CN103804591B - A kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof - Google Patents
A kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof Download PDFInfo
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Abstract
Invention relates to a kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof, this dirt dispersion agent is by the allyl sulphonic acid of 10 ~ 20wt%, and the acrylate of 10 ~ 20wt% and 60 ~ 80wt% maleic acid and/or itaconic acid cause one-step polymerization to form by inorganic peroxide in aqueous. The preparation method that this method also discloses this copolymer anti-scale disperser, by copolymer anti-scale disperser prepared by the method, its molecular structure comprises multiple functional group simultaneously, less add concentration time both had and hindered calcium carbonate scale preferably, resistance calcium phosphate scale and the performance stablizing zinc salt, the dispersive property of ferrum oxide is also better. This copolymer anti-scale disperser preparation method is simple, and cost is low, and dosage is few, and antiscaling dispersion is effective, and not phosphorous, and environmental protection can be widely used in industrial circulating cooling water system, has higher economic benefit and social benefit.<!--1-->
Description
Technical field
The present invention relates to circulating water cooling treatment field, be more particularly to a kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof.
Background technology
Along with sharply increasing of industrial scale and population, water resource is seriously deficient. Circulating cooling water consumption accounts for the 60 ~ 70% of water for industrial use, rationally saves the most direct way that recirculated cooling water is reduction industrial water consumption. The main method saving recirculated cooling water is to improve the cyclic utilization rate of recirculated cooling water, had both strengthened cycles of concentration, but this can bring serious corrosion and scale problems again to circulation, and water treatment technology is had higher requirement. In order to ensure circulation under the conditions such as high rigidity, high Cl-concentration, high organic concentration properly functioning, water treatment agent seems extremely crucial.
Dirt dispersion agent is common circulating water treatment water quality stabilizer, especially polycarboxylic acid salt's dirt dispersion agent, it can make to cause dirt salt in water and not deposit on the metal surface, can stop again particle aggregation sedimentation in water simultaneously, and maintain its suspended state, play scale inhibition, scattered double effects.
The domestic patent about polycarboxylic acid salt's dirt dispersion agent is a lot, such as CN01123146 " low-molecular-weight (methyl) acrylic acid (salt) based polymer and its production and use ", CN94117281.3 " poly-carboxylic salt water treatment agent and its production and use " etc., but along with industrial circulating cooling water processes continually developing of technique, complexity and the polytropy of circulation situation are deepened gradually, and the adaptability of water treatment agent is had higher requirement. Meanwhile, the kind of water treatment agent gets more and more, and sometimes one circulation routine to add 5 to 8 kinds of medicaments, substantially increases the expense of circulating water treatment, has also increased the weight of the complicated property of circulating water treatment.And multiple-quality water stabilizer adds the mutual conflict effect that easily produces, and reduces drug effect, gets half the result with twice the effort simultaneously. Additionally, the disclosed dirt dispersion agent majority delivered and apply is phosphorous, and this type of dirt dispersion agent enters into circulation can provide, for the antibacterial in water and algae, the nutrition enriched, it is easy to be decomposed, and the difficulty of circulation sterilization algae removal can be strengthened, affect circulation stable operation.
Summary of the invention
It is an object of the invention to provide a kind of Phosphate-free copolymer dirt dispersion agent, this copolymer anti-scale disperser has and hinders calcium carbonate scale, resistance calcium phosphate scale preferably and stablize the performance of zinc salt, and the dispersive property of ferrum oxide is also better. When adding concentration equally, antiscaling dispersion effect is better than existing conventional dirt dispersion agent.
The preparation method of a kind of Phosphate-free copolymer dirt dispersion agent, comprises the steps of
1) preparation of reagents:
Itaconic acid and/or maleic acid and inorganic reducing agent are dissolved in water, forms reagent I; Inorganic oxidizer is dissolved in water, form reagent II; Allyl sulphonic acid and acrylate are dissolved in water, forms reagent III;
2) polyreaction
Reagent II and reagent III is added in the reagent I that temperature is 75 ~ 85 DEG C,
Mixeding liquid temperature is risen to 85 ~ 95 DEG C, is incubated 1 ~ 5h;
Wherein,
In described polyreaction, the addition of reactant is:
Allyl sulphonic acid 10 ~ 20wt%;
Acrylate 10 ~ 20wt%;
Itaconic acid and/or maleic acid 60 ~ 80wt%;
Described inorganic reducing agent addition is the 8 ~ 14% of allyl sulphonic acid, acrylate and itaconic acid and/or maleic acid gross mass;
Described inorganic oxidizer addition is the 8 ~ 14% of allyl sulphonic acid, acrylate and itaconic acid and/or maleic acid gross mass;
3) product is cooled down, obtain described Phosphate-free copolymer dirt dispersion agent.
