CN104603175B - 聚酯 - Google Patents
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- C08G63/66—Polyesters containing oxygen in the form of ether groups
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Abstract
描述了根据下式(I)的聚酯,其中,R1和R2彼此独立地为H3C‑(OC2H4)n‑(OC3H6)m或者为HO‑(C3H6)或HO‑(C4H8),其中,所述‑(OC2H4)基团和所述‑(OC3H6)基团嵌段地排列,且由所述‑(OC3H6)基团组成的嵌段连接至COO基团,n基于摩尔平均计为40至50的数,m基于摩尔平均计为1至7的数,和a+b基于摩尔平均计为4至9的数。本发明的聚酯在碱性环境中具有有利的稳定性,具有有益的溶解度,并且有利地清澈地溶于碱性组合物,如碱性重垢洗涤液中,并且还具有有利的去污性质。
Description
本发明涉及新型聚酯和它们的制备方法。所述聚酯可被用作衣物去垢剂和织物护理产品中的去污剂。
术语“去污剂”适用于调整织物表面使后续脏污最小化并使织物的清洁在另外的洗涤周期中更容易的材料。
含有聚酯的衣物去垢剂组合物在现有技术中被广泛公开。
DE 102007013217 A1和WO2007/079850 A1公开了可用作洗涤和清洁组合物中的去污组分的阴离子型聚酯。
DE102007005532 A1描述了具有低粘度的去污的低聚酯和聚酯的水性制剂。所述水性制剂可以例如用于洗涤和清洁组合物中。
EP 0964015 A1公开了去污低聚酯,其可被用作去垢剂中的去污聚合物,且其使用包含3至6个羟基的多元醇制备。
EP 1661933 A1涉及通过二羧酸化合物、多元醇化合物和水溶性氧化烯加合物反应制备的在室温下可流动的、两亲性和非离子型低聚酯,以及它们作为洗涤和清洁组合物中的添加剂的用途。
然而,现有技术中所描述的许多聚酯需要在碱性环境中改进的稳定性。尤其是在碱性重垢洗涤液中,聚酯在引入时经常呈现出混浊,并由于碱性水解从而还丧失了去污能力。
因此,本发明的目的是提供新型聚酯,其在碱性环境中具有有利的稳定性,具有有益的溶解度,并且有利地清澈地溶于碱性组合物,如碱性重垢洗涤液中,并且还具有有利的去污性质。
令人惊讶地,该目的通过根据下式(I)的聚酯解决。
其中,
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m或者为HO-(C3H6)或HO-(C4H8),其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由-(OC3H6)基团组成的嵌段连接至COO基团,
n基于摩尔平均计为40至50的数,
m基于摩尔平均计为1至7的数,和
a+b基于摩尔平均计为4至9的数。
因此,本发明的主题是根据下式(I)的聚酯
其中,
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m或者为HO-(C3H6)或HO-(C4H8),其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至COO基团,
n基于摩尔平均计为40至50的数,
m基于摩尔平均计为1至7的数,和
a+b基于摩尔平均计为4至9的数。
在这些本发明的聚酯中,其中所述总和“a+b”基于摩尔平均计为4至9的数,所述变量“a”基于摩尔平均计优选为2.8至8.1的数,和所述变量“b”基于摩尔平均计优选为0.4至2.7的数。
在本发明的聚酯中,所述总和“a+b”基于摩尔平均计优选为5至8的数。
在这些优选的本发明的聚酯中,其中所述总和“a+b”基于摩尔平均计为5至8的数,所述变量“a”基于摩尔平均计优选为3.5至7.2的数,和所述变量“b”基于摩尔平均计优选为0.5至2.4的数。
在本发明的聚酯中,所述总和“a+b”基于摩尔平均计更优选为6至7的数。
在这些优选的本发明的聚酯中,其中所述总和“a+b”基于摩尔平均计为6至7的数,所述变量“a”基于摩尔平均计优选为4.2至6.3的数,和所述变量“b”基于摩尔平均计优选为0.6至2.1的数。在这些本发明的聚酯中,优选的是其中所述变量“a”基于摩尔平均计为4.8至5.6的数,和所述变量“b”基于摩尔平均计为1.2至1.4的数的那些聚合物。
在本发明的聚酯中,变量“m”基于摩尔平均计优选为2至5的数,且更优选为3。
在本发明的聚酯中,变量“n”基于摩尔平均计优选为43至47的数,更优选为44至46的数,且甚至更优选为45。
尤其优选的是根据式(I)的本发明的聚酯
其中,
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至COO基团,
