WO2005123981A1 - Pitting corrosion inhibitor for metal and method of inhibition - Google Patents

Pitting corrosion inhibitor for metal and method of inhibition Download PDF

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Publication number
WO2005123981A1
WO2005123981A1 PCT/JP2005/011406 JP2005011406W WO2005123981A1 WO 2005123981 A1 WO2005123981 A1 WO 2005123981A1 JP 2005011406 W JP2005011406 W JP 2005011406W WO 2005123981 A1 WO2005123981 A1 WO 2005123981A1
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Prior art keywords
copolymer
group
pitting corrosion
weight
corrosion inhibitor
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PCT/JP2005/011406
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French (fr)
Japanese (ja)
Inventor
Hideo Ootaka
Masayori Kouda
Keiichi Bessho
Masahiro Shiratani
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Kurita Water Industries Ltd.
Jsr Corporation
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Application filed by Kurita Water Industries Ltd., Jsr Corporation filed Critical Kurita Water Industries Ltd.
Priority to JP2006514850A priority Critical patent/JP4641027B2/en
Publication of WO2005123981A1 publication Critical patent/WO2005123981A1/en

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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors

Definitions

  • the present invention relates to a pitting corrosion inhibitor and an anticorrosive agent. More specifically, the present invention suppresses the progress of pitting of carbon steel in an open shield cooling water system without using heavy salts such as phosphorus compounds and salts, thereby effectively reducing heat and other facilities.
  • the present invention relates to a metal pitting corrosion inhibitor and a method for controlling pitting corrosion. Background sickle ''
  • Corrosion is one of the major P issues that occur in the cooling water system, along with fouling. Corrosion not only causes shortage of cooling water system equipment, leakage of products due to penetration of heat exchange tubes, contamination, etc., but also decreases heat efficiency of heat exchange due to adhesion of corrosion products. It causes indirect obstruction such as increase in pump pressure. Also, the occurrence of accidents in high-temperature, high-pressure processes could lead to personal injury. When the key 1 is applied to the cooling water and precipitates as a scale on the surface, or when microorganisms grow in the system and adhere to the slime force, the local corrosive force s progresses below the deposit. There are many.
  • the water treatment amount IJ used to prevent the formation of skeinole is a water treatment S containing a sulfonated product of Yonggen or its polymerization or copolymer.
  • ⁇ IJ force s has been proposed (Patent Document 1). Also contains phosphorus ⁇ 3 ⁇ 4rf,
  • Patent Document 1 Japanese Patent No. 2625914 (Page 1)
  • Patent Document 2 Japanese Patent Application Laid-Open No. 9-248555 (pages 2-3)
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-107782 (No. 2-3)
  • Non-Patent Document 1 J. AWWA 36 472 (1944)
  • the present invention relates to an H-leaked P water system, which suppresses the progress of pitting corrosion in a coal fumigation oka without using a phosphorus compound or a heavy salt such as ffilft salt, and is provided with equipment for contact with water such as heat exchange.
  • RCI can effectively suppress the progress of eating, and based on this finding, have led to the present invention.
  • R ⁇ R 6 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —S ⁇ 3 X, where X is a hydrogen atom, An alkali metal atom, an alkaline earth metal atom, an ammonium group or an amino group, and at least one of R ⁇ R 6 is 1 so 3 x.
  • R 7 to R 1 () is — (CH 2 ) ra COOM, and the remainder is hydrogen or Is an alkyl group having 1 to 8 carbon atoms, m is 0 to 8, and M is a hydrogen atom, an alkali ⁇ S, an alkaline earth atom, an ammonium group or an amino group.
  • Fig. 1 is a system diagram of the water flow test difficulties used in the difficult example.
  • reference numeral 1 denotes a tank
  • 2 denotes a pump
  • 3 denotes a charcoal pipe
  • 4 denotes a charcoal pipe
  • 5 denotes a copper pipe
  • 6 denotes a corrosion meter. Best mode for carrying out the invention
  • the metal pitting inhibitor of the present invention comprises (A) a compound having a carboxyl group represented by the HI formula [2] per mole of the sulfonated compound of ⁇ : gen represented by the general formula [1]: (B) a copolymer having 0.1 to 20 moles of a sulfone compound, and (B) 1 mole of maleic acid, 0.8 to 1.3 moles of an alkene having 4 to 10 carbon atoms And (C) azolized ⁇ (.
  • ⁇ ⁇ Scale 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, ⁇ Li Ichiru group having a carbon number of 6-2 0, or an SO 3 X, wherein X is a hydrogen atom, Al Chikarariroku atom, an alkaline earth metal atom, an Anmoniumu group or amino group, one at least of R ⁇ R 6 is an S_ ⁇ 3 X.
  • Examples of the sulfonated product of gen represented by Ichifunai [1] include sulfonic acid of gengen, its salt, and its salt ⁇ il ⁇ JS salt, and its ammonium salt is ami. Specific examples thereof include 2-methyl-1,3-butadiene-l-sulfonic acid, 2-methyl-l, 3-butadiene-l-sulfonic acid, and 2-methyl-l, 3-butadiene.
  • Examples of the unsaturated carboxyl group having a carboxyl group represented by the general formula [2] include, for example, atarilic acid, methacrylic acid, crotonic acid, isocrotonic acid, vinylinoleic acid, angryic acid, tiglinic acid, maleic acid, Fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid And so on.
  • the copolymer having a sulfone can be represented by the general formula [2] with respect to 1 mol of the sulfonated product of * ⁇ J It is a copolymer obtained by copolymerizing 0.1 to 20 mol of an unsaturated compound having a carboxyl group. More preferably, it is represented by the following formula [2] with respect to 1 mol of the compound represented by the general formula [1]. This is a copolymer obtained by copolymerizing 1.5 to 12 moles of the compound.
  • the weight average molecular weight of the copolymer having a sulfone is preferably from 3,000 to 15,000, more preferably from 5,000 to 12,000. Note that, in the present invention, the preferred amount of the polymer is a weight average molecular weight determined by gel permeation chromatography under the following conditions and determined by a polyethylene dalicol standard.
  • PEG standard GL Science's PEG standard substance (the molecular weight of 100 to 10,000, (A) the method for producing the (A) sulfonic acid group-containing copolymer used in the present invention is not particularly limited.
  • the sulfonated product of the formula [1] and the unsaturated compound having a carboxyl group represented by the formula [2] are dissolved in water and combined with the radical polymerization initiator. be able to.
  • the alkene having 4 to 10 carbon atoms used in the present invention includes, for example, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-11-pentene, 4-methylino-1-pentene , 1-heptene, 4-methynole-1-hexene, 5-methinole-1-hexene, 1-octene, 1-octenol, 1-heptene, 1-nonene, 1-decene.
  • a copolymer having a hydrophobic group is a copolymer obtained by copolymerizing 0.8 to 1.3 moles of an anoleken having 4 to L 0 carbon atoms with respect to 1 mole of maleic acid. And more preferably a copolymer obtained by copolymerizing 0.95 to 1.1 mol of an alkene having 4 to 10 carbon atoms per 1 mol of maleic acid. Even if the amount of alkene in 1 mole of maleic acid is 0.8 mono V * or more than 1.3 mono, the effect of suppressing pitting corrosion may not be sufficiently exhibited.
  • the weight-average weight of the polymer having a ⁇ ⁇ ⁇ group is preferably 4,000 to 500,000, preferably 5,000 to 3,500,000. It is more preferable to be.
  • the method for producing the copolymer (B) having a hydrophobic group used in the present invention is not particularly limited.
  • a radical polymerization initiator may be prepared by adding anhydrous maleic acid and an alkene without a solvent or under an organic solvent. And the resulting maleic anhydride / alkene copolymer is hydrolyzed.
  • (B) as a copolymer having a spine group a copolymer obtained by copolymerizing another monomer in addition to maleic acid and an alkene having 4 to 10 carbon atoms.
  • the (C) azole compound used in the present invention is an aromatic conjugate having a five-membered ring containing two or more hetero atoms, wherein at least one of the hetero atoms is a nitrogen atom.
  • the azozolization ⁇ 3 ⁇ 4) includes virazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazonole, thixazole, isoxoxazonole, thiazonole, isothiazonoole, oxoxadiazonole Thiadiazole, indazoinole, benzoimidazonole, benzotriazole, benzoxazole, benzothiazole, benzothiazole, benzothiazole, trinoretriazole and the like. Among these, benzotriazole and trinoletriazonole can be used for.
  • the pitting corrosion inhibitor of the present invention comprises: (A) 1 part by weight of a copolymer having sulfone
  • a copolymer having a group having a group content of 0.05 to 8 parts by weight is preferable, and a content of 0.2 to 1.5 parts by weight is more preferable, and 0.2 to 1.5 parts by weight is more preferable. More preferably, it contains parts by weight.
  • the pitting corrosion inhibitor of the present invention is (A) 1 part by weight of a copolymer having sulfone ⁇
  • the azole compound preferably contains 0.05 to 0.1 part by weight, more preferably 0.0007 to 0.07 part by weight.
  • the dosage form of the metal pitting inhibitor of the present invention there is no particular limitation on the dosage form of the metal pitting inhibitor of the present invention.
  • a copolymer having a snorenoic acid group ( ⁇ ) a copolymer having a spine group, and (C) an azole ( ⁇ ) a copolymer having a sulfonic acid group, ( ⁇ ) a copolymer having a hydrophobic group, and (C) an azolated ⁇ !
