TW542858B - Method and composition for inhibiting corrosion in aqueous systems - Google Patents
Method and composition for inhibiting corrosion in aqueous systems Download PDFInfo
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五、發明說明(1 ) 相關申請案件之對照參# 本申請案件為登記於1998年8月19日第09/136·884號 之部伤繼續申請案件,登記於1999年5月3日第〇9/3〇3,596 號之部份繼續申請案件,登記於1999年5月3曰第 09/3 04,181號之部份繼續申請案件,及登記於1999年$月口 曰第09/309,564號之部份繼續φ請案件。這些中請案件的 各揭示内容全部加入為參考資料。 金屬廣泛地被使用在含水相系統裝置的結構。“水相 系統”的意思是指任何包含其中含有或經常性接觸水相液 體系統的金屬。以水為主的液體通常是指液體中含有至少 大約50重量比的水,其餘的是固體(懸浮的及/或溶解的) 及/或非水相液體。水相液體一詞是要包括不只以水為主 的液體,同時也是主要非水相,但有足夠的水,至少大約 5重量比的水存在㈣體,使得水溶性處理組成份可以有 效的使心限制錢。這種非水相液體可以是與水互混或 不互混的。 但不限制於,以蒸發得到其冷 一般的水相系統包括 閉回路冷卻系統,鍋爐 置’逆滲透裝置,油品 ’氣體洗滌塔,鼓風爐 卻源的開放式再循環冷卻系統,密 和類似的蒸汽發生系統,熱交換震 生產系統’快速蒸發器,脫鹽工廠 ,紙和紙漿加工裝置,蒸汽發電廠,地熱系統,食物和飲 料加工裝置’魏蒸發器,採礦“,洗«置,土壤授 拌系統’住家或商業用途的密閉回路加熱系統,水相為主 的冷凌系、统,沈降系統,水相切割液體(例如用於 542858 五、發明說明( 消 礙磨’錢孔,拉肖,|,私处 拉、、、糸,旋轉,切割,縫製,磨床和螺 紋切割加工或非切宝彳士 ’、 口J成形,懸壓,拉絲或壓製加工), 相打磨系統,水抖r β , 一醇防/東系統,水/乙二醇水力液體 ,鐵表面預處理,聚合物塗覆系統等等。多種不同形態的 κ可乂使用於&種系統,例如新鮮水,半驗水,海水,食 鹽水,垃圾廢棄物,工業廢水等等。 < 〃可以用本發明組成物處理的水相系統可能含有溶解的 " 可月匕是自周圍空氣吸附氧得到的,或它們可以實質 的或凡王/又有氧。另外,水相系統中可能含有其他溶解的 孔體,如一iU匕碳,硫化氯或氨或可能實質的或完全的沒 有這些氣體。 在水相系統中可能遇到數個不同方式的腐敍。例如水 相系統可能在整個金屬表面均勻地腐姓。水相系統也可能 有局部化的腐敍H點或裂隙賴,只有在金屬表面的 -些位置發現腐蝕。通常’局部化腐蝕的控制可能是延長 金屬裝置在水相线中可料命的關鍵因子。特別是含有 高含量侵略性陰離子的水相系統’如氣化物和硫酸鹽,特 別可能受到-般化和局部化的攻擊。這些侵略性陰離子可 能以可造成問題的含量存在於用於水相系統的水源,或它 們可能在水相“中濃縮為有害的含量,因為它們是蒸發 水系統的一部份,如蒸發性的冷卻系統。 局部化腐蝕可能較一般的腐蝕對系統正常操作造成 大威脅’因為這種腐蝕集中發生於一個位置,可能造成 統攜帶液體流構造的穿孔。明顯的,這些穿孔可#芒成 項 頁 # 更系 漏 6 542858V. Description of the invention (1) References to related application cases # This application case is a case of continuing injury application registered on August 19, 1998 No. 09/136 · 884, and was registered on May 3, 1999. Part of 9 / 3〇3,596 continued to apply for the case, registered on May 3, 1999 No. 09/3 04,181, continued to apply for the case, and was registered in 1999 Yueyuekou No. 09 / 309,564 Part of the case continues. The disclosures of these cases are all incorporated as reference materials. Metals are widely used in the structure of aqueous phase system devices. By "aqueous phase system" is meant any metal that contains or regularly contacts an aqueous phase liquid system. Water-based liquids usually refer to liquids containing at least about 50% by weight of water, with the remainder being solid (suspended and / or dissolved) and / or non-aqueous liquids. The term aqueous phase liquid is intended to include not only water-based liquids, but also the non-aqueous phase, but there is sufficient water, and at least about 5 weight ratio of water is present in the carcass, so that the water-soluble components can effectively use Heart limits money. This non-aqueous liquid can be miscible or immiscible with water. But it is not limited to the common water phase system obtained by evaporation, including closed-loop cooling systems, boilers with 'reverse osmosis devices, oil' gas scrubbing towers, and open recirculation cooling systems from blast furnaces, dense and similar Steam generation system, heat exchange shock production system 'rapid evaporator, desalination plant, paper and pulp processing plant, steam power plant, geothermal system, food and beverage processing plant' Wei evaporator, mining ', washing «set up, soil mixing System 'Closed loop heating system for home or commercial use, water-based cooling systems, systems, sedimentation systems, water-phase cutting liquids (eg, for use in 542858 V. Description of the invention (In order to prevent grinding of money holes, Lashaw, |, Private parts, drawing, sewing, rotating, cutting, sewing, grinding and thread cutting processing or non-cutting jewelers', mouth J forming, suspension pressing, wire drawing or pressing processing), phase grinding system, water shaking r β, Mono alcohol / East system, water / glycol hydraulic liquid, iron surface pretreatment, polymer coating system, etc. Many different forms of κ can be used in & systems, for example Fresh water, semi-tested water, seawater, salt water, garbage waste, industrial wastewater, etc. <; The aqueous system that can be treated with the composition of the present invention may contain dissolved " Obtained, or they can be substantial or king / aerobic. In addition, the aqueous system may contain other dissolved pores, such as iU carbon, chlorine sulfide or ammonia or may be substantially or completely free of these gases. There may be several different types of corruption in the water phase system. For example, the water phase system may uniformly rot on the entire metal surface. The water phase system may also have localized corrosion points H or cracks, only in the metal Corrosion found at some locations on the surface. Often 'control of localized corrosion may be a key factor in extending the life expectancy of metal installations in the aqueous phase line. Especially aqueous systems containing high levels of aggressive anions' such as gaseous and sulfuric acid Salts are particularly likely to be attacked by generalization and localization. These aggressive anions may be present in problematic amounts in water sources used in aqueous systems, or they Can be concentrated in the water phase to harmful levels because they are part of an evaporative water system, such as an evaporative cooling system. Localized corrosion may pose a greater threat to the normal operation of the system than ordinary corrosion. 'Because of this corrosion Concentrations occur in one location, and may cause perforations that carry liquid flow structures. Obviously, these perforations can be # 芒 成 项 页 # More systematic leakage 6 542858
經濟部智慧財產局員工消費合作社印製 而要關掉整個水相系統才能夠整修。事實上,腐餘問 題常常造成巨大的維護費用,以及裝置損壞結果的費用。 口此水相系統中金屬腐蝕的抑制是重要的。 在下面的說明中,我們使用寡聚物,聚合物,共募聚 矛/、χΚ物這些詞彙。寡聚物的意思是指單一單體聚合 反應得到的物料,其中加人產物之單體單元的數目是在2 矛大、、勺10之間。$合物的意思、是指單一單體聚合反應得到 的=^有限制加人產物之單體單元的數目。共寡聚物 、^ ^疋扼夕於一種單體(包括2,3,4個等不同的單體) 水合反應得到的物料,加人產物之單體單元的總數目在2 矛大、力10之間。共聚物的意思是指多於一種的單體(包括2 ,3,4個等不同的單體)聚合反應得到的物料,沒有限制 加入產物之單體單元的數目。 在水相系統中,金屬,如鋼,發生下面的腐姓反應: Fe〇Fe2++2e- Fe(〇H)2+ 〇HOFe(OH)3+e· 當使用氧化還原電位高於腐蝕金屬或合金的四唑鏘化 。物,四唑鑰分子很快地在金屬,如鋼或不銹鋼,的表面 上發生還原作用,形成不可溶的物料而避免鋼再繼續腐蝕 〇 本發明方法包含用下面化學通式的四唑繙鹽處理工業 水: /、 裝— (請先閱讀背面之注意事項再填寫本頁) . ;線· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -I I I- 1 542858 五 經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the entire water phase system must be turned off for refurbishment. In fact, the problem of corrosion often results in huge maintenance costs and the cost of equipment damage. The suppression of metal corrosion in this aqueous phase system is important. In the following description, we use the terms oligomer, polymer, co-aggregation spear / χκ. The oligomer refers to the material obtained by the polymerization of a single monomer. The number of monomer units added to the product is between 2 and 10. The meaning of the $ compound means that the number of monomer units added to the product is limited by the polymerization of a single monomer. Co-oligomers, ^ ^ 疋 Condensed on a single monomer (including 2, 3, 4 and other different monomers) The material obtained by the hydration reaction, the total number of monomer units added to the product is 2 Between 10. Copolymer means the material obtained by polymerization of more than one monomer (including 2, 3, 4 and other different monomers). There is no limit to the number of monomer units added to the product. In aqueous systems, metals such as steel undergo the following scumming reactions: Fe〇Fe2 ++ 2e- Fe (〇H) 2+ 〇HOFe (OH) 3 + e · When the oxidation-reduction potential is higher than that of corrosive metals Or the tetrazole of the alloy. The tetrazolium molecule quickly reduces on the surface of metal, such as steel or stainless steel, to form insoluble materials to prevent the steel from continuing to corrode. The method of the present invention includes using a tetrazolium salt of the chemical formula Treatment of industrial water: / 、 Loading — (Please read the precautions on the back before filling this page).; Line · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -II I- 1 542858 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
發明說明(Invention Description (
其中Κ’ΙΜΑ可以是各種不同的有機的和無機的取代基 ,如由較低級録,芳基,Μ基,和雜環取代的芳基所 組成之族者’但是必須R|,R2stR3都不含有多於14個碳原 子’及η可以是1或2。 化合物中可含有正的或負的平衡離子來平衡上面構造 的電荷。這種化合物化學或電化學還原得到四唑啉和甲臢 ’很快地吸附於金屬表面’提供腐蝕保護的薄膜。 本發明者也發現一些下面化學通式的四唑鏘化合物: Ν=/ Ν R3 ^ η 其中R1 ’ R;2和R;可以是各種不同的有機的和無機的取代基 ’如由較低級烷基,分枝的較低級烷基,芳基,取代的芳 基,烷芳基,取代的烷芳基和雜環取代的芳基所組成之族 者,但是必須Ri,R2或R3都不含有多於14個碳原子,及 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) I ---I l· I I I ^ . I I--I I I « (請先閱讀背面之;i意事頊存填寫本頁) 542858 A7 五、發明說明( 經濟部智慧財產局員工消費合作社印製 可以是1或2,協同地與多種化合物合併,提供水相系統中 金屬一般和局部化腐蝕有效的保護。如果選擇要與四唑鏘 化合物合併的組成份也是水垢及/或沈積抑制劑,該組合 也會提供這些水相系統的水垢及/或沈積抑制。 陰離子及/或陽離子可以伴隨上面的構造來平衡決定 於使用的取代物的電荷。如果Ri,有都是中性的 ,則顯示於上面的化學式的構造會是正電荷的,就需要陰 離子種系。 用於平衡的陰離子及/或陽離子可以是任何如鹵基, 确酸根,亞石肖酸根,碳酸根,石炭酸氣根,硫酸根,鱗酸根 ,和過渡金屬含氧酸的陰離子及/或陽離子。 陰離子及/或陽離子可以伴隨上面的構造來平衡決定 於使用取代物的電荷。如果Ri,Μ%所有的都是中性的 ,然後顯示於上面化學式的構造會是正的電荷,就會需要 陰離子種系。例如如本發明的四唑鑽化合物是中性的。在 最簡單的情況下,如果所有的R!,心和心都是中性的,當 卜則需要一個單一負電荷的陰離子,如,的平衡離 子來平衡電荷。當n=2,則需要二個陰離子,各帶一個單 一負電荷或一個雙負電荷的陰離子,如SCV2,來平衡電 何。此外,例如伴隨Ri,&和&的電荷不是中性的,例如 如果這基團包括磺酸基,羧基及/或四級氮,必須存在有 伴卩远的平衡離子提供四唾|翁化合物的中性電荷。因此, 如如果n=2,Ri以一個單一羧基團(c〇〇·)取代,則該四 鏘化合物可以是一個氯化鋅鹽,其中Zn+2中和二個羧基電 例 口坐Wherein K′ΙΜΑ can be a variety of organic and inorganic substituents, such as those consisting of lower-order, aryl, M, and heterocyclic substituted aryl 'but must be R |, R2stR3 Not containing more than 14 carbon atoms' and η may be 1 or 2. Compounds can contain positive or negative counterions to balance the charge on the structure above. This compound is chemically or electrochemically reduced to obtain a thin film of tetrazoline and formazan which is quickly adsorbed on the metal surface to provide corrosion protection. The present inventors have also discovered some tetrazolium compounds of the general chemical formula: Ν = / Ν R3 ^ η where R1 'R; 2 and R; can be a variety of different organic and inorganic substituents' such as by lower Alkyl, branched lower alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and heterocyclic substituted aryl groups, but all must be Ri, R2, or R3 Does not contain more than 14 carbon atoms, and this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) I --- I l · III ^. I I--III «(Please read the back first (I intend to fill in this page) 542858 A7 V. Description of the invention (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be 1 or 2, which can be combined with a variety of compounds to provide general and local metal in the water phase system Effective protection against chemical corrosion. If the components chosen to be combined with the tetrazolium compound are also scale and / or deposition inhibitors, this combination will also provide scale and / or deposition inhibition for these aqueous systems. Anions and / or cations can With the above structure, the balance depends on the usage. If Ri is neutral, the structure of the chemical formula shown above will be positively charged, and an anion species is required. The anion and / or cation used for the balance can be any such as halo, indeed Anions and / or cations of acid, shoshate, carbonate, carbolic acid, sulfate, phosphonate, and transition metal oxo acids. Anions and / or cations can be balanced with the above structure depending on the use of substituents If all of Ri and M% are neutral, then the structure shown in the above chemical formula will be a positive charge, and an anion germline will be required. For example, the tetrazole diamond compound of the present invention is neutral. In the simplest case, if all R !, the heart and the heart are neutral, then a single negatively charged anion, such as the counter ion, is needed to balance the charge. When n = 2, two are needed Anions, each with a single negative charge or a double negative charge, such as SCV2, to balance the electric charge. In addition, for example, the charges accompanying Ri, & and & are not neutral, such as If this group includes a sulfonic group, a carboxyl group, and / or a quaternary nitrogen, there must be a counter ion with a distant counter ion to provide a neutral charge of the tetrasalene compound. Therefore, if n = 2, Ri has a single carboxyl group (C〇 ··) substitution, the tetrafluorene compound may be a zinc chloride salt, in which Zn + 2 neutralizes two carboxyl groups.
--------------裝--- (請先閱讀背面之注意事項再填寫本頁) 訂 線· 542858 A7 B7 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 五、發明說明(6 ) 荷,而cr中和二個環氮的正電荷。 這種可以如本發明使用的四唑鏘化合物的實施例包括 硝基藍四唑鏘氯化物(3,3,-(3,3,-二甲氧基-4,4M申聯苯基)-雙-[2-對-硝苯基-5-苯基-2H-四唑鏺氯化物]),此後稱之為 NBT,二苯乙烯基硝基藍四唑鏘氯化物(2,2,_二-對-硝苯 基-5,5 - 一本乙婦基-3,3’-[3,3’-二曱氧基-4,4’-伸聯笨基]二 四嗤鍇氯化物),此後稱之為DNBT,四硝基藍四唑鏘氯化 物(3,3’-(3,3’_二甲氧基-4,4,-伸聯苯基雙-[2,5-對-硝苯基 四唾鏘氯化物]),此後稱之為TNBT,及碘硝基四唑鐵氣 化物(2-(4-碘苯基)-3-(4-硝苯基)_5·苯基四唑繙氣化物), 此後稱之為INT。 水相系統中的金屬可以是任何可以避免腐蝕及/或長 水垢的金屬。例如這些金屬可以是非鐵金屬,如銅,鋁或 鐵金屬,如鐵,鋼,例如低碳鋼,和不銹鋼,例如鐵以為 主’含有絡為主要合金元素的合金,如含有大約m3〇% 之間Cr的鋼,它對許多環境有極佳的腐蝕抗性。 本發明甚至沒有添加入其他物料,包括其他抗腐钱及 /或水垢避免組成份’當單獨使用时鐵化合物時,也可 以用低濃度的四咕鐵化合物提供特別有利的結果。这特別 是當四唾鑕化合物使用的水相系統,在氧存在下’處理系統的pH為大約6或更大的情況,如冷卻水系統 汽發生系統’氣體洗嶋統,和紙毁和紙製造㈣: 本發明四唾錄化合物可較佳地以範圍自大如 約5…的活性處理含量加到水相系統 約至 蒸 大 (請先閱讀背面之注意事項再填寫本頁) · I--------^---------. t ® ® (cns)a4 (210 五 、發明說明(7) 25 ppm的處理含量是特別佳的。 一個較佳的觀點,本發 不銹鋼腐蝕的方法,1 曰。上制接觸水相系 、 7万居,其中包含引入該系 學式的四唾鑽化合物·· 夕一個下面化-------------- Install --- (Please read the precautions on the back before filling out this page) Threading · 542858 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Note (6), and cr neutralizes the positive charge of the two ring nitrogens. Examples of such tetrazolidine compounds that can be used in accordance with the present invention include nitroblue tetrazolium chloride (3,3,-(3,3, -dimethoxy-4,4M biphenyl)- Bis- [2-p-nitrophenyl-5-phenyl-2H-tetrazolium chloride]), hereinafter referred to as NBT, distyrylnitro blue tetrazolium chloride (2,2, _ Di-p-nitrophenyl-5,5-one ethynyl-3,3 '-[3,3'-dioxo-4,4'-extendylbenzyl] tetrakinium chloride ), Hereinafter referred to as DNBT, tetranitroblue tetrazolium chloride (3,3 '-(3,3'_dimethoxy-4,4, -extendylphenylbis- [2,5- P-Nitrophenyltetrasaline chloride]), hereinafter referred to as TNBT, and iodonitrotetrazole iron gaseous compound (2- (4-iodophenyl) -3- (4-nitrophenyl) _5 · Phenyltetrazole vaporizer), hereafter referred to as INT. The metal in the aqueous system can be any metal that can avoid corrosion and / or scale. For example, these metals can be non-ferrous metals such as copper, aluminum or iron. , Such as iron, steel, such as low-carbon steel, and stainless steel, such as iron-based alloys containing iron as the main alloying element, such as steel containing about Cr between about m3% It has excellent corrosion resistance to many environments. The invention does not even add other materials, including other anti-corrosion money and / or scale avoidance components. When used alone, iron compounds can also be used at low concentrations of four Curry compounds provide particularly favorable results. This is especially the case when the tetrasial compounds are used in an aqueous system where the pH of the treatment system is about 6 or greater in the presence of oxygen, such as a cooling water system steam generation system ' Washing system, and paper destruction and paper manufacturing: The four salivary compounds of the present invention can be preferably added to the water phase system with an active treatment content ranging from as large as about 5 ... to steaming (please read the precautions on the back first) (Fill in this page) · I -------- ^ ---------. T ® ® (cns) a4 (210 V. Description of the invention (7) 25 ppm is particularly good. A better point of view, the method of stainless steel corrosion in the present invention, is 1. The upper system is in contact with the water phase system, 70,000 residences, which includes the introduction of the tetra-sialite compound of the system formula ...