n基于摩尔平均计为44至46的数,
m基于摩尔平均计为3,和
a+b基于摩尔平均计为5至8的数。
在这些尤其优选的本发明的聚酯中,优选的是其中所述变量“a”基于摩尔平均计为3.5至7.2的数,和所述变量“b”基于摩尔平均计为0.5至2.4的数的聚酯。
特别优选的是根据式(I)的本发明的聚酯
其中,
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至COO基团,
n基于摩尔平均计为44至46的数,
m基于摩尔平均计为3,和
a+b基于摩尔平均计为6至7的数。
在这些特别优选的本发明的聚酯中,优选的是其中所述变量“a”基于摩尔平均计为4.2至6.3的数,和所述变量“b”基于摩尔平均计为0.6至2.1的数的聚酯。
在上述尤其优选和特别优选的本发明的聚酯中,所述变量“n”基于摩尔平均计优选为45。
极其优选的是根据式(I)的本发明的聚酯
其中,
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至COO基团,
n基于摩尔平均计为45,
m基于摩尔平均计为3,和
a+b基于摩尔平均计为6至7的数,
a基于摩尔平均计为4.8至5.6的数,和
b基于摩尔平均计为.2至1.4的数。
在本发明的聚酯中,用“a”标记的结构单元:用“b”标记的结构单元的摩尔比优选为70∶30至90∶10,且更优选为80∶20。
在本发明的聚酯中,用“a”标记的结构单元和用“b”标记的结构单元优选嵌段地、交替地或呈统计学分布,且更优选呈统计学排布。
在结构单元“H3C-(OC2H4)n-(OC3H6)m”中的基团-O-C2H4-为式-O-CH2-CH2-。
在用“a”标记的结构单元中、在结构单元“H3C-(OC2H4)n-(OC3H6)m”中以及在结构单元HO-(C3H6)中的基团-O-C3H6-为式-O-CH(CH3)-CH2-或-O-CH2-CH(CH3)-,即为下式:
在用“b”标记的结构单元中以及在结构单元HO-(C4H8)中的基团-O-C4H8-为式-O-CH(CH3)-CH(CH3)-,即为下式:
本发明的聚酯可以以基本形式,即本身使用,但也可以以水溶液形式提供。水溶液例如对于它们的处理有益和例如本发明的聚酯的计量非常容易。优选地,所述水溶液以25至70重量%的量包含本发明的聚酯,基于所述水溶液的总质量计。
因此,本发明的另一主题是水溶液,其以25至70重量%的量包含本发明聚酯,基于所述水溶液的总质量计。这些水溶液甚至可以由本发明的聚酯和水组成。
本发明的聚酯可以有利地用于洗涤或衣物去垢剂组合物。除本发明的聚酯以外,这些洗涤或衣物去垢剂组合物可包含一种或多种任选的成分,例如它们可包括通常用于衣物去垢剂组合物中的常规成分。任选成分的实例包括,但不限于:助洗剂,表面活性剂,漂白剂,漂白活性化合物,漂白活性剂,漂白催化剂,光漂白剂,染料转移抑制剂,颜色保护剂,抗再沉积剂,分散剂,织物软化和抗静电剂,荧光增白剂,酶,酶稳定剂,泡沫调节剂,消泡剂,降恶臭剂,防腐剂,消毒剂,水溶助剂,纤维润滑剂,抗收缩剂,缓冲剂,香料,加工助剂,着色剂,染料,颜料,抗腐蚀剂,填充剂,稳定剂和其它用于洗涤或衣物去垢剂组合物的常规成分。
本发明的聚酯在碱性环境中具有有利的稳定性,具有有益的溶解度,并且有利地清澈地溶于碱性组合物,如碱性重垢洗涤液中,并且还具有有利的去污性质。在洗涤或衣物去垢剂组合物中,它们产生有益的洗涤性能,尤其是在存储之后也是如此。此外,本发明的聚酯具有有利的泡沫抑制性质。这不仅在应用包含本发明聚酯的洗涤或衣物去垢剂组合物时是有利的,而且在处理本发明的聚酯时还有利地减少的起泡。
本发明的聚酯可以有利地通过以下方法来制备,所述方法包括首先在大气压下,在添加催化剂条件下,将对苯二甲酸二甲酯(DMT)、1,2-丙二醇(PG)、2,3-丁二醇(BG)、和H3C-(OC2H4)n-(OC3H6)m-OH加热至160至220℃的温度,然后在降低的压力下于160至240℃的温度继续反应,其中所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至羟基-OH,且n和m如对于本发明聚酯所定义。
因此、本发明的另一个主题是用于制备本发明的聚酯的方法,所述方法包括首先在大气压下,在添加催化剂条件下,将对苯二甲酸二甲酯(DMT)、1,2-丙二醇(PG)、2,3-丁二醇(BG)、和H3C-(OC2H4)n-(OC3H6)m-OH加热至160至220℃的温度,然后在降低的压力下于160至240℃的温度继续反应,其中所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至羟基-OH,且n和m如对于本发明聚酯所定义。
降低的压力优选表示0.1至900mbar的压力,且更优选0.5至500mbar的压力。
在本发明的一个优选的实施方案中,本发明的方法的特征在于:
