CN1050586C - Phosphinic sulfoacid carboxylic acid multicomponent copolymer and its synthetic method - Google Patents
Phosphinic sulfoacid carboxylic acid multicomponent copolymer and its synthetic method Download PDFInfo
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- CN1050586C CN1050586C CN 95108860 CN95108860A CN1050586C CN 1050586 C CN1050586 C CN 1050586C CN 95108860 CN95108860 CN 95108860 CN 95108860 A CN95108860 A CN 95108860A CN 1050586 C CN1050586 C CN 1050586C
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Abstract
The present invention discloses a phosphinic sulfoacid carboxylic acid multicomponent copolymer and a synthetic method thereof, which relates to a treatment medicament of industrial water and the manufacturing technology thereof, and commonly has the functions of scale prevention and corrosion inhibition. Acrylic monomer solution, sulfonic acid monomer solution, hydroxyalkyl ester monomer solution, and peroxide solution of an initiator are dropped into phosphinic water solution; at the reflux temperature of 60DEG C, thermal insulation is carried out for 20 to 180 minutes for copolymerisation and synthesis. The method makes synthesis reaction easily controlled. The copolymer can be used for the treatment and the seawater desalination of cooling water, boiler water and oil-field water.
Description
The present invention relates to Treatment of Industrial Water pharmaceutical products and manufacturing technology thereof, exactly, relate to a kind of novel texture multipolymer and synthetic method thereof that has scale inhibition and certain corrosion inhibition concurrently; Be phosphinic sulfoacid carboxylic acid multicomponent copolymer and synthetic method thereof.
European patent EP 0118970, U.S. Pat 4127483 and US4159946, all having introduced with vinylformic acid or vinylformic acid-hydroxyalkyl acrylate is monomer, with Hypophosporous Acid, 50 or Hypophosporous Acid, 50 sodium salt is phosphating synthetic phosphine polymers of carboxylic acid, it has the good scale inhibition and dispersion performance of polycarboxylic acid compound and the corrosion inhibition of phosphorous organic inhibitor concurrently, to Ca
+ 2Have high tolerance, and the silicon-dioxide in the water, earth are played dissemination, can stop the formation of salt crust such as calcium, magnesium, barium, iron, zinc, strontium effectively, the metallic conduit that contacts with water is had certain corrosion inhibition.
The phosphine polymers of carboxylic acid of above-mentioned patent introduction has the structure of following general formula:
In the formula: Z is H or metal ion.
In the formula: R is H or the straight or branched alkane that contains 1-18 carbon atom.
R ' is OX, and X is a metal ion.
R " be H or-CH
3,-CH
2CH
5
N is an integer.
The phosphine homopolymer of carboxylic acid of above-mentioned patent introduction and multipolymer are that hydroxyalkyl acrylate is a monomer with vinylformic acid or methyl (ethyl) vinylformic acid, with phospho acid or its salt be phosphating through polymerization or copolymerization, and phosphineization and synthesizing simultaneously.
The shortcoming of above-mentioned patent synthetic method is that whole initiator-benzoyl peroxides are put into reaction flask, and rapidly mix monomer was added in the reactor in 10 minutes, thereby make polyreaction comparatively fierceness be difficult to control, make molecular weight distribution be difficult for homogeneous simultaneously.And another patent is a solvent with the organism dioxane, and the polymerization process cycle is long, and dioxane is poisonous and inflammable.European patent EP 0118970 is to be solvent with water, but is initiator with water-fast benzoyl peroxide, and compatibility is poor, thereby initiator can not be given full play to its initiation.
In addition, the scale inhibition and dispersion performance of the phosphine polymers of carboxylic acid of above-mentioned formula I, formula II structural formula is still not ideal enough, and under multiple metal salt crust coexistence situation, how influenced scale inhibition effect is.
Purpose of the present invention, be to propose a kind of new water treatment agent-phosphinic sulfoacid carboxylic acid multipolymer and synthetic method thereof that has scale inhibition and certain corrosion inhibition concurrently with novel texture, when multiple metal salt crust coexists, can guarantee scale inhibition effect, in addition, synthesis technique is simple and reliable, is easy to control.
Phosphinic sulfoacid carboxylic acid multicomponent copolymer of the present invention has the novel texture that following formula (III) is expressed:
In the formula: R
1For
Or HR
2, R
4Be H or CH
3R
3Be hydroxyethyl (C
2H
4OH) or hydroxypropyl (C
3H
6OH); R
5Be methylene radical (CH
2-), or phenyl
Or 2-amide group-2-methyl-propyl group
Or for O (be main chain directly with-SO
3Z links to each other)
Z is hydrogen (H) or sodium ion;
M, n, l is positive integer, and m is 27-100, and n is 3-10, and l is 4-10.