這 經濟部智慧財產局員工消費合作社印製 之 美」其3係擇自由較低級院基,分枝的較低級院 二取代的芳基’㈣基’取代的院芳基和雜環取 方土組成之族者,但是必須R|,〜或〜都不含有多於 14個碳原子;及η為…,如果需要,這種四唾鏘化合物 任擇地含有伴隨的水溶性離子種系以得到中性電荷。 本水相系統Τ包括至少-個其它的水相系、统處理物料 一迖擇要使得泫物料不會實質的還原四唑鐯化合物。 種物料可以與四唑鏘化合物一起或分別地加入。 其他水相系統處理物料係擇自由下面化合物所組成〜 才矢者·無機磷酸鹽,硼酸鹽,亞硝酸鹽,在水中釋放金屬 陰離子的化合物,2,3-二羥基苯酸,ι,ι〇-啡啉,聚羧酸酯 ’煙基聚羧酸酯,烷基羥基羧酸,胺基羥基琥珀酸,羧基 胺’聚環氧琥珀酸,修飾的聚環氧琥珀酸,單膦酸,二 酸’膦酸基羧酸,羥基膦酸基羧酸,胺基膦酸,膦酸基 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 11 542858 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(8 ) 基胺氧化物’聚合的胺氧化物’聚峻聚胺基亞曱基鱗酸g旨 ,聚醚聚胺基-亞甲基鱗酸酯N-氧化物,亞胺基亞甲基鱗 酸,肌胺酸之長鏈脂肪酸衍生物;調聚的,共調聚的,聚 合的或共聚合的含碳羧酸酯,鹼金屬矽酸鹽,單氣填酸鹽 ’胺’ 一胺’烧醇胺胺’脂肪胺和二胺,四級化胺, 氧烷基化胺,烷基吡啶,四唑,咪唑啉和取代的味0坐,林, 酸胺胺’聚胺’聚伸烧基聚胺’苯續酸之院基衍生物,苯 酸鹽和取代的苯酸鹽,胺基苯酸鹽,水揚酸鹽,二聚酸_ 三聚酸,石油氧化物,硼葡萄糖酸鹽;木質素,木質石黃酸 鹽’鞣酸,直鏈C5-Cn單魏酸酷和C4-C15 α,ω-二叛酸g旨; 羧酸和氫硫基羧酸之胺鹽,胺基酸,聚胺基酸,羥基醚酸 和相關的内酯化合物,N-醯基亞胺基二乙酸;三以喷二_ 和三-魏酸,織·和填酸酯類;及單氟鱗酸鹽;它們的水溶 性鹽,及它們的混合物。 此外’如上面的說明,當本發明與其他化合物合併使 用時也提供有利的結果,如揭示於登記於1 998年8月19日 的第09/136,884號,登記於1999年5月3日的第09/303,596 號,登記於1999年5月3日的第09/304,181號,和登記於1999 年5月12曰的第09/309,564號等美國專利申請案件的化合 物,這些揭示内容在此加入作為參考資料。 可以與四唑鏘化合物合併,協同地提供改良的腐蝕保 護的化合物的實施例包括:無機磷酸鹽,如正磷酸鹽或聚 石粦酸鹽,硼酸鹽,亞硝酸鹽,和在水中釋放金屬陰離子的 化合物,其中該金屬陰離子係擇自由鉬酸根,鎢酸根,飢 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) -------- I--l·--I β — II--I I I I I π (請先閱讀背面之注意事項再填寫本頁) 12 542858 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明(9 ) 酸根’偏鈒酸根,鉻酸根所組成之族者或其混合物。 無機碟酸鹽可包括正碟酸鹽,聚碟酸鹽,其水溶性鹽 和其混合物,如正磷酸和焦磷酸之混合物或其水溶性鹽, 如其納鹽和鉀鹽。 蝴酸鹽可包含各種不同的硼酸鹽,如擇自四硼酸鹽, 偏硼酸鹽,及/或正硼酸鹽,如四硼酸鈉或四硼酸鈉水合 物的水溶性硼酸鹽。 _ 硝酸鹽可包括亞琐酸鹽,如亞硝酸鈉。 可以與四唾鏘化合物合併的附加物料包括聚丙烯酸或 聚順·丁烯二酸,如揭示於上面說明的登記於丨999年5月3 曰的美國申請案件第〇9/304·1 81號者。特別佳的聚丙烯酸 和聚順-丁婦二酸的分子量為大約8,〇〇〇或更少。 可以與四°坐鐵化合物合併的附加物料包括聚羧酸酯。 這些聚羧酸酯可以是簡單的脂肪化合物,脂肪鍵含有在4 個和大約20個之間的碳原子,該脂肪鏈以羧基基團多取代 _ (如CVCy α,ω—二羧酸酯或如化合物12,3,^ 丁烷四羧酸) 或其水溶性鹽或可以是聚合的化合物。聚合的聚羧酸酯可 以是含有羧基基團的乙烯不飽和單體的均聚物或共聚物( 包括二I物’四聚合物等)。這些聚致酸醋可包含一個得 自二個或更多個不同的乙烯不飽和單體聚合反應的共聚物 ,各單體含有一個或更多個羧基基團。這種聚合聚羧酸酯 的實施例包括聚丙烯酸,聚順-丁烯二酸,和聚順-丁烯二 酸酐,及其水溶性鹽。另外,聚羧酸酯可以是烴基聚羧酸 酯,如揭示於美國專利案件第4,957,704號者,在此加入 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) -------------裝-----:----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 13 經濟部智慧財產局員工消費合作社印製 542858 A7 ___ B7 五、發明說明(10) 作為參考資料。 可以與本發明四唑鏘化合物合併的附加物料包括具有 下面化學式的烷基羥基羧酸或這種烷基羥基羧酸的混合物: HOOC_(RB 1 )a_(RB2)b-(RB3)c-RB4 其中a,b,和c為0到6的整數,(a+b+c)>0,其中rb1,rB2 ,Rb3包含〇〇或CYZ,其中Y和Z分別擇自基團Η,OH, CHO,COOH,CH3,CH2(OH),CH(OH)2,CH2(COOH), CH(OH)CO〇H,CH2(CHO)和CH(OH)CHO,其選擇要使當 該分子寫為完全水合物的形式時,它最少有一個〇H基團 ,及Rw為Η或COOH,包括這些酸各種不同的立體異構物 和化學相當的環狀,脫水,和水合物形態,及在水中形成 上面化合物的可水解的酯類和縮醛,或這種烷基羥基羧酸 的水溶性鹽。這種羥基羧酸的實施例包括酒石酸,中酒石 酸,檸檬酸,葡萄糖酸,葡萄糖庚糖酸,丙酮二酸和糖質 酸,及其水溶性鹽。 可以與四唑鏘化合物合併的附加物料包括胺基羥基琥 拍酸化合物(或這種胺基羥基琥珀酸化合物的混合物),如 揭示於美國專利案件第5,183,590號者,在此加入作為參 考資料。適合的胺基羥基琥珀酸包括擇自由下面化學通式 化合物所組成之族者: |^C!This is the beauty printed by the employees ’cooperatives of the Intellectual Property Bureau of the Ministry of Economics. The third is to choose free lower-level courtyards, branched lower-level courtyards, and substituted aryl groups. People of soil composition, but must not have R |, ~ or ~ that do not contain more than 14 carbon atoms; and η is ..., if desired, this tetrasialyl compound optionally contains the accompanying water-soluble ion species to Get a neutral charge. The present aqueous phase system T includes at least one other aqueous phase system, which processes the materials one by one so that the materials do not substantially reduce the tetrazolium compound. This material can be added together or separately with the tetrazolium compound. Other water-phase system processing materials are composed of the following compounds ~ Talents · Inorganic phosphate, borate, nitrite, compounds that release metal anions in water, 2,3-dihydroxybenzoic acid, ι, ι〇 -Phenanthroline, polycarboxylates 'nicotinic polycarboxylates, alkyl hydroxycarboxylic acids, aminohydroxysuccinic acids, carboxyamines' polyepoxysuccinic acids, modified polyepoxysuccinic acids, monophosphonic acids, di Acid 'phosphonic acid carboxylic acid, hydroxyphosphonic acid carboxylic acid, aminophosphonic acid, basic phosphonic acid paper standard applicable to China National Standard (CNS) A4 (210 X 297 mm) 11 542858 A7 B7 Intellectual Property Bureau Printed by the staff consumer cooperative V. Description of the invention (8) Polyamine polyamine-methylene phosphonate N- Oxides, iminomethylene linoleic acid, long-chain fatty acid derivatives of sarcosinic acid; telomerized, co-telomerized, polymerized or copolymerized carbon-containing carboxylic acid esters, alkali metal silicates, mono Gas-filled salt 'amine' Monoamine 'Alcoholamine' Fatty and diamines, quaternary amines, oxyalkyl groups Amines, alkylpyridines, tetrazoles, imidazolines and substituted odorants, lin, acid amines, 'polyamines', polyalkylene polyamines, benzoic acid derivatives, benzoates and substituted benzenes Acid salt, amine benzoate salt, salicylate salt, dimer acid_trimer acid, petroleum oxide, borate gluconate; lignin, lignin xanthanate, tannic acid, linear C5-Cn mono-Wei Acid acid and C4-C15 α, ω-diamino acid g; amine salts of carboxylic and hydrothiocarboxylic acids, amino acids, polyamino acids, hydroxy ether acids and related lactone compounds, N-fluorene Diimino diacetic acid; tri- and di-weilic acid, weaving, and filling esters; and monofluorophosphoric acid salts; their water-soluble salts, and mixtures thereof. In addition, 'as explained above, the present invention also provides favorable results when used in combination with other compounds, such as disclosed in No. 09 / 136,884, registered on August 19, 1998, and registered on May 3, 1999. Compounds registered in U.S. Patent Application No. 09 / 303,596, No. 09 / 304,181 on May 3, 1999, and No. 09 / 309,564, dated May 12, 1999. These disclosures are in This is added as a reference. Examples of compounds that can be combined with tetrazolium compounds to provide improved corrosion protection synergistically include: inorganic phosphates, such as orthophosphate or polycarboxylate, borate, nitrite, and release of metal anions in water Compounds, in which the metal anion is selected from free molybdate, tungstate, and paper sizes. Applicable to China National Standard (CNS) A4 (210 X 297). -------- I--l ·- -I β — II--IIIII π (Please read the precautions on the back before filling out this page) 12 542858 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy A family or mixture of acid radicals. The inorganic dish salt may include ortho dish, poly dish salt, a water-soluble salt thereof, and a mixture thereof, such as a mixture of orthophosphoric acid and pyrophosphate, or a water-soluble salt thereof, such as a sodium salt and a potassium salt thereof. Phenates can include various borate salts, such as water-soluble borate salts selected from tetraborate, metaborate, and / or orthoborate, such as sodium tetraborate or sodium tetraborate hydrate. _ Nitrate can include phosphonates, such as sodium nitrite. Additional materials that can be combined with tetrasialyl compounds include polyacrylic acid or polycis-butenedioic acid, as disclosed in the above-mentioned U.S. Application No. 09/304 · 1 81, May 3, 999 By. Particularly preferred polyacrylic acid and polymaleic acid have a molecular weight of about 8,000 or less. Additional materials that can be combined with the four degree iron compound include polycarboxylates. These polycarboxylic acid esters can be simple fatty compounds with fatty bonds containing between 4 and about 20 carbon atoms. The fatty chains are more substituted with carboxyl groups (such as CVCy α, ω-dicarboxylic acid esters or Such as compound 12,3, butane tetracarboxylic acid) or a water-soluble salt thereof or may be a polymerized compound. The polymerized polycarboxylic acid ester may be a homopolymer or a copolymer (including a dimer, a tetramer, etc.) of an ethylenically unsaturated monomer containing a carboxyl group. These polyacids may comprise a copolymer derived from the polymerization of two or more different ethylenically unsaturated monomers, each monomer containing one or more carboxyl groups. Examples of such polymerized polycarboxylic acid esters include polyacrylic acid, polymaleic acid, and polymaleic anhydride, and water-soluble salts thereof. In addition, the polycarboxylic acid ester may be a hydrocarbon-based polycarboxylic acid ester, such as disclosed in US Patent Case No. 4,957,704, which is added to this paper standard applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) --- ---------- Install -----: ---- Order --------- line (Please read the precautions on the back before filling this page) 13 Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 542858 A7 ___ B7 V. Description of Invention (10) is for reference. Additional materials that can be combined with the tetrazolium compound of the present invention include an alkylhydroxycarboxylic acid having the following chemical formula or a mixture of such alkylhydroxycarboxylic acids: HOOC_ (RB 1) a_ (RB2) b- (RB3) c-RB4 Where a, b, and c are integers from 0 to 6, (a + b + c) > 0, where rb1, rB2, Rb3 contains 〇〇 or CYZ, where Y and Z are selected from the groups Η, OH, respectively, CHO, COOH, CH3, CH2 (OH), CH (OH) 2, CH2 (COOH), CH (OH) COOH, CH2 (CHO), and CH (OH) CHO are selected so that when the molecule is written as When fully hydrated, it has at least one OH group, and Rw is fluorene or COOH, including various stereoisomers of these acids and chemically equivalent cyclic, dehydrated, and hydrated forms, and in water Hydrolysable esters and acetals of the above compounds are formed, or water-soluble salts of such alkylhydroxycarboxylic acids. Examples of such hydroxycarboxylic acids include tartaric acid, middle tartaric acid, citric acid, gluconic acid, glucoheptonic acid, pyruvate, and glyconic acid, and water-soluble salts thereof. Additional materials that can be combined with tetrazolium compounds include aminohydroxysuccinic acid compounds (or mixtures of such aminohydroxysuccinic compounds), as disclosed in U.S. Patent Case No. 5,183,590, incorporated herein by reference data. Suitable aminohydroxysuccinic acids include those selected from the group consisting of compounds of the general chemical formula: | ^ C!
RC2~N h〇/^co2h 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -------L---1------- •--N請先閱讀背面之注意事項再填寫本頁} 訂---------· 14 542858 A7 B7 五、發明說明(11 其中RC1為Η或,任擇地以_〇H,-c〇2H,-S03H或笨基取 代的(^至匸4烷基,任擇地以-OH4-C〇2H取代的匕至匕環 烷基或苯基,及RC2為H,任擇地以_〇H4-C〇2H (特別是 包括-CH(C〇2H)CH(OH)(C〇2H)部份者)取代的Cl至c6烷基 ;及 ^C2RC2 ~ N h〇 / ^ co2h This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------- L --- 1 ------- • --N Please read the notes on the back before filling out this page} Order --------- · 14 542858 A7 B7 V. Description of the invention (11 where RC1 is Η or, optionally _〇H, -c〇 2H, -S03H or benzyl substituted (^ to 匸 4 alkyl, optionally substituted with -OH4-CO2H to d-cycloalkyl or phenyl, and RC2 is H, optionally with- H4-C〇2H (especially those including -CH (C〇2H) CH (OH) (C〇2H) moiety) substituted Cl to c6 alkyl; and ^ C2
H02CH02C
VV
^C2 I _ Zc-N C02H^ C2 I _ Zc-N C02H
HO〆 \〇HHO〆 \ 〇H
HO C02H 其中Rq為如上述者,及Zc係擇自由下面基團所組成之族 者:i)(CH2)k-其中 k是一個 2至 10的整數,ii)-(CH2)2-Xc-(CH2)2-其中 Xc為 _〇_,-S-,-NRcr 其中 rC3係擇自由 Η,Ci 至c:6烧基,羥基院基,羧基烧基,醯基, 成之族者’其中RC4係擇自由匕至匕烷基或苯甲基所組成 之族者,和下面化學通式的殘基: 裝-----=---^訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製HO C02H where Rq is as described above, and Zc is a group consisting of the following groups: i) (CH2) k- where k is an integer from 2 to 10, ii)-(CH2) 2-Xc- (CH2) 2-where Xc is _〇_, -S-, -NRcr where rC3 is selected from free fluorene, Ci to c: 6 alkynyl, hydroxyalkyl, carboxyl alkynyl, fluorenyl, adult group 'where RC4 is selected from the group consisting of free alkyl to benzyl or benzyl, and residues of the following general chemical formula: ----- = --- ^ Order --------- line (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
其中R(:2為如上述者, iii)含下面化學通式的殘基: 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 15 542858Where R (: 2 is as above, iii) residues with the following general chemical formula: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 15 542858
五、發明說明(12) 經濟部智慧財產局員工消費合作社印製 (CH2) — 其中Y為H’ Cl至C6烷基,烷氧基,鹵基,-CO,H,-S〇3H ’ m係獨立地為0或卜及p為1或2 ’及 (iv)含下面化學通式的殘基: (CH2)q/Q)S 一 (CRC5Rc6)t —、 (CH2)r^(CRc5RC6)t一 /、中Rc>rC6係獨立地為烧基,〇為9或^至^ 烷基,s為0, 1或2,喺獨立地為〇, 卜 2或3,及r為1或2或其水溶性鹽。這種胺基羥基琥珀酸化 口物較佳的貫施例包括亞胺基二(2_羥基琥珀酸),N,N,-雙 (2-羥基琥珀基}-1,6-己烷二胺,和n,n、雙(2_羥基琥珀基)_ 間-伸二甲笨二胺或其水溶性鹽。較佳的是使用正磷酸或 其水溶性鹽與至少一個胺基羥基琥珀酸的混合物。 可以與四唑鏘化合物合併的附加物料包括羧基胺化合 物’該化合為羧基化劑,如環氧琥珀酸,與包含多重氮原 子的胺’如聚乙烯聚胺,之反應產物,如揭示於國際專利 申請案件W0 96/33953者,在此加入作為參考資料。 可以與四化合物合併的附加物料包括下面化學通式的 聚環氧琥珀酸(此後稱之為PESAs): 本紙張尺度適用中國國家標準(cns)A4規格(210 X 297公釐) 16 -----:----1------- (請先閱讀背面之注意事項再填寫本頁) 一石、·1111111 542858 A7 五、發明說明(η)V. Description of the invention (12) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (CH2) — where Y is H'Cl to C6 alkyl, alkoxy, halo, -CO, H, -S〇3H 'm Are independently 0 or B and p is 1 or 2 'and (iv) residues containing the following general formula: (CH2) q / Q) S-(CRC5Rc6) t —, (CH2) r ^ (CRc5RC6) t- /, Rc > rC6 is independently alkynyl, 0 is 9 or ^ to ^ alkyl, s is 0, 1 or 2, 〇 is independently 0, bu 2 or 3, and r is 1 or 2 Or a water-soluble salt thereof. Preferred examples of such aminohydroxysuccinates include iminobis (2-hydroxysuccinic acid), N, N, -bis (2-hydroxysuccinyl) -1,6-hexanediamine , And n, n, bis (2-hydroxysuccinyl) _- m-dimethylbenzidinediamine or a water-soluble salt thereof. It is preferable to use a mixture of orthophosphoric acid or a water-soluble salt thereof with at least one aminohydroxysuccinic acid. Additional materials that can be combined with the tetrazolium compound include carboxyamine compounds 'which are combined into carboxylating agents, such as epoxysuccinic acid, and amines containing multiple nitrogen atoms,' such as polyethylene polyamines, as disclosed in International patent application case WO 96/33953 is hereby incorporated by reference. Additional materials that can be combined with the four compounds include polyepoxysuccinic acids of the following general formula (hereafter referred to as PESAs): This paper standard applies to China Standard (cns) A4 specification (210 X 297 mm) 16 -----: ---- 1 ------- (Please read the notes on the back before filling this page) One stone, · 1111111 542858 A7 V. Description of the invention (η)
HOHO
Rt c -Rt c-
Rt c-Rt c-
•H mto2c co2mt 其中1的範圍自大約2至大約50,較佳地2至25 ; MT為氫或 一個水溶性陽離子,如Na+,NH4+或K+,及RT為氫,CV4烧 基或取代的c“4烷基(較佳地1為氫)。較佳地Rt為氫,及: 的範圍自大約2至大約1 〇或自大約4至大約7。使用PESA5 於處理水相系統的方法已經揭示於美國專利案件第 5,062,962號和5,344,590號,各在此加入作為參考資料。 使用正墙酸鹽,聚環氧琥珀酸,丙烯酸/烯丙基羥基丙基 磺酸聚合物,和唑類組合作為腐蝕抑制方法已經被揭示於 美國專利案件第5,256,332號,在此加入作為參考資料。 車父佳的混合物包括正碟酸及/或其水溶性鹽和聚環氧琥珀 酸的混合物。 下面化學通式的修飾的聚環氧琥珀酸也可能有效的與 本發明化合物四唾鏘合併: ------------------:----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製• H mto2c co2mt where 1 ranges from about 2 to about 50, preferably 2 to 25; MT is hydrogen or a water-soluble cation, such as Na +, NH4 + or K +, and RT is hydrogen, CV4 alkyl or substituted c "4-alkyl (preferably 1 is hydrogen). Preferably Rt is hydrogen, and: ranges from about 2 to about 10 or from about 4 to about 7. Methods for treating aqueous phase systems using PESA5 have been disclosed In U.S. Patent Nos. 5,062,962 and 5,344,590, each of which is incorporated herein by reference. Orthowall acid salt, polyepoxysuccinic acid, acrylic / allylhydroxypropylsulfonic acid polymer, and azole combination are used as corrosion Inhibition methods have been disclosed in U.S. Patent Case No. 5,256,332, which is hereby incorporated by reference. The mixture of Chevron includes a mixture of orthoic acid and / or its water-soluble salt and polyepoxysuccinic acid. The modified polyepoxysuccinic acid of the formula may also be effectively combined with the compound tetrasialyl of the present invention: ------------------: ---- order ---- ----- line (Please read the notes on the back before filling out this page) Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs System
Zd-Zd-
lD2 R c D3 C-〇-j-h mdo2c co2md 其中Rdi ’當有存在’為H,取代的或未取代的烷基或芳 基部份’其碳鏈高達失去水相溶液溶解度的長度或乙稀不 飽和化合物聚合反應後得到的重複單元;RD2和RD3,各獨 本紙張尺度適用中國國家標準(CNS)A4規格(2〗0 X 297公爱) 17 經濟部智慧財產局員工消費合作社印製 542858 A7 ^___ _BT^ 五、發明說明(I4) 自立地為H,ci至C4烷基或取代的(^至匕烷基;20為0,S ,NH或NRD1,其中rdi為如上面說明者,u是一個大於1的 正整數;f是一個正的整數;及MD為Η,水溶性陽離子(如 ΝΗ4+ ’驗金屬)或未取代的1至3個碳原子較低級烷基基團 ’(當RD1不存在,ZD可以是md03S,其中MD為如上面說明 者)°使用這種化合物的方法已經被揭示於美國專利案件 第5,871,691號和5,489,666號,在此加入作為參考資料。 這種修飾的聚環氧琥珀酸的實施例包括如上面化學式的衍 生物’其中RD1為間-CH2_C6ivCH2-(間-伸二甲苯),心為· NH-,和RD3二者都是H,f為2,及]^為他或Η。實際 實施例通常是範圍為u的個別分子的混合物,此後稱之為 間-伸二甲苯二胺/PESA衍生物。 可以與四唑鐵化合物合併的附加化合物包括2,3-二羥 基苯酸和1,1 〇-啡σ林。 可以與四°坐鏺化合物合併的附加化合物包括下面化學 通式的單膦酸:lD2 R c D3 C-〇-jh mdo2c co2md where Rdi is' when present 'is H, a substituted or unsubstituted alkyl or aryl moiety' whose carbon chain is as long as it loses the solubility of the aqueous solution or ethene Repeated units obtained after polymerization of saturated compounds; RD2 and RD3, each unique paper size applies Chinese National Standard (CNS) A4 specifications (2〗 0 X 297 public love) 17 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 542858 A7 ^ ___ _BT ^ V. Description of the invention (I4) is independently H, ci to C4 alkyl or substituted (^ to alkyl; 20 is 0, S, NH or NRD1, where rdi is as described above, u Is a positive integer greater than 1; f is a positive integer; and MD is Η, a water-soluble cation (such as NΗ4 + 'metal test) or an unsubstituted lower alkyl group of 1 to 3 carbon atoms' (when RD1 does not exist, ZD can be md03S, where MD is as described above) ° The method of using this compound has been disclosed in US Patent Case Nos. 5,871,691 and 5,489,666, which are incorporated herein by reference. Examples of polyepoxysuccinic acids include Derivatives of the formula 'where RD1 is m-CH2_C6ivCH2- (m-xylene), the heart is · NH-, and both RD3 are H, f is 2, and] ^ is he or Η. Actual examples are usually Is a mixture of individual molecules in the range u, hereafter referred to as m-xylene diamine / PESA derivatives. Additional compounds that can be combined with tetrazolium iron compounds include 2,3-dihydroxybenzoic acid and 1,10- B. sigma. Additional compounds that can be combined with the four-degree sitting compound include monophosphonic acids of the following general formula:
