CA2016150A1 - Higher alkylbenzotriazoles as copper and copper alloy corrosion inhibitors - Google Patents

Abstract

TITLE OF THE INVENTION
"HIGHER ALKYLBENZOTRIAZOLES AS COPPER AND COPPER ALLOY
CORROSION INHIBITORS"
ABSTRACT OF THE INVENTION
Higher alkylbenzotriazoles are used to inhibit the corrosion of metallic surfaces in contact with an aqueous system. Systems and compositions containing higher alkylbenzotriazoles are also claimed.

Description

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`' ' TITLE OF THE INVENTION

"HIGHER ALKYLBENZOTRIAZOLES AS NOVEL COPPER AND COPPER
ALLOY CORROSION INHIBITORS"

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Benzotriazole, mercaptobenzothiazole and tolyltriazole are well known copper corrosion inhibitors. For example, see U.S. patent 4,675,158 :
and the references cited therein. Also, see U.S.
patent 4,744,950, which discloses the use of lower alkylbenzotriazoles as corrosion inhibitors and U.S.
patent 4,406,811, which discloses the use of benzotriazole/tolyltriazole blends in water treatment compositions for multimetal corrosion inhibition.
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- 2 - C-14~7 The instant invention relates to the use of higher alkylbenzotriazoles as corrosion inhibitors, particularly copper and copper alloy corrosion inhibitors. These compounds from long-lasting protective films on metallic surfaces, particularly copper and copper alloy surfaces, in contact with aqueous systems.

DESCRIPTION OF THE INVENTION

The instant invention is directed to a method of inhibiting the corrosion of metallic surfaces, particularly copper and copper alloy surfaces, in contact with an aqueous system, comprising adding to the aqueous system being treated an effective amount of a higher alkylbenzotriazole compound having the following structure:

Cn 11(2n + 0 4 3 5 ~ N

wherein n is greater than 6 and less than or equal to 12; and isomers of such compounds. Branched-chain C6-C12 alkyls can also be used, though straight chain cnmpounds are preferred as they are believed to provide more persistent films in the presence of chlorine.
The instant invention is also directed to an ~aqueous system whlch is in cuntact with a metallic surface, particularly a copper or copper alloy surface, and which contains a higher alkylbenzotrlazole.
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Compositions comprising water, particularly cooling water~ and a higher alkylbenzotriazole are also claimed.

The inventors have discovered that higher alkylbenzotriazoles are e~fective corrosion inhibitors. These compounds form durable, lung-lasting films on metallic surfaces, including but not limited to copper and copper alloy surfaces.
Higher alkylbenzotriazoles are especially ef~ective inhibitors of copper and copper alloy oorrosion, and can be used to protect multimetal systems, especially those containing copper or a copper alloy and one or more other metals.
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The instant inventors have also found that the instant alkylbenzotriazoles de-activate soluble copper ions, which prevent the galvanic deposition of copper ;
which concomminantly occurs with the galvanic dissolution of iron or aluminum in the presence of copper ions. This minimizes aluminum and iron corrosion. These compounds also indirectly limit the -above galvanic reaction by preventing the ~ormation o~ ;
soluble copper ions due to the corrosion of copper and copper alloys.
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Isomers of the above described higher alkylbenzotriazoles can also be used. The 5 and 6 isomers are interchangeable by a simple prototropic shift of the l position hydrogen to the 3 position and are believed to be ~unctionally equivalent. The 4 and 7 isomers are believed to function as well as or -better than the 5 or 6 isomers, though they are more difficult and expensive to manufacture. As used herein, the term ~Ihigher alkyIbenzotriazoles'i is intended to mean 5-alkyl benzotriazoles and 4, 6 and 7 -~; : ~;, ' : ~ '' . ' ... . ', ., .. ~ .. . . - . . ; :: , :

_ 4 _ -1487 position isomers thereof, wherein the alkyl chain length is greater than 6 but less than or equal to 12 carbons, branched or straight, preferably straight.

An effective amount of an instant higher alkylbenzotriazole should be used. As used herein, the term 'leffective amount" refers to that amount of a higher alkylbenzotriazole which effectively inhibits corrosion in a given aqueous system.

