CN1375059A - 用于工业用水系统的荧光化合物 - Google Patents
用于工业用水系统的荧光化合物 Download PDFInfo
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Abstract
本发明涉及具有化学结构式(I)的荧光化合物,其中R1和R2均为SO3M,或者R1和R2中的一个为SO3M,另一个为COOM,M选自H、Na、K、Rb、Cs、Li或铵。已发现这些惰性荧光化合物对氧化生物杀伤剂具有抵抗力。本发明还涉及一种通过具有所需官能团的1,8-萘二甲酸酐和合适的取代邻-苯二胺之间的缩合反应制备这些化合物的方法。可供选择的另一种方法是在诸如铁粉等合适的还原剂的作用下,邻-氨基-硝基-芳香化合物和各种具有不同取代官能团的1,8-萘二甲酸酐通过硝基的原位还原而缩合制备该荧光化合物。得到的荧光化合物可以在工业水系统中作为惰性荧光示踪剂使用。
Description
发明领域
本发明涉及荧光化合物。在一方面,本发明涉及的荧光化合物是通过化学合成并经过稳定性检验的在工业用水系统中使用的惰性示踪剂。本发明的另一方面是提供两种可供选择的生产荧光化合物的方法。
发明背景
早在80年代末就已知有使用惰性荧光化合物来追踪工业用水系统中水压的升高和下降的方法。
工业用水系统有许多类型。一种典型的工业用水系统是冷却塔,在冷却塔中水起着热交换的作用。为了最有效地在这类系统中使用处理剂和确保合适的水压条件,根据对环境有益的推荐使用量来决定加入该系统的处理剂的量是有利的。如果处理剂用量不够,污垢盐沉积和腐蚀现象就会发生;如果处理剂用量超过所需的量,就会造成处理剂的浪费以及相应的资金损失。
在运转中,通过使用由一种惰性荧光化合物构成的示踪剂对加入到流动水体中的处理剂的量进行连续监控的方法在美国专利4,783,314和4,992,380中已有记载。这些专利所含背景信息在此无需重复,其内容作为参考文献引用在本说明书中。
为了使这类荧光化合物在工业用水系统中有效,这些荧光化合物必须是对该系统不损耗,或者说是对该系统惰性。尽管确实有些荧光化合物具备作为惰性荧光示踪剂的功能,但是这种化合物并不多,因此,水系统,尤其是含有氧化生物杀伤剂的水系统需要不断开发新的荧光示踪化合物以满足工业的需求。
发明概要
本发明的第一方面是具有以下化学结构式(I)的荧光化合物:其中,R1和R2均为SO3M,或者R1和R2中的一个为SO3M,另一个为COOM,M选自H、Na、K、Rb、Cs、Li或铵。
本发明的第二方面是制备具有以下化学结构式(I)的荧光化合物的方法:其中,R1和R2前文已定义,该方法包括将结构式(II)的1,8-萘二甲酸酐与结构式(III)的邻-苯二胺缩合的步骤:其中,结构式(II)和结构式(III)中的R1和R2前文已定义。
本发明的第三方面是制备具有化学结构式(I)的荧光化合物的方法:其中该荧光化合物是将具有结构式(IV)的邻-氨基-硝基-芳香化合物与具有化学结构式(II)的1,8-萘二甲酸酐(R1前文已定义)通过缩合反应而得到,其中,R2如前文定义,这种缩合反应是通过使用合适的还原剂在硝基上发生原位还原而实现的。
本发明的第四方面是将化学结构式(I)的荧光化合物作为惰性荧光示踪剂在工业用水系统中的应用:其中,R1和R2如前文定义。发明详细描述
本发明是基于发现了一些以萘二甲酰亚氨基为基础的特定化合物。这些以苯二甲酰亚氨基为基础的化合物不仅能发出荧光,而且在氧化生物杀伤剂(如漂白剂、溴、稳态溴、稳态氯)的存在下也稳定。因此,这些以苯二甲酰亚氨基为基础的特定化合物在含有漂白剂和/或稳态溴的工业用水系统中作为惰性荧光示踪剂特别有用。
这些以萘二甲酰亚氨基为基础的化合物可以通过具有合适官能团的1,8-萘二甲酸酐与合适的取代邻-苯二胺之间的缩合而方便地制备。这类化合物也可以通过具有特定官能团的1,8-萘二甲酸酐和邻-氨基-硝基-芳香化合物在还原剂的作用下缩合而成。
本发明中的荧光化合物是以萘二甲酰亚氨基为基础的具有以下化学结构式(I)的化合物:其中,R1和R2可以均为SO3M,或者R1和R2中的一个为SO3M,另一个为COOM,M选自H、Na、K、Rb、Cs、Li或铵。
本发明的荧光化合物可以通过具有所需官能团的1,8-萘二甲酸酐和合适取代邻-苯二胺的一步缩合反应方便地制备。根据本发明,制备荧光化合物所需的合适的1,8-萘二甲酸酐选自具有以下化学结构式(II)的化合物:其中,R2已如前文定义。当R2为SO3K,则化合物II是4-磺酸-1,8-萘二甲酸酐钾盐,该化合物II可以从Aldrich化学公司(地址:P.O.Box2060,Milwaukee,WI 53201,USA;电话号码:(414)273-3850和(800)558-9160)获得。
