CN110066358A - A kind of without phosphorus Polymer corrosion inhibitor and its preparation method and application - Google Patents

A kind of without phosphorus Polymer corrosion inhibitor and its preparation method and application Download PDF

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Publication number
CN110066358A
CN110066358A CN201810064246.3A CN201810064246A CN110066358A CN 110066358 A CN110066358 A CN 110066358A CN 201810064246 A CN201810064246 A CN 201810064246A CN 110066358 A CN110066358 A CN 110066358A
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acid
cooh
polyethylene glycol
polymerization
coch
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CN110066358B (en
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孙飞
余正齐
傅晓萍
王金华
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1466—Monomers containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • C08F216/1425—Monomers containing side chains of polyether groups
    • C08F216/1433—Monomers containing side chains of polyethylene oxide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1466—Monomers containing sulfur
    • C08F216/1475—Monomers containing sulfur and oxygen

Abstract

The present invention relates to corrosion inhibiter fields, disclose a kind of without phosphorus Polymer corrosion inhibitor, wherein the without phosphorus Polymer corrosion inhibitor is indicated by general formula shown below:Wherein, R1For-H ,-COOH or phenyl；R2For-H ,-CH2COOH or C1‑C5Low-carbon alkyl；R3For-CO (CH2)kCOOH、‑COCH(OH)COOH、‑COCH(OH)CH2COOH、‑COCH2CH (OH) COOH ,-COCH (OH) CH (OH) COOH ,-COCH=CHCOOH ,-CO (o-C6H4)COOH、‑CO(p‑C6H4)COOH、‑COCH2C(OH)(COOH)CH2COOH、‑COC(OH)(CH2COOH)2,-COCH=C (COOH) CH2COOH、‑COCH2C (COOH)=CHCOOH ,-COC (CH2COOH)=CHCOOH；Degree of polymerization x is 1-5000；Degree of polymerization y is 1-5000；Degree of polymerization z is 1-5000；Degree of polymerization m is 1-100；Polymerization degree n is 1-100；Degree of polymerization k is 0-8.The invention also discloses the preparation method and applications of the without phosphorus Polymer corrosion inhibitor.Without phosphorus Polymer corrosion inhibitor provided by the invention has good corrosion mitigating effect.

Description

A kind of without phosphorus Polymer corrosion inhibitor and its preparation method and application
Technical field
The present invention relates to a kind of without phosphorus Polymer corrosion inhibitors and its preparation method and application.
Background technique
Corrosion inhibiting and descaling agent used in China's cold water process is substantially based on phosphorus line formulation, although basic from performance Requirement, but phosphorus line formulation Shortcomings can be reached: (1) there is the hidden danger for easily forming phosphoric acid salt crust in use, Influence heat transfer effect when water cooler longtime running；(2) breeding for promoting microorganism in circulation, consumes bulk sterilization Agent；(3) discharge of a large amount of phosphorus easily leads to the eutrophication of receiving water body.Therefore, exploitation, using phosphate-free corrosion inhibition antisludging agent to circulation Cold water process is of great significance.
Mostly contain polymers compositions in common corrosion inhibiting and descaling agent, such as hydrolysis of polymaleic anhydride (HPMA), polycyclic oxygen amber Amber acid (PESA), poly-aspartate (PASP), polyacrylic acid (PAA), maleic acid-acrylic acid copolymer (MA-AA), acrylic acid- Acrylic acid esters co-polymer, acrylic acid and hydroxypropyl acrylate copolymer (AA-HPA, T-225), acrylic acid-acrylic ester-sulphur Hydrochlorate copolymer, acrylic acid and 2- acrylamide-2-methyl propane sulfonic copolymer (AA-AMPS), acrylic acid and 3- allyloxy- 2- hydroxy-propanesulfonic acid copolymer (AA-AHPSE) etc..But except HPMA, PESA, PASP have certain corrosion inhibiting ability in addition to, it is other mostly It is not only unable to inhibition, promotes corrosion, instead in order to offset these increased etching extents, it is necessary to inhibiter consumption in formula is increased, Use cost is caused to increase.
