CN85106299A - 聚酯碎屑的解聚法 - Google Patents
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Abstract
将聚对苯二甲酸乙酯与乙二醇加入一盛有熔融BHT的反应釜，解聚后生成对苯二甲酸双一羟乙酯和/或其低聚物(BHT)。反应条件如下：(a)熔融BHT的二醇与酸组分的当量比应为1.3～2.0，(b)熔融BHT的酸组分与聚酯碎屑酸组分的重量比应为1/4～2/1，(c)聚酯碎屑与乙二醇的比率应使二醇与酸组分的当量比介于1.3～2.0之间。解聚温度为215-250℃，同时搅拌。反应完毕后将部分产物转移至聚合釜。
Description
本发明涉及主要成分为聚对苯二甲酸乙酯（下称PET）的聚酯碎屑的解聚以及回收高质量对苯二甲酸双羟乙酯和/或其低聚物（下称BHT）的方法。
因为聚酯（例如PET）的优良性质，所以它以纤维、薄膜、塑料等形式大量生产。有效利用生产过程中产生的纤维、薄膜和树脂碎屑对于降低工业成本是很有意义的。至今英国专利610，136和日本公开特许61447/1973的方法是用乙二醇（下称EG）通过聚酯碎屑的解聚得到BHT的，并且用所得到的BHT直接聚合再组合成聚酯。如果在上述的过程中一次加入所有的聚酯碎屑和全部EG，因为体系中的组分固化，反应体系得不到搅拌而产生下面的一些问题：解聚体系不均匀，因而也延长了解聚时间;大量使用EG是不经济的;由于所得的聚酯物理性质的降低〔特别是因副产物二甘醇（下称DEG）的存在而极度降低了其软化点〕而降低了其质量。用这种常规方法尚未能有效地解聚聚酯碎屑以制备高质量的再聚合聚酯。
本发明的任务是：（a）回收BHT，用于生产高质量的再聚合聚酯;（b）解聚时减少EG的消耗，以便最大限度降低DEG副产物和其他杂质，同时缩短解聚时间。
本发明提供了一种解聚聚酯碎屑的方法，聚酯碎屑的主要成分是聚对苯二甲酸乙酯，其步骤如下：
（1）在熔融的BHT存在下，批量或连续将乙二醇和聚酯碎屑加入反应釜作用一段时间，其条件是：
（a）熔融的BHT的二醇与酸组分的当量比应为1.3∶2.0
（b）熔融的BHT的酸组分与聚酯碎屑的酸组分的重量比应为1/4～2/1
（c）聚酯和EG的比应使二醇与酸组分的当量比介于1.3～2.0之间，
（2）在搅拌下解聚，温度为215～250℃。
按照本发明，可将解聚物自反应釜中取出移至聚合反应釜，余留一部分进行下一批聚酯碎屑的解聚。
本发明所用的聚酯碎屑可以是薄膜、块状物、纤维、小条或小球状物，只要它们能连续进入解聚反应釜。但其重量最好在1克左右或小于1克，以避免搅拌时产生沉积，纵使是将其连续加入BHT中。聚酯碎屑可以全部是由对苯二甲酸或其低级烷基酯和EG组成的PET。然而，所用的聚对苯二甲酸乙酯也可有部分酸和/或二醇组分为一个或多个其他酸或二醇所取代，这些酸是间苯二甲酸、邻苯二甲酸、二苯基羧酸、琥珀酸、己二酸、癸二酸、对羟基苯甲酸和其他二元酸;这些二醇是亚丙基二醇、亚丁基二醇、亚己基二醇和聚乙二醇。在聚酯碎屑中也可能含有色素和通常的添加剂，如抗热剂等。
聚酯碎屑的供料最好使用旋转加料器，这是因为它的定量特性和稳定性。但是，在这种情况下反应体系中产生的EG蒸气可能弄湿聚酯供应器内部，粘住碎屑。因此，最好安装向加料器和解聚反应釜之间吹入氮气的设备，而且再装一个控制阀以控制氮气的供给。
解聚反应釜中的BHT可用已知方法由芳香族二元酸与二醇或对苯二甲酸二甲酯与二元醇合成，或用已知方法产生低聚物，或按本发明的方法制备BHT。
在解聚反应釜中，要求BHT的酸组分对所加聚酯碎屑酸组分的重量比为1/4～2/1，最好是1/3～1/1，以便得到高质量BHT。比率低于1/4时，解聚作用将变得缓慢，反应需要较长的时间才能完成;另一方面，比率高于2/1时，则有比较大的一部分BHT长时间处于高温状态，这样可能引起副反应的产生，因而使得到的聚酯色泽性差、软化点低。
加EG的速度要使二醇和聚酯碎屑的酸组分的当量比率为1.3～2.0，最好是1.3～1.6，以便得到高质量的BHT。如果比率小于1.3，解聚后得到的BHT质量有所降低，结果使所得到的聚合物色泽（b-值）变差。
如果比率大于2.0，EG消耗增大，产生副反应产物DEG，由BHT所得到的聚酯软化点降低，同时也降低了此反应体系的沸点，使解聚时间增长。
解聚体系应保持在215～250℃，最好是220～240℃。低于215℃时，聚酯碎屑不能迅速溶解;高于250℃时，DEG副反应增加，使所得的聚合物软化点降低。
通常的酯交换反应釜和酯化反应釜可用于解聚反应，在解聚反应过程中，聚酯碎屑含有的小量湿气易蓄积于反应体系中而降低了反应体系的温度，因而反应时间增长，同时也降低了所得BHT的质量。为阻止湿气的蓄积，最好在解聚反应釜上加一精馏塔，把湿气蒸出反应体系。使用已知类型的精馏塔已足以能使EG和湿气分离。EG和聚酯碎屑是同时在固定时间加入的，这样它们几乎与初始的BHT有相同的二醇与酸组分当量比。可以将二者连续或间歇地加入，也可以将其中之一连续加入而将另一间歇加入。在间歇式加料时，最好将碎屑分成5份或5份以上。加料速度可以保持常数，也可以缓慢增加。
加入聚酯碎屑的速率对BHT质量的影响很大。如果速率太大，由于反应体系中的固化，聚酯碎屑得不到很好的搅拌，因而增加了解聚时间，由BHT所得到的聚合物软化点较低并且色泽较差;相反，如果速率太小，也会增加解聚时间，所得到的聚酯将会变质。
加入聚酯碎屑的时间虽然可受其重量及反应釜中存在的BHT的影响，但最好是60～90分钟或30～60分钟，如果BHT的酸组分和聚酯碎屑的酸组分的重量比各为1/4～3/4或3/4～2/1。
附图为适用于本发明的方法的设备例，现加以详细说明。