  • It can also be a two-drug type combining one species with another, or ( ⁇ ) a copolymer having a sulfone wake, ( ⁇ ) a copolymer having a spine group, and (C) an azo compound.
  • the one-drug type can be suitably used because the drug 3 ⁇ 4 ⁇ facility power s is simplified and the inlet port concentration ratio is kept constant.
  • an acid such as alkali metal oxide, mineral acid, or shelf acid to stabilize the pitting corrosion inhibitor.
  • an anticorrosive such as phosphorus » polymerized phosphate, phosphonic acid, ffif mouth, salt, anoremin ⁇ , molybdenum ⁇ :, etc. may be blended with the sorghum inhibitor of the present invention.
  • these anticorrosives can be recommended to aqueous systems.
  • the pitting corrosion inhibitor of the present invention comprises: (A) a copolymer having a sulfone fiber, ( ⁇ ) a copolymer having a spine group, and (C) an azole compound.
  • the total amount of the aqueous solution is 1 to 10 O mg / L, more preferably 10 to 7 O mg / L, and still more preferably 15 to 5 O mg / L3 ⁇ 43 ⁇ 4jn.
  • a mixture of (A) a copolymer having a sulfone moiety and (B) a copolymer having an experimental group can inhibit the formation of an anticorrosive film by a chelating action on human talent.
  • the # dexterity in the system corrodes and the concentration of ⁇ I in the water increases, the copper ions dissolved on the surface of the iron-based ⁇ g promote the corrosion.
  • (C) through the mouth of the azole compound It is presumed that the pitting corrosion in the water system is effectively suppressed because the formation of the copper film is key.
  • the depth of pitting corrosion can be reduced by 30 to 65%. Since the progress of pit depth is empirically proportional to the 1/3 power of time, the equipment pit (month), the thickness of the equipment: d (mm), the pit depth k for the first month (mm), the relationship of td 3 / k 3 is established, and the present invention can extend the length of the equipment by 3 to 20 times with the force s.
  • Polymer D isoprene-norethone-acrylic acid copolymer, monomer ratio 20:80, weight-average, good weight 7,500.
  • Polymer E isoprenesulfone / acrylic acid copolymer, molar ratio 10:90, weight average molecular weight 9,000.
  • Polymer G copolymer of isoprenesulfonic acid / acrinoleic acid, molar ratio 10:90, weight-average preferred amount 23,000.
  • Polymer H isoprene norephon ⁇ acrylic acid / 2-hydroxyethyl methacrylate copolymer, molar ratio 20:65:15, weight average molecular weight 6,500. ⁇
  • Polymer A maleic ⁇ / isobutylene copolymer, monole ratio 50:50, weight average weight 14,000.
  • Polymer B maleic ⁇ / 1-hexene copolymer, molar ratio 45:55, weight average molecular weight 20 000.
  • Heavy ⁇ f C maleic pentene copolymer, molar ratio 53:47, weight average molecular weight 6,500.
  • Weight F Polymaleic acid ⁇ Weight average molecular weight 600.
  • Polymer I maleic ⁇ 2-acrylamide-12-methylpropanesulfonic acid copolymer, monole J: 80:20, weight average molecular weight 2,000.
  • the pitting corrosion inhibitory effect was appreciated using the 3 ⁇ 4R test rig shown in Fig. 1.
  • the test water was sent from the 52-liter tank 1 by the pump 2 and passed through the coal pipe 3, the coal pipe 4, and the copper pipe 5 at a flow rate of 0.5m / s, and then circulated to the tank via the corrosion meter 6.
  • ⁇ 8 ⁇ 8 ⁇ alkalinity 30 OmgCaC0 3 ZL, calcium hardness 30 OmgCaC0 3 / L, from silica concentration 10 Omg Si0 2 / L, and 634mL / h supplied to the tank, the water over-ride U is overflow from the tank Was.
  • the trial ⁇ R if ⁇ time is 82 hours. Try J?
  • the test was conducted using (A) 32 mg / L of polymer D, (B) 8 mg / L of polymer A and (C) 1 mg / L of benzotriazole.
  • the maximum pit depth of the charcoal was 21 mm / 30 days, and the corrosion of the charcoal was 3.2 md d and that of the copper erosion was 0.9 m d d.
  • the test was performed by adding (A) 24 mg / L of polymer D, (B) 16 mg ZL of polymer A, and (C) lmg / L of benzotriazole.
  • the test was conducted by adding (ii) polymer-4 Omg / L and (C) benzotriazole 0.05 mg / L to test water.
  • the maximum pit depth of carbon steel was 0.30 mm / 30 days, the corrosion 3 ⁇ 4i of carbon steel was 3.6 mdd, and the corrosion ⁇ g of copper was 1.6 mdd.
  • Table 1 shows the results of Examples (1 to 0) and Comparative Examples (1) to (8).
  • Comparative Example 1 in which (B) a copolymer of maleic acid / isobutylene and (C) benzotriazole were used, and (A) a comparison in which only a copolymer of isoprenesulfonic acid and Zacrylic acid were suggested.
  • Example 2 Comparative Example 3, in which only (B) a copolymer of maleic acid Z alkene was advocated, and (C) a copolymer of (B) polymaleic acid and (B) Zisoptylene maleate and (C) trinoletriazole were added.
  • Comparative Example 4 Comparative Example 5, where (A) a copolymer of isoprenesulfonic acid Z-acrylic acid and (B) a copolymer of maleic acid Z 1-hexene were added, and Comparative Example 5, (A) Comparative Example 6, (D) maleic acid / copolymer of soprens nolephon ⁇ / acrylic acid Z and 2-hydroxyethyl methacrylate and (B) malein ⁇ / 1-hexene Copolymerization of 2-acrylamide-2-methylpropanesulfonic acid copolymer with (B) malein-isobutylene Comparative Example 7 was added to, (B) in Comparative Example 8 Only copolymers of maleic to 1-hexene was added Caro, the maximum depth of pitting corrosion of carbon Oka 0.
  • the metal pitting corrosion inhibitor and the pitting corrosion suppressing method of the present invention in an open circulation cooling water system, the progress of pitting corrosion in Sumitakeoka is suppressed without using heavy metal salts such as phosphorus compounds and salts. , Heat exchange ⁇ and other facilities that come into contact with water can be effectively extended.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

A pitting corrosion inhibitor for metal comprising (A) a sulfonated copolymer obtained by copolymerizing a sulfonated conjugated diene represented by the general formula [1] with a carboxylated unsaturated compound represented by the general formula [2] at a mole ratio of 1 : 0.1 to 1 : 20, (B) a copolymer having hydrophobic groups which is obtained by copolymerizing maleic acid with an alkene of 4 to 10 carbon atoms at a mole ratio of 1 : 0.8 to 1 : 1.3, and (C) an azole; and a method of inhibiting pitting corrosion of metal by adding the pitting corrosion inhibitor to an aqueous system in an amount of 1 to 100 mg/L in terms of the sum of the component (A), (B) and (C), wherein at least one of R1 to R6 is -SO3X and at least one of R7 to R10 is -(CH2)mCOOM. Use of the pitting corrosion inhibitor makes it possible to prolong effectively the duration of life of a unit having a carbon steel member in a water-contacting part in an open cooling water circulation system.

Description

明細書 金属の孔食抑制剤及 制方法 技術分野  Description Metal pitting corrosion inhibitor and control method Technical field
本発明は、 德の孔食抑制剤及 し食抑制 去に関する。 さらに詳しくは、 本発明は、 開谢盾環冷却水系において、 リン化合物や 塩などの重 ^塩を用いることなく、 炭素 鋼の孔食の進行を抑制し、 熱 などの設備の ^を効果的に延長することができる金 属の孔食抑制剤及ひ 7し食抑制 法に関する。 背景鎌 '  The present invention relates to a pitting corrosion inhibitor and an anticorrosive agent. More specifically, the present invention suppresses the progress of pitting of carbon steel in an open shield cooling water system without using heavy salts such as phosphorus compounds and salts, thereby effectively reducing heat and other facilities. The present invention relates to a metal pitting corrosion inhibitor and a method for controlling pitting corrosion. Background sickle ''
滅の腐食は、 ファゥリングとともに、 冷却水系にぉレヽて発生する重大な P轄の一つで ある。 腐食は、 冷却水系の設備の赫の短縮、 熱交難チューブの貫通による製品の漏曳、 汚染などの 的な障害を引き起こすのみならず、 腐食生成物の付着による熱交 «の熱 効率の低下、 ポンプ圧の上昇などの間接的な障害を発生させる。 また、 高温、 高圧プロセ スにおける事故の発生は、 人身事故にもつながりかねなレヽ。 冷却水中に?雜する荑鍵 1« 力 ¾¾|されてィ 面にスケールとして析出したり、 系内で微生物力増殖してスライム力付 着すると、 付着物の下部で局部腐食力 s進行することが多い。 腐^^にさらされた^ S表 面力 s全面で腐食する ^は、 腐食による装置の ^予測もしゃすく、 文様もたて いが、 実際の系では局部腐食が多く、 中でも、腐食した部分の間口の大きさに る深さの比が 大きレ、?し食が発生する が多 、。 このために、 水系におけるスケ一ノ^腐食の発生を防 止するために、 さまざまな手段が講じられている。  Corrosion is one of the major P issues that occur in the cooling water system, along with fouling. Corrosion not only causes shortage of cooling water system equipment, leakage of products due to penetration of heat exchange tubes, contamination, etc., but also decreases heat efficiency of heat exchange due to adhesion of corrosion products. It causes indirect obstruction such as increase in pump pressure. Also, the occurrence of accidents in high-temperature, high-pressure processes could lead to personal injury. When the key 1 is applied to the cooling water and precipitates as a scale on the surface, or when microorganisms grow in the system and adhere to the slime force, the local corrosive force s progresses below the deposit. There are many. ^ S exposed to rot ^ S Surface force s Corrosion on the entire surface ^ The corrosion of the equipment is predictable, and the pattern is very predictable, but the actual system has a lot of local corrosion, especially the corroded part The ratio of the depth to the size of the frontage is large. The eclipse often occurs. For this reason, various measures have been taken to prevent the occurrence of sky corrosion in water systems.