Summary of the invention
The purpose of the present invention is to provide a kind of without phosphorus Polymer corrosion inhibitor and preparation method thereof and its applications.
To achieve the goals above, the first aspect of the present invention provides a kind of without phosphorus Polymer corrosion inhibitor, wherein the nothing Phosphorus Polymer corrosion inhibitor is indicated by general formula shown below:
Wherein, R1For-H ,-COOH or phenyl；R2For-H ,-CH2COOH or C1-C5Low-carbon alkyl；R3For-CO (CH2)kCOOH、-COCH(OH)COOH、-COCH(OH)CH2COOH、-COCH2CH(OH)COOH、-COCH(OH)CH(OH)COOH、- COCH=CHCOOH ,-CO (o-C6H4)COOH、-CO(p-C6H4)COOH、-COCH2C(OH)(COOH)CH2COOH、-COC(OH) (CH2COOH)2,-COCH=C (COOH) CH2COOH、-COCH2C (COOH)=CHCOOH ,-COC (CH2COOH)=CHCOOH；
Degree of polymerization x is 1-5000；Degree of polymerization y is 1-5000；Degree of polymerization z is 1-5000；Degree of polymerization m is 1-100；The degree of polymerization N is 1-100；Degree of polymerization k is 0-8.
Preferably, R1For-COOH, R2For-H, R3For-CO (o-C6H4)COOH；Or R1For-H, R2For C1-C5Lower alkanes Base, R3For-COCH=CHCOOH；Or R1For-COOH, R2For-H, R3For-COCH=CHCOOH.
Preferably, degree of polymerization x is 10-200；Degree of polymerization y is 10-200；Degree of polymerization z is 10-200；Degree of polymerization m is 5-55； Polymerization degree n is 5-55；Degree of polymerization k is 0-4.
Second aspect of the present invention provides a kind of preparation method of without phosphorus Polymer corrosion inhibitor, wherein the preparation method packet It includes: under the conditions of free radical polymerization and in presence of water, unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters carboxyl being spread out Biology, allyloxy polyethylene glycol sulfonate are contacted with initiator and are reacted.
Third aspect present invention provides application of the without phosphorus Polymer corrosion inhibitor in recirculated cooling water.
Without phosphorus polymer provided by the invention has good corrosion inhibition, moreover, in the premise for not influencing treatment effect Under, preferable corrosion mitigating effect can be reached under lower density of corrosion inhibitor, is saved greatly cost.Furthermore the present invention The preparation process of the without phosphorus Polymer corrosion inhibitor provided is to carry out the monomer of three kinds of unsaturated double-bonds in the presence of initiator certainly It is polymerize by base, these three monomers are respectively that unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters carboxy derivatives, allyloxy are poly- Ethylene glycol sulfonate, the terpolymer that polymerization reaction obtains are without phosphorus Polymer corrosion inhibitor provided by the invention.Entire system Standby process is easy to operate without separating, and does not generate the three wastes, environmental-friendly.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, "at least one" refers to one or more kinds of mixtures.
According to the present invention, the without phosphorus Polymer corrosion inhibitor is indicated by general formula shown below:
Wherein, R1For-H ,-COOH or phenyl；R2For-H ,-CH2COOH or C1-C5Low-carbon alkyl；R3For-CO (CH2)kCOOH、-COCH(OH)COOH、-COCH(OH)CH2COOH、-COCH2CH(OH)COOH、-COCH(OH)CH(OH)COOH、- COCH=CHCOOH ,-CO (o-C6H4)COOH、-CO(p-C6H4)COOH、-COCH2C(OH)(COOH)CH2COOH、-COC(OH) (CH2COOH)2,-COCH=C (COOH) CH2COOH、-COCH2C (COOH)=CHCOOH ,-COC (CH2COOH)=CHCOOH.