从碎屑供应器3经过管4将聚酯碎屑连续加入解聚反应釜1，反应釜中有BHT，其二醇与酸组分的当量比为1.3～2.0，BHT与所用聚酯碎屑的酸组分重量比固定在1/4～2/1。在解聚反应釜1上连接一精馏塔7，以便将解聚体系中的湿气蒸出。现今所用的方法均可用来将碎屑加入解聚反应釜1。但是，在加料时反应体系产生的EG蒸气易于将碎屑供应器3的内部弄湿，使碎屑粘附于其上，并使加料速率不稳定，所以最好在碎屑供应器底部和解聚反应器1中间增加一设备以吹入氮气并用氮气封闭碎屑供应器。为使加入的碎屑重量准确而稳定起见，最好使用旋转加料器。另外，在加料器的前部装一个阀门5（特别是闸门在加料器和解聚反应釜之间加一阀门5′〔特别是非闸阀（no-Slide Valve）。打开阀5和5′由设备9连续吹入氮气以驱动供应器3，便可将碎屑连续加入解聚反应器。由解聚作用制取1～5顿的BHT，氮气供应速率最好为1～50升/分钟，以3～30升/分钟更好。加入聚酯碎屑后，将阀5和5′关封，同时以氮气封闭供应器。
在加入聚酯碎屑的同时，打开阀门6，流入EG，直到所需要的量为止。在加料和其后的解聚作用中将反应物不断加以搅拌。解聚作用时，反应体系内部温度应为215-250℃，解聚反应釜1中的二醇与酸组分的当量比应为1.3～2.0。
解聚所得到的BHT通过转移阀8部分地进入聚合反应釜进行再聚合。在常规的解聚过程中，EG和聚酯碎屑加到一起后再进行加热，这样将因其发生固化作用而不能搅拌，此不均匀的反应体系使解聚时间增长并且不恒定。
按本发明所述方法就可用搅拌桨2将解聚反应釜中的反应物进行搅拌，因而使解聚时间比较恒定。
本发明可得到用常规方法不能取得的下列效果：
A.解聚时间减少，
B.因为解聚时所用的EG消耗减少，经济效益增加。
C.与常规的聚酯比较，按本发明方法所得的BHT进行再聚合时所得的聚酯软化点高，色泽好，异物及种类少。
例1：
于装有精馏塔、搅拌器、加热器（图1）的解聚反应釜中加入2，142份BHT（EG与对苯二甲酸的当量比为1.5），然后加热至220℃使其熔融，再将1，850份颗粒大小约为0.5克的PET碎屑小球通过一碎屑供应管加到熔融的BHT中，碎屑供应管的下部有一氮气气封装置以阻止蒸气弄湿管道。与此同时，将292份EG连续加入反应釜，历时40分钟。用精馏塔将聚酯碎屑的湿气蒸出反应体系，迴流EG，解聚作用在65分钟内完成。反应体系应保持在230℃，EG和对苯二甲酸的当量比为1.5。此后，将2.142份（半量）所得产物过滤并转移到聚合反应釜中，使用的过滤器为折叠型高精度过滤器，孔径55μm。在聚合反应釜中加入0.37份磷酸和0.555份三氧化锑，60分钟内反应釜的温度升至290℃，压力升至0.05mmHg，聚合反应继续120分钟，得到的聚酯特性粘度为0.650（于邻-氯苯酚，25℃），软化点为256℃，色泽（b-值）为4.6。
例2：
解聚作用按例1之步骤进行，改变加EG的速率，并把EG和对苯二甲酸的当量比改为2.5、2.0、1.6、1.3和1.15。解聚时间和所得的聚合物的质量列于表1
表1
实验号 原料＊解聚时间 聚合物质量
（当量比） （分钟） 软化点（℃） 色泽（b-值）
1 2.5 124 247 4.2
2 2.0 91 253 4.3
3 1.6 75 257 4.8
4 1.3 63 258 4.8
5 1.15 52 258 5.3
＊当量比：EG/对苯二甲酸
按本发明的当量比所制得的聚合物均有很好的性质。
例3：
解聚作用按例1之步骤进行，改变反应体系中BHT的量（酸组分与碎屑的重量比）（见表2），解聚所需的时间和所得聚合物的质量也列于表2中。
表2
实验号 重量比＊解聚时间 聚合物质量
（分钟） 软化点（℃） 色泽（b-值）
6 1/5 130 258 4.4
7 1/4 110 258 4.4
8 1/3 90 258 4.4
9 1/2 80 257 4.5
10 1/1 70 257 4.5
11 1.5/1 60 256 4.7
12 2/1 55 254 4.8
13 3/1 50 252 4.9
＊BHT与碎屑酸组分的重量比
在本发明所述的BHT与碎屑酸组分重量比范围内，所有聚合物均有好的解聚性质和质量。
例4：
解聚作用按例1之步步骤进行，改变解聚温度（列于表3），所需的解聚时间以及由此所得到的聚合物的性质也列于表3中。
表3
实验号 解聚温度 解聚时间 聚合物质量
（℃） （分钟） 软化点（℃） 色泽（b-值）
14 260 51 257 5.4
15 250 57 257 4.9
16 240 63 257 4.7
17 230 65 256 4.6
18 220 70 257 4.5
19 215 90 254 4.4
20 210 未定 - -
反应体系的温度在本发明的温度范围内时所得到的所有聚合物均有好的解聚性质和质量。
例5：
解聚作用按例1之步骤进行，改变聚酯碎屑和乙二醇的给料时间（表4），所需之解聚时间和所得聚合物的质量也列入表4。
表4
实验号 碎屑给料时间 解聚时间 聚合物质量
（分钟） （分钟） 软化点（℃） 色泽（b-值）
21 30 60 257 4.5
40
22 40 70 257 4.5
23 60 90 255 4.7
例6：
解聚作用按例1之步骤进行，改变碎屑大小（表5）。解聚所需的时间和所得的聚合物质量也列于表5中。
表5
实验号 碎屑大小 解聚时间 聚合物质量
（克/粒） （分钟） 软化点（℃） 色泽（b-值）
24 1.0 85 257 4.8
25 0.5 65 257 4.7
26 0.3 60 257 4.7
27 9.04 55 258 4.6
Claims (5)
1、一种主要成分为对苯二甲酸乙二醇的聚酯的解聚方法，其步骤是
(1)在融熔的对苯二甲酸双羟乙酯和/或其低聚物(二者均称BHT)的存在下，将乙二醇和聚酯碎屑在一定时间内批量或连续加入反应釜，其条件为
(a)融熔BHT的二醇与酸组分的当量比应为1.3～2.0
(b)融熔BHT的酸组分与聚酯碎屑的酸组分的重量比应为1/4～2/1
(c)聚酯碎屑与乙二醇之比应使二醇与酸组分的当量比在1.3～2.0之间
(2)在搅拌下进行解聚，温度在215°～250℃之间。
2、根据权利要求1所述的聚酯解聚方法，其特征在于所用碎屑的大小为1克左右或在1克以下。
