CN1795233A - 降低熔融加工的聚酯中乙醛含量的方法 - Google Patents
降低熔融加工的聚酯中乙醛含量的方法 Download PDFInfo
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- CN1795233A CN1795233A CNA2004800144341A CN200480014434A CN1795233A CN 1795233 A CN1795233 A CN 1795233A CN A2004800144341 A CNA2004800144341 A CN A2004800144341A CN 200480014434 A CN200480014434 A CN 200480014434A CN 1795233 A CN1795233 A CN 1795233A
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- polyester
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Abstract
降低熔融加工的聚酯中乙醛含量的方法,包括将聚酯与用于从聚酯中清除乙醛的有机添加剂化合物混合。该有机添加剂化合物包括至少两个组分分子片段,每一组分分子片段包括至少两个取代氢的杂原子,该杂原子连接到每个组分分子片段的碳上。每一组分分子片段与聚酯中的乙醛反应,形成水和生成的有机化合物,该有机化合物包括含有所述至少两个杂原子的未架桥五元环或六元环。乙醛含量降低的聚酯尤其适合用于制备容器如用于包装饮料的容器。
Description
技术领域
本发明涉及聚酯制品如聚对苯二甲酸乙二醇酯容器。特别地,本发明涉及通过混入能够与乙醛反应的添加剂降低熔融加工的聚酯中乙醛含量。
背景技术
聚酯、尤其是聚对苯二甲酸乙二醇酯(PET)是多用途聚合物,它被广泛地用于纤维、膜和三维结构。对于PET来说,特别重要的用途是用于容器,尤其是用于食品和饮料的容器。在过去的20年间,这种用途成倍增长,并且继续增长。尽管有这种增长,PET仍存在约束其用途的一些主要缺陷。这种限制之一是当熔融加工时易于产生乙醛(AA)。因为AA是小分子,因此熔融加工过程中产生的AA能够从PET中迁移出来。当PET加工成容器时,随着时间的推移,AA将迁移到容器内部。尽管AA在许多饮料和食品中是天然香料,但是对于许多产品来说,由AA产生的味道被认为是不受欢迎的。例如,AA使水产生水果香味,但是这违背了该产品所追求的纯净味道。
通常,PET是由对苯二甲酸酯前体(或者是对苯二甲酸二甲酯或者是对苯二甲酸)和乙二醇的酯交换或酯化/聚合方法制成的。如果对于熔体聚合的PET的最终用途是用于食品包装,那么就要对PET进行称作固态聚合(SSP)的第二次操作,从而使分子量增加并除去熔融加工过程中产生的AA。将固态聚合的PET转变为容器最常用的方法包括干燥并重新熔融PET,将聚合物注射模塑成容器型坯(preform),随后拉伸吹塑型坯形成最终容器形状。在重新熔融PET形成容器型坯的过程中,产生了AA。对于利用最现代的注射模塑设备按照这种方式加工的PET来说,典型的型坯AA含量为6-8μg/g(ppm)。
以往,通过谨慎控制用于制备容器或型坯的熔融加工条件,和通过在聚合物制备过程中采用特殊加工条件,将AA对产品味道的影响降低到最低程度。对于其中AA的味道阈值足够高,或者其中容器的使用寿命足够短的大部分包装来说,该方法是成功的。然而,获得低AA含量的型坯需要相当高的费用。这种费用包括,PET熔体聚合(固态聚合)后需要进行单独的处理步骤,需要专门设计注射模塑设备,以及容器生产过程中需要连续跟踪型坯AA含量。对于其它应用,其中容器所需要的存放期更长,产品对AA所产生的味道更敏感,或者周围环境条件更温暖,就不可能通过采用这些方法将饮料的AA含量保持在味道阈值以下。例如,在水中,味道阈值被认为低于约40μg/L(ppb),往往希望存放期高达2年。对于装有约600ml饮料的PET瓶子来说,在型坯AA含量为8ppm的条件下,能够在短至一个月内引起饮料AA含量大于40ppb。
除了谨慎控制PET熔融加工的条件外,现有技术方法还包括通过使用特性粘度(IV)更低的树脂和/或使用熔融温度更低的PET树脂,对PET本身进行改性。然而,每种树脂改性方法都仅仅取得了部分成功,它们有它们自身的限制。例如,更低IV树脂制成的容器对环境因素如应力断裂失效抵抗性更低。更低熔融温度的树脂是通过增加PET树脂中共聚物含量达到的。然而,增加树脂的共聚物含量同时还增加了PET的拉伸比,这转化成降低了注射模塑和吹塑的生产率。
