CN102689992A - Terpolymer antisludging agent and preparation process thereof - Google Patents
Terpolymer antisludging agent and preparation process thereof Download PDFInfo
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- CN102689992A CN102689992A CN2012100406622A CN201210040662A CN102689992A CN 102689992 A CN102689992 A CN 102689992A CN 2012100406622 A CN2012100406622 A CN 2012100406622A CN 201210040662 A CN201210040662 A CN 201210040662A CN 102689992 A CN102689992 A CN 102689992A
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- scale inhibitors
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Abstract
The invention discloses a terpolymer antisludging agent which is formed by copolymerizing a mixed monomer consisting of three monomers, i.e. isopropenylancetylene phosphonic acid, acrylic acid and maleic anhydride by adopting a aqueous solution polymerization method; the number of the terpolymer antisludging agent is 5,000-20,000 relative to relative molecular weight; and based on 100 percent of the total sum of the three monomers, the mixed monomer comprises the following monomers in mass percentage: 3-7 percent of isopropenylancetylene phosphonic acid, 65-70 percent of acrylic acid and 25-30 percent of maleic anhydride. The terpolymer antisludging agent has the beneficial effects of good water solubility, high heat stability, low-phosphorous environment protection, good double effects of dispersion scale inhibition and slow release and the like. The invention also discloses a process for preparing the terpolymer antisludging agent, which is simple in preparation process and low in cost; and moreover, the process is stable and easy to control.
Description
Technical field
The present invention relates to the water conditioner preparing technical field, especially relate to a kind of terpolymer Scale inhibitors and preparation technology thereof.
Background technology
In industrial production, the consumption of recirculated cooling water is huge, and the cooling water system that industry is used is recycling in the process for a long time; Along with the increase of water coolant cycles of concentration, beginning such as mineral ion, mushroom enrichment will produce incrustation scale, rust deposite and corrosion inevitably; Making thermo-efficiency be the order of magnitude descends; Cause wasting mass energy, reduce the work-ing life of total system greatly, cause a lot of unnecessary loss; Therefore industrial circulating cooling water is carried out water treatment and become very important; In the industrial circulating cooling water treating processes, adopt mostly to add the method control fouling and the corrosion of throwing chemical agent, can prevent that incrustation scale and dirt from producing the chemical agent that perhaps suppresses its deposition growing and generally will all be referred to as Scale inhibitors.
Scale inhibitors form commonly used in industry mainly contains two kinds of inhibiter and dispersion agents, and inhibiter mainly contains following type: inorganic polymeric phosphate, organic multicomponent phosphoric acid; Glucono-and Weibull etc., present phosphorus line formulations that adopt in the circulating water system more, wherein the maximum of usefulness are the organic multicomponent phosphonic acids; For example HEDP (HDPE), ATMP (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP) etc., but because their molecular weight is low, functional group is less; Thereby influence its performance, in addition, contain a large amount of phosphorus in the organic multicomponent phosphonic acids; Can cause the eutrophication in waters on every side after the discharging, not meet environmental requirement.
Dispersion agent mainly be in, the water-soluble polymers of low relative molecular mass, comprise two big types of homopolymer and multipolymers, wherein homopolymer has ROHM and sodium salt, HPMA etc.; Homopolymer is because the limitation of its structure; The dispersing and antisludging ability is also limited, and the kind of multipolymer is then more, is main with two yuan of acrylic acid series and toxilic acid system or terpolymer; Though improved the dispersing and antisludging ability greatly, corrosion inhibition is relatively poor relatively.
For example, Chinese patent publication number CN101391194A openly day on March 25th, 2009, discloses a kind of have polymolecularity and stability, low terpolymer dispersants and preparation technology and the application that reaches environmental protection of preparation cost.Said terpolymer dispersants carries out free-radical polymerized forming by vinylformic acid, SSS, Propylene glycol monoacrylate or Rocryl 400; The number average relative molecular weight of terpolymer is 2000～40000, can be widely used in industries such as agricultural chemicals, pigment, dyestuff and coal water slurry.Its weak point is, though this terpolymer dispersants has improved its dispersing and antisludging performance, and corrosion inhibition is still relatively poor relatively.