The total time that reagent II and reagent III add controls to be 1 ~ 3h.
Described acrylate is at least one in acrylic acid methyl ester., ethyl acrylate, 2-methyl methacrylate and ethyl 2-methacrylate.
Described inorganic reducing agent is pyrosulfite or sulphite, it is preferred to sodium pyrosulfite or potassium metabisulfite, sodium sulfite or potassium sulfite.
Described inorganic oxidizer is persulfate, it is preferred to Ammonium persulfate., sodium peroxydisulfate or potassium peroxydisulfate.
A kind of Phosphate-free copolymer dirt dispersion agent, the molecular weight ranges of described Phosphate-free copolymer dirt dispersion agent is 3500 ~ 6500; Contain carboxyl, sulfonic acid group, its compositing monomer and ratio in molecular structure is simultaneously:
Allyl sulphonic acid, mass percent is 10 ~ 20%;
Acrylate, mass percent is 10 ~ 20%;
Itaconic acid and/or maleic acid, mass percent is 60 ~ 80%.
Acrylate at least one in acrylic acid methyl ester., ethyl acrylate, 2-methyl methacrylate and ethyl 2-methacrylate.
The using dosage of this Phosphate-free copolymer dirt dispersion agent is calculated as 4 ~ 30mg/L with valid density, and when adding concentration equally, antiscaling dispersion effect is better than existing conventional commercially available dirt dispersion agent.
Itaconic acid formal name used at school is methene succinic acid, methylene-succinic acid, is unsaturated binary organic acid. Its intramolecule contains two active carboxyls and a double bond, and double bond and carboxyl are conjugate relation so that the character in itaconic acid is very active, can with other monomer polymerizations different number of, carry out various additive reaction, esterification and polyreaction, be the important source material of chemosynthesis industry;Maleic acid is maleic acid, is simple unsaturated dicarboxylic acid, it is easy to be copolymerized with other unsaturated carboxylic acid and alkene class material; Acrylate is common polymerization single polymerization monomer, and its outstanding feature is that weatherability is superior, can improve polymer containing acrylate and meet the character that the degraded of light heat turns yellow in polymer monomers; Allyl sulphonic acid is unsaturated sulfonic acid, its can make copolymerization after product there is sulfonic acid group.
Beneficial effect
The present invention uses multiple aggregation technology by the bonding monomeis of more different functional groups to polymer molecule, the polymer that this preparation method obtains is because comprising multiple functional group simultaneously in its molecular structure, make it have more excellent performance, and application wider, stable in properties, have than other commercial copolymer dirt dispersion agents when adding concentration equally and hinder calcium carbonate scale preferably, hinder calcium phosphate scale and stablize the performance of zinc salt, the dispersive property of ferrum oxide is also better. This copolymer anti-scale disperser preparation method is simple, and cost is low, and dosage is few, and antiscaling dispersion is effective, and not phosphorous, and environmental protection can be widely used in industrial circulating cooling water system, has higher economic benefit and social benefit.
Detailed description of the invention
The following examples will assist in the explanation present invention, but does not limit to its scope.
Test raw water quality is in Table 1.
