CN106496415A - Fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer and its production and use - Google Patents
Fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer and its production and use Download PDFInfo
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- CN106496415A CN106496415A CN201611006490.1A CN201611006490A CN106496415A CN 106496415 A CN106496415 A CN 106496415A CN 201611006490 A CN201611006490 A CN 201611006490A CN 106496415 A CN106496415 A CN 106496415A
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- acrylic acid
- phosphino
- labeled
- fluorescently
- itaconic acid
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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
- 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
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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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
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer and its production and use, using 4 bromine, 1,8 naphthalic anhydride, ethanol andN,N1,3 propane diamine of dimethyl obtains 4 bromines for raw material reactionN‑(3‑N’,N’Dimethylaminopropyl) 1,8 naphthalimides, then again with ethanol and ethylene glycol monomethyl ether as mixed solvent, are reacted with n-butylamine, obtain product and obtain 4 fourth amino with allyl chloride reaction againN‑(3‑N’,N' dimethylaminopropyl) naphthalimide allyl ammonium chloride；Then fluorescent monomer and sodium hypophosphite, itaconic acid, acrylic acid are carried out copolymerization using water phase one-step synthesis and obtains fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer.Raw material of the present invention is easy to get, preparation method is simple, has the several functions such as fluorescent tracing function and inhibition, scale inhibition concurrently.
Description
Technical field
The present invention relates to a kind of preparation method of industrial circulating cooling water system corrosion inhibiting and descaling agent and correlated performance, belong to
The development of industrial circulation water treatment medicament and new technology development field, particularly a kind of fluorescently-labeled phosphino- acrylic acid itaconic acid
Copolymer and its production and use.
Background technology
In industrial circulating cooling water system, in order to prevent scaling and corrosion, it is necessary to using water treatment agent.Its medicine
The concentration of agent is a highly important parameter.Excessive concentration and too low, can all bring detrimental effect.At traditional detection water
Reason medicament technical process is numerous and diverse, interference factor is more, be unsatisfactory for the condition of on-line measurement and real-time control.
The on-line checking of water treatment agent and the research one of Automatic Dosing control technology is realized using fluorescent tracer technique
It is directly a focus.By applying fluorescent tracing type water treatment agent, medicine that can quickly, in Accurate Determining industrial circulating water system
The concentration (concentration of the polymer that can not be detected easily especially with chemical method) of agent, effectively regulates and controls adding for water treatment agent
Dosage, so that reduce pollution of the water treatment agent to environment to greatest extent.
The logical constant species method of water treatment agent is detected by fluorescent material, one kind is directly to carry out physical blending, will be glimmering
Light probe material carries out physical compounding with water treatment agent, compounds water process by the fluorescence intensity detection by quantitative of recirculated cooling water
The content of medicament, adds in time and supplements compounding water treatment agent, it is ensured that the scale inhibition effect of recirculating cooling water system.Such as Chinese patent
CN102645427A, CN104788349A, CN105883947A, CN105600953A etc..However, this method would generally be subject to
The impact of many factors so that fluorescence intensity is not accurate enough, so as to can not reaction cycle water Chinese medicine exactly content, cause
Scale inhibition effect is not good enough or the waste of medicament.Another is to obtain fluorescent tracing type medicament by the method for chemical modification.Mesh
Front common synthetic method mainly has two kinds, and one kind is obtained by polymer modification；Another kind is by water treatment agent monomer
With fluorescent chemicalses or copolymerization directly carried out by the monomer of its labelling obtain.In this respect, foreign countries from the beginning of the nineties in last century just
Have begun working on, studied with the Naclo companies and Rhom and Hass in the U.S. especially must compare many.And domestic current only Tianjin
University, Changzhou University, the unit such as Tianjin chemical research institute and Institutes Of Technology Of Nanjing are carrying out correlational study.But domestic at present grinds
Study carefully the modified aspect for being concentrated mainly on polymer, this requires that original water treatment agent must have can be with modified amido or carboxylic
Base, and the condition such as the higher such as High Temperature High Pressure of the condition required by polymer modification, therefore comparatively relatively difficult.Such as China
Patent CN l229091A discloses a kind of water treatment agent for having spike and antiscaling dispersion effect concurrently, but the water treatment agent is to pass through
(turning) amide reaction between organic fluorescence derivant is directly obtained with polymer reaction has fluorescently-labeled polymer, and this is anti-
High Temperature High Pressure should be required, and requires that polymer is without significantly decomposition in reaction, while great majority polymerization due to reaction raw materials seldom
All there is resolution problem in thing under this High Temperature High Pressure, therefore greatly limit the further exploitation and application of the technology.And pass through
The method of monomer copolymerization obtains spike type medicament, it is only necessary to synthesizes
Body, then water treatment agent monomer is can be obtained by under the conditions of relatively mild with which.