a)将对苯二甲酸二甲酯,1,2-丙二醇,2,3-丁二醇H3C-(OC2H4)n-(OC3H6)m-OH和催化剂添加至反应容器中,在惰性气体、优选氮气下加热至160至220℃的温度以除去甲醇,然后将压力降低至低于大气压,优选降低至200至900mbar的压力,且更优选降低至400至600mbar的压力以完成酯交换,和
b)在第二步骤中,在210℃至240℃的温度和在0.1至10mbar,且优选0.5至5mbar的压力继续反应以形成聚酯。
优选使用乙酸钠(NaOAc)和原钛酸四异丙酯(IPT)作为催化剂体系用于本发明的方法。
以下的实施例意欲详细阐述本发明,然而并不将本发明限制于此。除非另有明确说明,否则给出的所有百分比均为重量百分比(%重量或重量%)。
用于制备本发明聚酯的一般过程
聚酯合成通过使用乙酸钠(NaOAc)和原钛酸四异丙酯(IPT)作为催化剂体系由对苯二甲酸二甲酯(DMT)、1,2-丙二醇(PG)、2,3-丁二醇(BG)和甲基聚亚烷基二醇的反应进行。所述合成是一个两步过程。第一步为酯交换且第二步为缩聚。
酯交换
将对苯二甲酸二甲酯(DMT)、1,2-丙二醇(PG)、2,3-丁二醇(BG)、甲基聚亚烷基二醇、乙酸钠(无水)(NaOAc)和原钛酸四异丙酯(IPT)在室温下称量入反应容器。
为了熔融过程和均质化,通过氮气流搅动将混合物加热至170℃保持1小时,然后加热至210℃保持另外1小时。在酯交换期间将甲醇从反应中释放并从***蒸馏出来(蒸馏温度<55℃)。在210℃2h后关闭氮气并将压力在3h内降低到400mbar。
缩聚反应
将混合物加热至230℃。在230℃将压力在160min内降低到1mbar。一旦缩聚反应已经开始,1,2-丙二醇/2,3-丁二醇混合物就从体系中蒸馏出来。将混合物在230℃和1mbar的压力下搅拌4小时。将反应混合物冷却至140-150℃。使用氮气释放真空并将熔融聚合物转移到玻璃瓶中。
实施例I:
用量[g] | 用量[mol] | 原料[缩写] |
97.1 | 0.50 | DMT |
18.02 | 0.2 | BG |
60.88 | 0.8 | PG |
310.56 | 0.145 | H3C-(OC2H4)45-(OC3H6)3-OH |
0.5 | 0.0061 | NaOAc |
0.2 | 0.0007 | IPT |
获得根据式(I)的本发明的聚酯,其中
R1和R2为H3C-(OC2H4)n-(OC3H6)m,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由-(OC3H6)基团组成的嵌段连接至COO基团,
n基于摩尔平均计为45,
m基于摩尔平均计为3,和
a+b基于摩尔平均计为6至7的数,
a基于摩尔平均计为4.8到5.6的数,和
b基于摩尔平均计为1.2到1.4的数。
Claims (20)
1.根据下式(I)的聚酯
其中R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至COO基团,
n基于摩尔平均计为40至50的数,
m基于摩尔平均计为1至7的数,和
a+b基于摩尔平均计为4至9的数,
其特征在于,a基于摩尔平均计为2.8至8.1的数,和b基于摩尔平均计为0.4至2.7的数,
在用“a”标记的结构单元中以及在结构单元“H3C-(OC2H4)n-(OC3H6)m”中的基团-O-C3H6-为式-O-CH(CH3)-CH2-或-O-CH2-CH(CH3)-,和在用“b”标记的结构单元中的基团-O-C4H8-为式-O-CH(CH3)-CH(CH3)-。
2.根据权利要求1所述的聚酯,其特征在于,总和a+b基于摩尔平均计为5至8的数,a基于摩尔平均计为3.5至7.2的数,和b基于摩尔平均计为0.5至2.4的数。
3.根据权利要求1所述的聚酯,其特征在于,总和a+b基于摩尔平均计为6至7的数,a基于摩尔平均计为4.2至6.3的数,和b基于摩尔平均计为0.6至2.1的数。
4.根据权利要求3所述的聚酯,其特征在于,a基于摩尔平均计为4.8至5.6的数,和b基于摩尔平均计为1.2至1.4的数。
5.根据权利要求1至4中任一项所述的聚酯,其特征在于,m基于摩尔平均计为2至5的数。
6.根据权利要求5所述的聚酯,其特征在于,m基于摩尔平均计为3。
7.根据权利要求1至4中任一项所述的聚酯,其特征在于,n基于摩尔平均计为43至47的数。
8.根据权利要求7所述的聚酯,其特征在于,n基于摩尔平均计为44至46的数。
9.根据权利要求8所述的聚酯,其特征在于,n基于摩尔平均计为45。
10.根据权利要求1至4中任一项所述的聚酯,其特征在于,
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至COO基团;
n基于摩尔平均计为44至46的数,
m基于摩尔平均计为3,和
a+b基于摩尔平均计为5至8的数。