p f/0Hp f / 0H
Rf—P、0H 其中rf是一個c^c!2直鏈或支鏈烷基殘基,C2至Ci2直鏈 或支鏈烴烯基殘基,q至C12環烷基殘基,匕至匕。芳基殘 基或(^至C!2芳烷基殘基,其中RF可另外獨立地以擇自羥 基’胺基或i基的基團單一或多重取代;該二膦酸化合物 的化學通式為: 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) -----I ——— (請先閱讀背面之注意事項再填寫本頁) 訂---------. 18 542858 A7 B7 五、發明說明(15) H0, 0 〇Rf—P, 0H where rf is a c ^ c! 2 straight or branched chain alkyl residue, C2 to Ci2 straight or branched chain alkenyl residue, q to C12 cycloalkyl residue, d to d . Aryl residues or (^ to C! 2 aralkyl residues, where RF may additionally be independently single or multiple substituted with a group selected from a hydroxyl 'amine or i group; the general chemical formula of the diphosphonic acid compound For: This paper size applies Chinese National Standard (CNS) A4 specification (210 x 297 mm) ----- I ——— (Please read the precautions on the back before filling this page) Order ------ ---. 18 542858 A7 B7 V. Description of the invention (15) H0, 0 〇
0H0H
•P HO〆• P HO〆
、0H 其中RK是一個(:1至(:12直鏈或支鏈伸烷基殘基,(:2至(::1,直 鏈或支鏈伸烯基殘基,〇5至<:12伸環烷基殘基,(:6至(::1〇伸 芳基殘基或(1:7至C〗2伸芳烧基殘基,其中可另外獨立地 以擇自經基,胺基或_基的基團單一或多重取代,或其水 溶性鹽。一個這種二膦酸較佳的實施例為丨_羥基乙烷 二膦酸(HEDP)或其水溶性鹽。 可以與四唑鏘化合物合併的附加物料包括膦酸基羧酸 (或這種膦酸基魏酸的混合物),如揭示於美國專利案件第 及 經濟部智慧財產局員工消費合作社印製 3,886,204s虎 ’ 3,886,205 號 ’ 3,923,876 號,3,933,427 號, 4,020,101號和4,246,103號者,所有都在此加入作為參考 資料。較佳的是以下面化學通式定義之膦酸基羧酸: 0 Rhi I H0\ll \p- / —C-COOH I HO 1 CH2— COOH 0 H H0, H0/, 0H where RK is a (: 1 to (: 12 straight or branched chain alkylene residue, (: 2 to (:: 1, straight or branched chain alkylene residue, 05 to <: 12 cycloalkyl residues, (: 6 to (:: 10) aryl residues or (1: 7 to C) 2 arylene residues, which may additionally independently A single or multiple substitution of a radical or a radical, or a water-soluble salt thereof. A preferred embodiment of such a diphosphonic acid is _hydroxyethanediphosphonic acid (HEDP) or a water-soluble salt thereof. The additional materials incorporated in the oxazonium compound include a phosphonic acid (or a mixture of such phosphonic acid), as disclosed in U.S. Patent Case No. 3 and the Intellectual Property Office of the Department of Economics and Consumer Cooperatives, Tiger's No. 3,886,205 'Nos. 3,923,876, 3,933,427, 4,020,101 and 4,246,103, all of which are hereby incorporated by reference. Preferred phosphonate carboxylic acids defined by the following general formula: 0 Rhi I H0 \ ll \ p- / —C-COOH I HO 1 CH2— COOH 0 H H0, H0 /
——X—C ——COOH CHr—COOH 其中RH!為H ’ 1至4個碳原子的烧基,烴稀基或炔基 基,環烷基或芳烷基或擇自下面化學式的基團者: 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----------^---------^ (請先閱讀背面之注意事項再填寫本頁) 19 542858 A7 B7 五、發明說明(16) RH2 CH-CH5COOH 及 _ CH-——X—C ——COOH CHr—COOH where RH! Is an alkyl group of H ′ 1 to 4 carbon atoms, a dilute hydrocarbon group or an alkynyl group, a cycloalkyl group or an aralkyl group or a group selected from the following chemical formula By: This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---------- ^ --------- ^ (Please read the notes on the back first (Fill in this page again) 19 542858 A7 B7 V. Description of the invention (16) RH2 CH-CH5COOH and _ CH-
CH——COOH 其中RH2為H,1至4個碳原子的烷基或羧基;及XH係擇自 下面化學式的基團者:CH——COOH where RH2 is H, an alkyl or carboxyl group of 1 to 4 carbon atoms; and XH is selected from the group of the following formula:
COOHCOOH
COOHCOOH
COOH 一CH—' -CH- •c—,及 c- ch3 ch3 其中·Ρ〇3Η2基團為下面的膦酸基基團?/0Η—ρ\ \〇Η 或其水溶性鹽。一個這種較佳的膦酸基羧酸的實施例為3_ 膦酸基丁烷·1,2,4-三羧酸或其水溶性鹽。 可以與四。坐鏘化合物合併的附加物料包括羥基膦酸基 叛酸(或這種羥基膦酸基羧基化合物的混合物),如揭示於 美國專利案件第4,689,200號和4,847,017號者,二者在此 都加入作為參考資料。適合的羥基膦酸基羧酸包括含下面 化學通式者: -----J----L-------:----訂---------· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 Η0, ΗΟ〆 0 Re -C-XrCOOH—CH —'- CH— • c—, and c—ch3 ch3 where the · P03Η2 group is the following phosphonic acid group? / 0Η—ρ \ \ 〇Η or its water-soluble salt. An example of such a preferred phosphonic carboxylic acid is 3-phosphonic butane · 1,2,4-tricarboxylic acid or a water-soluble salt thereof. Can be with four. The additional materials incorporated in the perylene compound include hydroxyphosphonic acid (or a mixture of such hydroxyphosphonic acid carboxyl compounds), such as those disclosed in US Patent Nos. 4,689,200 and 4,847,017, both of which are incorporated herein by reference data. Suitable hydroxyphosphonocarboxylic acids include those containing the following general formula: ----- J ---- L -------: ---- Order --------- · (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Η0, ΗΟ〆0 Re -C-Xr
-COOH-COOH
OH 其中RE為H’ Ci至C!2直鏈或支鏈烷基殘基,(:2至(:】2直鏈 或支鏈烴烯基殘基,^至匕2環烷基殘基,C0sCiq芳基殘 基或C?至C12芳烷基殘基,XE是一個任擇的基團,當有存OH where RE is H 'Ci to C! 2 linear or branched alkyl residues, (: 2 to (:) 2 straight or branched chain alkenyl residues, ^ to 2 cycloalkyl residues C0sCiq aryl residue or C? To C12 aralkyl residue, XE is an optional group, when there is
542858 A7 B7 五、發明說明(17) 在,是一個(^至(21()直鏈或支鏈伸烷基殘基,C2sc1()直鏈 或支鏈伸烯基殘基或c6至C1G伸芳基殘基或其水溶性鹽。 一個這種羥基膦酸基羧酸較佳的實施例為2_羥基-膦酸基 乙酸或其水溶性鹽。 可以與四唑鏘化合物合併的附加物料包括胺基膦酸如 揭示於美國專利案件第3,619,427號,3,723·347號, 3,816,333 號,4,029,696 號,4,033,896 號,4,079,006 號, 4,163,733 號 ’ 4,307,038 號,4,308,147 號和 4,617,129 號者 ’所有都在此加入作為參考資料。適合的胺基膦酸包括含 下面化學通式者: \ ϊ/0Η542858 A7 B7 V. Description of the invention (17) is a (^ to (21 () straight or branched alkylene residue, C2sc1 () straight or branched alkylene residue or c6 to C1G extension An aryl residue or a water-soluble salt thereof. A preferred example of such a hydroxyphosphonic acid is 2-hydroxy-phosphonic acid or a water-soluble salt thereof. Additional materials that can be combined with the tetrazolium compound include Aminophosphonic acids are disclosed in U.S. Patent Nos. 3,619,427, 3,723.347, 3,816,333, 4,029,696, 4,033,896, 4,079,006, 4,163,733 '4,307,038, 4,308,147, and 4,617,129' All are added here for reference. Suitable aminophosphonic acids include those containing the following general formula: \ ϊ / 0Η
<4 OH 其中Rq是含大約一個至大約四個碳原子的較低級伸烷基 ,或胺,羥基或鹵基取代的較低級伸烷基;為RQ_p〇3H2 ,η,OH,胺基,取代的胺基或心為如前面定義者; 為Rgs或以下面化學通式代表的基團: I---I --I I l· I--^ · I I I---I I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製< 4 OH where Rq is a lower alkylene group containing about one to about four carbon atoms, or a lower alkylene group substituted with an amine, a hydroxyl group or a halogen group; RQ_p03H2, η, OH, amine Group, substituted amine group or group is as defined above; is Rgs or a group represented by the following chemical formula: I --- I --II l · I-^ · II I --- II (Please (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
其中RG5和RG6係各自獨立地擇自H,0H,胺基,取代的胺 基或如前面定義之Rf ;、為RG5,RG6或基團RG2-p〇3H2, 本紙張尺度適用中國國豕4示準(CNS)A4規格(210 χ 297公爱) ..... ^ - 21 - 542858 五、 發明說明(I8) 而…為如前面定義纟;V是一個i至大約15的整數;及 w疋一船到大約14的整數或其水溶性鹽。-個這種胺基 膦3夂的’、〜例為二乙三胺五(亞甲基膦酸)或其水溶性鹽。 可以與四。坐鏘化合物合併的附加物料包括水溶性鹏酸 基甲基胺氧化物(或這種水溶性膦酸基甲基胺氧化物的混 合物)如揭示於美國專利案件第5,〇51,532號,5娜別號 ’和5’167,866號者’所有都在此加入作為參考資料。適 合的膦酸基甲基胺氧化物包括含下面化學通式者·· Rai \2 —CF^POjH^ 經濟部智慧財產局員工消費合作社印製 其中RA1係擇自由烴基,和羥基取代的,烷氧基取代的, 羧基取代的和磺醯基取代的烴基所組成之族者;及係 擇自由烴基,和羥基取代的,烷氧基取代的,羧基取代的 和磺醯基取代的烴基,-CH2p〇3H2,及 0 ▲ —N ( C^P〇3^) 2 ; 所組成之族者,或ra !和Rm共同形成一個環上含3至5個碳 原子的脂肪環或該膦酸基甲基胺氧化物的水溶性鹽。烴基 包括不使胺氧化物非水溶性的烷基,芳基,和烷芳基基團 。一個這種膦酸基甲基胺氧化物較佳的實施例為Ν,Ν—雙_ 膦酸基甲基乙醇胺N-氧化物,此後稱之為EBO或其水溶性 5^ 〇Among them, RG5 and RG6 are independently selected from H, 0H, amine, substituted amine or Rf as defined above; RG5, RG6 or group RG2-p03H2, this paper standard applies to China National Standard 4 Specification (CNS) A4 (210 χ 297 public love) ..... ^-21-542858 V. Description of the invention (I8) And ... is as defined above; V is an integer from i to about 15; and w疋 One boat to an integer of about 14 or its water-soluble salt. An example of such an amine phosphine 3 夂 is diethylenetriaminepenta (methylenephosphonic acid) or a water-soluble salt thereof. Can be with four. The additional materials combined with the perylene compound include a water-soluble pentoic acid methylamine oxide (or a mixture of such water-soluble phosphonomethylamine oxides) as disclosed in U.S. Patent No. 5,051,532, All 5 Nabe 'and 5'167,866' are included here for reference. Suitable phosphonomethylamine oxides include those containing the following general formula: Rai \ 2 —CF ^ POjH ^ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where RA1 is a free hydrocarbon group, and a hydroxy-substituted, alkane A group consisting of oxy-substituted, carboxy-substituted and sulfofluorenyl-substituted hydrocarbon groups; and selected from free hydrocarbon groups, and hydroxy-substituted, alkoxy-substituted, carboxy-substituted and sulfonyl-substituted hydrocarbon groups,- CH2p〇3H2, and 0 ▲ —N (C ^ P〇3 ^) 2; the group of members, or ra! And Rm together form an aliphatic ring containing 3 to 5 carbon atoms on the ring or the phosphonic acid group Water-soluble salt of methylamine oxide. Hydrocarbyl groups include alkyl, aryl, and alkaryl groups that do not render the amine oxide water-insoluble. A preferred example of such a phosphonomethylamine oxide is N, N-bis-phosphonomethylethanolamine N-oxide, hereinafter referred to as EBO or its water-soluble 5 ^.
本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) A7 B7This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) A7 B7
542858 五、發明說明(19) 可以與四唑鐵化合物合併的附加物料包括聚合的胺氧 化物,如說明於美國專利案件第5,629,385號者,在此加 入作為參考資料,聚醚聚胺基亞甲基膦酸酯和聚醚聚胺基 亞甲基膦酸酯N·氧化物,如分別說明於美國專利案件第 5,338,477號和5,322,636號者,二者在此加入作為參考資 料,及亞胺基伸烷基膦酸,如說明於美國專利案件第 5,788,857號者,在此加入作為參考資料。 可以與四唑鏘化合物合併的附加物料包括含磷羧酸酯 物料(此後稱為P-羧酸鹽),這些物料為調聚的,共調聚的 ,聚合的或共聚合的化合物,包括至少一個有機磷基團和 多個羧酸酯基團。任擇地,當羧酸鹽得自含有非羧酸酯 取代基的單體,這些物料也可能包括其他取代基基團。磷 可以存在為一個終端基團。在該情況下,它可以是一個膦 酸基或終端型膦基形態的部份或可以加入化合物作為膦基 部份,其中磷直接結合於二個碳原子,這是一種有時候稱 為‘二烷基”膦基部份的組態。這些可能性圖式地顯示下面。 ^----------^---------^ (請先閱讀背面之注意事項再填寫本頁) Y—0—542858 V. Description of the invention (19) Additional materials that can be combined with tetrazolium iron compounds include polymerized amine oxides, such as those described in US Patent No. 5,629,385, which is hereby incorporated by reference, polyether polyaminomethylene Phosphonates and polyether polyaminomethylene phosphonate N · oxides, as described in U.S. Patent Nos. 5,338,477 and 5,322,636, respectively, both of which are incorporated herein by reference, and imine alkylene Phosphonic acid, as described in US Patent No. 5,788,857, is hereby incorporated by reference. Additional materials that can be combined with tetrazolium compounds include phosphorus-containing carboxylic acid ester materials (hereinafter referred to as P-carboxylates) that are telomerized, co-telomerized, polymerized, or copolymerized compounds, including at least One organophosphorus group and multiple carboxylate groups. Alternatively, when the carboxylate is obtained from a monomer containing non-carboxylic acid ester substituents, these materials may also include other substituent groups. Phosphorus may be present as a terminal group. In this case, it can be a phosphonate or terminal phosphine moiety or a compound can be added as a phosphine moiety where the phosphorus is directly bound to two carbon atoms, which is a type sometimes called 'di Configuration of "alkyl" phosphine. These possibilities are shown diagrammatically below. ^ ---------- ^ --------- ^ (Please read the notes on the back first (Fill in this page again) Y—0—
〇 I〇 I
C Η一C Η 一
0 I c ο 經濟部智慧財產局員工消費合作社印製 0 χ 膦酸基0 I c ο Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 0 χ Phosphonic acid group
XX
0 II-卜 0 I X 終端型膦基 垸基形態膦基 X可以是氫或一個陽離子種系,如鹼金屬離子,銨離 子或四級化胺基團。γ可以與X相同或可另外為一個取 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 23 經濟部智慧財產局員工消費合作社印製 542858 A7 一·· - 五、發明說明(20) " '' 的或未取代的烧基,芳基或貌芳基殘基,其中的取代物可 能含有或可能不含有缓酸醋。¥必須是要選擇使維持化合 物在水中足夠的溶解度。顯示的破原子是調聚物,共調聚 物’聚合物或共聚物石炭骨架% 一部份,&骨架含有至少二 個羧基基團,任擇地有其他磷加入物和任擇地有其他非I 基取代物。 P_羧酸鹽的平均分子量數較佳的少於1〇,〇〇〇,特別佳 的是低平均分子量數的募聚的或聚合的h羧酸鹽,如2,000 或更少,特別是1,000或更少。特別佳的是2個或更多個羧 酸酯取代於線形烷基殘基,較優先的是以丨,2气鄰接的)或 1,3-取代物的安排。p-羧酸鹽可能含有磷取代物或主要或 全部為膦酸基種系,主要或全部為終端型膦基種系,主要 或全部為二烧基膦基種系的取代物或含有這些取代形態的 混合物於個別分子上及/或於以特別製備方法產生的分子 的混合物。用於P-羧酸鹽的各種不同製備方法也可能產生 各種不同的無機碟種系作為合成的方法的一部份。當這種 P-魏酸鹽和伴隨的無機礙種系混合物與四唾鏘化合物合併 也被認為是在本發明範圍内。 適合用於本發明的P-羧酸鹽的製備方法及其單獨和與 其他水處理試劑組合在水相系統中作為腐蝕及/或水垢控 制劑之用法非限制的實施例揭示於美國專利案件第 2,957,93 1 號,4,046,707 號,4,088,678 號,4,105,55 1 號, 4,127,483 號,4,159,946 號,4,207,405 號,4,239,648 號, 4,563,284 號,4,621,127 號,4,681,686 號,5,023,000 號, 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 24 ----------Γ — ----l·---訂--------- (請先閱讀背面之注意事項再填寫本頁) 542858 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(21) 5,073,299 號,5,077,361 號,5,085,794 號,5,160,630 號, 5,216,099 號,5,229,030 號,5,256,302 號,5,256,746 號, 5,294,687 號,5,360,550 號,5,376,731 號,5,386,038 號, 5,409,571 號,5,606,105 號,5,647,995 號,5,681,479 號, 和5,783,728號及歐洲專利案件第283191A2號,360746B1 號,569731A2號,681995A3號,786018A1 號,792890A1 號,807635A1 號,807654A2號,和 861846A2號,所有的0 II-Bu 0 I X Terminal-type phosphinyl phosphonium phosphonium group X can be hydrogen or a cationic species, such as alkali metal ion, ammonium ion or quaternary amine group. γ can be the same as X or it can be another one. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love). 23 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 542858 A7. Note (20) " '' unsubstituted or unsubstituted alkyl, aryl or aryl residues, the substitutions of which may or may not contain bitten vinegar. ¥ must be chosen to maintain sufficient solubility of the compound in water. The broken atom shown is a part of the telomer, co-telomer 'polymer or copolymer charcoal skeleton, & the skeleton contains at least two carboxyl groups, optionally with other phosphorus additions and optionally with Other non-I substituents. The average molecular weight of the P_carboxylate is preferably less than 10,000, particularly preferred is the agglomerated or polymerized h carboxylate having a low average molecular weight, such as 2,000 or less, especially 1 10,000 or less. Particularly preferred is the arrangement of 2 or more carboxylic acid esters substituted with linear alkyl residues, more preferably adjacent by 2 or 2 gas) or 1,3-substituents. p-carboxylates may contain phosphorus substituents or are predominantly or entirely phosphonic acid-based species, mainly or wholly terminal phosphine-based species, mainly or wholly di-alkyl phosphine-based species, or contain these substitutions A mixture of morphologies on individual molecules and / or a mixture of molecules produced by a special preparation method. Various preparation methods for P-carboxylates may also produce a variety of inorganic dish species as part of the synthetic method. It is also considered to be within the scope of this invention when this P-weilate and the accompanying inorganic interfering germline mixture is combined with a tetrasialyl compound. A non-limiting example of a method for preparing a P-carboxylate suitable for use in the present invention and its use alone and in combination with other water treatment reagents as a corrosion and / or scale control agent in an aqueous system is disclosed in U.S. Patent Case No. 2,957,93 No. 1, 4,046,707, 4,088,678, 4,105,55 No. 1, 4,127,483, 4,159,946, 4,207,405, 4,239,648, 4,563,284, 4,621,127, 4,681,686, 5,023,000, this paper The scale is applicable to China National Standard (CNS) A4 (210 X 297 mm) 24 ---------- Γ----- l · --- order --------- ( Please read the notes on the back before filling this page) 542858 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (21) 5,073,299, 5,077,361, 5,085,794, 5,160,630, 5,216,099, 5,229,030 No. 5,256,302, 5,256,746, 5,294,687, 5,360,550, 5,376,731, 5,386,038, 5,409,571, 5,606,105, 5,647,995, 5,681,479, and 5,783,728 and European Patent Case No. 283191A2, 360746B1 No. 569731A2, No. 681995A3, No. 786018A1, No. 792890A1, No. 807635A1, No. 807654A2, and No. 861846A2, all
