CN1104219A - 增塑的乙酸纤维素、其制备方法及其在制造纤维中的应用 - Google Patents
增塑的乙酸纤维素、其制备方法及其在制造纤维中的应用 Download PDFInfo
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- CN1104219A CN1104219A CN94116156A CN94116156A CN1104219A CN 1104219 A CN1104219 A CN 1104219A CN 94116156 A CN94116156 A CN 94116156A CN 94116156 A CN94116156 A CN 94116156A CN 1104219 A CN1104219 A CN 1104219A
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- China
- Prior art keywords
- rhodia
- alcohol
- caprolactone
- plastifying
- cyclic ester
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- 238000002360 preparation method Methods 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 cyclic ester Chemical class 0.000 claims abstract description 41
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000002074 melt spinning Methods 0.000 claims abstract description 4
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- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims description 61
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 40
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- 238000006243 chemical reaction Methods 0.000 claims description 24
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 12
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
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- 125000003944 tolyl group Chemical group 0.000 claims description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
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Abstract
本发明涉及含有改性乙酸纤维素A成分的增塑
的乙酸纤维素,所述改性乙酸纤维素A含有环酯、尤
其ε-己内酯的接枝低聚物,该增塑的乙酸纤维素含
有环酯的低聚物B作为附加的增塑剂,其中低聚物
的末端羧基被沸点至少为约120℃和熔点不高于
180℃的醇或至少具有一个游离羟基的醇衍生物所
酯化,由式(I)描述组分A和B的重量比:
0.3≤A/(A+B)≤0.95 (I)
该增塑的乙酸纤维素用于熔融纺丝制造纤维。
Description
本发明涉及增塑的乙酸纤维素、其制备方法及其在制造纤维中的应用,所述增塑的乙酸纤维素包含一种改性的乙酸纤维素A成份,后者含有环酯、尤其ε-己内酯的接枝低聚物。
US-A-3922239公开了一种纤维素酯或醚的混合物,该酯或醚与聚合的环酯例如ε-己内酯低聚物相混合。该材料应是热塑性的。已表明该混合物的组分不具有令人满意的相容性。这表明在热塑加工时不能产生均匀的熔融。在加工时发现有一定程度甚至分解。
GB-A-2152944公开了增塑的乙酸纤维素,它是在催化剂存在下由含游离羟基的乙酸纤维素与环酯尤其是ε-己内酯反应得到的。乙酸纤维素与环酯的重量比在1/99和95/5之间,聚合温度在120和230℃之间。优选在干氮保护气中进行反应。反应混合物可以含有有机溶剂,该溶剂分子中不含活性氢并且与乙酸纤维素和环酯具有足够的相容性,例如二甲苯。作为催化剂尤其可以考虑有机酸;无机酸;碱金属,例如钠和钾;叔胺;烷基铝和其衍生物;例如三乙基铝;烃氧基钛化合物,例如钛酸四丁酯;有机金属化合物,例如辛酸锌和二月桂酸二丁基锌;以及金属卤化物,例如氯化锌。与含羟基乙酸纤维素反应的环酯的量优选在0.5和4.0摩尔单元/乙酸纤维素无水葡萄糖单元。通过“内”增塑降低了增塑乙酸纤维素的熔融温度,同时提高了分解温度。因此增塑的乙酸纤维素可有利地熔融纺成纤维,用于纺织领域和用于制造香烟过滤咀丝束。
需要改善GB-A-2152944中公开的方法和增塑的乙酸纤维素。使用接枝己内酯的乙酸纤维素(相当于无组分B的组分A,以后还将描述)要求高含量的己内酯,以保证熔融加工。这是比较昂贵的。此外值得追求的是进一步降低增塑乙酸纤维素的熔点,以便与干纺相比更好利用熔融纺丝的优点。干纺方法的缺点是,由于经济和生态的不利一定要回收加入的溶剂。
下述文献的现有技术没有超过上述GB-A-2152944:WO92/20738公开了可分解的纤维素酯,它含有亲水的分解活化剂。该活化剂在高潮湿环境下于纤维素酯中渗出并使其可分解。此外分解活化剂可是内酯,它还被看作是纤维素酯的增塑剂。另外可加入常规增塑剂。US-A-4529788涉及一种制造接枝聚合物的方法,其中在纤维素衍生物存在下使环酯进行催化开环聚合。接枝聚合物具有高透明性、良好的成膜性和高溶解性。J 61171719的德温特摘要86-242456/37涉及改进了与其它聚合物可混性的聚氨酯,其中有机二异氰酸酯与聚酯多元醇反应,该多元醇是在山梨醇存在下由内酯开环聚合得到的。另外,该聚合物改善了对热和溶剂的稳定性以及与其它聚合物的可混性。J60238317的德温特摘要86/106500描述了用于木材、金属、塑料材料等涂层的醇酸树脂,它含有一种在羟基纤维素衍生物存在下通过环酯开环得到的接枝聚合物。此外醇酸树脂具有改善了的硬度和耐候性并且是例如金属和木材的颜料的成分。
本发明的任务是改性开始时所述的增塑乙酸纤维素,使其熔点进一步降低,尤其是提出制造所述该类增塑乙酸纤维素的适宜方法,改进其经济性。
上述任务是由此完成的,增塑乙酸纤维素还含有环酯的低聚物形式的一种外加增塑剂B,其中低聚物的末端羧基被沸点至少为约120℃和熔点不高于约180℃的醇和/或至少具有游离羟基的醇衍生物所酯化,由式(Ⅰ)描述组分A和B的重量比:
0.3≤A/(A+B)≤0.95 (Ⅰ)