This multiple copolymer is that molecular weight is 3000-10000, and molecular weight distribution is 1.0-1.25.
The synthetic method of phosphinic sulfoacid carboxylic acid multicomponent copolymer of the present invention is to be solvent with water, with the superoxide is initiator, to contain carboxyl, hydroxyalkyl base and sulfonic compound is monomer, with Hypophosporous Acid, 50 (or its sodium salt) is phosphating, under conditions such as certain temperature, through polymerization and phosphine reaction and obtain phosphinic sulfoacid carboxylic acid multicomponent copolymer.
Its building-up process comprises:
Phosphating is made into the aqueous solution that weight percent is 4-18%, be warmed up to 60 ℃-105 ℃, while dropwise addition of acrylic acid class, sulfonic acid class, hydroxyalkyl ester three major types monomer solution and peroxide initiator solution, dropping temperature remains on 60 ℃-105 ℃, and constantly stir, after all raw materials dropwise,, kept 20-180 minute at 100 ℃-105 ℃.Cooling discharging then.
The monomeric proportion of composing of multipolymer three major types is:
Acrylic monomer is called monomer 1, accounts for the weight percent 50-85% of monomer total amount;
The hydroxyalkyl ester monomer is called monomer 2, accounts for the weight percent 5-30% of monomer total amount;
Sulfonic acid class monomer is called monomer 3, accounts for the weight percent 5-30% of monomer total amount.
According to method of the present invention, monomer solution and initiator solution are added drop-wise to simultaneously and carry out copolymerization and phosphineization in the phosphating aqueous solution; Be that copolymerization and phosphineization are once finished simultaneously.Owing to be to drip initiator, it is also easy to control that reaction process is relaxed.
Multipolymer phosphine structure is generated by the phosphating reaction.Phosphating comprises Hypophosporous Acid, 50, sodium hypophosphite.The phosphating consumption is the 3%-20% of monomer total amount.Contain acrylic acid monomer, comprise vinylformic acid, methacrylic acid.Contain the hydroxyalkyl ester monomer, comprise Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate and Rocryl 410.Contain sulfonic acid class monomer, comprise vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid etc.
Initiator is selected ammonium persulphate, Sodium Persulfate, Potassium Persulphate for use, or the mixture of they and hydrogen peroxide, and its consumption is the 5-25% of monomer total amount.
Phosphinic sulfoacid carboxylic acid multipolymer of the present invention, be in molecular chain, to introduce carboxyl, sulfonic group, hydroxyalkyl base and four kinds of organo-functional groups of phosphino-, it is not only a kind of multipolymer of novel texture, has more outstanding scale inhibition and dispersion performance and good inhibition synergism performance.Multipolymer of the present invention has sedimental ability in the multiple water of dispersion.For example except that common salt crust such as lime carbonate, calcium phosphate, calcium sulfate are had the good dissemination, depositions such as the ironic hydroxide in the disperse water system, zinc hydroxide well, and under multiple salt crust coexistence situation, still have good scale inhibition dispersion effect.In addition, multipolymer of the present invention has certain corrosion inhibition or inhibition synergism.Copolymer sheet of the present invention has revealed potion multi-purpose outstanding feature, and simultaneous test shows that it comprehensively disperses scale-inhibiting properties to be better than the performance of commercially available similar improved seeds.Moreover, multipolymer of the present invention can with composite uses such as inorganic phosphate, organophosphate, azole, zinc salt, molybdate, its scale inhibitor synergy significantly can be widely used in the cooling water system of each branch of industry, and feedwater, oil-field water or sea water desalinization etc. is located.
Further specify the present invention in conjunction with following embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
In that being housed, reflux exchanger, agitator, temperature take into account in the many mouthfuls of bottles that drip pipe, add 7 gram sodium hypophosphites, 10 gram sodium allyl sulfonates and 82 gram water, when being warming up to 95 ℃ under stirring, begin to drip the monomer solution of 75 gram vinylformic acid, 5 gram sodium allyl sulfonates, 15 gram Propylene glycol monoacrylates and 154 gram water and the initiator solution of forming by 6 gram ammonium persulphates and 49.5 gram water, dripped about 1.5 hours, drip the back and under reflux temperature, be incubated 1 hour, cool, obtain yellow solution, yield is 99%, and solid content is 30%, relative viscosity 1.044.
Embodiment 2
Device is with example 1, in many mouthfuls of bottles, add 7 gram sodium hypophosphites, 10 gram sodium allyl sulfonates and 82 gram water begin to drip 75 gram methacrylic acids when under agitation being warming up to 95 ℃, 5 gram sodium allyl sulfonates, the monomer solution of 15 gram Hydroxyethyl acrylates and 154 gram water and the initiator solution of forming by 10.5 gram ammonium persulphates and 49.5 gram water, dripped about 1.5 hours, and dripped the back reflux temperature and be incubated 1 hour down, cool, obtain the yellow solution product, yield 99%.
