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CN1250405A - 在熔融至型坯连续生产过程中用边角回收料连续生产聚酯制品的方法 - Google Patents

在熔融至型坯连续生产过程中用边角回收料连续生产聚酯制品的方法 Download PDF

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CN1250405A
CN1250405A CN98803424A CN98803424A CN1250405A CN 1250405 A CN1250405 A CN 1250405A CN 98803424 A CN98803424 A CN 98803424A CN 98803424 A CN98803424 A CN 98803424A CN 1250405 A CN1250405 A CN 1250405A
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L·C·特里斯
E·G·奥尔森
M·D·舍尔拜
小M·L·卡罗尔
M·P·埃卡特
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Abstract

生产聚酯制品的方法,它产生很少的或不产生聚酯废料。该方法提供了一种或多种二羧酸或其二烷基酯的酯化或酯基转移反应,缩聚反应,从而获得高分子量聚酯,以及聚酯用于生产所需产品的模塑或成型加工方法。在模塑过程中产生的边角料回用到该方法的酯化或酯基转移或缩聚部分中。选择性地,边角料还可以在模塑操作之前回用到中间体步骤中。

Description

在熔融至型坯连续生产过程中用边角回 收料连续生产聚酯制品的方法
发明领域
本发明涉及在包括回收步骤的熔体至成型(melt-to mold)连续生产过程中连续生产聚酯制品的方法。由聚酯前体制备聚酯熔体组合物，并在单程式、综合式过程中直接模塑或按照其他方式成型为有用的成型制品，其中模塑之前不需使熔体固化。来自模塑步骤的回用边角料聚酯在制造过程中多个点中的任何点加入到聚酯熔体物流中。
先有技术描述
聚酯被广泛用于各种各样的应用中，其中许多需要高分子量聚酯以获得可接受的性能。就这方面而言，现有技术上已知，聚酯可用来制造诸如食品及饮料容器之类的模塑制品。制备高分子量聚酯制品的传统方法涉及从前体聚酯到适度分子量的熔融相生产，随后是该无定形聚合物的切粒；结晶及固态缩聚，以便将分子量提高到要求的水平；继而，该聚酯再熔融并模塑为要求的制品。
聚酯模塑过程产生许多边角料，通常须回用以降低成本。传统上，边角料可返回到模塑过程中，这要求干燥并会导致因高分子量聚酯需较长时间熔融而造成聚合物降解的加剧。此外，边角料可通过输送并加入到生产粒料、纤维或薄膜的聚酯加工装置中来回用。迄今为止，尚不知道能利用聚酯前体起始物料、熔体、模塑的及回收的边角料聚酯作为原料连续生产成型制品，以便很少或不产生聚酯废料的综合方法。
先有技术描述过生产诸如瓶子型坯之类成型制品的连续熔融相方法，然而，它没有涉及将模塑步骤中产生的废聚酯循环返回到聚酯聚合物成型阶段中去的问题。在树脂生产期间将聚酯边角料加入到熔融相聚酯反应器中的方法是已知的。然而，这些方法未涉及生产模塑制品的综合方法。例如，美国专利3,703,488描述了一种方法，其中边角料与聚酯单体在挤塑机中混合，然后，使之降解到20～30的聚合度并由泵压入到反应器中。在美国专利4,138,374中，边角料被加入到紧靠最终熔融聚合反应器出口的前方。德国专利DE19503053及DE19505680描述了一种连续熔体至成型方法，然而，也未能涉及如何将回收边角料聚酯加入到聚合物成型步骤中去的问题。