11.根据权利要求10所述的聚酯,其特征在于,a基于摩尔平均计为3.5至7.2的数,和b基于摩尔平均计为0.5至2.4的数。
12.根据权利要求10所述的聚酯,其特征在于,
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至COO基团;
n基于摩尔平均计为44至46的数,
m基于摩尔平均计为3,和
a+b基于摩尔平均计为6至7的数。
13.根据权利要求12所述的聚酯,其特征在于,a基于摩尔平均计为4.2至6.3的数,和b基于摩尔平均计为0.6至2.1的数。
14.根据权利要求10所述的聚酯,其特征在于,n基于摩尔平均计为45。
15.根据权利要求1至4中任一项所述的聚酯,其特征在于,
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至COO基团;
n基于摩尔平均计为45,
m基于摩尔平均计为3,和
a+b基于摩尔平均计为6至7的数,
a基于摩尔平均计为4.8至5.6的数,和
b基于摩尔平均计为1.2至1.4的数。
16.根据权利要求1至3、6、8、9和11至14中任一项所述的聚酯,其特征在于,用“a”标记的结构单元︰用“b”标记的结构单元的摩尔比为70︰30到90︰10。
17.根据权利要求1至4、6、8、9和11至14中任一项所述的聚酯,其特征在于,用“a”标记的结构单元︰用“b”标记的结构单元的摩尔比为80︰20。
18.根据权利要求1至4、6、8、9和11至14中任一项所述的聚酯,其特征在于,用a标记的结构单元和用b标记的结构单元嵌段地、交替地或呈统计学分布。
19.根据权利要求18所述的聚酯,其特征在于,用a标记的结构单元和用b标记的结构单元呈统计学分布。
20.用于制备根据权利要求1至19中任一项所述的聚酯的制备方法,其特征在于,所述方法包括首先在大气压下,在添加催化剂条件下,将对苯二甲酸二甲酯,1,2-丙二醇,2,3-丁二醇和H3C-(OC2H4)n-(OC3H6)m-OH加热至160至220℃的温度,然后在降低的压力下于160至240℃的温度继续反应,其中,所述-(OC2H4)基团和所述-(OC3H6)基团嵌段地排列,且由所述-(OC3H6)基团组成的嵌段连接至羟基-OH。
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BR112015002129B1 (pt) * | 2012-07-31 | 2021-01-05 | Clariant Finance (Bvi) Limited | poliésteres e seus processos de preparação |
HUE043499T2 (hu) | 2013-03-28 | 2019-09-30 | Procter & Gamble | Poliéteramin-tartalmú tiszítószerek |
EP2966160A1 (en) | 2014-07-09 | 2016-01-13 | Clariant International Ltd. | Storage-stable compositions comprising soil release polymers |
ES2745826T3 (es) * | 2014-11-11 | 2020-03-03 | Clariant Int Ltd | Detergentes para ropa que contienen polímeros de liberación de suciedad |
CN107109306A (zh) | 2014-11-11 | 2017-08-29 | 科莱恩国际有限公司 | 包含污垢释放聚合物的衣物洗涤剂 |
US10808206B2 (en) | 2017-11-14 | 2020-10-20 | Henkel IP & Holding GmbH | Detergent boosters, detergent systems that include a detergent booster, and methods of laundering fabric |
EP3489340A1 (en) | 2017-11-28 | 2019-05-29 | Clariant International Ltd | Renewably sourced soil release polyesters |
WO2019224030A1 (en) | 2018-05-24 | 2019-11-28 | Clariant International Ltd | Soil release polyesters for use in detergent compositions |
JP2023515384A (ja) | 2020-02-14 | 2023-04-13 | ビーエーエスエフ ソシエタス・ヨーロピア | 生分解性グラフトポリマー |
