CN110066358B - Phosphorus-free polymer corrosion inhibitor and preparation method and application thereof - Google Patents
Phosphorus-free polymer corrosion inhibitor and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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- C08F216/1475—Monomers containing sulfur and oxygen
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Abstract
The invention relates to the field of corrosion inhibitors and discloses a phosphorus-free polymer corrosion inhibitor, wherein the phosphorus-free polymer corrosion inhibitor is represented by the following general formula:
wherein R is 1 is-H, -COOH or phenyl; r 2 is-H, -CH 2 COOH or C 1 ‑C 5 Lower alkyl of (a); r 3 is-CO (CH) 2 ) k COOH、‑COCH(OH)COOH、‑COCH(OH)CH 2 COOH、‑COCH 2 CH(OH)COOH、‑COCH(OH)CH(OH)COOH、‑COCH＝CHCOOH、‑CO(o‑C 6 H 4 )COOH、‑CO(p‑C 6 H 4 )COOH、‑COCH 2 C(OH)(COOH)CH 2 COOH、‑COC(OH)(CH 2 COOH) 2 、‑COCH＝C(COOH)CH 2 COOH、‑COCH 2 C(COOH)＝CHCOOH、‑COC(CH 2 COOH) ═ CHCOOH; the polymerization degree x is 1-5000; the polymerization degree y is 1-5000; the polymerization degree z is 1-5000; the polymerization degree m is 1-100; the polymerization degree n is 1-100; the polymerization degree k is 0-8. The invention also discloses a preparation method and application of the phosphorus-free polymer corrosion inhibitor. The phosphorus-free polymer corrosion inhibitor provided by the invention has a good corrosion inhibition effect.
Description
Technical Field
The invention relates to a phosphorus-free polymer corrosion inhibitor and a preparation method and application thereof.
Background
The corrosion and scale inhibitor used in the cooling water treatment in China is mainly based on a phosphorus formula, and although the performance of the corrosion and scale inhibitor can basically meet the use requirement, the phosphorus formula has the following defects: (1) the hidden danger of easy formation of phosphate scale exists in the use process, and the heat exchange effect of the water cooler in long-term operation is influenced; (2) promoting the reproduction of microorganisms in the circulating water system and consuming a large amount of bactericide; (3) the discharge of a large amount of phosphorus easily causes eutrophication of the receiving water body. Therefore, the development and the use of the phosphorus-free corrosion and scale inhibitor have important significance for the treatment of the circulating cooling water.
Most of the common corrosion and scale inhibitors contain polymer components, such as hydrolyzed polymaleic anhydride (HPMA), polyepoxysuccinic acid (PESA), Polyaspartic Acid (PASP), polyacrylic acid (PAA), maleic acid-acrylic acid copolymer (MA-AA), acrylic acid-acrylate copolymer, acrylic acid and hydroxypropyl acrylate copolymer (AA-HPA, T-225), acrylic acid-acrylate-sulfonate copolymer, acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid copolymer (AA-AMPS), acrylic acid and 3-allyloxy-2-hydroxypropanesulfonic acid copolymer (AA-AHPSE), and the like. However, except that HPMA, PESA and PASP have certain corrosion inhibition capability, most of the other corrosion inhibitors cannot inhibit corrosion but promote corrosion, and in order to offset the increased corrosion amount, the consumption of the corrosion inhibitor in the formula needs to be increased, which leads to increase of use cost.
Disclosure of Invention
The invention aims to provide a phosphorus-free polymer corrosion inhibitor, a preparation method and application thereof.
