CN105542055B - Multiple copolymer and its production and use - Google Patents
Multiple copolymer and its production and use Download PDFInfo
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
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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
- C02F5/12—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 containing nitrogen
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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
- C02F5/14—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 containing phosphorus
- C02F5/145—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 containing phosphorus combined with inorganic substances
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- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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Abstract
The invention belongs to water-treatment technology field, is related to a kind of multiple copolymer for industrial circulating water and its production and use, particular as anti-incrustation corrosion inhibitor application, especially as low-phosphorous environment-friendly corrosion inhibiting and descaling agent application.Multiple copolymer of the present invention be copolymerized using the unsaturated organic monomers containing carboxyl, the unsaturated organic monomers containing ester group and containing sulfonic unsaturated organic monomers obtained by, the Limiting Viscosity of the multiple copolymer is 0.035~0.055dL/g.Multiple copolymer of the present invention has the performances such as scale inhibition, scattered, inhibition, temperature resistance, can be used as dirt dispersion agent application；Low-phosphorous environment-friendly corrosion inhibiting and descaling agent application can be especially used as, applied to fields such as recirculating cooling water system, oil field flood pattern, seawater desalinations.
Description
Technical field
The invention belongs to water-treatment technology field, is related to a kind of multiple copolymer for industrial circulating water and its preparation side
Method and purposes, particular as anti-incrustation corrosion inhibitor application, especially as low-phosphorous environment-friendly corrosion inhibiting and descaling agent application.
Background technology
Industrialization development is increasing to the demand of water, especially huge in the enterprise water use amount such as thermoelectricity, chemical industry, energy
Greatly.In order to realize energy-conservation, emission reduction, the purpose for dropping energy consumption, these industrial enterprises generally employ recirculating cooling water system；But water
After being recycled for multiple times, concentration occurs in the material such as salt in water, causes the generation of fouling and corrosion.In order to suppress
Fouling and reduction are corroded, and maintain the stable operation of production, it is necessary to add the antisludging agent in circulating water treatment medicament.
Conventional antisludging agent is broadly divided into inorganic salts, organic phosphine compound class, natural polymer subclass and synthesis macromolecule
Class.Inorganic salts antisludging agent is used earliest, such as tertiary sodium phosphate, sodium tripolyphosphate, calgon, although carbon can be prevented
The formation of sour calcium dirt, but they easily generate calcium phosphate incrustation scale with the calcium ion in water, at the same again in promotion system bacterium algae breeding；
Gradually eliminated in circulating water treatment now.Organic phosphine compound class, such as ATMP, HEDP, PBTCA, although with fine
Chemical stability, temperature tolerance, concertedness and chelating Ca2+、Mg2+、Zn2+、Fe2+Ability and strong suppression Deng various metals ion
The ability of calcium carbonate scale processed, but because organic phosphine can make body eutrophication, it is unfavorable for environmental protection.Natural polymer subclass, it is such as wooden
Element, tannin, sodium humate etc., to Ca2+、Mg2+There is certain inhibitory action Deng salt crust crystal growth, but natural polymer has
It is unstable, easy decompose, the shortcomings of input amount is big, impurity content is high, high temperature easily decomposes, and antiscale and dispersion effect not as synthesis it is poly-
Compound, seldom directly use now.Synthesizing high score subclass, (such as polyacrylic, poly anhydride homopolymer are common
Polymers), there is resistance calcium carbonate scale performance, and preferable dispersibility well, and without exhaust emission.
Because country is to the more and more higher of environmental requirement, low-phosphorous or without phosphine green scale inhibitor is following development side
To；Therefore the synthesis high score subclass antisludging agent without phosphine becomes the direction of research, the especially antisludging agent with multiple functions
The emphasis even more studied.
The content of the invention
The present invention is to provide a kind of multiple copolymer and preparation method thereof to solve the technical problem of water process.This hair
Bright multiple copolymer contains the functional group of multiple performance, such as sulfonic group, ester group and highdensity hydroxy-acid group, therefore very well
Improve scale inhibition and dispersive property, also with corrosion inhibition and good heat-resisting property.