现已出乎意料地发现，能够提供这样一种以聚酯前体为起始物料制备成型制品的连续方法，在该方法中，在聚酯成型或模塑步骤期间来自模塑步骤的回收边角料聚酯被加入进去。这样一来，便获得一种可达到接近100％高收率的方法，并由此带来生产成本的降低及有待处置的废弃物的减少。边角料循环返回之前无需对型坯进行通常为防止水解降解所要求的干燥处理。在将聚合物加入到聚合过程中发生的任何水解降解并不妨事，因为，聚合物毕竟还要进行进一步的缩聚。边角料不需要在高分子量熔融状态停留显著延长的时间。这就减少了聚合物的降解，从而可改善颜色并减少乙醛的生成。也不需要将边角料输送到另外的单独聚酯加工过程中去。
发明概述
本发明提供一种成型模塑聚酯制品的连续生产方法，其包括：
a)使聚酯均聚物或共聚物前体在足以生成熔融聚酯均聚物或共聚物物料流的条件下在反应器中进行反应；
b)让熔融聚酯的物料流流入到至少一个模塑设备中，从而成型固体模塑制品并由此而产生聚酯边角料，其间不需使聚酯在进入模塑设备之前进行固化；
c)将聚酯边角料与固体模塑制品分离；以及
d)通过将聚酯边角料加入到熔融聚酯均聚物或共聚物或二者的前体物流中去而将聚酯边角料循环到步骤(a)。
附图简述
图1表示按照本发明的加工顺序的示意图。
优选实施方案详述
本发明的方法涉及通过至少一种二羧酸与至少一种二醇进行酯化反应生成聚酯的已知初始步骤，随后的经过缩聚生成高分子量聚酯；继而，将该聚酯成型为成型制品。该聚酯聚合物在熔融相中由单体制备而成，并直接加入到至少一个模塑或其他成型机中，其间不需要使聚酯在进入到模塑机之前固化。由模塑操作产生的边角料聚酯随后循环返回到该方法的聚合部分中去。
边角料聚酯包括从模塑制品上修整下来的聚酯、因质量缺陷剔除的制品以及不是在前面按照上述加工步骤a～c产生的，而是从消费者回收来的废料碎片。边角料可在熔融相加工步骤中加入到任何反应器中，包括在其中发生二羧酸或其二烷基酯的酯化或酯交换的，或者在其中发生缩聚的那些反应器。另外，边角料可加入到反应器和/或模塑操作之间的输送低聚物或聚合物的工艺管线中。边角料可以固体形式加入到反应器中，或者预先将其本身熔融之后再加入到反应器中。希望的是，将边角料磨碎，以便利对固体的操作。边角料还可以在由泵压入到反应器中之前通过令其与二醇、醇或水起反应(解聚)以降低其分子量而引入。
在本发明的实施中要制备聚酯组合物，其生产方法包括，使二元酸，如二羧酸或其低级烷基二酯，与二醇进行缩合。在可用于制成模塑聚酯制品的二羧酸及其低级烷基二酯当中有：对苯二甲酸；间苯二甲酸；邻苯二甲酸；萘二甲酸；琥珀酸；癸二酸；己二酸；壬二酸；联苯-甲酸；六氢化邻苯二甲酸类及双-对羧基苯氧基乙烷。特别有用的萘二甲酸包括2，6-、1，4-、1，5-或2，7-异构体，然而，1，2-、1，3-、1，6-、1，7-、1，8-、2，3-、2，4-、2，5-和/或2，8-异构体也可使用。二元酸可包含约2～约40个碳原子，包括间苯二甲酸、己二酸、戊二酸、壬二酸、癸二酸、富马酸，二聚的、顺式-或反式-1，4-环己烷二羧酸、萘二甲酸的各种异构体等。优选的二元酸包括对苯二甲酸、间苯二甲酸、萘二甲酸、环己烷二羧酸及其混合物。二元酸可以酸的形式、酸酐形式或其酯，如二甲酯的形式使用。这些酸和/或它们的低级烷基二酯中的一种或多种可与一种或多种二醇起反应，后者为包含约3～约10个碳原子的二醇，包括乙二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇、二甘醇、1，4-环己烷二醇、1，4-环己烷二甲醇、新戊二醇等。1，4-环己烷二甲醇可以是顺式-或反式-的形式或者是顺/反式混合物。优选的二醇包括乙二醇、1，4-环己烷二甲醇二甘醇及其混合物。由于一种或多种二酯可与一种或多种二醇起反应，故本发明的聚酯薄膜不只局限于均聚酯，而是也包括混杂的聚酯，如共聚酯乃至与其他单体的共聚物。
