CN1120128C - 稳定的羟胺溶液 - Google Patents
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- C01—INORGANIC CHEMISTRY
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/149—Stabilisation
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Abstract
本发明提供了稳定的羟胺溶液。尤其是，其中起稳定作用的化合物是环己二胺四乙酸、硫胺的盐酸盐或者其混合物的稳定的羟胺溶液及其它们的制备方法。
Description
技术领域
本发明涉及稳定的羟胺溶液。尤其是，其中起稳定作用的化合物是环己二胺四乙酸、硫胺的盐酸盐或者其混合物的稳定的羟胺溶液及其它们的制备方法。
背景技术
羟胺溶液用途很广。例如其溶液可用于合成、推进剂制备、照相处理、和溶剂。众所周知羟胺溶液由于固有的不稳定性，所以应用时很成问题。
已经试图用一些有稳定作用的化合物使羟胺溶液稳定，如美国专利3,647,449和3,145,082分别使用乙二胺四乙酸的二钠盐和四钠盐。然而，另一项美国专利3,647,449披露，乙二胺四乙酸的二钠盐是一种不合格的稳定剂，因为羟胺游离碱的分解，会明显增加气体的溢出量。见第3栏第10-22行；第4栏第19-22行。还有文献证实乙二胺四乙酸的四钠盐也是一种不能令人满意的稳定剂。见美国专利4,551,318的第1栏第17-20行。因此，需要一种有效的羟胺稳定剂。
发明内容
本发明发现，用环己二胺四乙酸(“CDTA”)作稳定化合物，可以有效地稳定羟胺水溶液。这一发现是意想不到的，因为在本技术领域，已经知道乙二胺四乙酸的二钠盐和四钠盐不是有效的羟胺稳定剂。本发明的另一个发现是单独使用硫胺的盐酸盐，或者与CDTA结合使用都是极好的羟胺稳定剂。因此，本发明提供了一种羟胺溶液及它们的制备方法，该溶液有较长的贮藏寿命，且即使存在危险的过渡金属离子仍具有稳定性。
更具体地说，本发明提供了一种羟胺溶液，该溶液包括羟胺水溶液和稳定量的选自CDTA、硫胺的盐酸盐及其混合物的化合物。此外，本发明还提供了一种制备稳定的羟胺溶液的方法，该方法包括在羟胺水溶液中加入稳定量的选自CDTA、硫胺的盐酸盐及其混合物的化合物。
具体实施方式
术语“羟胺水溶液”意味着在水或醇如C1～C4的链烷醇中，羟胺游离碱和/或羟胺盐的水溶液。已经知道，羟胺水溶液在室温下分解缓慢，但是随温度的升高而迅速分解。此外，当溶液是羟胺游离碱溶液时，分解更明显。可以推断羟胺分解是由于内部氧化-还原反应，它被温度升高、酸、碱和过渡金属离子而加剧。
可用任何常规方法制备本发明的羟胺水溶液。例如，可将碱如氢氧化铵或碱金属的氢氧化物加到羟胺盐水溶液中，由此形成羟胺游离碱和其盐的水溶液。适用的羟胺盐是那些羟胺与强无机酸，包括(但又不限于)硫酸、硝酸或盐酸，或者脂肪酸包括(但又不限于)乙酸和丙酸所形成的羟胺盐。通常，在该溶液中，羟胺游离碱和盐的用量是水溶液中羟胺游离碱的大约10～70重量％，优选的是大约25～50重量％。
还可以且优选地，用任何合适的惰性气体如氮气对羟胺水溶液进行吹洗，以便尽可能除去溶液中的氧气。可用惰性气体以大约50mL/min的流量吹洗大约1小时。
可通过在羟胺水溶液中加入稳定量的CDTA、硫胺的盐酸盐及其混合物而制备本发明的稳定的羟胺溶液。可直接加入CDTA、硫胺的盐酸盐及其混合物，或者优选地加入高达10重量％的浓缩液。
优选的用于本发明的CDTA异构体是反-1，2-环己二胺-N，N，N′，N′-四乙酸。CDTA包括其优选异构体都是市场有售的。硫胺的盐酸盐也是市场有售的。可用CDTA和硫胺盐的混合物稳定羟胺水溶液。然而，优选地单独使用CDTA。
CDTA、硫胺的盐酸盐及其混合物的稳定量是足以使羟胺溶液中的氧和金属离子两者之一或者两者都减活化的量。通常，在稳定的羟胺水溶液中该量大约是1～1000ppm，优选的大约是1～200ppm，更优选的大约是50～150ppm。本领域的普通技术人员应当知道，准确的用量取决于多种因素，包括溶液中羟胺游离碱和/或盐的浓度、贮藏和反应温度，以及过渡金属离子的杂质量。例如，当加入大约50～200ppm的CDTA时，含有50重量％羟胺游离碱的羟胺水溶液，在小于40℃的温度下，且铁浓度为0～15ppm时，能呈现很高的稳定性。
下面通过非限定性的实施例，进一步描述本发明。
实施例 实施例1
用一个150mL 4颈口圆底烧瓶，监测稳定的和不稳定的羟胺游离碱溶液的溢出气体。四个颈口中的一个颈口与25mL滴定管相连，穿过另一个颈口将热电偶插入羟胺溶液。另外两个颈口用于引入吹洗用的氮气，和监测溢出的气体。气体出口与一个倒置量筒相连，量筒内装满了水，用于收集溢出的气体。在上述装置中放入90～120克已知浓度的稳定的和不稳定的羟胺游离碱溶液。用一磁力搅拌棒连续进行搅拌，以大约500mL/m的流量引入氮气，引入时间达20分钟。使该装置恒温在5～50℃的温度。