More particularly, the higher alkylbenzotriazoles, inhibit the corrosion of metallic surfaces, especially copper and copper alloy surfaces, when added to an ;~
aqueous system in contact with such sur~aces at a concentration of at least about 0.1 ppm, preferably about 0.5 to 100 ppm and most preferably about 1-10 ppm. Maximum concentrations are determined by the economic considerations of the particular application, whlle minimum concentrations are determined by operating conditions such as pH, dissolved solids and 20 temperature. , The instant higher alkylbenzotriazoles may be prepared by any known method. For example, the ;
instant alkyl~enzotriazoles may be prepared by ;
25 contacting a 4-alkyl-1, 2-diaminobenzene with an ;
aqueous solution of sodium nitrite in the presence of an acid1 e.g., sulfuric acid, and then separating the resultant oily product from the aqueous solution. The 4-alkyl-1,2-diaminobenzene may be obtained from any ~` ;
number of sources.
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The instant compounds can be used as water treatment additives for industrial cooling water systems, gas scrubber systems or any water system which is in contact with a metallic surface, particularly surfaces containing copper and/or copper alloys. They can be fed alone or as part of a treatment package which includes, but is not limited to, biocides, scale inhibitors, dispexsants, defoamers and other corrosion inhibitors. The .instant higher lo alkylbenzotriazoles can be ~ed intermittantly or continuously.
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Treatment of cooling water which contacts copper or copper alloy surfaces, such as admiralty brass or 90/10 copper-nickel, requires the use of specific copper inhibitors. These inhibitors: ;

1. minimize the corrosion of the copper or copper alloy surfaces, including general corrosion, dealloying and galvan~c corrosion; and 2. minimize problems of galvanic "plating-out" of soluble copper ions onto iron or aluminum. Thus, soluble copper ions can enhance the corrosion of iron and/or aluminum components in contact with aqueous systems. This occurs through the reduction of copper ions by iron or aluminum ;
metal, which is concommitantly oxidized, resulting in the "plating-out" of copper metal onto the iron surface. This chemical reactlon not only destroys the iron or aluminum protective film but creates local galvanic cells which can cause pitting corrosion of iron or aluminum. -~
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Conventional copper inhibitors such as tolyltriazole, ben70triazole, and 2-mercaptobenzothiazole are commonly used as copper inhibitors in aqueous systems. They are generally fed continuously because of the limited durability of their protective films.

Continuous feed of an inhibitor generally makes it uneconomical to apply these conventional inhibitors to once-through systems or systems with high blowdown ~ -rates. Additionally, conventional inhibitors provide only limited protection against chlorine induced corrosion.

While 5-lower alkylbenzotriazoles are known which do not require continuous feeding in order to inhibit copper corrosion (See U.S. Patent 4,744,95û), These compounds provide relatively poor chlorination resistance.
' .: , An object of the instant invention is to provide inhibitors which produce more chlorine resistance protective films.
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This object is achieved through the use of higher alkylbenzotriazoles, to provide protectlve, durable hydrophobic films on metallic sur~aces, especially copper and copper alloy surfaces.

The instant alkylbenzotriazoles allow use of an 30 intermittent feed to cooling water systems. Depending ~ :
on water aggressiveness, the time between ~eedings may range from several days to months. This results in an ~ -:
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average lower inhibitor requirement and provides advantages relative to waste treatment and environmental impact.

The preferred alkylbenzotriazoles are within the range of C6-C10 alkylbenzotriazoles. The most preferred compounds are heptylbenzotriazole and octylbenzotriazole.

EXAMPLES
The following examples demonstrate the effectiveness of the instant compounds as copper and copper alloy corrosion inhibitors. They are not, however, intended to limit the scope of the invention in any way.

In these examples, copper specimens were pretreated by immersing them in aerated water at pH
7.5 and 50C. This water contained a specified concentration of inhibitor, which formed a protective film on the specimens.
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After 24 hours, the speclmens were transferred to inhibitor-free water of a highly corrosive nature to determine film persistency. Corrosion rates were measured using linear polarization to determine passivation.

