A tetra-arm star polymer containing a polyoxyethylene structure, and a preparation method, composition, and application thereof

Abstract

This invention discloses a four-armed star-shaped polymer containing a polyoxyethylene structure, its preparation method, composition, and applications. The polymer is prepared by mixing an unsaturated organic carboxylic acid compound, an unsaturated sulfonic acid compound, and water, stirring to obtain a reaction solution, and continuously stirring and heating the reaction solution. An aqueous solution of a polyether macromonomer compound and the initiator aqueous solution are added to the heated reaction solution, followed by polymerization and purification. The polymer structure contains a large number of carboxyl groups, sulfonic acid groups, and ether groups, as well as abundant polyoxyethylene groups and alkyl chains, giving the polymer good water solubility and excellent chelating properties for metal ions. The polymer prepared by this method shows good effects in cleaning, defoaming, and scale inhibition. Furthermore, compositions formed by combining the polymer with other corrosion and scale inhibitors exhibit good compatibility and can be used for scale inhibition in high-hardness water.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and in particular to a four-armed star-shaped polymer containing a polyoxyethylene structure, its preparation method, composition, and application. Background Technology

[0002] Inorganic salt scaling is one of the major challenges faced by many industrial water systems (such as circulating cooling water systems, membrane treatment devices, and oil and gas field water reinjection systems) during actual operation. The resulting reduced pipeline efficiency and under-scale corrosion pose a huge economic burden and safety risks to production enterprises.

[0003] To address this issue, adding chemical scale inhibitors has become a common practice. Chemical scale inhibitors can effectively inhibit the nucleation and growth of scale (calcium carbonate, calcium sulfate, etc.), thereby delaying or preventing the adhesion of scale to metal surfaces.

[0004] Generally, chemical scale inhibitors are divided into traditional phosphorus-based scale inhibitors and newer phosphorus-free scale inhibitors. Phosphorus-based scale inhibitors, such as hydroxyethylidene diphosphonic acid (HEDP) and 2-phospho-1,2,4-tricarboxylic acid butane (PBTCA), are widely used due to their excellent scale inhibition and corrosion inhibition properties. However, with increasingly stringent environmental policies, phosphorus-free water systems in various industries have become an inevitable trend and requirement. In recent years, phosphorus-free chemical systems have also developed rapidly, and currently, carboxylic acid polymers, represented by polyepoxysuccinic acid and polyaspartic acid, are widely used.

[0005] CN 110040857 A discloses a phosphorus-free green corrosion and scale inhibitor and its preparation method. The scale inhibitor comprises, by weight, 30-40 parts of polyepoxysuccinic acid, 10-20 parts of sodium gluconate, 10-15 parts of water-soluble polymaleic anhydride, 15-20 parts of lignin sulfonate, 10-15 parts of sodium polyacrylate, and 20-25 parts of water. In this corrosion and scale inhibitor, polyepoxysuccinic acid has both scale inhibition and corrosion inhibition effects. Combined with water-soluble polymaleic anhydride and sodium polyacrylate, it forms a scale inhibitor that inhibits the growth of metal ions in water. Sodium gluconate acts as a water quality stabilizer. The sulfonate ions of sodium lignin sulfonate enrich the types of scale-inhibiting functional groups and compensate for the solubility limitation effect of polyepoxysuccinic acid, thereby improving the overall scale and corrosion inhibition capacity of the scale inhibitor. This corrosion and scale inhibitor has good anti-corrosion and scale inhibition performance for circulating cooling water pipes, but the proportion of polyepoxysuccinic acid and sodium gluconate in the formula is very high, which increases the production cost. In actual use, it needs to be diluted by a large proportion.

[0006] Overall, the types and quantities of available phosphorus-free scale inhibitor systems remain limited, and their functions are often singular. Furthermore, certain shortcomings persist in practical applications, such as low calcium tolerance, unsatisfactory performance at high temperatures, and poor compatibility with certain water qualities. Therefore, there is an urgent need to prepare structurally stable polymers with multiple scale-inhibiting functional groups to expand the raw material selection for phosphorus-free scale inhibition systems and improve their performance. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention provides a four-armed star-shaped polymer containing a polyoxyethylene structure, its preparation method, composition, and application. The polymer exhibits excellent dispersibility and scale inhibition properties, high calcium tolerance, and adaptability to higher temperatures. It also possesses cleaning and defoaming functions, is biodegradable, and is an environmentally friendly, multifunctional, phosphorus-free scale inhibitor. Further compounding with other components yields corrosion and scale inhibitor products that demonstrate even better corrosion and scale inhibition effects, suitable for both low-hardness, low-alkalinity and high-hardness, high-alkalinity water qualities.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] One aspect of the present invention provides a four-armed star-shaped polymer containing a polyoxyethylene structure, the structure of which is shown in Formula I or Formula II:

[0010]

[0011]

[0012] Where a, b, c and d represent the degree of polymerization of the polyoxyethylene unit, and a+b+c+d=4~30;

[0013] Where x1, x2, x3, and x4 are The degree of aggregation of the units, x1, x2, x3 and x4, are each independently 1 to 2000;

[0014] Among them, y1, y2, y3 and y4 are or The degree of aggregation of the units, y1, y2, y3 and y4, are each independently between 1 and 2000;

[0015] Where R1 and R2 are defined by the following general formulas:

[0016] R1 = H or -CH3 or -(CH2) m COOH

[0017] R2 = H or -COOH

[0018] m = 1 to 10;

[0019] Wherein, R3 and R4 are defined by the following general formulas:

[0020] R3 = H or -CH3 or -(CH2) m COOH

[0021] R4 = H or -COOH

[0022] m = 1 to 10;

[0023] Wherein, R5 is the following general formula:

[0024]

[0025] n = 1 to 10;

[0026] Wherein, R6 is the following general formula:

[0027] R6 = H or -CH3.