特别优选的是,A/A+B的重量比为至少0.5至0.9,尤其0.7至0.9。如果低于上述式(Ⅰ)的下限值0.3,即低聚物B组成提高,那么软化范围下降到产品在室温下是软的。因此不再可能有合适的产品。如果超出0.95的上限值,那么决不可能热塑性加工或是造成困难实际上不能实现本发明。在约0.5值时得到足够的强度值和适宜的低的加工温度。约0.8的有利界限值导致较高的加工温度;该值提供的优点是,产品具有很好的机械强度并且生产是较经济的。
有选择适宜的醇和/或至少含游离羟基的醇衍生物时,本发明的限制如下:其沸点至少为约120℃,尤其至少为约140℃,其熔点不超过180℃,尤其不超过160℃。
醇可以是单元或多元醇,尤其是二元或三元醇。可涉及伯、仲或叔醇。它可以是饱和的,还可以是不饱和的,尤其有双键的,只要对所追求的效果没有负作用即可。例如烯丙醇是合适的。该醇可以是脂族的,芳香族的,脂环族的,或还可是杂环的。一元醇中特别合适的是:戊醇、己醇、辛醇、以及十二烷基醇或月桂醇,各自优选正构型,也可以考虑异构体,“蜡醇”,例如正十六烷醇或鲸蜡醇、二十六醇-[1]或三十烷醇。优选醇具有2至6个羟基。因此二元醇首当其冲,尤其1,2-二醇(乙二醇类),例如乙二醇,丙二醇;或其它低聚乙二醇,尤其二甘醇,三甘醇和四甘醇;以及三元醇,尤其1,2,3-丙三醇(甘油),1,2,4-丁三醇和1,2,6-己三醇。优选的四元醇为赤藓醇,五元醇为阿糖醇、阿东糖醇和木糖醇;六元醇为山梨醇,甘露糖醇和卫予醇。优选的芳香族醇尤其为苄醇、二苯基甲醇和三苯基甲醇,脂环醇尤其单元醇为环丁醇,环戊醇,环己醇和环庚醇,而二元脂环醇如尤其为环己二醇。
上述醇的衍生物也是合适的,例如烷氧基化形式,如尤其甲氧基化和乙氧基化形式。例如用烷氧基、尤其甲氧基或乙氧基取代上述二元醇和三元醇的羟基。满意的烷氧基优选具有1至4个碳原子。此处涉及醚键的形成。因此这样形成酯键,即一个或多个羟基与合适的羧酸酯化,其中尤其考虑醋酸。无论如何,不仅在酯化时而且也在醚化时,醇的至少一个羟基须可用于下述与环酯的化学反应。而且醇衍生物应在上述有关最低沸点或最高熔点的条件范围内。
为了获得特别好的效果,可以加入上述醇或醇衍生物的混合物,尤其是甘油和山梨醇的混合物,其中该混合物含有5-95%(质量)、尤其65-85%(质量)的山梨醇。
在选择环酯时本发明已给定范围。可涉及单环酯还涉及羟基羧酯的环双脂。单环酯是“内酯”,环双酯是“交酯”。特别适宜的环酯在环中含3至6个碳原子和一或两个氧原子,并可由下述式(Ⅰ)至(Ⅶ)表示:
在式(Ⅰ)至(Ⅶ)中,残基R1至R5可各自相互独立地,表示:氢;含1至10个碳原子的低级烷基,尤基1至4个碳原子的烷基,例如甲基,乙基,正丙基,异丙基和异丁基及其不同的异构体;含3至6个碳原子的环烷基,如尤其是环丙基,环丁基,环戊基及环己基;含7至18个碳原子的芳烷基,尤其是苄基和苯乙基;含7至18个碳原子的烷芳基,尤其是苄基和苯乙基;含7至18个碳原子的烷芳基,尤其甲苯基;以及含2至5个碳原子的杂环基,尤其在杂环中有至少一个氧、硫或氮原子,如尤其是环氧乙烷、四氮呋喃、二噁烷及吡喃的基团;以苯或或萘基形式存在的芳基,其中芳基中可用C1-C4烷基取代。
醇或醇衍生物对各酯的重量比可在很宽范围内变化。尤其对甘油和/或山梨醇与ε-己内酯的混合物来说,优选重量比在约90∶10和10∶90之间,尤其在约70∶30至40∶60之间。
在本发明的增塑乙酸纤维素中还存在未转化的乙酸纤维素。以上述两种相应的组分A和B为基计,优选未转化的乙酸纤维素的存在量低于10%(质量)。对于加入过量醇尤其甘油并且未与ε-己内酯键合的情况来说,这是不损害本发明所争取达到的效果的。由此,部分醇偶合到ε-己内酯上调和了未键合残留的醇与增塑的乙酯纤维素之间的相容性。在本发明的范围内还可以向材料中加入获得特别效果的不同的添加剂,例如颜料如二氧化钛。