In a specific embodiment of the invention, R1For-H, R2For-H, R3For-CO (CH2)kCOOH (k=0)；Or R1 For-H, R2For-H, R3For-COCH=CHCOOH；Or R1For-COOH, R2For-H, R3For-CO (o-C6H4)COOH；Or R1For- COOH, R2For-H, R3For-COCH (OH) CH2COOH or-COCH2CH(OH)COOH；Or R1For-H, R2For-CH2COOH, R3For- COCH=C (COOH) CH2COOH or-COCH2C (COOH)=CHCOOH or-COC (CH2COOH)=CHCOOH；Or R1For-H, R2For C1-C5Low-carbon alkyl (CH3), R3For-COCH=CHCOOH；Or R1For-COOH, R2For-H, R3For-COCH= CHCOOH.Under preferable case, in order to further increase the corrosion mitigating effect of the polymer, R1For-COOH, R2For-H, R3For-CO (o-C6H4)COOH；Or R1For-H, R2For C1-C5Low-carbon alkyl, R3For-COCH=CHCOOH；Or R1For-COOH, R2 For-H, R3For-COCH=CHCOOH.Wherein, the C1-C5Low-carbon alkyl be preferably in methyl, ethyl and propyl at least one Kind.
Wherein, degree of polymerization x is 1-5000, preferably 10-200；Degree of polymerization y is 1-5000, preferably 10-200；The degree of polymerization Z is 1-5000, preferably 10-200；Degree of polymerization m is 1-100, preferably 5-55；Polymerization degree n is 1-100, preferably 5-55；It is poly- Right k is 0-8, preferably 0-4.
According to the present invention, the preparation method of the without phosphorus Polymer corrosion inhibitor include: under the conditions of free radical polymerization and In presence of water, by unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters carboxy derivatives, allyloxy polyethylene glycol sulfonic acid Salt is contacted with initiator to be reacted.
In the case of, according to the invention it is preferred to, in presence of water, by unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters The method that carboxy derivatives, allyloxy polyethylene glycol sulfonate are contacted with initiator includes: by unsaturated carboxylic acid, allyloxy Polyethylene glycol monoesters carboxy derivatives, allyloxy polyethylene glycol sulfonate and water mixing, are warming up to 55-80 DEG C, are then added dropwise Initiator.
According to the present invention, the free radical polymerization condition generally comprises reaction temperature and reaction time, wherein for balance Esterification and the angle of raising reaction efficiency is promoted to set out, the reaction temperature is 75-110 DEG C, reaction time 1- 10h。
According to the present invention, unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters carboxy derivatives, allyloxy polyethylene glycol The mass ratio of sulfonate can be 1:(0.05-19): (0.05-19), further preferably 1:(0.1-10): (0.1-10), more Preferably 1:(0.5-5): (0.5-5).As long as water guarantees that reactant sufficiently dissolves as solvent, under preferable case, water Quality is unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters carboxy derivatives and allyloxy polyethylene glycol sulfonate gross mass 0.5-10 times.
According to the present invention, the selectable range of the unsaturated carboxylic acid is wider, in order to further increase corrosion mitigating effect, for The present invention, the unsaturated carboxylic acid is in acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and cinnamic acid It is one or more, in more preferable situation, the unsaturated carboxylic acid be one of maleic acid, maleic anhydride and methacrylic acid or It is a variety of.