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The characteristics of the pretreatment water and the aggressive water are given in Tables I and II, :.-respectively.

Corrosion results are given in Table III. The 5 results are reported as "Corrosion Rates After ;p~
Passivation" for the passivation step and as "Corrosion Rates In Inhibitor-Free Agressive Water"~

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-TABLE I ~ .

Composition of Pretreatment Water pH = 7.5 Ion Concentration (mg/L) ~ ,, Ca 260 Mg 115 :,~
Cl 476 Si:2 g ~ .

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Composition of Aggressive Water .:
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pH = 7 . 5 Ion Concentration (mg/L) Ca 750 as Ca+2 `
Mg 130 as Mg+~
Cl 24Q0 ::
so4 3200 :;:.

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Table III shows that heptylbenzotriazole and oxtyloxybenzotriazole provided 99% inhibition, even after 15 days exposure to aggressive water~ and that tolyltriazole, a conventional inhibitor, failed within one day. This is surprising in view of the teachings of U.S. Patent No 4,744,950.

Examples 6-9 - Chlorine Chemical Resistance In these examples, copper specimens were pretreated by immersing them in aeriated water at pH
7.5 and 50C. This water contained a specified ~
concentration o~ inhibitor, which formed a protective ~-film on the specimens.

After 24 hours, the specimens were transferred to ;
inhibitor-~ree water of the same composition as the pretreatment water. Chlorine was added so that a initial free residual of 1 mg/L chlorine was obtained. Corrosion rates were measured using linear 20 polarization over the course of one hour. The probes -were then transferred to fresh inhibitor-free, chlorine-free water and the corrosion rate was monitored to determine the recovery corrosion ra~e.

: ' This chlorination procedure was repeated 8 times i on a daily basis, plus an additional time after the weekend period.
': ' ' The water composition is given in Table IV.
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WATER COMPOSITION USED IN THE CHLORINE

Ion Concentration (mg!L~

Ca 88 Ng 24 ~:
Cl 70 '''' .
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The results are given in Table V. The copper specimens treated with heptylbenzotriazole and octylbenzotriazole were practically immune to the aggressiveness o~ chlorine. In contrast, the -butylbenzotriazole treated specimen showed progressively less corrosion protection in the presence of chlorine, and gave progressively higher recovery corrosion rates after each chlorination.
'"''' In further contrast, tolyltriazole treated specimens gave higher corrosion rates in the presence of chlorine and unacceptably high recovery corrosion rates following chlorination.
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EXAMPLES 10-13 - Chlorine Resistance These examples, which were run in a dynamic test unit, demonstrate the resistance of protective films ;
formed by heptylbenzotriazoles to corrosiveness caused by chlorine on heat-transfer brass tubes and on immersed copper coupons.
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The dynamlc test unit for these examples consisted of an 8L reservoir, a heater-circulator and a coil heater to provide the desired heat flux. The coil heater was designed to fit securely around the 3/8" OD
tubes used in the tests. flow through the tube was monitored by an in-line rotameter having a ~low capacity of 400 ml/min. The power input to the heater ' was controlled by a rheostat, which made it possible ~ ;
to vary temperature differences across the tubes. The ,:
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' " ';' ,, tube inlet and outlet temperatures were monitored by thermocouples attached to a digital readout having an accuracy of O.lOF. The system was entirely enclosed to minimize evaporation. The linear velocity through the heated tubes was 2.2 fps, which gave a NRe f approximately 9350. Heat ~luxes of 8,000-10,000 Btu/hr-ft2 were chosen as being representative of industrial practices.

The corrosion rates o~ the heated tubes were determined by the weight loss method described in "Standard Practice for Preparing, Cleaning and Evaluating Corrosion Test Specimens"; ASTM designation Gl-81. The corrosion rates of immersed specimens were determined by linear-polarization using a Petrolite -Model M1010 Corrosion Data Acquisition System. This method measures the corrosion rate at a particular time, and is thus useful for following the immediate effects of chlorine concentration on corrosion rates.