Content of the invention
It is an object of the invention to provide a kind of raw material is easy to get, the fluorescently-labeled phosphino- acrylic acid clothing of preparation method is simple
Health acid copolymer and its production and use.
The present invention technical solution be：
A kind of fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer, is characterized in that：The Polymer Formulation is：
Wherein：M, n are 1～20 integer.
The preparation method of described fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer, is characterized in that：Including following step
Suddenly：
4 bromines are obtained using 4 bromine, 1,8 naphthalic anhydride, ethanol and 1,3 propane diamine of N, N dimethyl for raw material reaction
N (3 N ', N ' dimethylaminopropyl) 1,8 naphthalimides, then molten as mixing with ethanol and ethylene glycol monomethyl ether again
Agent, is reacted with n-butylamine, obtains 4 fourth amino Ns (3 N ', N ' dimethylaminopropyl) naphthalimide, and the product is again
Fluorescent monomer 4 fourth amino N (3 N ', the N ' dimethylamino with fluorescent characteristic and double bond is obtained with allyl chloride reaction
Propyl group) naphthalimide allyl ammonium chloride；Then water phase one-step synthesis are adopted by 4 fourth amino N (3 of fluorescent monomer
N ', N ' dimethylaminopropyl) naphthalimide allyl ammonium chloride and sodium hypophosphite, itaconic acid, acrylic acid carries out altogether
Gather and obtain fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer.
Described fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer is being prepared with fluorescent tracing function and inhibition, resistance
Application in dirt, the water treatment agent of divergent function.
Realize that concrete technical scheme of the invention can be：
1. the synthesis of 4 bromine N (3 N', N' dimethylaminopropyl) 1,8 naphthalimides.Weigh 4 bromine, 1,8 naphthalene
In there-necked flask, it is solvent to add a certain amount of ethanol to acid anhydride, is slowly stirred, Deca N, 1,3 propane diamine of N dimethyl and second
The mixed liquor of alcohol, the ratio 1.2 of the amount of the material of 1,3 propane diamine of 1,8 naphthalene anhydride of wherein 4 bromine and N, N dimethyl:1.0～
1.0:Between 2.0, half an hour drips off, while being slowly increased to reflux temperature, is tracked with thin layer chromatography, until reaction terminates, cold
But filter, obtain yellow solid (I).
2. the synthesis of 4 fourth amino Ns (3 N', N' dimethylaminopropyl) 1,8 naphthalimides (II)：Weigh above-mentioned
The product of generation in there-necked flask adds ethylene glycol monomethyl ether, is slowly stirred, the mixed liquor of Deca n-butylamine and ethanol, its
Middle compound (II) is 1.0 with the ratio of the amount of substance of n-butylamine:1.5～1.0:2.It is slowly increased to flow back simultaneously.Use thin layer chromatography
Tracking, until reaction terminates, reduce pressure sucking filtration, removes excessive ethylene glycol monomethyl ether, obtains purpose product (II).
