CN1145931A - 改善了颜色特性的聚酯树脂 - Google Patents
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Abstract
一种具有改进了色泽特性的芳族聚酯树脂，用下述方法获得：在用二醇与芳族二羧酸的缩聚反应制备树脂阶段，向树脂中加入一种紫调色剂，它由9，10-蒽醌-2-羟基-4-对-甲苯胺构成，或具有与上述蒽醌化合物类似的吸收光谱的蒽酯化合物构成。
Description
本发明涉及具有改善了颜色特性的聚酯树脂。
如所已知那样，聚酯树脂的生产工艺，特别是用于生产纤维、薄膜和食品容器用的中空体的聚对苯二甲酸乙二酯及其共聚物的，是通过酯化反应或酯基转移反应进行的，用哪种方法由所用原料是对苯二甲酸或相应的二甲酯而定，随后是熔融状态下的缩聚反应，直到达到适于最终使用的聚合度。
上述缩聚反应可以用连续的或分批式的工艺进行。一般说，是通过把反应混合物加热到250℃至300℃、在760至0.5mmHg abs的减压范围内进行，反应的滞留时间60至200分钟。
在这些工艺条件下，由于提高了平均分子量因而也增加了在高温下滞留时间内反应物料的粘度，热降解现象会以较高的和非常高的程度发生，导致分子间断裂，特别是已形成的酯键的断裂和终止端羟基断裂，同时相伴的是乙烯基酯基团的形成和羧酸端基的增加。
作为乙烯基酯端基产生的结果，该聚合物会或多或少的带有由降解发生条件决定的黄色。
不管怎样优化工艺操作条件、加入热稳定剂(磷酸、亚磷酸和它们的衍生物)、优选聚合物催化剂(体系)的类型和质量，仍然必须调整聚合物的颜色，有必要加入二价钴盐(Co(CH3COO)22H2O，COCl2，庚酸钴，等)，它们的蓝染色作用能够使聚合物向较低频谱的呈黄色的吸收波段转移。
钴盐作为颜色调节剂的使用在文献中有广泛的记载。从80年代起，聚对苯二甲酸乙二酯在食品容器方面的发展越来越快，而技术上不允许该聚合物在相变阶段过滤的限制，使钴盐作为调色剂使用的缺点突出了：主要是由于形成了不溶的对苯二甲酸钴盐渣，以及这些化合物成本的上升。为了克服这个缺点，最近介绍了使用与这些钴盐作用相同的可溶于聚合物中的染料，形成一种蓝和红调色剂混合物，具有使聚合物向低频的呈黄色的吸收波段转移的功能。
在US-5235027中介绍了同时使用二种调色剂，它们分别是ESTOFIL BLUE-S-RBL和ESTOFIL RED-S-GFP。实际上，为了调整聚合物的颜色(Col L、Colb、Cola)，只使用仅对于Colb(蓝-黄范围)有影响的一种蓝调色剂是不够的，必须还要另加调整Cola的一种红色调色剂。
使用这些调色剂，若能完全很好地解决聚合物色泽调节问题(特别是加入红调色剂改善Cola)就好了，但是都出现了聚合物的色泽稳定问题，不论是在批量聚合过程中还是在更为显著的连续聚合过程中。
这种不稳定性主要是由于上述的调色剂不溶于通常的原料介质，即通常是由乙二醇构成的反应介质中，而是形成悬浮液。
特别是ESTOFIL RED-S-GFP的悬浮液沉降时间非常短，使得在通常的工业生产操作条件下极难维持予定的蓝、红比值而准确控制聚合物质量。
为了改正聚合物中已形成的颜色，建议使用紫调色剂。该调色剂是在挤出阶段加入到聚合物中。调色剂在熔融聚合物中的平均滞留时间比熔融缩聚阶段中聚合物的滞留时间短许多。在这个阶段中的温度也比挤出中所用的温度高不少。
再有，大多数聚合物为了应用在固态进行缩聚处理以增加特性粘度。这种处理一般在180和230℃的范围内，滞留时间相当长(几小时)。
由于上文指出的热学状况，在树脂制备阶段已加入的调色剂会有结构改变，从而改变在要求的频谱段的吸收能力。
在树脂制备阶段已经加入紫调色剂应该不允许在使用蓝和红调色剂混合物时的易变性。
我们发现，往熔融状态的酯化反应、酯基转移反应或缩聚反应混合物中加入紫调色剂-该紫调色剂从具有9，10-蒽醌-2-羟基-4-对-甲苯胺结构的蒽酯醌染料中选出-能够调整由于在熔融态缩聚反应过程中因聚酯树脂的分解反应而引起的不希望的颜色。
在缩聚反应的过程中，这类调色剂的存在允许得到在-2.5至0.0Cola和-6至0.5 Colb范围内的亨特色度(Hunter color)。
特别适用的紫调色剂是Samdoz出售的Sando-plast RBS-FP，具有9，10-蒽醌-2-羟基-4-对甲苯胺结构。除了具有与Sandoplast RBS-FP紫类似的吸收光谱之外，适用的紫调色剂在缩聚条件下-其中温度变化在250和300℃之间，滞留时间1小时以上-必须是稳定的。
验证热稳定性的合适的测试是指调色剂在结晶聚苯乙烯中保持颜色的能力，调色剂的重量浓度为0.05％，在300℃测试20分钟。