在选择本发明使用的乙酸纤维素原料时,本发明同样没有特别的限制。一般取代率(DS)在约1.2和2.95之间,尤其在约1.9和2.9之间,特别优选在约1.9和2.7之间。聚合度(DP)一般在约150和300之间,尤其在170和260之间。
可以根据下述方法A)和B)制造本发明的增塑乙酸纤维素。
本发明方法A)的特征在于,在催化剂存在下于熔融态低聚物B与含羟基的乙酸纤维素反应,其中低聚物B是环酯、尤其ε-己内酯与单和/或多官能醇和/或与含至少一个游离羟基的醇衍生物的反应产物。对此优选的是,使含羟基的乙酸纤维素与由ε-己内酯与甘油和/或山梨醇反应得到的低聚物B进行反应。
优选含羟基乙酸纤维素与低聚物B的重量比为约70∶30至30∶70。更优选的是,在方法A)中于熔融态下进行约2分至6小时的反应。优选熔融温度为190至220℃。优选的甘油和/或山梨醇对己内酯的重量比优选为约90∶10至10∶90,尤其为约70∶30至40∶60。
本发明方法B)的特征在于,在催化剂存在下于熔融态含羟基乙酸纤维素就地与环酯、尤其与ε-己内酯,和单和/或多官能醇和/或含至少一个游离羟基的醇衍生物进行反应。对此优选的是,含羟基乙酸纤维素与甘油和/或山梨醇和ε-己内酯进行反应。熔融温度优选为约160至210℃。优选的是,含羟基乙酸纤维素对优选的甘油和/或山梨醇和ε-己内酯原料的重量比在约90∶10和30∶70之间。此外,甘油和/或山梨醇对ε-己内酯的重量比优选为约90∶10至10∶90,尤其70∶30至40∶60。
如上所示,上述两种方法A)和B)有显著的共性。这也例如适合于上述使用醇或其衍生物的情况。
在为进行本发明的变形A)和B)方法而选择催化剂时,本发明不存在很大的限制。尤其可以考虑开头时在说明现在技术GB-A-2152944时提到的催化剂。优选有机金属化合物,如二月桂酸二丁基锌,二丁基氧化锌,乙酸丙酮锌,乙酸锌二水合物,丁醇钛(Ⅳ)(Titan(Ⅳ)butylat)和丙醇钛(Ⅳ)(Titan(Ⅳ)propylat)。对此在进行方法A)和B)时优选的是,在转化介质中催化剂的浓度为约0.1-1%(质量)。
下面将进一步说明本发明的两种方法,按特别优选的实施方式,由ε-己内酯和甘油形成增塑部分。如果非常明显,该实施方式也相应地适合于上述的其它环酯和其它醇或醇衍生物。
方法B)的优点在于,先由醇或醇的衍生物与起软化作用的环酯的混合物浸泡乙酸纤维素。这尤其适合于甘油和ε-己内酯添加物。与方法A)相比,可降低ε-己内酯含量(对于ε-己内酯和甘油的混合物来说),例如降到约25%(质量)。在方法B)中,ε-己内酯与乙酸纤维和甘油的羟基竞争。
按方法B)在含羟基乙酸纤维素存在下将ε-己内酯和甘油低聚合,然后可控制相容性问题,并明显降低了制造混合物的反应时间,同时也明显降低了ε-己内酯的需要量。例如在0.5%二月桂酸二丁基锌、1000ppm Irganox 1010(作用:抗氧剂)和500ppm I rgafos 168(作用:加工助剂)存在下于200℃使纤维素-2,5-乙酸酯与25%(质量)ε-己内酯和25%(质量)甘油反应2小时。ε-己内酯或甘油的剩余量低于1.5%(质量)。借助凝胶渗透色谱(GPC)的分析表明,除了接枝的纤维素-2,5-乙酸酯外还生成低聚己内酯B。
在本发明方法A)的优选方案中,首先将ε-己内酯和甘油以在下面例3中描述的方式转化成三羟基封端的低聚己内酯。低聚己内酯B在熔融态与含羟基的乙酸纤维素反应。因此基本进行下述过程:通过与游离羟基的反应或乙酰基的酯化反应,低聚己内酯部分接到乙酸纤维素链上。在制造低聚己内酯B时剩下的己内酯于熔融态就地接枝到乙酸纤维素或剩下的甘油上。因此不需要昂贵的低聚己内酯B的分离和纯化。
