CN1102936C - 生产聚酯树脂的改进的方法 - Google Patents
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Abstract
本发明提供通过将特性粘度为0.1-0.45dl/g的树脂固态缩聚来制备芳族聚酯树脂的方法，其中送入反应器的惰性气体的每小时质量流速与离开反应器的聚合物的每小时质量流速的重量比在0.1-0.6之间。
Description
本发明涉及聚酯树脂固态缩聚的改进的方法。
在芳族聚酯聚酯树脂中，有三种聚酯：聚对苯二甲酸乙二醇酯(PET)、对苯二甲酸与小比例的间苯二甲酸的共聚物和聚对苯二甲酸丁二醇酯在纤维和薄膜领域内特别有用，并被用作模塑材料。
对于纤维和薄膜，树脂的特性粘度一般在0.6-0.75dl/g之间，对于模塑材料这是用熔融缩聚难以直接获得的高特性粘度值。
通过在一般为190-230℃的温度下进行树脂的固态缩聚(SSP)可以将树脂的特性粘度提高到所需值(一般高于0.75dl/g)。
缩聚反应产物的消除对于该反应的进行十分需要。
在缩聚过程中，出现多种反应。导致PET分子量增加的主要反应是乙二醇的消除PET-COO-CH2-CH2-OH+HO-CH2-CH2-OCO-PET
↓
↓PET-COO-CH2-CH2-OOC-PET+HO-CH2-CH2-OH
其它反应导致端部羧基酯化和形成乙醛。
前已述及，缩聚反应的副产物通过相对于从结晶步骤中出来的聚合物进料方向逆流或并流通入气体而消除。
缩聚反应通常在纵向流化床反应器中进行，其中聚合物从上部进入，从下部出来，使惰性气体流在聚合物上通过。
象这种方法可以从例如US-A-4064112中得知，其中粒状聚合物被结晶到至少1.390克/立方厘米的密度，在强制运动结晶器中加热至220-260℃的温度，并在等于或低于结晶步骤所用的温度下操作的流化床反应器中进行缩聚反应。
在结晶步骤中，缩聚反应在230-245℃的温度下进行，以获得结晶度值相当于1.403-1.415克/立方厘米密度的值，在缩聚步骤中，温度为230-245℃，以获得最佳反应速率与低度聚合物降解的组合。
用惰性气体(最好是氮气)来除去在缩聚步骤中形成的副产物。在将气体中的副产物纯化后将气体循环。
当在循环气体中水的含量太高时，聚合物的水解大幅度增加；当乙二醇超过极限值时，反应速率便明显降低。
氧气和乙醛的值的高低决定了成型制品的褪色；对于食物用品，不允许高的乙醛值。为了限制待循环气体的纯化费用和保持气体流动所需的能耗，气体的每小时质量流速与离开反应器的聚合物的每小时质量流速的重量比保持在0.7∶1到3∶1的范围内，优选在1∶1到2∶1的范围内。
采用低于0.7的值(在实施例中为0.5和0.3)并且在US-A-4064112报导的条件下(结晶温度235℃；缩聚温度230℃)操作，聚合物的特性粘度不会明显增加。
此外，使用低于0.7的比值，可以增加通过反应器段的温度差。
US-A-4161578描述了一种结晶/固态缩聚法，其中粒状聚合物在装有在180-235℃的温度下操作的强制循环装置的设备中结晶，直至获得对应于至少1.385克/立方厘米密度的结晶度，并随后送入强制缩聚反应器中，其中聚合物在高于结晶步骤中所用的温度下加热。
在缩聚反应器中，使氮气与送入的聚合物逆流循环，流体的重量比率为0.7-3.5公斤氮气/公斤PET。在本发明人以前的一件专利申请中，本发明人发现，可以以低于0.6的比率R操作，有效地除去如此进行的SSP反应的副产物，获得高的反应动力学。
经过SSP的聚酯树脂的IV值不低于0.6dl/g。
以较低的起始IV操作以获得相同的最终IV，有机反应副产物的产生高得多，因此乙二醇和其它有机产物在惰性气体中的浓度对于采用的相同的气体/固体比率R也较高。在图1中，示出了两种情况下浓度(以公斤乙二醇/公斤氮气为单位)随着气体/固体比R(公斤氮气/公斤PET)的变化关系：a)从IV＝0.2出发，固态缩聚的目标IV＝0.8dl/g；b)从IV＝0.6出发，固态缩聚的目标IV＝0.8dl/g。业已发现，即使使用0.1-0.6的比率R，也惊人地能够有效地除去缩聚反应副产物，从而获得高的反应动力学，即使当待进行固态缩聚的聚酯树脂的具有0.1-0.45dl/g或0.1-0.30dl/g较低特性粘度时也是如此。
在气体鼓吹操作中使用这样低的比率能够高度节能。
所用的比值R最好在0.2-0.5之间。
在本发明的方法中，缩聚反应是在180-250℃之间的温度下进行的，优选在210-235℃下进行。待进行SSP反应的聚合物的结晶度一般在40-50％(重量)之间。
预聚物一般是球状或扁豆状颗粒，它是例如使聚合物通过带孔机头并在水浴中收集所得聚合物滴获得的。
离开SSP反应器的惰性气体流，经过纯化加工消除了其中的有机产物杂质。该操作是按照WO-A-9502446(其内容通过引用并入本文)描述的方法进行的。
在SSP反应器中的平均停留时间足够长，以使聚合物的特性粘度至少增加0.3dl/g；一般来说，停留时间为15-40小时。如果在结晶之前的步骤中将聚合物与含有两个或更多个能够与聚酯的OH和COOH端基反应的基团进行加成反应的多官能化合物以熔体状态混合，则特性粘度的动力学增加可以大大增强。这些化合物的实例是均苯四甲酸酐，一般为芳族或脂族四元羧酸的二酐。这些化合物的用量一般为聚合物的0.01-2％(重量)。
均苯四甲酸酐是优选的化合物。这些化合物的使用被描述在EP-B-422282和US-A-5243020，US-A-5334669和US-A-5338808(其内容通过引用并入本文)中。