对本方法特别有用的聚合物包括聚(对苯二甲酸乙二醇酯)、聚(萘二甲酸乙二醇酯)，以及包含最高约50mol％改性用二元酸和/或二醇的共聚酯。在属于本发明预期范围之内的聚酯当中，优选的是包含至少占主要含量的聚对苯二甲酸乙二醇酯的那些，最优选的是包含，按200mol％计，至少80mol％对苯二甲酸和80mol％乙二醇的那些。构成聚对苯二甲酸乙二醇酯模塑制品的聚合物是由两种不同方法之一的方法通过本身作为中间体的对苯二甲酸双(2-羟乙基)酯的聚合生成的。生成对苯二甲酸双(2-羟乙基)酯的一种方法是采用对苯二甲酸与乙二醇直接进行酯化，正如美国专利3,050,533中所描述的。在该方法中，反应副产物是水，该副产物水从反应产物中蒸馏除掉。生成对苯二甲酸双(2-羟乙基)酯的第二种方法是采用对苯二甲酸二烷基酯，优选对苯二甲酸二甲酯，与乙二醇进行酯交换。优选的是，2分子比例的乙二醇与1分子比例的对苯二甲酸二甲酯起反应。更优选的是，采用大于2分子比例的乙二醇/每分子比例的对苯二甲酸二烷基酯，因为，在这样的条件下初期的酯交换反应进行得较快、较完全。酯交换反应是在高温条件下进行的。例如，可采用从接近反应混合物的沸点直至高达250℃的温度。反应可在大气压、负压或正压下进行。酯交换反应的副产物之一是链烷醇。例如，若采用对苯二甲酸二甲酯，则生成甲醇。该链烷醇随后被从反应产物中除掉。
为了提高反应速率，可在酯交换反应中采用多种已知的催化剂。可使用的典型酯交换催化剂包括钛的醇盐、二月桂酸二丁基锡及氧化锑或三醋酸锑，可以单独使用或组合使用，任选地与锌、锰或镁的醋酸盐或苯甲酸盐和/或其他诸如本领域技术人员所熟悉的催化剂材料配合使用。还可任选地存在磷或钴化合物，它们可以从一开始就存在，也可在过程的任何方便的一点加入。
在生成了中间体对苯二甲酸双(2-羟乙基)酯之后，可通过在能实现二醇或水的移出条件下在高于二醇或反应混合物沸点的温度加热，使中间体转化为聚对苯二甲酸乙二醇酯。希望的话，该加热可在高达325℃的温度进行。加热期间，降低压力以提供使多余二醇或水迅速蒸出的条件。最终聚对苯二甲酸乙二醇酯聚合物的特性粘度，按照在25℃的邻氯苯酚中测定，超过0.3dL/g。更优选的是，聚合物的特性粘度，按照在25℃的邻氯苯酚中测定，为约0.4～约1.0dL/g。进一步优选的是，本发明所使用的聚对苯二甲酸乙二醇酯的特性粘度，按照在25℃的邻氯苯酚中测定，为约0.5～约0.7dL/g。优选的是，包含本发明聚合物的热塑性聚酯在结晶之前的熔点为约200℃～约330℃或更高，优选为约220℃～约290℃，最优选约250℃～约275℃。
适合用作聚酯共聚物中共聚单体的是诸如丙烯酸及甲基丙烯酸的以及芳族及脂族多元醇的醚、酯及部分酯之类的组分。此种共聚物的制备方法在现有技术中是众所周知的。
本发明的特征是，将从熔体至成型的连续过程中所生成的边角料聚酯加入到过程中。就是说，在按照如上所述制备了聚酯之后，在单程式的、综合的过程中将边角料聚酯加入到熔体中并成型为有用的成型模塑制品，不需要聚酯的中间固化阶段。
还可在熔体中加入许多不同种类的添加剂，具体视对最终制品所要求的性能之性质而定。此种添加剂包括但不限于，着色剂、抗氧剂、乙醛降低剂、稳定剂，例如紫外及热稳定剂，冲击性改性剂、聚合催化剂的减活化剂、熔体强度提高剂、抗静电剂、润滑剂、增链剂、成核剂、溶剂、填料、增塑剂等。
合适的着色剂包括染料和颜料。有用的着色剂包括但不限于：染料，如Victoria Pure Blue BO(碱性蓝7，CI 42595)，其市售品如BASF Flexo Blue 636(BASF公司，Parsippany，新泽西)、Rhodamine、Chalcozine、Victoria Blue及甲基紫；以及颜料，如蒽醌和酞菁类。苝栗红、酞菁蓝、酞菁绿和镉红也同样是有用的。