调色剂的其它必要特性是要能充分溶于制备树脂用的乙二醇或类似的二元醇中，并能覆盖住由于在制备树脂期间操作条件，特别是温度变化所引起的大范围内不希望的颜色。
由带有2-12个碳原子的脂肪族二醇类与芳族二羧酸起始生成树脂的反应用现有的技术进行。
优选的缩聚催化剂是由Sb化合物(Sb2O3、三乙酸锑)组成的。
其它催化剂由诸如Ti和/或Ge的化合物组成。在由对苯二甲酸二甲酯和类似的烷基酯类起始制备树脂的情况下，可以用乙酸锌类的化合物作酯基转移的催化剂。为了稳定预聚合物，加入足够量的热稳定剂，例如有机亚磷酸盐或磷酸盐。
熔融态下的缩聚反应温度一般是在150至300℃之间，在真空下进行操作(0.5至几个mmHg)。优选使紫调色剂用于改善聚对苯二甲酸乙二酯和下列共聚物的颜色，后者中高达20％的苯二甲酸衍生单元是被芳族二羧酸，例如间苯二酸、2，6-萘二甲酸及它们的混合物单元取代，更优选用于改善聚对苯二甲酸丁二酯及聚(亚烷基)萘二甲酸酯的颜色。
这类树脂可用于生产纤维和薄膜，或通过挤-吹或注一吹成型生产诸如饮料容器这类制品。
提供以下实施例来具体说明本发明，但不限定本发明。
实施例1
制备一种分散体，在100份的乙二醇(EG)中含有0.01份VioletSandoplast RSB-FP调色剂(分散体A)。把这种分散体装在设置有搅拌桨的搅拌容器中，用下述工艺生产10批PBT。
PET的生产工艺
在一高压釜中，使100份的对苯二甲酸(TPA)和44.8份的EG、2.4份的分散体A及0.032份的Sb2O3混合。把混合物在1.5巴下加热到260℃，同时用填充蒸馏塔除去酯化反应产生的水。平均反应时间190分钟后产生的低聚混合物加热到280℃，同时压力减至1mmHg。
平均聚合170分钟之后得到以下特征的聚合物：
特性粘度(IV)dl/g 0.600±0.01
Color L 75±1
Color b -6±1
Color a -1±0.5
比较实施例1
采用跟实施例1所述相同的工艺制备含有0.005份的Red EstofilSGFP和0.005份Blue SRBL的分散体。用这种分散体按实施例1中所述的相同工艺生产10批。平均酯化和聚合的时间分别为190分钟和170分钟。
产生的聚合物的平均质量性能为：
特性粘度(IV)dl/g 0.600±0.01
Color L 74±2
Color b 4.5±2
Color a -2±1比较实施例1，注意到色度L减少而色度b和a增加了，尤其在使用长期存放过的调色剂分散体制造的最后几批的情况中。
按照ASTM 4603.86，以100ml 60/40的重量比的苯酚和四氯乙烷混合物中溶有0.5g聚合物的溶液在25℃测定特性粘度。
按照已知的方法在150℃下经过1小时对聚合物结晶颗粒测定a和b的亨特色度级(Hunter Color)。
Claims (5)
1.芳族聚酯树脂，具有在-2.5和0.0之间的Cola与-6和0.5之间的Colb的亨特色度值(Hunter color values)，用下述方法获取：在酯化反应或酯基转移反应和在熔融态的连续缩聚反应中制取树脂阶段，加入一种紫调色剂，它具有类似于9，10-蒽醌-2-羟基-4-对-甲苯胺的吸收光谱，并且在300℃在聚苯乙烯结晶中以0.05％重量的浓度能够耐热稳定20分钟以上。
2.根据权利要求1的树脂，其中，蒽醌化合物是9，10-蒽醌-2-羟基-4-对-甲苯胺。
3.根据权利要求1的树脂，其中，调色剂是一种蒽醌化合物，它具有类似于9，10-蒽醌-2-羟基-4-对-甲苯胺的吸收光谱，并且具有在300℃在聚苯乙烯结晶中以0.05％重量浓度耐热20分钟以上的热稳定性。
4.根据前述各权利要求的聚酯树脂，从下列中选出：聚对苯二甲酸乙二酯、对苯二酸-乙二醇共聚物类，其中高达20摩尔％的对苯二甲酸单元被芳族二羧酸类衍生的单元取代，后者从间苯二酸和2，6-萘二甲酸及它们的混合物中选出。
5.由上述各权利要求的树脂制备的制品。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT95MI001636A IT1277362B1 (it) | 1995-07-27 | 1995-07-27 | Resine poliestere con migliorate caratteristiche di colore |
| ITMI95A001636 | 1995-07-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1145931A true CN1145931A (zh) | 1997-03-26 |
Family