[0028] Another aspect of the present invention provides a method for preparing the above-mentioned four-armed star-shaped polymer containing a polyoxyethylene structure, the method comprising:

[0029] Monomer preparation: Pentaerythritol ethoxy compound and unsaturated organic carboxylic acid compound were mixed under stirring, heated and stirred continuously to prepare unsaturated carboxylic acid modified polyether macromonomer compound;

[0030] Polymerization reaction: The unsaturated carboxylic acid-modified polyether macromonomer compound is dissolved in water to prepare an aqueous solution of the polyether macromonomer compound, and the initiator is dissolved in water to prepare an aqueous solution of the initiator; the unsaturated organic carboxylic acid compound, the unsaturated sulfonic acid compound and water are mixed and stirred to obtain a reaction solution, the reaction solution is continuously stirred and heated, and the aqueous solution of the polyether macromonomer compound and the aqueous solution of the initiator are added to the heated reaction solution; after the addition is completed, the temperature is raised again and the reaction is continuously stirred to prepare an aqueous solution of a four-armed star-shaped polymer containing a polyoxyethylene structure;

[0031] Product collection: The aqueous solution of the polymer was purified and separated to obtain a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0032] Furthermore, the structure of the pentaerythritol ethoxylate compound is as follows:

[0033]

[0034] Where a, b, c and d represent the degree of polymerization of the polyoxyethylene unit, and a+b+c+d=4~30;

[0035] The structural formula of the unsaturated organic carboxylic acid compound used in the monomer preparation is:

[0036]

[0037] Where R1 and R2 are defined by the following general formulas:

[0038] R1 = H or -CH3 or -(CH2) m COOH

[0039] R2 = H or -COOH

[0040] m = 1 to 10;

[0041] The structural formula of the unsaturated organic carboxylic acid compound in the polymerization reaction is:

[0042]

[0043] Wherein, R3 and R4 are defined by the following general formulas:

[0044] R3 = H or -CH3 or -(CH2) m COOH

[0045] R4 = H or -COOH

[0046] m = 1 to 10;

[0047] The unsaturated sulfonic acid compound is an unsaturated sulfonic acid or an unsaturated sulfonate, and its structure is as follows:

[0048] H₂C=CH-R₅-SO₃Na(H)

[0049] Wherein, R5 is the following general formula:

[0050] or or

[0051] n = 1 to 10;

[0052] Wherein, R6 is the following general formula:

[0053] R6 = H or -CH3.

[0054] Furthermore, in the preparation of the monomer, the molar ratio of pentaerythritol ethoxy compound to unsaturated organic carboxylic acid compound is 1:1 to 5;

[0055] The stirring rate is 20–2000 rpm, and the mixing time is 0.5–2 h.

[0056] The heating temperature is 60-80℃, and the reaction time is 1-5 hours with continuous stirring.

[0057] Furthermore, the monomer preparation is carried out under anhydrous and nitrogen-protected conditions;

[0058] The purification and separation process in the product collection is as follows:

[0059] Acetone was added to the aqueous solution of the polymer, and the insoluble matter was collected, washed, and dried.

[0060] Furthermore, in the polymerization reaction, the mass ratio of the polyether macromonomer compound, the unsaturated organic carboxylic acid compound, and the unsaturated sulfonic acid compound is (1):(4-8000):(4-8000);

[0061] The sum of the initial concentrations of the aqueous solution of the polyether macromonomer compound, the unsaturated organic carboxylic acid compound in the reaction solution, and the unsaturated sulfonate in the reaction solution is 5–40 wt.%.

[0062] The initiator is 1-3% of the total mass of the polyether macromonomer compound, the unsaturated organic carboxylic acid compound, and the unsaturated sulfonic acid compound.

[0063] The stirring speed is 20–2000 rpm;

[0064] The heating temperature is 65–75°C;

[0065] The reheating temperature is 75–95°C, and the continuous stirring reaction time is 1–5 hours.

[0066] Furthermore, in the polymerization reaction, the aqueous solution of the polyether macromonomer compound and the aqueous solution of the initiator are added simultaneously to the heated reaction solution, and the addition is completed in 0.5 to 2 hours.

[0067] Furthermore, the initiator in the polymerization reaction is at least one of ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyronitrile, tert-butyl peroxide, and diacyl peroxide.

[0068] The present invention also provides a four-armed star-shaped polymer composition containing a polyoxyethylene structure, the composition comprising the above-described polymer or the polymer prepared by the above-described preparation method, and a corrosion and scale inhibitor.