本发明方法中使用的聚酯树脂包括C2-C12二醇(例如乙二醇、丁二醇、1，4-环己烷二甲醇)与二元芳族羧酸(例如对苯二甲酸、2，6-萘二甲酸)或这些化合物的反应性衍生物(例如低级烷基酯，如对苯二甲酸二甲酯)的缩聚产物。
聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯是优选的树脂。
部分对苯二甲酸单元可以被衍生自其它二元羧酸(例如间苯二甲酸和萘二甲酸)的单元替代。替代的量为0.5-20％(重量)。
提出下面的实施例用来说明但不是限制本发明。
在说明书及实施例中所述的特性粘度是按照ASTM4603-86的方法，用0.5克聚合物在100毫升60/40苯酚/四氯甲烷中的溶液在25℃下测定的。
实施例1
将预先结晶使结晶度值达到40％的、IV＝0.20dl/g的粒状PET在215℃下加热后，以5公斤/小时的质量流速送入流动床反应器中进行固态缩聚。将氮气逆流送入反应器中，其质量流速应足以使气体与送入的聚合物之间的重量比(R)为0.4。
将聚合物在215℃下保温，停留时间应足够的长，使得特性粘度增加0.55dl/g。
聚合物的最终IV值为0.75dl/g。
停留时间为30小时。
实施例2
按照实施例1进行试验，不同的是送入的聚合物的温度和在反应器中保温的温度为225℃。
30小时的停留时间后，聚合物的IV值为0.88dl/g。实施例3
按照实施例1进行试验，不同的是送入含有2％间苯二甲酸的COPET。
30小时的停留时间后，获得0.78dl/g的IV值。
实施例4
按照实施例1进行试验，不同的是送入在203℃的温度下加热的、IV＝0.18dl/g的聚对苯二甲酸丁二醇酯，并在该温度下将其在缩聚反应器中保温，
30小时的停留时间后，获得0.96dl/g的IV值。比较例
重复实施例1的试验，不同的是比值R为0.05。经过30小时的停留时间后，最终的IV值为0.40dl/g。
Claims (9)
1.芳族聚酯树脂固态缩聚的连续法，其中树脂的特性粘度(IV)为0.15-0.30dl/g；树脂从移动床反应物的上部送入，从下部放出；惰性气体环绕树脂上下流动，反应器温度保持在180-250℃之间，树脂的停留时间足够长，使得聚合物的特性粘度至少增加0.3dl/g，其特征在于气体与离开反应器的聚合物的每小时质量流率比R在0.1-0.6之间。
2.按照权利要求1的方法，其中比值R在0.2-0.5之间。
3.按照权利要求1的方法，其中反应器的温度在210-235℃之间。
4.按照权利要求1的方法，其中惰性气体是氮气。
5.按照权利要求4的方法，其中使氮气环绕聚合物向下流动。
6.按照权利要求1的方法，其中聚酯树脂选自聚对苯二甲酸乙二醇酯、含有0.5-20％来自间苯二甲酸的单元的共聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯。
7.按照权利要求1的方法，其中将氮气纯化除去有机杂质，直至以甲烷的当量表示的杂质量低于10ppm，然后将其循环到反应器中。
8.按照权利要求1-7中任一项的方法，其中向进行固态缩聚的树脂中加入0.01-2％重量的四羧酸二酐。
9.根据权利要求8的方法，其中二酐是均苯四甲酸二酐。
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| Application Number | Priority Date | Filing Date | Title |
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| IT96MI001098A IT1283083B1 (it) | 1996-05-30 | 1996-05-30 | Procedimento perfezionato per la produzione di resine poliestere |
| ITMI96A001098 | 1996-05-30 |
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| EP (1) | EP0810250B1 (zh) |
| JP (1) | JP4678897B2 (zh) |
| KR (1) | KR100482902B1 (zh) |
| CN (1) | CN1102936C (zh) |
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| DE (1) | DE69722997T2 (zh) |
| ES (1) | ES2198515T3 (zh) |
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|---|---|---|---|---|
| IT1283644B1 (it) * | 1996-08-01 | 1998-04-23 | Sinco Eng Spa | Procedimento perfezionato per la produzione di resine poliestere |
| IT1304797B1 (it) * | 1998-12-23 | 2001-03-29 | Sinco Ricerche Spa | Procedimento per la preparazione di resine poliestere (mg33). |
| EP1156914B1 (en) * | 1999-02-04 | 2007-03-14 | Bühler Ag | Process for upgrading plastic material |
