CN1788036A - 减少尼龙－6预聚物中的己内酰胺及其低聚物的方法 - Google Patents

减少尼龙－6预聚物中的己内酰胺及其低聚物的方法 Download PDF

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CN1788036A
CN1788036A CNA2004800111742A CN200480011174A CN1788036A CN 1788036 A CN1788036 A CN 1788036A CN A2004800111742 A CNA2004800111742 A CN A2004800111742A CN 200480011174 A CN200480011174 A CN 200480011174A CN 1788036 A CN1788036 A CN 1788036A
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hexanolactam
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A·W·阿尔索普
C·E·坎普
J·M·伊瓦西克
D·拉亚戈帕兰
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C08G69/18—Anionic polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

公开了一种在制备尼龙－6聚合物过程中从尼龙－6预聚物减少低分子量杂质，即己内酰胺和其低聚物，的方法。

Description

减少尼龙-6预聚物中的己内酰胺及其低聚物的方法
技术领域
本发明涉及一种制备聚酰胺的方法。更具体地说，本发明涉及一种在制备尼龙-6聚合物期间从尼龙-6预聚物中除去低分子量杂质，特别是己内酰胺和己内酰胺环状二聚体，的方法。
背景技术
聚酰胺在传统上通过二酸如己二酸和二胺如六亚甲基二胺的缩聚，或者，通过内酰胺如ε-己内酰胺的聚合，进行制备。己知包括通过ω-氨基腈与水的反应制备聚酰胺的其它方法。美国专利2,245,129公开了通过在水存在下加热ω-氨基腈制备聚酰胺。美国专利6,069,228叙述了一种借助形成预聚物生产聚酰胺聚合物的方法。
从ε-己内酰胺或ω-氨基己腈生产的聚酰胺预聚物含有大量的己内酰胺及其低聚物杂质。在本文中所用术语“预聚物”指的是生产尼龙-6所用的聚合物材料。在预聚物中己内酰胺及其低聚物的量必须减少，以便制造具有适于工业应用的质量的聚合物。已经报告，通过在低于大气压的压力和高温下蒸发能减少挥发性杂质含量(参见WO2001074925 A1，EP 989150 A1)。
尼龙-6预聚物能够通过加热己内酰胺和水来得到。在使用这个方法时，尼龙-6预聚物一般含有约8wt％己内酰胺，和约1wt％己内酰胺二聚物。工业应用理想的是，尼龙-6预聚物含有1wt％以下己内酰胺和0.1％以下己内酰胺环状二聚体。
减少在尼龙-6预聚物中己内酰胺及其低聚物含量的工业实施方法涉及用水进行萃取。该工艺有效降低己内酰胺及其低聚物的含量，但是，其需要长的停留时间。典型的水萃取工业步骤花费约24hr并应用热水(约100℃)。
出于成本的原因，对于大规模生产工艺而言，减少水萃取步骤停留时间和/或使用较低温度的水应当是有利的。
本发明为水萃取持续时间较短的、尼龙-6预聚物达到理想纯度的工艺创造了条件。
US 6,525,167公开了一种生产具有降低了可萃取物含量的聚酰胺的方法。该文所述方法使用至少10bar的第一压力降，和至少20bar的第二压力降。其中，该参考专利没有公开如何在通过较小压力降继以水萃取制得的尼龙预聚物中获得低分子杂质。
发明内容
本发明公开了一种从包含己内酰胺、己内酰胺低聚物和尼龙-6预聚物的预聚物混合物中除去己内酰胺及其低聚物的方法；所述方法包括：(a)使熔融态所述预聚物混合物经受突然压力降排料；(b)使自步骤(a)排出的预聚物混合物与水接触生成预聚物相和水相，其接触时间应足以使至少一部分己内酰胺和低聚物被萃取到水相中；和(c)使预聚物相与水相分离。
具体实施方式
本发明公开一种制备尼龙-6预聚物的方法，其中，萃取预聚物所需的水接触持续时间较短，和其中获得的预聚物含有1wt％或更少的己内酰胺和/或0.1wt％或更少的己内酰胺环状二聚体。
在本发明工艺中，尼龙-6预聚物熔体首先保持在约250pis(1724KPa)压力下，然后使其经受至少50psi(345KPa)的突然降力降。压力降可以跨越喷嘴来完成。替代地，当制备预聚物工艺在大气压下进行时，然后为得到50psi压力降，总是必须再加压。如果系统已经为50psig或更高，那末则不需再加压。然后将预聚物熔体排入水中。这可以通过使预聚物熔体经模头孔排出来完成。典型的模头孔具有约0.25英寸(in)的直径。预聚物在与水接触之后被固化。这个步骤能够萃取低分子量物料如己内酰胺和己内酰胺环状二聚体。优选搅拌水和尼龙-6预聚物的混合物。预聚物与水的典型接触时间为约5min～约60min。
在本发明方法中，排出的聚合物与水接触一段时间，但是一般不超过约1hr。优选，排出的聚合物与水接触约5min的时间。水温为约10℃～约50℃。优选水温为约15～约25℃。
在本发明的另一个实施方案中，尼龙-6预聚物在与水接触前固化。通过使聚合物冷却能够完成预聚物固化。冷却可以通过使用能使预聚物固化的空气、氮气或其它介质来完成。然后将包含尼龙-6预聚物的固体相与水相分离。以下述非限定性实施例说明本发明。
实施例
实施例1：压力降与己内酰胺预聚物固化
将27.8g的含有6.8wt％己内酰胺和0.7wt％环状二聚体的6.2RV(相对粘度)尼龙-6预聚物，与2.2g水和0.3g氮一起，加入到反应器中。加热所得混合物至240℃，经混合，迫使其通过0.0762cm直径的孔，孔上游压力为600psi。所得尼龙-6粉末的RV为4.4，己内酰胺含量为9.8wt％，环状二聚体含量为0.8wt％。使所得粉末在烧杯中与冷水(20℃)接触15秒。过滤烧杯中内容物，使粉末与水分离，这样致使粉末和水的另外接触时间又有约30秒。通过这个过程，粉末的己内酰胺含量下降到1.8wt％，环状二聚体含量降到0.2wt％。压力降为600psig。该实施例说明，仅仅压力降没有导致可萃取物的显著减少。该工艺需要随后与水接触，以便减少可萃取杂质。
实施例2：压力降、再加压、随后和水接触与己内酰胺预聚物固化
将75wt％己内酰胺水溶液在高压釜中加热至272℃，并保持250psig压力2hr。然后，在保持温度恒定的同时，在15min内降低压力至大气压，随后用氮气再加压至50psig，并保持30min。最后，产物迅速经0.635cm直径的两个孔以连续线料的形式排出，将其收集在冷水大桶中。在与水接触5min之后，取出产物，经分析，得出RV为18，己内酰胺和环状二聚体含量分别为3.6wt％和0.4wt％。
实施例3：将压力降施加于氨基己腈预聚物，随后与水接触
将251b 6-氨基己腈和101b水加入高压釜中，并加热至260℃。在该步骤中开始以100cc/min进行水喷射，并继续加热至275℃。卸压设定为600psig，和保持水喷射3hr。然后经过90min降低压力至50psig，同时温度下降到260℃。在压力下降之后，产物经0.635cm直径的2个孔排出，射流进入冷水大桶中。在接触2min之后，取出产物并进行分析。聚合物RV为7.9，其己内酰胺和环状二聚体含量分别为2.0wt％和0.61wt％。