[0069] Furthermore, the corrosion and scale inhibitor comprises:

[0070] Polyepoxysuccinic acid and / or polyepoxysuccinate, sodium gluconate, inorganic zinc salts and citric acid.

[0071] Furthermore, the composition also includes water.

[0072] The composition was prepared in 100 parts by weight, and the formulations of each component were as follows:

[0073] 0.1–15 parts of a four-armed star-shaped polymer containing a polyoxyethylene structure;

[0074] 0.1 to 10 parts of polyepoxysuccinic acid and / or polyepoxysuccinate;

[0075] Sodium gluconate 0.1–5 parts;

[0076] Inorganic zinc salt 0.1–5 parts;

[0077] Citric acid 0.1–5 parts;

[0078] Water is the remainder.

[0079] Furthermore, the inorganic zinc salt is at least one of zinc sulfate, zinc chloride, and zinc nitrate.

[0080] The present invention also provides several applications of the above-described polymer, the polymer obtained by the above-described preparation method, and the above-described composition.

[0081] The application of the above-described polymer and the polymer prepared by the above-described method in cleaning.

[0082] The application of the above-described polymer and the polymer prepared by the above-described method in defoaming.

[0083] Application of the above-described polymer and the polymer prepared by the above-described method in scale inhibition.

[0084] An application of the above composition in corrosion and scale inhibition.

[0085] The advantages of this invention compared to the prior art are as follows:

[0086] (1) This invention provides a novel four-armed star-shaped polymer with a polyoxyethylene structure and its preparation method. The polymer is rich in phosphorus-free compounds containing carboxylic acid groups and sulfonic acid groups. It is prepared from inexpensive, readily available, non-toxic and harmless raw materials. The polymer has excellent dispersibility and scale inhibition properties, high calcium tolerance, and can adapt to higher temperatures. It also has cleaning and defoaming functions, is biodegradable, and can be used as an environmentally friendly multifunctional phosphorus-free scale inhibitor.

[0087] (2) The four-armed star-shaped polymer with polyoxyethylene structure prepared in this invention is combined with polyepoxysuccinic acid, sodium gluconate, inorganic zinc salt and citric acid. The composition can effectively reduce the amount of other corrosion inhibitors in the composition without affecting the treatment effect, thus achieving the effect of reducing costs. The polymer, sodium gluconate, inorganic zinc salt and citric acid in the composition work together to enhance the corrosion and scale inhibition effect and reduce the cost of raw materials. Attached Figure Description

[0088] Figure 1 The structural formula of the four-armed star-shaped polymer containing a polyoxyethylene structure in this invention is I;

[0089] Figure 2 The structural formula of the four-armed star-shaped polymer containing a polyoxyethylene structure in this invention is II;

[0090] Figure 3 The nuclear magnetic resonance spectrum of the four-armed star polymer containing a polyoxyethylene structure prepared in Example 1 of this invention;

[0091] Figure 4 The structural formula of the four-armed star-shaped polymer containing a polyoxyethylene structure determined in Example 1 of the present invention is shown. Detailed Implementation

[0092] In a first aspect, the present invention provides a four-armed star-shaped polymer containing a polyoxyethylene structure. This polymer is a phosphorus-free compound rich in carboxylic acid and sulfonic acid groups, prepared from inexpensive, readily available, non-toxic, and harmless raw materials. The structural formula of the four-armed star-shaped polymer containing the polyoxyethylene structure is as follows: Figure 1 Equation I shown, or as... Figure 2 Equation II as shown:

[0093] Where a, b, c and d represent the degree of polymerization of the polyoxyethylene unit, and a+b+c+d=4~30;

[0094] Where x1, x2, x3, and x4 are The degree of aggregation of the units, x1, x2, x3 and x4, are each independently 1 to 2000;

[0095] Among them, y1, y2, y3 and y4 are or The degree of aggregation of the units, y1, y2, y3 and y4, are each independently between 1 and 2000;

[0096] Where R1 and R2 are defined by the following general formulas:

[0097] R1 = H or -CH3 or -(CH2) m COOH

[0098] R2 = H or -COOH

[0099] m = 1 to 10;

[0100] Wherein, R3 and R4 are defined by the following general formulas:

[0101] R3 = H or -CH3 or -(CH2) m COOH

[0102] R4 = H or -COOH

[0103] m = 1 to 10;

[0104] Wherein, R5 is the following general formula:

[0105] or or

[0106] n = 1 to 10;

[0107] Wherein, R6 is the following general formula:

[0108] R6 = H or -CH3.

[0109] The structural formula reveals a large number of polar groups, including carboxyl, sulfonic acid, and ether groups, indicating excellent dispersibility in aqueous solutions and strong chelating properties for metal ions. It also shows great potential for dispersing calcium carbonate, calcium phosphate, and zinc scale. This structure allows the four-armed star-shaped polymer containing a polyoxyethylene structure to function not only as a standalone corrosion and scale inhibitor, but its excellent dispersibility in aqueous solutions also enables it to be compounded with other agents possessing corrosion and scale inhibition properties.