According to the present invention, the allyloxy polyethylene glycol monoesters carboxy derivatives are by allyloxy polyethylene glycol and binary Carboxylic acid and/or dicarboxylic acids acid anhydrides or tricarboxylic acid carry out esterification and are made.Wherein, the esterification condition is general Including reaction temperature and reaction time, wherein it sets out for the angle that balance promotes esterification and improves reaction efficiency, institute Stating reaction temperature can be 70-130 DEG C, and the reaction time can be 1-6h.Wherein, allyloxy polyethylene glycol and dicarboxylic acids And/or dicarboxylic acids acid anhydrides or tricarboxylic acid be when carrying out esterification, allyloxy polyethylene glycol and dicarboxylic acids and/or The molar ratio of dicarboxylic acids acid anhydrides or tricarboxylic acid is 1:0.9-1.1 (when allyloxy polyethylene glycol and dicarboxylic acids and two When first carboxylic acid anhydride is reacted, molar ratio refers to allyloxy polyethylene glycol, with rubbing for the total amount of dicarboxylic acids and dicarboxylic acids acid anhydrides That ratio；When allyloxy polyethylene glycol and dicarboxylic acids or dicarboxylic acids anhydride reaction, molar ratio refers to the poly- second two of allyloxy Alcohol, the molar ratio with dicarboxylic acids or dicarboxylic acids acid anhydrides).
According to the present invention, the selectable range of the dicarboxylic acids, dicarboxylic acids acid anhydrides and tricarboxylic acid is wider, preferably In the case of, the dicarboxylic acids is selected from oxalic acid, malonic acid, tartronic acid, succinic acid, malic acid, tartaric acid, maleic two One of acid, fumaric acid, glutaric acid, adipic acid, phthalic acid and terephthalic acid (TPA) are a variety of；The dicarboxylic acids Acid anhydrides is selected from one of succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride and phthalic anhydride or a variety of；It is described Tricarboxylic acid is citric acid and/or aconitic acid.
According to the present invention, the allyloxy polyethylene glycol sulfonate is carried out by allyloxy polyethylene glycol and sulfamic acid Sulfonating reaction is made.Wherein, the molar ratio of the allyloxy polyethylene glycol and sulfamic acid is 1:0.9-1.1.The sulfonation Reaction condition generally comprises reaction temperature and reaction time, wherein promotes esterification for balance and improves reaction efficiency Angle set out, the condition of the sulfonating reaction include: reaction temperature be 100-120 DEG C, reaction time 2-8h.
According to the present invention, wherein the selectable range of the initiator is wider, in order to further increase corrosion mitigating effect, needle To the present invention, the initiator is selected from one of ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate or a variety of.The initiator is logical It is often used in the form of initiator solution, the concentration and dosage of initiator solution are the conventional selection of this field.For example, drawing The mass fraction for sending out agent aqueous solution can be 5-50%, and under preferable case, the quality of initiator is insatiable hunger in initiator solution With the 0.01-0.2 of carboxylic acid, allyloxy polyethylene glycol monoesters carboxy derivatives and allyloxy polyethylene glycol sulfonate gross mass Times, the time for adding of initiator is 0.25-5h.
The present invention also provides application of the without phosphorus Polymer corrosion inhibitor in recirculated cooling water.
Application according to the present invention, it is preferable that relative to every liter of recirculated cooling water, the addition of the without phosphorus Polymer corrosion inhibitor Amount is 2-20mg, preferably 5-12mg.
Below with reference to embodiment, the present invention will be described in detail, but the present invention is not limited to this.
Various raw materials used in embodiment are commercially available.
Corrosion inhibition evaluation experimental is referring to China Petrochemical Corporation's " cooling moisture in the embodiment of the present invention and comparative example Analysis and experimental method " in 404 methods carry out.Test water used in the embodiment of the present invention and comparative example is to be matched with Beijing tap water The preparation water of system, Beijing tap water quality are shown in Table 1.Prepare water are as follows: by 0.368g ZnCl2It is dissolved in the tap water of the Beijing 44kg, i.e., Zn2+Concentration is 4mg/L.Wherein, relative to every liter of preparation water, the without phosphorus Polymer corrosion inhibitor of the embodiment preparation of addition has Imitating concentration is respectively 2mg/L, 6mg/L and 10mg/L；The effective concentration of the without phosphorus polymer of the comparative example of addition is respectively 2mg/ L, 6mg/L and 10mg/L；Any without phosphorus polymer is not added in comparative example 3.Experimental result is shown in Table 2.