Along with the develop rapidly of modern industry and improving constantly to environmental requirement; People to water technology require increasingly high; Synthesize new multipolymer through changing monomer or initiator; Thereby obtain high-efficiency environment friendly, good economy performance more, and to have multi-functional Scale inhibitorss such as dispersing and antisludging and inhibition be present both at home and abroad RESEARCH ON SCALE INHIBITOR direction.
Summary of the invention
The present invention is in order to overcome the above-mentioned deficiency of prior art; A kind of good water solubility, the high and low phosphorus environmental protection of thermostability are provided; And the terpolymer Scale inhibitors that has dispersion preferably and corrosion inhibition simultaneously, and a kind of preparation technology of said terpolymer Scale inhibitors.
To achieve these goals, the present invention adopts following technical scheme:
A kind of terpolymer Scale inhibitors of the present invention; The mix monomer that described terpolymer Scale inhibitors is made up of isopropylene and phosphonic acid, vinylformic acid, three kinds of monomers of maleic anhydride adopts the water solution polymerization process copolymerization to form; The number average relative molecular weight of described terpolymer Scale inhibitors is 5000～20000, and each monomeric mass percent is in the mix monomer:
Isopropylene and phosphonic acid: 3～7%;
Vinylformic acid: 65～70%;
Maleic anhydride: 25～30%;
Three's sum is 100%.
The isopropylene and phosphonic acid molecule has undersaturated carbon-to-carbon double bond and phosphonyl group, makes it very easily carry out polymerization with other monomers, and phosphonyl group has dispersing and antisludging performance and corrosion inhibition preferably; Can generate toxilic acid after maleic anhydride is water-soluble; Because the carboxylic acid quantity that contains of toxilic acid is more, carboxyl has stability and temperature tolerance preferably, so the terpolymer that has a large amount of carboxyls after the copolymerization has better water solubility and temperature tolerance; Can be used for the pyritous water conditioning, and carboxyl is to Ca
2+, Mg
2+Have stronger sequestering power, also have the dispersing and antisludging performance, therefore can improve the dispersing and antisludging performance of terpolymer; Therefore; The mix monomer that isopropylene and phosphonic acid, vinylformic acid, three kinds of monomers of maleic anhydride are formed adopts water solution polymerization process to carry out copolymerization, obtains a kind of terpolymer that has hydroxyl, carboxyl and the multiple hydrophilic radical of phosphonyl group simultaneously, and this terpolymer is good water solubility, thermostability height not only; But also the double effects of tool inhibition and dispersing and antisludging; In addition, the phosphorus content of this terpolymer itself is lower, and is very favourable to the protection environment; The size of molecular weight of copolymer is most important to the dispersive ability of Scale inhibitors, and number average relative molecular weight of the present invention is controlled at 5000～20000, has dispersion effect preferably.
A kind of preparation technology of above-mentioned terpolymer Scale inhibitors may further comprise the steps:
(1) chain-transfer agent is dissolved in obtains chain-transfer agent solution in the deionized water, while stirring heating.Chain-transfer agent is used to control the molecular weight of multipolymer, and the number average relative molecular weight that makes the terpolymer Scale inhibitors that makes is 5000～20000.
(2) initiator is mixed with mix monomer obtain reaction mixture.Initiator is used for trigger monomer and carries out polyreaction.
(3) when the resulting chain-transfer agent solution of step (1) is warming up to 75～90 ℃, under agitation splash into the resulting reaction mixture of step (2), insulation reaction 5～6h promptly obtains the terpolymer Scale inhibitors after being cooled to room temperature.Splash into initiator and mix monomer again after chain-transfer agent solution is warming up to 75～90 ℃; When being mixed, chain-transfer agent also make chain-transfer agent reach best temperature of reaction; And can after initiator and mix monomer splash into, can carry out polyreaction at once, and make reaction more abundant.
As preferably, described chain-transfer agent is a sodium sulfite anhy 96, and its consumption is 1～3% of a mix monomer total mass.
As preferably, the consumption of the described deionized water of step (1) is 100～110 times of sodium sulfite anhy 96 weight.
As preferably, described initiator is a Potassium Persulphate, and its consumption is 2～5% of a mix monomer total mass.