同理,适宜制备本发明的荧光化合物的合适的邻-苯二胺化合物具有以下化学结构式(III)的化合物:其中,式(III)中的R1前文已定义。当R1为COOH,化合物III是3,4-二氨基苯甲酸时,该化合物III可以从Aldrich获得。当R1为SO3H,化合物III为3,4-二氨基苯磺酸时,该化合物可以从Bayer.AG的有机化学业务部门获得,地址:Leverkusan,D-51368,Germany;电话号码+49 21430-8514。
在本发明的优选实施方案中,这类荧光化合物可以通过合适取代的萘二甲酸酐与合适取代的邻-苯二胺之间的一步缩合反应得到。
也可以将具有结构式(IV)所示的邻-氨基-硝基-芳香化合物(其中R1如前文所定义):与具有合适官能团的1,8-萘二甲酸酐进行缩合,这种缩合是在适宜的还原剂(例如铁粉,但不限于铁粉)的存在中通过原位还原硝基的方式进行的。当R1为SO3M,化合物IV是邻硝基苯胺对磺酸(以及其盐)时,该化合物可以从Bayer AG获得。当R1为COOH,化合物IV为4-氨基-3-硝基苯甲酸时,该化合物可以获自ACROS Organics(其为FisherScientific的一个部门,地址:600 Business Center Drive,Pittsburgh PA15205,电话号码:1-800-227-6701)。当R1为SO3M,则化合物IV为2-硝基苯胺-4-磺酸和它的盐,该化合物IV可以从TCI America(地址:9211 North Harborgate Street,Portland OR 97203,电话号码:800-423-8616)获得。
荧光被定义为分子吸收短波长(高频)的光子(光)后,重新发射出的长波长(低频)的光子(能量)的过程。在荧光过程中,能量的吸收和辐射(发射)是特定分子(结构)的独特性质。光被分子吸收后,电子被激发到一个较高的能态。假设所有的过多能量并未因与其他分子碰撞而损耗,那么这些被激发的电子在激发态保留大约10-8秒后回到基态。能量在电子回到基态的过程中释放。吸收光和释放光的波长之间的差称为斯托克斯移动。根据能量守恒原理,发射光波长总是大于激发光波长或与之相等,其中的能量差作为热量被物质的原子空间结构吸收。
当这类化合物的荧光特性被检验后,发现本发明的化合物在380nm以上有荧光信号激发值。因此,这些化合物就有与Nalco化学公司的惰性示踪剂1,3,6,8-芘四磺酸四钠盐(PTSA)不同的荧光信号。PTSA可以从Nalco化学公司获得,地址:One Nalco Center,Naperville,IL 60563;电话号码:(630)305-1000。本发明的示踪剂的荧光信号与PTSA的荧光信号不重合,因此它可以和PTSA共同使用,以达到在工业用水系统中的监测和控制目的。
本发明中的惰性荧光化合物显示其最大激发波长和发射波长分别在385~400nm和510~530nm的范围。本发明中的化合物所提供的宽光谱操作范围可以增强这些作为惰性荧光示踪剂的化合物的效用。另外,最大激发波长和发射波长之间的巨大差异(称为斯托克斯移动)可以使背景烃类物质所造成的干扰降至最低,因为很少有化合物具有这样大的斯托克斯移动。
这项发明中的荧光化合物可以在需要惰性荧光示踪剂的任何工业用水系统中使用。这种系统的例子包括冷却塔系统(包括开放式循环、闭合式循环和单程系统);石油井,钻孔岩层,地热井和其它油田开采领域;锅炉和锅炉水系统;矿物加工水,包括洗矿,矿物浮选和精选;造纸厂蒸煮器,洗涤器,漂白装置和白水系统;纸浆工业的黑液蒸发器;气体洗涤器和空气洗涤器;冶金工业的连铸加工;空调和制冷系统;工业和石油加工水;间接接触的冷却和加热水,例如巴氏杀菌水;水回收和净化系统;膜过滤水系统;食品加工流水线(肉,蔬菜,甜菜,甘蔗,谷物,家禽,水果和大豆);废水处理系统,以及净化器;液-固设备,城市污水处理系统和工业或城市水系统。
当使用本发明中的荧光化合物作为工业用水系统中的惰性示踪剂时,在实际情况允许条件下,一般希望使用最少量的荧光化合物。当然,必须知道加到水系统中的荧光化合物的量至少满足荧光信号能够被检测器检测。一般情况下,这种水系统中取样处的惰性荧光化合物的浓度至少为约0.01ppb,不能超过约10ppm。优选的荧光化合物的浓度大约在50ppb和500ppb之间。最优选的是荧光化合物的浓度在大约100ppb和400ppb之间。当然,往这个水系统中加入超过10ppm的惰性荧光化合物并检测该化合物的荧光信号是可能的,但是任何超过10ppm的惰性荧光化合物的使用量都是对这种惰性荧光化合物的不必要的浪费。
