JPH0436147B2 - - Google Patents
Info
- Publication number
- JPH0436147B2 JPH0436147B2 JP11551184A JP11551184A JPH0436147B2 JP H0436147 B2 JPH0436147 B2 JP H0436147B2 JP 11551184 A JP11551184 A JP 11551184A JP 11551184 A JP11551184 A JP 11551184A JP H0436147 B2 JPH0436147 B2 JP H0436147B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxylamines
- diethylhydroxylamine
- yield
- present
- stannic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000002443 hydroxylamines Chemical class 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 12
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229940079864 sodium stannate Drugs 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LFMTUFVYMCDPGY-UHFFFAOYSA-N n,n-diethylethanamine oxide Chemical compound CC[N+]([O-])(CC)CC LFMTUFVYMCDPGY-UHFFFAOYSA-N 0.000 description 4
- -1 olefin compounds Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229940082044 2,3-dihydroxybenzoic acid Drugs 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical class [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 241000482268 Zea mays subsp. mays Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- ZKXYINRKIDSREX-UHFFFAOYSA-N n,n-dipropylhydroxylamine Chemical compound CCCN(O)CCC ZKXYINRKIDSREX-UHFFFAOYSA-N 0.000 description 1
- JQDZCJWPDXZTEW-UHFFFAOYSA-N n,n-ditert-butylhydroxylamine Chemical compound CC(C)(C)N(O)C(C)(C)C JQDZCJWPDXZTEW-UHFFFAOYSA-N 0.000 description 1
- GUQRKZPMVLRXLT-UHFFFAOYSA-N n-cyclohexylhydroxylamine Chemical compound ONC1CCCCC1 GUQRKZPMVLRXLT-UHFFFAOYSA-N 0.000 description 1
- RRUADNNEIGVWSQ-UHFFFAOYSA-N n-ethyl-n-methylhydroxylamine Chemical compound CCN(C)O RRUADNNEIGVWSQ-UHFFFAOYSA-N 0.000 description 1
- VDUIPQNXOQMTBF-UHFFFAOYSA-N n-ethylhydroxylamine Chemical compound CCNO VDUIPQNXOQMTBF-UHFFFAOYSA-N 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
産業上の利用分野
この発明はヒドロキシルアミン類の安定化法に
関するものである。
ヒドロキシルアミン類、特にアルキル基等で置
換されたヒドロキシルアミン類は、強い還元力を
有し、種々の化学反応に用いられる他、酸化防止
剤、ラジカル重合の禁止剤として広い用途を有し
ている。
特にＮ，Ｎ−ジエチルヒドロキシルアミンやヒ
ドロキシルピペリジンなどの低毒性の置換ヒドロ
キシルアミンは、ブタジエン、スチレン等のオレ
フイン化合物のポツプコーン重合禁止剤として広
く用いられている。
本発明は酸化に対して不安定で、製造時や貯蔵
時に分解しやすいこれらのヒドロキシルアミンを
安定化する手段を提供するものである。
従来の技術
Ｎ，Ｎ−ジアルキルヒドロキシルアミン類の安
定化剤としては、米国特許第1033260に記載され
ているような、ジアルキルジチオカルバメート類
のアルカリ金属塩が知られている。また、ヒドロ
キシルアミンの安定化剤としてフエノール類が知
られている（特公昭52−48118）．
発明が解決しようとする問題点
しかしヒドロキシルアミン類、特に窒素原子が
アルキル基やアルキレン基で置換されたヒドロキ
シルアミンは、強い還元力をもち、極めて容易に
酸化される。そして通常の酸化防止効果にもとず
く安定剤では十分な安定化効果が得られず、劣化
し易かつた。
本発明は、きわめて劣化の早いヒドロキシルア
ミン類を安定化し、それにより例えば高温を用い
る熱分解法においてもヒドロキシルアミン類を収
率よく製造することを可能にし、また製品の長期
間貯蔵を可能にするための安定化方法を提供する
ものである。酸化などの副反応防止は、逐次的に
起る異常反応の可能性による危険を防ぎ、安全を
確保するためにも重要である。
従来ヒドロキシルアミン類の製造方法として、
アミン類の酸化、３級アミンオキシドの熱分解お
よびアルドキシムの水素添加等の方法が知られて
いるが、生成したヒドロキシルアミン類が酸化さ
れやすいため、一般に生成物を速やかに系外に取
出す等の工夫が必要である。特に熱分解法では、
熱による劣化が著しく、また酸化法では更に酸化
されて収率が低下してしまうことが常である。し
かし、系外へ取出す方法にも限界があり、系内に
滞留する間に一部が劣化することは避けられなか
つた。また、製品ヒドロキシルアミン類を輸送あ
るいは貯蔵する際にも酸素、光、熱による劣化が
著しいため安定化剤の使用は不可避であるが、従
来の安定化剤は、十分満足な性能を有するもので
なかつた。
問題点を解決するための手段