I 在此都加入作為參考資料。檢視這些專利案件中較好的, 有多種製造適用於本發明P-羧酸鹽的製備方法。本發明的 目標不是要限定任何特別製程或方法來製造適用於本發明 的P羧酸酯。一般而言,它們可以用一個含磷物料與一個 或更多個可聚合的單體反應得到,至少其中一個含有羧基 基團或以另外如水解’氧化等等的反應,在最後化合物可 以產生羧基的基團(聚合反應步驟之後),這種單體在此後 稱之為羧基單體。揭示於文獻的方法通常包含將含碟的物 _ 料與一個或更多個不飽和單體反應,至少其中一個為叛基 單體,以產生P羧酸酯寡聚物或聚合物。適合的羧基單體 的實施例包括丙烯酸,順-丁烯二酸,順-丁烯二酸酐,甲 基丙烯酸’分解烏頭酸,巴豆酸,乙烯乙酸,反-丁稀二 酸,檸康酸,甲基-反·丁烯二酸,丙烯腈,甲基丙稀睛, α-亞甲基戊二酸,環己烯二羧酸,順-1,2,3,6-四氫酞酸酐 ’ 3,6·環氧-1,2,3,6·四氫酞酸酐,5 -降冰片烯-2,3-二叛酸 酐,雙環[2·2·2]-5-辛稀-2,3-二叛酸酐,3-曱基_1,2,6_四氫 酞酸酐,及2-曱基1,3,6·四氫酞酸酐。較佳的羧基單體為 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) -----^----^--------- (請先閱讀背面之注意事項再填寫本頁) 25 經濟部智慧財產局員工消費合作社印製 542858 A7 B7 五、發明說明(22) 丙烯酸,順-丁烯二酸,分解烏頭酸,和順-丁烯二酸酐。 雖然較佳的是P-羧酸鹽物料含有一個攜帶羧基團殘基 的主要部份’較佳的可以使用一個共寡聚的或共聚合的P 羧酸酯’該P羧酸酯含有衍生自至少一個羧基單體的殘基 和一個次要部份(少於總產品50重量百分比),得自至少另 一個非羧基單體的單體的殘基。有多種適合的非羧基單體 ’包括’例如2-丙稀酿胺-2_甲基丙烧石黃酸(Lubrizol Corporation以AMPSTMi市出售),2-羥基-3-(2-丙烯氧基) 丙烷磺酸,2-甲基-2-丙烯基-1-磺酸,烯丙基磺酸,烯丙 氧基苯績酸,苯乙稀石黃酸,乙稀石黃酸,烯丙基膦酸,乙稀 膦酸,異丙烯基膦酸,磷乙基甲基丙烯酸酯,丙烯酸或甲 基丙烯酸的羥基烷基和CrC4烷基酯類,丙烯醯胺,烯丙 基取代的丙稀醯胺,稀丙基醇,2-乙稀σ比唆,4-乙烯σ比。定 ,Ν-乙烯吡咯酮,Ν-乙烯甲醯胺,Ν-乙烯咪唑,乙烯乙 酸酯,水解的乙烯乙酸酯,和苯乙烯。 特別包括於Ρ_羧酸鹽類的是下面化學通式的膦聚合物 ?严I have included it here as a reference. Examining these patent cases, it is preferable that there are various methods for preparing P-carboxylates suitable for use in the present invention. The object of the present invention is not to limit any particular process or method for making P carboxylic acid esters suitable for use in the present invention. In general, they can be obtained by reacting a phosphorus-containing material with one or more polymerizable monomers, at least one of which contains a carboxyl group or by another reaction such as hydrolysis' oxidation, etc., and the final compound can generate a carboxyl group. Group (after the polymerization step), this monomer is hereinafter referred to as a carboxyl monomer. The methods disclosed in the literature generally involve reacting a dish-containing material with one or more unsaturated monomers, at least one of which is a tether monomer, to produce a Pcarboxylate oligomer or polymer. Examples of suitable carboxyl monomers include acrylic acid, maleic acid, maleic anhydride, methacrylic acid's decomposed aconitic acid, crotonic acid, ethylene acetate, trans-succinic acid, citraconic acid, Methyl-trans-butenedioic acid, acrylonitrile, methyl acrylic, α-methyleneglutaric acid, cyclohexene dicarboxylic acid, cis-1,2,3,6-tetrahydrophthalic anhydride ' 3,6 · epoxy-1,2,3,6 · tetrahydrophthalic anhydride, 5-norbornene-2,3-dibenzyl anhydride, bicyclo [2 · 2 · 2] -5-octane-2, 3-diamino acid anhydride, 3-fluorenyl1,2,6_tetrahydrophthalic anhydride, and 2-fluorenyl 1,3,6 · tetrahydrophthalic anhydride. The better carboxyl monomer is based on Chinese paper standard (CNS) A4 specification (210 X 297 public love) ----- ^ ---- ^ --------- (Please read first Note on the back, please fill in this page again) 25 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 542858 A7 B7 V. Description of the invention . Although it is preferred that the P-carboxylate material contains a major portion carrying a carboxyl group residue, 'preferably a co-oligomeric or copolymerized P-carboxylic acid ester can be used' which contains The residue of at least one carboxyl monomer and a minor portion (less than 50 weight percent of the total product) are derived from the residue of at least one other non-carboxyl monomer. There are a variety of suitable non-carboxyl monomers 'including', such as 2-propenamine-2_methylpropanesulfuric acid (sold by the Lubrizol Corporation as AMPSTMi), 2-hydroxy-3- (2-propenyloxy) Propanesulfonic acid, 2-methyl-2-propenyl-1-sulfonic acid, allylsulfonic acid, allyloxybenzoic acid, phenethelite, ethionite, allylphosphine Acids, ethylene phosphonic acid, isopropenylphosphonic acid, phosphoethyl methacrylate, hydroxyalkyl and CrC4 alkyl esters of acrylic or methacrylic acid, allylamine, allyl-substituted allylamine , Dilute propyl alcohol, 2-ethene σ ratio 唆, 4-ethene σ ratio. N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, ethylene acetate, hydrolyzed ethylene acetate, and styrene. Particularly included in the P_carboxylates are phosphine polymers of the following general formula:
rj1~pC ΟΧ; 其中乂3為11,鹼金屬原子,鹼土金屬原子或銨或胺殘基; 及R』2是一個下面包含二個不同殘基的共聚物殘基 + CH2CH(RJ2)七 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------------- (請先閱讀背面之注意事項再填寫本頁) 訂---------· 26 542858rj1 ~ pC OX; where 乂 3 is 11, alkali metal atom, alkaline earth metal atom or ammonium or amine residue; and R′2 is a copolymer residue containing two different residues below + CH2CH (RJ2) seven Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------------- (Please read the precautions on the back before filling this page) Order- ------- · 26 542858
經濟部智慧財產局員工消費合作社印製 五、發明說明(23) 其中z是一個範圍自2至1〇〇的整數,其中第一殘基中的Rj 2 為-COOH,第二殘基中的Rj2 為-CONHC^CHACI^SOaXj, 其中Χ』為如之前定義者。 適合的用於本發明P-羧酸鹽物料非限制的實施例包括 Belsperse 161,Belclene 400,Belclene 494,Belclene 500 ( 所有都是FMC corporation上市產品),膦酸基琥珀酸,和 _ Brieorr 288(Albright and Wilson的一種產品)。Bricorr 288 被說明為一種組成物,基本上由一個高達5〇%重量比的膦 酸基琥ίό酸’以組成物重量計,一個膦酸化鹼金屬順-丁 稀一酸酯二聚物,重量不多於次要部份,以二聚物重量計 ’較高膦酸化順-丁烯二酸酯寡聚物組成;及組成物大約 0.5至大約5%重量比的驗金屬罐酸鹽。 可以與四。坐鏘化合物合併的附加物料包括肌胺酸的長 鏈脂肪酸衍生物(或這種肌胺酸脂肪酸衍生物的混合物)或 其水溶性鹽。一個這種衍生物的實施例是Ν-月桂醯基肌 k 胺酸。 本發明四唾鐳化合物也可能與水溶性驗金屬石夕酸鹽, 如偏矽酸鈉合併。這種矽酸鹽是已知於文獻中當作鐵金屬 和铭腐蝕抑制劑的,二者都是在液體中主要是水的系統以 及以二醇為主的水相系統,這些系統通常用於内燃機引擎 作為防凍冷凍劑。矽酸鈉鹽可用一般的化學式 Na2〇*SiO,yH2〇代表,其中X是在大約1至大約3·5的範圍 。可以使用市面的矽酸鈉溶液,其中的矽對驗的莫耳比是 大約3.3。Si〇2:Na2〇莫耳比低至大約ι:ι的更多鹼溶液或 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 裝-----·_----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 27 542858 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(24)Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (23) where z is an integer ranging from 2 to 100, where Rj 2 in the first residue is -COOH, and in the second residue Rj2 is -CONHC ^ CHACI ^ SOaXj, where X ′ is as defined before. Non-limiting examples of suitable P-carboxylate materials for use in the present invention include Belsperse 161, Belclene 400, Belclene 494, Belclene 500 (all of which are marketed by the FMC corporation), phosphonic succinic acid, and Brieorr 288 ( A product of Albright and Wilson). Bricorr 288 is illustrated as a composition consisting essentially of a phosphonic succinic acid of up to 50% by weight, based on the weight of the composition, a phosphonated alkali metal cis-butyric acid dimer, weight Not more than minor parts, a 'higher phosphonated maleic acid oligomer composition by weight of the dimer; and a composition of about 0.5 to about 5% by weight of a metallurgical pot salt. Can be with four. The additional materials combined with the sitting compound include a long-chain fatty acid derivative of sarcosinate (or a mixture of such sarcosinic fatty acid derivatives) or a water-soluble salt thereof. An example of one of these derivatives is N-lauric acid. The tetrasalium compounds of the present invention may also be combined with water-soluble metallolithic acid salts, such as sodium metasilicate. This silicate is known in the literature as an iron metal and corrosion inhibitor, both of which are mainly water systems in liquids and glycol-based water phase systems. These systems are commonly used in The internal combustion engine acts as an antifreeze refrigerant. The sodium silicate can be represented by the general chemical formula Na2 * SiO, yH2O, where X is in the range of about 1 to about 3.5. A commercially available sodium silicate solution can be used, in which the silicon mole ratio is approximately 3.3. Si〇2: Na2〇 More than alkaline solution as low as about ι: ι or this paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) Packing ----- · _-- --Order --------- line (please read the precautions on the back before filling this page) 27 542858 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (24)
Si〇2:Na20莫耳比高達大約3.5:1的更少鹼溶液也可以使用 。其他鹼金屬矽酸鹽,特別是矽酸鉀鹽也可以使用。當使 用水溶性鹼金屬矽酸鹽於本發明實例,合併矽酸鹽與其他 抑制劑及/或矽安定劑可能是有利的。這種適合的組合的 實施例揭示於美國專利案件第3,711,246號,4,085,063號 ,4,404,114號,5,137,657號,5,262,078號,5,578,246號 ,和5,589,106號,所有在此都加入作為參考資料。 本發明四峻纟翁化合物也可與水溶性單碳酸鹽合併。 使用這種鹽作為金屬表面腐蝕抑制劑已經被揭示於美國專 利案件第4,132,572號和4,613,450號,二者在此都加入作 為參考資料。如揭示於美國專利案件第5,182,028號者, 在此加入作為參考資料,這種鹽也有碳酸鈣水垢控制及鐵 和錳安定的用途。 多種適合與本發明四唑鏘物料組合的附加水相系統腐 蝕抑制劑是已知於文獻的。這種抑制劑非限制的實施例可 以在下面文獻找到:Corrosion Inhibitors,C.C. Nathan, ed·, NACE, 1973 ; I.L. Rozenfeld, Corrosion Inhibitors,Less alkaline solutions of SiO2: Na20 molar ratios up to about 3.5: 1 can also be used. Other alkali metal silicates, especially potassium silicates, can also be used. When using water-soluble alkali metal silicates in the examples of the present invention, it may be advantageous to combine silicates with other inhibitors and / or silicon stabilizers. Examples of such suitable combinations are disclosed in U.S. Patent Nos. 3,711,246, 4,085,063, 4,404,114, 5,137,657, 5,262,078, 5,578,246, and 5,589,106, all of which are incorporated herein by reference. The quaternium compound of the present invention can also be combined with a water-soluble monocarbonate. The use of this salt as a metal surface corrosion inhibitor has been disclosed in U.S. Patent Nos. 4,132,572 and 4,613,450, both of which are incorporated herein by reference. As disclosed in U.S. Patent No. 5,182,028, which is incorporated herein by reference, this salt also has calcium carbonate scale control and iron and manganese stabilization applications. A variety of additional aqueous phase system corrosion inhibitors suitable for use in combination with the tetrazolidine materials of the present invention are known in the literature. Non-limiting examples of such inhibitors can be found in the following documents: Corrosion Inhibitors, C.C. Nathan, ed., NACE, 1973; I.L. Rozenfeld, Corrosion Inhibitors,
McGraw-Hill, 1981 ; Metals Handbook, 9th Ed., Vol. 13 -Corrosion,pp. 478-497 ; Corrosion Inhibitors for Corrosion Control, B.G. Clubley, ed.5 The Royal Society of Chemistry, 1990 ; Corrosion Inhibitors, European Federation ofMcGraw-Hill, 1981; Metals Handbook, 9th Ed., Vol. 13 -Corrosion, pp. 478-497; Corrosion Inhibitors for Corrosion Control, BG Clubley, ed. 5 The Royal Society of Chemistry, 1990; Corrosion Inhibitors, European Federation of
Corrosion Publications Number 11, The Institute of Materials, 1994 ; Corrosion, Vol. 2 - Corrosion Control, L.L. Sheir, R.A. Jarman, and G.T. Burstein, eds·,Butterworth- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------1 ——----l·---訂--------- (請先閱讀背面之注意事項再填寫本頁) 28 經濟部智慧財產局員工消費合作社印製 542858 A7 __________ B7 五、發明說明(25)Corrosion Publications Number 11, The Institute of Materials, 1994; Corrosion, Vol. 2-Corrosion Control, LL Sheir, RA Jarman, and GT Burstein, eds ·, Butterworth- This paper standard applies to China National Standard (CNS) A4 (210 X 297 mm) --------- 1 -------- l · --- Order --------- (Please read the precautions on the back before filling this page) 28 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 542858 A7 __________ B7 V. Description of Invention (25)
Heinemann, 1994? pp. 17:10-17:39 ; Y.I. Kuznetsov. OrganicHeinemann, 1994? Pp. 17: 10-17: 39; Y.I. Kuznetsov. Organic
Inhibitors of Corrosion of Metals,Plenum,1996 ;及VS Sastri,Corrosion Inhibitors: Principles and Applications·Inhibitors of Corrosion of Metals, Plenum, 1996; and VS Sastri, Corrosion Inhibitors: Principles and Applications ·
Wiley,1998。這種抑制劑包括胺(如嗎福啉,環己基胺, 苯甲基胺),烷醇胺,醚胺,二胺,脂肪胺和二胺,四級 化胺’氧院基化胺,烧基σ比咬;四唾類,如揭示於美國專 I 利案件弟5,744,069號者,在此加入作為參考資料;味σ坐 啉和取代的咪唑啉,醯胺胺’聚胺,包括聚伸烷基聚胺, 如揭示於美國專利案件第5,275,744號者,在此加入作為 參考資料,苯磺酸,苯酸鹽和取代的苯酸鹽的烷基衍生物 (如對-二級-丁基苯酸,如揭示於美國專利案件第5,2 7 5,7 4 4 號者’在此加入作為參考資料)’胺基苯酸鹽,水楊酸鹽 ,二聚酸-三聚酸,石油氧化物,硼葡萄糖鹽;木質素, 鞣酸,和其礦酸化及/或羧酸化衍生物(如木質確酸鹽); 直鏈C^-Ch單羧酸酯,羧酸和氫硫基羧酸胺鹽,如揭示於 丨美國專利案件第5,7 7 9,9 3 8號者,在此加入作為參考資料 ,胺基酸,聚胺基酸,及其衍生物,如揭示於美國專利案 件第 4,971,724 號,5,531,934 號,5,616,544 號,5,75〇,〇7〇 號,和5,785,896號者,在此加入作為參考資料;羥基醚 酸和相關的内酯化合物,如揭示於美國專利案件第 5,055,230號者,在此加入作為參考資料,N•醯基肌胺酸 ,N-醯基亞胺基二乙酸;三吖畊二_和三_羧酸,如揭示於 美國專利案件第4,402,907號者,在此加入作為參考資料 ,及磷·和磷酸酯類(如乙氧化醇),如揭示於美國專利 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) ^ „----^--------- (請先閱讀背面之注意事項再填寫本頁) 29 542858 A7 B7 五、發明說明(26) h 5,611.991 件第 3,873,465 號,3,932,3〇3 號,4,〇66,398 號 號者,在此加入作為參考資料。 在本發明的實例中,以使用附加試劑加強或加入本發 明組合另外的功能性可能是有利的。適合的附加試劑包括 分散劑,銅腐蝕抑制劑,鋁腐蝕抑制劑,水溶性金屬鹽及 其螯合物’水垢和沈積控制劑,多價螯合劑,防珠劑,氧 化性和非氧化性生物制劑,非離子的和離子的冷凌溫度抑 制劑,PH調節劑,惰性和活性示蹤劑,非水溶性的和水 溶性的潤滑劑,表面活性劑,辦硬度調節冑,和呈色劑。 當水相系統含有懸浮的顆粒化物質,通常需要用分散 劑來維持系統的澄清度。多種可用於本發明實例聚合的和 非聚合的分散劑是已知於文獻的。較佳的是a)得自一個或 更多個乙烯不飽和單體聚合反應的水溶性石黃酸化聚合物或 共聚物,單體中至少一個含有石黃酸化功能性,或其水溶性 鹽,或b)分子量<10,〇〇〇的二異丁烯和順-丁烯二酸酐的共 聚物’或其水溶性鹽。特別佳的是大約3:1重量比的丙烯 酉文和稀丙基沒基丙基續酸酯驗共聚物或其水溶性鹽。 可與本發明四唑鏘化合物合併的附加試劑包括銅腐蝕 抑制劑,包括雜環形態的銅抑制劑,如唑類化合物。如已 知於文獻的,唑類通常用於提供以銅為主的合金之腐蝕保 護。然而,也如文獻已知的,在一些系統内,唑類和類似 的雜環形態的銅抑制劑另外再提供以鐵為主的金屬及/或 鋁的腐蝕保護,使用這種物料於這些目的被認為是在本發 明範圍内。因為一個熟悉文獻者可以很快地瞭解,使用銅 本紙張尺度適用中國國家標準(CNS)A4 #見格⑽X 297公爱 542858Wiley, 1998. Such inhibitors include amines (such as morpholine, cyclohexylamine, benzylamine), alkanolamines, etheramines, diamines, fatty amines and diamines, quaternary amines, oxygenated amines, and Basic sigma bite; Tetrasaloids, such as those disclosed in US Patent No. 5,744,069, are hereby incorporated as reference materials; sigma oxoline and substituted imidazoline, amidoamine 'polyamine, Including polyalkylene polyamines, as disclosed in U.S. Patent No. 5,275,744, incorporated herein by reference, benzenesulfonic acid, benzoate and substituted benzoate alkyl derivatives (such as para-secondary -Butyl benzoic acid, as disclosed in U.S. Patent Case Nos. 5, 2 7 5, 7 4 4 'Add here for reference)' Aminobenzoate, salicylate, dimer acid-trimer Acids, petroleum oxides, boron glucose salts; lignin, tannic acid, and its mineralized and / or carboxylated derivatives (such as ligninates); linear C ^ -Ch monocarboxylic acid esters, carboxylic acids and hydrogen Thiocarboxylic acid amine salts, as disclosed in US Patent Case No. 5, 7 7 9, 9 3 8 are added here as reference materials, amino acids, polyamino acids And its derivatives, such as those disclosed in U.S. Patent Nos. 4,971,724, 5,531,934, 5,616,544, 5,75,007, and 5,785,896, are incorporated herein by reference; hydroxy ethers Acids and related lactone compounds, such as those disclosed in U.S. Patent Case No. 5,055,230, are hereby incorporated by reference, N • fluorenylsarcosinic acid, N-fluorenimine diacetic acid; triazine di_ and Tri-carboxylic acids, such as those disclosed in U.S. Patent No. 4,402,907, are hereby incorporated by reference, and phosphorus and phosphate esters (such as ethoxylated alcohols), as disclosed in the US patent. CNS) A4 specifications (210 X 297 public love) ^ -------- ^ --------- (Please read the notes on the back before filling out this page) 29 542858 A7 B7 V. Description of the invention (26 ) h 5,611.991 pieces 3,873,465, 3,932,30, 3, 4,66,398, which are hereby incorporated by reference. In the examples of the present invention, additional functions are used to enhance or add additional functions of the combination of the present invention. Sex may be advantageous. Suitable additional reagents include Powders, copper corrosion inhibitors, aluminum corrosion inhibitors, water-soluble metal salts and their chelates' scale and sedimentation control agents, sequestering agents, anti-bead agents, oxidizing and non-oxidizing biological agents, non-ionic and Ionic cold temperature inhibitors, pH regulators, inert and active tracers, water-insoluble and water-soluble lubricants, surfactants, hardness regulators, and colorants. When aqueous systems contain suspensions Dispersants are usually required to maintain the clarity of the system. A variety of polymeric and non-polymeric dispersants that can be used in the examples of this invention are known in the literature. It is preferred that a) the water-soluble luteinized polymer or copolymer obtained from the polymerization of one or more ethylene unsaturated monomers, at least one of the monomers contains a lutein-functionalizing function, or a water-soluble salt thereof, Or b) a copolymer of diisobutylene and maleic anhydride with a molecular weight < 10,000, or a water-soluble salt thereof. Particularly preferred is an acrylic copolymer and a diisopropyl propyl dibasic acid ester copolymer or a water-soluble salt thereof in a weight ratio of about 3: 1. Additional agents that can be combined with the tetrazolium compound of the present invention include copper corrosion inhibitors, including copper inhibitors in heterocyclic forms, such as azole compounds. As known in the literature, azoles are often used to provide corrosion protection for copper-based alloys. However, as is known in the literature, in some systems, azoles and similar heterocyclic copper inhibitors additionally provide corrosion protection for iron-based metals and / or aluminum. Use this material for these purposes It is considered to be within the scope of the present invention. Because a person familiar with the literature can quickly understand that the copper paper size is applicable to the Chinese National Standard (CNS) A4 #See Grid X 297 Public Love 542858