3、根据权利要求1所述的聚酯解聚的方法，其特征在于使用一个氮气封闭的碎屑供给器。
4、根据权利要求1所述的聚酯解聚的方法，其特征在于在解聚过程中将湿气蒸出反应体系。
5、从主要成分为邻苯二甲酸乙二醇的聚酯重新制取聚合物的方法。其步骤是：
（1）在融熔的对苯二甲酸对羟乙酯和/或其低聚物（二者均称为BHT）的存在下，将乙二醇和聚酯碎屑在一定时间内批量或连续加入反应釜，条件是：
（a）融熔BHT的二醇和酸组分的当量比应为1.3～2.0
（b）融熔BHT的酸组分与聚酯碎屑的酸组分的重量比应为1/4～2/1
（c）聚酯碎屑与乙二醇的比应使二醇与酸组分的当量比在1.3～2.0之间
（2）在搅拌下解聚，解聚温度为215°～250℃。
（3）将部分解聚产物移至聚合反应釜，其余留在解聚反应釜中以备再进行聚酯碎屑解聚之用。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59104482A JPS60248646A (ja) | 1984-05-25 | 1984-05-25 | ポリエステル屑の解重合方法 |
| US06/735,837 US4609680A (en) | 1984-05-25 | 1985-05-20 | Process for the depolymerization of polyester scrap |
| EP19850303572 EP0174062A3 (en) | 1984-05-25 | 1985-05-21 | Process for the depolymerization of polyester scrap |
| KR1019850003586A KR850008352A (ko) | 1984-05-25 | 1985-05-24 | 폴리에스테르 부스러기(屑)의 해중합(解重合)방법 |
| CN85106299.7A CN1004004B (zh) | 1984-05-25 | 1985-08-21 | 聚酯碎屑的解聚法 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59104482A JPS60248646A (ja) | 1984-05-25 | 1984-05-25 | ポリエステル屑の解重合方法 |
| CN85106299.7A CN1004004B (zh) | 1984-05-25 | 1985-08-21 | 聚酯碎屑的解聚法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106299A true CN85106299A (zh) | 1987-02-18 |
| CN1004004B CN1004004B (zh) | 1989-04-26 |
Family
ID=76224748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106299.7A Expired CN1004004B (zh) | 1984-05-25 | 1985-08-21 | 聚酯碎屑的解聚法 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4609680A (zh) |
| EP (1) | EP0174062A3 (zh) |
| JP (1) | JPS60248646A (zh) |
| KR (1) | KR850008352A (zh) |
| CN (1) | CN1004004B (zh) |
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Families Citing this family (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5236959A (en) * | 1992-03-12 | 1993-08-17 | Hoechst Celanese Corporation | Process for recycling polyester/cotton blends |
| US5223544A (en) * | 1992-03-31 | 1993-06-29 | Shell Oil Company | Process for the removal of foreign materials from a post-consumer plyethylene terephthalate feed stream |
| JPH09510245A (ja) * | 1994-03-11 | 1997-10-14 | モンサント・カンパニー | 難燃性再利用ポリエステル組成物 |
| US5532404A (en) * | 1994-05-27 | 1996-07-02 | E. I. Du Pont De Nemours And Company | Monomer recovery process for contaminated polymers |
| US5710315A (en) * | 1994-05-27 | 1998-01-20 | E. I. Du Pont De Nemours And Company | Monomer recovery process for contaminated polymers |
| US5559159A (en) * | 1995-12-07 | 1996-09-24 | Eastman Chemical Company | Process including depolymerization in polyester reactor for recycling polyester materials |