本発明者らは、これらヒドロキシルアミン類の
劣化対策につき根本的に究明した結果、ヒドロキ
シルアミンの酸化・劣化の原因は単に雰囲気中の
酸素だけによるものでなく、ヒドロキシルアミン
類を工業的に製造する際に装置から混入して、反
応液や製品中に存在しやすいある種の金属、例え
ば、鉄、銅などの微量が酸素による酸化を促進す
ることによる影響が大きいことを見出し、更にこ
れらの金属の悪影響を防ぐのに錫酸の添加が有効
であることを見出して本発明を完成した。
すなわち本発明は錫酸を添加することを特徴と
するヒドロキシルアミン類の安定化法である
ヒドロキシルアミン類
本発明の対象とするヒドロキシルアミン類は、
一般式
で表わすことができる。式中R1はアルキル基で
ありR2は水素原子またはアルキル基である。但
しR1またはR2においてアルキル基とは、本来の
アルキル基（炭素数６以下の低級アルキル基が普
通である）のほかに、シクロアルキル基（C5〜
C6）、低級アルケニル基やそれらの低級アルキル
置換体をも便宜上含み、またR1とR2が連なつて
テトラメチレン基またはペンタメチレン基を形成
する場合およびそれらの低級アルキル置換体をも
含むものとする。
例えばＮ−メチルヒドロキシルアミン、Ｎ，Ｎ
−ジメチルヒドロキシルアミン、Ｎ−メチル−Ｎ
−エチルヒドロキシルアミン、Ｎ−エチルヒドロ
キシルアミン、Ｎ，Ｎ−ジエチルヒドロキシルア
ミン、Ｎ，Ｎ−ジプロピルヒドロキシルアミン、
Ｎ，Ｎ−ジ−tert−ブチルヒドロキシルアミン、
Ｎ−シクロヘキシルヒドロキシルアミン，Ｎ−ヒ
ドロキシルピペリジン等が本発明の対象物であ
り、それらの代表的なものはＮ，Ｎ−ジエチルヒ
ドロキシルアミンである。
錫酸の添加
本発明の特徴をなす安定化剤は錫酸である。錫
酸は普通アルカリ金属塩、代表的には最も入手し
やすく、効果も優れている錫酸ナトリウムとして
用いられる。塩でない錫酸や、カリウム、リチウ
ム、カルシウム、マグネシウム等その他の金属の
塩でもヒドロキシルアミン類の安定性を害しない
限りは用いることができる。
ヒドロキシルアミン類は、液体または溶液状態
において、錫酸の添加により著しく安定化され
る。最も普通の実施形態は、ヒドロキシルアミン
類またはその原料を含む水溶液中に錫酸を添加し
溶解させるものである。その他、有機溶媒溶液や
液体状や塩酸塩水溶液など、いろいろな状態のヒ
ドロキシルアミン類に錫酸を添加してもよい。添
加量は、安定化させるべきヒドロキシルアミン類
の環境、すなわち金属の混入程度、処理温度など
に応じてきめられ、鉄や銅などの原子の存在量に
対して過剰量、通常３〜30モル倍程度加える。
0.1ppmから10000ppm、特に１〜300ppmの添加
が普通に用いられる。
発明の効果
本発明による錫酸に添加は、ヒドロキシルアミ
ン類の実際の使用条件下、例えばアミンオキシド
の熱分解温度で、水の存在下、金属またそのイオ
ンが混入している状態で長時間安定化効果を発揮
し、製造時の収率低下を十分抑制する。また、ヒ
ドロキシルアミン類の製品を長期間貯蔵すること
を可能にする。
以下具体例に基づいて本発明を説明する。
Ｎ，Ｎ−ジエチルヒドロキシルアミンとジエチ
ルアミンの定量分析は、0.1N塩酸を用いて求め
た自動滴定曲線に基づいて計算した。
実施例 １
トリエチルアミンオキシド（TEAO）水溶液
を熱媒液体中に滴下し、生成物を溜去しつつ120
℃で熱分解させることにより、Ｎ，Ｎ−ジエチル
ヒドロキシルアミンを製造した（特公昭39−
13056参照）。この間、原料TEAO中にFe3+イオ
ン1.4ppmを含む場合の収率（対TEA0）は86.2％
であり、Ｎ，Ｎ−ジエチルヒドロキシルアミンの
分解により副生するジエチルアミンの収率は7.4
％である。
錫酸ナトリウムを添加したところ（添加量は
Fe3+イオンに対するモル比）第１表のようにＮ，
Ｎ−ジエチルヒドロキシルアミン（DEHA）の
収率は改善されジエチルアミン（DEA）の副生
は減少した。
INDUSTRIAL APPLICATION FIELD This invention relates to a method for stabilizing hydroxylamines. Hydroxylamines, especially hydroxylamines substituted with alkyl groups, etc., have strong reducing power and are used in various chemical reactions, and have a wide range of uses as antioxidants and radical polymerization inhibitors. . In particular, low toxicity substituted hydroxylamines such as N,N-diethylhydroxylamine and hydroxylpiperidine are widely used as popcorn polymerization inhibitors for olefin compounds such as butadiene and styrene. The present invention provides a means to stabilize these hydroxylamines, which are unstable to oxidation and prone to decomposition during production and storage. Prior Art As stabilizers for N,N-dialkylhydroxylamines, alkali metal salts of dialkyldithiocarbamates, as described in US Pat. No. 1,033,260, are known. Phenols are also known as stabilizers for hydroxylamine (Japanese Patent Publication No. 48118/1983). Problems to be Solved by the Invention However, hydroxylamines, particularly hydroxylamines in which the nitrogen atom is substituted with an alkyl group or an alkylene group, have strong reducing power and are extremely easily oxidized. Further, stabilizers