Multiple copolymer of the present invention, it is characterised in that the multiple copolymer is to use unsaturated organic list containing carboxyl
Body, the unsaturated organic monomers containing ester group and it is copolymerized containing sulfonic unsaturated organic monomers, generation obtains the limit
Viscosity number is 0.035~0.055dL/g multiple copolymer.
Further, in multiple copolymer of the present invention, the copolymerization is to use aqueous solution polymerization method, with oxidationreduction
Initiation system is initiation system, addition chain-transferring agent, catalyst, obtained by above-mentioned monomer copolymerization.
Multiple copolymer of the present invention, it is characterised in that the weight proportion of each component is as follows：
In above-mentioned technical proposal, the unsaturated organic monomers containing carboxyl are：Acrylic acid, methacrylic acid, the rhizome of Chinese monkshood
At least one of acid, itaconic acid, maleic anhydride etc.；
In above-mentioned technical proposal, the unsaturated organic monomers containing ester group are：Methyl acrylate, methyl methacrylate
At least one of ester, hydroxy propyl methacrylate, hydroxypropyl acrylate, hydroxy-ethyl acrylate, vinyl acetate etc.；
It is described to be containing sulfonic unsaturated organic monomers in above-mentioned technical proposal：Sodium vinyl sulfonate, pi-allyl sulphur
At least one of sour sodium, methylpropene sodium sulfonate, 2- acrylamide-2-methyl propane sulfonics, styrene sulfonic acid etc..Above-mentioned technology
In scheme, in the oxidation-reduction trigger system, oxidant is：In ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide etc. at least
It is a kind of；Reducing agent is：In sodium sulfite, sodium hydrogensulfite, sodium thiosulfate, sodium hypophosphite, Vc, ferrous sulfate, diethylamine etc.
At least one；The mass ratio of oxidant and reducing agent is：Oxidant 4-8 parts, reducing agent 1-2 parts.It is preferred that oxidant 4, reduction
1 part of agent.
In above-mentioned technical proposal, the chain-transferring agent is isopropanol, normal propyl alcohol, TGA, mercaprol, mercaptoethanol
At least one of Deng.
In above-mentioned technical proposal, the catalyst be in copper sulphate, ferric sulfate, ammonium ferric sulfate, ironic citrate etc. at least
It is a kind of.
Multiple copolymer of the present invention uses the reason for above-mentioned preparation principle and main material as follows：(1) aqueous solution is as poly-
Bonding solvent, avoid causing pollution to environment using organic solvent, reduce separated and dissolved recovery cost, allow it directly plus
Enter into recirculated cooling water, or used after being compounded with multiple water treatment agent, so as to reduce the cost of production；The aqueous solution is molten
Agent, make the system viscosity of its polymeric solution low, be advantageous to conduct heat, easy control of temperature, reduce the generation of gel effect, so as to more
Good maintenance reaction temperature, is advantageous to the generation of chain transfer reaction, realizes the controllable of molecular weight.(2) oxidation-reduction reaction is used
System can reduce the activation energy needed for polymerisation, reduce its temperature reacted, the time of polymerization as initiation system
Shorten；So as to reduce the energy consumption of the production of the polymer, reduce manually-operated cost.(3) catalyst is added, is made a variety of
The speed of the polymerisation of monomer is accelerated, and shortens the converging operation time, while polymeric reaction temperature is low, so as to beneficial to energy-conservation and
It is easy to the control of production process, is less prone to implode.
The preparation method of multiple copolymer of the present invention, comprises the following steps：
(1) compound method of raw material：
Weight proportion according to following each components weighs each component：
Then component A, B component, component C are configured to respectively：
Component A：Oxidant prepares the aqueous solution as concentration 40-60%；
B component：Unsaturated organic monomers containing carboxyl, the unsaturated organic monomers containing ester group, preparation turn into concentration
For the 40-60% aqueous solution；
Component C：Reducing agent, chain-transferring agent, catalyst, containing sulfonic unsaturated organic monomers, it is solid to add water to control
Content is 33-35%.
Due to containing sulfonic unsaturated organic monomers, such as ALS, methylpropene sodium sulfonate, vinyl sulphur
Sour sodium etc. has certain inhibition and chain transfer, therefore the left and right of regulation molecular weight is played as bed material, is advantageous to
Control the Limiting Viscosity of polymer.