| US5635584A (en) * | 1995-12-07 | 1997-06-03 | Eastman Chemical Company | Process including glycolysis and subsequent purification for recycling polyester materials |
| DE19643479B4 (de) * | 1996-10-22 | 2006-04-20 | Zimmer Ag | Verfahren zur Herstellung von Polyethylenterephthalat aus Polyethylenterephthalat-Abfall |
| US6214893B1 (en) | 1997-11-14 | 2001-04-10 | Mitsubishi Heavy Industries, Ltd. | Polyester decomposition process and polyester monomerization system |
| US6410607B1 (en) | 1999-02-10 | 2002-06-25 | Eastman Chemical Company | Glycolysis process for recycling of post-consumer pet |
| FR2825701B1 (fr) * | 2001-06-08 | 2003-09-12 | Ct D Etudes Sur Le Recyclage D | Procede de synthese de diols par alcoolyse de polyesters en milieu fondu en reacteur discontinu ou continu, application au recyclage des polyesters |
| KR100430627B1 (ko) * | 2001-07-10 | 2004-05-10 | 주식회사 코오롱 | 알칼리 이용성 폴리에스테르의 제조방법 |
| ATE374794T1 (de) * | 2001-10-16 | 2007-10-15 | Teijin Ltd | Verfahren zur rezyklierung von pet-flaschen |
| US20030134915A1 (en) * | 2001-12-17 | 2003-07-17 | Scantlebury Geoffrey Raymond | Production of transparent polyester using waste |
| JPWO2003051815A1 (ja) * | 2001-12-18 | 2005-04-28 | 株式会社アイエス | ポリエステルのエチレングリコール分解生成溶液の脱イオン処理方法 |
| BRPI0408055A (pt) * | 2003-02-27 | 2006-02-14 | Petrecycle Pty Ltd | processo para o tratamento de uma composição para remover seus contaminantes e composição livre de contaminantes |
| US7297721B2 (en) * | 2003-06-20 | 2007-11-20 | Futura Polyesters Limited | Process for controlled polymerization of a mixed polymer |
| US7812077B2 (en) * | 2003-12-17 | 2010-10-12 | Sabic Innovative Plastics Ip B.V. | Polyester compositions, method of manufacture, and uses thereof |
| US8067493B2 (en) * | 2003-12-30 | 2011-11-29 | Sabic Innovative Plastics Ip B.V. | Polymer compositions, method of manufacture, and articles formed therefrom |
| US7807745B2 (en) * | 2006-01-27 | 2010-10-05 | Sabic Innovative Plastics Ip B.V. | Molding compositions containing polycarbonate and modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET) |
| US7511081B2 (en) * | 2004-03-26 | 2009-03-31 | Do-Gyun Kim | Recycled method for a wasted polymer which is mixed polyester polyamide and reclaimed materials thereof |
| US7902264B2 (en) * | 2006-01-27 | 2011-03-08 | Sabic Innovative Plastics Ip B.V. | Polytrimethylene terephthalate (PTT) derived from polyethylene terephthalate (PET) and containing PET residues |
| WO2007089747A1 (en) * | 2006-01-27 | 2007-08-09 | General Electric Company | Articles derived from compositions containing modified polybutylene terephthalate (pbt) random copolymers derived from polyethylene terephthalate (pet) |