The Reliable Evaluating Methods of Their Performance of copolymer is as follows:
Resistance calcium carbonate scale performance takes the former water of test, and by the Ca in former water2+��HCO3 -Mend 800mg/L (with CaCO3Meter) form test water, add copolymer anti-scale disperser so that it is valid density reaches 20mg/L, in 80 �� 1 DEG C of water bath with thermostatic control inside holding 10h, sample analysis water remains after cooling Ca2+Concentration, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance computing formula is: scale inhibition performance=(C-C0)/(C1-C0)��100%
C: actual measurement Ca2+Concentration
C0: the Ca of blank sample2+Concentration
C1: the Ca in former water2+Concentration
Resistance calcium phosphate scale performance takes the former water of test, and by the Ca in former water2+��HCO3 -Mend 600mg/L (with CaCO3Meter), PO4 3-Mend 5mg/L (with PO4Meter) form test water, add copolymer anti-scale disperser so that it is valid density reaches 12mg/L, in 80 �� 1 DEG C of water bath with thermostatic control inside holding 10h, remains positive phosphorus content after cooling in sample analysis water, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance computing formula is: scale inhibition performance=(C-C0)/(C1-C0)��100%
C: survey positive phosphorus content
C0: the positive phosphorus content of blank sample
C1: the positive phosphorus content in former water
Resistance zinc dirt performance takes the former water of test, and by the Ca in former water2+��HCO3 -Mend 600mg/L (with CaCO3Meter), Zn2+Mend 5mg/L (in Zn) and form test water, add copolymer anti-scale disperser so that it is valid density reaches 12mg/L, in 80 �� 1 DEG C of water bath with thermostatic control inside holding 10h, sample analysis water remains after cooling zinc ion content, makees blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance computing formula is: scale inhibition performance=(C-C0)/(C1-C0)��100%
C: actual measurement zinc ion content
C0: the zinc ion content of blank sample
C1: the zinc ion content in former water
Resistance ferrum dirt performance takes the former water of test, and by the Ca in former water2+��HCO3 -Mend 600mg/L (with CaCO3Meter), total ferrum mend 5mg/L (in Fe) formed test water, add copolymer anti-scale disperser, its valid density is made to reach 12mg/L, in 80 �� 1 DEG C of water bath with thermostatic control inside holding 10h, sample analysis water remains after cooling iron ion content, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance computing formula is: scale inhibition performance=(C-C0)/(C1-C0)��100%
C: actual measurement total iron content
C0: the total iron content of blank sample
C1: the total iron content in former water
Analysis method:
The computational methods valid density of valid density=commodity concentration �� solid content.
Ca2+ method for measurement of concentration is with reference to the assay method of Ca2+ concentration in " boiler feed water and cooling water analysis method " GB6905.3-86; PO43-method for measurement of concentration is with reference to the assay method of PO43-concentration in " water quality phosphorus yield molybdate spectrophotography " ISO6878/1; Zn2+ method for measurement of concentration is with reference to Zn in " the cooling water analysis of middle petrochemical industry and test method " Q/SH3155.S08.004-20062+The assay method of concentration; Total iron determination method is with reference to the assay method of total concentration of iron in " the cooling water analysis of middle petrochemical industry and test method " Q/SH3155.S08.005-2006. The assay method of solid content is with reference to the assay method of solid matter in " boiler feed water and cooling water analysis method " GB/T14415-93.
Water quality tested by table 1
| Title | Ca2+ | Total alkalinity | Cl- | SO4 2- | pH | Positive phosphorus | Zn2+ | Total ferrum | SiO2 |
| Recycled water | 284 | 247 | 208 | 270 | 8.13 | 0.39 | 0.14 | 0.52 | 69 |
Note: pH is without unit, and its counit is mg/L, Ca2+, total alkalinity, total hardness is all with CaCO3Meter, positive phosphorus is with PO4Meter, Zn2+In Zn, total ferrum is in Fe, lower same.
Embodiment 1
Weighing itaconic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, acrylic acid methyl ester. 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, acrylic acid methyl ester. mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 5000, and the scale-inhibiting properties of product is in Table 2.
Embodiment 2
Weighing itaconic acid 80g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 10g, ethyl acrylate 10g, be dissolved in 60ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, ethyl acrylate mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 39.1%, and molecular weight is 5250, and the scale-inhibiting properties of product is in Table 2.
Embodiment 3
Weighing maleic acid 60g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 20g, 2-methyl methacrylate 20g, be dissolved in 80ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, 2-methyl methacrylate mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 36.7%, and molecular weight is 4700, and the scale-inhibiting properties of product is in Table 2.
Embodiment 4
Weighing maleic acid 72g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer;Weigh Ammonium persulfate. 11g, be dissolved in 60ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 11g, 17g in ethyl 2-methacrylate, it is dissolved in 70ml water, mix homogeneously, adds constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips mixed solution in ammonium persulfate solution and allyl sulphonic acid, ethyl 2-methacrylate; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 35.7%, and molecular weight is 4750, and the scale-inhibiting properties of product is in Table 2.
Embodiment 5
Weighing itaconic acid 68g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 60ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 19g, acrylic acid methyl ester. 13g, be dissolved in 80ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, acrylic acid methyl ester. mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 34.7%, and molecular weight is 5050, and the scale-inhibiting properties of product is in Table 2.