In order to achieve the above objects, a first aspect of the present invention provides a phosphorus-free polymer corrosion inhibitor, wherein the phosphorus-free polymer corrosion inhibitor is represented by the following general formula:
wherein R is 1 is-H, -COOH or phenyl; r 2 is-H, -CH 2 COOH or C 1 -C 5 A lower alkyl group of (a); r is 3 is-CO (CH) 2 ) k COOH、-COCH(OH)COOH、-COCH(OH)CH 2 COOH、-COCH 2 CH(OH)COOH、-COCH(OH)CH(OH)COOH、-COCH＝CHCOOH、-CO(o-C 6 H 4 )COOH、-CO(p-C 6 H 4 )COOH、-COCH 2 C(OH)(COOH)CH 2 COOH、-COC(OH)(CH 2 COOH) 2 、-COCH＝C(COOH)CH 2 COOH、-COCH 2 C(COOH)＝CHCOOH、-COC(CH 2 COOH)＝CHCOOH；
The polymerization degree x is 1-5000; the polymerization degree y is 1-5000; the polymerization degree z is 1-5000; the polymerization degree m is 1-100; the polymerization degree n is 1-100; the polymerization degree k is 0-8.
Preferably, R 1 is-COOH, R 2 is-H, R 3 is-CO (o-C) 6 H 4 ) COOH; or R 1 is-H, R 2 Is C 1 -C 5 Lower alkyl of (2), R 3 is-COCH ═ CHCOOH; or R 1 is-COOH, R 2 is-H, R 3 is-COCH ═ CHCOOH.
Preferably, the degree of polymerization x is from 10 to 200; the polymerization degree y is 10-200; the polymerization degree z is 10-200; the polymerization degree m is 5-55; the polymerization degree n is 5-55; the polymerization degree k is 0-4.
The second aspect of the invention provides a preparation method of a phosphorus-free polymer corrosion inhibitor, wherein the preparation method comprises the following steps: under the condition of free radical polymerization and in the presence of water, unsaturated carboxylic acid, allyloxy polyethylene glycol monoester carboxyl derivative and allyloxy polyethylene glycol sulfonate are contacted with an initiator to react.
The third aspect of the invention provides the application of the phosphorus-free polymer corrosion inhibitor in circulating cooling water.
The phosphorus-free polymer provided by the invention has a good corrosion inhibition effect, and can achieve a good corrosion inhibition effect under a lower corrosion inhibitor concentration on the premise of not influencing the treatment effect, so that the cost is greatly saved. In addition, the preparation process of the phosphorus-free polymer corrosion inhibitor provided by the invention is that three monomers with unsaturated double bonds are subjected to free radical polymerization in the presence of an initiator, the three monomers are respectively unsaturated carboxylic acid, allyloxy polyethylene glycol monoester carboxyl derivatives and allyloxy polyethylene glycol sulfonate, and the terpolymer obtained by polymerization reaction is the phosphorus-free polymer corrosion inhibitor provided by the invention. The whole preparation process does not need separation, is simple and convenient to operate, does not generate three wastes, and is environment-friendly.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, "at least one" means one or a mixture of two or more.
According to the invention, the phosphorus-free polymer corrosion inhibitor is represented by the following general formula:
wherein R is 1 is-H, -COOH or phenyl; r is 2 is-H, -CH 2 COOH or C 1 -C 5 A lower alkyl group of (a); r 3 is-CO (CH) 2 ) k COOH、-COCH(OH)COOH、-COCH(OH)CH 2 COOH、-COCH 2 CH(OH)COOH、-COCH(OH)CH(OH)COOH、-COCH＝CHCOOH、-CO(o-C 6 H 4 )COOH、-CO(p-C 6 H 4 )COOH、-COCH 2 C(OH)(COOH)CH 2 COOH、-COC(OH)(CH 2 COOH) 2 、-COCH＝C(COOH)CH 2 COOH、-COCH 2 C(COOH)＝CHCOOH、-COC(CH 2 COOH)＝CHCOOH。
In a particular embodiment of the invention, R 1 is-H, R 2 is-H, R 3 is-CO (CH) 2 ) k COOH (k ═ 0); or R 1 is-H, R 2 is-H, R 3 is-COCH ═ CHCOOH; or R 1 is-COOH, R 2 is-H, R 3 is-CO (o-C) 6 H 4 ) COOH; or R 1 is-COOH, R 2 is-H, R 3 is-COCH (OH) CH 2 COOH or-COCH 2 CH (OH) COOH; or R 1 is-H, R 2 is-CH 2 COOH，R 3 is-COCH ═ C (COOH) CH 2 COOH or-COCH 2 C (COOH) CHCOOH or-COC (CH) 2 COOH) ═ CHCOOH; or R 1 is-H, R 2 Is C 1 -C 5 Lower alkyl (CH) of 3 )，R 3 is-COCH ═ CHCOOH; or R 1 is-COOH, R 2 is-H, R 3 is-COCH ═ CHCOOH. Preferably, R is chosen to further increase the corrosion inhibiting effect of the polymer 1 is-COOH, R 2 is-H, R 3 is-CO (o-C) 6 H 4 ) COOH; or R 1 is-H, R 2 Is C 1 -C 5 Lower alkyl of (A), R 3 is-COCH ═ CHCOOH; or R 1 is-COOH, R 2 is-H, R 3 is-COCH ═ CHCOOH. Wherein, the C 1 -C 5 The lower alkyl group of (b) is preferably at least one of a methyl group, an ethyl group and a propyl group.