[0110] A second aspect of the present invention provides a method for preparing a four-armed star-shaped polymer containing a polyoxyethylene structure, the method comprising:

[0111] Monomer preparation: Pentaerythritol ethoxy compound and unsaturated organic carboxylic acid compound were mixed under stirring, heated and stirred continuously to prepare unsaturated carboxylic acid modified polyether macromonomer compound;

[0112] Polymerization reaction: The unsaturated carboxylic acid-modified polyether macromonomer compound is dissolved in water to prepare an aqueous solution of the polyether macromonomer compound, and the initiator is dissolved in water to prepare an aqueous solution of the initiator; the unsaturated organic carboxylic acid compound, the unsaturated sulfonic acid compound and water are mixed and stirred to obtain a reaction solution, the reaction solution is continuously stirred and heated, and the aqueous solution of the polyether macromonomer compound and the aqueous solution of the initiator are added to the heated reaction solution; after the addition is completed, the temperature is raised again and the reaction is continuously stirred to prepare an aqueous solution of a four-armed star-shaped polymer containing a polyoxyethylene structure;

[0113] Product collection: The aqueous solution of the polymer was purified and separated to obtain a four-armed star-shaped polymer containing a polyoxyethylene structure;

[0114] The unsaturated sulfonic acid compound is an unsaturated sulfonic acid or an unsaturated sulfonate.

[0115] It should be noted that the proportions of the monomers and the amount of initiator added during the polymerization reaction can be adjusted according to actual needs. Polymers with different unit ratios can usually be synthesized by adjusting the monomer ratios, while the control of the initiator amount and the polymerization reaction time can be used to synthesize four-armed star polymers containing polyoxyethylene structures with different degrees of polymerization (molecular weight).

[0116] In a third aspect of the invention, the prepared four-armed star-shaped polymer containing a polyoxyethylene structure is used for corrosion and scale inhibition in calcium-containing water bodies.

[0117] A fourth aspect of the invention provides several applications of the prepared four-armed star-shaped polymer containing a polyoxyethylene structure: applying the polymer to inhibit scale in calcium-containing water; compounding the polymer with a corrosion and scale inhibitor to obtain a corrosion and scale inhibitor composition and applying it to inhibit corrosion and scale in calcium-containing water; applying the polymer to cleaning; and applying the polymer to defoaming.

[0118] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments and accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0119] Unless otherwise specified, in the embodiments of the present invention, the reaction between pentaerythritol ethoxylate and unsaturated carboxylic acids (maleic acid, itaconic acid, fumaric acid, and acrylic acid) is a complete reaction, that is, pentaerythritol ethoxylate is completely converted into unsaturated carboxylic acid-modified polyether macromonomer compounds, which can be used for subsequent reactions or operations without any treatment. Although in the embodiments of the present invention only zinc sulfate is used as the inorganic zinc salt, the inorganic zinc salt can be at least one of zinc sulfate, zinc chloride, and zinc nitrate.

[0120] Example 1

[0121] A four-armed star-shaped polymer containing a polyoxyethylene structure is prepared by the following method:

[0122] Weigh out 0.05 mol of pentaerythritol ethoxylate. 0.24 mol of maleic acid was placed in a flask and mixed at 300 rpm for 1 h under anhydrous and nitrogen protection conditions at 25 °C. The mixture was then heated to 70 °C and stirred continuously for 3 h to obtain an unsaturated carboxylic acid modified polyether macromonomer compound.

[0123] At 25°C, 0.05 mol of the unsaturated carboxylic acid-modified polyether macromonomer compound was mixed with 1500 g of deionized water and stirred at 1400 rpm for 0.2 h to prepare a 24.6 wt.% aqueous solution of the unsaturated carboxylic acid-modified polyether macromonomer compound (concentration 4.1 wt.%). The solution was then transferred to a constant pressure dropping funnel. Potassium persulfate was mixed with 50 g of deionized water and stirred at 300 rpm for 0.2 h. The resulting potassium persulfate aqueous solution was then transferred to another constant pressure dropping funnel.

[0124] At 25°C, 0.4 mol of itaconic acid and 0.4 mol of 2-acrylamide-2-methylpropanesulfonic acid were weighed and mixed with 1500 g of deionized water. The mixture was then transferred to a flask and stirred at 600 rpm for 0.5 h. The temperature was then raised to 70°C to obtain a reaction solution (itaconic acid concentration was 3.5 wt.%, and 2-acrylamide-2-methylpropanesulfonic acid concentration was 5.5 wt.%). An aqueous solution of unsaturated carboxylic acid-modified polyether macromonomer and an aqueous solution of potassium persulfate were added to the reaction solution over 1 h through two constant-pressure dropping funnels. After the addition was complete, the temperature was raised again to 80°C and the reaction was stirred continuously for 2 h. Heating and stirring were stopped, and the mixture was cooled to 25°C to obtain an aqueous solution of a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0125] Acetone was added to the aqueous solution of the polymer, the insoluble matter was collected by filtration, and the polymer was dried in a constant temperature oven at 60°C for 12 hours to obtain a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0126] The mass of potassium persulfate is 2% of the total mass of the unsaturated carboxylic acid-modified polyether macromonomer compound, itaconic acid, and 2-acrylamide-2-methylpropanesulfonic acid.