通过测量从量筒中置换的水量，监测以时间为函数的气体溢出量。通常试验为24小时。对稳定的羟胺溶液，一般气体溢出量与试验时间之间是线性关系。为了进行比较，用24小时结束时测得的总气体量除以羟胺溶液的初始重量和时间，计算平均气体溢出速率：
平均气体速率＝总溢出气体(μL)/g羟胺溶液/小时
按该总程序，在该气体溢出装置中，在40℃的温度下，测试120克含有53重量％羟胺游离碱、54ppm反-1，2-环己二胺-N，N，N′，N′-四乙酸和6.04ppm FeIII的羟胺溶液样品。根据测量结果，得出平均气体溢出速率是17.5μL/g/h，结果如表1所示。该溢出速率表明，即使溶液中有6.04ppm铁，羟胺溶液也非常稳定，而对比较用的不稳定溶液，即使溶液中没有铁，气体溢出速率仍有大约188μL/g/h。实施例2-5
用实施例1所述的步骤，测试含有53重量％羟胺游离碱、53ppm反-1，2-环己二胺-N，N，N′，N′-四乙酸、和FeIII离子浓度分别是0、3.02、9.13和12.08ppm的羟胺溶液。结果概括在表1中。
表1
| 实施例 | FeIII(ppm) | 气体溢出量(μL/g/h) |
| 1 | 6.04 | 17.5 |
| 2 | 00 | 2.8 |
| 3 | 3.02 | 8.5 |
| 4 | 9.13 | 26.1 |
| 5 | 12.08 | 54.1 |
结果显示出，在40℃的温度下，且有高达12.08ppm FeIII时，53ppm的CDTA能生成非常稳定的羟胺游离碱溶液。实施例6-9
采用实施例1所述的步骤，在40℃的温度下，测试分别含有3.19、6.15、9.12和11.96 FeIII离子浓度的、Nisshin化学公司销售的FH-50稳定的羟胺游离碱溶液。结果概述在表2中，与实施例1-5的测试结果相比，含有53重量％羟胺游离碱、54ppm反-1，2-环己二胺-N，N，N′，N′-四乙酸的稳定溶液比市场有售的稳定溶液更稳定。
表2
实施例10-22
| 实施例 | FeIII浓度(ppm) | 气体溢出量(μL/g/h) |
| 6 | 3.19 | 20.5 |
| 7 | 6.15 | 24.5 |
| 8 | 9.12 | 153.0 |
| 9 | 11.96 | 13,764 |
按照实施例1所述的步骤，在40℃的温度下，测试羟胺游离碱为53重量％，和含有不同量反-1，2-环己二胺-N，N，N′，N′-四乙酸和FeIII的稳定的羟胺游离碱溶液。结果概述在表3中。
表3
| 实施例 | CDTA浓度(ppm) | FeIII浓度(ppm) | 气体溢出量(μL/g/h) |
| 10 | 77 | 0 | 3.1 |
| 11 | 77 | 2.86 | 9.0 |
| 12 | 77 | 6.11 | 14.4 |
| 13 | 77 | 9.01 | 19.6 |
| 14 | 77 | 11.98 | 33.0 |
| 15 | 101 | 2.98 | 9.8 |
| 16 | 101 | 6.08 | 12.2 |
| 17 | 101 | 8.96 | 24.3 |
| 18 | 101 | 12.08 | 40.1 |
| 19 | 101 | 14.99 | 52.6 |
| 20 | 199 | 6.30 | 27.0 |
| 21 | 199 | 12.19 | 58.0 |
| 22 | 199 | 14.99 | 75.0 |
表3所示的结果表明，对53重量％羟胺游离碱溶液来说，即使FeIII浓度为15ppm，采用CDTA也能得到优异的稳定性。实施例23
用Pleasant Grove，Utah量热科学公司出品的等温微量量热计，测量溶液中羟胺分解过程中放出的热量。微量量热法是一种超灵敏热量测量技术，其灵敏度大约为±0.5微焦耳/秒，相当于8年内蒸发一滴水。
等温微量量热计由恒温空气和水浴、带有四个量池的铝块和一个辅助电子系统组成，四个量池中一个是参考池，三个是测量池。水浴及所用仪器的运行范围是5～75℃。当热量穿过一个连接在各个量池与恒温热阱器之间的珀尔帖(Peltier)电-热效应仪时，该电-热效应仪上的热量产生了电压。该电压与羟胺溶液分解过程中放出热量的热流量成正比。
将羟胺溶液样品装在一个10mL用聚四氟乙烯衬里的、顶部卷曲的瓶塞密封的管形瓶中。将大约5克稳定的或不稳定的羟胺溶液加到配衡后的样品容器中，重量准确到1mg。然后将样品的管形瓶放在充满氮气的干燥袋中，在将管形瓶在干燥袋中密封之前，用氮气吹洗样品30分钟。然而再次测量样品的重量。
在将样品管形瓶放入量热计的量池之前，使管形瓶在微量量热计的空气浴中至少预平衡2小时到测试温度。在这段时间中，记录来自空量热计量池的热流率。然后将管形瓶转移到量池中，并以时间为函数记录的热流率。在至少两天的时间里监测装载样品的热流率，以验证初始分解速率是可测量的，并不迅速变化。然后，以一定的时间间隔，在至少几百小时的时间里，测量热流率，以确定分解是否与时间有相关性。然后计算平均热流/g羟胺溶液，以微瓦/g计。