例えば、 ボイラー、 熱交換器、 凑 器、 配管などの水系において、 スケーノレ生成を防止 するために用いる水処額 IJとして、 殳ジェンのスルホン化物又はその重合 しくは共 重合体を含有する水処 S^IJ力 s提案されている (特許文献 1 )。 また、 リンを含有 ~¾rf、  For example, in water systems such as boilers, heat exchangers, water heaters, and pipes, the water treatment amount IJ used to prevent the formation of skeinole is a water treatment S containing a sulfonated product of Yonggen or its polymerization or copolymer. ^ IJ force s has been proposed (Patent Document 1). Also contains phosphorus ~ ¾rf,
ィオンと不溶' を生ずることがなく、 スケール及 亏れ防止効果に優れ、 その効果 力 s長期間 するとともに、 腐食抑制効果にも優れた水処3¾として、 殳ジエンス ルホン艦しくはその塩、 (メタ)アクリル赚しくはその塩、 及び、 (メタ)アクリル酸 2 一ヒドロキシェチル又は (メタ)アクリルアミドー 2—メチルアルカンスルホン^ =しくは その塩より合成される 3成分系共重合体を含有する水処額 IJが提案されてレ、る(特許文献 さらに、 リン系薬剤及ひ 系薬剤を全く使用することなく、 !]水系における S材 料の腐食を効果的に防止することができる防食 去として、 P7の Mアル力リ度を Am gCaC03ZL、 カルシウム硬度を BmgCaC03/L、 シリカ濃度を CmgSi02ZL、 マグネ シゥム硬度を DmgCaCC /L ランジェリア指数を E、 水素イオン指数を pH、 水温を t°Cとしたとき、 (1) 2.41 o gA+ 1 o gB≥6.4及ぴ C≥50、 (2) 1 o gC+ 1 o gD+2 pH+8.511 o g t≥ 33, 又は、 (3) l o gB+l o gC 3.4及び E ≥1.5を満たす水質に調整し、 水溶性ァ-オンポリマーを勸口する防食方法力 S提案され ている (赚文献 3)。 また、 纖汚染問題を惹き起こすことなく、 水系と接する金属の腐 食を効果的に防止なレ、し抑制する方法として、 開 ¾盾環冷却水系にお!ヽて、 水中の S i O 2濃度を [S i O2] (mgSi02/L), カルシウム硬度を [C aH] (mgCaC03/L)としたとき、 ランジェリア指数が 1.5以上で、 力、つ、 [S i02]X[CaH] 2, 000となるように 水質を調整し、 次いで、 重量平均^"量 1, 000〜 20, 000のマレイン酸、 無水マレ ィン^ Xはこれらの水溶性塩とィソブチレンとの共重合体を 口する方法が提案されてい る (特許文献 4)。 It is a water treatment that does not produce water and insolubles, has excellent scale and spread prevention effects, has a long-lasting effect, and has excellent corrosion control effects. Contains (meth) acrylic or its salts, and ternary copolymers synthesized from (meth) acrylic acid 2-hydroxyethyl or (meth) acrylamido-2-methylalkanesulfone or its salts IJ has been proposed for the amount of water to be treated (Patent Document Furthermore, without the use of any phosphorus-based agent及Hi drugs,!] As anticorrosion can effectively prevent corrosion of the S materials in aqueous systems, the M Al force Li of the P7 Am gCaC0 3 ZL when calcium hardness BmgCaC0 3 / L, silica concentration CmgSi0 2 ZL, Magne Shiumu hardness DmgCaCC / L lingerie a exponent E, pH hydrogen ion exponent, the water temperature was set to t ° C, (1) 2.41 o gA + 1 o gB ≥ 6.4 and C ≥ 50, (2) 1 o g C + 1 o g D + 2 pH + 8.511 ogt ≥ 33, or (3) Adjust the water quality to satisfy lo g B + lo g C 3.4 and E ≥ 1.5. However, an anticorrosion method that suggests a water-soluble aion polymer has been proposed (赚 Reference 3). Also, without causing the纖pollution problems, prevention of corrosion of metal in contact with aqueous effectively les, as a method teeth suppressing, Te Contact!ヽthe open ¾ shield ring cooling water systems, water S i O 2 the concentration [S i O 2] (mgSi0 2 / L), when the calcium hardness and [C aH] (mgCaC0 3 / L), with lingerie a index of 1.5 or more, the force, one, [S i0 2] X The water quality was adjusted to be [CaH] 2,000, and then the weight-average amount of maleic anhydride and maleic anhydride ^ X was from 1,000 to 20,000, and the water-soluble salt was mixed with isobutylene. A method of ingesting a polymer has been proposed (Patent Document 4).
これらの手段によれば、 スケール防止ないし^!腐食抑制効果は得られるが、 孔食抑制 に る 効的な効果は得られなレヽ。 マレイン酸ーィソブチレン共重合体とカルシウム硬 度、 シリカ濃度を利用する防食雄は、 7質上の制限が多く、 孔食の抑制も不十分である 齢がある。 炭酸カルシウムの飽和指数と腐食傾向/スケール傾向の関係については、 J. W. R y z n e rが報告してレ、る(非特許文献 1 )。 リズナ一指数 6以上の水質では腐食傾 向、 リズナー指数 6未満の水質ではスケール ί頃向となる。 しかし、 一般的にスケーノ W頃向 の水質では平均の腐食艇は低くなるが、 孔食のような局部腐食が起きる があり、 機 器の 延長には不十分である。  According to these measures, scale prevention or ^! Corrosion suppression effect can be obtained, but no effective effect of pitting corrosion control can be obtained. Anticorrosion males using maleic acid-isobutylene copolymer, calcium hardness and silica concentration have many qualities, and their pitting corrosion is not sufficiently controlled. The relationship between the saturation index of calcium carbonate and the tendency to corrosion / scale tendency has been reported by J. W. Ryzner (Non-Patent Document 1). Corrosion tends to occur in water quality with a Rizna index of 6 or more, and tends to scale around in water quality with a Rizna index of 6 or less. However, in general, the average quality of boats in the water quality around Skeno W is low, but local corrosion such as pitting may occur, which is not enough to extend the equipment.
[特許文献 1] 特許第 2625914号公報 (第 1頁)  [Patent Document 1] Japanese Patent No. 2625914 (Page 1)
[特許文献 2] 特開平 9— 248555 報 (第 2— 3頁)  [Patent Document 2] Japanese Patent Application Laid-Open No. 9-248555 (pages 2-3)
[特許文献 3] 特開 2004— 107782 報 (第 2— 3Μ)  [Patent Document 3] Japanese Patent Application Laid-Open No. 2004-107782 (No. 2-3)
[特許文献 4] ^平 4— 33868号公報 (第 1—2頁)  [Patent Document 4] ^ Hei 4-33868 (pages 1-2)
[非特許文献 1] J . AWWA 36 472(1944)  [Non-Patent Document 1] J. AWWA 36 472 (1944)
本発明は、 H漏環 P水系において、 リン化合物や ffilft塩などの重 塩を用いるこ となく、 炭蒸岡の孔食の進行を抑制し、熱交«などの水と接する設備の^ Ϊを効果的に  The present invention relates to an H-leaked P water system, which suppresses the progress of pitting corrosion in a coal fumigation oka without using a phosphorus compound or a heavy salt such as ffilft salt, and is provided with equipment for contact with water such as heat exchange. Effectively
2 延長することができる^ Sの孔食抑制剤及ひ孔食抑制;^去を することを目的としてな されたものである。 発明の開示 2 It can be prolonged ^ S pitting corrosion inhibitor and pitting corrosion inhibition ^ ^ It was made for the purpose of removing. Disclosure of the invention
本発明者らは、 上記の IS を解決すべく鋭意 を重ねた結果、 (A) 殳ジェンのスル ホンィ とカルボキシル R K基を有する不飽和化合物との共重合体、 (B)マレイン酸とアルケ ンとの共重合体及び (C)ァゾ Cール化合物を含有する薬剤を水系に勵ロすることにより、 孔 一  As a result of the present inventors' earnest efforts to solve the above-mentioned IS, (A) a copolymer of sulfonyi of chlorogen and an unsaturated compound having a carboxyl RK group, (B) a maleic acid and an alkene By pumping a copolymer containing a copolymer with and a (C) azole compound into an aqueous system,
食の進行を効果的に抑制し得るこ RCIとを見いだし、 この知見に基づレ、て本発明を するに 至った。 R CI The present inventor has found that RCI can effectively suppress the progress of eating, and based on this finding, have led to the present invention. R CI
すなわち、 本発明は、  That is, the present invention
( 1 ) (A)—拭 [ 1 ]で表される雜ジェンのスルホン化物 1モルに対して、 ~¾式 [ 2] で表されるカルボキシル基を有する不飽和化合物 0. 1〜2 0モルを共重合したスルホン 酸基を有する共重合体、 (B)マレイン酸 1モルに対して、 炭素数 4〜: L 0のアルケン 0. 8 - 1. 3モルを共重合した疎水基を有する共重合体及ぴ (C)ァゾール化合物を含有する ことを糊敷とする^ の孔食抑制剤、  (1) (A) —A carboxyl group-containing unsaturated compound represented by the formula [2] 0.1 to 20 mol per 1 mol of the sulfonated compound of the benzene represented by the formula [1] (B) a copolymer having a hydrophobic group obtained by copolymerizing 0.8 to 1.3 mol of an alkene having 4 to 0 carbon atoms with respect to 1 mol of maleic acid. A pitting corrosion inhibitor containing a polymer and (C) an azole compound as a glue sheet,
R 5 R 5
/  /
= C  = C
4 \ ϋ 6  4 \ ϋ 6
(ただし、 式中、 R^R6は、 水素原子、 炭素数 1〜8のアルキル基、 炭素数 6〜2 0の ァリール基、 又は— S〇3Xであり、 ここで Xは水素原子、 アルカリ金属原子、 アルカリ 土類金属原子、 アンモニゥム基もしくはアミノ基であり、 R^R6の少なくとも 1つは一 s o3xである。 ) (Where R ^ R 6 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —S〇 3 X, where X is a hydrogen atom, An alkali metal atom, an alkaline earth metal atom, an ammonium group or an amino group, and at least one of R ^ R 6 is 1 so 3 x.)