Wherein the polymerization degree x is 1-5000, preferably 10-200; the degree of polymerization y is 1 to 5000, preferably 10 to 200; the degree of polymerization z is from 1 to 5000, preferably from 10 to 200; the polymerization degree m is 1-100, preferably 5-55; the polymerization degree n is 1-100, preferably 5-55; the degree of polymerization k is from 0 to 8, preferably from 0 to 4.
According to the invention, the preparation method of the phosphorus-free polymer corrosion inhibitor comprises the following steps: under the condition of free radical polymerization and in the presence of water, unsaturated carboxylic acid, allyloxy polyethylene glycol monoester carboxyl derivative and allyloxy polyethylene glycol sulfonate are contacted with an initiator to react.
According to the present invention, preferably, the method for contacting an unsaturated carboxylic acid, an allyloxypolyethylene glycol monoester carboxyl derivative, an allyloxypolyethylene glycol sulfonate, and an initiator in the presence of water comprises: mixing unsaturated carboxylic acid, allyloxy polyethylene glycol monoester carboxyl derivative, allyloxy polyethylene glycol sulfonate and water, heating to 55-80 ℃, and then dropwise adding an initiator.
According to the present invention, the radical polymerization conditions generally include a reaction temperature and a reaction time, wherein the reaction temperature is 75 to 110 ℃ and the reaction time is 1 to 10 hours from the viewpoint of promoting the esterification reaction in equilibrium and improving the reaction efficiency.
According to the invention, the mass ratio of the unsaturated carboxylic acid, the allyloxy polyethylene glycol monoester carboxyl derivative and the allyloxy polyethylene glycol sulfonate can be 1 (0.05-19) to (0.05-19), more preferably 1 (0.1-10) to (0.1-10), and more preferably 1 (0.5-5) to (0.5-5). The water is used as a solvent as long as the reactant is sufficiently dissolved, and preferably, the mass of the water is 0.5 to 10 times of the total mass of the unsaturated carboxylic acid, the allyloxypolyethylene glycol monoester carboxyl derivative and the allyloxypolyethylene glycol sulfonate.
According to the present invention, the selection range of the unsaturated carboxylic acid is wide, and in order to further improve the corrosion inhibition effect, according to the present invention, the unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and cinnamic acid, and more preferably, the unsaturated carboxylic acid is one or more of maleic acid, maleic anhydride and methacrylic acid.
According to the invention, the allyloxy polyethylene glycol monoester carboxyl derivative is prepared by esterification reaction of allyloxy polyethylene glycol and dicarboxylic acid and/or dicarboxylic acid anhydride or tricarboxylic acid. Wherein, the esterification reaction conditions generally include a reaction temperature and a reaction time, wherein, from the viewpoint of promoting the esterification reaction and improving the reaction efficiency, the reaction temperature may be 70 to 130 ℃ and the reaction time may be 1 to 6 hours. Wherein, the molar ratio of the allyloxypolyethylene glycol to the dicarboxylic acid and/or dicarboxylic acid anhydride or tricarboxylic acid is 1:0.9-1.1 when the allyloxypolyethylene glycol is reacted with the dicarboxylic acid and/or dicarboxylic acid anhydride or tricarboxylic acid anhydride (the molar ratio refers to the molar ratio of the allyloxypolyethylene glycol to the total amount of the dicarboxylic acid and dicarboxylic acid anhydride when the allyloxypolyethylene glycol is reacted with the dicarboxylic acid or dicarboxylic acid anhydride, and the molar ratio refers to the molar ratio of the allyloxypolyethylene glycol to the dicarboxylic acid or dicarboxylic acid anhydride when the allyloxypolyethylene glycol is reacted with the dicarboxylic acid or dicarboxylic acid anhydride).