按照上述一般步骤，在等温微量量热计中测试4.716克的含53重量％羟胺游离碱的羟胺溶液样品。在17.4小时后，测得热流率为920.3微瓦/g，结果如表4所示。实施例24-27
采用实施例23的步骤，在40℃的温度下，与含有不同铁离子的FH-50一起，测试含有53重量％羟胺游离碱和不同反-1，2-环己二胺四乙酸和FeIII离子浓度的稳定的羟胺溶液，上述FeIII离子由Fe(NO3)3制得。微量量热的测试结果如表4所示。
表4
| 样品 | 游离碱(重量％) | CDTA(ppm) | FeIII浓度(ppm) | 热流率(微瓦/g) |
| 23 | 53 | 0 | 0 | 920.3 |
| 24 | 53 | 54 | 0 | 6.9 |
| 25 | 53 | 54 | 302 | 47.0 |
| 26 | 53 | 54 | 6.04 | 85.5 |
| 27 | 53 | 54 | 9.13 | 161.2 |
| 28 | 53 | 54 | 12.08 | 3760.0 |
| 29 | 53 | 77 | 0 | 6.5 |
| 30 | 53 | 77 | 2.86 | 47.5 |
| 31 | 53 | 77 | 6.11 | 95.5 |
| 32 | 53 | 77 | 9.01 | 130.6 |
| 33 | 53 | 77 | 1.98 | 319.2 |
| 34 | 53 | 101 | 0 | 5.2 |
| 35 | 53 | 101 | 2.98 | 34.7 |
| 36 | 53 | 101 | 6.08 | 108.7 |
| 37 | 53 | 101 | 8.96 | 119.6 |
| 38 | 53 | 101 | 12.08 | 1542.0 |
| 39 | 53 | 1 | 14.99 | 185.0 |
| 40 | 53 | 199 | 0 | 5.5 |
| 41 | 53 | 199 | 6.30 | 73.6 |
| 42 | 53 | 199 | 12.19 | 137.0 |
| 43 | 53 | 199 | 14.00 | 159.9 |
| 44 | FH-50 | - | 0 | 13.0 |
| 45 | FH-50 | - | 3.19 | 68.3 |
| 46 | FH-50 | - | 6.15 | 146.0 |
| 47 | FH-50 | - | 9.12 | 6838.0 |
表4的结果说明，CDTA是一种有效的稳定剂。实施例48-66
采用实施例23的步骤，在40℃和50℃的温度下，测试含有不同量羟胺游离碱和不同量反-1，2-环己二胺四乙酸、硫胺盐酸盐(THIM)、1，2-菲咯啉(PHEN)、乙二胺四乙酸的四钠盐(EDTA)和FeIII离子的稳定溶液。微量量热计的测试结果如表5所示。结果说明，与EDTA相比，CDTA是非常好的稳定剂。上述结果还说明，单独使用THIM以及与CDTA联合使用都可以作为有效的稳定剂。
表5
实施例67-76
| 样品 | 试验温度(℃) | ％HA | CDTA(ppm) | THIM(ppm) | PHEN(ppm) | EDTA(ppm) | FeIII(ppm) | 热流率(微瓦/g) |
| 48 | 40 | 53.1 | 100.0 | 0 | 0 | 0 | 0 | 5.4 |
| 49 | 40 | 53.0 | 0 | 104.8 | 0 | 0 | 0 | 8.6 |
| 50 | 40 | 53.0 | 0 | 0 | 100.1 | 0 | 0 | 138 |
| 51 | 40 | 53.0 | 0 | 0 | 0 | 101.0 | 0 | 246 |
| 52 | 50 | 21.2 | 100.6 | 0 | 0 | 0 | 8.9 | 245 |
| 53 | 50 | 21.2 | 91.1 | 99.9 | 0 | 0 | 9.1 | 250 |
| 54 | 50 | 21.2 | 105.1 | 0 | 101.8 | 0 | 8.9 | 190 |
| 55 | 50 | 21.2 | 150.0 | 0 | 0 | 0 | 9.1 | 246 |
| 56 | 50 | 21.2 | 150.2 | 101.6 | 0 | 0 | 9.0 | 248 |
| 57 | 50 | 21.2 | 150.1 | 0 | 100.1 | 0 | 8.8 | 240 |
| 58 | 50 | 21.2 | 150.0 | 0 | 0 | 0 | 12.0 | 320 |
| 59 | 50 | 21.2 | 150.2 | 101.6 | 0 | 0 | 12.1 | 326 |
| 60 | 50 | 21.2 | 150.1 | 0 | 100.0 | 0 | 12.1 | 325 |
| 61 | 50 | 21.2 | 150.0 | 0 | 0 | 0 | 15.1 | 400 |
| 62 | 50 | 21.2 | 150.2 | 101.6 | 0 | 0 | 15.3 | 415 |