(2) synthesis technique：
Using A and B component as dropping material, component C is as bed material
Synthesis technique comprises the following steps：
In the reactor equipped with reflux condenser and agitating device, component C is added, after stirring and dissolving is complete, is heated up to
At 45~50 DEG C, start that component A is added dropwise, at 50~55 DEG C, time for adding is controlled in 2.0~2.5h for dropping temperature control.Component A
After being added dropwise 5~10 minutes, start that B component is added dropwise, at 50~55 DEG C, time for adding is controlled in 1.5~2.0h for dropping temperature control.
After component A completion of dropwise addition, 55~60 DEG C are warming up to, continues 1.5~2.0h of stirring reaction, is cooled to 40 DEG C of dischargings, i.e., much
Membered copolymer.
In synthesis technique of the present invention, there is following key technology control point：
1) when preparing component C, the solid content of general control product is in 33~35% examining primarily for the following aspects
Consider：Firstth, in macromolecular polymerization reaction, easily occur " sudden and violent poly- " phenomenon after reaction system viscosity increases, influence product matter
Amount and the potential threat that blast is brought to production, therefore, solid content is unsuitable too high；Second aspect, the product are water-soluble high score
Son, it is also to be compounded with other products during use, if solid content is too high, compound property can be influenceed in compound process；Therefore C groups
Divide by regulating capacity to control product solid content 33~35%.
2) time for adding：It is typically all the time for adding of strict control reaction monomers and anti-for Raolical polymerizable
Temperature, rather than regulation rate of addition are answered, is on the one hand that the half-life period of oxidant determines, on the other hand, for polymerisation
Speech, it is relatively slow to be added dropwise the rate of addition at initial stage, and middle and later periods rate of addition is added dropwise can relatively fast, therefore, in the present invention instead
During answering, time for adding is determined according to oxidant half-life period, it is however generally that, the half-life period under these conditions of oxidant is about
For 4~5 hours, thus course of reaction total time also control at 4~5 hours, control the time for adding of component A 2.0~
2.5h.The time for adding of B component is controlled to control in 1.5~2.0h.
The invention described above multiple copolymer has the performances such as scale inhibition, scattered, inhibition, temperature resistance, can be answered as dirt dispersion agent
With；Low-phosphorous environment-friendly corrosion inhibiting and descaling agent application can be especially used as, applied to recirculating cooling water system, oil field flood pattern, sea
The fields such as water desalination.
The positive effect of the present invention is：The present invention uses water solution polymerization process, using oxidation-reduction trigger system, adds
The method of catalyst and chain-transferring agent, makes the cost of its polymerization reduce, and the viscosity of polymerization system is low, easy control of temperature,
Narrow molecular weight distribution；Temperature needed for the polymerization is low, and energy consumption is low, high conversion rate, and the production time shortens, and has saved and has been produced into
This, produces, production process energy-conserving and environment-protective without " three wastes " in process of production.The multiple copolymer due to containing carboxyl, sulfonic group,
The groups such as ester group and its degree of polymerization are also suitable for, the functional group containing multiple performance, such as sulfonic group, ester group and highdensity carboxylic
Acid groups, therefore scale inhibition and dispersive property are improved well, also with corrosion inhibition and good heat-resisting property.The present invention
Multiple copolymer dirt dispersion agent is widely used, can be applied to the neck such as recirculating cooling water system, oil field flood pattern, seawater desalination
Domain.The preparation method of product of the present invention is simple, and cost is low, and easily operated, easily promotes.
Embodiment
It is described further below in conjunction with example, but it is not as a limitation of the invention.