在这里使用的术语“惰性”的意思是指惰性荧光示踪剂不受同一系统中的其它化合物,或者其他系统变数如冶金组合物,微生物活性,生物杀伤剂的浓度,热交换或所有的热含量的明显或显著影响。为了定量“不受明显或显著影响”的含义,这种陈述意味着惰性荧光化合物在所接触的工业用水系统的正常情况下,该惰性荧光化合物的荧光信号没有超过10%的变化。工业用水系统中接触的正常情况是工业用水系统领域的普通技术人员所知道的。
当然,将荧光化合物置于不正常的工业用水系统中,也有可能使荧光信号产生超过10%的变化。例如,如果本发明的化合物中的一种(二磺基萘二甲酰亚胺即DSN)遇到超过42000ppm的焦磷酸盐(作为PO4)或遇到超过34000ppm的钠(作为Na+),这种化合物的荧光信号变化将超过10%。本发明的化合物中的另一种(羧基磺基萘二甲酰亚胺即CSN)假设当它遇到超过3100ppm的硅酸盐(作为SiO2)或者遇到超过41000ppm的钠(作为Na+),它的荧光信号变化将会超过10%。
已发现本发明的化合物当其接触标准化学组分的工业用水系统,它们能够保持惰性。但是,也发现本发明的化合物的惰性会随着pH的改变而受到威胁。已发现DSN化合物在pH范围从大约2到大约9能保持惰性,而CSN化合物在pH范围从大约5到大约10能保持惰性。在这些pH值范围内操作这种水系统时,DSN和CSN都是有效的惰性示踪剂。
本发明提供的荧光化合物的优点是已发现它们对氧化生物杀伤剂的降解作用呈现惰性。因此,它们在使用氧化生物杀伤剂使微生物的活性最小化的系统中特别有用。
实施例
以下实施例意在说明本发明并教示本领域的普通技术人员理解和应用本发明。这些实施例在任何情况下都不意在限制本发明。
实施例I二磺基萘二甲酰亚胺(DSN)的制备(其中R1为SO3Na,R2为SO3K)
往一个100ml的圆底长颈烧瓶加入3.16份4-磺基-1,8-萘二甲酸酐钾盐;2.4份3-硝基-4-氨基苯磺酸钠盐;1份铁粉和30份冰醋酸。该混合物回流加热并剧烈搅拌6小时。冷却后,通过过滤收集橙/黄色固体,用去离子水和异丙醇清洗,然后真空干燥,得到4.21份标题化合物。该物质通过在100份沸甲醇中搅拌4份该粗固体,并过滤热悬浮液,可进一步纯化。真空干燥后可得到3.65份黄黑色的化合物。
实施例II羧基磺化萘二甲酰亚胺(CSN)的制备(其中R1为COOH(用碳酸钾转变为COOK,R2为SO3K))
往一个100ml的圆底长颈烧瓶加入3.16份4-磺基-1,8-萘二甲酸酐钾盐;1.55份3,4-二氨基苯甲酸和30份冰醋酸。将混合物回流加热并剧烈搅拌6小时;由此悬浮液的颜色从棕褐色转变为暗黑色。冷却后,过滤收集黄色固体,并用去离子水清洗,真空干燥后得到4.10份标题化合物。
取1份标题化合物,将其悬浮在100份去离子水中,通过加入碳酸钾改变溶液的pH值使之略微偏碱性,即可制得CSN的水溶液。实施例III结构式I的化合物对氧化生物杀伤剂的稳定性
氧化生物杀伤剂的稳定性检验可以通过以下方式进行。在所需pH条件下,用所需阳离子和阴离子浓度制备模拟水溶液。为了这些实验,模拟冷却水含有360ppm钙(作为CaCO3),200ppm镁(作为CaCO3),300ppm碱物质(作为CaCO3)和用来防止CaCO3沉淀的15ppm的膦酸酯。该冷却水用HCl或NaOH调节所需的pH值。检验在pH9的条件下进行。
3个琥珀色的瓶子根据实验样品的需要分别贴上标签,分别往每个贴标签的瓶中加入25ml的模拟水,然后往其中一个瓶子(标签B)加入30μl的1200ppm的漂白储备液;第二个瓶子(标签)加入30μl的1200ppm的液体稳态溴储备液,这种液体稳态溴储备液作为STA-BR-EXTM可以从Nalco化学公司获得;第三个瓶子(标签N)加入30μl蒸馏水。
游离氯和结合氯的总量可以在样品制备完之后立即测量;24小时后进行荧光分析。这些瓶子在黑暗中放置24小时。24小时后,标签N的样品作为参照样品,进行荧光测量。在氧化生物杀伤剂存在条件下,荧光损耗的百分率可以用以下公式计算得到:
荧光损耗%=[(N样品光强度-B样品或S样品的光强度)/N样品光强度]×100%
氧化生物杀伤剂的稳定性实验数据在表I中列出。作为比较,已知的惰性荧光示踪剂包括:1-甲氧基芘-3,6,8-三磺酸,三钠盐(从MolecularProbe获得,地址:4849 Pitchford Avenue,Eugene,Oregon 97402,电话号码:(541)465-8300)和芘-1,3,6,8-四磺酸,四钠盐(PTSA)。
表I:萘二甲酰亚胺的氧化生物杀伤剂稳定性数据
化合物 | 激发波长(nm) | 发射波长(nm) | 在1ppm漂白剂(视为Cl2)存在下,24小时以上的荧光损耗(%) | 在1ppm稳态溴(作为Cl2)存在下,24小时以上的荧光损耗(%) |
实施例I的化合物二磺基萘二甲酰亚胺 | 387 | 510 | 0% | 0% |
