CN1016786B - 一步法合成交联羧甲基羟丙基纤维素复合醚工艺 - Google Patents
一步法合成交联羧甲基羟丙基纤维素复合醚工艺Info
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Abstract
本发明属于水溶性高分子纤维素醚合成领域。
本发明提供一步完成醚化、交联、纯化纤维素复合醚的合成工艺。在碱性介质中利用亲水有机溶剂作稀释剂,纤维素与醚化剂、交联剂反应,交联剂用量为0.1~3.5%(纤维素重)、羟丙基化醚化剂用量为30~250%(纤维素重),羧甲基化醚化剂用量为10~94%(纤维素重)。本工艺反应均匀,有机稀释剂容易回收,交联剂用量少、产物粘度高,热稳定性,抗盐性,抗酸性好,并可制取不同DS和MS的产物。
Description
本发明属于水溶性高分子纤维素醚合成工艺。
羧甲基羟丙基纤维素复合醚(CMHPC)的合成法有先羧甲基化后羟丙基化或先羟丙基化后羧甲基化等方法。但这两种方法,不但醚化分两步进行,而且中间产物也经纯化处理,合成路线长,耗用化学药品量大,反应周期长,产物降聚程度大,粘度低。而且,为了获得取代均匀的产物,往往使用大浴比或多组份混和的有机溶剂作稀释剂。由于溶剂分离回收困难,而经济效果不满意。
本发明的目的是将两步法醚化和两步纯化,简化为一步醚化,并同时完成交联反应作改性,一步纯化制取反应均匀,高粘度,抗盐性良好的羧甲基羟丙基纤维素复合醚。本工艺利用低浴比廉价亲水有机溶剂作稀释剂,醚化效率高。由于羧甲基化和羟丙基化均在碱催化下进行,故此两种取代反应可以同时一步进行。大分子间的羟基的交联也可以在碱催化下完成。所以只要有适当的碱量,则羧甲基化,羟丙基化,以及分子交联可能一步完成,并不引起大量的付反应。日本特公昭61-157,501将交联反应用于制备离子型的高粘度级羧甲基纤维素钠,是通过纤维素未被取代的羟基上实现交联的。而本发明除此之外,交联尚发生在已取代的羟丙基上的游离羟基,故交联效果更好。产物粘度提高更明显。而且,本发明制备的是离子与非离子型复合醚,比上述专利文献中的单醚性能优越。产物有更好的抗二价盐、抗酸性能。本工艺把碱化,醚化,和交联反应,均在同一捏和式反应器内进行。采用廉价的含水亲水有机溶剂作稀释剂。碱化剂是碱金属氢氧化物,可用氢氧化钠或氢氧化钾。由于碱化合并,两种醚化反应又能起“消晶”作用,故用碱量比两步法低,而付反应少。碱用量为20~30%(纤维素量),可随制取不同的羧甲基取代度DS和不同的羟丙基取代度MS而作调整。碱化可在室温下保持20分钟以上,则可保证碱化完全。有机溶剂可用甲醇、乙醇、异丙醇、叔丁醇、丙酮等,用量为纤维素重的0.8-5.0倍。醚化反应在真空下进行,羧甲基化醚剂-氯醋酸(MCA),溶于一部分有机溶剂中,和羟丙基化醚化剂氧化丙烯(PO)以及交联剂环氧氯丙烷(EP)或三氯乙酸可籍真空加入反应器中,用量视制取不同取代度的产物而异,羧甲基取代度DS=0.03-0.94的产物,MCA用量为10-94%纤维素重。羟丙基取代度MS=0.19-4.01的产物,PO用量为30-250%纤维素重,交联剂用量为0.1-3.5%纤维素重。醚化后的碱性粗产物可用无机酸如盐酸、硫酸、磷酸或有机酸如醋酸中和。中和的产物可用甲醇、乙醇、丙酮等溶剂洗涤纯化。