First, the synthesis instantiation of multiple copolymer dirt dispersion agent：
Example 1：
Component A：2 parts of hydrogen peroxide (content is 27% or so hydrogen peroxide), 2 parts of ammonium persulfate, preparation turns into 40% water
Solution；
B component：15 parts of acrylic acid, totally 5 parts of aconitic acid, 2 parts of methyl methacrylate, 2 parts of hydroxy-ethyl acrylate, acrylic acid
2 parts of hydroxypropyl acrylate, preparation turn into 59% aqueous solution；
Component C：0.5 part of Vc, 0.5 part of sodium hydrogensulfite, 2 parts of isopropanol, 2 parts of TGA, ammonium ferric sulfate 0.025
Part, 0.025 part of copper sulphate, 3 parts of sodium vinyl sulfonate, 2 parts of ALS, 2 parts of methylpropene sodium sulfonate, deionized water 34
Part；
According to above-mentioned component C distribution, in the reactor equipped with reflux condenser and agitating device, stirring dress is opened
Put, prepare component C, steam heating is passed through after preparing.When temperature rises to 45 DEG C, start that component A, dropping temperature control is added dropwise
At 50~55 DEG C, time for adding is controlled in 2.0h.After component A is added dropwise 5 minutes, start that B component is added dropwise, dropping temperature is controlled 50
~55 DEG C, time for adding is controlled in 1.5h.After component A completion of dropwise addition, 55~60 DEG C are warming up to, continues stirring reaction 2.0h,
40 DEG C of dischargings are cooled to, that is, obtain required multiple copolymer.
Example 2
Component A：2 parts of hydrogen peroxide (27% or so hydrogen peroxide), 2 parts of potassium peroxydisulfate, preparation turn into 40% aqueous solution；
B component：15 parts of acrylic acid, 5 parts of itaconic acid, 5 parts of aconitic acid, 1 part of methyl acrylate, 1 part of vinyl acetate, methyl
2 parts of hydroxypropyl acrylate, preparation turn into 54% aqueous solution；
Component C：0.5 part of ferrous sulfate, 0.5 part of sodium hypophosphite, 2 parts of normal propyl alcohol, 2 parts of TGA, 2 parts of mercaprol,
0.05 part of ferric sulfate, 0.05 part of copper sulphate, 2 parts of ALS, 2 parts of 2- acrylamide-2-methyl propane sulfonics, deionized water
25 parts；
According to above-mentioned component C distribution, in the reactor equipped with reflux condenser and agitating device, stirring dress is opened
Put, prepare component C, steam heating is passed through after preparing.When temperature rises to 45 DEG C, start that component A, dropping temperature control is added dropwise
At 50~55 DEG C, time for adding is controlled in 2.5h.After component A is added dropwise 7 minutes, start that B component is added dropwise, dropping temperature is controlled 50
~55 DEG C, time for adding is controlled in 2.0h.After component A completion of dropwise addition, 55~60 DEG C are warming up to, continues stirring reaction 2.0h,
40 DEG C of dischargings are cooled to, that is, obtain required multiple copolymer.
Example 3
Component A：2 parts of potassium peroxydisulfate, 2 parts of ammonium persulfate, preparation turn into 50% aqueous solution；
B component：5 parts of acrylic acid, 15 parts of methacrylic acid, 5 parts of aconitic acid, 5 parts of itaconic acid, 1 part of methyl methacrylate,
1 part of hydroxy-ethyl acrylate, preparation turn into 50% aqueous solution；
Component C：0.5 part of sodium thiosulfate, 0.5 part of diethylamine, 2 parts of normal propyl alcohol, 2 parts of TGA, 2 parts of mercaprol,
2 parts of mercaptoethanol, 0.05 part of ammonium ferric sulfate, 0.05 part of ironic citrate, 0.05 part of copper sulphate, 1 part of methylpropene sodium sulfonate, 2- third
1 part of acrylamide -2- methyl propane sulfonic acids, 1 part of styrene sulfonic acid, 16 parts of deionized water；
According to above-mentioned component C distribution, in the reactor equipped with reflux condenser and agitating device, stirring dress is opened
Put, prepare component C, steam heating is passed through after preparing.When temperature rises to 45 DEG C, start that component A, dropping temperature control is added dropwise
At 50~55 DEG C, time for adding is controlled in 2.5h.After component A is added dropwise 10 minutes, start that B component is added dropwise, dropping temperature control exists
50~55 DEG C, time for adding is controlled in 2.0h.After component A completion of dropwise addition, 55~60 DEG C are warming up to, continues stirring reaction
2.0h, 40 DEG C of dischargings are cooled to, that is, obtain required multiple copolymer.