3. the synthesis of 4 fourth amino Ns (3 N', N' dimethylaminopropyl) 1,8 naphthalimide allyl ammonium chlorides
The product (II) of above-mentioned generation is weighed in there-necked flask, add DMF, be slowly stirred, Deca benzyl chloride and DMF's is mixed
Liquid is closed, wherein compound (II) is 1.0 with the amount of substance ratio of benzyl chloride:2～1.0:6, while slowly rising high-temperature, backflow.With thin
Layer chromatography is tracked, until reaction terminates, vacuum distillation removes excessive DMF, and cooling obtains crude product, with washing with acetone, obtains
To purpose product (III) (FT).
4. the synthesis of FT AA IA：One is put in the four-hole boiling flask equipped with separatory funnel, thermometer and reflux condensing tube
Quantitative deionized water, itaconic acid, catalyst, sodium hypophosphite and fluorescent monomer (FT), are heated to 90 100 DEG C under agitation,
Under the protection of nitrogen, a certain amount of Ammonium persulfate. of Deca, acrylic acid and sodium sulfite solution, temperature control is at 90 DEG C 100
DEG C, dripping off in 3 4h, continue 1 2h of insulation, cooling discharging obtains final product the product F T AA IA of the present invention.The polymer has fluorescence
The several functions such as tracking function, inhibition, scale inhibition and dispersion.
The present invention principle be：Chemicals are easy to get as reaction raw materials with anhydrides, amine and benzyl chloride etc., using gentleer
Reaction condition synthesis the fluorescent monomer containing double bond, then targetedly select some function admirables, be easy to be polymerized, close
It is polymerized into the conventional monomer of water treatment agent, in water treatment agent molecule in addition to conventional hydroxy-acid group is introduced, prior
It is to be firstly introduced phosphino- group, so that the analog copolymer has fluorescent tracing function.The copolymer itself has to Calcium Carbonate
There is excellent scale inhibition and dispersion performance, it may have certain corrosion inhibition, be a kind of water treatment agent of high comprehensive performance.
Compared with prior art, its remarkable advantage is：
The raw material of synthesis fluorescent monomer and polymer is easy to get, and reaction condition is gentle, and obtained fluorescent monomer is used for synthesizing
During fluorescent polymer water treatment agent, other compositions in the other structures or system of polymer are not interfered with, polymer is excited
Wavelength and launch wavelength are respectively 474nm and 554nm, in visible region, can use fixed Instrument measuring, so as to reduce
In the interference that ultraviolet region is caused.
During quo of Conventional Water Treatment Programs compound use, fluorescence intensity is substantially unchanged with recirculated water for fluorescent polymer, while copolymerization
Thing concentration is in good linear relationship with fluorescence intensity, and its linearly dependent coefficient is 0.9997, the detection of polymer FT AA IA
Lower limit is 0.19mg L 1.When therefore, used in recirculated water, the change that can pass through fluorescence intensity is accurate, timely, quick
Concentration of the medicament in circulation is determined, online dosing, quantitative control is realized, such that it is able to greatly simplify execute-in-place,
Raise the management level.
The present invention is introduced into the functional groups such as carboxyl, phosphino- group in molecule first so that the polymer has fluorescent tracing concurrently
The several functions such as function and inhibition, scale inhibition.Fluorescent monomer and itaconic acid, acrylic acid, ortho phosphorous acid receive the water treatment agent after copolymerization
Chemical feeding quantity reaches 71.29% to the corrosion inhibition rate of carbon steel when being 30mg/L；Chemical feeding quantity be 12mg/L when to the scale inhibition performance of Calcium Carbonate be
89.3%, the incrustation scale of formation is easily washed away, shows that its dispersive property is preferable.
Description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the excitation spectrum of fluorescent monomer of the present invention and emission spectrum schematic diagram.
Fig. 2 is the relation schematic diagram of the concentration with fluorescence intensity of fluorescent monomer of the present invention.
Fig. 3 is the excitation spectrum of present copolymer FT AA IA and launching light spectrogram.
Fig. 4 is the graph of relation of the concentration with fluorescence intensity of present copolymer FT AA IA.