According to the invention, the dicarboxylic acid, dicarboxylic acid anhydride and tricarboxylic acid can be selected in a wide range, and preferably, the dicarboxylic acid is one or more selected from oxalic acid, malonic acid, hydroxymalonic acid, succinic acid, malic acid, tartaric acid, maleic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid and terephthalic acid; the dicarboxylic acid anhydride is selected from one or more of succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride and phthalic anhydride; the tricarboxylic acid is citric acid and/or aconitic acid.
According to the invention, the allyloxy polyethylene glycol sulfonate is prepared by sulfonation of allyloxy polyethylene glycol and sulfamic acid. Wherein the molar ratio of the allyloxy polyethylene glycol to the sulfamic acid is 1: 0.9-1.1. The sulfonation reaction conditions generally include a reaction temperature and a reaction time, wherein the sulfonation reaction conditions include, from the viewpoint of equilibrium promotion of the esterification reaction and improvement of the reaction efficiency: the reaction temperature is 100-120 ℃, and the reaction time is 2-8 h.
According to the invention, wherein the initiator is selected from a wide range, in order to further improve the corrosion inhibition effect, the initiator is selected from one or more of ammonium persulfate, sodium persulfate and potassium persulfate. The initiator is generally used in the form of an aqueous initiator solution, the concentration and amount of which are conventional in the art. For example, the mass fraction of the aqueous initiator solution may be 5 to 50%, and preferably, the mass of the initiator in the aqueous initiator solution is 0.01 to 0.2 times the total mass of the unsaturated carboxylic acid, the allyloxypolyethylene glycol monoester carboxyl derivative and the allyloxypolyethylene glycol sulfonate, and the dropping time of the initiator is 0.25 to 5 hours.
The invention also provides application of the phosphorus-free polymer corrosion inhibitor in circulating cooling water.
According to the application of the invention, the phosphorus-free polymeric corrosion inhibitor is preferably added in an amount of 2-20mg, preferably 5-12mg, per liter of circulating cooling water.
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
The various starting materials used in the examples were all obtained commercially.
The corrosion inhibition performance evaluation experiments in the embodiment and the comparative example are carried out according to a 404 method in cooling water analysis and experiment methods of general companies of petrochemical industry in China. The test water used in the examples and comparative examples of the present invention was prepared from Beijing tap water, and the quality of the Beijing tap water is shown in Table 1. The preparation water comprises: 0.368g of ZnCl 2 Dissolving in 44kg of Beijing tap water, namely Zn 2+ The concentration was 4 mg/L. Wherein, the effective concentrations of the phosphorus-free polymer corrosion inhibitor prepared by the added embodiment are respectively 2mg/L, 6mg/L and 10mg/L relative to each liter of preparation water; the effective concentrations of the added phosphorus-free polymer of the comparative example were 2mg/L, 6mg/L, and 10mg/L, respectively; comparative example 3 did not add any phosphorus-free polymer. The results are shown in Table 2.
TABLE 1 quality of Beijing-derived tap water
In the present invention, the average corrosion rate is defined as the average thickness of the coupon corrosion per unit time, and the calculation formula of the average corrosion rate is:
in the formula: v-corrosion rate, mm/a;
c-calculation constant, 8.76X 10 7 ；
Δ W-Corrosion weight loss of test piece, g;
s-surface area of test piece, cm 2 ；
t is corrosion test time, h;
rho-density of test piece material, kg/dm 3 。
Example 1
Allyloxypolyethylene glycol (27.8g, 0.1mol) having a molecular weight of 278 (i.e., m ═ 5) and oxalic acid (9.0g, 0.1mol) were added to a reaction vessel to conduct an esterification reaction at a reaction temperature of 70 ℃ for 2 hours, thereby producing allyloxypolyethylene glycol oxalic acid monoester derivatives.
