 1996-03-07
BG61698B1 (bg) 1998-03-31
BR9405331A (pt) 1999-08-31
WO1994025492A1 (de) 1994-11-10
NZ265216A (en) 1996-03-26
SK155894A3 (en) 1995-06-07
DE4492565D2 (de) 1995-06-01
KR0161706B1 (ko) 1998-11-16
JP2716589B2 (ja) 1998-02-18
EP0649436B1 (de) 1996-01-24
CA2137783A1 (en) 1994-11-10
LV11329A (lv) 1996-06-20
CZ316994A3 (en) 1995-10-18
AT399348B (de) 1995-04-25
HUT70891A (en) 1995-11-28
KR950702208A (ko) 1995-06-19
NO944605L (no) 1994-11-30
US5486230A (en) 1996-01-23
PL307047A1 (en) 1995-05-02
ATE133424T1 (de) 1996-02-15
GB2284207A (en) 1995-05-31
AU670873B2 (en) 1996-08-01
ES2085185T3 (es) 1996-05-16

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