乙醛降低剂包括聚酰胺，如美国专利5,266,413、5,258,233和4,8837,115中公开的那些；聚酯酰胺、尼龙6以及其他脂族聚酰胺，如日本专利申请Sho 62182065(1987)中所公开的；乙二胺四乙酸，如美国专利4,357,461公开的；烷氧基化多元醇，如美国专利5,250,333中所公开的；双(4-β-羟基乙氧基苯基)砜，如美国专利4,330,661中所公开的；沸石化合物，如美国专利5,104,965中所公开的；5-羟基间苯二甲酸，如美国专利4,093,593中所公开的；聚(间苯二甲酸乙二醇酯)，如美国专利4,403,090中所公开的；超临界二氧化碳，如美国专利5,049,647及4,764,323中所公开的；以及质子酸催化剂，如美国专利4,447,595及4,424,337中所公开的。
合适的冲击性改性剂是乙烯丙烯酸甲酯。抗静电剂包括硬脂酰氨基丙基二甲基-β-羟乙基铵的硝酸盐，如美国专利4,302,505中所公开的。
熔体的溶剂包括醇，如甲醇、乙醇、丙醇、丁醇、苯甲醇及苯氧基乙醇；酮，如丙酮、甲乙酮、甲基异丁基酮、环己酮、二异丁基酮等；酯，如乙酸乙酯、乙酸丁酯、乙酸戊酯、甲酸甲酯、丙酸乙酯、邻苯二甲酸二甲酯、苯甲酸乙酯、甲基溶纤剂乙酸酯、乙二醇单乙基醚乙酸酯及乳酸乙酯；芳烃，如甲苯、二甲苯、苯、乙苯；卤代烃，如四氯化碳、三氯乙烯、氯仿、1，1，1-三氯乙烷、1，2-二氯乙烷、单氯代苯、氯萘；醚，如四氢呋喃、(二)乙醚、乙二醇单乙基醚、乙二醇单甲基醚、丙二醇单甲基醚等；二甲基甲酰胺、二甲基亚砜、N-乙烯基吡咯烷酮等，及其混合物。
特别有利的实施方案是加入聚合催化剂减活化剂，优选在聚合物物料流离开聚合反应器的一点加入。此种减活化剂可包括诸如磷酸酯、磷酸三钠、磷酸三钾、烷基或芳族胺、酰胺、醇盐等化合物。在该实施方案中，聚合反应期间一直保持着充分的催化活性，从而极大地缩短了聚合需要的时间。一旦达到所要求的分子量之后，就使聚合催化剂大大减活。借助这样的技术，在过程余下的全部时间里进一步发生副反应的可能大大减少，因而生产出的制品具有卓越的颜色和热稳定性。
抗氧剂包括诸如苯酚，特别是位阻酚之类的化合物，包括Irganox1010，汽巴嘉基公司出品；硫化物；有机硼化合物；有机磷化合物；N，N’-六亚甲基双(3，5-二叔丁基-4-羟基氢化肉桂酰胺)，由汽巴嘉基公司以商品名“Irganox 1098”出售。稳定剂包括位阻胺，苯并三唑，羟基二苯酮等。合适的稳定剂是分子量为2,000的缩水甘油基醚双酚A。
填料可选自各种各样的矿物、金属、金属氧化物、硅质材料、金属盐及其混合物。属于这些类型填料的例子是二氧化钛、氧化铝、氢氧化铝、长石、石棉、滑石、碳酸钙、粘土、碳黑、石英、磨石，以及其他形式的二氧化硅、高岭土、膨润土、石榴石、云母、滑石粉、贝得石、氧化钙、氢氧化钙等。
合适的增塑剂的例子包括邻苯二甲酸二辛酯、邻苯二甲酸二丁酯、邻苯二甲酸丁酯、甘醇酸丁酯、磷酸三甲苯酯、聚酯系列增塑剂及氯化石蜡。
成核剂包括羧酸的碱金属盐，它们可通过有机羧酸与第I族金属的碱起反应生成第I族金属的盐来制备。合适的包含羧酸的化合物包括诸如苯甲酸和取代的苯甲酸之类的芳族酸；诸如新戊酸之类的脂族酸，诸如硬脂酸、棕榈酸的脂肪酸及二聚酸。优选的成核剂是硬脂酸钠。其他成核剂包括金属盐离聚物，如碱金属盐离聚物。可用于本发明的离聚物包括公开在美国专利4,381,376、4,603,172和4,412,040中的那些。
以上列举的聚酯改性剂与聚酯的典型掺混比例，以改性后聚酯总重量为基准，为约0.01～约15wt％。