Embodiment 6
Weighing itaconic acid 72g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 50ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 17g, ethyl acrylate 11g, be dissolved in 100ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, ethyl acrylate mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 33.7%, and molecular weight is 5150, and the scale-inhibiting properties of product is in Table 2.
Embodiment 7
Weighing maleic acid 68g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 13g, 2-methyl methacrylate 19g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, 2-methyl methacrylate mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 4750, and the scale-inhibiting properties of product is in Table 2.
Embodiment 8
Weighing maleic acid 70g, sulfinic acid sodium 8g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh sodium peroxydisulfate 8g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, ethyl 2-methacrylate 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, ethyl 2-methacrylate mixed solution; Control dropping for 2h;Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.1%, and molecular weight is 4800, and the scale-inhibiting properties of product is in Table 2.
Embodiment 9
Weighing itaconic acid 70g, sulfinic acid potassium 14g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh potassium peroxydisulfate 14g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, acrylic acid methyl ester. 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, acrylic acid methyl ester. mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 38.7%, and molecular weight is 4800, and the scale-inhibiting properties of product is in Table 2.
Embodiment 10
Weighing itaconic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, ethyl acrylate 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 75 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, ethyl acrylate mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 5200, and the scale-inhibiting properties of product is in Table 2.
Embodiment 11
Weighing maleic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, 2-methyl methacrylate 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 85 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, 2-methyl methacrylate mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 4650, and the scale-inhibiting properties of product is in Table 2.
Embodiment 12
Weighing maleic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, ethyl 2-methacrylate 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, ethyl 2-methacrylate mixed solution; Control dropping for 1h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 4650, and the scale-inhibiting properties of product is in Table 2.
Embodiment 13
Weighing itaconic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I;Weigh allyl sulphonic acid 15g, acrylic acid methyl ester. 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, acrylic acid methyl ester. mixed solution; Control dropping for 3h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 5000, and the scale-inhibiting properties of product is in Table 2.
Embodiment 14
Weighing itaconic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, ethyl acrylate 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, ethyl acrylate mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 85 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 5300, and the scale-inhibiting properties of product is in Table 2.
Embodiment 15
Weighing maleic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, acrylic acid methyl ester. 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, acrylic acid methyl ester. mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 95 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 4400, and the scale-inhibiting properties of product is in Table 2.
Embodiment 16
Weighing maleic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, ethyl acrylate 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, ethyl acrylate mixed solution; Control dropping for 2h; Dropwise, be incubated 1h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 4500, and the scale-inhibiting properties of product is in Table 2.
Embodiment 17
Weighing itaconic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, acrylic acid methyl ester. 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, acrylic acid methyl ester. mixed solution; Control dropping for 2h; Dropwise, be incubated 5h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 5050, and the scale-inhibiting properties of product is in Table 2.
Embodiment 18
Weighing itaconic acid 35g, maleic acid 35g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, acrylic acid methyl ester. 15g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, acrylic acid methyl ester. mixed solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 4800, and the scale-inhibiting properties of product is in Table 2.
Embodiment 19
Weighing itaconic acid 70g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, acrylic acid methyl ester. 8g, ethyl acrylate 7g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, crylic acid ester mixture solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 5050, and the scale-inhibiting properties of product is in Table 2.
Embodiment 20
Weighing itaconic acid 50g, maleic acid 20g, burnt sulfinic acid sodium 11g, measure 90ml water, stirring makes it dissolve, and is equipped with in the four-hole boiling flask of agitator, reflux condenser, constant pressure funnel and thermometer; Weigh Ammonium persulfate. 11g, be dissolved in 40ml water, add constant pressure funnel I; Weigh allyl sulphonic acid 15g, acrylic acid methyl ester. 5g, ethyl acrylate 10g, be dissolved in 70ml water, mix homogeneously, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 80 DEG C, drips ammonium persulfate solution and allyl sulphonic acid, crylic acid ester mixture solution; Control dropping for 2h; Dropwise, be incubated 3h in 90 DEG C; Cool down to obtain product. The solid content of gained copolymer anti-scale disperser is 37.9%, and molecular weight is 4950, and the scale-inhibiting properties of product is in Table 2.
Comparative example 1
Acrylic acid/allyl sulphonic acid copolymer, purchased from Shouguang, Shandong company of Song Chuan commercial auxiliaries company limited, trade mark AA-SAS.