| JP4567139B2 (ja) * | 2000-04-03 | 2010-10-20 | 帝人株式会社 | 交互共重合ポリエステルの製造方法 |
| US6451966B1 (en) | 2001-08-10 | 2002-09-17 | E. I. Du Pont De Nemours And Company | Method for increasing solid state polymerization rate |
| JP4828163B2 (ja) * | 2005-06-01 | 2011-11-30 | 三井化学株式会社 | ポリエチレンテレフタレートの製造方法 |
| US7585104B2 (en) * | 2005-09-12 | 2009-09-08 | Uop Llc | Rotary processor |
| US10604620B2 (en) | 2011-12-22 | 2020-03-31 | Polymetrix Ag | Process for solid-state polycondensation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1190801A (en) * | 1966-05-12 | 1970-05-06 | Eastman Kodak Co | Manufacture of Linear Polyesters |
| US4064112A (en) * | 1975-12-31 | 1977-12-20 | Zimmer Aktiengesellschaft | Process for the continuous production of high molecular weight polyethylene terephthalate |
| US4161578A (en) * | 1978-05-12 | 1979-07-17 | Bepex Corporation | Process for solid phase polymerization of polyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4165420A (en) * | 1977-11-10 | 1979-08-21 | The Goodyear Tire & Rubber Company | Solid state polymerization of polyester prepolymer |
| US4205157A (en) * | 1979-04-02 | 1980-05-27 | The Goodyear Tire & Rubber Company | Method for production of high molecular weight polyester with low catalyst level and low carboxyl content |
| US4226973A (en) * | 1979-06-22 | 1980-10-07 | Standard Oil Company (Indiana) | Process for upgrading prepolymer particles |
| US4374975A (en) * | 1982-02-02 | 1983-02-22 | The Goodyear Tire & Rubber Company | Process for the production of high molecular weight polyester |
| US4876326A (en) * | 1987-03-26 | 1989-10-24 | The Goodyear Tire & Rubber Company | Solid state polymerization of polyester prepolymers |
| DE68922102T2 (de) * | 1989-10-13 | 1995-10-19 | Phobos Nv | Verfahren zur kontinuierlichen Herstellung von hochmolekularen Polyester-Harzen. |
| IT1245598B (it) * | 1991-03-29 | 1994-09-29 | M & G Ricerche Spa | Processo per la produzione di resine poliestere ad elevato peso molecolare |
| IT1245597B (it) * | 1991-03-29 | 1994-09-29 | M & G Ricerche Spa | Processo per la produzione di resine poliestere ad elevato peso molecolare |
| IT1265166B1 (it) * | 1993-07-16 | 1996-10-31 | Sinco Eng Spa | Procedimento per la purificazione di gas inerti |
| DE4338484C1 (de) * | 1993-11-11 | 1994-12-01 | Veitsch Radex Ag | Verwendung eines feuerfesten, keramischen Steins auf Basis von MgO zur Auskleidung von Zement-Drehrohröfen |