Allyloxypolyethylene glycol (27.8g, 0.1mol) having a molecular weight of 278 (i.e., n ═ 5) and sulfamic acid (9.7g, 0.1mol) were added to the reaction vessel and reacted at 100 ℃ for 2h to produce allyloxypolyethylene glycol sulfonate.
Adding three polymerization monomers, namely acrylic acid (1.0g), allyloxy polyethylene glycol oxalate monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) into a reaction kettle, uniformly stirring, dropwise adding 1g of 10 mass percent ammonium persulfate solution at 60 ℃ for 15min, heating to 80 ℃ after dropwise adding, reacting for 2h, and cooling to room temperature to obtain brown solution, namely the phosphorus-free polymer corrosion inhibitor.
Example 2
Allyloxypolyethylene glycol (27.8g, 0.1mol) with a molecular weight of 278 (i.e. m ═ 5) and maleic anhydride (9.8g, 0.1mol) were added to a reaction vessel to carry out an esterification reaction at a reaction temperature of 80 ℃ for 2 hours, yielding an allyloxypolyethylene glycol maleic acid monoester derivative.
Allyloxypolyethylene glycol (27.8g, 0.1mol) having a molecular weight of 278 (i.e., n ═ 5) and sulfamic acid (9.7g, 0.1mol) were added to the reaction vessel and reacted at 110 ℃ for 3h to produce allyloxypolyethylene glycol sulfonate.
Adding three polymerization monomers, namely acrylic acid (1.0g), allyloxy polyethylene glycol maleic acid monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) into a reaction kettle, uniformly stirring, dropwise adding 2g of 10 mass percent ammonium persulfate solution at 60 ℃, dropwise adding for 30min, heating to 80 ℃ after dropwise adding, reacting for 2h, and cooling to room temperature to obtain brown solution, namely the phosphorus-free polymer corrosion inhibitor.
Example 3
Allyloxypolyethylene glycol (49.8g, 0.1mol) having a molecular weight of 498 (i.e., m is 10) and phthalic acid (16.6g, 0.1mol) were added to a reaction vessel to carry out an esterification reaction at 80 ℃ for 3 hours, thereby producing allyloxypolyethylene glycol phthalic acid monoester derivative.
Allyloxypolyethylene glycol (49.8g, 0.1mol) of molecular weight 498 (i.e., n-10) was added to the reaction kettle with sulfamic acid (9.7g, 0.1mol) and reacted at 110 ℃ for 3h to produce allyloxypolyethylene glycol sulfonate.
Adding three polymerization monomers, namely maleic anhydride (1.0g), allyloxy polyethylene glycol phthalate monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) into a reaction kettle, uniformly stirring, dropwise adding 2g of sodium persulfate solution with the mass fraction of 20% at the temperature of 60 ℃ for 1h, heating to 80 ℃ after dropwise adding, reacting for 3h, and cooling to room temperature to obtain a phosphorus-free brown solution, namely the polymer corrosion inhibitor.
Example 4
Allyloxy polyethylene glycol (11.6g, 0.01mol) with a molecular weight of 1160 (i.e. m ═ 25) and malic acid (1.34g, 0.01mol) were added to a reaction kettle to carry out an esterification reaction at a reaction temperature of 80 ℃ for 2 hours, yielding an allyloxy polyethylene glycol malic acid monoester derivative.
Allyloxypolyethylene glycol (11.6g, 0.01mol) having a molecular weight of 1160 (i.e., n ═ 25) and sulfamic acid (0.97g, 0.01mol) were added to a reaction vessel and reacted at 120 ℃ for 4h to produce allyloxypolyethylene glycol sulfonate.
Adding three polymerization monomers, namely maleic acid (1.0g), allyloxy polyethylene glycol malic acid monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) into a reaction kettle, uniformly stirring, dropwise adding 3g of 10 mass percent sodium persulfate solution at 65 ℃ for 1h, heating to 90 ℃ after dropwise adding, reacting for 3h, and cooling to room temperature to obtain brown solution, namely the phosphorus-free polymer corrosion inhibitor.