Example 4
Component A：2 parts of hydrogen peroxide (27% or so hydrogen peroxide), 2 parts of potassium peroxydisulfate, 2 parts of ammonium persulfate, preparation turns into
52% aqueous solution；
B component：15 parts of acrylic acid, 5 parts of maleic anhydride, 5 parts of itaconic acid, 5 parts of aconitic acid, 1 part of vinyl acetate, acrylic acid
1 part of hydroxypropyl acrylate, preparation turn into 60% aqueous solution；
Component C：0.5 part of sodium sulfite, 0.5 part of sodium thiosulfate, 0.5 part of Vc, 2 parts of isopropanol, 2 parts of mercaptoethanol,
0.05 part of ammonium ferric sulfate, 0.05 part of ferric sulfate, 0.05 part of copper sulphate, 1 part of ALS, 2- acrylamide -2- methyl-props
1 part of sulfonic acid, 1 part of styrene sulfonic acid, 30 parts of deionized water；
According to above-mentioned component C distribution, in the reactor equipped with reflux condenser and agitating device, stirring dress is opened
Put, prepare component C, steam heating is passed through after preparing.When temperature rises to 45 DEG C, start that component A, dropping temperature control is added dropwise
At 50~55 DEG C, time for adding is controlled in 2.5h.After component A is added dropwise 10 minutes, start that B component is added dropwise, dropping temperature control exists
50~55 DEG C, time for adding is controlled in 2.0h.After component A completion of dropwise addition, 55~60 DEG C are warming up to, continues stirring reaction
2.0h, 40 DEG C of dischargings are cooled to, that is, obtain required multiple copolymer.
Example 5
Component A：3 parts of hydrogen peroxide (27% or so hydrogen peroxide), 3 parts of potassium peroxydisulfate, 2 parts of ammonium persulfate, preparation turns into
50% aqueous solution；
B component：15 parts of methacrylic acid, 5 parts of maleic anhydride, 5 parts of itaconic acid, 5 parts of aconitic acid, 1 part of methyl acrylate, first
1 part of base hydroxypropyl acrylate, preparation turn into 60% aqueous solution；
Component C：0.5 part of sodium hydrogensulfite, 0.5 part of sodium hypophosphite, 0.5 part of ferrous sulfate, 0.5 part of ethylenediamine, normal propyl alcohol 2
Part, 2 parts of mercaprol, 0.05 part of ammonium ferric sulfate, 0.05 part of ferric sulfate, 0.05 part of ironic citrate, 1 part of sodium vinyl sulfonate, first
1 part of base sodium allylsulfonate, 1 part of 2- acrylamide-2-methyl propane sulfonics, 25 parts of deionized water；
According to above-mentioned component C distribution, in the reactor equipped with reflux condenser and agitating device, stirring dress is opened
Put, prepare component C, steam heating is passed through after preparing.When temperature rises to 45 DEG C, start that component A, dropping temperature control is added dropwise
At 50~55 DEG C, time for adding is controlled in 2.5h.After component A is added dropwise 10 minutes, start that B component is added dropwise, dropping temperature control exists
50~55 DEG C, time for adding is controlled in 2.0h.After component A completion of dropwise addition, 55~60 DEG C are warming up to, continues stirring reaction
2.0h, 40 DEG C of dischargings are cooled to, that is, obtain required multiple copolymer.