As preferably, the reaction mixture in the step (3) dropwises in 1～1.5h.Rate of addition is too fast, can cause polyreaction too violent, and the too fast meeting of rate of addition makes reaction insufficient, therefore controls reaction mixture and in 1～1.5h, dropwises, and can make copolyreaction comparatively steady, and reaction is comparatively abundant.
The invention provides and a kind ofly contain carboxyl, hydroxyl and phosphonyl group simultaneously, and the terpolymer Scale inhibitors of excellent performance, compared with prior art, beneficial effect of the present invention is:
(1) maleic anhydride can generate toxilic acid after water-soluble; Because the carboxylic acid quantity that toxilic acid contains is more; And carboxyl has stability and temperature tolerance preferably, and the terpolymer Scale inhibitors temperature tolerance of the present invention that is therefore aggregated into by maleic anhydride is good, can be used for the pyritous water conditioning;
(2) terpolymer Scale inhibitors of the present invention contains the multiple hydrophilic radical of hydroxyl, carboxyl and phosphonyl group, so good water solubility, and dispersing property is superior to general small molecules dispersion agent and homopolymer, and also has corrosion inhibition preferably simultaneously;
(3) the isopropylene and phosphonic acid phosphorus content is low, and the phosphorus content of the terpolymer Scale inhibitors of the present invention that therefore is polymerized by it is also lower, helps environmental protection.
The present invention also provides a kind of preparation technology of described terpolymer Scale inhibitors; In the aqueous solution through control the molecular weight ranges of formed multipolymer as chain-transfer agent with sodium sulfite anhy 96; Come trigger monomer to carry out polymerization through Potassium Persulphate as initiator; Make isopropylene and phosphonic acid, vinylformic acid, maleic anhydride be copolymerized into a kind of terpolymer that contains carboxyl, hydroxyl and phosphonyl group simultaneously; Aqueous solution copolymerization method not only preparation technology is simple, and is with low cost, and process stabilization is easy to control.
Embodiment
Below in conjunction with embodiment the explanation of further detailed complete is done in invention, in the present invention, if not refer in particular to, all equipment and raw material etc. all can be buied from market or the industry is commonly used, and all measuring methods are well-known to those skilled in the art.
Among the embodiment, the mensuration of the corrosion inhibition of terpolymer Scale inhibitors adopts the static corrosion weight loss method, reference standard SY/T5273-2000 " oil field extracted water is used the inhibiter method of evaluating performance ", and test condition is: temperature: 40 ℃; Test(ing) medium: 1mol/L HCl solution 2000ml; Soak time: 4 hours; Test sample: the test piece of A3 carbon steel, 50 * 25 * 2mm, parallel appearance is three parts.
The mensuration of the scale-inhibiting properties of terpolymer Scale inhibitors adopts the tosca method; Reference standard GB/T16632-2008 " mensuration of water conditioner scale-inhibiting properties-tosca method ", the water conditioner sample solution: 0.1mg terpolymer Scale inhibitors is formulated by adding in the 1ml water; Measure temperature and be respectively 60 ℃ and 80 ℃.
The number-average molecular weight of terpolymer Scale inhibitors adopts the Ubbelohde viscometer method to measure.
Embodiment 1
In being furnished with the four-hole boiling flask of magnetic stirring apparatus, add deionized water and sodium sulfite anhy 96; Potassium Persulphate is mixed the back to add in the tap funnel with isopropylene and phosphonic acid, vinylformic acid, three kinds of monomeric mix monomers of maleic anhydride; The add-on of each material is as shown in table 1, on four-hole boiling flask, inserts TM, reflux condensing tube and tap funnel again, when heating four-hole boiling flask to temperature while stirring and being 75 ℃; After initiator in the tap funnel and mix monomer dropwised in 1h; 75 ℃ of insulation reaction 5h then just obtain binary polymerization type Scale inhibitors after being cooled to room temperature, and using the Ubbelohde viscometer method to record its number-average molecular weight is 16800.
Gained binary polymerization type Scale inhibitors is carried out the mensuration of corrosion inhibition and dispersing and antisludging performance, measure the result respectively shown in table 2 and table 3.