based on ordinary antioxidant effects could not provide a sufficient stabilizing effect and were susceptible to deterioration. The present invention stabilizes hydroxylamines that deteriorate extremely quickly, thereby making it possible to produce hydroxylamines in good yield even in thermal decomposition methods using high temperatures, and making it possible to store products for a long period of time. The present invention provides a stabilization method for Prevention of side reactions such as oxidation is also important to prevent dangers due to the possibility of sequential abnormal reactions and to ensure safety. Conventional methods for producing hydroxylamines include:
Methods such as oxidation of amines, thermal decomposition of tertiary amine oxide, and hydrogenation of aldoximes are known, but since the generated hydroxylamines are easily oxidized, it is generally necessary to quickly remove the products from the system. Some effort is needed. Especially in the pyrolysis method,
Deterioration due to heat is significant, and oxidation methods usually result in further oxidation and a decrease in yield. However, there are limits to the method of taking it out of the system, and it is inevitable that some of it will deteriorate while it remains in the system. In addition, when transporting or storing product hydroxylamines, the use of stabilizers is unavoidable because they are significantly degraded by oxygen, light, and heat, but conventional stabilizers do not have sufficiently satisfactory performance. Nakatsuta. Means for Solving the Problems As a result of fundamental investigation into countermeasures against deterioration of these hydroxylamines, the present inventors found that the cause of oxidation and deterioration of hydroxylamine is not simply due to oxygen in the atmosphere, but also due to hydroxyl amines. When amines are manufactured industrially, trace amounts of certain metals, such as iron and copper, which tend to be mixed in from the equipment and present in the reaction solution or product, have a large effect because they promote oxidation by oxygen. They found that the addition of stannic acid is effective in preventing the adverse effects of these metals, and completed the present invention. That is, the present invention is a method for stabilizing hydroxylamines, which is characterized by adding stannic acid. Hydroxylamines targeted by the present invention are:
general formula It can be expressed as In the formula, R 1 is an alkyl group, and R2 is a hydrogen atom or an alkyl group. However, the alkyl group in R 1 or R 2 refers to not only the original alkyl group (usually a lower alkyl group with 6 or less carbon atoms) but also a cycloalkyl group (C5 to
C6), lower alkenyl groups and their lower alkyl substituents are also included for convenience, and cases where R 1 and R 2 are linked to form a tetramethylene group or pentamethylene group and their lower alkyl substituents are also included. . For example, N-methylhydroxylamine, N,N