R7 R 9 R 7 R 9
\ /  \ /
c = c
Figure imgf000005_0001
c = c
Figure imgf000005_0001
(ただし、 式中、 R7〜R1()の少なくとも 3は—( C H2) raC O OMであり、 残余は水素又 は炭素数 1〜 8のアルキル基であり、 mは 0〜8であり、 Mは水素原子、 アルカリ^ S、 アルカリ土類 原子、 アンモニゥム基又はアミノ基である。 ) 、 (Wherein, at least 3 of R 7 to R 1 () is — (CH 2 ) ra COOM, and the remainder is hydrogen or Is an alkyl group having 1 to 8 carbon atoms, m is 0 to 8, and M is a hydrogen atom, an alkali ^ S, an alkaline earth atom, an ammonium group or an amino group. ),
( 2) (A)スルホン酸基を有する共重合体 1重量部に対して、 (B)疎水基を有する共重合 体 0 · 0 5〜 8重量部及び(C)ァゾール化合物 0. 0 0 5〜0. 1重量部を含有する(1 )記 載の の孔食抑制剤、 及ぴヽ  (2) With respect to 1 part by weight of the copolymer having the sulfonic acid group (A), 0.5 to 8 parts by weight of the copolymer having the hydrophobic group (B) and 0.05 to 5 parts by weight of the azole compound (C). The pitting corrosion inhibitor according to (1), which contains 0.1 parts by weight;
( 3 ) ( 1 )又は(2)記載の金属の孔食抑制剤を、 (A)スルホン酸基を有する共重合体、 (B)疎水基を有する共重合体及び (C)ァゾール化合物の合計として、 水系に 1〜1 0 0 m g /L添カロすることを糊敷とする^の孔食抑制方法、  (3) A total of (A) a copolymer having a sulfonic acid group, (B) a copolymer having a hydrophobic group, and (C) an azole compound, As a method of controlling pitting corrosion of ^ with the addition of 1 to 100 mg / L of calo in the water system,
を するものである。 It is what you do.
さらに、 本発明の好ましい として、  Further, as a preferable example of the present invention,
(4) ァゾール化合物が、 トリァゾールである(1 )又は(2)記載の金属の孔食抑制剤、 及 び、  (4) The metal pitting corrosion inhibitor according to (1) or (2), wherein the azole compound is triazole, and
(5) トリアゾールが、 ベンゾトリアゾール又はトリノレトリアゾールである( 4 )記載の金 属の孔食抑制剤、  (5) The metal pitting corrosion inhibitor according to (4), wherein the triazole is benzotriazole or torinoletriazole,
を挙げることができる。 図面の簡単な説明 Can be mentioned. Brief Description of Drawings
F i g . 1は難例で用いた通水試難置の系統図である。 図中、符号 1はタンク、 2 はポンプ、 3は炭靡岡管、 4は炭 ¾ ^管、 5は銅管、 6は腐食計を表す。 発明を実施するための最良の开$態  Fig. 1 is a system diagram of the water flow test difficulties used in the difficult example. In the figure, reference numeral 1 denotes a tank, 2 denotes a pump, 3 denotes a charcoal pipe, 4 denotes a charcoal pipe, 5 denotes a copper pipe, and 6 denotes a corrosion meter. Best mode for carrying out the invention
本発明の金属の孔食抑制剤は、 (A)一般式 [ 1 ]で表される^:ジェンのスルホン化物 1 モルに対して、 HI殳式 [ 2 ]で表されるカルボキシル基を有する不飽和化合物 0. 1 - 2 0 モルを共重合したスルホン^ ¾を有する共重合体、 (B)マレイン酸 1モルに対して、 炭素 数 4〜1 0のアルケン 0. 8〜: 1. 3モルを共重合した ] <基を有する共重合体及ぴ (C)ァ ゾール化 ^(を含有する。  The metal pitting inhibitor of the present invention comprises (A) a compound having a carboxyl group represented by the HI formula [2] per mole of the sulfonated compound of ^: gen represented by the general formula [1]: (B) a copolymer having 0.1 to 20 moles of a sulfone compound, and (B) 1 mole of maleic acid, 0.8 to 1.3 moles of an alkene having 4 to 10 carbon atoms And (C) azolized ^ (.
Figure imgf000006_0001
ただし、 一般式 [ 1 ]において、 !^〜尺6は、 水素原子、 炭素数 1〜8のアルキル基、 炭素 数 6〜 2 0のァリ一ル基、 又は一 S O3Xであり、 ここで Xは水素原子、 アル力リ録原 子、 アルカリ土類金属原子、 アンモニゥム基もしくはアミノ基であり、 R^R6の少なく とも 1つは一 S〇3Xである。
Figure imgf000006_0001
However, in general formula [1],! ^ ~ Scale 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, § Li Ichiru group having a carbon number of 6-2 0, or an SO 3 X, wherein X is a hydrogen atom, Al Chikarariroku atom, an alkaline earth metal atom, an Anmoniumu group or amino group, one at least of R ^ R 6 is an S_〇 3 X.
R7 R9 R 7 R 9
\ /  \ /
C = C  C = C
/ \  / \
P 8 ϋ 1 0 .  P 8 ϋ 10.
^ 1 -[ 2] ^ 1- [2]
ただし、 一般式 [ 2]において、 !^〜尺1。の少なくとも一つは一(CH2)mCOOMであり、 歹餘«7|素又は炭素数 1〜8のアルキル基であり、 mは 0〜8であり、 Μί¾Κ素原子、 了 ノレカリ雄、 アルカリ 原子、 アンモニゥム基又はアミノ基である。 However, in general formula [2],! ^ ~ Shaku 1 . At least one of which is 1 (CH 2 ) m COOM, is a system or an alkyl group having 1 to 8 carbon atoms, m is 0 to 8, and is a hydrogen atom, It is an atom, an ammonium group or an amino group.
一舟拭 [ 1 ]で表される ジェンのスルホン化物としては、 殳ジェンのスルホン酸、 及ぴそのアル力リ銻塩、 アル力リ ±il^JS塩、 ァンモニゥム はァミ ^などが挙げ られ、 その具体的化合物としては例えば、 2—メチルー 1 , 3—ブタジ工ン一 1一スルホ ン酸、 2—メチルー 1 , 3—ブタジエン一 3—スルホン酸、 2—メチル一1, 3—プタジェ ン一 4ースノレホン酸、 1, 3—ペンタジェンー 1—スルホン酸、 1 , 3—ペンタジェン一 2 ースルホン酸、 1, 3—ペンタジェン一 3—スルホン酸、 1, 3—ペンタジェン一 4—スル ホン酸、 2, 3—ジメチルブタジエン一 1—スルホン酸、 2—メチル一1, 3—ペンタジェ ンー4ースルホン酸、 3—メチル一 1 , 3—ペンタジェン一 1—スルホン酸、 2—メチノレ - 1 , 3ーブタジェン一 1, 3—ジスノレホン酸、 2—メチノレ一 1, 3—ブタジェン一 1 , 4— ジスノレホン酸、 2—メチルー 1, 3—ブタジエン一 1—スルホン酸ナトリウム (ィソプレン スルホン酸ナトリゥム)、 2—メチノレ一 1 , 3—ブタジエン一 1—スノレホン酸力リゥム、 2 —メチルー 1, 3—ブタジエン一 1ースルホン酸アンモニゥム等が挙げられ、 これらの中 では 2—メチノレー 1 , 3—ブタジェン一 1ースルホン酸ナトリウム(ィソプレンスルホン酸 ナトリウム)、 2ーメチノレー 1, 3一ブタジエン一 1— ノレホン酸力リゥム、 2ーメチノレー 1 , 3—プタジェン一 1ースルホン酸アンモユウムが好ましレヽ。  Examples of the sulfonated product of gen represented by Ichifunai [1] include sulfonic acid of gengen, its salt, and its salt ± il ^ JS salt, and its ammonium salt is ami. Specific examples thereof include 2-methyl-1,3-butadiene-l-sulfonic acid, 2-methyl-l, 3-butadiene-l-sulfonic acid, and 2-methyl-l, 3-butadiene. 1-4-Snorleonic acid, 1,3-pentadiene-1-sulfonic acid, 1,3-pentadiene-2-sulfonic acid, 1,3-pentadiene-3-sulfonic acid, 1,3-pentadiene-4-sulfonic acid, 2, 3-dimethylbutadiene-1-sulfonic acid, 2-methyl-1,3-pentagen-4-sulfonic acid, 3-methyl-1,3-pentadiene-1-sulfonic acid, 2-methynole-1,3-butadiene-1, 3-dishonolefonic acid, 2-methinole 1,3-butadiene 1,4-dishonolefonic acid, 2-methyl-1,3-butadiene-11-sodium sulfonate (isoprene sodium sulfonate), 2-methynole-1,3-butadiene 1-1-snolephonic acid And 2-methyl-1,3-butadiene-1-sulfonic acid ammonium, among which sodium 2-methinolate 1,3-butadiene-1-sulfonic acid (sodium isoprenesulfonate), 2-methylinolate 1,3 Preferred are 1-butadiene 1-norephonic acid rim, 2-methinolay 1,3-butadiene 1-ammonium sulfonate.