CN115151595A (zh) | 2020-02-21 | 2022-10-04 | 巴斯夫欧洲公司 | 具有改进的生物降解性的烷氧基化聚亚烷基亚胺或烷氧基化多胺 |
EP3933017A1 (en) | 2020-07-03 | 2022-01-05 | The Procter & Gamble Company | Fabric and home care product comprising a sulfatized esteramine |
EP3988634A1 (en) | 2020-10-23 | 2022-04-27 | The Procter & Gamble Company | Dishwashing composition having improved sudsing |
EP4006131A1 (en) | 2020-11-30 | 2022-06-01 | The Procter & Gamble Company | Method of laundering fabric |
EP4267654A1 (en) | 2020-12-23 | 2023-11-01 | Basf Se | Amphiphilic alkoxylated polyamines and their uses |
EP4134421A1 (en) | 2021-08-12 | 2023-02-15 | The Procter & Gamble Company | Detergent composition comprising detersive surfactant and graft polymer |
EP4134420A1 (en) | 2021-08-12 | 2023-02-15 | The Procter & Gamble Company | Detergent composition comprising detersive surfactant and biodegradable graft polymers |
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WO2024119298A1 (en) | 2022-12-05 | 2024-06-13 | The Procter & Gamble Company | Fabric and home care composition comprising a polyalkylenecarbonate compound |
WO2024129520A1 (en) | 2022-12-12 | 2024-06-20 | The Procter & Gamble Company | Fabric and home care composition |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4661267A (en) * | 1985-10-18 | 1987-04-28 | The Procter & Gamble Company | Fabric softener composition |
US4702857A (en) * | 1984-12-21 | 1987-10-27 | The Procter & Gamble Company | Block polyesters and like compounds useful as soil release agents in detergent compositions |
CN1434835A (zh) * | 2000-02-11 | 2003-08-06 | 纳幕尔杜邦公司 | 用于产生聚(对苯二甲酸丙二醇酯)的连续方法 |
CN1507465A (zh) * | 2001-06-02 | 2004-06-23 | �������˹��ĭ�ۺ���ɷ�����˾ | 生产聚对苯二甲酸丁二酯的方法 |
EP1661933A1 (de) * | 2004-11-24 | 2006-05-31 | SASOL Germany GmbH | Fließfähige, amphiphile und nichtionische Oligoester |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1191499A (en) * | 1967-09-29 | 1970-05-13 | Ici Ltd | Production of Aromatic Polyesters |
ATE73150T1 (de) * | 1984-12-21 | 1992-03-15 | Procter & Gamble | Blockpolyester und aehnliche verbindungen, verwendbar als verschmutzungsentferner in waschmittelzusammensetzungen. |