Example 6
Component A：3 parts of hydrogen peroxide (27% or so hydrogen peroxide), 3 parts of ammonium persulfate, preparation turn into 42% aqueous solution；
B component：10 parts of methacrylic acid, 5 parts of maleic anhydride, 10 parts of acrylic acid, 1 part of methyl methacrylate, acrylic acid
1 part of hydroxyl ethyl ester, 2 parts of vinyl acetate, preparation turn into 57% aqueous solution；
Component C：0.5 part of sodium sulfite, 0.5 part of Vc, 0.5 part of ferrous sulfate, 2 parts of isopropanol, 2 parts of normal propyl alcohol, sulfydryl
2 parts of ethanol, 0.05 part of copper sulphate, 0.05 part of ironic citrate, 5 parts of maleic anhydride, 1 part of sodium vinyl sulfonate, methacrylic sulfonic acid
1 part of sodium, 2 parts of styrene sulfonic acid, 27 parts of deionized water；
According to above-mentioned component C distribution, in the reactor equipped with reflux condenser and agitating device, stirring dress is opened
Put, prepare component C, steam heating is passed through after preparing.When temperature rises to 45 DEG C, start that component A, dropping temperature control is added dropwise
At 50~55 DEG C, time for adding is controlled in 2.0h.After component A is added dropwise 7 minutes, start that B component is added dropwise, dropping temperature is controlled 50
~55 DEG C, time for adding is controlled in 1.5h.After component A completion of dropwise addition, 55~60 DEG C are warming up to, continues stirring reaction 2.0h,
40 DEG C of dischargings are cooled to, that is, obtain required multiple copolymer.
Example 7
Component A：2 parts of hydrogen peroxide (27% or so hydrogen peroxide), 3 parts of potassium peroxydisulfate, 3 parts of ammonium persulfate, preparation turns into
59% aqueous solution；
B component：5 parts of methacrylic acid, 10 parts of maleic anhydride, 5 parts of aconitic acid, 5 parts of itaconic acid, 5 parts of acrylic acid, methyl-prop
1 part of e pioic acid methyl ester, 1 part of hydroxy propyl methacrylate, preparation turn into 60% aqueous solution；
Component C：0.5 part of sodium thiosulfate, 0.5 part of sodium hypophosphite, 0.5 part of ferrous sulfate, 0.5 part of Vc, TGA 2
Part, 2 parts of mercaprol, 0.05 part of ammonium ferric sulfate, 0.05 part of ironic citrate, 0.05 part of copper sulphate, 1 part of sodium vinyl sulfonate, 2-
1 part of acrylamide-2-methyl propane sulfonic, 1 part of styrene sulfonic acid, 31 parts of deionized water；
According to above-mentioned component C distribution, in the reactor equipped with reflux condenser and agitating device, stirring dress is opened
Put, prepare component C, steam heating is passed through after preparing.When temperature rises to 45 DEG C, start that component A, dropping temperature control is added dropwise
At 50~55 DEG C, time for adding is controlled in 2.0h.After component A is added dropwise 5 minutes, start that B component is added dropwise, dropping temperature is controlled 50
~55 DEG C, time for adding is controlled in 1.5h.After component A completion of dropwise addition, 55~60 DEG C are warming up to, continues stirring reaction 2.0h,
40 DEG C of dischargings are cooled to, that is, obtain required multiple copolymer.
Technical indicator is shown in Table 1：
The copolymer technical indicator of table 1
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Solid content % | 33.0 | 33.1 | 35.0 | 34.8 | 34.2 | 33.3 | 34.5 |
| Content of monomer % | 0.07 | 0.10 | 0.12 | 0.17 | 0.15 | 0.13 | 0.16 |
| PH value (1% aqueous solution) | 2.69 | 2.68 | 2.61 | 2.62 | 2.66 | 2.63 | 2.62 |
| Density g/cm3(20℃) | 1.14 | 1.15 | 1.19 | 1.16 | 1.16 | 1.15 | 1.17 |
| Limiting Viscosity dL/g | 0.048 | 0.050 | 0.055 | 0.042 | 0.038 | 0.045 | 0.035 |
2nd, the application of multiple copolymer dirt dispersion agent
Each embodiment is applied in water process, its medicament is formulated as：In a kettle add 10 parts of zinc sulfate, 36 parts it is soft
Change water and 2 parts of industrial sulphuric acid (H2SO4), it is stirred well to after zinc sulfate is completely dissolved, sequentially adds 2- phosphonic acids-butane -1,2,4-
5 parts of tricarboxylic acids (PBTCA), 1 part of ATMP (ATMP), 2 parts of 2- HPAAs (HPAA), multi-component Copolymerization
37 parts of thing (one kind in the multiple copolymer of each example synthesis), is stirring evenly and then adding into 2 parts of BTAs (BTA), 1 part of sulfydryl
Benzothiazole and 4 parts of industrial alcohols, stir transparent to solution, that is, obtain anti-incrustation corrosion inhibitor.