一般式 [ 2]で表されるカルボキシル基を有する不飽和化^!としては、 例えば、 アタリ ル酸、 メタクリノレ酸、 クロトン酸、 イソクロトン酸、 ビニノレ酢酸、 アングリ力酸、 チグリ ン酸、 マレイン酸、 フマル酸、 ィタコン酸、 シトラコン酸、 メサコン酸、 アコニット酸な どを挙げることができる。 Examples of the unsaturated carboxyl group having a carboxyl group represented by the general formula [2] include, for example, atarilic acid, methacrylic acid, crotonic acid, isocrotonic acid, vinylinoleic acid, angryic acid, tiglinic acid, maleic acid, Fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid And so on.
本発明にぉレ、て、 (A)スルホン藤を有する共重合体は、 1 ]で表される *ί殳ジ ェンのスルホン化物 1モルに対して、 一般式 [ 2 ]で表されるカルボキシル基を有する不飽 和化合物 0. 1-20モルを共重合した共重合体であり、 より好ましくは一般式 [ 1 ]で表 される化合物 1モルに対して、 殳式 [ 2 ]で表される化合物 1. 5-1 2モルを共重合し た共重合体である。 一^ [ 1 ]で表されるィ匕合物 1モルに る一^ [ 2 ]で表されるィ匕 合物の量が 0. 1モル未満であっても、 20モノレを超えても、 孔食を抑制する効果が十分 に発現しないおそれがある。 (A)スルホン を有する共重合体の重量平均分子量は、 3, 000〜1 5, 000であることが好ましく、 5, 000〜1 2, 000であることがより 好ましレヽ。 なお、 本発明にぉレヽて、 重合体の好量は、 下記条件のゲルパーミエーション クロマトグラフィーにより測定し、 ポリエチレンダリコール標 2^斗に^^して求めた重 量平均分子量である。  According to the present invention, (A) the copolymer having a sulfone can be represented by the general formula [2] with respect to 1 mol of the sulfonated product of * ίJ It is a copolymer obtained by copolymerizing 0.1 to 20 mol of an unsaturated compound having a carboxyl group. More preferably, it is represented by the following formula [2] with respect to 1 mol of the compound represented by the general formula [1]. This is a copolymer obtained by copolymerizing 1.5 to 12 moles of the compound. Even if the amount of the compound represented by 1 [2] in 1 mol of the compound represented by 1 [1] is less than 0.1 mol or more than 20 monoles, The effect of suppressing pitting corrosion may not be sufficiently exhibited. (A) The weight average molecular weight of the copolymer having a sulfone is preferably from 3,000 to 15,000, more preferably from 5,000 to 12,000. Note that, in the present invention, the preferred amount of the polymer is a weight average molecular weight determined by gel permeation chromatography under the following conditions and determined by a polyethylene dalicol standard.
使用カラム: トーソー TSK— Ge l G3000PWXL及び G4000 PWXL  Columns used: Tosoh TSK—Gel G3000PWXL and G4000 PWXL
0. 2mo 1 e/L-Na C 1水赚  0.2mo 1 e / L-Na C 1 water 赚
検出 ¾: R I  Detection ¾: R I
分离鲦件 カラム温度 40°C 溶離液流量 0. 6mL/m i n  Column temperature 40 ° C Eluent flow rate 0.6 mL / min
0. 4% 200 μ L·  0.4% 200 μL
PEG標■斗: GLサイエンス ¾ の PEG標準物質 (分子量百 ~¾万の 10, 本発明に用いる(A)スルホン酸基を有する共重合体の製^法に特に制限はなく、 例え ば、 一般式 [1]で表される 殳ジェンのスルホン化物と ~拭 [2]で表されるカルボキシ ル基を有する不飽和化合物を水に溶解し、 ラジカル重合開½ ^を用いて水? 鍾合するこ とができる。  PEG standard: GL Science's PEG standard substance (the molecular weight of 100 to 10,000, (A) the method for producing the (A) sulfonic acid group-containing copolymer used in the present invention is not particularly limited. The sulfonated product of the formula [1] and the unsaturated compound having a carboxyl group represented by the formula [2] are dissolved in water and combined with the radical polymerization initiator. be able to.
本発明にぉレ、ては、 (A)スルホン ^¾を有する共重合体として、 一舟拭 [ 1 ]で表される 殳ジェンのスノレホン化物と一般式 [ 2 ]で表されるカルボキシル基を有する不飽和化合物 にカロえて、 さらに他の単量体を共重合した共重合体を用レ、ることができる。  In the present invention, (A) As a copolymer having a sulfone ^ 、, as a copolymer having a snorolefon of 殳 ジ ェ ン and a carboxyl group represented by a general formula [2] It is possible to use a copolymer obtained by copolymerizing another monomer with the unsaturated compound.
本発明に用いる炭素数 4〜10のアルケンとしては、 例えば、 1ーブテン、 イソブチレ ン、 1一ペンテン、 3—メチルー 1—ブテン、 1一へキセン、 3—メチルー 1一ペンテン、 4ーメチノレー 1—ペンテン、 1—へプテン、 4ーメチノレ一 1一へキセン、 5—メチノレ一 1 —へキセン、 1—ォクテン、 5—メチノレー 1—ヘプテン、 1—ノネン、 1—デセンなどを 挙げることができる。 本発明において、 (B)疎水基を有する共重合体は、 マレイン酸 1モルに対して、 炭素数 4〜: L 0のァノレケン 0 · 8〜: 1 · 3モルを共重合した共重合体であり、 より好ましくはマレ ィン酸 1モルに対して、 炭素数 4〜 1 0のアルケン 0. 9 5〜 1 . 1モルを共重合した共重 合体である。 マレイン酸 1モルに文汁るァルケンの量が 0. 8モノ V*満であっても、 1 . 3 モノレを超えても、 孔食を抑制する効果が十分に発現しないおそれがある。 (Β)Ϊ^Κ基を有 する重合体の重量平均奸量は、 4, 0 0 0〜 5 0 , 0 0 0であること力 S好ましく、 5 , 0 0 0〜3 5, 0 0 0であることがより好ましレヽ。 The alkene having 4 to 10 carbon atoms used in the present invention includes, for example, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-11-pentene, 4-methylino-1-pentene , 1-heptene, 4-methynole-1-hexene, 5-methinole-1-hexene, 1-octene, 1-octenol, 1-heptene, 1-nonene, 1-decene. In the present invention, (B) a copolymer having a hydrophobic group is a copolymer obtained by copolymerizing 0.8 to 1.3 moles of an anoleken having 4 to L 0 carbon atoms with respect to 1 mole of maleic acid. And more preferably a copolymer obtained by copolymerizing 0.95 to 1.1 mol of an alkene having 4 to 10 carbon atoms per 1 mol of maleic acid. Even if the amount of alkene in 1 mole of maleic acid is 0.8 mono V * or more than 1.3 mono, the effect of suppressing pitting corrosion may not be sufficiently exhibited. (Β) The weight-average weight of the polymer having a Ϊ ^ Κ group is preferably 4,000 to 500,000, preferably 5,000 to 3,500,000. It is more preferable to be.
本発明に用いる(B)疎水基を有する共重合体の製造方法に特に制限はなく、 例えば、 無 水マレイン酸とアルケンを無溶媒で、 又は、 有機溶媒の被下に、 ラジカル重合開始剤を 用いて重合し、 得られた無水マレイン酸/アルケンの共重合体を加水^ することによつ て得ることができる。  The method for producing the copolymer (B) having a hydrophobic group used in the present invention is not particularly limited. For example, a radical polymerization initiator may be prepared by adding anhydrous maleic acid and an alkene without a solvent or under an organic solvent. And the resulting maleic anhydride / alkene copolymer is hydrolyzed.