五、發明說明(2*7) 經濟部智慧財產局員工消費合作社印製 抑制劑於本發明實例可能加強本發明組成物保護特別金屬 系統的性能及/或可能延伸到多金屬系統的應用性。 適合的唑類化合物包括三唑,四唑,吡唑,σ米唑,異 h唑,哼唑,異噻唑,和噻唑,所有都任擇地以烷基,芳 基,芳烷基,烷基醇,和烴烯基基團取代,包括揭示於美 國專利案件第2,6185608號,2,742,369號,和2,941,953號 和摘述於美國專利案件第4,1〇1,441號者,所有在此都加 入作為參考資料。適合的唑類和相關雜環化合物的實施例 包括苯并三唑,甲苯三唑,烷基或烷氧基取代的苯并三唑 ,其中該取代發生於苯環的4或5位置,2_氫硫基苯并噻唑 ’ 2·氫硫基笨并三唑,丨,^·三唑,4_苯基-ns·三唑,I,〕· 奈并二唾,4-硝基笨并三唾,σ比唾,6-叾肖基引唾,4-笨甲 基°比唾,4,5-二甲基。比唾,3·烯丙基a比嗤,咪唑,腺嗓呤 ’鳥嗓呤,苯并咪唑,5_曱基苯并咪唑,2_苯基咪唑,2一 苯甲基咪唑,4-烯丙基咪唑,4-(β-羥基乙基)咪唑,嗓吟 ’ 4-甲基咪唑,黃嘌呤,次黃嘌呤,2-甲基咪唑,異1。坐 ,苯并異哼唑,3-氫硫基苯并異哼唑,哼唑,2_氫硫基哼 唾’ 2-氫硫基苯并哼唑,異噻唑,弘氫硫基異噻唑,2_氫 硫基苯并異噻唑,苯并異噻唑,噻唑,2,5-二氫硫基噻二 0坐’ 2,5-二氫硫基苯并三σ坐,5,5,-亞甲基•雙-苯并三嗤, 及4,5,6,7-四氫苯并三σ坐。另外適合的。坐類包括揭示於美 國專利案件第 3,985,503 號,4,298,568 號,4,734,257 號, 4,744,950 號,4,874,579 號,5,217,686 號,和 5,236,626 號 者在此加入作為參考資料’和揭不於美國專利案件第 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)V. Description of the invention (2 * 7) The inhibitor printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs on the examples of the present invention may enhance the performance of the composition of the present invention to protect special metal systems and / or may extend to the applicability of multi-metal systems. Suitable azole compounds include triazole, tetrazole, pyrazole, sigmazole, isohazole, humazole, isothiazole, and thiazole, all of which are optionally alkyl, aryl, aralkyl, alkyl Alcohol, and alkenyl group substitutions, including those disclosed in U.S. Patent Nos. 2,6185608, 2,742,369, and 2,941,953, and those summarized in U.S. Patent Nos. 4,101,441, all in This is added as a reference. Examples of suitable azoles and related heterocyclic compounds include benzotriazole, toltriazole, alkyl or alkoxy substituted benzotriazole, where the substitution occurs at the 4 or 5 position of the benzene ring, 2_ Hydrosulfanylbenzothiazole '2. Hydrosulfanylbenzotriazole, 丨, ^ · triazole, 4-phenyl-ns · triazole, I,] · Nenobisalan, 4-nitrobenzotriazole Saliva, σ is better than saliva, 6- 叾 Shokyloin, salivary, 4-benzylmethyl ° saliva, 4,5-dimethyl. Bisal, 3, allyl a than fluorene, imidazole, adenine's guanine, benzimidazole, 5-fluorenyl benzimidazole, 2-phenylimidazole, 2-benzylimidazole, 4-ene Propylimidazole, 4- (β-hydroxyethyl) imidazole, groan '4-methylimidazole, xanthine, hypoxanthine, 2-methylimidazole, iso-1. Sitting, benzoisohumazole, 3-hydrothiobenzoisohumazole, humazole, 2_hydrothiobenzyl '2-hydrothiobenzoxazole, isothiazole, hydrothiothioisothiazole, 2-Hydroxythiobenzoisothiazole, benzoisothiazole, thiazole, 2,5-dihydrothiothiodioxo '2,5-dihydrothiobenzotrisigma, 5,5, -sub Methyl-bis-benzotrifluorene, and 4,5,6,7-tetrahydrobenzotrisigma. Also suitable. The categories include those disclosed in U.S. Patent Cases Nos. 3,985,503, 4,298,568, 4,734,257, 4,744,950, 4,874,579, 5,217,686, and 5,236,626, which are hereby incorporated by reference 'and disclosed in the U.S. Patent Case, which is applicable to the paper standard. China National Standard (CNS) A4 specification (210 X 297 mm)
-I 裝----------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 31 542858 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(28 ) 5,156,769號的i•笨基_5_氫硫基四&,在此加人作為參考 資料。適合的唾類包括混合的組成物,如包括至少㈣, 以重量計,5_甲基苯并三唾異構物的甲苯三吐組成物,如 揭不於美國專利案件第5,503,775號者,在此加入作為參 考資料。當水㈣統使用“素為主的氧化性生物制劑( 如氯)時’特別適合的是耐鹵素唑類,提供改良的腐蝕性 能,沒有不良氣味’減少生物制劑的消耗。這種耐自素唑 類非限制的實施例揭示於美國專利案件第5,772,919號, M63,463號和5,863,464號,在此加入作為參考資料,盆 中包括氣-甲笨三唾’漠-甲苯三唾,單齒基苯并三峻,二 画基苯并三唾,和單自基和n笨并三錢合物。 較佳的唑類為甲苯三唑,笨并三唑和耐鹵素唑,特別 是氣·甲笨三。坐。 可以與本發明四唑鐯化合物合併的附加試劑包括鋁腐 蝕抑制齊卜較佳的是水溶性硝酸鹽,肖別是硝酸納,确酸 鹽與驗金屬石夕酸鹽的組合。 可以與本發明四唑鏘化合物合併的附加試劑包括擇自 鋅錳,鋁,錫,鎳,釔,和稀土金屬(原子序57至71)之 族的金屬的水溶性金屬鹽及/或這種金屬的有機金屬螯合 物,其中該有機螯合物要選擇可提供金屬離子需要量的水 溶解度。如文獻已知的’這種金屬鹽和螯合物可以使用來 提供另外的腐蝕保護。 使用鋅離子作為腐蝕抑制劑是已知於文獻的,特別是 與其他水處理試劑組合,如磷酸鹽,膦酸鹽,卜羧酸鹽, 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) ----- (請先閱讀背面之注意事項再填寫本頁) ----訂--------- 32 542858-I Pack ---------- Order --------- Line (Please read the notes on the back before filling this page) 31 542858 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs V. Description of the invention (28) No. 5,156,769 i • benzyl_5_hydrosulfanyl tetra & Suitable salivas include mixed compositions, such as toluene triturate compositions that include at least pyrene, by weight, 5-methylbenzotrisialyl isomers, as disclosed in U.S. Patent No. 5,503,775, in This is added as a reference. When the water system uses "peptide-based oxidizing biological agents (such as chlorine)", it is particularly suitable for halogenated azoles that provide improved corrosion performance and no unpleasant odors. "Reduces the consumption of biological agents. Non-limiting examples of azoles are disclosed in U.S. Patent Cases Nos. 5,772,919, M63,463 and 5,863,464, which are incorporated herein by reference, and the basin includes qi-methylbenzyl salivary 'mo-toluene trisial, monodentate Benzotriazine, dimethylbenzotrisalyl, and monobenzyl and n-benzyltriestate. The preferred azoles are tolutriazole, benzotriazole, and halogen-resistant azole, especially chloroform Stupid. Sit. The additional reagents that can be combined with the tetrazolium compound of the present invention include aluminum corrosion inhibition, preferably water-soluble nitrate, and sodium nitrate, as well as a combination of salt and metal oxalate. Additional reagents that can be combined with the tetrazolium compound of the present invention include water-soluble metal salts selected from the group consisting of zinc manganese, aluminum, tin, nickel, yttrium, and rare earth metals (atomic numbers 57 to 71) and / or Organometallic chelate of a metal, wherein the organic chelate The compound is selected to provide the water solubility required for the metal ions. As known in the literature, 'this metal salt and chelate can be used to provide additional corrosion protection. The use of zinc ions as corrosion inhibitors is known in the literature. , Especially in combination with other water treatment reagents, such as phosphates, phosphonates, and carboxylates, this paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) ----- (please first Read the notes on the back and fill out this page) ---- Order --------- 32 542858
發明說明(29) 經濟部智慧財產局員工消費合作社印製 叛馱鹽和羥基羧酸鹽。較佳的鋅離子源是硫酸,氣,乙酸 或肖的鋅鹽和氧化鋅溶解於驗得到的鋅酸離子。特別佳 的是硫酸鹽和氯鹽和鋅酸離子。 錳離子與胺基膦酸酯和與P-羧酸鹽組合使用於水處理 已經分別被揭示於美國專利案件第4,64〇,818號和歐洲專 利案件第283 191A2號,二者在此都加入作為參考資料。 在水相系統中使用釔和原子序57至71鑭系金屬陽離子及/ 或其有機的螯合物作為腐蝕抑制已經被揭示於美國專利案 件第4,749,550號和5,130,052號,二者在此都加入作為參 考資料較仏的鑭鹽為鑭,镨,和敍者,及含有其混合物 的上市物料。 本發明可以與四唑鏘化合物合併的附加試劑包括水垢 和沈積控制劑。雖然許多前面說明的本發明組合同時提供 腐餘和水垢及/或沈積控制(特別對碳酸妈水垢),也可能 有B守候必須使用附加試劑來控制特別種系(如硫酸鋇或草 酸鈣)的長水垢及/或沈積。適合用於控制各種這種種系的 試劑是已知於文獻的。 可以與本發明四唑鏘化合物合併的附加試劑包括多價 螯合劑。這種試劑需要用以避免金屬(如鐵,銅)或鹼土離 子堵塞水相系統或干擾系統中腐蝕抑制劑或其他試劑適當 的功能。這種多價螯合劑是已知於文獻的,在一些情況下 ’可以可選擇有效於特定離子者。適合的多價螯合劑非限 制的貫施例包括乙二胺四(乙酸)氮基三乙酸,和n,n_:(2_ 每基乙基)甘胺酸或其水溶性鹽。 --------------裝·---L----訂---------線 f ,清先閱讀背面之注意事項再填寫本頁}Description of the Invention (29) Betrayal salts and hydroxycarboxylates are printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Preferred sources of zinc ions are sulfuric acid, gaseous, acetic or zinc salts of zinc and zinc oxide dissolved in the detected zinc acid ions. Particularly preferred are sulfate and chloride salts and zincate ions. The use of manganese ions in combination with aminophosphonates and P-carboxylates in water treatment has been disclosed in U.S. Patent No. 4,64,818 and European Patent Case No. 283 191A2, both of which are here Add as reference. The use of yttrium and atomic numbers 57 to 71 lanthanide metal cations and / or their organic chelates as corrosion inhibitors in aqueous systems has been disclosed in U.S. Patent Nos. 4,749,550 and 5,130,052, both of which are here The lanthanum salts that are added as reference materials are lanthanum, osmium, and Syria, and listed materials containing their mixtures. Additional agents that can be combined with the tetrazolium compound of the present invention include scale and deposition control agents. Although many of the previously described combinations of the present invention provide both rot and scale and / or deposition control (especially for carbonate carbonate scales), there may also be B-waiting that additional reagents must be used to control specific species (such as barium sulfate or calcium oxalate) Long scale and / or deposits. Suitable reagents for controlling a variety of such germlines are known in the literature. Additional agents that can be combined with the tetrazolium compound of the invention include sequestering agents. This reagent needs to be used to prevent metals (such as iron, copper) or alkaline earth ions from blocking the aqueous system or interfering with the proper function of corrosion inhibitors or other reagents in the system. Such sequestrants are known in the literature, and in some cases may be selected to be effective on specific ions. Non-limiting examples of suitable sequestrants include ethylenediamine tetra (acetic acid) nitrotriacetic acid, and n, n _ :( 2_perylethyl) glycine or a water-soluble salt thereof. -------------- Installation --- L ---- Order --------- line f, please read the notes on the back before filling this page}
542858 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(30) 可以與本發明四。坐鐵化合物合併的附加試劑包括防沐 劑。適合的防沫劑的實施例包括矽酮(如聚二 ,二硬脂基癸二酿胺,二硬脂基己二醯胺和衍;·自;7乙) 燒或環氧丙炫縮合作用的相關產物,及脂肪醇,如癸酿醇 和其環氧乙烷縮合物。 可以與本發明四唑鏘化合物合併的附加試劑包括生物 制劑。可能必須在水相系統和本發明組成物進料源使用生 物制劑以控制微生物生長。氧化性和非氧化性生物制劑都 可以使用於這些目的。適合的氧化性生物制劑包括至少一 個下面化合物:氣,次氯酸鹽,溴,次溴酸鹽,氣及/或 提供溴化合物(如溴氯乙内醯脲),過乙酸,無機過氧化物 和過氧化物產生物,二氧化氣,和臭氧。適合的非氧化性 生物制劑包括至少一個下面化合物:胺,四級銨化合物( 如N-烷基二甲基苯甲基銨氣化物),2_溴_2_硝基丙烷-^ 二醇’ β-溴硝基笨乙烯,十二烷基胍氫氣酸鹽,2,2-二漠_ 3 -氮基丙fe胺,戊二酿,氯盼,含硫化合物如楓,亞甲基 雙硫氰酸酯和胺基甲酸酯,異噻唑酮,溴化丙醯胺,三叮 併(例如terbuthylazine,和三吖啡衍生物,如揭示於美國 專利案件第5,534,624號者,在此加入作為參考資料),鱗 化合物,有機金屬化合物,如三丁基錫氧化物,和這種生 物制劑的混合物。一個較佳的非氧化性生物制劑是一個混 合物,其中包含(a)2-溴-2-硝基丙烷-1,3-二醇(BNPD)和(b) 一個大約75% 5-氯-2-甲基-4-異噻唑-3-酮和大約25% 2-甲 基-4-異噻唑-3-酮的混合物,該BNPD(a)對該混合物(b)重 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -----j----訂--------- (請先閱讀背面之注意事項再填寫本頁) 34 542858542858 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (30) It can be related to the present invention. Additional reagents that incorporate iron compounds include anti-foam agents. Examples of suitable anti-foaming agents include silicones (such as polybis, distearyl sebacamide, distearyl adipamide, and derivatives; · from; 7B) fired or propylene oxide Related products, and fatty alcohols, such as decanol and its ethylene oxide condensate. Additional agents that can be combined with the tetrazolium compound of the present invention include biological agents. It may be necessary to use biologics in the aqueous system and the feed of the composition of the invention to control microbial growth. Both oxidizing and non-oxidizing biological agents can be used for these purposes. Suitable oxidative biological agents include at least one of the following compounds: gas, hypochlorite, bromine, hypobromite, gas and / or the supply of bromine compounds (such as bromochlorohydantoin), peracetic acid, inorganic peroxides And peroxides, dioxide, and ozone. Suitable non-oxidizing biological agents include at least one of the following compounds: amines, quaternary ammonium compounds (such as N-alkyldimethylbenzyl ammonium vapors), 2-bromo_2_nitropropane- ^ diol ' β-bromonitrobenzyl ethylene, dodecylguanidine hydrochloride, 2,2-diamo_3-aminopropylamine, glutaric acid, chloropan, sulfur compounds such as maple, methylene disulfide Cyanate esters and carbamates, isothiazolones, propylammonium bromide, tributyl (such as terbuthylazine, and triacrine derivatives, as disclosed in U.S. Patent No. 5,534,624, incorporated herein by reference Information), scale compounds, organometallic compounds such as tributyltin oxide, and mixtures of this biological agent. A preferred non-oxidizing biological agent is a mixture containing (a) 2-bromo-2-nitropropane-1,3-diol (BNPD) and (b) an approximately 75% 5-chloro-2 -A mixture of methyl-4-isothiazol-3-one and about 25% 2-methyl-4-isothiazol-3-one, the BNPD (a) to this mixture (b) the weight of the paper applies to the country of China Standard (CNS) A4 specification (210 X 297 mm) ----- j ---- Order --------- (Please read the precautions on the back before filling this page) 34 542858
五、發明說明(31) 置比為大約16:1至大約1:1 ’如揭示於美國專利案件第 4,732,905號者,在此加入作為參考資料。 可以與本發明四讀化合物合併的附加試劑包括冷;東 溫度抑制劑。這種試劑需要用於如冷;東,除濕,和内燃機 引擎的冷m统的水相系統。此抑制劑本質上可以是離 子的或非離子的。適合_子試劑非限制的實施例包括氯 化好氯化鈉,漢化鐘,和氯化鐘。適合的非離子試劑的 實施例為水溶性醇’如乙二醇,丙二醇,乙醇,甘油,丙 醇,甲醇,及其混合物。 可以與本發明四唑鏘化合物合併的附加試劑包括pH 調節劑。適合的試劑非限制的實施例包括氫氧化鈉,氫氧 化鉀,氫氧化鋰,鹽酸,硫酸,硝酸,二氧化碳,氨,有 機&L如草I,驗金屬碳酸鹽,和驗金屬碳酸氫鹽。 备本發明組成物用於包含在表面和金屬之間移動接觸 的水相系、、充(如3有幫浦裝置系統或包含金屬切割或成形 應用遇到者),該系統可能需要使用潤滑劑來改善切割操 作性能或減少接觸及/或金屬表面的磨損。這種潤滑劑可 以是水浴性或非水溶性的。適合的非水溶性的有機潤滑劑 如天然油或合成油,包括揭示於美國專利第5,7丨6,9丨7號 者’在此加入作為參考資料。適合的水溶性潤滑劑包括揭 不於美國專利案件第3,720,695號,4,053,436號,4,289,636 號,4,402,839 號,4,425,248 號,4,636,321 號,4,758,359 號 ’ 4,895,668 號,5,401,428 號,5,547,595 號,5,616,544 號,和5,6 5 3,6 9 5號者,在此加入作為參考資料。一些潤 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 x 297公爱) I - I I (請先閱讀背面之注意事項再填寫本頁) ·. -丨線- 經濟部智慧財產局員工消費合作社印製 35 542858 五、發明說明(π) 滑劑(如揭示於美國專利案件第4,405,426號和5·4〇丨,428號 者,所有在此都加入作為參考資料)可能對本發明組成物 另外供改良的腐敍抑制性能。 在含有本發明組成份混合物安定產品的配方内或本發 明組成物應用到特別水相系統(特別是系統中存在明顯比 例的非水相液體者)時,另外使用表面活性劑是有利的。 這種表面活性劑本質上可以是陰離子的,陽離子的,兩性 的或非離子的,匕們是已知於文獻的。這種試劑可以加到 本务明組成物作為多種功能(如作為乳化劑,分散劑,水 合劑,防沫劑,潤滑劑,腐蝕抑制劑)。為達到特定目的 使用特定的適當表面活性劑的方法是已知於熟悉文獻者。 當使用有限水溶解度的添加物於本發明組成物時,使用表 面活性劑疋特別需要的(如當使用非水溶性的有機潤滑劑 或以微;;容的物料為主的附加腐姓抑制齊j,如月旨肪酸衍生物) 4 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 可以與本發明四唾鏘化合物合併的附加試劑包括妈硬 度調節劑。文獻中已經知道,許多水相系統腐餘抑制劑, 特別是-般用於處理開放式再循環冷卻系統者的效率決定 於二水中小!的溶解妈的存在。雖然本發明組成物的效 =比較不受溶_的影響’在本發明實例中系統中增加溶 解舞的濃度是有利的。適合的鹤硬度調節劑非限制的實施 例包括碳酸氫舞,碳_,氣㈣,硫_,和乙酸㈣ 及氫氧化鈣和氧化辦。 可以與本發明四嗤鏘化合物合併的附加試劑包括呈色 本紙張尺ϋ家標準各⑵〇 X 297立 36 542858 A7 B7 五、發明說明(33 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製V. Description of the invention (31) The ratio is about 16: 1 to about 1: 1 ′ As disclosed in US Patent No. 4,732,905, it is incorporated herein by reference. Additional reagents that can be combined with the fourth reading compounds of the invention include cold; east temperature inhibitors. This reagent needs to be used in cold water systems such as cold, dehumidifier, and cold engine systems of internal combustion engines. This inhibitor may be ionic or non-ionic in nature. Non-limiting examples of suitable reagents include sodium chloride, sodium chloride, and bell chloride. Examples of suitable non-ionic agents are water-soluble alcohols such as ethylene glycol, propylene glycol, ethanol, glycerol, propanol, methanol, and mixtures thereof. Additional agents that can be combined with the tetrazolium compound of the present invention include pH adjusters. Non-limiting examples of suitable reagents include sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrochloric acid, sulfuric acid, nitric acid, carbon dioxide, ammonia, organic & ascorbic acid I, metal carbonate, and metal carbonate . The composition of the present invention is used for the aqueous phase system, including the mobile contact between the surface and the metal (such as a 3 pump system or a metal cutting or forming application encountered), the system may require the use of lubricants To improve cutting performance or reduce contact and / or metal surface wear. This lubricant may be water-bathable or water-insoluble. Suitable water-insoluble organic lubricants, such as natural oils or synthetic oils, including those disclosed in U.S. Patent Nos. 5,7, 6,9, and 7, are incorporated herein by reference. Suitable water-soluble lubricants include U.S. Patent Nos. 3,720,695, 4,053,436, 4,289,636, 4,402,839, 4,425,248, 4,636,321, 4,758,359 '4,895,668, 5,401,428, 5,547,595, and 5,616,544, and 5,6 5 3,6 9 No. 5 are hereby incorporated as reference materials. Some paper sizes are subject to the Chinese National Standard (CNS) A4 (21 × 297 Public Love) I-II (Please read the precautions on the back before filling this page) ·.-Line-Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by a consumer cooperative 35 542858 V. Description of the invention (π) Lubricants (such as those disclosed in US Patent Nos. 4,405,426 and 5.40, 428, all of which are incorporated herein as reference materials) may affect the composition of the present invention In addition for improved rot suppression performance. It is advantageous to additionally use a surfactant in a formulation containing a stable product of the component mixture of the present invention or when the composition of the present invention is applied to a special aqueous phase system (especially a non-aqueous phase liquid in a significant proportion of the system). Such surfactants can be anionic, cationic, amphoteric or nonionic in nature, and knives are known in the literature. This reagent can be added to this composition for various functions (e.g. as emulsifier, dispersant, hydrating agent, anti-foaming agent, lubricant, corrosion inhibitor). Methods for using specific suitable surfactants for specific purposes are known to those familiar with the literature. When using additives with limited water solubility in the composition of the present invention, the use of surfactants is particularly needed (such as when using water-insoluble organic lubricants or micro-; j, such as a fatty acid derivative of the month) 4 Additional reagents printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs that can be combined with the tetrasialyl compound of the present invention include a hardness regulator. It is known in the literature that the efficiency of many water phase system residue inhibitors, especially those used to treat open recirculation cooling systems, is determined by the small amount of secondary water! The presence of the dissolved mother. Although the effect of the composition of the present invention is relatively unaffected by dissolution, it is advantageous to increase the concentration of dissolution dance in the system of the example of the present invention. Non-limiting examples of suitable crane hardness modifiers include bicarbonate, carbon, tritium, sulfur, and thallium acetate and calcium hydroxide and oxidizing agents. Additional reagents that can be combined with the tetrazine compounds of the present invention include coloring papers, paper standards, house standards, 297, 297, 36, 542,858, A7, and B7. V. Description of the invention