Fig. 5 is the graph of a relation of the scale inhibitor dosage with scale-inhibiting properties of present copolymer FT AA IA.
Fig. 6 is the present invention plus not commensurability PAA, ATMP, HEDP, and HPMA is to copolymer
The curve chart of the fluorescence intensity of FT AA IA.
Specific embodiment
Embodiment 1 weighs 4 bromine, 1,8 naphthalene anhydride 10g (36.09mmol) in there-necked flask, adds 30mL ethanol, slowly
The mixed liquor of stirring, Deca N, 1,3 propane diamine 9.1mL (72.18mmol) of N dimethyl and 20mL ethanol, half an hour drip
Complete, while being slowly increased to reflux temperature, tracked with thin layer chromatography, until reaction terminates, cold filtration obtains yellow solid, second
Alcohol recrystallization, obtains target product (I).
Product (I) 5g (13.84mmol) of above-mentioned generation is weighed in there-necked flask, 20mL ethylene glycol monomethyl ether is added, is delayed
The mixed liquor of slow stirring, Deca n-butylamine 2.7mL (27.7mmol) and 10mL ethanol, while being slowly increased to 130 DEG C, uses thin layer
Chromatogram tracking, until reaction terminates, reduce pressure sucking filtration, removes excessive ethylene glycol monomethyl ether, and DMF recrystallization obtain purpose product
(II).
Product (II) 0.5g (1.415mmol) of above-mentioned generation is weighed in there-necked flask, 5mL DMF is added, is slowly stirred
Mix, the mixed liquor of Deca benzyl chloride 0.46mL (5.658mmol) and 5mL DMF, while be slowly increased to 110 DEG C, with thin layer chromatography with
Track, until reaction terminates, vacuum distillation removes excessive DMF, and cooling obtains crude product, with washing with acetone, and recrystallization, obtain
Arrive purpose product fluorescent monomer (FT).
The excitation wavelength and launch wavelength of the fluorescent monomer that synthesis is obtained is respectively 474nm and 554nm, sees accompanying drawing 1.Here
Under the conditions of, the fluorescent monomer has very strong fluorescence intensity, and its concentration and relative intensity of fluorescence are in good linear relationship, its
Linearly dependent coefficient can reach 0.998.Monitoring lower-cut is 4.5 × 10‐3mgL‐1.As a result see accompanying drawing 2.
Embodiment 2 is put into the deionization of 90mL in the four-hole boiling flask equipped with separatory funnel, thermometer and reflux condensing tube
Water, itaconic acid 46.8g (0.36mol), catalyst 0.0276g (0.1mmol), sodium hypophosphite 8.5g (0.08mol) and fluorescence
Monomer (FT) 0.04g, is warming up to backflow (100 DEG C) under agitation, leads to nitrogen deoxygenation, and under the protection of nitrogen, Deca is certain
Amount Ammonium persulfate. 10ml (0.684g Ammonium persulfate .s, account for monomer mass 1.3%), acrylic acid 5.76g (0.04mol) and Asia
Sodium bisulfate 23ml solution (4.16g accounts for the 8% of monomer mass), drips off in 3.5h, continuation insulation 1.5h, cooling discharging, i.e.,
Obtain product F T AA IA (brown liquid) of the invention
Embodiment 3 is put into the deionization of 80mL in the four-hole boiling flask equipped with separatory funnel, thermometer and reflux condensing tube
Water, itaconic acid 41.6g (0.32mol), catalyst 0.0276g (0.1mmol), sodium hypophosphite 8.5g (0.08mol) and fluorescence
Monomer (FT) 0.4g, is warming up to backflow (100 DEG C) under agitation, leads to nitrogen deoxygenation, and under the protection of nitrogen, Deca is a certain amount of
Ammonium persulfate. 20ml (0.75g Ammonium persulfate .s, account for monomer mass 1.5%), acrylic acid 8.64g (0.06mol) and sulfurous
Sour hydrogen sodium 23ml solution (5.0g accounts for the 10% of monomer mass), drips off in 3h, continues insulation 2h, and cooling discharging obtains final product this
Bright product F T AA IA (brown liquid)
The excitation wavelength of the polymer is similar to the wavelength of fluorescent monomer with launch wavelength, also respectively 474nm and 554nm
See accompanying drawing 3, that is, wavelength is not moved after being polymerized.Meanwhile, the concentration of polymer and relative intensity of fluorescence have good line
Sexual intercourse, linearly dependent coefficient are 0.9997.Monitoring lower-cut is 0.19mg L‐1.As a result see accompanying drawing 4.