另一种现有技术方法是在PET中混入添加剂,该添加剂选择性地与所生成的AA发生反应,或者选择性地清除所生成的AA。就此,Igarashi(美国专利4,837,115)公开了使用胺基封端的聚酰胺和含有胺基的小分子。Igarashi教导,因为胺基能够与AA反应形成亚胺因此是有效的,其中胺氮代替了AA羰基中的氧。Igarashi还教导,基本上任何胺都是有效的。Mills(美国专利5,258,233;5,650,469;和5,340,884)以及Long(美国专利5,266,416)要求保护使用各种聚酰胺,尤其是低分子量聚酰胺。Turner和Nicely(WO97/28218)要求保护使用聚酯酰胺。据信,这些聚酰胺和聚酯酰胺按照与Igarashi所述相同的方式与AA发生反应。
尽管这些AA清除剂有效地降低了熔融加工的PET的AA含量,但是它们还是有缺陷。尤其是,为了明显降低AA含量需要较高含量的聚酰胺,并且当混入这些含胺添加剂时,PET出现非常明显的变黄现象。该颜色的形成被认为是由于亚胺基本身的颜色导致的,因此是不可避免的。黄色的形成内在地限制了将这种方法用于其中可对PET微染色以掩盖该颜色的制品中。不幸地是,目前使用的大多数PET制品是纯净无色的。
另一个描述于美国专利6,274,212中的AA清除剂的现有技术方法使用了热稳定的有机添加剂,该添加剂与AA反应时形成了未架桥的五元环或六元环结构和水。因为未架桥五元环或六元环结构没有导致内在的形成颜色,因此与上述酰胺或胺基添加剂相比,该发明的AA清除剂颜色要好得多。该发明中所描述的有机添加剂具有至少两个氢原子取代的杂原子,该杂原子连接到有机添加剂化合物的碳原子上,所述有机添加剂与聚酯中的乙醛反应生成水和有机化合物,该有机化合物含有包括所述至少两个杂原子的未架桥五元环或六元环。这些添加剂在螯合AA方面非常有效。然而,由于优选添加剂如苯甲酰亚氨酰胺的蒸汽压较高,因此在注射模塑方法中由于蒸发损失一些清除剂。这种较高的蒸汽压还造成型坯形成过程中形成模沉积物,这就需要更频繁的清洁和维修模具。鉴于相同的理由,将添加剂混入PET母炼胶的效率较低,因为添加剂在干燥过程中容易从PET中损失。
在该专利内容中,有关所提供的添加剂的另一个潜在观点是它们的迁移能力。优选较低分子量的分子,这比希望的具有更高的提取率。因此,尽管这些AA清除剂能够成功地降低用模塑固态聚合的树脂制成的型坯和饮料中的AA含量,但是如果起始AA含量较高以及需要更高含量的AA清除剂时,它们几乎没有实用性。当型坯是用直接来自熔体相聚合而没有中间造粒和固态聚合的PET熔体形成时,就是这种情况。
因此,尽管美国专利6,274,212所覆盖的小分子AA清除剂是有效的,但是仍需要改进的AA清除剂。
发明概述
本发明通过提供一种降低熔融加工的聚酯中乙醛含量的方法解决了上述需求,所述方法包括将至少一种有机添加剂化合物与聚酯混合。本发明的有机添加剂化合物包括至少两个组分分子片段,每一组分分子片段包括至少两个取代氢的杂原子,该杂原子连接到各个组分分子片段的碳上。有机添加剂化合物中的组分分子片段分别与聚酯中的乙醛反应,形成水和生成的有机分子片段,该有机分子片段包括含有所述至少两个杂原子的未架桥五元环或六元环。生成的有机片段不会给使用该处理的聚酯制成的容器包装的饮料带来异味,也不使聚酯明显变色。将这些有机添加剂化合物与聚酯混合不需要特殊的设备或处理步骤,并且该有机添加剂化合物在聚酯的熔融加工温度下是基本上热稳定的。
有机添加剂化合物具有至少两倍于单独的组分分子片段的分子量,因此更小可能从聚酯中提取出来,因此用量能够较高。并且,因为该有机添加剂化合物能以较高含量使用,因此添加剂化合物可以用于将熔融相PET树脂的AA含量降低至可接受水平,因此能够直接进行预制操作,而无需中间的固态聚合步骤。
另外,上述有机添加剂化合物比对应的组分分子片段具有明显更低的蒸汽压,因此更不容易蒸发。鉴于此,它们在制备聚酯制品过程中不沾在工具和模具上。这种低蒸汽压和高热稳定性还能够使添加剂化合物混入聚酯树脂中,并在固态聚合以及随后的干燥过程中保持其活性。由于本发明添加剂的热稳定性和低挥发性,将它们加入聚酯的时间就不是特别重要。因此,为了降低由固态聚合的PET制成的型坯中的AA含量,有机添加剂化合物可以在熔融聚合步骤结束时加入,在干燥前作为母炼胶加入到SSP树脂中,或者在注射模塑前瞬间在再次熔融SSP树脂时加入。