[0127] Figure 3 This is the NMR spectrum of the four-armed star-shaped polymer containing a polyoxyethylene structure in this embodiment. According to... Figure 3 The characterization results determined the structural formula of the four-armed star-shaped polymer containing a polyoxyethylene structure, such as... Figure 4 As shown, this result demonstrates the successful preparation of a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0128] Example 2

[0129] A four-armed star-shaped polymer containing a polyoxyethylene structure is prepared by the following method:

[0130] Weigh out 0.05 mol of pentaerythritol ethoxylate. 0.2 mol of itaconic acid was placed in a flask and mixed at 300 rpm for 1 h under anhydrous and nitrogen protection conditions at 25 °C. The mixture was then heated to 70 °C and stirred continuously for 3 h to obtain an unsaturated carboxylic acid modified polyether macromonomer compound.

[0131] At 25°C, 0.05 mol of the unsaturated carboxylic acid-modified polyether macromonomer compound was mixed with 1000 g of deionized water and stirred at 1500 rpm for 0.2 h. The resulting aqueous solution of the unsaturated carboxylic acid-modified polyether macromonomer compound (concentration 7.3 wt.%) was transferred to a constant pressure dropping funnel. Tert-butyl peroxide was mixed with 50 g of deionized water and stirred at 500 rpm for 0.2 h. The resulting aqueous solution of tert-butyl peroxide was transferred to another constant pressure dropping funnel.

[0132] At 25°C, 0.4 mol of itaconic acid and 1.2 mol of sodium methacrylate were weighed and mixed with 2500 g of deionized water. The mixture was then transferred to a flask and stirred at 800 rpm for 0.5 h. The temperature was then raised to 70°C to obtain a reaction solution (itaconic acid concentration 2.08 wt.%, sodium methacrylate concentration 7.6 wt.%). An aqueous solution of unsaturated carboxylic acid-modified polyether macromonomer and an aqueous solution of potassium persulfate were added to the reaction solution over 1 h through two constant-pressure dropping funnels. After the addition was complete, the temperature was raised again to 80°C and the reaction was stirred continuously for 3 h. Heating and stirring were stopped, and the mixture was cooled to 25°C to obtain an aqueous solution of a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0133] Acetone was added to the aqueous solution of the polymer, the insoluble matter was collected by filtration, and the polymer was dried in a constant temperature oven at 60°C for 12 hours to obtain a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0134] The mass of the tert-butyl peroxide is 2% of the total mass of the unsaturated carboxylic acid-modified polyether macromonomer compound, itaconic acid, and sodium methacrylate.

[0135] Example 3

[0136] A four-armed star-shaped polymer containing a polyoxyethylene structure is prepared by the following method:

[0137] Weigh out 0.05 mol of pentaerythritol ethoxylate. 0.25 mol of fumaric acid was placed in a flask and mixed at 300 rpm for 1 h under anhydrous and nitrogen protection conditions at 25 °C. The mixture was then heated to 75 °C and stirred continuously for 2.5 h to obtain an unsaturated carboxylic acid modified polyether macromonomer compound.

[0138] At 25°C, 0.05 mol of the unsaturated carboxylic acid-modified polyether macromonomer compound was mixed with 1500 g of deionized water and stirred at 1300 rpm for 0.2 h. The resulting aqueous solution of the unsaturated carboxylic acid-modified polyether macromonomer compound (concentration 5.3 wt.%) was transferred to a constant pressure dropping funnel. Potassium persulfate was mixed with 50 g of deionized water and stirred at 300 rpm for 0.2 h. The resulting aqueous solution of potassium persulfate was transferred to another constant pressure dropping funnel.

[0139] At 25°C, 1.2 mol of acrylic acid and 1.2 mol of sodium vinyl sulfonate were weighed and mixed with 2500 g of deionized water. The mixture was then transferred to a flask and stirred at 900 rpm for 0.5 h. The temperature was then raised to 70°C to obtain a reaction solution (acrylic acid concentration 3.5 wt.%, sodium vinyl sulfonate concentration 6.2 wt.%). An aqueous solution of unsaturated carboxylic acid-modified polyether macromonomer and an aqueous solution of potassium persulfate were added to the reaction solution over 2 h through two constant-pressure dropping funnels. After the addition was complete, the temperature was raised again to 80°C and the reaction was stirred continuously for 3 h. Heating and stirring were stopped, and the mixture was cooled to 25°C to obtain an aqueous solution of a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0140] Acetone was added to the aqueous solution of the polymer, the insoluble matter was collected by filtration, and the polymer was dried in a constant temperature oven at 60°C for 12 hours to obtain a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0141] The mass of potassium persulfate is 2% of the total mass of the unsaturated carboxylic acid-modified polyether macromonomer compound, acrylic acid, and sodium vinyl sulfonate.

[0142] Example 4

[0143] A four-armed star-shaped polymer containing a polyoxyethylene structure is prepared by the following method:

[0144] Weigh out 0.05 mol of pentaerythritol ethoxylate. 0.2 mol of acrylic acid was placed in a flask and stirred at 300 rpm for 1 h under anhydrous and nitrogen protection conditions at 25 °C. The mixture was then heated to 75 °C and stirred continuously for 4 h to obtain an unsaturated carboxylic acid modified polyether macromonomer compound.