在方法A)中,优化原料甘油和ε-己内酯的重量比对于得到有益的增塑乙酸纤维素是重要的。为了研究不同长度低聚己内酯对本发明力求的增塑乙酸纤维素性能的影响,使甘油对ε-己内酯的重量比在1∶1和1∶9之间变化。这相当于甘油/ε-己内酯的摩尔比为1∶1.24或1∶7.3。低聚己内酯B的平均分子量(重均)为5100或8000(用聚苯乙烯校准的GPC)。在该试验中,低聚己内酯与乙酸纤维素的熔合表明,在高ε-己内酯含量(90%质量)时在熔融态与乙酸纤维素即使长时间反应也不能达到充分的混合。在制造低聚己内酯时使甘油/ε-己内酯混合物中ε-己内酯混合物中ε-己内酯的百分数在约75-90%(质量)之间变化。较高分子量三羟基封端的低聚己内酯例如与纤维素-2,5-乙内酯是不能混合的。含约66%(质量)ε-己内酯的己内质基低聚己内酯B对乙酸纤维素是特别适宜的增塑剂。与就地用ε-己内酯接枝的区别是该方法的熔融粘度和反应时间明显高。
在进行方法A)时反应温度是重要的。如此上述相应的低聚己内酯在温度低于190℃时是不熔融的。在反应温度为180℃时,6小时后也达不到组分间的充分混合,所以得不到熔融态。优选在高于约200℃、尤其约210℃至220℃进行熔融反应。
在两种方法中,通过在反应结束时使用真空可将单体己内酯和甘油的剩余量降低至可忽略值(0.1质量%己内酯,0.2质量%甘油)。
进一步的试验表明,在两种方法中提高乙酸纤维素的量导致加工时粘度上升。软化点和熔点随着低聚己内酯B量的增加而下降,而分解点则上升。随着乙酸纤维素量的降低分子量(MW)下降。随着三羟基封端的低聚己内酯量的增加样品的软化性增加;拉伸应力、伸长、E模量和断裂伸长下降。高乙酸纤维素量使特性向纯乙酸纤维素方向推移,然而已内酯量的影响更明显。
催化剂的浓度对方法A)中得到的增塑乙酸纤维素有影响。在捏和机中随着增加催化剂浓度迅速达到最大粘度,例如在浓度为0.1%(质量)的DBTDL(二月桂酸二丁基锌)的情况下为115分钟、为0.5%(质量)时为95分钟和为1%(质量)时为85分钟。这表明催化剂浓度的提高明显提高了反应速度。
与用ε-己内酯和甘油的就地接枝(方法B)相比持续更长时间(1小时),直到在有利熔融温度产生熔融由此生成所希望的熔合物。
本发明的优点尤其在于,可以得到一种增塑的乙酸纤维素,与现有技术的产品比较其熔点降低了,而且可更经济地制造该产物。本发明增塑的乙酸纤维素尤其适合于熔融纺丝制造纤维。
下面依据不同的实施例及比较例和关于不同试验物质的物理性质的试验报告进一步说明本发明。
1.比较例(用ε-己内酯就地接枝含羟基的乙酸纤维素)。
在测量捏合机(IKAVISC-Me β kneter)中于表1的条件下将由抗氧剂Irganox1010(商标)(1000ppm)(化学名称:季戊四醇的2,6-二叔丁基-1-羟基苯基)丙酸酯,ciba Geigy公司售)、加工助剂Irgafos 168(商标)(500ppm)(化学名称:酚,-2,4-二(1,1-二甲基乙基)-,亚磷酸酯(3∶1),ciba Geigy公司售)和剩余量的含羟基乙酸纤维素(DS:2、5和DP:220)组成的混合物在真空(40毫巴)下加热到100℃。在N2气氛下将该混合物加热到反应温度。在小心添加ε-己内酯和催化剂(二月桂酸二丁基锌/DBTDL)后开始反应,并在规定期间和轻微N2过压下捏和。自动记录粘度。切断恒温器后继续捏和至冷却到160℃,然后加真空直至110℃以除去未反应的单体。在温热状态下取出粗产品。得到的硬化物质在锤式破碎机中捣碎。
在下述表Ⅰ和Ⅱ中给出了详细的工艺参数:
注解:*)时间由实际反应时间和30分钟冷却阶段组成。
实施例1(纤维素-2,5-乙酸酯与改性甘油的熔合物)