实施例II的化合物羧基磺基萘二甲酰亚胺 | 398 | 519 | 0% | 3% |
比较例1-甲氧基芘-3,6,8-三磺酸,三钠盐 | 404 | 430 | 12% | 2% |
比较例1,3,6,8-芘-四磺酸,四钠盐 | 365 | 400 | 0% | 0% |
表中数据表明,荧光损耗(%)越低,效果越好。
结果显示本发明的化合物在氧化生物杀伤剂以冷却水系统中的典型浓度存在的条件下稳定。因此,他们作为示踪剂在冷却水系统中具有很大的用途。而且,除了本发明的惰性荧光化合物,已知不存在具有380nm以上的激发波长并在氧化生物杀伤剂存在的条件下稳定的其它化合物。
本说明书中描述的具体实施例主要意在例示本发明。毫无疑问,对本领域的技术人员而言会有超出这些描述的种种改变,这些改变应理解为构成本发明的一部分,它们将落在附加的权利要求的意图和范围之内。
Claims (18)
1.具有化学结构式I的荧光化合物:
式中,R1和R2均为SO3M,或者R1和R2中的一个为SO3M,另一个为COOM,其中M选自H、Na、K、Rb、Cs、Li或铵。
4.化学结构式I的化合物作为惰性荧光示踪剂在工业用水系统中的应用:式中,R1和R2均为SO3M,或者R1和R2中的一个为SO3M,另一个为COOM,其中M选自H、Na、K、Rb、Cs、Li或铵。
4.如权利要求1的化合物,其中R1和R2均为SO3M。
5.如权利要求1的化合物,其中R1为SO3M,R2为COOM。
6.如权利要求1的化合物,其中R1为COOM,R2为SO3M。
7.如权利要求2的方法,其中R1和R2均为SO3M。
8.如权利要求2的方法,其中R1为SO3M,R2为COOM。
9.如权利要求2的方法,其中R1为COOM,R2为SO3M。
10.如权利要求3的方法,其中R1和R2均为SO3M。
11.如权利要求3的方法,其中R1为SO3M,同时R2为COOM。
12.如权利要求3的方法,其中R1为COOM,R2为SO3M。
13.如权利要求4的应用,其中R1和R2均为SO3M。
14.如权利要求4的应用,其中R1为SO3M,R2为COOM。
15.如权利要求4的应用,其中R1为COOM,R2为SO3M。
16.如权利要求4的应用,其中所述工业用水系统是冷却塔。
17.如权利要求4的应用,其中在所述工业用水系统中的所述荧光化合物的浓度至少为约0.01ppb,不超过大约10ppm。
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BR112023021412A2 (pt) | 2021-04-15 | 2023-12-19 | Mc Us 3 Llc | Inibidores metabólicos para controlar biofilme |
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US2835674A (en) * | 1954-03-31 | 1958-05-20 | Hoechst Ag | Process of preparing derivatives of 1.4.5.8-naphthalene-tetracarboxylic acid |
US2820037A (en) * | 1956-05-24 | 1958-01-14 | Gen Aniline & Film Corp | Benzimidazobenzoisoquinolines |
FI752346A (zh) * | 1974-09-13 | 1976-03-14 | Ciba Geigy Ag | |
US4172202A (en) * | 1975-04-29 | 1979-10-23 | Hoechst Aktiengesellschaft | Process for the preparation of 4-amino-1,8-naphthalimides |
JPS5857463B2 (ja) * | 1975-12-16 | 1983-12-20 | 三菱化学株式会社 | スイヨウセイセンリヨウノセイゾウホウホウ |
US4783314A (en) | 1987-02-26 | 1988-11-08 | Nalco Chemical Company | Fluorescent tracers - chemical treatment monitors |
US4992380A (en) | 1988-10-14 | 1991-02-12 | Nalco Chemical Company | Continuous on-stream monitoring of cooling tower water |