聚酯均聚物或共聚物前体在反应器中反应之后，熔融聚酯均聚物或共聚物可任选地经过过滤，混合或以其他方式接受搅拌，脱除挥发分，然后，流入到至少一个模塑设备中，从而成型为固体模塑制品，其中在进入模塑设备之前不需要将聚酯固化。
优选采用过滤器使熔体均化并除掉杂质。熔体过滤器和混合器在现有技术中是熟知的，其例子可见诸于美国专利5,564,827。脱挥发分的目的在于除去熔体中的气体及其他挥发成分。脱挥发分在典型的情况下是在带有真空脱气功能的排气式双或多螺杆挤塑机中实现的，此种设备在现有技术中是熟知的。脱挥发分的例子可见诸于美国专利5,376,702、5,458,478和5,308,892。
就本发明的目的而言，模塑包括由熔体生产成型固体制品的任何已知方法。在本发明的特别有用的实施方案中，边角料聚酯被投入到向一个或多个模塑机器供料的熔融相反应器中。任选地，可在紧接加入点之后并在进入模塑机之前的熔体物料流中设置一个混合段。本发明的组合物可用于制造成型制品如结构件，例如用诸如注塑、气体辅助注塑、吹塑、挤塑热成型等方法。模塑可在市售的机器上进行，例如在150吨Cincinnati模塑机上。边角料聚酯的可能加入点包括：在熔融相反应器中，即，在酯化或酯交换或者随后的缩聚期间；在聚合反应刚刚完成之后；在紧靠熔体分配管中的混合元件之前；在紧靠分配阀之前；以及向模塑机加料的管线中。要知道，其他的加入点也是可能的，而且，在任何给定的过程中可采用一个以上的加入点。
在优选的实施方案中，与步骤(a)中生产的新聚酯相掺混的再循环的聚酯边角料的量，以整个过程产出的聚酯总重量为基准，为约1wt％或更低～约60wt％。更优选的是，与步骤(a)中生产的新聚酯相掺混的再循环聚酯边角料的量，以整个过程所产出的聚酯总重量为基准，为约1wt％或更低～约25wt％，最优选约1wt％或更低～约10wt％。
图1表示按照本发明的加工顺序的一种实施方案示意图。聚酯前体在一个或多个反应器2中进行反应；流经：任选的过滤器4；任选的混合器6；以及任选的挥发分脱除器8，最后进入到适当的模塑机10中，整个过程连续进行，不需聚酯的中间固化或再熔融阶段。要知道，聚合反应器2还可包含涉及通过酯化或酯交换随后聚合之顺序而进行聚酯熔融相制备的两个或更多个反应步骤。在这种情况下，所说的加入可发生在前体聚酯制备阶段，或结晶并进一步聚合阶段，或者二者，或者在这两个阶段之间。来自模塑步骤的再循环聚酯可加入到该序列的步骤的一个或多个点中。再循环聚酯的加入可在一个或多个聚合反应器2中进行；可在聚合反应器2之前但在过滤器4之后；在过滤器4中过滤期间；在过滤器4以后但在混合器6混合之前；在混合器6中进行混合期间；在混合器6中混合之后但在进入到挥发分脱除器8之前；在挥发分脱除器8中进行脱挥发分期间；或者在挥发分脱除器8中进行脱挥发分之后但在模塑机10中进行模塑之前进行。属于本发明范围考虑范围的还包括，将再循环聚酯加入到使用者要求的不同点。还应当指出的是，多个聚合反应器、过滤器、混合器及挥发分脱除器可向一个或多个模塑机供料，其连接方式既可以是串联的，也可以是并联的。
下面，给出非限定性实施例以说明本发明。然而，要知道，提供这些实施例仅为说明的目的，无意从任何意义上对本发明的范围作出界定。
实例1