-dimethylhydroxylamine, N-methyl-N
-ethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, N,N-dipropylhydroxylamine,
N,N-di-tert-butylhydroxylamine,
N-cyclohexylhydroxylamine, N-hydroxylpiperidine, etc. are objects of the present invention, and a typical example thereof is N,N-diethylhydroxylamine. Addition of stannic acid The stabilizing agent that characterizes the present invention is stannic acid. Stannic acid is commonly used as an alkali metal salt, typically sodium stannate, which is the most readily available and most effective. Non-salt stannic acid and salts of other metals such as potassium, lithium, calcium, and magnesium can also be used as long as they do not impair the stability of the hydroxylamines. Hydroxylamines, in liquid or solution state, are significantly stabilized by the addition of stannic acid. The most common embodiment is to add and dissolve stannic acid into an aqueous solution containing the hydroxylamines or raw materials thereof. In addition, stannic acid may be added to hydroxylamines in various states such as an organic solvent solution, a liquid state, or an aqueous hydrochloride solution. The amount added is determined depending on the environment of the hydroxylamines to be stabilized, i.e. the degree of metal contamination, the processing temperature, etc., and is usually an excess amount, usually 3 to 30 times the amount of atoms such as iron or copper. Add degree.
Additions from 0.1 ppm to 10,000 ppm, especially from 1 to 300 ppm are commonly used. Effects of the Invention The addition to stannic acid according to the present invention is stable for a long time in the presence of water and in the presence of metals or their ions under the conditions of actual use of hydroxylamines, for example at the thermal decomposition temperature of amine oxide. It exhibits a chemical effect and sufficiently suppresses yield loss during production. It also allows products of hydroxylamines to be stored for long periods of time. The present invention will be explained below based on specific examples. Quantitative analysis of N,N-diethylhydroxylamine and diethylamine was calculated based on an automatic titration curve determined using 0.1N hydrochloric acid. Example 1 An aqueous solution of triethylamine oxide (TEAO) was dropped into a heat transfer liquid, and the product was distilled off at 120°C.
N,N-diethylhydroxylamine was produced by thermal decomposition at
13056). During this period, the yield (vs. TEA0) was 86.2% when the raw material TEAO contained 1.4 ppm of Fe 3+ ions.
The yield of diethylamine produced by the decomposition of N,N-diethylhydroxylamine is 7.4.
%. When sodium stannate was added (the amount added was
molar ratio to Fe 3+ ions) As shown in Table 1, N,
The yield of N-diethylhydroxylamine (DEHA) was improved and the by-product of diethylamine (DEA) was reduced.