Some conventional dirt dispersion agents such as ATMP (ATMP), HEDP (1 hydroxyl ethane, 1,1 di 2 ethylhexyl phosphonic acid),
Four kinds of medicaments such as HPMA (hydrolytic polymaleic anhydride), PAA (polyacrylic acid) are on its fluorescence intensity substantially without impact.As a result see accompanying drawing
5.
Embodiment 4 evaluates the corrosion inhibition of 2 fluorescent polymer of embodiment using rotary hanging plate method.Experimental condition is as follows：
Temperature：50℃；Material：(surface area is 12.6cm to A3 carbon steel standard test pieces2)；Medicament：The product of embodiment 2；Plus
Concentration：30mg·L‐1；Test period：72h；Test water is Nantong tap water, while doing the blank experiment of not adding medicine.Press
It is 71.29% that the method measures the medicament to the corrosion inhibition rate of carbon steel.
Embodiment 5 evaluates scale-inhibiting properties of the fluorescent polymer to Calcium Carbonate using static scale inhibition method.Experimental condition is as follows：
Temperature：80℃；Medicament：The product of embodiment 2；Adding consistency：Respectively 2,4,6,8,10,12,14,16mg L‐1；Test period：10h；Test configurations water：Ca2+250mg·L‐1, HCO3 ‐250mg·L‐1(with CaCO3Meter), cycles of concentration is
1.5 again；The blank experiment of not adding medicine is done simultaneously.The medicament is according to said method measured for 12mg L‐1To the scale inhibition performance of Calcium Carbonate it is
89.3%.As a result see accompanying drawing 6.
Claims (3)
1. a kind of fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer, is characterized in that：The Polymer Formulation is：
Wherein：M, n are 1～20 integer.
2. a kind of preparation method of the fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer described in claim 1, is characterized in that：
Comprise the following steps：
4 bromine N are obtained using 4 bromine, 1,8 naphthalic anhydride, ethanol and 1,3 propane diamine of N, N dimethyl for raw material reaction
(3 N ', N ' dimethylaminopropyl) 1,8 naphthalimides, then again with ethanol and ethylene glycol monomethyl ether as mixed solvent,
React with n-butylamine, obtain 4 fourth amino Ns (3 N ', N ' dimethylaminopropyl) naphthalimide, the product again with alkene
Propyl chloride reaction obtains the 4 fourth amino N of fluorescent monomer (3 N ', N ' dimethylaminopropyl) with fluorescent characteristic and double bond
Naphthalimide allyl ammonium chloride；Then water phase one-step synthesis are adopted by fluorescent monomer 4 fourth amino N (3 N ', N '
Dimethylaminopropyl) naphthalimide allyl ammonium chloride carries out copolymerization with sodium hypophosphite, itaconic acid, acrylic acid and obtains
Fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer.