1 Beijing tap water quality of table
In the present invention, the definition of average corrosion rate is the average thickness of test piece corrosion in the unit time, average corrosion speed The calculation formula of rate are as follows:
In formula: v --- corrosion rate, mm/a；
C --- computational constant is 8.76 × 107；
The corrosion weight loss of Δ W --- test piece, g；
The surface area of S --- test specimen, cm2；
T --- corrosion test time, h；
The density of ρ --- strip materials, kg/dm3。
Embodiment 1
By molecular weight be 278 (i.e. m=5) allyloxy polyethylene glycol (27.8g, 0.1mol) and oxalic acid (9.0g, It 0.1mol) is added in reaction kettle, carries out esterification, reaction temperature is 70 DEG C, reaction time 2h, generates the poly- second of allyloxy Glycol oxalic acid monoesters derivative.
By molecular weight be 278 (i.e. n=5) allyloxy polyethylene glycol (27.8g, 0.1mol) and sulfamic acid (9.7g, It 0.1mol) is added in reaction kettle, 2h is reacted at 100 DEG C, generate allyloxy polyethylene glycol sulfonate.
By three kinds of polymerized monomers --- acrylic acid (1.0g), allyloxy polyethylene glycol oxalic acid monoesters derivative (3.0g), Allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) are added in reaction kettle, stir evenly, drip at 60 DEG C Adding 1g mass fraction is 10% ammonium persulfate solution, and time for adding 15min is warming up to 80 DEG C after being added dropwise, and reacts 2h, It is cooled to room temperature, gained brown solution is without phosphorus Polymer corrosion inhibitor.
Embodiment 2
By molecular weight be 278 (i.e. m=5) allyloxy polyethylene glycol (27.8g, 0.1mol) and maleic anhydride (9.8g, It 0.1mol) is added in reaction kettle, carries out esterification, reaction temperature is 80 DEG C, reaction time 2h, generates the poly- second of allyloxy Glycol maleic acid monoester derivative.
By molecular weight be 278 (i.e. n=5) allyloxy polyethylene glycol (27.8g, 0.1mol) and sulfamic acid (9.7g, It 0.1mol) is added in reaction kettle, 3h is reacted at 110 DEG C, generate allyloxy polyethylene glycol sulfonate.
By three kinds of polymerized monomers --- acrylic acid (1.0g), allyloxy polyethylene glycol maleic acid monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) are added in reaction kettle, stir evenly, 60 The ammonium persulfate solution that 2g mass fraction is 10% is added dropwise at DEG C, time for adding 30min is warming up to 80 DEG C after being added dropwise, 2h is reacted, is cooled to room temperature, gained brown solution is without phosphorus Polymer corrosion inhibitor.
Embodiment 3
The allyloxy polyethylene glycol (49.8g, 0.1mol) and phthalic acid for being 498 (i.e. m=10) by molecular weight (16.6g, 0.1mol) is added in reaction kettle, carries out esterification, and reaction temperature is 80 DEG C, reaction time 3h, generates allyl Oxygroup polyethylene glycol phthalic monoester derivative.
The allyloxy polyethylene glycol (49.8g, 0.1mol) and sulfamic acid for being 498 (i.e. n=10) by molecular weight (9.7g, 0.1mol) is added in reaction kettle, and 3h is reacted at 110 DEG C, generates allyloxy polyethylene glycol sulfonate.
By three kinds of polymerized monomers --- maleic anhydride (1.0g), allyloxy polyethylene glycol phthalic monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) are added in reaction kettle, stir evenly, 60 The sodium peroxydisulfate solution that 2g mass fraction is 20% is added dropwise at DEG C, time for adding 1h is warming up to 80 DEG C, reaction after being added dropwise 3h is cooled to room temperature, and gained brown solution is without phosphorus Polymer corrosion inhibitor.