DE19826356A1 (de) | 1998-06-12 | 1999-12-16 | Clariant Gmbh | Schmutzablösevermögende Oligoester |
DE102005061058A1 (de) | 2005-12-21 | 2007-07-05 | Clariant Produkte (Deutschland) Gmbh | Anionische Soil Release Polymere |
DE102007005532A1 (de) * | 2007-02-03 | 2008-08-07 | Clariant International Limited | Wässrige Oligo- und Polyesterzubereitungen |
DE102007013217A1 (de) | 2007-03-15 | 2008-09-18 | Clariant International Ltd. | Anionische Soil Release Polymere |
EP2135931B1 (en) * | 2008-06-16 | 2012-12-05 | The Procter & Gamble Company | Use of soil release polymer in fabric treatment compositions |
US8779084B2 (en) * | 2009-07-01 | 2014-07-15 | Solvay (China) Co., Ltd. | Process for producing polyether-polyester block copolymer |
WO2012104157A1 (en) * | 2011-01-31 | 2012-08-09 | Unilever Plc | Soil release polymers |
EP2670788B1 (en) * | 2011-01-31 | 2015-03-11 | Unilever PLC | Alkaline liquid detergent compositions |
WO2012104156A1 (en) * | 2011-01-31 | 2012-08-09 | Unilever Plc | Soil release polymers |
BR112015002129B1 (pt) * | 2012-07-31 | 2021-01-05 | Clariant Finance (Bvi) Limited | poliésteres e seus processos de preparação |
-
2013
- 2013-07-24 WO PCT/EP2013/002195 patent/WO2014019659A1/en active Application Filing
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- 2013-07-24 MX MX2015001510A patent/MX2015001510A/es unknown
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4702857A (en) * | 1984-12-21 | 1987-10-27 | The Procter & Gamble Company | Block polyesters and like compounds useful as soil release agents in detergent compositions |
US4661267A (en) * | 1985-10-18 | 1987-04-28 | The Procter & Gamble Company | Fabric softener composition |
CN1434835A (zh) * | 2000-02-11 | 2003-08-06 | 纳幕尔杜邦公司 | 用于产生聚(对苯二甲酸丙二醇酯)的连续方法 |
CN1507465A (zh) * | 2001-06-02 | 2004-06-23 | �������˹��ĭ�ۺ���ɷ�����˾ | 生产聚对苯二甲酸丁二酯的方法 |
EP1661933A1 (de) * | 2004-11-24 | 2006-05-31 | SASOL Germany GmbH | Fließfähige, amphiphile und nichtionische Oligoester |
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