[0145] At 25°C, 0.05 mol of the unsaturated carboxylic acid-modified polyether macromonomer compound was mixed with 1250 g of deionized water and stirred at 1200 rpm for 0.2 h. The resulting aqueous solution of the unsaturated carboxylic acid-modified polyether macromonomer compound (concentration 4.2 wt.%) was transferred to a constant pressure dropping funnel. Azobisisobutyronitrile was mixed with 50 g of deionized water and stirred at 300 rpm for 0.2 h. The resulting aqueous solution of azobisisobutyronitrile was transferred to another constant pressure dropping funnel.

[0146] At 25°C, 1.2 mol of methacrylic acid and 1.2 mol of acrylonitrile sulfonic acid were weighed and mixed with 2500 g of deionized water. The mixture was then transferred to a flask and stirred at 500 rpm for 0.5 h. The temperature was then raised to 70°C to obtain a reaction solution (methacrylic acid concentration 4.1 wt.%, acrylonitrile sulfonic acid concentration 5.9 wt.%). An aqueous solution of unsaturated carboxylic acid-modified polyether macromonomer and an aqueous solution of azobisisobutyronitrile were added to the reaction solution over 2 h through two constant-pressure dropping funnels. After the addition was complete, the temperature was raised again to 80°C and the reaction was stirred continuously for 3 h. Heating and stirring were stopped, and the mixture was cooled to 25°C to obtain an aqueous solution of a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0147] Acetone was added to the aqueous solution of the polymer, the insoluble matter was collected by filtration, and the polymer was dried in a constant temperature oven at 60°C for 12 hours to obtain a four-armed star-shaped polymer containing a polyoxyethylene structure.

[0148] The mass of the azobisisobutyronitrile is 2% of the total mass of the unsaturated carboxylic acid-modified polyether macromonomer compound, methacrylic acid, and acrylonitrile sulfonic acid.

[0149] Example 5

[0150] A corrosion and scale inhibitor composition, wherein the formulation comprises, by weight, the following:

[0151] Five parts of a four-armed star-shaped polymer containing a polyoxyethylene structure;

[0152] 5 parts of polyepoxysuccinic acid;

[0153] Two parts sodium gluconate;

[0154] 2 parts zinc sulfate;

[0155] Citric acid 2 parts;

[0156] 84 parts water;

[0157] The four-armed star-shaped polymer containing a polyoxyethylene structure was prepared by the method of Example 1.

[0158] Example 6

[0159] A corrosion and scale inhibitor composition, wherein the formulation comprises, by weight, the following:

[0160] Eight parts of a four-armed star-shaped polymer containing a polyoxyethylene structure;

[0161] 2 parts of polyepoxysuccinic acid;

[0162] 3 parts sodium gluconate;

[0163] 3 parts zinc sulfate;

[0164] Citric acid 3 parts;

[0165] 81 parts water;

[0166] The four-armed star-shaped polymer containing a polyoxyethylene structure was prepared using the method of Example 2.

[0167] Example 7

[0168] A corrosion and scale inhibitor composition, wherein the formulation comprises, by weight, the following:

[0169] 10 parts of a four-armed star-shaped polymer containing a polyoxyethylene structure;

[0170] 2 parts of polyepoxysuccinic acid;

[0171] 1 part sodium gluconate;

[0172] 4 parts zinc sulfate;

[0173] Citric acid 2 parts;

[0174] 81 portions of water.

[0175] The four-armed star-shaped polymer containing a polyoxyethylene structure was prepared using the method described in Example 3.

[0176] Application Example 1

[0177] To investigate the scale inhibition performance of the four-armed star-shaped polymer with a polyoxyethylene structure obtained in the embodiments of the present invention, the scale inhibition rate of the polymers described in Examples 1 to 4 of the present invention was determined. The test method was based on GB / T 16632-2019 "Determination of Scale Inhibition Performance of Water Treatment Agents - Calcium Carbonate Deposition Method", with some modifications, and a static scale inhibition method was used for evaluation. In the calcium carbonate inhibition test, 600 mg / L calcium hardness water was prepared as a simulated water sample. The calcium sulfate inhibition test was basically the same as the calcium carbonate inhibition test, except that sodium sulfate was used instead of sodium bicarbonate; and 8000 mg / L calcium hardness water was prepared as a simulated water for calcium sulfate scale inhibition. The concentration of the four-armed star-shaped polymer with a polyoxyethylene structure added in the test was 60 ppm, and the test temperature was controlled at 80℃ in a water bath for 16 h. The scale inhibition rate results of the polymer are shown in Table 1.

[0178] Table 1. Results of scale inhibition rate determination of polymers

[0179] Scale inhibition rate (calcium carbonate inhibition) % Scale inhibition rate (calcium sulfate inhibition) % Example 1 99.15 97.23 Example 2 96.54 94.74 Example 3 97.28 96.43 Example 4 98.37 94.29

[0180] The measurement results in Table 1 show that the polymers prepared in Examples 1 to 4 of this invention have a very good scale inhibition effect in high-calcium water bodies.