The ~ollowing procedure was ~ollowed relative to the test specimens:

1. Cleaned specimens were placed in the test unit described above, and a specified amount of inhibitor was added.

The specimens were then allowed to passivate for 24 hours at which time they were placed in inhibitor-free water.

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2. Chlorine was added to give ~n initial concentration of 1 mg/L free chlorine. The corrosion rate o~ each specimen was monitored -for one hour. The chlorine concentration ~ ~ -normally decreased ~rom 1 mg/L to about 0.7 mgJL during this tlme. !:

3. A~ter one hour, each specimen was placed in fresh inhibitor-free, chlorinle-free water.
The decrease in corrosion ratle, i.e. the ;
recovery corrosion rate, was then measured for each specimen. ~`
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4. Steps 2 and 3 were repeated in 24 hour cycles for a total of four cycles, with one ;
additional cycle following a weekend period.

5. After a seven ~ay period, the weight loss of the neated tube was determined.

The composition of the water used in these tests is given in Table VI. ~";

The results are shown in Table VII. The corrosion rates o~ the heat-transfer Adniralty brass tubes show the cumulative corr~sion which occurred during the 7-day test period. As can be seen, heptylbenzotriazole gave over 85 percent corrosion protection while butylbenzotriazoIe gave the sane corrosion protection. This is surprising in view of the teachings of Holander U.5.#4,744,950.
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TABLE VI
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Ion Concentration (mg/L) Ca 260 Mg 115 ' Cl 476 , so4 460 '' si2 9 ~ '' pH :

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TABLE VII

EFFECT OF CHLORINATION ON CORROSION RATES OF HEAT-TRANSFER
ADMIRALTY BRASS TUBES AND IMMERSED COPPER PROBES

Copper-Probes Max. Recovery ~ .
Admiralty Corrosion Rates duringCorrosion Rate Ex. Conc. Brass Tubes Cl Contact during 18 hr. after No. Inhibitor mg!L (by wt. loss~ ~ CP* The ~ast Chlorination Q 12 Removal None 0 3.4 5 1.5 ;
11 Heptyl BT 10 0.5 86 0.01 < 0.01 ~
12 Butyl BT 5 0.5 86 0.03 0.01 : :

13 Tolyltriazole 5 2.2 36 2 1.0 ~.

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- 20 - C-1487 , Also, tolyltriazole, which is a widely used inhibitor, gave only 36 percent corrosion protection.
Also, the immersed copper probes treated with heptylbenzotriazole was not significantly affected by exposure to chlorine over the 1 hour contact time while the copper probes treated with tolyltriazole and the untreated probes experienced dramatically higher corrosion rates in the presence of chlorine. ~ .

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~ C-1487 EXAMPLES 14 - 16 - Film Persistenc~

The experimental procedure of Examples 17-1~ was used~ However 9 no chlorine was added to the system.
The purpose of thîs test was to determ:ine the persistency o~ the protective film forrned by the inhibitor after the inhibitor had been exhausted ~rom the system due to replacement of the original water.

The results are shown in Table VII:[, which shows that heptylbenzotriazole provided durable protection throughout the two (2) week test. This is especially 10 surprising in view of the practically complete ';
depletion of original inhibitor concentration by the fifth day. The test was terminated after two t2) weeks only due to practical limitations of time and expense.
EXAMPLES 17-19 - Dynamic Pilot Cooling Tower Tests , ~ . . .
These examples illustrate the outstanding chlorine resistance and film persistency of heptylbenzotriazole in a dynamic system which simulates the operational variations commonly found in industrial cooling towers. Operational ~actors simulated include blow-down, heat transfer surfaces, dynamic ~low, evaporative-cooling, cycles of concentration, and customary chlorination practices.