| 63 | 50 | 21.2 | 150.0 | 0 | 0 | 0 | 15.1 | 391 |
| 64 | 50 | 27.8 | 150.0 | 0 | 0 | 0 | 9.1 | 262 |
| 65 | 50 | 27.8 | 150.0 | 0 | 0 | 0 | 12.2 | 344 |
| 66 | 50 | 27.8 | 150.0 | 0 | 0 | 0 | 15.1 | 423 |
采用实施例23的步骤，在40℃的温度下，测试含有48.6重量％羟胺游离碱和来自硫酸铁或硝酸铁的FeII和FeIII离子的稳定羟胺溶液。结果如表6所示。
表6
| 实施例 | 试验温度(℃) | ％HA | CDTA(ppm) | 来自硫酸盐的FeII(ppm) | 来自硫酸盐的FeIII(ppm) | 来自硝酸盐的FeIII(ppm) | 热流率(微瓦/g) |
| 67 | 40 | 48.6 | 105 | 3.62 | 0 | 0 | 92.54 |
| 68 | 40 | 48.6 | 105 | 6.14 | 0 | 0 | 100.30 |
| 69 | 40 | 48.6 | 105 | 9.02 | 0 | 0 | 147.16 |
| 70 | 40 | 48.6 | 123 | 5.96 | 0 | 0 | 86.38 |
| 71 | 40 | 48.6 | 123 | 8.95 | 0 | 0 | 136.08 |
| 72 | 40 | 48.6 | 123 | 11.95 | 0 | 161.87 | |
| 73 | 40 | 48.6 | 105 | 0 | 3.05 | 0 | 76.97 |
| 74 | 40 | 48.6 | 105 | 0 | 6.03 | 0 | 131.60 |
| 75 | 40 | 48.6 | 105 | 0 | 9.07 | 0 | 147.85 |
| 76 | 40 | 48.6 | 122 | 0 | 0 | 15.02 | 197.97 |
表6所示的结果说明，无论FeII和FeIII离子来自硫酸盐还是硝酸盐，CDTA对FeII和FeIII离子都是有效的。实施例77-83
采用实施例23的步骤，在40℃的温度下，测试含有48.6重量％羟胺游离碱和铁锈、FeO和Fe2O3的稳定羟胺溶液。结果如表7所示。
表7
| 实施例 | CDTA(ppm) | FeO(ppm) | Fe2O3(ppm) | 热流率(微瓦/g) |
| 77 | 105 | 0 | 0 | 21.1 |
| 78 | 105 | 190 | 0 | 89.3 |
| 79 | 105 | 689 | 0 | 198.9 |
| 80 | 105 | 1135 | 0 | 429.9 |
| 81 | 105 | 0 | 113 | 87.3 |
| 82 | 105 | 0 | 236 | 82.3 |
| 83 | 105 | 0 | 510 | 159.8 |
表7所示的结果表明，即使在有铁锈存在的情况下，CDTA也是有效的。实施例84-85
采用实施例23所示的步骤，测试含有30重量％硫酸胲和11ppm铁离子的稳定和不稳定溶液。结果如表8所示。
表8
| 实施例 | CDTA浓度(ppm) | FeIII浓度(ppm) | 热流率(微瓦/g) |
| 84 | 0 | 11 | 0.792±0.016 |
| 85 | 120 | 11 | 0.298±0.014 |
上述结果表明，加入CDTA能显著地降低稳定溶液的分解速率。
Claims (4)
1.一种羟胺溶液，该溶液含有羟胺水溶液和稳定剂，其中稳定剂的用量以羟胺溶液的重量计为1～1000ppm且该稳定剂选自硫胺的盐酸盐和硫胺的盐酸盐与环己二胺四乙酸的混合物。
2.权利要求1的溶液，其中环己二胺四乙酸是反-1，2-环己二胺-N，N，N′，N′-四乙酸。
3.一种稳定羟胺溶液的方法，该方法包括在羟胺水溶液中加入稳定剂的步骤，其中稳定剂的用量以羟胺溶液的重量计为1～1000ppm并且所述稳定剂选自硫胺的盐酸盐和硫胺的盐酸盐与环己二胺四乙酸的混合物。
4.权利要求3的方法，其中环己二胺四乙酸是反-1，2-环己二胺-N，N，N′，N′-四乙酸。
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| US08/848,369 | 1997-04-30 | ||
| US08/848369 | 1997-04-30 | ||
| US08/848,369 US5906805A (en) | 1997-04-30 | 1997-04-30 | Stabilized hydroxylamine solutions |
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| EP (1) | EP0979209B1 (zh) |