可以在聚酯加工的不同阶段,将聚酯与有机添加剂化合物混合。在一个实施方案中,可以通过制备聚酯熔体并将添加剂化合物与聚酯熔体混合而将聚酯与有机添加剂化合物混合。添加剂化合物可以在熔融加工前或者熔融加工后加入聚酯。在一个实施方案中,在形成聚酯制品前并不将聚酯熔体固化。
本发明还包括用于制备具有降低的乙醛含量的聚酯制品的组合物,包括聚酯和上述有机添加剂化合物;本发明还包括用上述有机添加剂化合物制成的聚酯制品,以及相应的制备聚酯制品的方法。
此外,本发明包括用上述组合物制成的容器和容器型坯,以及包括了该容器中的饮料的包装饮料。
附图的简要说明
图1是根据本发明优选实施方案制备的注射模塑容器型坯的截面图。
图2是由本发明优选实施方案制备的图1的型坯制成的吹塑容器的截面图。
图3是根据本发明优选实施方案制备的包装饮料的透视图。
发明实施方案的详述
如上所述,本发明涉及通过在熔融加工过程中在聚酯中混入低含量的有机添加剂化合物,实质性降低熔融加工的聚酯、尤其是PET中乙醛(AA)含量的方法。该有机添加剂化合物通过与AA化学反应清除了聚酯中AA。
本发明中合适的有机添加剂化合物包括至少两个组分分子片段,每一组分分子片段包括至少两个取代氢的杂原子,该杂原子连接到各个组分分子片段的碳上。该化合物中的组分分子片段分别与聚酯中的乙醛反应,形成水和生成的有机分子片段,该有机分子片段包括含有所述至少两个杂原子的未架桥五元环或六元环。
该有机添加剂化合物具有至少两倍于组分分子片段的分子量,是热稳定的,比美国专利6,274,212中所述添加剂具有明显更低的蒸汽压,基本上不能从聚酯中提取出来。因此,本发明的有机添加剂化合物能以高的含量与聚酯混合,因此在直接熔融型坯操作中有效地将乙醛含量降低至可接受水平。
能够与AA反应的每个分子片段中的杂原子包括氧(O)、氮(N)和硫(S)。组分分子片段中的杂原子应当至少一个与活性氢(H)连接,并且在与AA缩合过程中应当分离出水。含有这些杂原子的优选官能团包括胺(NH2和NHR),羟基(OH),羧基(CO2H),酰胺(CONH2和CONHR),氨磺酰(SO2NH2)和硫醇基(SH)。这些官能团有必要空间排列,以使当与AA缩合时,能够形成未架桥的五元环或六元环。优选地,结构排列使之能够形成六元环。尤其优选地,有机添加剂的杂原子连接到预先形成的环上。最优选地,预先形成的环是芳环,因此生成的有机化合物的未架桥五元环或六元环就连接到芳环上。
合适的有机添加剂化合物在熔融加工聚酯所要求的温度下基本上是热稳定的。还优选地,有机添加剂上存在的官能团对于聚酯上存在的酯键相对不反应。高热稳定性以及与酯键的低反应性增加了能够与AA缩合的未反应有机添加剂化合物的含量,因此降低了达到有效AA清除所需要的量。根据热重分析(TGA),分解温度高于270℃的化合物是希望的,更优选分解温度高于300℃的化合物。在低于约200℃的温度下通过分子内消除反应发生分解的化合物几乎不可能是有效的。
满足上述条件并且有效地降低熔融加工的聚酯中的AA含量的添加剂的实例包括但不限于:1,2-二(2-氨基苯甲酰氨基)乙烷,1,2-二(2-氨基苯甲酰氨基)丙烷,1,3-二(2-氨基苯甲酰氨基)丙烷,1,3-二(2-氨基苯甲酰氨基)戊烷,1,5-二(2-氨基苯甲酰氨基)己烷,1,6-二(2-氨基苯甲酰氨基)己烷和1,2-二(2-氨基苯甲酰氨基)环己烷。尤其优选的是其中组分分子片段来自邻氨基苯甲酰胺的添加剂化合物,这是因为它们价格低,高效,易于与PET混合。
通常,合适的有机添加剂化合物具有下述通式之一所示的组分分子片段:
上述通式中,X和Y表示包括至少一个活性氢(用H表示)和至少一个杂原子如O、N或S的官能团。优选的组分分子片段是具有环状结构、优选包括芳环的那些。
能够形成五元环或六元环但是缺乏必要的热稳定性的分子的实例包括四亚乙基戊胺、半胱氨酸、天冬酰胺和1,3-二氨基戊烷。不能够形成五元环或六元环并且不能降低熔融加工的聚酯中AA含量的分子的实例包括邻氨基苯甲酸甲酯、2-氨基二甲基对苯二甲酸酯和硬脂胺。应当注意,Igarashi教导,诸如这些添加剂有效地降低了PET的AA含量。
使AA含量达到所要求降低程度的所需要的有机添加剂化合物的量取决于所用的具体添加剂化合物,以及所要求的降低量。相对来说更有效的有机添加剂化合物在含量500-1000ppm之间时能够使AA含量降低90%以上;但是需要时,如在型坯操作的熔体中,有机添加剂化合物的用量可以大于2000ppm。