77 J這種°式A彳的用法非限制的實施例包括改善產品外觀, 黧助產品確認,和作為使用比色法可以控制的自動進料控 制系統的添加物。這種試劑非限制的實施例包括水溶性染 料。 令人驚許的,本發明者發現四唑鏘化合物協同地與多 種已·^的水垢及/或腐餘抑制劑合併提供大大增加一般的 腐蝕和凹點腐蝕的性能。本組合有效於大的鈣硬度和pH 犯圍,包括低硬度水。在一些情況下,當使用本組合與沒 有使用四唑鏘化合物的處理方法比較,甚至當維持總活性 處理含量一定時,也得到減少一個或更多個級次量的腐蝕 率〇 本發明四唑鑽化合物是已知為可還原的種系。雖然反 應機制細節還沒有被深入研究,還不完全被瞭解,一般相 信一個本發明新穎的組成物腐蝕抑制效應的要素是可溶的 四唑鎩化合物在腐蝕金屬表面還原成為一個較不可溶的和 保護性的薄膜。這個還原作用可以是多步驟方法,保護性 的薄膜可能含有數個中間還原產物。很可能的,一些這種 中間還原產物可能不是保護性的薄膜的一部份,但仍然7 能可以再進一步還原,形成抑制腐蝕薄膜。這種四唑鏘 合物抑制腐蝕的中間還原產物也被認為在範圍本發明= 四唑鏘化合物保護性的作用加上附加水處理劑的保 性作用提供有效的水相系統腐蝕控制。在許多情況下 加水處理劑也提供對抗水形成水垢和沈積的保護,在這 情況下,本發明組合是有效於控制腐蝕和長水垢/沈S 訂 線 化 護 附 4b 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 542858 A7 五、發明說明(Μ) 經濟部智慧財產局員工消費合作社印製 附加水處理劑可能提供組成物其他需要的性質(如分散顆 粒化物質的能力)。然而,一些水處理劑(如脫氧劑)可能 使四唑鎩化合物直接在溶液中還原,使四唑鏘化合物本$ 或強力抑制腐蝕中間還原產物不能在金屬表面形成保護性 的薄膜。因此,在水相溶液中,特別使用條件下,實質還 原四唑鏘化合物的水處理劑不適合與本發明使用。使用條 件包括這種考量作為四唾鐳化合物和還原四唾鐵水處理劑 相對比例(如使用不實質還原存在的四唑鏺化合物量的減 少水處理劑的量的用法仍然在本發明範圍内)。使用的條 件也包括四唑鏘化合物和其他種系的絕對濃度,溫度, 間,改變四唑纟翁化合物和還原四唑鐳水處理試劑之間交 作用的附加氧化劑及/或還原劑或其他化合物的存在或 存在,催化性表面(如金屬表面)的存在或不存在等等。 悉文獻者可很快地測定在使用條件下是否特別試劑實質的 還原四唑鏘化合物。因為四唑鏘化合物還原產物通常是較 冰色的,而原始物料則否,得到此測定的簡單方法包括 視覺觀察和比色法。 延伸上面的說明,水相系統不含有影響四唑鏘化合 腐蝕抑制性,使得四唑鑕化合物不抑制腐蝕的物料。因〜 ,該四唑鑕化合物不被物料實質的還原而使四唑鑽化合物 不此抑制腐蝕。此外,任何使四唑鏘化合物及/或附加物 料不能腐蝕抑制及/或預防長水垢的物料較佳地不包括於 水相系統中,或較佳地包含不影響使四唑鏘化合物達到腐 餘抑制及/或避免長水垢的量。 時 不 熟 的 物 此77 J. Examples of non-limiting uses of the formula A 彳 include improved product appearance, assisted product identification, and additions as an automatic feed control system that can be controlled using a colorimetric method. Non-limiting examples of such agents include water-soluble dyes. Surprisingly, the present inventors have discovered that the tetrazolium compound synergistically combines with various scale and / or residue inhibitors to provide properties that greatly increase general corrosion and pitting corrosion. This combination is effective for large calcium hardness and pH violations, including low hardness water. In some cases, when this combination is compared with a treatment method without using a tetrazolium compound, even when the total active treatment content is maintained, a corrosion rate of one or more orders of magnitude is reduced. The tetrazole of the present invention Drilling compounds are known as reducible germlines. Although the details of the reaction mechanism have not been thoroughly studied and are not fully understood, it is generally believed that an element of the corrosion inhibitory effect of the novel composition of the present invention is the reduction of a soluble tetrazolium compound on a corroded metal surface to a more insoluble and Protective film. This reduction can be a multi-step process, and the protective film may contain several intermediate reduction products. It is possible that some of these intermediate reduction products may not be part of a protective film, but still can be further reduced to form a corrosion-resistant film. This intermediate reduction product of the tetrazolium compound for inhibiting corrosion is also considered to be within the scope of the present invention = the protective effect of the tetrazolium compound plus the protective effect of the additional water treatment agent provides effective corrosion control of the aqueous system. In many cases, the water treatment agent also provides protection against water formation of scale and sedimentation. In this case, the combination of the present invention is effective in controlling corrosion and long scale / sinking. Threading protection 4b This paper standard applies to Chinese national standards (CNS) A4 specification (210 X 297 public love) 542858 A7 V. Description of the invention (M) Additional water treatment agent printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs may provide other required properties of the composition (such as the ability). However, some water treatment agents (such as deoxidants) may reduce the tetrazolium compound directly in the solution, making the tetrazolium compound costly or strongly inhibit the corrosion. The intermediate reduction products cannot form a protective film on the metal surface. Therefore, in an aqueous solution, a water treatment agent that substantially reduces a tetrazolium compound is not suitable for use in the present invention under special use conditions. The conditions of use include such considerations as the relative ratio of the tetrasialide compound and the reduced tetrasialide water treatment agent. . The conditions used also include the absolute concentration, temperature, and temperature of the tetrazolium compound and other germline, additional oxidants and / or reducing agents or other compounds that change the interaction between the tetrazolium compound and the reduced tetrazolium water treatment reagent. The presence or absence of, the presence or absence of catalytic surfaces (such as metal surfaces), and so on. Those familiar with the literature can quickly determine whether the reagent is a substantial reduction of the tetrazolium compound under the conditions of use. Because the reduced product of the tetrazolium compound is usually ice-colored, and the original material is not, simple methods for obtaining this determination include visual observation and colorimetry. Extending the above description, the aqueous system does not contain materials that affect the corrosion inhibitory properties of the tetrazolium compound, so that the tetrazolium compound does not inhibit corrosion. Because ~, the tetrazolium compound is not substantially reduced by the material, so that the tetrazolium compound does not inhibit corrosion. In addition, any material that prevents the tetrazolium compound and / or additional materials from corrosion inhibition and / or the prevention of scale formation is preferably not included in the aqueous system, or preferably does not affect the tetrazolium compound's ability to achieve decay. Suppress and / or avoid the amount of scale. Unfamiliar
本紙張尺度翻巾關家鮮(CNS)A4規格⑵〇 x 297公釐) -----------—Γ—訂--------- (請先閱讀背面之注意事項再填寫本頁) 542858 經濟部智慧財產局員工消費合作社印製 A7 r-----Ε__ 五、發明說明(35) 们車乂仏的本發明實例中,大約0.5至10,000 ppm 白勺四唾鐵化合物和水相系統處理物料的組合加到需要處理 的火相系、、先,大約10至1000PPm的該組合是特別佳的。其 h才系、洗處理物料與四唾鐵化合物的重量比較佳地是大 、勺100,1到丨·20,而重量比大約20:1到1:1是特別佳的。 本备明組成物可以應用的水相系統pH範圍自大約5至 _ 大、力12 pH較佳地在大約6至大約丨〇的範圍内。 本毛明組成份可在填充系統時,用有效濃度以泥漿進 料^ ^ ”水相〆夜體混合投予水相系統。當在系統(如開放 式冷部系統)内用於處理水相系統的一個或更多個處理組 成份從系統排出或由於化學的或物理的方法而消耗,則需 要補充來、准持處理效率,本發明組成物可以用連續的方式 用門、貝的方式或用兩種方式的組合(如使用連續的低量 進料’需要時以泥漿進料補充)進料到系統。決定於應用 K車乂好的疋合併本發明組成物從一個進料供應源一起 ^ 一次處理進料,或,另外,將組成份分為二個或更多個處 、原各源獨立地用足以維持系統内濃度需要的速率連續 的或間‘的進料到系統。各處理源可以使用單一或多進料 點進入水相系統。 處理進料的時效和速率可以用多種已知於文獻的方法 控制。-個適合的方法是使用計量幫浦或其他進料系統裝 置匕們可以用各種不同的組態,以固定速率,以一定時 私表’、以其他系統組件,如補充幫浦或增壓幫浦產生的訊 5虎或以*員比為主或以電腦為主進料控制系統產生的訊號 t @ S ^#iT(CNS)A4 (21〇Τ297 ^ )----- “免 -39 - ^----------^---------^ (請先閱讀背面之注意事項再填寫本頁) 542858 A7 經濟部智慧財產局員工消費合作社印製 水 實 ,153 五、發明說明(3〇 連續進料。適合的進㈣統非限制的實施例已經揭示於美 國專利案件第 4,648,043 號,4,659·459 號,4,897,797 號, 5,〇56,036號,5.G92J39號和5,695,〇92號。進料控制系統 可使用下面相關的訊號:一個或更多個處理組成份的濃度 ’-個或更多個加到處理的惰性或活性示縱劑物料的濃度 ,一個或更多個系統性能測定值(如得自腐蝕率計,水^ 價測器,熱移轉偵測裝置,檢測水中腐織物量的分析裝 置,如總鐵或溶解鐵或其他金屬組成份等等的數值),二 個或更多個系統的物理特性數值(如溫度,流動率,導電 性)’ -個或更多個系統的化學特性數值(如阳,辦硬度, 氧化還原電位,驗度)或這些訊號的組合,來進料並維持 足夠在特別水相系統中有效性能的處理含量。另外,最好 在一些系、统中使用控㈣釋放(此後也稱之為$漸釋放或 時效釋放)輸送系統於一些或所有本發明化合物。在這種 控制的釋放系統中’要進料的物料灌輸進人或另外加到控 制釋放系統填充料内。適合的控制釋放輸送系統包括將填 充料暴露於水相系統中的液體者或液體流進料到水相系統 ’而處理組成份以各種不同的方法的動作逐漸地釋放入系 統(如擴散’溶解’滲透壓差異),它可另外設計改變釋放 率,來配合水相液體的特性,如溫度,流動率,pH, 硬度,導電性等等。這種控制的釋放輸❹統非限制的 施例已經被揭示於美國專利案件第3,985,298號,4,22〇, 號 ’ 5,3 16,774號,5,364,627號,和 5,391,369號。 ---------^---------. (請先閱讀背面之注意事項再填寫本頁) 當使用的進料系統利用處理或示縱劑組成份的測定漢The size of this paper is turned over (CNS) A4 size ⑵〇x 297 mm) ------------- Γ-order --------- (Please read the back Note: Please fill in this page again) 542858 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 r ----- Ε__ 5. Description of the invention (35) In the example of the invention of our car, about 0.5 to 10,000 ppm The combination of a tetrasial compound and the material processed in the aqueous phase system is particularly preferred when it is added to the fire phase system to be processed. First, about 10 to 1000 PPm. Its weight is relatively large, the weight of the washing treatment material and the tetrasialo compound is relatively large, the spoon is 100,1 to 丨 · 20, and the weight ratio of about 20: 1 to 1: 1 is particularly good. The pH of the aqueous phase system to which the composition of the present invention can be applied ranges from about 5 to _large, and the pH of the force 12 is preferably in the range of about 6 to about 〇. This Maoming composition can be fed to the water phase system with an effective concentration of ^ ^ "water phase and nocturnal body" when filling the system. When used in the system (such as an open cold section system) to treat the water phase One or more processing components of the system are discharged from the system or consumed due to chemical or physical methods, and need to be supplemented to maintain the processing efficiency. The composition of the present invention can be used in a continuous manner using a door, shell or Feed the system in a combination of two methods (such as using a continuous low-volume feed, supplemented with mud feed when needed). It is determined by the use of a K-car, which combines the composition of the present invention from one feed supply source together ^ Process the feed at one time, or, in addition, divide the components into two or more locations, each source independently using a continuous or intermittent feed to the system at a rate sufficient to maintain the concentration in the system. Each process The source can enter the aqueous system using single or multiple feed points. The time and rate of processing the feed can be controlled using a variety of methods known in the literature. A suitable method is to use a metering pump or other feed system device Daggers can use a variety of different configurations, at a fixed rate, at a certain time, to private watches', to other system components, such as supplementary or booster pumps produced by the 5th Tiger, or to the main staff ratio or computer The signal generated by the main feed control system t @ S ^ # iT (CNS) A4 (21〇Τ297 ^) ----- "FREE -39-^ ---------- ^ --- ------ ^ (Please read the notes on the back before filling out this page) 542858 A7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 153 V. Description of the invention (30 continuous feed. Suitable feed Non-limiting examples of the system have been disclosed in U.S. Patent Cases Nos. 4,648,043, 4,659.459, 4,897,797, 5, 〇56,036, 5.G92J39, and 5,695, 〇92. The feed control system can use the following related Signal: Concentration of one or more processing components'-One or more concentration of inert or active peptizer material added to the process, one or more system performance measurements (if obtained from a corrosion rate meter , Water valence detector, thermal transfer detection device, analysis device to detect the amount of rotten fabric in water, such as total iron or dissolved iron or other metals Values of components, etc.), physical property values of two or more systems (eg temperature, flow rate, conductivity) '-chemical property values of one or more systems (eg, yang, hardness, redox potential) , Test) or a combination of these signals to feed and maintain a sufficient processing performance in a particular aqueous system. In addition, it is best to use controlled release (also referred to as $ gradual hereinafter) in some systems and systems Release or aging release) delivery system to some or all of the compounds of the invention. In this controlled release system, the 'material to be fed is infused into a person or otherwise added to the filler of a controlled release system. Suitable controlled release delivery systems include The filler is exposed to the liquid in the aqueous system or the liquid stream is fed into the aqueous system 'and the processing components are gradually released into the system in a variety of different actions (such as diffusing' dissolving 'the osmotic pressure difference). It can be designed to change the release rate to match the characteristics of the aqueous liquid, such as temperature, flow rate, pH, hardness, conductivity, etc. Non-limiting examples of such controlled release systems have been disclosed in U.S. Patent Cases Nos. 3,985,298, 4,220, '5,3,774, 5,364,627, and 5,391,369. --------- ^ ---------. (Please read the precautions on the back before filling out this page) When using the feed system, use the processing or measuring agent composition
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度,14些濃度可以用連續的,半連續的或批次形態的分析 技術測定,包括光譜法方法(uv,可見光放射,可見光吸 收,1R’Raman’榮光’鱗光等),電化學的方法(包括PH ’ ORP,和離子特定電極測定法),層析法(Gc,Lc),決 定於抗體結合或釋放的方法,以化學為主的分析/比色方 法,如the Hach Company上市者等等。一個適合的光譜儀 法說明於美國專利案件第5,242,6〇2號,在此加入作為參 考貧料。一個適合用於調節水處理試劑系統内濃度的方法 揭示於美國專利案件第5,411,889號。美國專利案件第 5,855,791號,纟此加人作為參考㈣,這些案件揭示適 a的方法以些性此偵測器和系統特性為主,用於測定 腐姓和堵塞抑制劑進料率。 可能任擇地使用的示蹤劑化合物可以是不作為特別處 理功能的化合物,此後稱之為惰性示蹤劑,或可以是也很 快地被偵測的水處理化合物,這種處理化合物此後稱之為 活性示蹤劑。適合的示蹤劑包括可溶的鋰鹽,如氣化鋰, 過渡金屬,如說明於美國專利案件第4,966,7u號者,在 此加入作為參考資料,和螢光惰性示蹤劑,如說明於美國 專利案件第4,783,3 14號者,在此加入作為參考資料。適 合的螢光惰性示蹤劑包括單-,二·,和三磺酸化萘(如萘 石黃酸或萘二磺酸的水溶性鹽)。適合的活性示蹤劑包括螢 光標記的聚合物,如說明於美國專利案件第5,丨7丨,45〇號 者,在此加入作為參考資料,和含有光惰性,隱藏的可檢 測部份的聚合物,當與光活化劑接觸會吸收光線,如說 本紙張尺度適用中國國家標準(CNS)A4規格(21G X 297公爱) ^ — (請先閱讀背面之注意事項再填寫本頁) . •線· 經濟部智慧財產局員工消費合作社印製 41 542858 A7 五、發明說明(38 ) 於美國專利案件第5·654,198號者,在此加入作為參考資 料,及以唑類為主的銅腐蝕抑制劑,如曱苯三唑,和水、、容 性鉬酸鹽和鎢酸鹽。 雖然許多與四唑鏘化合物合併的化合物是已知的腐蝕 抑制劑,它們通常被認為只在特別的鈣硬度和ρΗ條件下 有效。例如一些膦酸基羧酸酯,如2-膦酸基丁烷-:1,2,4一三 羧酸(PBTC)通常只在pH超過8和水中含有一定量的鈣硬度 (如> 200 mg/卜以CaC〇3計)有效的作為腐蝕抑制劑。如下 面的證實,PBTC與四唑鏘化合物的組合在pH 76,只含 有1〇〇 mg/丨鈣,以CaC〇3計,的水中是很有效的。類似= 結果也在其他組合看到。最好在許多水相系統有“耐受,,水 PH和硬度的處理,也就是在大範圍的這些條件下可以 行得很好。 使用四唑鏘化合物可明顯的減少需要的總處理劑量, 有效地限制水相系統中的腐蝕。四唑鏘化合物的組合許多 是與主要或特定使用為水垢及/或沈積抑制劑的物料。然 而’這些組合有效地同時用於長水垢/沈積和腐触的控制 項 進 訂 4 濟 部 智 慧 財 員 工 消 費 印 測試方法知條件 本發明處理的腐姓抑制活性用燒杯腐姓測試儀器 (町A)評估。BCTA由_個2公升燒杯,上面m空 乱/C〇2授動器,!〇〗〇低碳鋼(LCS)測試管,—個LCS 電化學碳針,和磁授拌棒組成。測試溶液的體積紅9公 升。在測試期間空氣/⑶此㈣« 1以得到電化學腐 本紙張尺5顧中_緖i^Ns)A4祕(細χ撕公爱 542858 五、發明說明(39) 钱測定的參考資料電極和對電極是以⑽如一⑶架構。 燒杯沈浸於水浴中以控制溫度。在測試期間,以極化電 技術定期地從碳針取得電化學的腐减據。所有的測試都 ^120〇F進行,使用4〇〇 RpM攪拌率。除非另外說明,測 忒期間為18小時。各測試報告二個數值;ec(_是在測 心間測疋的電化學腐姓率的平均數值,而ec(i8小時)是 在測4終點腐㈣的數值。後項數值更被認為是預期長期 腐钱率的指標。 在所有的測。式中,沈浸於燒杯中的測試管在測試期間 都被拍下片。對於—些測試,測試管上的凹點深度以顧 微鏡技術測定(參考ASTM G 4694,5·2 4)。這些凹 點測定測試’使用二個測試管,每—測試管測定高達胸 凹點(每一邊高達10個)。 除非另外特別說明,測試水含有1〇〇mg/l Ca (以CaC〇3 計),50 mg/丨Mg (以CaC_),刚mg/丨氣化物,和⑽邮 4S文鹽。使用這種水在86,7·6,和68的pH進行測試。 14些阳值相對的“M”驗度為川,32,和4 mg/ι (所有的都 疋以C a C Ο 3計)。 經濟部智慧財產局員工消費合作社印製 較困難在這種測試水控制鐵金屬腐蝕。相對較低的鈣 硬度使依賴料抑制劑難以有效地作用。相對較高的硫酸 鹽和氣化物含量(對肖定約含量)使得水對鐵金屬具有侵略 性’特別是對於凹點腐蝕。 為了避免在測試期間發生碳酸鈣及/或磷酸鈣沈積, δ午多測试在測試水加入5 mg/卜聚合反應度為大約5的 (210 x 297 公釐) 本紙張尺度適用中國國家標準(CNS)A4規;fi 542858 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(40) 環氧號ίό酸(PES A),和5 mg/1活性的丙稀酸和稀丙基經基 丙基磺酸酯醚鈉鹽共聚物(AA/AHPSE)來進行。對一些測 試只用5 mg/1的AA/AHPSE共聚物。 同時進行添加和取代(固定抑制劑含量)測試。在前面 的測試形態,一個低含量的四唑鏘化合物(2至5 mg/Ι)加到 一個第二組成物。在後項測試,第二組成物減少一個特定 量(2至5 mg/1),而以相同量的四唑鏘化合物取代。 性能實施例 實施例# 1 在pH 8.6進行測試的BCTA結果顯示於表1。使用於這 些測試的四唑繙化合物為NBT。Belcor 575是FMC出售的 說基膦酸基乙酸。Bricorr 288是Albright and Wilson出售 的一個膦酸基琥珀酸,膦酸化順-丁烯二酸二聚物,磷酸 ’和一個以重量計次要部份的較高膦酸化的順·丁烯二酸 券水物的混合物。Dequest 2060為Monsanto出售的二乙三 胺五(亞曱基膦酸)。Bayhibit AM為Bayer出售的2-膦酸基 丁烷-1,2,4-三羧酸。Goodrite κ·752 是一個 b F Goodrich 出售的聚丙烯酸酯。 如從表1可看到的,在所有的情況,除了 Bricorr 288 ,添加或取代低含量的NBT協同地改善腐蝕性能。這種如 特別測试條件的因素可能使Bricorr 288得到這種情況。 