[0181] Application Example 2

[0182] To investigate the corrosion resistance of the corrosion-inhibiting and scale-inhibiting compositions obtained in the embodiments of the present invention, the corrosion rate performance of the corrosion-inhibiting and scale-inhibiting compositions described in Examples 5 to 7 of the present invention was determined. The test method followed GB / T18175-2014 "Determination of Corrosion Inhibition Performance of Water Treatment Agents - Rotary Coating Method," and an RCC-II type rotary coating corrosion tester was used for evaluation. Specific test conditions were as follows: the indoor test temperature was controlled at 45℃, the coating rotation speed was controlled at 75 rpm, and the samples were naturally exposed to air. Unless otherwise specified, the test period was 72 hours. The corrosion test was conducted in a 2L beaker with two test pieces installed simultaneously, and the average value was taken. The calcium hardness of the simulated corrosion solution was approximately 100 mg / L, and the concentration of the added corrosion-inhibiting and scale-inhibiting composition was 60 ppm. The corrosion rate results are shown in Table 2, with the blank in the table representing the control group without any added corrosion-inhibiting and scale-inhibiting composition. It is worth noting that, generally speaking, the lower the water hardness and alkalinity, the less likely it is to form scale, but the more likely it is to corrode; conversely, the higher the hardness and alkalinity, the more likely it is to form scale but less likely to corrode. For water with a hardness of 100 mg / L, the corrosion rate of carbon steel is generally required to be controlled to be below 0.075 mm / a by corrosion inhibitors to meet the requirements.

[0183] Table 2 Results of corrosion rate

[0184] Corrosion rate (mm / a) blank 0.587 Example 5 0.012 Example 6 0.018 Example 7 0.013

[0185] As can be seen from the corrosion rate results in Table 2, the corrosion and scale inhibitor compositions provided in Examples 5 to 7 of the present invention have a good corrosion inhibition effect and can be used for corrosion inhibition of carbon steel materials in circulating water.

[0186] To investigate the scale inhibition performance of the corrosion and scale inhibitor compositions obtained in the embodiments of the present invention, the scale inhibition rate of the corrosion and scale inhibitor compositions described in Examples 5-7 of the present invention was determined. The test method was based on GB / T 16632-2019 "Determination of Scale Inhibition Performance of Water Treatment Agents - Calcium Carbonate Deposition Method", with some modifications, and a static scale inhibition method was used for evaluation. In the experiment, calcium hardness solutions of different concentrations were prepared as simulated water samples, the concentration of the added corrosion and scale inhibitor composition was 60 ppm, and the test temperature was controlled at 80℃ in a water bath for 16 hours. The scale inhibition rate results are shown in Table 3. It is worth noting that for water with a calcium hardness of 600 mg / L, a scale inhibition rate of over 85% is generally required to meet the requirements.

[0187] Table 3. Results of scale inhibition rate determination of corrosion and scale inhibitory compositions.

[0188]

[0189] The test results in Table 3 show that the corrosion and scale inhibitor compositions provided in Examples 5 to 7 have a good scale inhibition effect. When the water calcium hardness is 700 mg / L, the scale inhibition rate is still above 90%.

[0190] In summary, the four-armed star-shaped polymer containing a polyoxyethylene structure of the present invention, combined with other corrosion and scale inhibitors, exhibits excellent scale inhibition effect and better adaptability to high-hardness water with a high tendency to scale. The corrosion and scale inhibitor composition provided by the present invention is suitable for water hardness ranges of 100-800 mg / L, controls the corrosion rate to below 0.02 mm / a, and achieves a scale inhibition rate of over 85%.

[0191] Application Example 3

[0192] In actual circulating water systems, some biological slime, grease, etc., may adhere to the surface, generally requiring periodic cleaning. The polymers prepared in Examples 1-4 of this invention have abundant polyoxyethylene groups and alkyl chains, giving them amphiphilic properties and enabling them to peel and disperse biological slime and grease, thus exhibiting certain cleaning performance. The cleaning performance of the polymers prepared in Examples 1-4 of this invention was tested, and the specific steps are as follows:

[0193] Step 101: First, obtain a 20# carbon steel metal test piece as the test object. Its size is 30×15×3mm. Polish it with 220-grit sandpaper, clean and dry it, and weigh it as m1. Then place the test piece in a clean glass container and weigh the sum of the mass of the test piece and the clean glass container as m2.

[0194] Step 102: Coat the test piece with rust-preventive oil, the amount of which should be such that it does not drip after hanging for 60 seconds. Then place it in a glass container and weigh it to m3. Further add the polymer and deionized water to the glass container (the concentration of the polymer in the water should be controlled at 200 ppm). After soaking at 35°C for 10 minutes, place the glass container on a rotary shaker and shake for 5 minutes.

[0195] Step 103: Remove the sample, hang it to dry at room temperature for 10 minutes, weigh it (m4), and calculate the cleaning ability η of the polymer according to the following formula:

[0196]

[0197] Where m1, m2, m3, and m4 are all in g, and η is in %.

[0198] The cleaning efficiency of the polymers prepared in Examples 1 to 4 was tested using the above method, and the specific test results are shown in Table 1:

[0199] Table 4 shows the cleaning efficiency results of the polymers prepared in Examples 1-4.

[0200] Cleaning efficiency / % Example 1 85.3 Example 2 82.4 Example 3 87.6 Example 4 92.5

[0201] As shown in Table 4, the polymers provided in Examples 1-4 possess a certain cleaning ability, all exceeding 80%. These results also demonstrate that the polymers of Examples 1-4 of the present invention can be used as cleaning agents.