3. the fluorescently-labeled phosphino- acrylic acid itaconic acid copolymer described in a kind of claim 1 is being prepared with fluorescent tracing work(
Can be with the application in inhibition, scale inhibition, the water treatment agent of divergent function.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611006490.1A CN106496415B (en) | 2016-11-16 | 2016-11-16 | Phosphino- acrylic acid itaconic acid copolymer of fluorescent marker and its preparation method and application |
| CN201810953024.7A CN109265607B (en) | 2016-11-16 | 2016-11-16 | Use of fluorescently labeled phosphino acrylic itaconic acid copolymers |
| CN201810952920.1A CN109265606B (en) | 2016-11-16 | 2016-11-16 | Fluorescently labeled phosphino acrylic itaconic acid copolymers |
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| CN201611006490.1A CN106496415B (en) | 2016-11-16 | 2016-11-16 | Phosphino- acrylic acid itaconic acid copolymer of fluorescent marker and its preparation method and application |
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| CN201810953024.7A Division CN109265607B (en) | 2016-11-16 | 2016-11-16 | Use of fluorescently labeled phosphino acrylic itaconic acid copolymers |
| CN201810952920.1A Division CN109265606B (en) | 2016-11-16 | 2016-11-16 | Fluorescently labeled phosphino acrylic itaconic acid copolymers |
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| CN201611006490.1A Active CN106496415B (en) | 2016-11-16 | 2016-11-16 | Phosphino- acrylic acid itaconic acid copolymer of fluorescent marker and its preparation method and application |
| CN201810953024.7A Active CN109265607B (en) | 2016-11-16 | 2016-11-16 | Use of fluorescently labeled phosphino acrylic itaconic acid copolymers |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109324025A (en) * | 2018-09-30 | 2019-02-12 | 毅康科技有限公司 | A kind of monitoring method of circulation sewerage disposing chemical content |
| CN110615542A (en) * | 2019-09-23 | 2019-12-27 | 沈阳防锈包装材料有限责任公司 | Fluorescent tracing type gas-liquid dual-phase corrosion and scale inhibitor and preparation method thereof |
| CN112867920A (en) * | 2019-05-28 | 2021-05-28 | 诺力昂化学品国际有限公司 | Method for controlling scale in water systems |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781857A (en) * | 2004-12-03 | 2006-06-07 | 南京理工大学 | Methoxy group naphthyl fluorescence marked water treating agent and its preparing method |
| CN100410287C (en) * | 2005-09-30 | 2008-08-13 | 南京理工大学 | Phosphine-based Marpropy multipolymer containing fluorescent base-group and its production |
| CN101381168B (en) * | 2008-07-04 | 2010-09-08 | 南通大学 | Fluorescence labeling acrylic acid-sodium acrylic sulphonate co-polymer water treatment agent and preparation method thereof |
| CN101475266A (en) * | 2009-01-09 | 2009-07-08 | 东南大学 | Fluorescent tracing scale inhibitor and preparation thereof |
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2016
- 2016-11-16 CN CN201810952920.1A patent/CN109265606B/en active Active
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109324025A (en) * | 2018-09-30 | 2019-02-12 | 毅康科技有限公司 | A kind of monitoring method of circulation sewerage disposing chemical content |
| CN109324025B (en) * | 2018-09-30 | 2021-07-27 | 毅康科技有限公司 | Method for monitoring water treatment agent content in circulating water system |
| CN112867920A (en) * | 2019-05-28 | 2021-05-28 | 诺力昂化学品国际有限公司 | Method for controlling scale in water systems |
| CN114206787A (en) * | 2019-05-28 | 2022-03-18 | 诺力昂化学品国际有限公司 | Method for controlling carbonate scale in water system |
| CN112867920B (en) * | 2019-05-28 | 2022-07-15 | 诺力昂化学品国际有限公司 | Method for controlling scale formation in water systems |
| CN110615542A (en) * | 2019-09-23 | 2019-12-27 | 沈阳防锈包装材料有限责任公司 | Fluorescent tracing type gas-liquid dual-phase corrosion and scale inhibitor and preparation method thereof |
| CN110615542B (en) * | 2019-09-23 | 2023-12-05 | 沈阳防锈包装材料有限责任公司 | Fluorescent tracing type gas-liquid double-phase corrosion and scale inhibitor and preparation method thereof |
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| CN109265606A (en) | 2019-01-25 |
| CN109265607A (en) | 2019-01-25 |
| CN109265607B (en) | 2020-09-15 |
| CN109265606B (en) | 2020-09-15 |
| CN106496415B (en) | 2018-10-12 |
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