| US7923506B2 (en) * | 2006-01-27 | 2011-04-12 | Sabic Innovative Plastics Ip B.V. | Molding compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET) |
| WO2007089653A2 (en) * | 2006-01-27 | 2007-08-09 | General Electric Company | Molding compositions containing polyalkylene terephthalates and modified polybutylene terephthalate (pbt) random copolymers derived from pet |
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| US20100168317A1 (en) * | 2008-12-30 | 2010-07-01 | Cahoon-Brister Kristen | Poly(butylene terephthalate) compositions, methods of manufacture, and articles thereof |
| US20100168321A1 (en) * | 2008-12-30 | 2010-07-01 | Cahoon-Brister Kristen | Poly(butylene terephthalate) compositions, methods of manufacture, and articles thereof |
| KR101240338B1 (ko) | 2010-04-19 | 2013-03-07 | 웅진케미칼 주식회사 | 폐폴리에스테르를 이용한 재생 폴리에스테르 단섬유 및 그 제조방법 |
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| WO2012115984A2 (en) | 2011-02-21 | 2012-08-30 | Felice Kristopher M | Polyurethane dispersions and methods of making and using same |
| JP2014520008A (ja) | 2011-06-10 | 2014-08-21 | フェリス、クリストファー、エム． | 透明アクリルコーティング |
| BR112014026101B1 (pt) | 2012-04-20 | 2021-02-02 | Perpetual Global Technologies Limited | flocos de misturas de éster e métodos para a produção dos mesmos |
| US9732026B2 (en) | 2012-12-14 | 2017-08-15 | Resinate Technologies, Inc. | Reaction products containing hydroxyalkylterephthalates and methods of making and using same |
| US9255194B2 (en) | 2013-10-15 | 2016-02-09 | International Business Machines Corporation | Methods and materials for depolymerizing polyesters |
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| WO2021072020A1 (en) | 2019-10-08 | 2021-04-15 | Eastman Chemical Company | Catalyst systems for crystallizable reactor grade resins with recycled content |
| EP4048726A1 (en) | 2019-10-25 | 2022-08-31 | Eastman Chemical Company | Copolyesters produced from recycled copolyesters |
| IT201900025039A1 (it) | 2019-12-20 | 2021-06-20 | Garbo S R L | Processo per purificare il bis(2-idrossietil)tereftalato. |
| US20230113079A1 (en) * | 2020-03-31 | 2023-04-13 | Unitika Ltd. | Biaxially-stretched polyester resin film and manufacturing method for same |
| CA3174911A1 (en) | 2020-04-13 | 2021-10-21 | Bruce Roger Debruin | Chemical recycling of plastic dry fines |
| US11814492B2 (en) | 2020-12-02 | 2023-11-14 | International Business Machines Corporation | Polyester recycling process with pre-reaction purification |