| IT1271073B (it) * | 1994-11-21 | 1997-05-26 | M & G Ricerche Spa | Procedimento per la cristallizzazione di resine poliestere |
-
1996
- 1996-05-30 IT IT96MI001098A patent/IT1283083B1/it active IP Right Grant
-
1997
- 1997-05-23 EP EP97108351A patent/EP0810250B1/en not_active Revoked
- 1997-05-23 AT AT97108351T patent/ATE243721T1/de active
- 1997-05-23 DE DE69722997T patent/DE69722997T2/de not_active Expired - Lifetime
- 1997-05-23 ES ES97108351T patent/ES2198515T3/es not_active Expired - Lifetime
- 1997-05-28 CA CA002206369A patent/CA2206369C/en not_active Expired - Lifetime
- 1997-05-29 US US08/865,390 patent/US5739269A/en not_active Expired - Lifetime
- 1997-05-29 MX MX9703991A patent/MX9703991A/es unknown
- 1997-05-29 CN CN97105420A patent/CN1102936C/zh not_active Expired - Lifetime
- 1997-05-29 JP JP13992497A patent/JP4678897B2/ja not_active Expired - Lifetime
- 1997-05-30 KR KR1019970021842A patent/KR100482902B1/ko active IP Right Grant
-
1998
- 1998-06-03 HK HK98104788A patent/HK1005660A1/xx not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1190801A (en) * | 1966-05-12 | 1970-05-06 | Eastman Kodak Co | Manufacture of Linear Polyesters |
| US4064112A (en) * | 1975-12-31 | 1977-12-20 | Zimmer Aktiengesellschaft | Process for the continuous production of high molecular weight polyethylene terephthalate |
| US4064112B1 (en) * | 1975-12-31 | 1994-09-13 | Davy Mckee Aktiengesellschaft | Process for the continuous production of high molecular weight polyethylene terephalate |
| US4161578A (en) * | 1978-05-12 | 1979-07-17 | Bepex Corporation | Process for solid phase polymerization of polyester |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI961098A1 (it) | 1997-11-30 |
| ES2198515T3 (es) | 2004-02-01 |
| MX9703991A (es) | 1998-04-30 |
| EP0810250B1 (en) | 2003-06-25 |
| EP0810250A3 (en) | 1998-03-18 |
| DE69722997D1 (de) | 2003-07-31 |
| JP4678897B2 (ja) | 2011-04-27 |
| DE69722997T2 (de) | 2003-12-18 |
| US5739269A (en) | 1998-04-14 |
| CN1168389A (zh) | 1997-12-24 |
| IT1283083B1 (it) | 1998-04-07 |
| KR970074820A (ko) | 1997-12-10 |
| ITMI961098A0 (it) | 1996-05-30 |
| HK1005660A1 (en) | 1999-01-22 |
| ATE243721T1 (de) | 2003-07-15 |
| JPH1053644A (ja) | 1998-02-24 |
| CA2206369A1 (en) | 1997-11-30 |
| EP0810250A2 (en) | 1997-12-03 |
| CA2206369C (en) | 2006-01-31 |
| KR100482902B1 (ko) | 2005-10-12 |
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