Embodiment 4
The allyloxy polyethylene glycol (11.6g, 0.01mol) and malic acid for being 1160 (i.e. m=25) by molecular weight (1.34g, 0.01mol) is added in reaction kettle, carries out esterification, and reaction temperature is 80 DEG C, reaction time 2h, generates allyl Oxygroup polyethylene glycol malic acid monoester derivates.
The allyloxy polyethylene glycol (11.6g, 0.01mol) and sulfamic acid for being 1160 (i.e. n=25) by molecular weight (0.97g, 0.01mol) is added in reaction kettle, and 4h is reacted at 120 DEG C, generates allyloxy polyethylene glycol sulfonate.
By three kinds of polymerized monomers --- maleic acid acid (1.0g), allyloxy polyethylene glycol malic acid monoester derivates (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) are added in reaction kettle, stir evenly, 65 The sodium peroxydisulfate solution that 3g mass fraction is 10% is added dropwise at DEG C, time for adding 1h is warming up to 90 DEG C, reaction after being added dropwise 3h is cooled to room temperature, and gained brown solution is without phosphorus Polymer corrosion inhibitor.
Embodiment 5
The allyloxy polyethylene glycol (24.8g, 0.01mol) and aconitic acid for being 2480 (i.e. m=55) by molecular weight (1.74g, 0.01mol) is added in reaction kettle, carries out esterification, and reaction temperature is 120 DEG C, reaction time 4h, generates alkene Propoxyl group polyethylene glycol aconitic acid monoester derivates.
The allyloxy polyethylene glycol (24.8g, 0.01mol) and sulfamic acid for being 2480 (i.e. n=55) by molecular weight (0.97g, 0.01mol) is added in reaction kettle, and 4h is reacted at 120 DEG C, generates allyloxy polyethylene glycol sulfonate.
By three kinds of polymerized monomers --- itaconic acid (1.0g), allyloxy polyethylene glycol aconitic acid monoester derivates (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) are added in reaction kettle, stir evenly, 65 The potassium persulfate solution that 3g mass fraction is 20% is added dropwise at DEG C, time for adding 1h is warming up to 90 DEG C, reaction after being added dropwise 3h is cooled to room temperature, and gained brown solution is without phosphorus Polymer corrosion inhibitor.
Embodiment 6
The allyloxy polyethylene glycol (49.8g, 0.1mol) and maleic anhydride for being 498 (i.e. m=10) by molecular weight (9.8g, 0.1mol) is added in reaction kettle, carries out esterification, and reaction temperature is 80 DEG C, reaction time 3h, generates allyl oxygen Base polyethylene glycol maleic acid monoester derivative.
The allyloxy polyethylene glycol (24.8g, 0.01mol) and sulfamic acid for being 2480 (i.e. n=55) by molecular weight (0.97g, 0.01mol) is added in reaction kettle, and 4h is reacted at 120 DEG C, generates allyloxy polyethylene glycol sulfonate.
By three kinds of polymerized monomers --- methacrylic acid (1.0g), allyloxy polyethylene glycol maleic acid monoester derivative (3.0g), allyloxy polyethylene glycol sulfonate (3.0g) and distilled water (20.0g) are added in reaction kettle, stir evenly, 65 The ammonium persulfate solution that 2g mass fraction is 20% is added dropwise at DEG C, time for adding 1h is warming up to 90 DEG C, reaction after being added dropwise 4h is cooled to room temperature, and gained brown solution is without phosphorus Polymer corrosion inhibitor.
Embodiment 7
The allyloxy polyethylene glycol (49.8g, 0.1mol) and maleic anhydride for being 498 (i.e. m=10) by molecular weight (9.8g, 0.1mol) is added in reaction kettle, carries out esterification, and reaction temperature is 80 DEG C, reaction time 3h, generates allyl oxygen Base polyethylene glycol maleic acid monoester derivative.
The allyloxy polyethylene glycol (24.8g, 0.01mol) and sulfamic acid for being 2480 (i.e. n=55) by molecular weight (0.97g, 0.01mol) is added in reaction kettle, and 4h is reacted at 120 DEG C, generates allyloxy polyethylene glycol sulfonate.