本発明にぉ ヽては、 (B) ϊ棘基を有する共重合体として、 マレイン酸と炭素数 4〜 1 0 のアルケンに加えて、 さらに他の単量体を共重合した共重合体を用レヽることができる。 本発明に用いる(C)ァゾール化合物は、 ヘテロ原子 2個以上を含む五員環を有する芳香 衡匕合物であって、 ヘテロ原子の少なくとも 1個が窒素原子である化合物である。 ァゾー ル化^ ¾)としては、 ビラゾール、 ィミダゾール、 1, 2, 3—トリァゾール、 1 , 2, 4ート リアゾール、 テトラゾーノレ、 才キサゾール、 ィソォキサゾーノレ、 チアゾーノレ、 イソチアゾ 一ノレ、 ォキサジァゾ一ノレ、 チアジアゾール、 ィンダゾ一ノレ、 ベンゾィミダゾーノレ、 ベンゾ トリァゾール、 ベンゾォキサゾール、 ベンゾィソ才キサゾ一ノレ、 ベンゾチアゾール、 トリ ノレトリァゾールなどを挙げることができる。 これらの中で、ベンゾトリアゾール及びトリ ノレトリァゾーノレを に用いることができる。  In the present invention, (B) as a copolymer having a spine group, a copolymer obtained by copolymerizing another monomer in addition to maleic acid and an alkene having 4 to 10 carbon atoms. Can be used. The (C) azole compound used in the present invention is an aromatic conjugate having a five-membered ring containing two or more hetero atoms, wherein at least one of the hetero atoms is a nitrogen atom. The azozolization ^ ¾) includes virazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazonole, thixazole, isoxoxazonole, thiazonole, isothiazonoole, oxoxadiazonole Thiadiazole, indazoinole, benzoimidazonole, benzotriazole, benzoxazole, benzothiazole, benzothiazole, benzothiazole, trinoretriazole and the like. Among these, benzotriazole and trinoletriazonole can be used for.
本発明の の孔食抑制剤は、 (A)スルホン^ ¾を有する共重合体 1重量部に対して、 The pitting corrosion inhibitor of the present invention comprises: (A) 1 part by weight of a copolymer having sulfone
( B ) 基を有する共重合体 0. 0 5 - 8重量部を含有すること力 S好ましく、 0.:!〜 4重 量部を含有することがより好ましく、 0. 2 5〜1 . 5重量部を含有することがさらに好ま しレ、。 ( A)スルホン纖を有する共重合体 1重量部に财る( B )疎水基を有する共重合体 の量が 0 : 0 5重量部未満であっても、 8重量部を超えても、 孔食を抑制する効果が十分 に発現しなレヽおそれがある。 (B) A copolymer having a group having a group content of 0.05 to 8 parts by weight is preferable, and a content of 0.2 to 1.5 parts by weight is more preferable, and 0.2 to 1.5 parts by weight is more preferable. More preferably, it contains parts by weight. (A) 1 part by weight of the copolymer having sulfone fiber (B) Even if the amount of the copolymer having a hydrophobic group is less than 0:05 parts by weight or more than 8 parts by weight, There is a risk that the effect of suppressing food will not be sufficiently exhibited.
本発明の録の孔食抑制剤は、 (A)スルホン^ ¾を有する共重合体 1重量部に対して、 The pitting corrosion inhibitor of the present invention is (A) 1 part by weight of a copolymer having sulfone ^
(C)ァゾール化合物 0 · 0 0 5〜0. 1重量部を含有すること力 S好ましく、 0. 0 0 7〜0. 0 7重量部を含有することがより好ましレヽ。 (A)スルホン纖を有する共重合体 1重量部 に财る(C)ァゾール化合物の量が 0. 0 0 5重量部未満であると、 孔食を抑制する効果 が十分に発現しなレヽぉそれがある。 (A)スルホン を有する共重合体 1重量部に女什る (C)ァゾール化合物の量は、 0. 1重量部以下で十分な孔食抑制効果が発現し、 通常は(C) The azole compound preferably contains 0.05 to 0.1 part by weight, more preferably 0.0007 to 0.07 part by weight. (A) 1 part by weight of a copolymer having sulfone fiber If the amount of the (C) azole compound is less than 0.05 part by weight, the effect of suppressing pitting corrosion may not be sufficiently exhibited. When the amount of the (C) azole compound is less than 0.1 part by weight, a sufficient pitting corrosion inhibiting effect is exhibited.
(A)スルホン^ ¾を有する共重合体 1重量部に対して 0 · 1重量部を超える(C)ァゾール ィ匕合物を含有させる必要はなレ、。 (A) It is not necessary to contain more than 0.1 parts by weight of the (C) azole conjugate with respect to 1 part by weight of the copolymer having sulfone.
本発明の金属の孔食抑制剤の剤型に特に制限はなく、 例えば、 (A)スノレホン酸基を有す る共重合体、 (Β) ί棘基を有する共重合体及び (C)ァゾール化^ ¾を含有する 1剤型とす ることができ、 ( Α)スルホン酸基を有する共重合体、 ( Β )疎水基を有する共重合体及び (C)ァゾール化^!の任意の 2種と他の 1種を組み合わせた 2剤型とすることもでき、 あ るいは、 (Α)スルホン醒を有する共重合体、 (Β) ϊ棘基を有する共重合体及び (C)ァゾ ール化合物を別々に添加する3剤型とすることもできる。 これらの中で、 1剤型は、 薬剤 ¾λ設備力 s簡 匕され、 添口濃度比も一定に保たれるので、 好適に用いることができる。 1剤にする際には、 孔食抑制剤の安定化のために、 7酸化アルカリや、 鉱酸、 棚酸など の酸類を添卩することができる。 また、 防食効果を高めるために、 リン »、 重合リン酸 塩、 ホスホン酸、 ffif口、塩、 ァノレミン^^、 モリプデン^:などの防食剤を、 本発明の孑し食 抑制剤に配合することができ、 あるいは、 これらの防食剤を水系に勸ロすることもできる。 本発明の金属の孔食抑制方法においては、 本発明の の孔食抑制剤を、 (A)スルホン 纖を有する共重合体、 (Β) ϊ棘基を有する共重合体及び (C)ァゾール化合物の合計とし て、 水系に 1〜1 0 O m g/L、 より好ましくは 1 0〜7 O m g/L、 さらに好ましくは 1 5〜5 O m g/L¾¾jnする。 (A)スルホン酸基を有する共重合体、 (B)疎水基を有する 共重合体及ぴ (C)ァゾール化合物の合言十の添カロ量が 1 m g/L未満であると、 の孔食 を抑制する効果が + に発現しないおそれがある。 (A)スルホン酸基を有する共重合体、There is no particular limitation on the dosage form of the metal pitting inhibitor of the present invention. For example, (A) a copolymer having a snorenoic acid group, (Β) a copolymer having a spine group, and (C) an azole (剤) a copolymer having a sulfonic acid group, (Β) a copolymer having a hydrophobic group, and (C) an azolated ^! It can also be a two-drug type combining one species with another, or (Α) a copolymer having a sulfone wake, (Β) a copolymer having a spine group, and (C) an azo compound. In the form of a three- drug composition in which a cooling agent compound is separately added. Among these, the one-drug type can be suitably used because the drug ¾λ facility power s is simplified and the inlet port concentration ratio is kept constant. When one agent is used, it is possible to add an acid such as alkali metal oxide, mineral acid, or shelf acid to stabilize the pitting corrosion inhibitor. Further, in order to enhance the anticorrosion effect, an anticorrosive such as phosphorus », polymerized phosphate, phosphonic acid, ffif mouth, salt, anoremin ^^, molybdenum ^ :, etc. may be blended with the sorghum inhibitor of the present invention. Alternatively, these anticorrosives can be recommended to aqueous systems. In the method for inhibiting metal pitting corrosion of the present invention, the pitting corrosion inhibitor of the present invention comprises: (A) a copolymer having a sulfone fiber, (Β) a copolymer having a spine group, and (C) an azole compound. The total amount of the aqueous solution is 1 to 10 O mg / L, more preferably 10 to 7 O mg / L, and still more preferably 15 to 5 O mg / L¾¾jn. (A) a copolymer having a sulfonic acid group, (B) a copolymer having a hydrophobic group, and (C) a pitting corrosion of less than 1 mg / L when the addition amount of the azole compound is less than 1 mg / L. There is a possibility that the effect of suppressing + may not be exhibited. (A) a copolymer having a sulfonic acid group,
(B) Sfek基を有する共重合体及ぴ (C)ァゾール化合物の合計の勸ロ量が 1 0 O m g/Lを 超えると、 スルホン^ ¾を有する共重合体のキレート作用により防 ^^膜の形成が遅くな つたり、 イオンと共重合体がキレート化合物を形成して^するなどの障害が発生す るおそれがある。 (B) When the total amount of the copolymer having the Sfek group and the (C) azole compound exceeds 10 O mg / L, the chelating action of the copolymer having the sulfone ^^ prevents the membrane from being formed. There is a risk that the formation of ions may be slowed down, or that the ion and the copolymer may form a chelate compound to form an obstacle.
本発明にぉレ、て、 (A)スルホン隨を有する共重合体と(B)驗基を有する共重合体の 混合物は、 § 才質に対してキレート作用により防食皮膜の形成を阻害する齢がある。 系 内の #辭才質が腐食して水中の^ I同イオ^度が高まると、 鉄系^ gの表面に溶解した銅ィ オン力 して腐食を促進する。 本発明においては、 (C)ァゾール化合物の添口により、 銅の防触膜の形成が鍵されるので、効果的に水系における德の孔食が抑制されると 推定される。 According to the present invention, a mixture of (A) a copolymer having a sulfone moiety and (B) a copolymer having an experimental group can inhibit the formation of an anticorrosive film by a chelating action on human talent. There is. When the # dexterity in the system corrodes and the concentration of ^ I in the water increases, the copper ions dissolved on the surface of the iron-based ^ g promote the corrosion. In the present invention, (C) through the mouth of the azole compound, It is presumed that the pitting corrosion in the water system is effectively suppressed because the formation of the copper film is key.