Example 5
Allyloxy polyethylene glycol (24.8g, 0.01mol) with a molecular weight of 2480 (i.e. m is 55) and aconitic acid (1.74g, 0.01mol) are added into a reaction kettle for esterification reaction at 120 ℃ for 4h to generate allyloxy polyethylene glycol aconitic acid monoester derivative.
Allyloxypolyethylene glycol (24.8g, 0.01mol) having a molecular weight of 2480 (i.e., n ═ 55) and sulfamic acid (0.97g, 0.01mol) were added to a reaction vessel and reacted at 120 ℃ for 4h to produce allyloxypolyethylene glycol sulfonate.
Adding three polymerization monomers, namely itaconic acid (1.0g), allyloxy polyethylene glycol aconitic acid monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) into a reaction kettle, uniformly stirring, dropwise adding 3g of potassium persulfate solution with the mass fraction of 20% at 65 ℃, dropwise adding for 1h, heating to 90 ℃ after dropwise adding, reacting for 3h, and cooling to room temperature to obtain brown solution, namely the phosphorus-free polymer corrosion inhibitor.
Example 6
Allyloxypolyethylene glycol (49.8g, 0.1mol) having a molecular weight of 498 (i.e., m ═ 10) and maleic anhydride (9.8g, 0.1mol) were added to a reaction vessel to conduct an esterification reaction at 80 ℃ for 3 hours, thereby producing an allyloxypolyethylene glycol maleic acid monoester derivative.
Allyloxypolyethylene glycol (24.8g, 0.01mol) having a molecular weight of 2480 (i.e., n ═ 55) and sulfamic acid (0.97g, 0.01mol) were added to a reaction vessel and reacted at 120 ℃ for 4h to produce allyloxypolyethylene glycol sulfonate.
Adding three polymerization monomers, namely methacrylic acid (1.0g), allyloxy polyethylene glycol maleic acid monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) into a reaction kettle, uniformly stirring, dropwise adding 2g of 20 mass percent ammonium persulfate solution at 65 ℃ for 1h, heating to 90 ℃ after dropwise adding, reacting for 4h, and cooling to room temperature to obtain a phosphorus-free brown solution, namely the polymer corrosion inhibitor.
Example 7
Allyloxypolyethylene glycol (49.8g, 0.1mol) having a molecular weight of 498 (i.e., m ═ 10) and maleic anhydride (9.8g, 0.1mol) were added to a reaction vessel to conduct an esterification reaction at 80 ℃ for 3 hours, thereby producing an allyloxypolyethylene glycol maleic acid monoester derivative.
Allyloxypolyethylene glycol (24.8g, 0.01mol) having a molecular weight of 2480 (i.e., n ═ 55) and sulfamic acid (0.97g, 0.01mol) were added to a reaction vessel and reacted at 120 ℃ for 4 hours to produce allyloxypolyethylene glycol sulfonate.
Adding three polymerization monomers, namely maleic anhydride (4.0g), allyloxy polyethylene glycol maleic acid monoester derivative (2.5g), allyloxy polyethylene glycol sulfonate (0.5g) and distilled water (20.0g) into a reaction kettle, uniformly stirring, dropwise adding 2g of 20 mass percent ammonium persulfate solution at 65 ℃, dropwise adding for 1h, heating to 90 ℃ after dropwise adding, reacting for 3h, and cooling to room temperature to obtain a phosphorus-free brown solution, namely the polymer corrosion inhibitor.
Comparative example 1
Commercially available acrylic acid-2-acrylamido-2-methylpropanesulfonic acid polymer (AA-AMPS).
Comparative example 2
Acrylic acid-allyloxy polyoxyethylene sulfonate copolymer AA-APES is prepared according to published documents (synthesis and performance research of AA/APES scale inhibitors, Wuyuanhong, etc., chemical man-hour journal 2010, 24(5), 12-14).
Comparative example 3
Blank control run, without any polymer added.