By three kinds of polymerized monomers --- maleic anhydride (4.0g), allyloxy polyethylene glycol maleic acid monoester derivative (2.5g), allyloxy polyethylene glycol sulfonate (0.5g) and distilled water (20.0g) are added in reaction kettle, stir evenly, 65 The ammonium persulfate solution that 2g mass fraction is 20% is added dropwise at DEG C, time for adding 1h is warming up to 90 DEG C, reaction after being added dropwise 3h is cooled to room temperature, and gained brown solution is without phosphorus Polymer corrosion inhibitor.
Comparative example 1
Commercially available acrylic acid -2- acrylamide-2-methyl propane sulfonic polymer (AA-AMPS).
Comparative example 2
According to open source literature (synthesis of AA/APES antisludging agent and performance study, Wu Yuanhong etc., when chemical industry, print, 2010,24 (5), 12-14) prepare acrylic acid-allyloxy polyoxyethylene sulfonic acid salt copolymer AA-APES.
Comparative example 3
Blank control test is not added with any polymer.
2 corrosion inhibition evaluation experimental result (corrosion rate: mm/a) of table
As shown in Table 2, compared to comparative example 3 (blank control test), it is slow to add without phosphorus polymer of the invention Agent, i.e. embodiment 1 to embodiment 7 are lost, with the increase of concentration, corrosion rate is greatly reduced, when drug concentration is 10mg/L, The corrosion rate of embodiment 1 to embodiment 7 is below 0.0650mm/a, and wherein the corrosion rate of embodiment 7 is only 0.0274mm/ a.It is indicated above that the corrosion inhibition of the without phosphorus Polymer corrosion inhibitor provided by the invention is good.And adding comparative example 1 can aggravate Corrosion, concentration more high corrosion rate is bigger, and the corrosion rate of comparative example 2 decreases, and shows the corrosion mitigating effect for having certain, But corrosion mitigating effect is undesirable.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (13)

1. a kind of without phosphorus Polymer corrosion inhibitor, which is characterized in that the without phosphorus Polymer corrosion inhibitor is indicated by general formula shown below:
Wherein, R1For-H ,-COOH or phenyl；R2For-H ,-CH2COOH or C1-C5Low-carbon alkyl；R3For-CO (CH2)kCOOH、- COCH(OH)COOH、-COCH(OH)CH2COOH、-COCH2CH (OH) COOH ,-COCH (OH) CH (OH) COOH ,-COCH= CHCOOH、-CO(o-C6H4)COOH、-CO(p-C6H4)COOH、-COCH2C(OH)(COOH)CH2COOH、-COC(OH) (CH2COOH)2,-COCH=C (COOH) CH2COOH、-COCH2C (COOH)=CHCOOH ,-COC (CH2COOH)=CHCOOH；It is excellent Choosing, R1For-COOH, R2For-H, R3For-CO (o-C6H4)COOH；Or R1For-H, R2For C1-C5Low-carbon alkyl, R3For-COCH =CHCOOH；Or R1For-COOH, R2For-H, R3For-COCH=CHCOOH；
Degree of polymerization x is 1-5000；Degree of polymerization y is 1-5000；Degree of polymerization z is 1-5000；Degree of polymerization m is 1-100；Polymerization degree n is 1-100；Degree of polymerization k is 0-8.
2. without phosphorus Polymer corrosion inhibitor according to claim 1, wherein degree of polymerization x is 10-200；Degree of polymerization y is 10- 200；Degree of polymerization z is 10-200；Degree of polymerization m is 5-55；Polymerization degree n is 5-55；Degree of polymerization k is 0-4.
3. a kind of preparation method of without phosphorus Polymer corrosion inhibitor, which is characterized in that the preparation method includes:
Under the conditions of free radical polymerization and in presence of water, by unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters carboxyl Derivative, allyloxy polyethylene glycol sulfonate are contacted with initiator and are reacted.