Obtained product total phosphorus is about 0.7% (in terms of P), adds concentration and controls in 40~60mg/L, uses Posterior circle water
System sewerage total phosphorus is about 0.28~0.42mg/L (in terms of P), and national grade one discharge standard is total phosphorus≤0.5mg/L (with P
Meter).Multiple copolymer i.e. of the present invention is applied to recirculated water corrosion inhibiting and descaling agent, and low-phosphorousization of product can be achieved, and discharge is full
Sufficient national grade one discharge standard.
1st, performance measurement
Scale-inhibiting properties determine：Calcium carbonate scale-inhibiting properties assay method
Using standard GB/T/T 16632-2008《The measure tosca method of water treatment agent scale-inhibiting properties》Surveyed
It is fixed.
Under calcium hardness 800mg/L (with calcium carbonate) and total alkalinity 350mg/L (with calcium carbonate) condition of water quality, add
Enter anti-incrustation corrosion inhibitor, determine the scale inhibition performance of various concentrations medicament.Measure the results are shown in Table 2.
The static properties scale inhibition of table 2 is tested
Corrosion inhibition assay method
Using standard GB/T/T 18175-2000《The measure rotary hanging plate method of water treatment agent corrosion inhibition》Surveyed
It is fixed.Condition of water quality and static test condition are shown in Table 3, and test result is shown in Table 4.
The corrosion inhibition condition determination of table 3
4 static corrosion inhibition of table is tested
2nd, dynamic analog test method
Using chemical industry standard HG/T 2160-2008《Dynamic analogue test of cooling water method》With GB 50050-2007
《Code for design of industrial recirculating cooling water treatment》It is measured.
On dynamic analog device, scale inhibition of each embodiment anticorrosion-antiscaling property under high concentration multiple condition of water quality is evaluated
Corrosion inhibition.
Experiment using somewhere surface water does recirculated cooling water moisturizing, and it is 800mg/L (with calcium carbonate to control calcium ion concentration
Meter), basicity be 150 ± 10mg/L (with calcium carbonate), addition anti-incrustation corrosion inhibitor, concentration 40mg/L.Quality of groundwater is shown in Table
5, testing result is shown in Table 6.
The quality of groundwater of table 5
The dynamic simulation experiment of table 6
Above-mentioned experimental result shows that there is multi-component copolymer dirt dispersion agent of the present invention steady zinc effect well to make with scale inhibition
With.Apply in water treatment agent, when the concentration of water treatment agent is 40~60mg/L (recirculated water Chinese medicine agent concentration), equipment water side is glued
Attached speed is 11.0~12.0mcm, carbon steel test tube rate of corrosion is 0.019~0.022mm/a, stainless steel test tube rate of corrosion is
0.0009~0.0015mm/a, brass test tube rate of corrosion are 0.0018-0.0021mm/a, are superior to national standard《Industrial cycle
Cold water process design specification》GB50050-2007 requirement.
Explanation of nouns：
1st, Limiting Viscosity, method of testing are shown in GB/T 22593-2008, water treatment agent Limiting Viscosity assay method general rule.
Claims (5)
1. multiple copolymer, it is characterised in that：The multiple copolymer uses the unsaturated organic monomers containing carboxyl, contains ester
Unsaturated organic monomers of base and obtained by being copolymerized containing sulfonic unsaturated organic monomers, the pole of the multiple copolymer
Limit viscosity number is 0.035~0.055dL/g；The copolymerization is to use aqueous solution polymerization method, using oxidation-reduction trigger system to draw
Hair system, addition chain-transferring agent, catalyst are unsaturated organic containing ester group using the unsaturated organic monomers containing carboxyl
Monomer and contain sulfonic unsaturated organic monomers copolymerization gained；
The weight proportion of each component is as follows：
Wherein：
The unsaturated organic monomers containing carboxyl are：In acrylic acid, methacrylic acid, aconitic acid, itaconic acid, maleic anhydride
At least one；
The unsaturated organic monomers containing ester group are：Methyl acrylate, methyl methacrylate, methacrylic acid hydroxypropyl
At least one of ester, hydroxypropyl acrylate, hydroxy-ethyl acrylate, vinyl acetate；
It is described to be containing sulfonic unsaturated organic monomers：Sodium vinyl sulfonate, ALS, methacrylic sulfonic acid
At least one of sodium, 2- acrylamide-2-methyl propane sulfonics, styrene sulfonic acid；
In the oxidation-reduction trigger system, oxidant is：At least one of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide；
Reducing agent is：In sodium sulfite, sodium hydrogensulfite, sodium thiosulfate, sodium hypophosphite, Vc, ferrous sulfate, diethylamine at least
It is a kind of；
The chain-transferring agent is at least one of isopropanol, normal propyl alcohol, TGA, mercaprol, mercaptoethanol；
The catalyst is at least one of copper sulphate, ferric sulfate, ammonium ferric sulfate, ironic citrate.