TABLE 2 Corrosion inhibition Performance evaluation test results (corrosion rate: mm/a)
From the results of table 2, it can be seen that the addition of the phosphorus-free polymer corrosion inhibitor of the present invention, i.e., examples 1 to 7, significantly decreases the corrosion rate with increasing concentration compared to comparative example 3 (blank control test), and the corrosion rates of examples 1 to 7 are all below 0.0650mm/a when the concentration of the agent is 10mg/L, wherein the corrosion rate of example 7 is only 0.0274 mm/a. Therefore, the phosphorus-free polymer corrosion inhibitor provided by the invention has good corrosion inhibition performance. And the corrosion is accelerated by adding the comparative example 1, the corrosion rate is higher when the concentration is higher, and the corrosion rate of the comparative example 2 is reduced, which shows that the corrosion inhibitor has a certain corrosion inhibition effect, but the corrosion inhibition effect is not ideal.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. A phosphorus-free polymer corrosion inhibitor is characterized by being represented by the following general formula:
wherein R is 1 is-H, -COOH or phenyl; r 2 is-H, -CH 2 COOH or C 1 -C 5 Lower alkyl of (a); r 3 is-COCH = CHCOOH, -CO (C:)o-C 6 H 4 )COOH、-CO(p-C 6 H 4 )COOH、-COCH=C(COOH)CH 2 COOH、-COCH 2 C(COOH)=CHCOOH、-COC(CH 2 COOH)=CHCOOH；
Degree of polymerizationxIs 1 to 200; degree of polymerizationyIs 1 to 200; degree of polymerizationzIs 1 to 200; degree of polymerizationmIs 1 to 55; degree of polymerizationnIs 1-55.
2. The phosphorus-free polymeric corrosion inhibitor of claim 1, wherein R is 1 is-COOH, R 2 is-H, R 3 is-CO (o-C 6 H 4 ) COOH; or R 1 is-H, R 2 Is C 1 -C 5 Lower alkyl of (A), R 3 is-COCH = CHCOOH; or R 1 is-COOH, R 2 is-H, R 3 is-COCH = CHCOOH.
3. The phosphorus-free polymeric corrosion inhibitor of claim 1, wherein the degree of polymerizationxIs 10 to 200; degree of polymerizationyIs 10 to 200; degree of polymerizationzIs 10 to 200; degree of polymerizationmIs 5 to 55; degree of polymerizationnIs 5-55.
4. A method for preparing the phosphorus-free polymer corrosion inhibitor of claim 1, wherein the method comprises:
under the condition of free radical polymerization and in the presence of water, unsaturated carboxylic acid, allyloxy polyethylene glycol monoester carboxyl derivative and allyloxy polyethylene glycol sulfonate are contacted with an initiator to react;
wherein the unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and cinnamic acid;
the allyloxy polyethylene glycol monoester carboxyl derivative is prepared by esterification reaction of allyloxy polyethylene glycol and dicarboxylic acid and/or dicarboxylic acid anhydride or tricarboxylic acid;
the dicarboxylic acid is one or more selected from maleic acid, fumaric acid, phthalic acid and terephthalic acid; the dicarboxylic acid anhydride is selected from one or more of succinic anhydride, maleic anhydride and phthalic anhydride; the tricarboxylic acid is aconitic acid.
5. The production method according to claim 4, wherein the method of contacting the unsaturated carboxylic acid, allyloxypolyethylene glycol monoester carboxyl derivative, allyloxypolyethylene glycol sulfonate with the initiator in the presence of water comprises: mixing unsaturated carboxylic acid, allyloxy polyethylene glycol monoester carboxyl derivative, allyloxy polyethylene glycol sulfonate and water, heating to 55-80 ℃, and then dropwise adding an initiator.
6. The production method according to claim 4 or 5, wherein the radical polymerization conditions include: the reaction temperature is 75-110 ℃, and the reaction time is 1-10 h.