该有机添加剂化合物对于降低由乙二醇和二酸或该酸的二酯制成的聚酯中的AA是最有效的。该聚酯包括聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚己二酸乙二醇酯、聚间苯二甲酸乙二醇酯、以及它们的混合物或共聚物。可能作为共聚单体存在的其它二醇包括环己烷二甲醇、二甘醇、1,2-丙二醇、新戊二醇、1,3-丙二醇和1,4-丁二醇。
将所要求的有机添加剂化合物混入聚酯中的方法并不重要,因为当在制备或使用聚酯的任何阶段中加入时,该添加剂化合物都是有效的。该添加剂化合物可以分散在液体载体中,在进行注射模塑之前立即与聚酯颗粒混合。它们也可以通过在干燥前将添加剂在水中的浆料喷洒在颗粒上而混入。它们可以通过将添加剂的熔体或悬浮液注射到预先熔融的聚酯中而混入。它们还可以通过制备添加剂与PET的母炼胶,然后在干燥前按照所需含量将母炼胶颗粒与PET颗粒混合并注射模塑而混入。
下面等式说明本发明合适的有机添加剂化合物的组分分子片段与乙醛的缩合反应,生成水和带有未架桥环的生成化合物:
上述等式中,X和Y表示包括至少一个活性氢(用H表示)和至少一个杂原子如O、N或S的官能团。如果有预形成的环,其优选为芳环。
按照本发明所述的消除乙醛的方法可以应用于用于输送或存储饮料的任何类型的聚酯基容器。合适的容器包括但不限于:瓶子、鼓桶、卡拉夫瓶、冷却器等。包括聚酯和有机添加剂化合物的组合物特别适用于制备容器如用于包装饮料的容器,这是因为它降低了乙醛含量。由于降低了乙醛含量,容器几乎不给饮料带来异味。这对于诸如水的饮料来说特别重要,所述诸如水的饮料没有浓烈的味道来掩盖乙醛的味道和气味。
可以利用常规方法如注射模塑和吹塑,用本发明的组合物制备容器。典型的方法是用聚酯组合物和有机添加剂化合物制成型坯,然后吹塑成饮料容器。合适的型坯和容器结构及其制备方法的实例公开在美国专利5,888,598中,该说明书全部内容引入本文作参考。所得容器可以根据常规制造方法用于制造包装饮料。
因此,根据本发明的一个实施方案,在聚酯基容器中提供了瓶装饮料,其中聚酯基容器包括了上述有机添加剂化合物。本发明另一个实施方案是由本发明聚酯组合物制成的容器型坯。然后,通过常规方法将该型坯制成饮料容器。有机添加剂化合物可以在开始制备PET时,或者随后用PET颗粒制备型坯过程中加入聚酯中。通过熔融加工PET颗粒,或者开始制备或合成PET过程中不经过制备PET颗粒的中间步骤或者不经过制备型坯前固化PET的步骤而立即熔融加工PET,来制备型坯。该实施方案中,预计聚酯可通过熔融相聚合至所需分子量而生产,然后直接转变成成形制品。该实施方案中,在制备成形制品前加入有机添加剂化合物。
在防止乙醛从聚酯容器中迁移到任何类型饮料中以防止饮料产生异味方面,本发明是有用的。根据所用的饮料类型,乙醛的味道阈值不同。然而,优选地是,饮料中乙醛浓度降低至大约低于40ppb。更优选地,饮料中乙醛浓度降低至低于20ppb。
如上所述,本发明可以用于改善任何类型饮料的味道,所述饮料包括但不限于水、可乐、苏打水、醇类饮料、果汁等。然而,它特别适用于防止敏感产品如水产生异味。
转向图1,其说明了聚酯容器型坯10。该型坯10是本发明聚酯组合物经注射模塑制成的,包括有螺纹的颈部螺口12,它下端终止于加盖凸缘14。在加盖凸缘14的下面,通常是一圆柱形部分16,它终止于逐渐增加外径以逐渐增加壁厚的部分18。部分18下面是伸长体部分20。
可将图1所示的型坯10吹塑形成图2所示的容器22。容器22包括外壳24,该外壳24包括限定了瓶口28的有螺纹颈部螺口26,有螺纹颈部螺口下面的加盖凸缘30,从加盖凸缘延伸下来的圆锥体部分32,从圆锥体部分延伸下来的瓶体部分34,以及容器底部的瓶底36。如图3所示,该容器10适合用于制备包装饮料38。包装饮料38包括装在容器22中的饮料如碳酸苏打饮料,和密封容器瓶口28的盖子40。
型坯10、容器22和包装饮料38仅仅是利用本发明组合物的应用实例。应当理解,本发明的组合物可以用于制备具有各种构型的多种制品、型坯和容器。
上面描述了本发明,下面将通过实施例进一步进行描述,这些实施例决不能被解释为对本发明范围强加的限制。相反,应当清楚地知道,在阅读了本发明说明书后,在不偏离本发明精神和/或后面权利要求的范围的前提下,本领域技术人员可以提出多种其它实施方案、改变方法和其等价方案。
这些实施例中,AA含量的测试方法如下:在工艺达到平衡后,将制备的三个型坯代表粉碎通过2mm筛子,通过在密封小瓶中150℃下加热30分钟,使包括在聚酯中的AA解吸。然后,利用配有火焰离子化检测器的气相色谱分析解吸的AA。饮料中AA含量的测试方法如下:取5ml等分试样饮料,将等分试样放入20ml小瓶中,加入1g氯化钠,在85℃下解吸含有的AA 10分钟,随后用配有火焰离子化检测器的气相色谱分析饮料的顶部空间。