将下表Ⅱ规定量的三羟基终端的低聚物B(表Ⅳ的试样12,按例3制造)放入测量捏和机(Me β kneter)中。在N2气氛下加热到规定温度。添加纤维素-2,5-乙酸酯、Irganox 1010、Irgafos168和DBTDL之后自动测绘测量曲线。
在规定反应期后于真空(40毫巴)下使温度达到110℃。在温热时取出粗产品。得到的硬化物质在锤式破碎机中捣碎。从下述表Ⅱ中可看出详细的参数。
注解:*)时间由实际反应时间和30分钟冷却阶段组成
实施例2(纤维素-2,5-乙酸酯与ε-己内酯和甘油的熔合体)
在测量捏和机中将表Ⅲ规定量的抗氧剂Irganox1010(1000ppm)、加工助剂Irgafos 168(500ppm)和纤维素-2,5-乙酸酯混合并在真空(40毫巴)下加热到100℃。在氮气氛下加热到反应温度。小心添加ε-己内酯、甘油和催化剂之后开始反应并在规定时间内于轻微N2过压下捏和。切断恒温器后继续捏和直至冷却到160℃,然后抽真空(40毫巴),直至温度达到110℃,以除去未反应的单体。在温热时取出粗产品,得到的硬化物质在锤式破碎机中捣碎。在下述表Ⅲ中给出反应参数。
实施例3(按实施例1用甘油基低聚物B制造)
将下面表Ⅳ中规定比例的甘油和ε-己内酯及0.5%(质量)DBTDL在测量搅拌机中于5小时加热到220℃。在冷却期间用真空(1小时)除去过剩的ε-己内酯。装入储仓中的产品还是热的,数小时后它凝固成蜡状稠性的白黄色物质。
表Ⅳ
Claims (27)
1、含有一种改性乙酸纤维素A成分的增塑的乙酸纤维素,所述改性乙酸纤维素A含有环酯、尤其ε-己内酯的接枝低聚物,其特征在于,增塑的乙酸纤维素还含有一种环酯的低聚物B形式的外加增塑剂,其中低聚物B的末端羟基被沸点至少为约120℃和熔点不高于约180℃的醇和/或至少具有一个游离羟基的醇衍生物所酯化,由式(Ⅰ)描述组分A和B的重量比:
0.3≤A/(A+B)≤0.95 (Ⅰ)
2、根据权利要求1的增塑的乙酸纤维素,其特征在于,醇或醇衍生物的沸点至少为约140℃和/或醇和醇衍生物的熔点不高于160℃。
3、根据权利要求1或2的增塑的乙酸纤维素,其特征在于,醇是多官能醇。
4、根据权利要求3的增塑的乙酸纤维素,其特征在于,多官能醇是甘油和/或山梨醇。
5、根据上述权利要求中至少一项的增塑的乙酸纤维素,其特征在于,重量比A/(A+B)为大约0.5至0.9,尤其为大约0.7至0.9。
6、根据上述权利要求中至少一项的增塑的乙酸纤维素,其特征在于,醇或醇衍生物对环酯的重量比在大约90∶10和10∶90之间,尤其在约70∶30至40∶60之间。
7、根据上述权利要求中至少一项的增塑的乙酸纤维素,其特征在于,环酯是单酯或环双酯,其中在环中含有3至6个碳原子和1或2个氧原子。
9、根据权利要求8的增塑的乙酸纤维素,其特征在于,环酯是以β-、δ-、ε-和高环节己内酯形式存在的单酯。
10、根据权利要求9的增塑的乙酸纤维素,其特征在于,环酯是ε-己内酯。
11、权利要求1至10至少一项的增塑的乙酸纤维素的制造方法,其特征在于,在催化剂存在下于熔融态使低聚物B与含羟基的乙酸纤维素反应,所述低聚物B是环酯、尤其ε-己内酯与单和/或多官能醇和/或与含至少一个游离羟基的醇衍生物的反应产物。
12、根据权利要求11的方法,其特征在于,使用二月桂酸二丁基锌、二丁基氧化锌、乙酰丙酮锌、乙酸锌二水合物、丁醇钛(Ⅳ)(Titan(Ⅳ)butylat)和/或丙醇钛(Ⅵ)(Titan(Ⅵ)propylat)作为催化剂。
13、根据权利要求11或12的方法,其特征在于,含羟基的乙酸纤维素与通过ε-己内酯与甘油和/或山梨醇的反应而得到的低聚物B进行反应。