Embodiment 3
Device is with example 1, in many mouthfuls of bottles, add 7 gram Hypophosporous Acid, 50,20 gram sodium allyl sulfonates and 82 gram water, begin Dropwise 50 gram vinylformic acid when under agitation being warming up to 75 ℃, 10 gram sodium allyl sulfonates, the monomer solution of 20 gram Propylene glycol monoacrylates and 154 gram water and the initiator solution of forming by 10.5 gram ammonium persulphates and 49.5 gram water, dripped about 1.5 hours, drip back insulation 3 hours, obtain the yellow solution product, yield 99%.
Embodiment 4
Device is with example 1, in many mouthfuls of bottles, add 7 gram potassium hypophosphites, 5 gram sodium allyl sulfonates and 82 gram water, begin to drip 85 gram vinylformic acid when under agitation being warming up to 60 ℃, 5 gram allyl sulphonic acids, the monomer solution of 5 gram Rocryl 410s and 154 gram water and the initiator solution of forming by 10.5 gram Sodium Persulfates and 49.5 gram water, dripped about 3 hours, drip back insulation 30 minutes, obtain the yellow solution product, yield 99%.
Embodiment 5
Device is with example 1, in many mouthfuls of bottles, add 7 gram sodium hypophosphites, 20 gram vinyl sulfonic acid sodium and 82 gram water begin Dropwise 50 gram vinylformic acid, 5 gram vinyl sulfonic acid when under agitation being warming up to 100 ℃, the monomer solution of 25 gram hydroxyethyl methylacrylates and 102.8 gram water and the initiator solution of forming by 34% hydrogen peroxide, 10.8 grams, 4.3 gram Potassium Persulphates and 89.9 gram water, dripped about 2 hours, and dripped back insulation 1 hour, cool, obtain the yellow solution product, yield 99%.
Embodiment 6
Device is with example 1, and except the Sodium styrene sulfonate with equivalent replaces the sodium allyl sulfonate of example 1, other condition obtains the yellow solution product, yield 99% with example 1.
Embodiment 7
Device is with example 1, and except the 2-acrylamido-2-methyl-propyl sulfonic acid sodium with equivalent replaces the sodium allyl sulfonate of example 1, other condition obtains the yellow solution product, yield 99% with example 1.
Embodiment 8
Device is with example 1, and except replacing 7 of example 1 to restrain the sodium hypophosphites with 4 gram sodium hypophosphites, other condition obtains the yellow solution product, yield 99% with example 1.
Embodiment 9
Device is with example 1, and except replacing 7 of example 1 to restrain the sodium hypophosphites with 20 gram sodium hypophosphites, other condition obtains the yellow solution product, yield 99% with example 1.
Embodiment 10
Device is with example 1, and except the 6 gram ammonium persulphates that replace example 1 with 10.5 ammonium persulphates, other condition obtains the yellow solution product, yield 99% with example 1.
Embodiment 11
Device is with example 1, and except 10.5 ammonium persulphates with 2.5 gram ammonium persulphates replacement examples 1, other condition obtains the yellow solution product, yield 99% with example 1.
Embodiment 12
Scale inhibition and dispersion performance test condition and result
Test conditions:
(1) lime carbonate scale inhibition performance test condition
Ca
2+(with CaCO
3Meter) 600ppm, PH=9,80 ℃, 6 hours, polymkeric substance add-on 4ppm;
(2) calcium phosphate scale inhibition performance test condition
Ca
2+(with CaCo
3Meter) 250ppm, PO
4 3-6ppm, PH=9,80 ℃, 6 hours, polymkeric substance add-on: 4ppm;
(3) iron dirt test condition:
Fe
2+: 9ppm, PH=9,80 ℃, 6 hours, polymkeric substance add-on 2ppm;
(4) zinc dirt test condition: Zn
2+7.8ppm, PH=9,80 ℃, 6 hours, polymkeric substance add-on: 4ppm.