Embodiment 2
In being furnished with the four-hole boiling flask of magnetic stirring apparatus, add deionized water and sodium sulfite anhy 96; Potassium Persulphate is mixed the back to add in the tap funnel with isopropylene and phosphonic acid, vinylformic acid, three kinds of monomeric mix monomers of maleic anhydride; The add-on of each material is as shown in table 1, on four-hole boiling flask, inserts TM, reflux condensing tube and tap funnel again, when heating four-hole boiling flask to temperature while stirring and being 90 ℃; After initiator in the tap funnel and mix monomer dropwised in 1h; 80 ℃ of insulation reaction 6h then just obtain binary polymerization type Scale inhibitors after being cooled to room temperature, and using the Ubbelohde viscometer method to record its number-average molecular weight is 13500.
Gained binary polymerization type Scale inhibitors is carried out the mensuration of corrosion inhibition and dispersing and antisludging performance, measure the result respectively shown in table 2 and table 3.
Embodiment 3
In being furnished with the four-hole boiling flask of magnetic stirring apparatus, add deionized water and sodium sulfite anhy 96; Potassium Persulphate is mixed the back to add in the tap funnel with isopropylene and phosphonic acid, vinylformic acid, three kinds of monomeric mix monomers of maleic anhydride; The add-on of each material is as shown in table 1, on four-hole boiling flask, inserts TM, reflux condensing tube and tap funnel again, when heating four-hole boiling flask to temperature while stirring and being 80 ℃; After initiator in the tap funnel and mix monomer dropwised in 1.5h; 90 ℃ of insulation reaction 5.5h then just obtain binary polymerization type Scale inhibitors after being cooled to room temperature, and using the Ubbelohde viscometer method to record its number-average molecular weight is 7800.
Gained binary polymerization type Scale inhibitors is carried out the mensuration of corrosion inhibition and dispersing and antisludging performance, measure the result respectively shown in table 2 and table 3.
Embodiment 4
In being furnished with the four-hole boiling flask of magnetic stirring apparatus, add deionized water and sodium sulfite anhy 96; Potassium Persulphate is mixed the back to add in the tap funnel with isopropylene and phosphonic acid, vinylformic acid, three kinds of monomeric mix monomers of maleic anhydride; The add-on of each material is as shown in table 1, on four-hole boiling flask, inserts TM, reflux condensing tube and tap funnel again, when heating four-hole boiling flask to temperature while stirring and being 75 ℃; After initiator in the tap funnel and mix monomer dropwised in 1.2h; 79 ℃ of insulation reaction 5h then just obtain binary polymerization type Scale inhibitors after being cooled to room temperature, and using the Ubbelohde viscometer method to record its number-average molecular weight is 10500.
Gained binary polymerization type Scale inhibitors is carried out the mensuration of corrosion inhibition and dispersing and antisludging performance, measure the result respectively shown in table 2 and table 3.
The add-on proportioning table of each material among table 1 embodiment
Each embodiment corrosion inhibition of Fig. 2 is measured the result
Each embodiment dispersing and antisludging performance measurement result of Fig. 3
From table 2 and table 3, can obviously find out; The terpolymer Scale inhibitors that the present invention makes not only has better water solubility; And, also have corrosion inhibition preferably keeping its good dispersing and antisludging performance simultaneously, reached the double effects of inhibition and dispersing and antisludging.
Claims (6)
1. terpolymer Scale inhibitors; It is characterized in that; The mix monomer that described terpolymer Scale inhibitors is made up of isopropylene and phosphonic acid, vinylformic acid, three kinds of monomers of maleic anhydride adopts the water solution polymerization process copolymerization to form; The number average relative molecular weight of described terpolymer Scale inhibitors is 5000～20000, and each monomeric mass percent is in the mix monomer:
Isopropylene and phosphonic acid: 3 ~ 7%;
Vinylformic acid: 65 ~ 70%;
Maleic anhydride: 25 ~ 30%;
Three's sum is 100%.