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| DE10008080A1 (de) * | 2000-02-22 | 2001-08-23 | Basf Ag | Stabilisator für Hydroxylaminlösungen |
| JP4582602B2 (ja) * | 2000-03-24 | 2010-11-17 | ビーエーエスエフ ソシエタス・ヨーロピア | ヒドロキシルアミン水溶液およびその製造方法 |
| JP3503115B2 (ja) * | 2000-06-27 | 2004-03-02 | 東レ・ファインケミカル株式会社 | フリーヒドロキシルアミン水溶液の製造方法 |
| US6605421B2 (en) * | 2001-03-29 | 2003-08-12 | Konica Corporation | Aqueous solution containing hydroxylamine salt and storing method thereof |
| KR100887695B1 (ko) | 2001-10-03 | 2009-03-11 | 바스프 에스이 | 안정화된 히드록실아민 용액 및 히드록실아민 용액의 안정화 방법 |
| US6867327B2 (en) * | 2002-12-16 | 2005-03-15 | Basf Aktiengesellschaft | Preparation and purification of hydroxylamine stabilizers |
| US7396519B2 (en) * | 2004-01-26 | 2008-07-08 | San Fu Chemical Company, Ltd. | Preparation of a high purity and high concentration hydroxylamine free base |
| JP2007119277A (ja) * | 2005-10-26 | 2007-05-17 | Showa Denko Kk | ヒドロキシルアミンの安定化剤、安定化方法および安定化されたヒドロキシルアミン溶液 |
| US8991176B2 (en) | 2012-03-28 | 2015-03-31 | GM Global Technology Operations LLC | Fluid drive mechanism for turbocharger |
| CN108017556A (zh) * | 2016-11-04 | 2018-05-11 | 深圳市志邦科技有限公司 | 一种异氰酸酯类交联剂用封闭剂的合成新方法 |
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| US4551318A (en) * | 1983-12-28 | 1985-11-05 | Basf Aktiengesellschaft | Stabilized solutions of hydroxylamine or its salts in water or alcohols, and their preparation |
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| US3145082A (en) * | 1959-12-07 | 1964-08-18 | Dow Chemical Co | Stabilized hydroxylamine and its method of preparation |
| US3480392A (en) * | 1967-08-24 | 1969-11-25 | Sinclair Research Inc | Hydroxylamine solutions stabilized with a hydroxamic acid and method for their preparation |
| US3480391A (en) * | 1967-08-24 | 1969-11-25 | Sinclair Research Inc | Hydroxylamine solutions stabilized with an amide oxime and method for their preparation |
| US3544270A (en) * | 1968-08-13 | 1970-12-01 | Sinclair Oil Corp | Aqueous hydroxylamine solutions stabilized with hydroxyurea or hydroxythiourea derivatives |
| US3647449A (en) * | 1970-06-08 | 1972-03-07 | Eastman Kodak Co | Neutralizing bath for use in photographic processing |