7. The production method according to claim 4 or 5, wherein the mass ratio of the unsaturated carboxylic acid, the allyloxypolyethylene glycol monoester carboxyl derivative, the allyloxypolyethylene glycol sulfonate is 1 (0.05-19) to (0.05-19); the mass of the water is 0.5 to 10 times of the total mass of the unsaturated carboxylic acid, the allyloxy polyethylene glycol monoester carboxyl derivative and the allyloxy polyethylene glycol sulfonate.
8. The process according to claim 7, wherein the mass ratio of the unsaturated carboxylic acid, the allyloxypolyethylene glycol monoester carboxyl derivative and the allyloxypolyethylene glycol sulfonate is 1 (0.1-10) to (0.1-10).
9. The method according to claim 8, wherein the mass ratio of the unsaturated carboxylic acid, the allyloxypolyethylene glycol monoester carboxyl derivative and the allyloxypolyethylene glycol sulfonate is 1 (0.5-5) to (0.5-5).
10. The production process according to claim 4 or 5, wherein the allyloxypolyethylene glycol is esterified with a dicarboxylic acid and/or a dicarboxylic acid anhydride, or a tricarboxylic acid in a molar ratio of 1:0.9 to 1.1; the esterification reaction conditions include: the reaction temperature is 70-130 ℃, and the reaction time is 1-6 h.
11. The production method according to claim 4 or 5, wherein the allyloxy polyethylene glycol sulfonate is produced by sulfonation of allyloxy polyethylene glycol with sulfamic acid, wherein the molar ratio of allyloxy polyethylene glycol to sulfamic acid is 1: 0.9-1.1; the conditions of the sulfonation reaction include: the reaction temperature is 100-120 ℃, and the reaction time is 2-8 h.
12. The production process according to claim 4 or 5, wherein the initiator is selected from one or more of ammonium persulfate, sodium persulfate and potassium persulfate, the initiator is used in the form of an aqueous initiator solution, the mass fraction of the aqueous initiator solution is 5 to 50%, the mass of the initiator in the aqueous initiator solution is 0.01 to 0.2 times of the total mass of the unsaturated carboxylic acid, the allyloxypolyethylene glycol monoester carboxyl derivative and the allyloxypolyethylene glycol sulfonate, and the dropping time of the initiator is 0.25 to 5 hours.
13. Use of the phosphorus-free polymeric corrosion inhibitor according to any one of claims 1 to 3 or obtained by the preparation method according to any one of claims 4 to 12 in circulating cooling water.
14. Use according to claim 13, wherein the phosphorus-free polymeric corrosion inhibitor is added in an amount of 2-20mg per litre of circulating cooling water.
15. Use according to claim 14, wherein the phosphorus-free polymeric corrosion inhibitor is added in an amount of 5-12mg per litre of circulating cooling water.
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| US9221700B2 (en) * | 2010-12-22 | 2015-12-29 | Ecolab Usa Inc. | Method for inhibiting the formation and deposition of silica scale in aqueous systems |
| CN102219311B (en) * | 2011-03-23 | 2012-11-14 | 山东大学 | Novel multi-carboxyl and phosphorus-free polycarboxylic acid scale inhibitor and preparation method thereof |
| CN102910745B (en) * | 2012-08-01 | 2014-01-01 | 东南大学 | Fluorescent tracing green environmental-friendly polyglycol type water treatment agent and preparation method thereof |
| CN105366823B (en) * | 2014-08-29 | 2018-05-18 | 中国石油化工股份有限公司 | Phosphate-free corrosion inhibition antisludging agent composition and phosphate-free corrosion inhibition antisludging agent and its application and application of the copolymer in inhibition |
| CN105036367A (en) * | 2015-09-08 | 2015-11-11 | 山东天庆科技发展有限公司 | Phosphorus-free corrosion and scale inhibitor with sterilizing effect and preparation method and application thereof |
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| EP0184894B2 (en) * | 1984-11-09 | 1993-03-31 | Calgon Corporation | Carboxylic-sulfonic-polyalkylene oxide polymers and their use as scale and corrosion inhibitors |
| CN1738844A (en) * | 2003-01-13 | 2006-02-22 | 巴斯福股份公司 | Partially esterified copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, vinylaromatic compounds and other monoethylenically unsaturated monomers containing heteroatoms |
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