| DE102021212695A1 (de) | 2021-11-11 | 2023-05-11 | Thyssenkrupp Ag | Vorrichtung und verfahren zur herstellung eines polyester-depolymerisats sowie vorrichtung und verfahren zur herstellung eines polyesters |
| EP4276131A1 (en) | 2022-05-10 | 2023-11-15 | Polymetrix AG | Method for the preparation of a polyester |
| WO2023217707A1 (en) | 2022-05-10 | 2023-11-16 | Polymetrix Ag | Method for the preparation of a polyester |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB610136A (en) * | 1946-03-28 | 1948-10-12 | Royden Lewis Heath | Degradation of aromatic linear polyesters |
| NL297660A (zh) * | 1962-09-27 | |||
| NL301426A (zh) * | 1962-12-06 | |||
| NL128500C (zh) * | 1963-11-12 | 1900-01-01 | ||
| GB1221657A (en) * | 1967-06-29 | 1971-02-03 | Agfa Gevaert Nv | Preparation of moulding material starting from polyethylene terepthalate |
| US3884850A (en) * | 1970-02-13 | 1975-05-20 | Fiber Industries Inc | Continuous atmospheric depolymerization of polyester |
| JPS5027510B2 (zh) * | 1971-12-03 | 1975-09-08 | ||
| US4439549A (en) * | 1982-11-22 | 1984-03-27 | Texaco Inc. | Novel aromatic polyester polyol mixtures made from polyethylene terephthalate residues and alkylene oxides |
| US4485196A (en) * | 1983-09-26 | 1984-11-27 | Texaco Inc. | Liquid phase polyols which are alkylene oxide adducts of terephthalic esters from recycled polyethylene terephthalate |
-
1984
- 1984-05-25 JP JP59104482A patent/JPS60248646A/ja active Granted
-
1985
- 1985-05-20 US US06/735,837 patent/US4609680A/en not_active Expired - Lifetime
- 1985-05-21 EP EP19850303572 patent/EP0174062A3/en not_active Withdrawn
- 1985-05-24 KR KR1019850003586A patent/KR850008352A/ko not_active Application Discontinuation
- 1985-08-21 CN CN85106299.7A patent/CN1004004B/zh not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731760A (zh) * | 2012-07-17 | 2012-10-17 | 龙福环能科技股份有限公司 | 一种将回收聚酯瓶片料熔体醇解后再聚合的方法 |
| CN102731760B (zh) * | 2012-07-17 | 2014-03-26 | 龙福环能科技股份有限公司 | 一种将回收聚酯瓶片料熔体醇解后再聚合的方法 |
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| CN104710601B (zh) * | 2015-01-23 | 2016-08-24 | 树业环保科技股份有限公司 | 废旧pet材料脱色回收制备高纯pet切片的方法及制品 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0331190B2 (zh) | 1991-05-02 |
| US4609680A (en) | 1986-09-02 |
| CN1004004B (zh) | 1989-04-26 |
| EP0174062A2 (en) | 1986-03-12 |
| KR850008352A (ko) | 1985-12-16 |
| EP0174062A3 (en) | 1987-05-27 |
| JPS60248646A (ja) | 1985-12-09 |
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