本紙張尺度適用中國國豕標準(CNS)A4規格(210 X 297公爱 -----:--------l·---訂--------- (請先閱讀背面之注意事項再填寫本頁) 542858 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(41) 表1 pH 8.6Degree, 14 concentrations can be measured by continuous, semi-continuous or batch morphological analysis techniques, including spectroscopic methods (uv, visible light emission, visible light absorption, 1R'Raman 'glory' scale light, etc.), electrochemical methods (Including PH 'ORP, and ion-specific electrode assays), chromatography (Gc, Lc), methods that depend on antibody binding or release, chemical-based analysis / colorimetric methods, such as the marketer of the Hach Company, etc. Wait. A suitable spectrometer method is described in U.S. Patent Case No. 5,242,602, which is hereby incorporated by reference. A suitable method for adjusting the concentration in a water treatment reagent system is disclosed in U.S. Patent No. 5,411,889. U.S. Patent Case No. 5,855,791, which is hereby incorporated by reference, reveals that the appropriate method is based on the characteristics of this detector and system, and is used to determine the feed rate of rotten and clogging inhibitors. A tracer compound that may be optionally used may be a compound that does not function as a special treatment, hereinafter referred to as an inert tracer, or may be a water treatment compound that is also detected quickly, and such a treatment compound is hereinafter referred to as Is an active tracer. Suitable tracers include soluble lithium salts, such as lithium gaseous, transition metals, as described in U.S. Patent Case No. 4,966,7u, incorporated herein by reference, and fluorescent inert tracers, as described In U.S. Patent Case No. 4,783,3, 14 is hereby incorporated by reference. Suitable fluorescently inert tracers include mono-, di-, and trisulfonated naphthalenes (such as the water-soluble salts of naphthalene flavonic acid or naphthalenedisulfonic acid). Suitable active tracers include fluorescently labeled polymers, such as those described in U.S. Patent Case No. 5, 丨 7 丨, No. 45, incorporated herein by reference, and containing photo-inert, hidden detectable portions The polymer will absorb light when in contact with the photoactivator. For example, the paper size applies the Chinese National Standard (CNS) A4 (21G X 297 public love) ^ — (Please read the precautions on the back before filling this page) • Line · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs' Consumer Cooperatives 41 542858 A7 V. Description of Invention (38) In the US Patent Case No. 5.654,198, here are incorporated as reference materials, and mainly azoles Copper corrosion inhibitors, such as benzotriazole, and water, capacitive molybdate and tungstate. Although many compounds combined with tetrazolium compounds are known corrosion inhibitors, they are generally considered to be effective only under exceptional calcium hardness and pH conditions. For example, some phosphonate carboxylic acid esters, such as 2-phosphonobutane-: 1,2,4 monotricarboxylic acid (PBTC), usually contain only a certain amount of calcium hardness (such as > 200) in pH over 8 and water mg / bu as CaC03) effective as a corrosion inhibitor. It was confirmed as follows that the combination of PBTC and tetrazolium compound was very effective in water at pH 76, containing only 100 mg / calcium in terms of CaCO3. Similar = results are also seen in other combinations. It is best to have "tolerance," water pH and hardness treatment in many aqueous systems, that is, it can work well under a wide range of these conditions. The use of tetrazolium compounds can significantly reduce the total treatment dose required, Effectively limits corrosion in aqueous systems. Many combinations of tetrazolium compounds are with materials that are primarily or specifically used as scale and / or deposition inhibitors. However, 'these combinations are effective for both scale / deposition and rust contact simultaneously The control items of the Ministry of Education of Jibei Smart Wealth Co., Ltd. Consumer Test Method Known Conditions The inhibitory activity of the rotten surname treated by the present invention was evaluated with a beaker rotten surname tester (machi A). Co2 actuator, 〇〗 〇 Low carbon steel (LCS) test tube, an LCS electrochemical carbon needle, and a magnetic stir bar. The volume of the test solution is 9 liters red. ㈣ «1 to get electrochemical rot paper ruler 5 Gu Zhong _ 绪 i ^ Ns) A4 secret (fine χ tear public love 542858 V. Description of the invention (39) reference for the determination of the electrode and counter electrode are as follows: Architecture. Beaker immersed in water bath In order to control the temperature. During the test, the electrochemical corrosion reduction data was obtained periodically from the carbon needle by polarized electric technology. All tests were performed at 120 ° F, using a stirring rate of 400 RpM. Unless otherwise stated, the measurement The duration of the radon is 18 hours. Two values are reported for each test; ec (_ is the average value of the electrochemical survivorship rate measured in the test heart, and ec (i8 hours) is the value at the end of the test. The value of the term is considered as an indicator of the expected long-term rate of rotten money. In all measurements, the test tube immersed in the beaker was photographed during the test. For some tests, the depth of the pit on the test tube Quantitative micro-mirror techniques (refer to ASTM G 4694, May 24). These pit test tests use two test tubes, each measuring up to chest pits (up to 10 on each side). Unless otherwise specified Note that the test water contained 100 mg / l Ca (calculated as CaC03), 50 mg / 丨 Mg (calculated as CaC_), just mg / 丨 gas, and 4S sodium salt. Using this water at 86 , PH of 6,6, and 68. 14 The relative "M" test for positive values is Sichuan, 32, and 4 mg / (All are calculated as C a C 0 3). It is more difficult for employees of the Intellectual Property Bureau of the Ministry of Economic Affairs to print consumer cooperatives in this test to control the corrosion of ferrous metals in this test water. The relatively low calcium hardness makes it difficult to effectively rely on material inhibitors. Effect. Relatively high sulfate and gaseous content (content of Schrodinger) makes water aggressive to ferrous metals, especially for pitting corrosion. In order to avoid calcium carbonate and / or calcium phosphate deposition during the test, δ Noon test is added in test water with 5 mg / Bu polymerization reaction degree of about 5 (210 x 297 mm) This paper size applies to Chinese National Standard (CNS) A4 regulations; fi 542858 A7 B7 Employees ’intellectual property bureau consumption Printed by the cooperative V. Description of the invention (40) Epoxy resin (PES A), and 5 mg / 1 active acrylic acid and dipropyl propyl sulfonate ether sodium salt copolymer (AA / AHPSE ) To proceed. For some tests only 5 mg / 1 AA / AHPSE copolymer was used. Simultaneous addition and substitution (fixed inhibitor content) tests. In the previous test form, a low content of a tetrazolium compound (2 to 5 mg / 1) was added to a second composition. In the latter test, the second composition was reduced by a specific amount (2 to 5 mg / 1) and replaced with the same amount of tetrazolium compound. Performance Examples Example # 1 The results of BCTA tested at pH 8.6 are shown in Table 1. The tetrazole compound used in these tests was NBT. Belcor 575 is a monophosphonic acid sold by FMC. Bricorr 288 is a phosphonic succinic acid, phosphonated maleic-butenedioic acid dimer sold by Albright and Wilson, Phosphoric Acid 'and a higher phosphonized maleic acid, a minor portion by weight Water mixture of coupons. Dequest 2060 is diethylenetriaminepenta (phosphoranylidenephosphonic acid) sold by Monsanto. Bayhibit AM is a 2-phosphonic acid butane-1,2,4-tricarboxylic acid sold by Bayer. Goodrite κ · 752 is a polyacrylate sold by b F Goodrich. As can be seen from Table 1, in all cases, except for Bricorr 288, the addition or replacement of low levels of NBT synergistically improved the corrosion performance. Such factors as special test conditions may cause this situation to Bricorr 288. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love -----: -------- l · --- order --------- (please (Please read the notes on the back before filling out this page) 542858 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (41) Table 1 pH 8.6
含有 5 mg/1 活性PESA和5 mg/1 活性AA/AHPSE mg/1 抑制劑 mg/1 EC EC (所有都是活性劑) NET avg 18 0 - 0 58 50 0 - 2 24 24 0 - 5 7.7 5.5 20 L-酒石酸 0 6.2 8.5 20 L-酒石酸 2 2.6 3.2 20 L-酒石酸 5 2.7 2.7 15 HEDP 0 2.5 2.0 10 HEDP 0 3.0 2.1 7 HEDP 3 2.2 2.2 15 Belcor 575 0 3.8 2.8 10 Belcor 575 0 5.6 4.6 7 Belcor 575 3 1.7 1.2 15 Bricorr 288 0 3.8 2.9 10 Bricorr 288 0 4.7 4.0 7 Bricorr 288 3 6.2 4.4 15 Goodrite K-752 0 25 53 12 Goodrite K-752 3 8.8 17 15 Dequest 2060 0 4.0 3.2 10 Dequest 2060 0 7.3 8.8 7 Dequest 2060 3 3.6 2.7 15 Bayhibit AM 0 6.1 5.7 10 Bayhibit AM 0 8.1 9.1 7 Bayhibit AM 3 3.3 3.0 實施例#2 在pH 7.6,含有AA/AHPSE和PESA的情況下進行測試 的腐蝕結果顯示於表2。只含AA/AHPSE的結果顯示於表3 (請先閱讀背面之注意事項再填寫本頁) 裝 訂 線 45 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 542858Contains 5 mg / 1 active PESA and 5 mg / 1 active AA / AHPSE mg / 1 inhibitor mg / 1 EC EC (all are active agents) NET avg 18 0-0 58 50 0-2 24 24 0-5 7.7 5.5 20 L-tartaric acid 0 6.2 8.5 20 L-tartaric acid 2 2.6 3.2 20 L-tartaric acid 5 2.7 2.7 15 HEDP 0 2.5 2.0 10 HEDP 0 3.0 2.1 7 HEDP 3 2.2 2.2 15 Belcor 575 0 3.8 2.8 10 Belcor 575 0 5.6 4.6 7 Belcor 575 3 1.7 1.2 15 Bricorr 288 0 3.8 2.9 10 Bricorr 288 0 4.7 4.0 7 Bricorr 288 3 6.2 4.4 15 Goodrite K-752 0 25 53 12 Goodrite K-752 3 8.8 17 15 Dequest 2060 0 4.0 3.2 10 Dequest 2060 0 7.3 8.8 7 Dequest 2060 3 3.6 2.7 15 Bayhibit AM 0 6.1 5.7 10 Bayhibit AM 0 8.1 9.1 7 Bayhibit AM 3 3.3 3.0 Example # 2 The corrosion results of tests performed at pH 7.6 with AA / AHPSE and PESA are shown in the table 2. The results with AA / AHPSE only are shown in Table 3 (Please read the notes on the back before filling this page) Binding Line 45 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 542858
。在這些水中,8)為3 mpy或更少者被認為 工業應用是可接受的腐料。在—些㈣於表㈣情^ 存在有时錯化合物的腐解是不可接受的。’然而,第— 組成份與四唑鏘化合物的組合協同的改善情況是明顯的, -個熟悉文獻者可很快地敎需要的有效抑制劑總量以及 四唾鏘化合物和其他組成份用以得到目標應用需要的腐姓 保護需要的相對比例。 这個上面說明的在pH 86結果的趨勢也在pH以看到 ’ B£ic.T:L._288的測試結果以圖式顯示於1,更清楚地說 明使用四㈣化合物NET與此物料組合得到的協同改善。 實施例#3 在pH 6.8進行測試的腐蝕結果顯示於下 — I ---------訂------- (請先閱讀背面之注咅?事項再填寫本頁) !壽! 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 46 542858 A7 B7 五、發明說明(43) 經濟部智慧財產局員工消費合作社印製 表2 pH 7.6,含有 5 mg/1 活性PESA和 5 mg/1 活性AA/AHPSE 抑制劑 mg/1 EC EC mg/ (所有都是活性劑) NBT avg 18 0 - 0 67 87 0 - 2 65 73 0 - 5 28 32 0 - 5 40 36 10 Goodrite K-752 0 19 37 10 Goodrite K-752 2 27 38 10 Goodrite K-752 5 11 12 20 Goodrite K-752 0 11 11 20 Goodrite K-752 2 7.4 6.9 20 Goodrite K-752 5 1.3 0.7 20 Goodrite K-732 0 14 23 25 Goodrite K-732 0 7.4 8.0 20 Goodrite K-732 2 6.4 5.6 20 Goodrite K-732 5 0.9 0.4 20 Goodrite K-752和 K-732以50:50混合 0 12 18 20 Goodrite K-752和 K-732以50:50混合 2 7.8 8.8 20 Goodrite K-752和 K-732以50:50混合 5 1.3 0.6 25 A 0 15 17 20 A 5 1.8 1.1 25 B 0 9.4 7.7 20 B 5 2.0 1.0 25 C 0 19 19 20 C 5 1.1 0.5 5 0-P04 0 4.1 3.0 5 0-P04 2 0.9 0.3 5 o-po4 5 0.8 0.4 20 Bricorr 288 0 5.3 4.6 15 Bricorr 288 5 1.1 0.4 20 Bayhibit AM 0 12 8.7 15 Bayhibit AM 5 2.0 0.5 A : N,N’-雙(2-羥基琥珀基)-6,6-己烷二胺鈉鹽 B :亞胺基二(2-羥基琥珀酸)鈉鹽 C : N,N’-雙(2-羥基琥珀基)-間-二曱苯二胺鈉鹽 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 47 •-------------裝--- (請先閱讀背面之注意事項再填寫本頁) 訂: .線. 542858 A7 B7 五、發明說明(44 ) 經濟部智慧財產局員工消費合作社印製 表3 pH 7.6,含有 5 mg/1 活性AA/AHPSE 抑制劑 mg/1 EC EC mg/1 (所有都是活性劑) NBT avg 18 0 - 3 56 63 0 - 5 59 58 0 - 10 33 19 0 - 15 16 11 0 - 20 10 5 20 Bricorr 288 0 5.6 5.5 17 Bricorr 288 3 1.8 0.4 15 Bricorr 288 5 1.6 0.3 10 Bricorr 288 10 0.7 0.2 5 Bricorr 288 15 5.8 3.2 10 Bricorr 288 5 1.9 0.7 5 Bricorr 288 5 20 16 25 PESA 0 13 18 30 PESA 0 11 13 10 PESA 5 13 12 20 PESA 5 1.8 0.8 30 PESA 5 1.0 1.0 25 檸檬酸 0 14 13 30 檸檬酸 0 12 14 10 檸檬酸 5 21 16 20 檸檬酸 5 2.3 0.9 30 擰檬酸 5 1.3 0.4 30 Goodrite K-732 0 6.1 6 10 Goodrite K-732 5 9.7 10 20 Goodrite K-732 5 0.8 0.5 30 Goodrite K-732 5 0.7 0.3 25 Belclene 200 0 14 13 30 Belclene 200 0 14 12 10 Belclene 200 5 6.8 6.3 20 Belclene 200 5 1.3 0.7 30 Belclene 200 5 1.2 0.7 25 2,3-二羥基苯酸 0 7.7 7.0 20 2,3-二羥基苯酸 5 0.97 0.49 25 1,2,3,4-丁烷四羧酸 0 12 23 20 1,2,3,4-丁烷四羧酸 5 9.3 7.5 75 四蝴酸納(Borax) 0 64 77 70 四蝴酸納(Borax) 5 58 51 30 亞硝酸鹽(亞硝酸鈉) 0 59 62 25 亞硝酸鹽(亞硝酸鈉) 5 36 45 60 亞硝酸鹽(亞硝鈉酸) 0 25 41 55 亞硝酸鹽(亞硝酸鈉) 5 11 14 ------------—=—訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 48 542858 A7 B7 五、發明說明(45) 經濟部智慧財產局員工消費合作社印製 表3-續. In these waters, 8) of 3 mpy or less is considered an acceptable humus for industrial applications. In some cases, it is unacceptable that the decay of the wrong compound sometimes exists. 'However, the synergistic improvement of the combination of the first component and the tetrazolium compound is obvious. A person familiar with the literature can quickly determine the total amount of effective inhibitors that are needed, as well as the tetrasial compound and other components. Get the relative proportions of rotten name protection needed for the target application. The above-mentioned trend at pH 86 results is also seen at pH to see 'B £ ic.T: L._288. The test results are shown graphically at 1, which more clearly illustrates the use of the tetrafluorene compound NET with this material combination Get synergistic improvements. Example # 3 The corrosion results tested at pH 6.8 are shown below — I --------- Order ------- (Please read the note on the back? Matters before filling out this page)! life! Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives This paper is printed in accordance with the Chinese National Standard (CNS) A4 (210 X 297 public love) 46 542858 A7 B7 V. Description of the invention (43) Printed by the Employees Cooperative of the Intellectual Property Bureau of the Ministry of Economics Table 2 pH 7.6 with 5 mg / 1 active PESA and 5 mg / 1 active AA / AHPSE inhibitor mg / 1 EC EC mg / (all are active agents) NBT avg 18 0-0 67 87 0-2 65 73 0-5 28 32 0-5 40 36 10 Goodrite K-752 0 19 37 10 Goodrite K-752 2 27 38 10 Goodrite K-752 5 11 12 20 Goodrite K-752 0 11 11 20 Goodrite K-752 2 7.4 6.9 20 Goodrite K-752 5 1.3 0.7 20 Goodrite K-732 0 14 23 25 Goodrite K-732 0 7.4 8.0 20 Goodrite K-732 2 6.4 5.6 20 Goodrite K-732 5 0.9 0.4 20 Goodrite K-752 and K-732 to 50:50 mix 0 12 18 20 Goodrite K-752 and K-732 mix 50:50 2 7.8 8.8 20 Goodrite K-752 and K-732 mix 50:50 5 1.3 0.6 25 A 0 15 17 20 A 5 1.8 1.1 25 B 0 9.4 7.7 20 B 5 2.0 1.0 25 C 0 19 19 20 C 5 1.1 0.5 5 0-P04 0 4.1 3.0 5 0-P04 2 0.9 0.3 5 o-po4 5 0.8 0.4 20 Bricorr 288 0 5.3 4.6 15 Bricorr 288 5 1.1 0.4 20 Bayhibit AM 0 12 8.7 15 Bayhibit AM 5 2.0 0.5 A: N, N'-bis (2-hydroxysuccinyl) -6,6-hexanediamine sodium salt B: Sub Aminobis (2-hydroxysuccinic acid) sodium salt C: N, N'-bis (2-hydroxysuccinyl) -m-diphenylenediamine sodium salt This paper is in accordance with China National Standard (CNS) A4 specifications ( 210 X 297 mm) 47 • ------------- Install --- (Please read the precautions on the back before filling this page) Order: .line. 542858 A7 B7 V. Description of the invention (44) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Table 3, pH 7.6, containing 5 mg / 1 active AA / AHPSE inhibitor mg / 1 EC EC mg / 1 (all active agents) NBT avg 18 0-3 56 63 0-5 59 58 0-10 33 19 0-15 16 11 0-20 10 5 20 Bricorr 288 0 5.6 5.5 17 Bricorr 288 3 1.8 0.4 15 Bricorr 288 5 1.6 0.3 10 Bricorr 288 10 0.7 0.2 5 Bricorr 288 15 5.8 3.2 10 Bricorr 288 5 1.9 0.7 5 Bricorr 288 5 20 16 25 PESA 0 13 18 30 PESA 0 11 13 10 PESA 5 13 12 20 PESA 5 1.8 0.8 30 PESA 5 1.0 1.0 25 Citric acid 0 14 13 30 Citric acid 0 12 14 10 Citric acid 5 21 16 20 Citric acid 5 2.3 0.9 30 Citric acid 5 1.3 0.4 30 Goodrite K-732 0 6.1 6 10 Goodrite K-732 5 9.7 10 20 Goodrite K-732 5 0.8 0.5 30 Goodrite K-732 5 0.7 0.3 25 Belclene 200 0 14 13 30 Belclene 200 0 14 12 10 Belclene 200 5 6.8 6.3 20 Belclene 200 5 1.3 0.7 30 Belclene 200 5 1.2 0.7 25 2,3-dihydroxybenzoic acid 0 7.7 7.0 20 2,3-dihydroxybenzene Acid 5 0.97 0.49 25 1,2,3,4-butanetetracarboxylic acid 0 12 23 20 1,2,3,4-butanetetracarboxylic acid 5 9.3 7.5 75 Borax 0 64 77 70 Borax 5 58 51 30 Nitrite (sodium nitrite) 0 59 62 25 Nitrite (sodium nitrite) 5 36 45 60 Nitrite (sodium nitrite) 0 25 41 55 Nitrite Salt (Sodium Nitrite) 5 11 14 ------------— = — Order --------- (Please read the precautions on the back before filling this page) The paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 48 542858 A7 B7 V. Description of invention (45) Printed by the Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs 3-Continue
pH 7.6,含有 5 mg/1 活性AA/AHPSE mg/1 抑制劑 (所有都是活性劑) mg/1 NBT EC avg EC 18 25 中酒石酸 0 9.4 7.7 20 中酒石酸 5 1.7 0.93 30 葡萄糖酸 5 3.6 2.2 20 N-月桂醯基肌胺酸 0 46 73 15 N-月桂醯基肌胺酸 5 30 30 25 1,1〇-啡啉 0 59 66 20 1,10-啡啉 5 40 25 30 Belsperse 161(含膦基基團之寡聚PAA) 0 5.2 4.4 25 Belsperse 161(含膦基基團之寡聚PAA) 5 1.1 0.31 30 低分子量聚丙烯酸(PAA),含膦酸終端基 團,鈉鹽 0 6.6 7.1 25 低分子量(PAA),含膦酸終端基團,鈉鹽 5 1.7 0.84 30 Belclene 500 (含膦基基團的寡聚PAA) 0 14 17 25 Belclene 500 (含膦基基團的寡聚PAA) 5 2.5 0.93 30 Belclene 400 (AA : AMPS含次膦酸鹽) 0 11 10 25 Belclene 400 (AA : AMPS含次膦酸鹽) 5 3.3 1.2 30 Belclene 494 (AA : AMPS含終端膦酸酯) 0 8.3 7.7 25 Belclene 494 (AA : AMPS含終端膦酸酉旨) 5 7.2 7.2 聚丙烯酸酯 25 Goodrite K-732 5 1.1 0.35 20 Goodrite K-732 5 1.5 0.65 30 Goodrite K-732 5 0.96 0.43 修飾的聚環氧琥珀酸 25 間-伸二曱苯二胺/PESA衍生物鈉鹽# 1 5 0.98 0.48 25 間-伸二曱苯二胺/PESA衍生物鈉鹽#2 5 1.7 0.62 25 間-伸二曱苯二胺/PESA衍生物鈉鹽# 3 5 1.7 0.72 25 間-伸二曱苯二胺/PESA衍生物鈉鹽# 4 5 1.8 0.73 ----------------- (請先閱讀背面之注意事項再填寫本頁) --線- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 49 542858 A7 B7 五、發明說明(46) 經濟部智慧財產局員工消費合作社印制衣 表4 pH 6.8 含有 5 mg/1 活性PESA和 5 mg/1 活性AA/AHPSE mg/1 抑制劑 (所有都是作為活性劑) mg/1 ΝΒΤ EC avg EC 18 0 - 0 71 80 0 - 5 67 67 25 A 0 20 20 20 A 0 3.7 1.5 25 B 0 13 14 20 B 5 2.0 0.6 25 C 0 21 19 20 C 5 2.7 2.1 25 丙酮二酸 0 6.2 5.3 20 丙嗣二酸 5 2.3 1.9 25 L-酒石酸 0 17 17 20 L-酒石酸 5 4.3 2.0 25 糖質酸 0 13 12 20 糖質酸 5 2.2 0.9 7 0-P04 0 4.5 4.1 7 0-P04 2 1.4 1.0 7 0-P04 5 1.0 0.6 20 Bricorr 288 0 5.0 6.2 15 Bricorr 288 5 1.3 0.5 20 HEDP 0 7.3 5.9 15 HEDP 5 1.0 0.6 20 Belcor 575 0 5.7 8.5 15 Belcor 575 5 0.7 0.6 20 鉬酸鹽,Mo04 0 15 33 15 鉬酸鹽,Mo04 5 11 12 30 鉬酸鹽,Mo04 0 8.1 11 25 鉬酸鹽,Mo04 5 2.8 3.1 25 Goodrite K-732 0 8.8 8.4 20 Goodrite Κ-732 5 3.8 1.8 ----------------:----訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 50 542858pH 7.6 with 5 mg / 1 active AA / AHPSE mg / 1 inhibitor (all are active agents) mg / 1 NBT EC avg EC 18 25 medium tartaric acid 0 9.4 7.7 20 medium tartaric acid 5 1.7 0.93 30 gluconic acid 5 3.6 2.2 20 N-lauric acid sarcosinate 0 46 73 15 N-lauric acid sarcosinate 5 30 30 25 1,10-morpholine 0 59 66 20 1,10-morpholine 5 40 25 30 Belsperse 161 (including Phosphine-based oligomeric PAA) 0 5.2 4.4 25 Belsperse 161 (phosphine-based oligomeric PAA) 5 1.1 0.31 30 Low molecular weight polyacrylic acid (PAA), containing phosphonic acid terminal groups, sodium salt 0 6.6 7.1 25 Low molecular weight (PAA), phosphonic acid-containing terminal group, sodium salt 5 1.7 0.84 30 Belclene 500 (oligomeric PAA with phosphine group) 0 14 17 25 Belclene 500 (oligomeric PAA with phosphine group) 5 2.5 0.93 30 Belclene 400 (AA: AMPS with phosphinate) 0 11 10 25 Belclene 400 (AA: AMPS with phosphinate) 5 3.3 1.2 30 Belclene 494 (AA: AMPS with terminal phosphonate) 0 8.3 7.7 25 Belclene 494 (AA: AMPS with terminal phosphonic acid) 5 7.2 7.2 Polyacrylate 25 Goodrite K-732 5 1.1 0.35 20 Goodrite K-732 5 1.5 0.65 30 Goodr ite K-732 5 0.96 0.43 Modified polyepoxysuccinic acid 25 meta-diphenylene diamine / PESA derivative sodium salt # 1 5 0.98 0.48 25 meta-diphenylene diamine / PESA derivative sodium salt # 2 5 1.7 0.62 25 meta-diphenylene diamine / PESA derivative sodium salt # 3 5 1.7 0.72 25 meta-diphenylene diamine / PESA derivative sodium salt # 4 5 1.8 0.73 ---------- ------- (Please read the precautions on the back before filling this page) --Line- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 49 542858 A7 B7 V. Invention Instructions (46) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 4 pH 6.8 Contains 5 mg / 1 active PESA and 5 mg / 1 active AA / AHPSE mg / 1 inhibitor (all as active agents) mg / 1 ΝΒΤ EC avg EC 18 0-0 71 80 0-5 67 67 25 A 0 20 20 20 A 0 3.7 1.5 25 B 0 13 14 20 B 5 2.0 0.6 25 C 0 21 19 20 C 5 2.7 2.1 25 Pyruvate 0 6.2 5.3 20 Malonic acid 5 2.3 1.9 25 L-tartaric acid 0 17 17 20 L-tartaric acid 5 4.3 2.0 25 Sugar acid 0 13 12 20 Sugar acid 5 2.2 0.9 7 0-P04 0 4.5 4.1 7 0-P04 2 1.4 1.0 7 0-P04 5 1. 0 0.6 20 Bricorr 288 0 5.0 6.2 15 Bricorr 288 5 1.3 0.5 20 HEDP 0 7.3 5.9 15 HEDP 5 1.0 0.6 20 Belcor 575 0 5.7 8.5 15 Belcor 575 5 0.7 0.6 20 Molybdate, Mo04 0 15 33 15 Molybdate, Mo04 5 11 12 30 Molybdate, Mo04 0 8.1 11 25 Molybdate, Mo04 5 2.8 3.1 25 Goodrite K-732 0 8.8 8.4 20 Goodrite Κ-732 5 3.8 1.8 ------------ ----: ---- Order --------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 50 542858