在熔融相反应器中制备用3.5mol％1，4-环己烷二甲醇(30/70mol％顺-、反式-混合物)改性的经过滤的聚对苯二甲酸乙二醇酯(PET)，特性粘度IhV达到0.64，然后喂入到排气式双螺杆反应器中。经过在275℃的温度及0.75托(mm汞柱)的压力下停留25min的时间之后，聚合物的IhV达到0.75且残余乙醛为5ppm。这里所使用的术语“IhV”是指，聚合物按照以0.5g聚合物溶于苯酚(60体积％)和四氯乙烷(40体积％)100mL混合物中的溶液测定的特性粘度。随后，聚合物经过由分配管和阀门组成的系统泵压入到模塑机中，其间平均停留时间为约7min。每个模塑机在聚合物被冷却到200℃以下之前所具有的停留时间为约40s。具有0.75IhV的模塑型坯中的残余乙醛含量为15ppm。模塑机生产出模塑瓶，同时产生聚酯边角料。边角料中的一部分是出于质量的考虑而剔除的瓶子。将合格的瓶子与边角料分开，边角料作为进料返回熔融相反应器。
实例2
重复实例1的过程，不同的是，在紧接最终双螺杆反应器后面的工艺物料流中增设注料口。在加入口后面的管线中设置静态混合元件。生产出瓶子，分离掉边角料，边角料作为进料返回熔融相反应器。另外，采用回转气阀或单螺杆挤出机对通过加入口的经过或未经过聚合的再循环的、熔融的边角料聚酯实施计量。
实例3
PET在熔融相反应器中被制备到特性粘度等于0.74且最终熔体温度达285℃，经过滤，然后分成数股分配到10台排气式挤塑机中并流入到10台模塑机中。每股的流速等于1台多腔瓶子模塑机的能力。生产出瓶子，分离掉边角料聚酯，其中包括因质量不佳而剔除的瓶子，边角料作为进料返回熔融相反应器。再循环的聚酯边角料还经由模塑机前面的一点加入到熔融PET物料流中。
实例4
PET经过在270℃下的熔融相反应器中制备后达到0.75的特性粘度。反应器的出料分成10股料流，分别喂入10个脱气站和10台多腔瓶子模塑机。生产出瓶子，分离掉边角料聚酯，该边角料作为进料返回熔融相反应器中。由模塑机产生的边角料再循环聚酯还在脱气站末端处加入，然后聚合物经由静态混合段注入。生产出的瓶子之间在颜色或乙醛含量上没有明显差异。

Claims (19)

1.一种用于成型模塑聚酯制品的连续生产方法，其包括：
a)使聚酯均聚物或共聚物前体在足以生成熔融聚酯均聚物或共聚物物料流条件下在反应器中进行反应；
b)让熔融聚酯的物料流流入到至少一个模塑设备中，从而成型固体模塑制品并由此而产生聚酯边角料，其间不需使聚酯在进入模塑设备之前进行固化；
c)将聚酯边角料与固体模塑制品分离；以及
d)通过将聚酯边角料加入到熔融聚酯均聚物或共聚物或二者的前体的物料流中去而将聚酯边角料再循环到步骤(a)。
2.权利要求1的方法，其中在步骤(b)期间还附加地实施边角料再循环。
3.权利要求1的方法，其中在步骤(a)及(b)之间还附加地实施边角料再循环。
4.权利要求1的方法，其中步骤(a)的反应包括步骤i)酯化或酯交换，随后是ii)缩聚，且酯化或酯交换期间实施边角料再循环。
5.权利要求1的方法，其中步骤(a)的反应包括步骤i)酯化或酯交换，随后是ii)缩聚，且缩聚期间实施边角料再循环。
6.权利要求1的方法，其中步骤(a)的反应包括步骤i)酯化或酯交换，随后是ii)缩聚，且在步骤i)和ii)期间均实施边角料再循环。
7.权利要求1的方法，其中步骤(a)的反应包括步骤i)酯化或酯交换，随后是ii)缩聚，且在步骤(i)与(ii)之间实施边角料再循环。
8.按照权利要求1的方法，其中步骤(a)还包括在熔融聚酯物料流流入模塑设备以前对熔融聚酯均聚物或共聚物物料流实施过滤、混合及脱挥发分中的一个或多个步骤；以及在过滤、混合和/或脱挥发分之前或期间和/或之后实施边角料再循环。
9.按照权利要求1的方法，其中步骤(b)采用多台模塑设备实施。
10.按照权利要求1的方法，其中聚酯是均聚物。
11.按照权利要求1的方法，其中聚酯是包含共聚物的聚酯。
12.按照权利要求1的方法，其中聚酯是聚对苯二甲酸乙二醇酯的均聚物。
13.按照权利要求1的方法，其中步骤(a)所生产的聚酯均聚物或共聚物的特性粘度，再次在25℃下在邻氯苯酚中测定时，为约0.4～约1.0dL/g。