14、根据权利要求11至13中至少一项的方法,其特征在于,熔融温度为大约190至220℃。
15、根据权利要求11至14中至少一项的方法,其特征在于,催化剂的浓度为大约0.1至1%(质量)。
16、根据权利要求11至15中至少一项的方法,其特征在于,含羟基的乙酸纤维素对低聚物B的重量比为大约70∶30至30∶70。
17、根据权利要求13至16中至少一项的方法,其特征在于,甘油和/或山梨醇对ε-己内酯的重量比为大约90∶10至10∶90,尤其为大约70∶30至40∶60。
18、根据权利要求11至17中至少一项的方法,其特征在于,在熔融态进行大约2分钟至6小时的反应。
19、权利要求1至10至少一项的增塑的乙酸纤维素的制造方法,其特征在于,在催化剂存在下于熔融态使含羟基的乙酸纤维素就地与环酯、尤其与ε-己内酯,和单和/或多官能醇和/或含至少一个游离羟基的醇衍生物进行反应。
20、根据权利要求19的方法,其特征在于,使用二月桂酸二丁基锌、二丁基氧化锌、乙酰丙酮锌、乙酸锌二水合物、丁醇钛(Ⅳ)(Titan(Ⅳ)butylat和/或丙醇钛(Ⅳ)(Tian(Ⅳ)propylat)作为催化剂。
21、根据权利要求19或20的方法,其特征在于,使用含2至6个羟基的多官能团。
22、根据权利要求19至21中至少一项的方法,其特征在于,含羟基乙酸纤维素与甘油和/或山梨醇和ε-己内酯进行反应。
23、根据权利要求19至22中至少一项的方法,基特征在于,熔融温度为大约160至210℃。
24、根据权利要求19至23中至少一项的方法,其特征在于,催化剂的浓度为大约0.1至1%(质量)。
25、根据权利要求22至24中至少一项的方法,其特征在于,含羟基的乙酸纤维素对由甘油和/或山梨醇和ε-己内酯组成的初始混合物的重量比为90∶10至30∶70。
26、根据权利要求22到25中至少一项的方法,其特征在于,甘油和/或山梨醇对ε-己内酯的重量比为大约90∶10至10∶90,尤其为大约70∶30至40∶60。
27、权利要求1至10的增塑的乙酸纤维素用于熔融纺丝制造纤维。
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TWI393807B (zh) * | 2010-03-26 | 2013-04-21 | Taiwan Textile Res Inst | 高伸長率纖維素母粒之製備方法與應用 |
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EP0636649A3 (de) | 1995-10-25 |
RU2106359C1 (ru) | 1998-03-10 |
EP0636649B1 (de) | 1997-12-03 |
JP3124988B2 (ja) | 2001-01-15 |
ES2110155T3 (es) | 1998-02-01 |
RU94026773A (ru) | 1996-08-10 |
EP0636649A2 (de) | 1995-02-01 |
US5480922A (en) | 1996-01-02 |
JPH07179662A (ja) | 1995-07-18 |
DE4325352C1 (de) | 1994-09-01 |
BR9402965A (pt) | 1995-04-11 |
DE59404710D1 (de) | 1998-01-15 |
KR0147411B1 (ko) | 1998-08-01 |
CA2128812A1 (en) | 1995-01-29 |
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