本发明的一步法合成工艺,使用混和溶剂较单组份的亲水有机溶剂极性低,对羧甲基化更有利,PO既是双组份中的有机稀释剂又是羟丙基化的醚化剂,随着反应进行,系统中只存有单一的亲水有机溶剂,溶剂的回收和循环使用十分方便。因此,本发明既具有多组份有机稀释剂能使醚化反应均匀,又避免多组份有机稀释剂分离回收困难的特点。而且交联剂用量少,产物粘度高,热稳定性好,不影响溶剂的回收。本工艺可以制取不同DS和MS产物以控制产物的离子和非离子性质,并使之具有能溶于某些含水极性有机溶剂的性质。本发明工艺可
采用棉绒纤维素,木材纤维素或草类纤维素为原料。所提供的一步法合成工艺还可以合成交联羧烷基羟烷基纤维素复合醚。
表1是本发明一步法(实例1-10)与二步法的产物分析指标比较。二步法合成路线长,产物粘度低至24和40厘泊,抗盐性,抗酸性,有机溶剂溶解性并不比一步法优越。本发明一步法产物粘度较之高得多。实例1-4随交联剂EP用量增加,产物粘度提高,但抗盐性有下降趋势。即随交联剂用量增大,盐粘度,盐粘比值降低,抗酸性及在有机溶剂溶解的溶液粘度也有相似现象。实例5由于没有加交联剂,粘度较实例1-4产物低,但仍比二步法高。实例6和7尽管采用低聚合度木浆或甘蔗渣浆当原料,但用本发明制取的产物,粘度仍较二步法中用高聚合度棉绒浆制造的产物高得多。实例8-10是用不同的醚化剂量以制取不同DS和MS的产物。提高DS,离子性更突出,抗一价盐性能好,但抗二价盐性能减弱。提高MS则非离子性更突出,抗二价盐性、抗酸性、有机溶剂溶解性增加,但抗一价盐性能减弱。
表2是市售的各种纤维素醚性能分析指标。从表中可见,非离子型纤维素醚HPC,HPMC,MC只能抗二价盐,不能抗一价盐。离子型聚阴离子型纤维素DRISPAC只能抗一价而不能抗二价盐。只有HEC才有较好综合抗盐性和抗酸性,但有机溶剂溶解性较差。比较表1和表2可见。本发明合成的交联CMHPC兼备了离子型和非离子型纤维素醚的优点,具有良好的综合抗盐性,抗酸性,和某些有机溶剂溶解性等性质。
由于产物有优良的抗一价和二价盐特性,是高矿化度地层钻井工程的泥浆处理剂;本产物经交联改性有良好热稳定性,可用作深井钻井工程的泥浆处理剂。由于产物粘度高,可作为工业良好的增稠剂,悬浮剂和稳定剂,它克服了离子型羧甲基纤维素醚抗酸性差,在pH<3介质中失效的缺点,从而使它在上述应用范围广得多。又由于具有有机溶剂的溶解性和增稠性,本发明的产物作为增稠剂应用范围尚可扩展到日用化工领域中。
实例1-4
氢氧化钠139克溶于180克水中,与含有交联剂EP(实例1,2,3,4中EP用量分别为0.4,0.9,1.2,2.4克)的95%乙醇300克相混和配制成碱化液,碱化液与200克棉绒纤维素(聚合度1450)相配合,分别喷入和投入5升捏和机中,排除空气至真空度680mmHg,籍真空加入122.6克PO,用夹套水维持碱化温度13-19℃,碱化20分钟,加入140.7克MCA溶于112克95%乙醇的溶液。在30分钟内将温度升至78℃,维持该温度120分钟。反应终止,通入夹套冷却水将温度降至50℃,开启通大气阀门,启盖,取出的粗产物用18%醋酸中和,用70%乙醇洗涤两次,每次1600ml,离心分离的母液蒸馏回收,产物在70℃干燥,产物分析及性质列于表1。
实例5
除碱化液组成改为氢氧化钠158克,水160克,95%乙醇324克,不加入EP。醚化剂MCA改为189克溶于150克95%乙醇等不同外,其余操作与实例1-4同。产物分析及性质列于表1。
实例6