本発明の の孔食抑制剤及ぴ孔食抑制方法によれば、 一 間の孔食の深さを 30〜 65 %減少することができる。 孔食深さの進行は、 経験的に時間の 1/3乗に比例するの で、設備赫 t (月)、 設備の: 厚さ d (mm)、 初期 1ヶ月間の孔食深さ k (mm)の間に、 t-d3/k3 とい,う関係が成り立ち、 本発明により設備の を 3〜20倍に延長する こと力 sでさる。 実施例 According to the pitting corrosion inhibitor and the pitting corrosion suppressing method of the present invention, the depth of pitting corrosion can be reduced by 30 to 65%. Since the progress of pit depth is empirically proportional to the 1/3 power of time, the equipment pit (month), the thickness of the equipment: d (mm), the pit depth k for the first month (mm), the relationship of td 3 / k 3 is established, and the present invention can extend the length of the equipment by 3 to 20 times with the force s. Example
以下に、 実施例を挙げて本発明をさらに詳細に説明するが、 本発明はこれらの実施例に よりなんら限定されるものではな!/、。  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. /.
なお、 難例及び比較例においては、 下記の重合体 (すべてナトリウム:^)を用いた。 In the difficult examples and the comparative examples, the following polymers (all sodium: ^) were used.
(A) スルホン酸基を有する共重合体 (A) Copolymer having sulfonic acid group
重合体 D:イソプレンスノレホン^ ァクリル酸共重合体、 モノレ比 20 : 80、 重量平均 好量 7, 500。  Polymer D: isoprene-norethone-acrylic acid copolymer, monomer ratio 20:80, weight-average, good weight 7,500.
重合体 E:イソプレンスルホン^ ァクリル酸共重合体、 モル比 10 : 90、 重量平均 分子量 9, 000。  Polymer E: isoprenesulfone / acrylic acid copolymer, molar ratio 10:90, weight average molecular weight 9,000.
重合体 G:イソプレンスルホン酸/ァクリノレ酸共重合体、 モル比 10 : 90、 重量平均 好量 23, 000。  Polymer G: copolymer of isoprenesulfonic acid / acrinoleic acid, molar ratio 10:90, weight-average preferred amount 23,000.
重合体 H:ィソプレンスノレホン^ ァクリル酸/メタクリル酸 2―ヒドロキシェチル共 重合体、 モル比 20 : 65 : 15、 重量平均分子量 6, 500。 ·  Polymer H: isoprene norephon ^ acrylic acid / 2-hydroxyethyl methacrylate copolymer, molar ratio 20:65:15, weight average molecular weight 6,500. ·
(B) 餘隨を有する共重合体  (B) Copolymer having an enemy
重合体 A:マレイン^/イソブチレン共重合体、 モノレ比 50 : 50、 重量平均 量 1 4, 000。  Polymer A: maleic ^ / isobutylene copolymer, monole ratio 50:50, weight average weight 14,000.
重合体 B:マレイン^ /1—へキセン共重合体、 モル比 45 : 55、 重量平均分子量 2 0, 000。  Polymer B: maleic ^ / 1-hexene copolymer, molar ratio 45:55, weight average molecular weight 20 000.
重^ f本 C:マレイン ペンテン共重合体、 モル比 53 : 47、 重量平均分子量 6, 500。  Heavy ^ f C: maleic pentene copolymer, molar ratio 53:47, weight average molecular weight 6,500.
(D) その他の重合体  (D) Other polymers
重 本 F:ポリマレイン酸ヽ 重量平均分子量 600。 重合体 I :マレイン^ 2—アクリルアミド一 2—メチルプロパンスルホン酸共重合体、 モノレ J:匕 80 : 20、 重量平均分子量 2, 000。 Weight F: Polymaleic acid ヽ Weight average molecular weight 600. Polymer I : maleic ^ 2-acrylamide-12-methylpropanesulfonic acid copolymer, monole J: 80:20, weight average molecular weight 2,000.
また、 F i g. 1に示す ¾R試難置を用いて、 孔食抑制効果を謝面した。 水量 52L のタンク 1から、 ポンプ 2により試験水を送り、 流速 0.5m/sで炭麵管 3、 炭麵 管 4及び銅管 5を通過したのち、 腐食計 6を経由してタンクに循環した。 ρΗ8· 8、 Μ アルカリ度 30 OmgCaC03ZL、 カルシウム硬度 30 OmgCaC03/L、 シリカ濃度 10 Omg Si02/ Lの を、 タンクに 634mL/h供給し、 過乗 Uの水をタンクより溢流 させた。 試^ Rの if^時間は、 82時間である。 試 Jの?踏を 30°Cに調整し、 タンク 底部の曝気管から 10 LZm i nの空気を送って曝気した。 30日間連続して したの ち、 炭禁岡管 3で最大孔食深さ (mm/ 30日)を測定した。 また、 腐食計により、 1日 1 回、 分極抵抗法で炭雜岡と銅の腐食速度 (md d=mg · dm—2' day-1)を測定し、 3 0日間の平均値を算出した。 In addition, the pitting corrosion inhibitory effect was appreciated using the ¾R test rig shown in Fig. 1. The test water was sent from the 52-liter tank 1 by the pump 2 and passed through the coal pipe 3, the coal pipe 4, and the copper pipe 5 at a flow rate of 0.5m / s, and then circulated to the tank via the corrosion meter 6. . ρΗ8 · 8, Μ alkalinity 30 OmgCaC0 3 ZL, calcium hardness 30 OmgCaC0 3 / L, from silica concentration 10 Omg Si0 2 / L, and 634mL / h supplied to the tank, the water over-ride U is overflow from the tank Was. The trial ^ R if ^ time is 82 hours. Try J? The steps were adjusted to 30 ° C, and aeration was performed by sending 10 LZmin of air from the aeration tube at the bottom of the tank. After 30 consecutive days, the maximum pit depth (mm / 30 days) was measured at the charcoal-prohibited Oka pipe 3. Also, the corrosion rate (md d = mg · dm— 2 'day- 1 ) of coal mine and copper was measured once a day by the polarization resistance method using a corrosion meter, and the average value for 30 days was calculated. .
麵列 1 Row 1
試 に、 (A)重合体 D 32mg/L, (B)重合体 A 8 m g /L及ぴ (C)ベンゾトリア ゾール lmg/Lを して試験を行つた。 炭細の最大孔食深さは 21 mm/ 30 日であり、 炭麵の腐食艇は 3.2md d,銅の腐食艇は 0 · 9 m d dであった。  The test was conducted using (A) 32 mg / L of polymer D, (B) 8 mg / L of polymer A and (C) 1 mg / L of benzotriazole. The maximum pit depth of the charcoal was 21 mm / 30 days, and the corrosion of the charcoal was 3.2 md d and that of the copper erosion was 0.9 m d d.
霞例 2 Kasumi example 2
試 に、 (A)重合体 D24mg/L、 (B)重合体 A 16mgZL及び (C)ベンゾトリ ァゾール lmg/Lを添卩して試験を行つた。  The test was performed by adding (A) 24 mg / L of polymer D, (B) 16 mg ZL of polymer A, and (C) lmg / L of benzotriazole.
実施例 3 Example 3
試 に、 (A)重合体 D 2 Omg/L, (B)重合体 A 2 Om g/L及び (C)ベンゾトリ ァゾーノレ 0.5mg/Lとトリノレトリァゾーノレ 0.5mgZLを^]卩して試験を行った。 麵列 4〜10  In the test, (A) polymer D 2 Omg / L, (B) polymer A 2 Omg / L, (C) benzotriazonole 0.5mg / L and trinoretriazonole 0.5mgZL were tested. Was done.麵 Row 4-10
試^ *に、 第 1表に示す (A)スルホン酸基を有する共重合体、 (Β)ϊ棘基を有する共重 合体及び( C)ァゾール化合物を^ ¾ロして試験を行つた。  In the test, * (A) a copolymer having a sulfonic acid group, (ii) a copolymer having a spine group, and (C) an azole compound shown in Table 1 were tested.
比較例 1 ' Comparative Example 1 '
試験水に、 (Β)重合体 Α4 Omg/L及び(C)ベンゾトリアゾール 0.05mg/Lを 添口して試験を行った。 炭素鋼の最大孔食深さは 0.30mm/30日であり、 炭素鋼の 腐食 ¾i は 3 · 6 m d d、銅の腐食 ¾gは 1.6 m d dであった。 The test was conducted by adding (ii) polymer-4 Omg / L and (C) benzotriazole 0.05 mg / L to test water. The maximum pit depth of carbon steel was 0.30 mm / 30 days, the corrosion ¾i of carbon steel was 3.6 mdd, and the corrosion 銅 g of copper was 1.6 mdd.
比較例2〜8
Figure imgf000013_0001
第 l表に示す化 勿を添 して赚を行つた。
Comparative Examples 2 to 8
Figure imgf000013_0001
赚 was performed with the chemicals shown in Table l.
実施体 (ゾ (/)重pァルLーmg例 1〜 0及び比較例 1〜 8の結果を、 第 1表に示す。Table 1 shows the results of Examples (1 to 0) and Comparative Examples (1) to (8).