US5006311A (en) | 1990-03-23 | 1991-04-09 | Nalco Chemical Company | Monitoring performance of a treating agent added to a body of water |
JPH07145909A (ja) | 1993-08-20 | 1995-06-06 | Nalco Chem Co | ボイラー系のpH/ホスフェートのプログラム制御方法 |
US5411889A (en) | 1994-02-14 | 1995-05-02 | Nalco Chemical Company | Regulating water treatment agent dosage based on operational system stresses |
US5389548A (en) | 1994-03-29 | 1995-02-14 | Nalco Chemical Company | Monitoring and in-system concentration control of polyelectrolytes using fluorochromatic dyes |
US5705394A (en) * | 1995-04-17 | 1998-01-06 | Nalco Chemical Company | Tagged epichlorohydrin-dimethylamine copolymers for use in wastewater treatment |
US5958788A (en) * | 1997-05-28 | 1999-09-28 | Nalco Chemical Company | Luminol tagged polymers for treatment of industrial systems |
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1999
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102816454A (zh) * | 2012-06-28 | 2012-12-12 | 大连理工大学 | 一类含酯基的1,8-萘酰亚胺类荧光二向性染料、其制备方法及应用 |
CN102816454B (zh) * | 2012-06-28 | 2013-11-20 | 大连理工大学 | 一类含酯基的1,8-萘酰亚胺类荧光二向性染料、其制备方法及应用 |
CN102774969A (zh) * | 2012-07-24 | 2012-11-14 | 浙江浙能能源技术有限公司 | 一种可生物降解的无磷阻垢缓蚀剂及制备方法 |
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EP1228376B1 (en) | 2006-05-10 |
DE60027916T2 (de) | 2006-09-14 |
TWI320411B (en) | 2010-02-11 |
TW200706539A (en) | 2007-02-16 |
CN1205212C (zh) | 2005-06-08 |
CA2384421A1 (en) | 2001-05-17 |
NO321914B1 (no) | 2006-07-17 |
TWI290924B (en) | 2007-12-11 |
EP1228376A1 (en) | 2002-08-07 |
AU777901B2 (en) | 2004-11-04 |
ES2263512T3 (es) | 2006-12-16 |
EP1228376A4 (en) | 2003-05-02 |
WO2001035107A1 (en) | 2001-05-17 |
AU3267101A (en) | 2001-06-06 |
US6358746B1 (en) | 2002-03-19 |
KR20020042835A (ko) | 2002-06-07 |
DE60027916D1 (de) | 2006-06-14 |
ATE326015T1 (de) | 2006-06-15 |
JP2003513979A (ja) | 2003-04-15 |
JP4842479B2 (ja) | 2011-12-21 |
NO20021132D0 (no) | 2002-03-07 |
CA2384421C (en) | 2012-06-26 |
NO20021132L (no) | 2002-05-02 |
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