下述实施例说明了本发明的有机添加剂化合物在降低熔融加工的PET中AA含量的用途。实施例1、9、10、13、14、16、19、21和22是对比实施例,说明了不含有本发明AA清除剂(或现有技术)下的AA含量。
实施例1-9中,在单孔(unit-cavity)Arburg压机上注射模塑26.5g型坯。所有这些实施例中,都是将0.84IV的PET干燥至湿度低于约50ppm,将含有选定添加剂的配方分散在PET上。(应当理解,所有实施例中所用的IV表示根据ASTM D 4603-96测试的特性粘度)。在280℃下进行注射模塑,周期29秒。实施例2-8说明了在固态聚合的PET中使用本发明的添加剂化合物。实施例9说明了邻氨基苯甲酰胺作为清除剂的活性,说明了本发明的添加剂具有类似于邻氨基苯甲酰胺的AA清除活性。
表1
实施例 | 添加剂化合物 | ppm添加剂 | 型坯AA含量(ppm) |
1 | 无 | -- | 16.57 |
2 | 1,2-二(2-氨基苯甲酰氨基)乙烷 | 1000 | 2.08 |
3 | 1,6-二(2-氨基苯甲酰氨基)己烷 | 1000 | 1.62 |
4 | 1,5-二(2-氨基苯甲酰氨基)己烷 | 1000 | 1.58 |
5 | 1,3-二(2-氨基苯甲酰氨基)戊烷 | 1000 | 2.69 |
6 | 1,2-二(2-氨基苯甲酰氨基)丙烷 | 1000 | 6.00 |
7 | 1,2-二(2-氨基苯甲酰氨基)丙烷 | 1000 | 6.36 |
8 | 1,3-二(2-氨基苯甲酰氨基)丙烷 | 1000 | 2.10 |
9 | 邻氨基苯甲酰胺 | 1000 | 1.87 |
实施例10-13说明了在没有经过固态聚合并且起始AA含量非常高的PET树脂中使用本发明的添加剂1,6-二(2-氨基苯甲酰氨基)己烷。
表2
实施例 | 树脂 | 添加剂化合物 | ppm添加剂 | AA含量(ppm) |
10 | 无定形0.80IV | 无 | -- | 58.23 |
11 | 无定形0.80IV | 1,6-二(2-氨基苯甲酰氨基)己烷 | 1000 | 5.03 |
12 | 无定形0.80IV | 1,6-二(2-氨基苯甲酰氨基)己烷 | 2000 | 1.45 |
13 | 无定形0.80IV | 邻氨基苯甲酰胺 | 1000 | 6.27 |
实施例14和15中,将起始AA含量为35ppm的PET在Rheometrics熔体流变计中在最大N2吹扫下在280℃下保持为熔体,总停留时间如下表所示,然后在水中急速冷却,并分析AA含量。实施例14中,PET含有1000ppm邻氨基苯甲酰胺,实施例15中,PET含有1000ppm 1,6-二(2-氨基苯甲酰氨基)己烷。从这些结果可以看出,1,6-二(2-氨基苯甲酰氨基)己烷比邻氨基苯甲酰胺保持效率的实间更长。
表3
对比树脂AA:35ppm | 实施例14挤出物AA含量(ppm)邻氨基苯甲酰胺(1000ppm) | 实施例15挤出物AA含量(ppm)1,6-二(2-氨基苯甲酰氨基)己烷(1000ppm) |
熔体停留时间 | ||
Std注射模塑(2min) | 11.08 | 8.42 |
4min | 2.50 | 2.60 |
6min | 3.60 | 2.44 |
10min | 6.81 | 3.72 |
15min | 71.53 | 8.34 |
下面实施例16-19中,将上面实施例10-13的型坯吹成瓶子。瓶子中装满臭氧化的水,然后在40℃下存放。在下表所示时间下取出水样品,并分析AA含量。由这些实施例可以看出,本发明的AA清除剂1,6-二(2-氨基苯甲酰氨基)己烷在降低饮料AA含量方面具有类似于邻氨基苯甲酰胺的功效。
表4
实施例 | 添加剂 | ppm添加剂 | 饮料中AA含量(ppb) | ||
7天 | 14天 | 28天 | |||
16 | -- | -- | 179 | 410 | 730 |
17 | 1,6-二(2-氨基苯甲酰氨基)己烷 | 1000 | 30 | 41 | 51 |
18 | 1,6-二(2-氨基苯甲酰氨基)己烷 | 2000 | 11 | 15 | 10 |
19 | 邻氨基苯甲酰胺 | 1000 | 18 | 22 | 18 |