A7 B7 五、發明說明(47) 抑制凹點生長效率A7 B7 V. Description of the invention (47) Inhibit pit growth efficiency
在pH 8.6以酒石酸測試不同暴露次數的凹點深度結^ 顯不於表5。如結果顯示,添加入NBT是很有效於限制Q 點的生長。凹點是非碟抑制劑,如酒石酸的特別問題。 表5 凹點深度對沈浸時間的函數20 mg/1酒石酸, pH8.6含有5rngパ活性PESA和5mg/l活性AA/AHPSE 的測試凹點深度,微米;表列的數值為平均值 添加物 沈浸時間 無 2 mg/1 NBT 5 mg/1 NBT _ 18 56 34 18 42 89 23 21 66 130 30 30 90 134 44 30 貫施例# 5 在PH 7.6,正-磷酸鹽測試的凹點深度和凹點數的數 據顯示於表6。這些結果顯示NBT是有效於減少凹點深度 和凹點密度。 表6 -------------裝-----:----訂. (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 凹點深度和數目7 mg/1 0-P04,pH 7.6,18小時 測試含有 5 mg^mPESA和 5 mg/1 活性 AA/AHPSE 凹點深度,微米;表列的數值為平均值 添加物 無 2mg/l NBT 5 mg/1 NBT —!度 22 11 9 凹點數目 80* 39 18 *有更多凹點,但總沒得到凹點數目 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 51 mg/1 抑制劑 (作為活性劑) mg/1 NBT EC (avg) EC (18) 總 凹點數 Max PD Avg PD Min PD 10 HEDP 0 3.0 2.1 8 48 42 40 7 HEDP 3 2.2 2.2 20 23 14 8 10 Bayhibit AM 0 8.1 9.1 11 82 58 38 7 Bayhibit AM 3 3.4 3.0 20 68 30 7 542858 A7 B7 五、發明說明(48) 實施例# 6 顯示於表7是在10 mg/1總加入抑制劑得到的凹點數據 ’该結果再證實NBT的凹點成長抑制性質。雖然凹點密度 高於含有NBT的處理,但是凹點深度明顯地降低。在 Bayhibit AM的情況可清楚地看到NBT明顯的對一般腐蝕 率的控制。 A1 PH 8.6之結果The depth of the pits tested with tartaric acid at pH 8.6 for different exposure times is not as significant as shown in Table 5. As the results show, the addition of NBT is very effective in limiting Q-point growth. Dimples are a particular problem with non-dish inhibitors such as tartaric acid. Table 5 Depth of pits as a function of immersion time 20 mg / 1 tartaric acid, pH 8.6 Test pit depths containing 5rng パ active PESA and 5mg / l active AA / AHPSE, micrometers; the values in the table are average addition immersion No time 2 mg / 1 NBT 5 mg / 1 NBT _ 18 56 34 18 42 89 23 21 66 130 30 30 90 134 44 30 Example # 5 At pH 7.6, the pit depth and pit of the ortho-phosphate test The data of the numbers are shown in Table 6. These results show that NBT is effective in reducing pit depth and pit density. Table 6 ------------- Installation -----: ---- Order. (Please read the precautions on the back before filling out this page) Depth and number of pits 7 mg / 1 0-P04, pH 7.6, 18 hours test contains 5 mg ^ mPESA and 5 mg / 1 active AA / AHPSE pit depth, micron; the values in the table are average values 2mg / l NBT 5 mg / 1 NBT —! Degree 22 11 9 Number of pits 80 * 39 18 * There are more pits, but the number of pits is not always obtained X 297 mm) 51 mg / 1 Inhibitor (as active agent) mg / 1 NBT EC (avg) EC (18) Total number of pits Max PD Avg PD Min PD 10 HEDP 0 3.0 2.1 8 48 42 40 7 HEDP 3 2.2 2.2 20 23 14 8 10 Bayhibit AM 0 8.1 9.1 11 82 58 38 7 Bayhibit AM 3 3.4 3.0 20 68 30 7 542858 A7 B7 V. Description of the invention (48) Example # 6 is shown in Table 7 at 10 mg / 1 Pit data obtained by total addition of inhibitors' This result confirms the pit growth inhibitory properties of NBT. Although the pit density was higher than that of the NBT-containing treatment, the pit depth was significantly reduced. In the case of Bayhibit AM, it is clear that NBT clearly controls the general corrosion rate. Results of A1 PH 8.6
含有5 mg/1丙稀酸/1-稀丙氧基經基丙烧石黃酸的 共聚物和5 mg/1 PESA PD=$測試終點測試管測定的凹點深度,微米 _最大深度,Avg=平均深度,Min=最小深度Contains 5 mg / 1 acrylic acid / 1-dilute propoxy copolymer of propylene propionite flavonic acid and 5 mg / 1 PESA PD = $ end point of the test tube, micron_maximum depth, Avg = Average depth, Min = minimum depth
Olij實施例-其他測試水 水相系統’如冷卻塔等等,中水的硬度和pH可能有 很大的變化。能有效的作用於廣大的硬度範圍和pH範圍 而同時抑制腐蝕和沈積的抑制劑配方是大大有利的。另外 最好在一些必須使用未循環水的系統,這種系統通常含低 鈣(<100 mg/1 Ca ’ 以 CaC〇3計)和相對中性的 ρΗ(6.5-7·5), 使用的抑制劑需要不依賴鹼性pH,高硬度條件來有效地 作用,如許多目前使用的處理情況。這種系統的實施例為 密閉回路冷卻系、統,單循環的冷卻系统,熱水加熱系統等 等。下面的實施例再確認含有四唑鐳化合物的抑制劑配方 -----^----訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製Olij Example-Other Test Waters Aqueous phase systems' such as cooling towers, etc. The hardness and pH of the reclaimed water may vary greatly. Inhibitor formulations that are effective in a wide range of hardness and pH ranges while inhibiting corrosion and sedimentation are greatly advantageous. In addition, it is best to use uncirculated water in such systems, which usually contain low calcium (< 100 mg / 1 Ca 'based on CaC03) and relatively neutral ρΗ (6.5-7 · 5) Inhibitors need to be independent of alkaline pH, high hardness conditions to function effectively, as in many currently used processing situations. Examples of such systems are closed loop cooling systems, systems, single cycle cooling systems, hot water heating systems, and the like. The following examples reconfirm the inhibitor formula containing tetrazolium and radium compounds ----- ^ ---- Order --------- (Please read the precautions on the back before filling this page) Ministry of Economy Printed by the Intellectual Property Bureau Staff Consumer Cooperative
52 542858 A7 B7 五、發明說明(49) 的廣泛效率,當以本揭示說明的四唑鏘化合物與其他組成 份合併使用,得到的改善超過已知於文獻的物料。 實施例#7 低pH,低硬度 表8顯示水中含有15 mg/1 Ca,以CaC03計,7.6 mg/1 Mg ,以 CaC〇3計,71 mg/1 Cl,48 mg/1 S04,力口入 5 mg/1 活性 AA/AHPSE,在pH 7.0的結果。當加入5 mg/1 NBT,腐钱 ) 率明顯的減少。 --------------裝—— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表8 mg/1 處理劑 mg/1 NBT EC avg EC (18) 10 0-P04 0 12 9.7 10 0-P04 5 1.2 0 67 20 Bricorr 288 0 10 9.2 20 Bricorr 288 5 0.96 0.21 20 HEDP 0 9.1 9.0 20 HEDP 5 0.89 0.13 20 Belcor 575 0 5.9 5.8 20 Belcor 575 5 0.51 0.21 15 EBO 0 14 15 15 EBO 5 1.1 0.55 30 Goodrite K-732 0 6.1 6.4 30 Goodrite K-732 5 0.48 0.12 60 L-酒石酸 0 13 12 60 L·酒石酸 5 2.4 1.2 20 丙酮二酸 0 5.3 6.3 20 丙酮二酸 5 1.1 0.70 20 糖質酸 5 2.1 1.1 〇-P〇4 :正填酸鹽 HEDP :羥基亞乙基二膦酸 · 線' 53 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 542858 A7 五 發明說明(50) 較低pH,較高硬度 在阳 6·8’ 水中含有 500 mg/l Ca,以 CaC03 計,250 mg/l Mg ’以 CaC〇3計 ’ 7 mg/1 MAlk,以 CaC03計,354 mg/1 氣 化物’和500 mg/丨硫酸鹽進行bCTA測試的結果顯示於表9 所有測试都含有5 mg/1活性aa/AHPSE。這種條件通常 在開放式再循環冷卻系統遇到,該系統中的來源水(補充 水)因為洛發而被濃縮數倍,並加入硫酸維持較低的pH。 在k些’収系列中’各對比較(含有和不含NBT)的總抑制 劑濃度維持-定或接近—定。在各情況下,取代部份抑制 劑或抑制劑與耐混合得到明顯改善的腐祕能。如前面 的說明’不是所有與时鐵化合物的組合提供可接受的腐 但在所有情況的組合都有改善性能。熟悉文獻者^特別的水相系統中得到滿意性能需要的適當含I和比率。 --------I--I ----(請先閱讀背面之注意事項再填寫本頁) I I ·11!111 經濟部智慧財產局員工消費合作社印製52 542858 A7 B7 V. Extensive efficiency of invention description (49). When the tetrazolium compound described in this disclosure is used in combination with other components, the improvement is more than that of materials known in the literature. Example # 7 Low pH, low hardness Table 8 shows that water contains 15 mg / 1 Ca, calculated as CaC03, 7.6 mg / 1 Mg, calculated as CaC03, 71 mg / 1 Cl, 48 mg / 1 S04, Likou Add 5 mg / 1 active AA / AHPSE, results at pH 7.0. When 5 mg / 1 NBT was added, the rate of corruption was significantly reduced. -------------- Packing—— (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 8 mg / 1 Processing agent mg / 1 NBT EC avg EC (18) 10 0-P04 0 12 9.7 10 0-P04 5 1.2 0 67 20 Bricorr 288 0 10 9.2 20 Bricorr 288 5 0.96 0.21 20 HEDP 0 9.1 9.0 20 HEDP 5 0.89 0.13 20 Belcor 575 0 5.9 5.8 20 Belcor 575 5 0.51 0.21 15 EBO 0 14 15 15 EBO 5 1.1 0.55 30 Goodrite K-732 0 6.1 6.4 30 Goodrite K-732 5 0.48 0.12 60 L-tartaric acid 0 13 12 60 L · tartaric acid 5 2.4 1.2 20 pyruvate 0 5.3 6.3 20 Pyruvate 5 1.1 0.70 20 Glycosylic acid 5 2.1 1.1 〇-P〇4: Ortho-acid salt HEDP: Hydroxyethylene diphosphonic acid · Line '53 This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 542858 A7 Fifth invention description (50) Lower pH, higher hardness Contains 500 mg / l Ca in 6.8 ′ water, as CaC03, 250 mg / l Mg 'in CaC 〇3 count '7 mg / 1 MAlk, calculated as CaC03, 354 mg / 1 gaseous matter' and 500 mg / 丨 sulfate bCTA test results are shown in Table 9 All tests Containing 5 mg / 1 active aa / AHPSE. This condition is often encountered in open recirculation cooling systems where the source water (make-up water) is concentrated several times due to Lovat and sulfuric acid is added to maintain a lower pH. The total inhibitor concentration of each pair of comparisons (with and without NBT) in the 'collection series' is maintained-fixed or near-fixed. In each case, the substitution of some inhibitors or inhibitors with significantly improved corrosion resistance was achieved. As stated earlier, not all combinations with iron compounds provide acceptable decay, but in all cases the combination has improved performance. Those familiar with the literature ^ appropriate I and ratios required for satisfactory performance in particular aqueous systems. -------- I--I ---- (Please read the notes on the back before filling out this page) I I · 11! 111 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
本紙張尺度適用中國國家標準(CNS)A4規格(21〇 297公釐) 54 542858 A7 B7 i、發明說明(51) 表9 mg/1 處理#1 mg/1 處理#2 mg/1 NBT EC (avg) EC (18) 10 0-P〇4 - - 0 7.5 5^0^ 5 o-p〇4 - - 5 2.3 Γό ^ 7 0-P〇4 3.0 Pyro-P04 0 2.9 _ 1.2 5.5 0-P04 2.5 Pyro-P04 3 0.99 037 ^ 4 0-P04 2.0 Pyro-P04 3 1.6 —----- 〇·77 20 Bricorr 288 - - 0 31 49 15 Bricorr 288 - - 5 13 13^ 16 Bricorr 288 4 0-P〇4 0 2.6 1.6^ 12 Bricorr 288 3 0-P04 5 1.5 0^92^ 25 糖質 - - 0 34 ~ 60^ 20 糖質 - - 5 13 lT^ 15 糖質 4 0-P〇4 0 7.9 -- 8.2 12 糖質 3 0-P〇4 5 2.1 1.3 16 D 4 〇-P〇4 0 12 ------ 7.7 12 D 3 0-P04 5 1.9 〇~89^ D :亞胺基-二(2-羥基琥珀酸)鈉鹽 --------------裝--- f請先閱讀背面之注咅?事項再填寫本頁}This paper size applies the Chinese National Standard (CNS) A4 specification (21〇297 mm) 54 542858 A7 B7 i. Description of the invention (51) Table 9 mg / 1 treatment # 1 mg / 1 treatment # 2 mg / 1 NBT EC ( avg) EC (18) 10 0-P〇4--0 7.5 5 ^ 0 ^ 5 op〇4--5 2.3 Γό ^ 7 0-P〇4 3.0 Pyro-P04 0 2.9 _ 1.2 5.5 0-P04 2.5 Pyro -P04 3 0.99 037 ^ 4 0-P04 2.0 Pyro-P04 3 1.6 ------- 〇 77 20 Bricorr 288--0 31 49 15 Bricorr 288--5 13 13 ^ 16 Bricorr 288 4 0-P〇 4 0 2.6 1.6 ^ 12 Bricorr 288 3 0-P04 5 1.5 0 ^ 92 ^ 25 Glycan--0 34 ~ 60 ^ 20 Glycan--5 13 lT ^ 15 Glycan 4 0-P〇4 0 7.9- 8.2 12 Glycan 3 0-P〇4 5 2.1 1.3 16 D 4 0-P〇4 0 12 ------ 7.7 12 D 3 0-P04 5 1.9 0 ~ 89 ^ D: imino-bis ( 2-Hydroxysuccinic acid) sodium salt -------------- pack --- f Please read the note on the back first? Matters refill this page}
經濟部智慧財產局員工消費合作社印製 實施例#9 高pH,中硬度的水 表 10顯示 pH 8.6,含有 360 mg/1 Ca,以 CaC03計,18〇 mg/1 Mg,以 CaC03計,255 mg/1 α,220 mg/1 S04,和 3〇〇Printed by Example # 9 Employee Consumer Cooperative of the Bureau of Intellectual Property, Ministry of Economic Affairs, Water meter 10 with high pH and medium hardness shows pH 8.6, contains 360 mg / 1 Ca, calculated as CaC03, 180 mg / 1 Mg, calculated as CaC03, 255 mg / 1 α, 220 mg / 1 S04, and 3〇〇
mg/1 Malk,以CaC〇3計,的測試水得到的結果。所有測試 都含有5 mg/1活性AA/AHPSE。這種條件通常在開放式再 循環冷卻系統遇到,該系統中的來源水(補充水)由於蒸發 ,已經被濃縮數倍,而pH被控制於中等的pH 8範圍使其 較容易控制鐵的腐餘。從這些結果明顯看到在這些條件下 添加入四嗤鐵化合物的效率Q 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) --線· 55 542858 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(52) 表10 mg/1 處理#1 mg/1 處理#2 mg/1 NBT EC (avg) EC (18) 10 PESA - - 0 11 15 5 PESA - - 5 6.7 20 PESA - - 0 7.6 7.0 10 PESA - - 5 4.5 2.7 20 PESA - - 5 2.5 1.7 10 PESA 10 L-酒石酸 0 7.3 4.3 10 PESA 10 L-酒石酸 5 2.5 1.9 10 Acumer™ 4210 - - 0 11 7.8 10 Acumer™ 4210 - - 5 3.7 1.6 20 Acumer™ 4210 - - 0 6.4 4.1 20 Acumer™ 4210 - - 5 2.2 2.0 10 Acumer™ 4210 10 PESA 0 6.4 4.3 10 Acumer™ 4210 10 PESA 5 2.6 2.0 10 Acumer™ 4210 10 L-酒石酸 0 5.4 3.5 10 Acumer™ 4210 10 L-酒石酸 5 1.9 1.6mg / 1 Malk, as CaCO3, in test water. All tests contained 5 mg / 1 active AA / AHPSE. This condition is usually encountered in open recirculation cooling systems, where the source water (make-up water) has been concentrated several times due to evaporation, and the pH is controlled to a medium pH 8 range making it easier to control iron. Corruption. It is clear from these results that the efficiency of adding the tetramium iron compound under these conditions Q The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm)-line · 55 542858 A7 B7 Intellectual Property Printed by the Bureau ’s Consumer Cooperatives 5. Description of the invention (52) Table 10 mg / 1 Processing # 1 mg / 1 Processing # 2 mg / 1 NBT EC (avg) EC (18) 10 PESA--0 11 15 5 PESA-- 5 6.7 20 PESA--0 7.6 7.0 10 PESA--5 4.5 2.7 20 PESA--5 2.5 1.7 10 PESA 10 L-tartaric acid 0 7.3 4.3 10 PESA 10 L-tartaric acid 5 2.5 1.9 10 Acumer ™ 4210--0 11 7.8 10 Acumer ™ 4210--5 3.7 1.6 20 Acumer ™ 4210--0 6.4 4.1 20 Acumer ™ 4210--5 2.2 2.0 10 Acumer ™ 4210 10 PESA 0 6.4 4.3 10 Acumer ™ 4210 10 PESA 5 2.6 2.0 10 Acumer ™ 4210 10 L-tartaric acid 0 5.4 3.5 10 Acumer ™ 4210 10 L-tartaric acid 5 1.9 1.6
Acumer4210 :聚順-丁烯二酸,由Rohm&Haas供應 實施例#10 另外的四σ坐鐳化合物 以ΝΒΤ和三個另外的四唑鏘化合物:二苯乙烯基硝基 藍四唑鏘氣化物(DNBT),四硝基藍四唑鐯氣化物(ΤΝΒΤ) ,和2-(4-碘苯基)-3-(4-硝苯基)-5-苯基四唑鐯氣化物(ΙΝΤ) ,在pH 7.6得到的數據顯示於表11。測試水與實施例2相 同。和DNBT與Belclene 200的組合不同,揭示於本發明四 唑鏘化合物與其他物料組合的協同交互作用是很明顯的。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------Γ — ----l·---訂--------- (請先閱讀背面之注意事項再填寫本頁) 56 542858 A7 B7 五、發明說明(53) 表11 抑制劑 (所有都是逢性劑) mg/1 四°坐錯化合物 mg/1 EC avg EC 18 - - DNBT 25 15 13 - - TNBT 25 12 9.0 - - INT 25 9.0 5.7 - - NBT 20 10 5 Bricorr 288 25 - - 4.4 4.2 Bricorr 288 20 DNBT 5 1.5 0.9 Bricorr 288 20 TNBT 5 1.1 0.8 Bricorr 288 20 INT 5 4.0 3.7 Bricorr 288 15 NET 5 1.6 0.4 Belclene 200 25 - - 15 13 Belclene 200 20 DNBT 5 21 22 Belclene 200 20 TNBT 5 5.5 5.2 Belclene 200 20 INT 5 6.7 11 Belclene 200 20 NET 5 1.3 0.7 ---------------裝—— (請先閱讀背面之注意事項再填寫本頁) 線· 本發明已經以其特別的實例作為說明,明顯的,本發 明許多其他的形態和修飾對熟悉文獻者是很清楚的。附隨 的申請專利範圍和本發明通常要涵蓋所有在本發明真正的 精神和範圍内的這種明顯的形態和修飾。 經濟部智慧財產局員工消費合作社印製 57 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)Acumer4210: polycis-butenedioic acid, supplied by Rohm & Haas Example # 10 Additional tetrasigmadium compound with NTB and three additional tetrazolium compounds: distyrylnitroblue tetrazolium gas (DNBT), tetranitroblue tetrazolium hydrazone (TNBT), and 2- (4-iodophenyl) -3- (4-nitrophenyl) -5-phenyltetrazolium hydride (ILT) The data obtained at pH 7.6 are shown in Table 11. The test water was the same as in Example 2. Unlike the combination of DNBT and Belclene 200, the synergistic interactions of the tetrazolium compound disclosed in the present invention with other material combinations are obvious. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) --------- Γ — ---- l · --- Order --------- ( Please read the precautions on the back before filling out this page) 56 542858 A7 B7 V. Description of the invention (53) Table 11 Inhibitors (all of which are potent agents) mg / 1 Four ° misplacement compound mg / 1 EC avg EC 18 --DNBT 25 15 13--TNBT 25 12 9.0--INT 25 9.0 5.7--NBT 20 10 5 Bricorr 288 25--4.4 4.2 Bricorr 288 20 DNBT 5 1.5 0.9 Bricorr 288 20 TNBT 5 1.1 0.8 Bricorr 288 20 INT 5 4.0 3.7 Bricorr 288 15 NET 5 1.6 0.4 Belclene 200 25--15 13 Belclene 200 20 DNBT 5 21 22 Belclene 200 20 TNBT 5 5.5 5.2 Belclene 200 20 INT 5 6.7 11 Belclene 200 20 NET 5 1.3 0.7 ------ --------- Equipment—— (Please read the notes on the back before filling this page) Thread · The present invention has been described with its specific examples. Obviously, many other forms and modifications Those familiar with the literature are clear. The scope of the accompanying patent application and the present invention should generally cover all such obvious forms and modifications within the true spirit and scope of the present invention. Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
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US09/136,884 US6187262B1 (en) | 1998-08-19 | 1998-08-19 | Inhibition of corrosion in aqueous systems |
US09/303,596 US6585933B1 (en) | 1999-05-03 | 1999-05-03 | Method and composition for inhibiting corrosion in aqueous systems |
US09/304,181 US6379587B1 (en) | 1999-05-03 | 1999-05-03 | Inhibition of corrosion in aqueous systems |
US30956499A | 1999-05-12 | 1999-05-12 | |
US50572200A | 2000-02-17 | 2000-02-17 |
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