Comparative example 2
Acrylic acid/Hydroxypropyl acrylate copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark T225.
Embodiment and the comparative example scale-inhibiting properties in test water is in Table 2.
The scale-inhibiting properties of table 2 embodiment and comparative example
Above example and comparative example illustrate, the copolymer anti-scale disperser of the present invention has the resistance CaCO of excellence3Dirt, Ca3(PO4)2Dirt, stablize zinc salt and stablize the performance of ferrum oxide.
Claims (7)
1. a preparation method for Phosphate-free copolymer dirt dispersion agent, comprises the steps of
1) preparation of reagents:
Itaconic acid and/or maleic acid and inorganic reducing agent are dissolved in water, forms reagent I; Inorganic oxidizer is dissolved in water, form reagent II; Allyl sulphonic acid and acrylate are dissolved in water, forms reagent III;
2) polyreaction
Adding reagent II and reagent III in the reagent I that temperature is 75��85 DEG C, the total time of reagent II and reagent III addition controls to be 1��3h;
Mixeding liquid temperature is risen to 85��95 DEG C, is incubated 1��5h;
Wherein,
In described polyreaction, the addition of reactant is:
Allyl sulphonic acid 10��20wt%;
Acrylate 10��20wt%;
Itaconic acid and/or maleic acid 60��80wt%;
Inorganic reducing agent addition is the 8��14% of allyl sulphonic acid, acrylate and itaconic acid and/or maleic acid gross mass;
Inorganic oxidizer addition is the 8��14% of allyl sulphonic acid, acrylate and itaconic acid and/or maleic acid gross mass;
3) product is cooled down, obtain described Phosphate-free copolymer dirt dispersion agent;
The molecular weight ranges of described Phosphate-free copolymer dirt dispersion agent is 4400��6500.
2. the preparation method of Phosphate-free copolymer dirt dispersion agent as claimed in claim 1, it is characterised in that described acrylate is at least one in acrylic acid methyl ester., ethyl acrylate, 2-methyl methacrylate and ethyl 2-methacrylate.
3. the preparation method of Phosphate-free copolymer dirt dispersion agent as claimed in claim 1, it is characterised in that described inorganic reducing agent is pyrosulfite or sulphite.
4. the preparation method of Phosphate-free copolymer dirt dispersion agent as claimed in claim 3, it is characterised in that described inorganic reducing agent is sodium pyrosulfite, potassium metabisulfite, sodium sulfite or potassium sulfite.
5. the preparation method of Phosphate-free copolymer dirt dispersion agent as claimed in claim 1, it is characterised in that described inorganic oxidizer is persulfate.
6. the preparation method of Phosphate-free copolymer dirt dispersion agent as claimed in claim 5, it is characterised in that described inorganic oxidizer is Ammonium persulfate., sodium peroxydisulfate or potassium peroxydisulfate.
7. the Phosphate-free copolymer dirt dispersion agent that the preparation method as described in any one in claim 1��6 prepares, contain carboxyl, sulfonic acid group, its compositing monomer and ratio in the molecular structure of described Phosphate-free copolymer dirt dispersion agent is simultaneously:
Allyl sulphonic acid 10��20wt%;
Acrylate 10��20wt%;
Itaconic acid and/or maleic acid 60��80wt%.
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| CN102674568A (en) * | 2012-06-13 | 2012-09-19 | 威海翔宇环保科技有限公司 | Phosphate-free copolymer dirt dispersion agent and preparation method thereof |
| CN102730847A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | Non-phosphorus composite anti- incrustation corrosion inhibiter and its application in water treatment |
| CN102745823A (en) * | 2011-04-19 | 2012-10-24 | 南京林业大学 | Quadripolymer-type corrosion-inhibition scale inhibitor PMAHS and preparation method thereof |
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| CN102730847A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | Non-phosphorus composite anti- incrustation corrosion inhibiter and its application in water treatment |
| CN102745823A (en) * | 2011-04-19 | 2012-10-24 | 南京林业大学 | Quadripolymer-type corrosion-inhibition scale inhibitor PMAHS and preparation method thereof |
| CN102674568A (en) * | 2012-06-13 | 2012-09-19 | 威海翔宇环保科技有限公司 | Phosphate-free copolymer dirt dispersion agent and preparation method thereof |
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