实施例20-21中,将实施例17和19的瓶子内装满含有3%乙酸的水,并在70℃下放置2小时,随后存放在40℃下。定期取出样品,并分析提取进入饮料中的清除剂的含量。从这些实施例可以看出,即使在比邻氨基苯甲酰胺可接受的浓度更高的浓度下,本发明的添加剂比邻氨基苯甲酰胺具有低的多的提取率。
表5
40℃下存放后饮料中ppb添加剂 | ||||||||||||
实施例 | 添加剂 | 添加剂ppm | 1天 | 2天 | 3天 | 5天 | 6天 | 10天 | 19天 | 22天 | 30天 | 52天 |
20 | 1,6-二(2-氨基苯甲酰氨基)己烷 | 1000 | n/a | 0.5 | n/a | 1.0 | n/a | 1.0 | 1.3 | 1.1 | 1.1 | 1.0 |
21 | 邻氨基苯甲酰胺 | 500 | 23.5 | n/a | 27.1 | n/a | 33.2 | 33.2 | n/a | n/a | n/a | n/a |
n/a表示没有分析。
实施例22和23
实施例22中,将0.80IV的无定形PET树脂在80℃下干燥3天,然后于280℃下挤出。实施例23中,在挤出前向PET树脂中加入1000ppm 1,6-二(2-氨基苯甲酰氨基)己烷。将这两种树脂都挤成颗粒,然后在表6所示的温度下结晶2小时。结晶后,将树脂在177℃下干燥2小时,然后再次在前述挤出条件下挤出。含有1000ppm 1,6-二(2-氨基苯甲酰氨基)己烷的PET树脂中的AA含量明显低于对比树脂,这说明本发明的AA清除剂即使在长时间暴露于高温下也仍然具有功效。结果表明了使用1,6AAA二聚体作为树脂溶液的可能性。它幸免于结晶和干燥条件。因此,能够使用熔体来制备型坯,其中当注射模塑机没有准备好,或者具有过量的反应器容量时,需要管线支流。
表6
AA(ppm) | 实施例220.80IV无定形PET | 实施例23含有1,6-二(2-氨基苯甲酰氨基)己烷的0.80IV无定形PET |
挤出物AA含量 | 21.76ppm | 5.22ppm |
1、160℃下结晶2小时后挤出物中AA含量 | 17.38ppm | 0.18ppm |
2、170℃下结晶2小时后挤出物中AA含量 | 16.57ppm | 0.16ppm |
3、180℃下结晶2小时后挤出物中AA含量 | 11.19ppm | 0.27ppm |
1、再次挤出 | 23.81ppm | 4.07ppm |
2、再次挤出 | 26.70ppm | 4.27ppm |
3、再次挤出 | 24.08ppm | 4.11ppm |
应当理解,上面实施例涉及本发明的具体实施方案,在不偏离后面权利要求限定的本发明范围的前提下,可以作出多种改变。
Claims (26)
1.一种降低熔融加工的聚酯中乙醛含量的方法,包括将聚酯与有机添加剂化合物混合,所述有机添加剂化合物包括至少两个组分分子片段,每一组分分子片段包括至少两个取代氢的杂原子,该杂原子连接到组分分子片段的碳上,每个组分分子片段与聚酯中的乙醛反应,形成水和生成的有机分子片段,该有机分子片段包括含有所述至少两个杂原子的未架桥五元环或六元环。
2.权利要求1的方法,其中杂原子选自氧、硫和氮。
3.权利要求1的方法,其中所述组分分子片段中的至少一个包括预形成的环。
4.权利要求3的方法,其中预形成的环是芳环。
5.权利要求4的方法,其中生成的有机分子片段的未架桥五元环或六元环连接到芳环上。
6.权利要求1的方法,其中两个杂原子都是氮。
7.权利要求1的方法,其中所述组分分子片段中的至少一个是邻氨基苯甲酰胺衍生物。
8.权利要求1的方法,其中添加剂化合物选自1,2-二(2-氨基苯甲酰氨基)乙烷、1,2-二(2-氨基苯甲酰氨基)丙烷、1,3-二(2-氨基苯甲酰氨基)丙烷、1,3-二(2-氨基苯甲酰氨基)戊烷、1,5-二(2-氨基苯甲酰氨基)己烷和1,6-二(2-氨基苯甲酰氨基)己烷。
9.权利要求1的方法,其中添加剂化合物是1,6-二(2-氨基苯甲酰氨基)己烷。
10.权利要求1的方法,其中添加剂化合物是靛红酸酐与选自1,2-二氨基乙烷、1,6-二氨基己烷、1,3-二氨基丙烷、1,5-二氨基己烷、1,2-二氨基丙烷或1,3-二氨基戊烷的胺之间的反应产物。
11.权利要求1的方法,其中添加剂化合物以约50ppm至约2000ppm的量与聚酯混合。
12.权利要求1的方法,其中有机添加剂化合物的至少一个组分分子片段包括至少两个官能团,所述至少两个官能团中的每一个包括所述至少两个取代氢的杂原子中的至少一个,所述至少两个官能团选自胺、羟基、羧基、酰胺、氨磺酰和硫醇基。