ID=11372066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96111792A Pending CN1145931A (zh) | 1995-07-27 | 1996-07-26 | 改善了颜色特性的聚酯树脂 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5618908A (zh) |
| EP (1) | EP0758663B1 (zh) |
| JP (1) | JP3576320B2 (zh) |
| KR (1) | KR100409115B1 (zh) |
| CN (1) | CN1145931A (zh) |
| AU (1) | AU705353B2 (zh) |
| CA (1) | CA2181870C (zh) |
| DE (1) | DE69612709T2 (zh) |
| ES (1) | ES2158199T3 (zh) |
| IT (1) | IT1277362B1 (zh) |
| MX (1) | MX9603061A (zh) |
| TW (1) | TW399068B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329750C (zh) * | 2002-05-07 | 2007-08-01 | 美利肯公司 | 用作聚酯中有机调色剂的新组合物 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6489433B2 (en) | 2001-02-23 | 2002-12-03 | E. I. Du Pont De Nemours And Company | Metal-containing composition and process therewith |
| EP2289687A1 (de) | 2007-05-16 | 2011-03-02 | Entex Rust & Mitschke GmbH | Verfahren zur Verarbeitung von zu entgasenden Produkten |
| US8111923B2 (en) | 2008-08-14 | 2012-02-07 | Xerox Corporation | System and method for object class localization and semantic class based image segmentation |
| DE102008044487A1 (de) * | 2008-08-29 | 2010-03-04 | Lurgi Zimmer Gmbh | Verfahren zur Herstellung von Polymeren mit neutralem Farbton |
| MX2017014225A (es) | 2015-05-07 | 2018-04-20 | Fina Technology | Polietileno para un rendimiento superior de termoformacon de extrusion de lamina. |
| KR102117170B1 (ko) | 2018-12-26 | 2020-05-29 | 이용근 | 폴리에스테르 흡음보드 표면 전사방법 |
| KR20230012808A (ko) | 2021-07-16 | 2023-01-26 | 이용근 | 폴리에스테르 흡음보드 표면 전사장치 및 이를 이용한 폴리에스테르 흡음보드 표면 전사방법 |
| KR200495432Y1 (ko) | 2021-08-04 | 2022-05-20 | 이순권 | 절첩 구조를 갖는 폴리에스테르 흡음보드를 이용한 장식보드 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1286499B (de) * | 1962-01-25 | 1969-01-09 | Bayer Ag | Egalisiermittel fuer das Faerben von Polyestergebilden |
| JPS5319205B2 (zh) * | 1973-03-27 | 1978-06-20 | ||
| JP2572759B2 (ja) * | 1986-12-03 | 1997-01-16 | 三菱化学株式会社 | 静電荷像現像用トナ− |
| DE4125167A1 (de) * | 1991-07-30 | 1993-02-04 | Zimmer Ag | Modifiziertes co-polyethylenterephthalat |