2. the preparation technology of a terpolymer Scale inhibitors as claimed in claim 1 is characterized in that, described preparation technology may further comprise the steps:
Chain-transfer agent is dissolved in obtains chain-transfer agent solution in the deionized water, heating while stirring;
Initiator mixed with mix monomer obtain reaction mixture;
When the resulting chain-transfer agent solution of step (1) is warming up to 75 ~ 90 ℃, under agitation splash into the resulting reaction mixture of step (2), insulation reaction 5 ~ 6h promptly gets the terpolymer Scale inhibitors after being cooled to room temperature.
3. the preparation technology of terpolymer Scale inhibitors according to claim 2 is characterized in that, described chain-transfer agent is a sodium sulfite anhy 96, and its consumption is 1 ~ 3% of a mix monomer total mass.
4. the preparation technology of terpolymer corrosion inhibiting and descaling agent according to claim 3 is characterized in that, the consumption of the described deionized water of step (1) is 100 ~ 110 times of sodium sulfite anhy 96 weight.
5. the preparation technology of terpolymer Scale inhibitors according to claim 2 is characterized in that, described initiator is a Potassium Persulphate, and its consumption is 2 ~ 5% of a mix monomer total mass.
6. the preparation technology of terpolymer Scale inhibitors according to claim 2 is characterized in that, the reaction mixture in the step (3) dropwises in 1 ~ 1.5h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708633A (en) * | 2013-12-03 | 2014-04-09 | 山东省泰和水处理有限公司 | Novel polymer water treatment reagent and synthesis method thereof |
| CN103803722A (en) * | 2012-11-15 | 2014-05-21 | 中国石油化工股份有限公司 | Non-phosphorus copolymer antiscale dispersant and preparation method thereof |
| CN104031259A (en) * | 2014-06-12 | 2014-09-10 | 南京师范大学 | Multiple-carboxyl terpolymer as well as preparation method and application thereof |
| CN106084127A (en) * | 2016-08-08 | 2016-11-09 | 安徽炎胜新材料科技有限公司 | A kind of preparation method softening the quadripolymer removed for hard scale |
| CN106565903A (en) * | 2016-11-14 | 2017-04-19 | 武汉宜田科技发展有限公司 | Preparation method of novel scale-inhibiting terpolymer used in strongly acidic environment |
| CN106591847A (en) * | 2016-11-14 | 2017-04-26 | 武汉宜田科技发展有限公司 | Anti-deposition agent for wet-process phosphate filtering system pipeline |
| CN106630199A (en) * | 2016-11-24 | 2017-05-10 | 辽宁石油化工大学 | Preparation method of environment-friendly oilfield reinjection water terpolymer scale inhibitor |
| CN113717313A (en) * | 2021-08-02 | 2021-11-30 | 佳化化学（茂名）有限公司 | Carboxylic acid copolymer and preparation method and application thereof |
| CN114426339A (en) * | 2021-12-30 | 2022-05-03 | 中国石油化工股份有限公司 | Oil field barium sulfate dispersion scale inhibitor and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103803722A (en) * | 2012-11-15 | 2014-05-21 | 中国石油化工股份有限公司 | Non-phosphorus copolymer antiscale dispersant and preparation method thereof |
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| CN103708633A (en) * | 2013-12-03 | 2014-04-09 | 山东省泰和水处理有限公司 | Novel polymer water treatment reagent and synthesis method thereof |
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| CN106591847A (en) * | 2016-11-14 | 2017-04-26 | 武汉宜田科技发展有限公司 | Anti-deposition agent for wet-process phosphate filtering system pipeline |
| CN106591847B (en) * | 2016-11-14 | 2019-06-18 | 武汉宜田科技发展有限公司 | A kind of phosphoric acid by wet process filtration system pipeline anti-deposition agent |
| CN106630199A (en) * | 2016-11-24 | 2017-05-10 | 辽宁石油化工大学 | Preparation method of environment-friendly oilfield reinjection water terpolymer scale inhibitor |
| CN113717313A (en) * | 2021-08-02 | 2021-11-30 | 佳化化学（茂名）有限公司 | Carboxylic acid copolymer and preparation method and application thereof |
| CN114426339A (en) * | 2021-12-30 | 2022-05-03 | 中国石油化工股份有限公司 | Oil field barium sulfate dispersion scale inhibitor and preparation method thereof |
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Application publication date: 20120926 |