| JPS5248118B2 (zh) * | 1972-01-22 | 1977-12-07 | ||
| DE2246610C3 (de) * | 1972-09-22 | 1980-01-03 | Agfa-Gevaert Ag, 5090 Leverkusen | Photographischer Farbentwickler |
| JPS57100908A (en) * | 1980-12-16 | 1982-06-23 | Nisshin Kako Kk | Stabilization of hydroxylamine or solution containing it by addition of 8 hydroxyquinoline |
| JPS595573B2 (ja) * | 1981-10-20 | 1984-02-06 | 日進化工株式会社 | ヒドロキシルアミンの安定化剤 |
| JPS595575B2 (ja) * | 1981-10-20 | 1984-02-06 | 日進化工株式会社 | ヒドロキシルアミンの安定化剤 |
| JPS595574B2 (ja) * | 1981-10-20 | 1984-02-06 | 日進化工株式会社 | ヒドロキシルアミンの安定化剤 |
| JPS5869843A (ja) * | 1981-10-20 | 1983-04-26 | Nisshin Kako Kk | ヒドロキシルアミンの安定化剤 |
| DE3343600A1 (de) * | 1983-12-02 | 1985-06-13 | Basf Ag, 6700 Ludwigshafen | Stabilisierte loesungen von hydroxylamin oder dessen salze |
| DE3345734A1 (de) * | 1983-12-17 | 1985-06-27 | Basf Ag, 6700 Ludwigshafen | Stabilisierte loesungen von hydroxylamin oder dessen salze in wasser oder alkoholen sowie deren herstellung |
| DE3345733A1 (de) * | 1983-12-17 | 1985-06-27 | Basf Ag, 6700 Ludwigshafen | Stabilisierte loesungen von hydroxylamin oder dessen salze in wasser oder alkoholen sowie deren herstellung |
| JPS60260541A (ja) * | 1984-06-07 | 1985-12-23 | Daicel Chem Ind Ltd | ヒドロキシルアミン類の安定化法 |
| US5227146A (en) * | 1991-05-23 | 1993-07-13 | American Cyanamid Company | Stabilization of aqueous hydroxylamine solutions |
| US5141730A (en) * | 1991-05-23 | 1992-08-25 | American Cyanamid Company | Stabilization of hydroxylamine solutions |
| DE19547759A1 (de) * | 1995-12-20 | 1997-06-26 | Basf Ag | Stabilisierte Hydroxylaminlösungen |
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| US4551318A (en) * | 1983-12-28 | 1985-11-05 | Basf Aktiengesellschaft | Stabilized solutions of hydroxylamine or its salts in water or alcohols, and their preparation |
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| CN1268100A (zh) | 2000-09-27 |
| EP0979209B1 (en) | 2003-06-18 |
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| JP2001522345A (ja) | 2001-11-13 |
| DE69815673D1 (de) | 2003-07-24 |
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