除原料改为聚合度780的木材纤维素(木浆),EP用量1.8克等不同外,其余同实例1-4,产物分析及性质列于表1。
实例7
除原料改为聚合度750的甘蔗渣纤维素(蔗渣浆)EP改为2.4克等不同外,其余同实例1-4。产物分析及性质列于表1。
实例8
氢氧化钠137克溶于139克水中,与含有交联剂EP1.8克的95%乙醇,300克混合,配制成碱化液,碱化液与200克棉绒纤维素相配合,分别喷入和投入5升捏和机中,排除空气至真空度680mmHg,用夹套冷却水维持碱化温度14-22℃,碱化20分钟,加入90.5克MCA溶于72克95%乙醇的溶液,以及367克PO,在30分钟内,将温度升至83℃,维持该温度135分钟,反应终止冷凝回收PO.启盖。粗产物用冰醋酸中和,用70%丙酮洗涤两次,每次1500ml,离心的精制产物在60-70℃真空干燥。产物分析及性质列于表1。
实例9
氢氧化钠84克溶于89克水中,与含有EP0.6克的95%乙醇,200克相混合配制成碱化液,碱化液与200克棉绒纤维素相配合,分别喷入和投入5升捏和机中,用夹套冷却水维持碱化温度19-24℃,碱化20分,排除空气至真空度680mmHg,籍真空加入40.2克MCA,溶于32克95%的乙醇溶液以及409克PO,在30分钟内升温度至80℃,维持该温度150分钟,反应过程,捏和
机从正压逐渐降至负压。反应终止,回收PO,粗产物用冰醋酸中和,用80%丙酮洗涤两次,每次1500ml,离心精制产物在60-70℃,真空干燥,产物分析及性质列于表1。
实例10除碱化液组成改为氢氧化钠97克,水109克,95%乙醇20克,EP1.8克。醚化剂改为MCA20.1克溶于16克95%乙醇。PO用量改为510.6克等不同以外,其余醚化操作同实例9,反应粗产物用85%磷酸中和至pH3,用90℃以上的热水倾侧法洗涤3次,每次用热水1500ml,产物在90℃烘干。
Claims (6)
1、一种一步法合成交联羧甲基羟丙基纤维素复合醚工艺,它包括在含水亲水有机溶剂和碱性介质中,纤维素与醚化剂、交联剂反应,其特征为在捏和式反应器中一步法完成碱化,羧甲基化和羟丙基化两种醚化反应以及分子间交联反应,并一步完成粗产物纯化。交联剂用量为0.1~3.5%(纤维素重量),羟丙基化醚化剂用量为30~250%(纤维素重量),羧甲基化醚化剂用量为10~94%(纤维素重量)。
2、根据权利要求1中所述的工艺,其特征为羧甲基醚化剂可以是一氯醋酸或其钠盐,羟丙基化醚化剂可以是氯化丙烯。
3、根据权利要求1中所述的工艺,其特征为含水亲水有机溶剂可以是甲醇、乙醇、异丙醇、叔丁醇,其用量为0.8-5.0倍纤维素重量。
4、根据权利要求1中所述的工艺,其特征为交联剂可以是环氧氯丙烷,三氯乙酸。
5、根据权利要求1中所述的工艺,其特征为纤维素可以是棉绒纤维素,或水材纤维素,或草类纤维素。
6、根据权利要求1所述的工艺,其特征为所指的一步法合成工艺可以合成交联羧烷基羟烷基纤维素复合醚。
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CN104193829B (zh) * | 2014-08-25 | 2016-04-06 | 四川北方硝化棉股份有限公司 | 球状醋酸丁酸纤维素的生产方法 |
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