【表】
なお、特にFe3+イオンを含まない原料を用い
た場合の収率は98.1％である。
実施例 ２
実施例１と同様の方法において、原料トリエチ
ルアミンオキシド中にCu2+イオン3.4ppmを含む
場合のＮ，Ｎ−ジエチルヒドロキシルアミン収率
は95.3％（DEA副生2.5％）であつた。
錫酸ナトリウムを12.0（添加量はCu2+イオンに
対するモル比）添加したところ、Ｎ，Ｎ−ジエチ
ルヒドロキシルアミンの収率は96.6％（DEA副
生1.5％）に向上した。
実施例 ３
Fe3+イオンを0.7ミリモル／１含むＮ，Ｎ−ジ
エチルヒドロキシルアミン水溶液（初期濃度20.5
重量％）を70℃で５日間保つた後、Ｎ，Ｎ−ジエ
チルヒドロキシルアミンを定量したところ、7.5
％にまで低下していた。加熱前に錫酸ナトリウム
を2.5ミリモル／１加えた場合は、15.8％であつ
た。錫酸ナトリウム添加量5.0ミリモル／１の場
合は加熱後の濃度19.7％であつた。
比較例
実施例３と同様の試験を下記の物質について行
なつたが、いずれも効果がなかつた。
ピロガロール、カテコール、２，３−ジヒドロ
キシナフタレン、２，３−ジヒドロキシ安息香
酸、４−tert−プチルカテコール
EDTA−2Na塩を添加した場合も、ほとんど
のDEHAが１日で消失してしまい、慣用の金属
封鎖剤ではDEHAの安定化効果が認められなか
つた。
ジエチルジチオカルバミン酸亜鉛５ミリモル／
１を添加した場合は、70℃で５日間保つた後の
Ｎ，Ｎ−ジエチルヒドロキシルアミン濃度は12.3
％であり、添加量を10ミリモル／１としても13.2
％としか残つていなかつた。[Table] Note that the yield is 98.1% when raw materials containing no Fe 3+ ions are used. Example 2 In the same method as in Example 1, the yield of N,N-diethylhydroxylamine was 95.3% (DEA by-product 2.5%) when 3.4 ppm of Cu 2+ ions were contained in the raw material triethylamine oxide. When sodium stannate was added at a molar ratio of 12.0% to Cu 2+ ions, the yield of N,N-diethylhydroxylamine was improved to 96.6% (DEA by-product: 1.5%). Example 3 N,N-diethylhydroxylamine aqueous solution containing 0.7 mmol/1 Fe 3+ ion (initial concentration 20.5
% by weight) at 70°C for 5 days, N,N-diethylhydroxylamine was quantified and found to be 7.5
%. When 2.5 mmol/1 sodium stannate was added before heating, the concentration was 15.8%. When the amount of sodium stannate added was 5.0 mmol/1, the concentration after heating was 19.7%. Comparative Example Tests similar to those in Example 3 were conducted on the following substances, but none had any effect. Pyrogallol, catechol, 2,3-dihydroxynaphthalene, 2,3-dihydroxybenzoic acid, 4-tert-butylcatechol Even when EDTA-2Na salt was added, most of the DEHA disappeared within a day, and conventional metals No stabilizing effect of DEHA was observed with the sequestrant. Zinc diethyldithiocarbamate 5 mmol/
When 1 was added, the N,N-diethylhydroxylamine concentration after being kept at 70℃ for 5 days was 12.3
%, and assuming the amount added is 10 mmol/1, it is 13.2
There was only % left.
Claims (1)
ルアミン類の安定化法。1. A method for stabilizing hydroxylamines, characterized by adding stannic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11551184A JPS60260541A (en) | 1984-06-07 | 1984-06-07 | Method for stabilizing hydroxylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11551184A JPS60260541A (en) | 1984-06-07 | 1984-06-07 | Method for stabilizing hydroxylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60260541A JPS60260541A (en) | 1985-12-23 |
| JPH0436147B2 true JPH0436147B2 (en) | 1992-06-15 |
Family
ID=14664330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11551184A Granted JPS60260541A (en) | 1984-06-07 | 1984-06-07 | Method for stabilizing hydroxylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60260541A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5141730A (en) * | 1991-05-23 | 1992-08-25 | American Cyanamid Company | Stabilization of hydroxylamine solutions |
| US5906805A (en) * | 1997-04-30 | 1999-05-25 | Alliedsignal Inc. | Stabilized hydroxylamine solutions |
| JP6996306B2 (en) * | 2017-01-16 | 2022-02-04 | 三菱ケミカル株式会社 | Method for producing bisphenol compound |
-
1984
- 1984-06-07 JP JP11551184A patent/JPS60260541A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60260541A (en) | 1985-12-23 |
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