The pllot cooling tower system used contained two single tube heat exchangers. Cooling water flowed in ~series through the shell side~ (annular space) o~ the -heat exchangers and hot water was circulated through the tubes in series, counterflow. In addition to the `
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main recirculation circuit through the cooling tower, the system also contained a recycle loop from the outlet of the No. ~ Heat Exchanger to the inlet o~ the No. 1 Heat Exchanger for the purpose of maintaining cooling water linear velocity in the heat exchangers.
The heat exchanger shells were ~abricated of Plexiglass to permit observation of the heat exchanger surfaces during the test run. For these tests, a -~
90/10 copper/nickel tube was placed in the No. 2 Heat Exchanger.
~' Instrumentation for monitoring and control of test variables included a pH and conductivity indicator~
controller, PAIR corrosion rate indicators, a temperature indicator/controller, and rotometers ~or air and water flows.

PAIR probes for continuous monitoring of 90/10 coppertnickel corrosion rates were installed after the outlet of the No. 2 Heat Exchanger. A corrosion test zo coupon of 90/10 copper/nickel was installed in the recycle loop. The PAIR cells and the corrosion test loop were fabricated o~ Plexiglass to permit observation of the Corrater electrodes and the corrosion coupons.
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The cleaning procedures employed to prepare tubes, `~ `
corrosion coupons and PAIR electrodes for use in these ``
tests are described in ASTM standard Gl-81.
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In preparation for these tests, stainless steel tubes were installed in the heat exchangers and the system was filled with makeup water. The system required three days for the recirculating water to concentrate to the target cycles of concentration.
The target water composition was the same for Examples 10-13. After the target cycles were reached, the stainless ~teel tubes were removed and the test specimens installed (tubes, coupons, and PAIR
electrodes). At this time, blowdown commenced and the desired copper inhibitor was added.

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The results are shown in Table IX. The inhibitor was allowed to deplete by gradually replacing the cooling water. Thus, after three (3) days, less than 15 one-eighth of the original inhibitor concentration was `
present, and after five (5) days, practically no inhibitor remained. Table IX shows the corrosion rate Just prior to the addit~on of chlorine to the system and the maximum corrosion rate recorded while chlorine was present. Chlorine was added so that between 0.2 mg/L to 0.5 mg/L free residual of chlorine was present. The chlorine concentration was then allowed to dissipate through blow-down, evaporation, and reaction.
As can be seen in Table IX 9 heptylbenzotriazole effectively passivated the 90/lû copper/niokel ;!~
specimens and dramatically reduced the aggressiveness of chlorine even, surprisingly, when all of the 30 inhibitor had depleted. In contrast, -~
butylbenzotriazole afforded only minimal protection ~ against attack by chlorine, as seen by both the ; deteriorating recovery corrosion rate and the larse corrosion rate experienced during the chlorination.
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This is surprising especially in view of the -.
teachings of Holander, USP 4,744,950.

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TABLE VIII

INHIBITION PERSISTENCY OF HFXYLBENZOTRIAZOLE :
IN THE PILOT COOLING TOWER

Example 14 Example 15 Exa~ple 16 Blank Heptylbenzotriazole Butylbenzotriazole Day(no inhibitor)5 mgLL Initial Charge5 mg/L Initial Charge ~:
0 13 4.5 8 `
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11 1.8 0.03 0.15 12 2.0 0.03 0.20 ~:~
13 1.5 0.03 0.25 :.

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* a pH excursion to pH 5 occurred on the 10th day, the pH was corrected by :
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Claims (7)

1. A method of inhibiting corrosion in an aqueous system which is in contact with a metallic surface, comprising adding to said system an effective amount of a compound selected from the group of compounds having the following formula:

wherein n is greater than 6 and less than equal to 12.

2. The method of Claim 1, wherein about 0.1 to about 10.0 mg/l of said compound is added to said aqueous system.

3. The method of Claim 1, wherein said compound is selected from the group consisting of heptylbenzotriazole and octylbenzotriazole.

4. The method of Claim 2, wherein said compound is selected from the group consisting of heptylbenzotriazole and octylbenzotriazole.

5. The method of Claim 1, wherein said metallic surface is a copper or copper alloy surface.

6. The method of Claim 2, wherein said surface is a copper or copper alloy surface.

7. A composition comprising: a) the water of an aqueous system; and b) compounds selected from the group of compounds having the following formula:

wherein n is greater than 6 and less than or equal to 12.