O
Figure imgf000013_0002
第 1表に見られるように、 (A)イソプレンスルホン酸とアクリル酸の共重合体、 (B)マ レイン酸とアルケンの共重合体及び(C)ベンゾトリァゾール又はべンゾトリァゾールとト リノレトリアゾールを試^ zKに添ロした «例 1〜 1 0では、 炭 岡の最大孔食の深さが 0. 1 7 - 0. 2 7 mm/ 3 0日で、 孔食抑制効果が発現している。 また、 炭聽岡の腐 ¾¾¾ 力 S i . 3〜3. 8 m d d、 同の腐食 力 0. 7 -0. 9 m d で、 炭 ¾1岡と $同の腐食も抑制 されている。
O
Figure imgf000013_0002
As can be seen in Table 1, (A) a copolymer of isoprenesulfonic acid and acrylic acid, (B) a copolymer of maleic acid and alkene, and (C) benzotriazole or benzotriazole and trinoletriazole. «Examples 1 to 10 show that the maximum pitting depth of Sumioka is 0.17-0.27 mm / 30 days, and the pitting corrosion inhibiting effect appears. I have. In addition, the corrosive power of Suitanoka is S i. 3 to 3.8 mdd, and the same corrosion power is 0.7 to 0.9 md.
これに対して、 (B)マレイン酸/ィソブチレンの共重合体と(C)ベンゾトリァゾールを ロした比較例 1、 ( A)イソプレンスルホン酸 Zァクリル酸の共重合体のみを勸 Πした比 較例 2、 (B)マレイン酸 Zアルケンの共重合体のみを勸口した比較例 3、 (D)ポリマレイ ン酸と( B )マレイン酸 Zィソプチレンの共重合体と(C)トリノレトリアゾールを添ロした比 較例 4、 (A)ィソプレンスルホン酸 Zァクリル酸の共重合体と(B)マレイン酸 Z 1—へキ センの共重合体を添カロした比較例 5、 (A)ィソプレンスノレホン^/ァクリル酸 Zメタクリ ノレ酸 2—ヒドロキシェチルの共重合体と(B)マレイン^/ 1一へキセンの共重合体を^]口 した比較例 6、 (D)マレイ / 2—アクリルアミドー 2—メチルプロパンスルホン酸の 共重合体と(B)マレイン^ ィソブチレンの共重合体を添 した比較例 7、 (B)マレイン 1—へキセンの共重合体のみを添カロした比較例 8では、 炭 岡の最大孔食の深さが 0. On the other hand, Comparative Example 1 in which (B) a copolymer of maleic acid / isobutylene and (C) benzotriazole were used, and (A) a comparison in which only a copolymer of isoprenesulfonic acid and Zacrylic acid were suggested. Example 2, Comparative Example 3, in which only (B) a copolymer of maleic acid Z alkene was advocated, and (C) a copolymer of (B) polymaleic acid and (B) Zisoptylene maleate and (C) trinoletriazole were added. Comparative Example 4, Comparative Example 5, where (A) a copolymer of isoprenesulfonic acid Z-acrylic acid and (B) a copolymer of maleic acid Z 1-hexene were added, and Comparative Example 5, (A) Comparative Example 6, (D) maleic acid / copolymer of soprens nolephon ^ / acrylic acid Z and 2-hydroxyethyl methacrylate and (B) malein ^ / 1-hexene Copolymerization of 2-acrylamide-2-methylpropanesulfonic acid copolymer with (B) malein-isobutylene Comparative Example 7 was added to, (B) in Comparative Example 8 Only copolymers of maleic to 1-hexene was added Caro, the maximum depth of pitting corrosion of carbon Oka 0.
3 0〜0. 4 8 mm/ 3 0日で、 孔食抑制効果はほとんど発現していなレヽ。 また、 炭聽岡 の腐食避が 3. 4〜6. 2 m d d、 銅の腐食速度が 1 . 5 ~ 2. 2 m d dで、 銅に ¾ "る腐 食抑制効果が弱い。 ァゾール化^)を勵 Pしていない系では銅が腐食し、 溶出した銅ィォ ンカ S炭翁岡の表面に ®¾し、 炭菌岡の腐食が加速されたと考えられる。 産業上の利用可能性 In the range of 30 to 0.48 mm / 30 days, the pitting corrosion inhibitory effect was hardly exhibited. In addition, the anticorrosion of Sumiueoka is 3.4-6.2 mdd, the corrosion rate of copper is 1.5-2.2 mdd, and the corrosion inhibiting effect of copper is weak. In the system that does not promote P, the copper corroded, and the eluted copper ionka S appeared on the surface of Sumioka, and it is considered that the corrosion of Saccharomyces oka was accelerated.
本発明の金属の孔食抑制剤及ひ孔食抑制方法によれば、 開放循環冷却水系において、 リ ン化合物や 塩などの重金属塩を用いることなく、 炭聽岡の孔食の進行を抑制し、 熱交 ^^などの水と接する設備の ^を効果的に延長することができる。  ADVANTAGE OF THE INVENTION According to the metal pitting corrosion inhibitor and the pitting corrosion suppressing method of the present invention, in an open circulation cooling water system, the progress of pitting corrosion in Sumitakeoka is suppressed without using heavy metal salts such as phosphorus compounds and salts. , Heat exchange ^^ and other facilities that come into contact with water can be effectively extended.

Claims

請求の範囲 ' The scope of the claims '
1 . (A)—般式 [ 1 ]で表される ジェンのスルホン化物 1モルに対して、 —默 [ 2 ]で 表されるカルボキシル基を有する不飽和化合物 0. 1〜 2 0モルを共重合したスルホン酸 基を有する共重合体、 (B)マレイン酸 1モルに対して、 炭素数 4〜: L 0のアルケン 0. 8 〜: 1 . 3モルを共重合した疎水基を有する共重合体及び (C)ァゾール化合物を含有するこ とを難とする^ Sの孔食抑制剤。
Figure imgf000015_0001
1. (A) —0.1 mol to 20 mol of a carboxyl group-containing unsaturated compound represented by silence [2] per mol of the sulfonated gen represented by general formula [1] (B) a copolymer having a hydrophobic group obtained by copolymerizing 0.8 to 1.3 moles of an alkene having 4 to 0 carbon atoms with respect to 1 mole of maleic acid. A pitting corrosion inhibitor of ^ S, which makes it difficult to contain the compound and the (C) azole compound.
Figure imgf000015_0001
R R4 R RR 4 R
(ただし、 式中、 R^R6は、 水素原子、 炭素数:!〜 8のアルキル基、 炭素数 6〜2 0の ァリール基、 又は一 S OsXであり、 ここで Xは水素原子、 アルカリ金属原子、 アルカリ 土類 原子、 アンモ-ゥム基もしくはァミノ基であり、 R^R6の少なくとも 1つは一 S O。Xである。 ) (Wherein, R ^ R 6 is a hydrogen atom, an alkyl group having from 8 to 8 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or one SO s X, wherein X is a hydrogen atom, An alkali metal atom, an alkaline earth atom, an ammonium group or an amino group, and at least one of R ^ R 6 is SO.X.)
R 7 R 9 R 7 R 9
\ /  \ /
C = C  C = C
/ 8 \ 1 0  / 8 \ 10
- ^ , ··[ 2]  -^, ··· [2]
(ただし、 式中、 〜1 1()の少なくともーっは一(〇 ) 111〇001\ 1でぁり、 残余 ίお素又 は炭素数:!〜 8のアルキル基であり、 mは 0〜8であり、 Mは水素原子、 アルカリ録、 アルカリ z¾S條原子、 アンモニゥム基又はアミノ基である。 ) (However, in the formula, one is Sukunakutomo' of ~ 1 1 () (〇) 111 Rei_001 \ 1 Deari, residual ί your Motomata the number of carbon atoms:! Is an alkyl group of ~ 8, m is 0 And M is a hydrogen atom, an alkali group, an alkali zsS atom, an ammonium group or an amino group.)
2. (A)スルホン纏を有する共重合体 1重量部に対して、 (B)疎水基を有する共重合体 0. 0 5 - 8重量部及び (C)ァゾール化合物 0. 0 0 5〜 0. 1重量部を含有する請求の範 囲 1曾^の金属の孔食抑制剤。  2. With respect to 1 part by weight of the copolymer having the sulfone group (A), 0.05 to 8 parts by weight of the copolymer having the hydrophobic group (B) and 0.05 to 5 parts by weight of the azole compound (C) Claims containing 1 part by weight of metal pitting corrosion inhibitor.
3. 請求の範囲 1又は 2記載の の孔食抑制剤を、 (A)スルホン赌を有する共重合体、 (B)疎水基を有する共重合体及び (C)ァゾール化合物の合計として、 水系に 1〜: L 0 0 m g_/L添ロすることを糊敷とする^ Sの孔食抑制方法。  3. The pitting corrosion inhibitor according to claim 1 or 2 is added to an aqueous system as a total of (A) a copolymer having a sulfone group, (B) a copolymer having a hydrophobic group, and (C) an azole compound. 1 to: L 0 0 mg_ / L A method of suppressing pitting corrosion of ^ S using glue matting.
PCT/JP2005/011406 2004-06-17 2005-06-15 Pitting corrosion inhibitor for metal and method of inhibition WO2005123981A1 (en)

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GB2529723A (en) * 2014-09-01 2016-03-02 Schlumberger Holdings Corrosion inhibition

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CN105039995B (en) * 2015-07-09 2017-08-29 潍坊友容实业有限公司 A kind of special anti-incrustation corrosion inhibitor of salt-soda soil salt discharge hidden pipe and preparation method thereof

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JP2011214064A (en) * 2010-03-31 2011-10-27 Kurita Water Ind Ltd Pitting-corrosion retarder and method for retarding pitting corrosion
WO2014136012A1 (en) * 2013-03-04 2014-09-12 Schlumberger Technology B.V. Corrosion inhibition
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GB2529723A (en) * 2014-09-01 2016-03-02 Schlumberger Holdings Corrosion inhibition
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