2. the preparation method of the multiple copolymer described in claim 1, it is characterised in that：Comprise the following steps：
(1) compound method of raw material：Weight proportion according to following each components weighs each component：
Then component A, B component, component C are configured to respectively：
Component A：Oxidant prepares the aqueous solution as concentration 40-60%；
B component：Unsaturated organic monomers containing carboxyl, the unsaturated organic monomers containing ester group, it is 40- to prepare as concentration
60% aqueous solution；
Component C：Reducing agent, chain-transferring agent, catalyst, containing sulfonic unsaturated organic monomers, add water to control solid content
For 33-35%；
(2) synthesis technique：Using A and B component as dropping material, component C is as bed material；
Comprise the following steps：
A, in the reactor equipped with reflux condenser and agitating device, component C is added, after stirring and dissolving is complete, is heated up to 45
At~50 DEG C, start that component A is added dropwise, at 50~55 DEG C, time for adding is controlled in 2.0~2.5h for dropping temperature control；
B, after component A is added dropwise 5~10 minutes, start that B component is added dropwise, at 50~55 DEG C, time for adding controls for dropping temperature control
In 1.5~2.0h；
C, after component A completion of dropwise addition, 55~60 DEG C are warming up to, continues 1.5~2.0h of stirring reaction, is cooled to 40 DEG C of dischargings,
Produce multiple copolymer.
3. the multiple copolymer described in claim 1 is used as dirt dispersion agent application.
4. the multiple copolymer described in claim 1 is used as low-phosphorous environment-friendly corrosion inhibiting and descaling agent application.
5. the application according to claim 3 or 4, it is characterised in that：Applied to recirculating cooling water system, oil-field flooding system
System, seawater desalination.
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| CN107082845A (en) * | 2017-05-10 | 2017-08-22 | 西安工程大学 | A kind of terpolymer antisludging agent and preparation method thereof |
| CN107010740B (en) * | 2017-06-12 | 2020-08-25 | 西安工程大学 | Scale inhibitor for sewage treatment and preparation method thereof |
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| CN109879451B (en) * | 2019-04-04 | 2022-06-03 | 河北省科学院能源研究所 | Preparation method of copolymer water treatment agent |
| CN111003820B (en) * | 2019-12-27 | 2020-11-27 | 东北石油大学 | Solid slow-release scale inhibitor and preparation method thereof |
| CN111003823A (en) * | 2019-12-30 | 2020-04-14 | 山东天庆科技发展有限公司 | Novel efficient non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN112920296A (en) * | 2021-02-01 | 2021-06-08 | 西南石油大学 | Dispersing agent for dissolving barium sulfate scale and preparation method thereof |
| CN114874377A (en) * | 2021-06-07 | 2022-08-09 | 上海保立佳新材料有限公司 | High-molecular copolymer dispersant for water-based paint and preparation method thereof |
| CN115947887B (en) * | 2021-10-08 | 2024-02-13 | 中国石油化工股份有限公司 | Tackifier for drilling fluid and preparation method and application thereof |
| CN114806524B (en) * | 2022-04-08 | 2024-06-14 | 西南石油大学 | Scale inhibitor for oilfield extrusion process, preparation method thereof, sleeve agent for oilfield extrusion process and application thereof |
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