Claims (6)

1.一种从包含己内酰胺、己内酰胺低聚物和尼龙-6预聚物的预聚物混合物中除去己内酰胺及其低聚物的方法；所述方法包括：
(a)使熔融态所述预聚物混合物经受突然压力降排料；
(b)使自步骤(a)排出的预聚物混合物与水接触生成预聚物相和水相，其接触时间应足以使至少一部分己内酰胺和低聚物被萃取到水相中；和
(c)使预聚物相与水相分离。
2.权利要求1的方法，其中，使从步骤(a)排出的预聚物，在步骤(b)中与水接触之前，固化。
3.按照权利要求1和2的方法，其中，固化的聚合物混合物与水接触的时间不超过约60min。
4.按照权利要求1的方法，其中，在步骤(a)中的压力降为至少约50psi。
5.按照权利要求1的方法，在步骤(b)中所用的水的温度为约10℃～约50℃。
6.按照权利要求1的方法，其中，在步骤(a)中压力降排料通过喷嘴完成。
CNB2004800111742A 2003-04-28 2004-04-16 减少尼龙－6预聚物中的己内酰胺及其低聚物的方法 Expired - Fee Related CN100348644C (zh)

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US9988491B2 (en) 2013-10-22 2018-06-05 Empire Technology Development Llc Methods and compounds for producing nylon 6,6
US9982094B2 (en) 2013-10-22 2018-05-29 Empire Technology Development Llc Compounds and methods for producing nylon 6
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ATE336535T1 (de) 2006-09-15
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