13.权利要求1的方法,其中在聚酯的熔融加工温度下,所述有机添加剂化合物基本上是热稳定的。
14.权利要求1的方法,其中有机添加剂化合物的热分解温度高于约270℃。
15.权利要求1的方法,其中有机添加剂化合物的热分解温度高于约300℃。
16.权利要求1的方法,其中有机添加剂化合物基本上不与聚酯反应。
17.权利要求1的方法,还包括熔融加工聚酯,其中在熔融加工前将添加剂化合物加入到聚酯中。
18.权利要求1的方法,还包括熔融加工聚酯,其中在熔融加工后将添加剂化合物加入到聚酯中。
19.根据下述方法制备的聚酯制品,所述方法包括:
将聚酯与有机添加剂化合物混合,所述有机添加剂化合物包括至少两个组分分子片段,每一组分分子片段包括至少两个取代氢的杂原子,该杂原子连接到组分分子片段的碳上,每个组分分子片段与聚酯中的乙醛反应,形成水和生成的有机分子片段,该有机分子片段包括含有所述至少两个杂原子的未架桥五元环或六元环;
用聚酯制成制品。
20.权利要求19的聚酯制品,其中制品是型坯。
21.权利要求19的聚酯制品,其中制品是容器。
22.包括装在权利要求21的容器中的饮料的包装饮料。
23.制备聚酯制品的方法,包括:
将聚酯与有机添加剂化合物混合,所述有机添加剂化合物包括至少两个组分分子片段,每一组分分子片段包括至少两个取代氢的杂原子,该杂原子连接到组分分子片段的碳上,每个组分分子片段与聚酯中的乙醛反应,形成水和生成的有机分子片段,该有机分子片段包括含有所述至少两个杂原子的未架桥五元环或六元环;
用聚酯制成制品。
24.权利要求23的方法,其中制品是型坯。
25.权利要求23的方法,其中制品是容器。
26.用于制备乙醛含量降低的聚酯制品的组合物,其包括聚酯和有机添加剂化合物,所述有机添加剂化合物包括至少两个组分分子片段,每一组分分子片段包括至少两个取代氢的杂原子,该杂原子连接到组分分子片段的碳上,每个组分分子片段与聚酯中的乙醛反应,形成水和生成的有机分子片段,该有机分子片段包括含有所述至少两个杂原子的未架桥五元环或六元环。
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-
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- 2004-05-14 KR KR1020057022616A patent/KR100943539B1/ko active IP Right Grant
- 2004-05-14 DE DE602004015448T patent/DE602004015448D1/de not_active Expired - Lifetime
- 2004-05-14 SI SI200430823T patent/SI1627012T1/sl unknown
- 2004-05-14 PL PL04752305T patent/PL1627012T3/pl unknown
- 2004-05-14 DK DK04752305T patent/DK1627012T3/da active
- 2004-05-14 WO PCT/US2004/015248 patent/WO2004106424A1/en active Search and Examination
- 2004-05-14 CN CNB2004800144341A patent/CN100404598C/zh not_active Expired - Fee Related
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- 2004-05-14 EA EA200501869A patent/EA010584B1/ru not_active IP Right Cessation
- 2004-05-14 EP EP04752305A patent/EP1627012B1/en not_active Expired - Lifetime
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- 2004-05-14 ES ES04752305T patent/ES2308207T3/es not_active Expired - Lifetime