4. preparation method according to claim 3, wherein in presence of water, by unsaturated carboxylic acid, the poly- second of allyloxy The method that diol monoester carboxy derivatives, allyloxy polyethylene glycol sulfonate are contacted with initiator include: by unsaturated carboxylic acid, Allyloxy polyethylene glycol monoesters carboxy derivatives, allyloxy polyethylene glycol sulfonate and water mixing, are warming up to 55-80 DEG C, Then initiator is added dropwise.
5. preparation method according to claim 3 or 4, wherein the free radical polymerization condition includes: that reaction temperature is 75-110 DEG C, reaction time 1-10h.
6. preparation method according to claim 3 or 4, wherein unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters carboxyl Derivative, allyloxy polyethylene glycol sulfonate mass ratio be 1:(0.05-19): (0.05-19), further preferably 1: (0.1-10): (0.1-10), more preferably 1:(0.5-5): (0.5-5)；The quality of water is unsaturated carboxylic acid, the poly- second of allyloxy 0.5-10 times of diol monoester carboxy derivatives and allyloxy polyethylene glycol sulfonate gross mass.
7. preparation method according to claim 3 or 4, wherein the unsaturated carboxylic acid is selected from acrylic acid, metering system One of acid, maleic acid, maleic anhydride, itaconic acid and cinnamic acid are a variety of.
8. preparation method according to claim 3 or 4, wherein the allyloxy polyethylene glycol monoesters carboxy derivatives Esterification is carried out by allyloxy polyethylene glycol and dicarboxylic acids and/or dicarboxylic acids acid anhydrides or tricarboxylic acid to be made；Its In, when allyloxy polyethylene glycol carries out esterification with dicarboxylic acids and/or dicarboxylic acids acid anhydrides or tricarboxylic acid, alkene The molar ratio of propoxyl group polyethylene glycol and dicarboxylic acids and/or dicarboxylic acids acid anhydrides or tricarboxylic acid is 1:0.9-1.1；Institute State esterification condition include: reaction temperature be 70-130 DEG C, reaction time 1-6h.
9. preparation method according to claim 8, wherein the dicarboxylic acids is selected from oxalic acid, malonic acid, hydroxyl the third two Acid, succinic acid, malic acid, tartaric acid, maleic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid and to benzene One of dioctyl phthalate is a variety of；The dicarboxylic acids acid anhydrides is selected from succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride With one of phthalic anhydride or a variety of；The tricarboxylic acid is citric acid and/or aconitic acid.
10. preparation method according to claim 3 or 4, wherein the allyloxy polyethylene glycol sulfonate is by allyl oxygen Base polyethylene glycol and sulfamic acid carry out sulfonating reaction and are made, wherein the molar ratio of allyloxy polyethylene glycol and sulfamic acid For 1:0.9-1.1；The condition of the sulfonating reaction includes: that reaction temperature is 100-120 DEG C, reaction time 2-8h.
11. preparation method according to claim 3 or 4, wherein the initiator be selected from ammonium persulfate, sodium peroxydisulfate and One of potassium peroxydisulfate is a variety of, and the initiator is used in the form of initiator solution, the quality of initiator solution Score is 5-50%, and the quality of initiator is unsaturated carboxylic acid, allyloxy polyethylene glycol monoesters carboxyl in initiator solution 0.01-0.2 times of derivative and allyloxy polyethylene glycol sulfonate gross mass, the time for adding of initiator are 0.25-5h.
12. without phosphorus Polymer corrosion inhibitor of any of claims 1 or 2 or the preparation side as described in any one of claim 3-11 Application of the without phosphorus Polymer corrosion inhibitor that method obtains in recirculated cooling water.
13. application according to claim 12, wherein relative to every liter of recirculated cooling water, the without phosphorus polymer inhibition The additional amount of agent is 2-20mg, preferably 5-12mg.
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