Test result
Commercially available terpolymer: No1 vinylformic acid/hydroxyethyl methylacrylate/methyl methacrylate No2 acrylic acid/sodium allyl sulfonate
| The sample title | Scale inhibition performance (%) | |||
| Lime carbonate | Calcium phosphate | The iron dirt | The zinc dirt | |
| Example 10 | 72 | 60 | 63 | 88 |
| Example 2 | 69 | 56 | 66 | / |
| Commercially available terpolymer No1 | 66 | 48 | 58 | 86 |
| Commercially available terpolymer No2 | 64 | 40 | 60 | / |
Claims (7)
1. phosphinic sulfoacid carboxylic acid multicomponent copolymer is characterized in that having following structure:
In the formula: R
1For
Or HR
2, R
4Be H or methyl, R
3Be hydroxyethyl (C
2H
4OH) or hydroxypropyl (C
3H
6OH), R
5Be methylene radical (CH
2-) or phenyl [
], or 2-amide group-2-methyl-propyl group
Or for O (be main chain directly with-SO
3Z links to each other)
Z is H or sodium Metal 99.5 ion,
M, n, l are positive integer, and wherein, m is 27-100, and n is 3-10, and 1 is 4-10;
The molecular weight of this multiple copolymer is 3000-10000, and molecular weight distribution is 1.0-1.25.
2. synthetic method of the phosphinic sulfoacid carboxylic acid multicomponent copolymer of structure according to claim 1, it is characterized in that three kinds of monomer acrylic acid or the like, hydroxyalkyl ester, sulfonic acid class solution and peroxide initiator solution, be added drop-wise to simultaneously and carry out copolymerization and phosphineization in the phosphating aqueous solution, its building-up process comprises: phosphating is made into the aqueous solution that weight percent is 4-18%, while dropwise addition of acrylic acid class under agitation condition, hydroxyalkyl ester, three kinds of monomer solutions of sulfonic acid class and peroxide initiator solution, dropping temperature is 60 ℃-105 ℃, it is 50-85% that the proportion of composing of three kinds of polymer monomers is respectively the weight percent that (1) acrylic acid or the like accounts for the monomer total amount, (2) to account for the weight percent of monomer total amount be 5-30% to hydroxyalkyl ester, (3) to account for the weight percent of monomer total amount be 5-30% to the sulfonic acid class, after all raw materials dropwise, under 100 ℃-105 ℃, kept 20-180 minute, then cooling discharging.
3. according to the described synthetic method of claim 2, it is further characterized in that described acrylic monomer, hydroxyalkyl ester monomer and sulfonic acid class monomer are respectively:
(1) acrylic monomer: comprise vinylformic acid, or methacrylic acid,
(2) hydroxyalkyl ester monomer: comprise Hydroxyethyl acrylate, or Propylene glycol monoacrylate, or hydroxyethyl methylacrylate or Rocryl 410,
(3) sulfonic acid class monomer: comprise vinyl sulfonic acid, or allyl sulphonic acid, or styrene sulfonic acid, or 2-acrylamido-2-methyl-propyl sulfonic acid, or the sodium salt of its above-mentioned sulfonic acid.
4. according to the described synthetic method of claim 2, what it was further characterized in that described phosphating is Hypophosporous Acid, 50 or sodium hypophosphite.
5. according to the described synthetic method of claim 2, it is further characterized in that the add-on of phosphating Hypophosporous Acid, 50 or sodium hypophosphite is that the weight percent of monomer total amount is 3-20%.
6. according to the described synthetic method of claim 2, it is further characterized in that the composition that adds peroxide initiator is an ammonium persulphate, or Sodium Persulfate, or Potassium Persulphate, or the mixture of hydrogen peroxide superoxide above-mentioned with it, its consumption is that the weight percent of monomer total amount is 5-25%.
7. according to the described synthetic method of claim 2, it is further characterized in that the scope of synthesis reaction temperature is 75 ℃-105 ℃, and it is 40-120 minute that building-up reactions solution dropwises back hold-time scope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95108860 CN1050586C (en) | 1995-08-30 | 1995-08-30 | Phosphinic sulfoacid carboxylic acid multicomponent copolymer and its synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95108860 CN1050586C (en) | 1995-08-30 | 1995-08-30 | Phosphinic sulfoacid carboxylic acid multicomponent copolymer and its synthetic method |
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| Publication Number | Publication Date |
|---|---|
| CN1144197A CN1144197A (en) | 1997-03-05 |
| CN1050586C true CN1050586C (en) | 2000-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95108860 Expired - Fee Related CN1050586C (en) | 1995-08-30 | 1995-08-30 | Phosphinic sulfoacid carboxylic acid multicomponent copolymer and its synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2180004B1 (en) * | 2008-10-22 | 2011-05-18 | Clariant Finance (BVI) Limited | Olefinically unsaturated phosphonate compounds, polymers made therefrom and their use |
| CN102198982B (en) * | 2010-03-26 | 2013-03-27 | 中国石油天然气股份有限公司 | Scale and corrosion inhibitor for circulating cooling water |
| CN106868512B (en) * | 2016-12-22 | 2019-03-19 | 德蓝水技术股份有限公司 | A kind of high temperature resistant acidification corrosion inhibitor and preparation method thereof |
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1995
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