| EP0618503B1 (en) * | 1993-02-08 | 1999-05-19 | Fuji Photo Film Co., Ltd. | Image forming method including heat development while covering surface of light-sensitive material |
| JP3115745B2 (ja) * | 1993-07-12 | 2000-12-11 | 富士写真フイルム株式会社 | 感光材料 |
-
1995
- 1995-07-27 IT IT95MI001636A patent/IT1277362B1/it active IP Right Grant
-
1996
- 1996-07-22 DE DE69612709T patent/DE69612709T2/de not_active Expired - Lifetime
- 1996-07-22 EP EP96111746A patent/EP0758663B1/en not_active Expired - Lifetime
- 1996-07-22 US US08/681,323 patent/US5618908A/en not_active Expired - Lifetime
- 1996-07-22 ES ES96111746T patent/ES2158199T3/es not_active Expired - Lifetime
- 1996-07-23 CA CA002181870A patent/CA2181870C/en not_active Expired - Lifetime
- 1996-07-23 AU AU60640/96A patent/AU705353B2/en not_active Expired
- 1996-07-25 KR KR1019960030236A patent/KR100409115B1/ko not_active IP Right Cessation
- 1996-07-26 CN CN96111792A patent/CN1145931A/zh active Pending
- 1996-07-26 MX MX9603061A patent/MX9603061A/es unknown
- 1996-07-26 JP JP19732896A patent/JP3576320B2/ja not_active Expired - Lifetime
- 1996-07-26 TW TW085109134A patent/TW399068B/zh not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329750C (zh) * | 2002-05-07 | 2007-08-01 | 美利肯公司 | 用作聚酯中有机调色剂的新组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0758663A3 (en) | 1997-10-08 |
| DE69612709D1 (de) | 2001-06-13 |
| CA2181870C (en) | 2007-10-09 |
| EP0758663B1 (en) | 2001-05-09 |
| KR970006362A (ko) | 1997-02-19 |
| EP0758663A2 (en) | 1997-02-19 |
| US5618908A (en) | 1997-04-08 |
| TW399068B (en) | 2000-07-21 |
| ITMI951636A0 (it) | 1995-07-27 |
| MX9603061A (es) | 1998-04-30 |
| CA2181870A1 (en) | 1997-01-28 |
| KR100409115B1 (ko) | 2004-06-04 |
| ITMI951636A1 (it) | 1997-01-27 |
| IT1277362B1 (it) | 1997-11-10 |
| JPH09111102A (ja) | 1997-04-28 |
| AU6064096A (en) | 1997-01-30 |
| JP3576320B2 (ja) | 2004-10-13 |
| DE69612709T2 (de) | 2001-08-23 |
| AU705353B2 (en) | 1999-05-20 |
| ES2158199T3 (es) | 2001-09-01 |
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