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- 2004-05-14 AU AU2004242600A patent/AU2004242600B2/en not_active Ceased
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Cited By (9)
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CN102300915A (zh) * | 2009-02-20 | 2011-12-28 | 彩色矩阵控股公司 | 减少聚酯中的乙醛的方法以及由该方法得到的聚酯 |
CN102300915B (zh) * | 2009-02-20 | 2013-07-24 | 彩色矩阵控股公司 | 减少聚酯中的乙醛的方法以及由该方法得到的聚酯 |
CN107428429A (zh) * | 2015-04-03 | 2017-12-01 | 东洋制罐集团控股株式会社 | 多层容器 |
CN108026324A (zh) * | 2015-08-21 | 2018-05-11 | 彩色矩阵控股公司 | 减少聚合材料中醛含量的方法 |
CN108026324B (zh) * | 2015-08-21 | 2020-04-03 | 彩色矩阵控股公司 | 减少聚合材料中醛含量的方法 |
CN111234311A (zh) * | 2015-08-21 | 2020-06-05 | 彩色矩阵控股公司 | 减少聚合材料中醛含量的方法 |
CN111234311B (zh) * | 2015-08-21 | 2021-09-03 | 彩色矩阵控股公司 | 减少聚合材料中醛含量的方法 |
CN110305452A (zh) * | 2019-05-30 | 2019-10-08 | 贵州千叶药品包装股份有限公司 | 一种低乙醛含量的药用聚酯瓶及其制备方法 |
CN110305452B (zh) * | 2019-05-30 | 2021-07-27 | 贵州千叶药品包装有限公司 | 一种低乙醛含量的药用聚酯瓶及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
ES2308207T3 (es) | 2008-12-01 |
EP1627012A1 (en) | 2006-02-22 |
DK1627012T3 (da) | 2008-11-10 |
ATE402978T1 (de) | 2008-08-15 |
SI1627012T1 (sl) | 2008-10-31 |
EA010584B1 (ru) | 2008-10-30 |
BRPI0409823A (pt) | 2006-05-09 |
PL1627012T3 (pl) | 2008-12-31 |
KR20060025537A (ko) | 2006-03-21 |
PT1627012E (pt) | 2008-09-04 |
CN100404598C (zh) | 2008-07-23 |
JP2006528995A (ja) | 2006-12-28 |
WO2004106424A1 (en) | 2004-12-09 |
KR100943539B1 (ko) | 2010-02-22 |
NZ543057A (en) | 2008-10-31 |
CA2524905A1 (en) | 2004-12-09 |
BRPI0409823B1 (pt) | 2013-09-10 |
AU2004242600B2 (en) | 2009-10-29 |
CY1108337T1 (el) | 2014-02-12 |
EA200501869A1 (ru) | 2006-06-30 |
EP1627012B1 (en) | 2008-07-30 |
JP4825675B2 (ja) | 2011-11-30 |
DE602004015448D1 (de) | 2008-09-11 |
ZA200509104B (en) | 2006-11-29 |
AU2004242600A1 (en) | 2004-12-09 |
MXPA05011132A (es) | 2005-12-14 |
CA2524905C (en) | 2012-10-30 |
US6762275B1 (en) | 2004-07-13 |
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