14.按照权利要求1的方法，其中聚酯还包含选自着色剂、抗氧剂、乙醛降低剂、稳定剂、冲击性改性剂、聚合催化剂减活化剂、抗静电剂、润滑剂、成核剂、溶剂、填料、增塑剂及熔体强度改进剂中的一种或多种成分。
15.按照权利要求1的方法，其中再循环的聚酯边角料与步骤(a)中生产的聚酯的掺混比例，以该方法产出的聚酯总重量为基准，为约1～约60wt％。
16.按照权利要求1的方法，其中再循环的聚酯边角料与步骤(a)中生产的聚酯的掺混比例，以该方法产出的聚酯总重量为基准，为约1～约25wt％。
17.按照权利要求1的方法，其中再循环的聚酯边角料与步骤(a)中生产的聚酯的掺混比例，以该方法产出的聚酯总重量为基准，为约1～约10wt％。
18.权利要求1的方法，其还包括将额外的聚酯再循环到步骤(a)中的步骤，该额外的聚酯不是此前由步骤a～c所生产的。
19.权利要求1的方法，其包括聚酯均聚物或共聚物前体在多个反应器中在足以生产出多股熔融聚酯均聚物或共聚物物料流的条件下进行反应，以及使这些多股熔融聚酯物料流流入到至少一个模塑设备中。
CN98803424A 1997-03-20 1998-03-19 在熔融至型坯连续生产过程中用边角回收料连续生产聚酯制品的方法 Expired - Lifetime CN1107581C (zh)

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CN104669463B (zh) * 2013-12-30 2016-05-11 河南华鑫网业有限公司 一种物理浮选法处理聚酯网生产废弃边角料的分离方法
CN104999593A (zh) * 2015-07-31 2015-10-28 兴安宸亿工贸有限公司 一种废旧聚对苯二甲酸乙二醇酯的回收再利用方法
CN106313368A (zh) * 2016-09-18 2017-01-11 厦门德菲尔特新材料有限公司 一种板片材边角料回收工艺及其装置
CN106313368B (zh) * 2016-09-18 2018-11-30 厦门德菲尔特新材料有限公司 板片材边角料回收工艺、装置及运用该装置回收处理的方法
CN114426663A (zh) * 2020-10-29 2022-05-03 中国石油化工股份有限公司 一种聚酯生产中循环eg的二氧化钛去除方法
CN114426663B (zh) * 2020-10-29 2024-04-02 中国石油化工股份有限公司 一种聚酯生产中循环eg的二氧化钛去除方法
TWI761195B (zh) * 2021-04-29 2022-04-11 南亞塑膠工業股份有限公司 由回收膜形成聚酯材的方法
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EP0968076A1 (en) 2000-01-05
US5945460A (en) 1999-08-31
DE69808055T2 (de) 2003-06-05
WO1998041375A1 (en) 1998-09-24
CA2285444A1 (en) 1998-09-24
JP2001517164A (ja) 2001-10-02
BR9808275A (pt) 2000-05-16
AU6764098A (en) 1998-10-12
EP0968076B1 (en) 2002-09-18
JP4138890B2 (ja) 2008-08-27
CN1107581C (zh) 2003-05-07
AR010409A1 (es) 2000-06-07
DE69808055D1 (de) 2002-10-24
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