[0202] Application Example 4

[0203] Due to the presence of microorganisms, a certain amount of quaternary ammonium salt is often used as a bactericide and algaecide in the daily operation of circulating water systems. Quaternary ammonium salt has a strong foaming ability, which often leads to foaming in the circulating water, especially immediately after its addition. This foaming is detrimental to the normal operation of pumps and other systems. The polymer of this invention, with its unique four-armed star-shaped molecular structure containing polyoxyethylene structures, effectively reduces the interfacial strength of the gas-water interface after being adsorbed onto it, thus achieving a defoaming effect and possessing a certain foam-suppressing function.

[0204] The polymers prepared in Examples 1-4 of this invention were subjected to defoaming performance testing, specifically as follows:

[0205] Using dodecyl dimethyl benzyl ammonium chloride (DDBAC) as the test material, simulated water with a calcium hardness and alkalinity of 500 mg / L was used as the test water quality. A 200 ppm DDBAC aqueous solution was prepared for the blank group; a mixed solution with 200 ppm DDBAC and 200 ppm polymer concentration was prepared for the experimental group. A high-speed stirrer was used at 10,000 rpm for 2 minutes to simulate foam, and the foam was immediately poured into a 1000 ml graduated cylinder to measure the foam volume. Specific test results are shown in Table 5.

[0206] Table 5 shows the defoaming performance test results of the polymers prepared in Examples 1-4.

[0207] Foam volume (ml) Blank (200ppm DDBAC) 575 Example 1 135 Example 2 156 Example 3 128 Example 4 119

[0208] As can be seen from Table 5, the polymers prepared in Examples 1 to 4 of the present invention have good defoaming properties and can be used as defoaming agents.

[0209] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a four-armed star-shaped polymer containing a polyoxyethylene structure, characterized in that, The method includes: Monomer preparation: Pentaerythritol ethoxy compound and unsaturated organic carboxylic acid compound were mixed under stirring, heated and stirred continuously to prepare unsaturated carboxylic acid modified polyether macromonomer compound; Polymerization reaction: The unsaturated carboxylic acid-modified polyether macromonomer compound is dissolved in water to prepare an aqueous solution of the polyether macromonomer compound, and the initiator is dissolved in water to prepare an aqueous solution of the initiator; the unsaturated organic carboxylic acid compound, the unsaturated sulfonic acid compound and water are mixed and stirred to obtain a reaction solution, the reaction solution is continuously stirred and heated, and the aqueous solution of the polyether macromonomer compound and the aqueous solution of the initiator are added to the heated reaction solution; after the addition is completed, the temperature is raised again and the reaction is continuously stirred to prepare an aqueous solution of a four-armed star-shaped polymer containing a polyoxyethylene structure; Product collection: The aqueous solution of the polymer was purified and separated to obtain a four-armed star-shaped polymer containing a polyoxyethylene structure; The structure of the pentaerythritol ethoxy compound is as follows: Where a, b, c and d represent the degree of polymerization of the polyoxyethylene unit, and a+b+c+d=4~30; The structural formula of the unsaturated organic carboxylic acid compound used in the monomer preparation is: Where R1 and R2 are defined by the following general formulas: m=1~10； The structural formula of the unsaturated organic carboxylic acid compound in the polymerization reaction is: Wherein, R3 and R4 are defined by the following general formulas: m=1~10； The unsaturated sulfonic acid compound is an unsaturated sulfonic acid or an unsaturated sulfonate, and its structure is as follows: Wherein, R5 is the following general formula: n=1~10; Wherein, R6 is the following general formula: 。 2. The preparation method according to claim 1, characterized in that, In the preparation of the monomer, the molar ratio of pentaerythritol ethoxy compound to unsaturated organic carboxylic acid compound is 1:1~5; The stirring rate is 20~2000 rpm, and the mixing time is 0.5~2 h; The heating temperature is 60~80℃, and the reaction time is 1~5h with continuous stirring.

3. The preparation method according to claim 2, characterized in that, The monomer preparation was carried out under anhydrous and nitrogen protection conditions; The purification and separation process in the product collection is as follows: Acetone was added to the aqueous solution of the polymer, and the insoluble matter was collected, washed, and dried.

4. The preparation method according to claim 1, characterized in that, In the polymerization reaction, the mass ratio of the polyether macromonomer compound, the unsaturated organic carboxylic acid compound, and the unsaturated sulfonic acid compound is 1:(4~8000):(4~8000). The sum of the initial concentrations of the aqueous solution of the polyether macromonomer compound, the unsaturated organic carboxylic acid compound in the reaction solution, and the unsaturated sulfonate in the reaction solution is 5~40 wt.%. The initiator is 1-3% of the total mass of the polyether macromonomer compound, the unsaturated organic carboxylic acid compound, and the unsaturated sulfonic acid compound. The stirring speed is 20~2000 rpm; The heating temperature is 65~75℃; The reheating temperature is 75~95℃, and the continuous stirring reaction time is 1~5h.

5. The preparation method according to claim 4, characterized in that, In the polymerization reaction, the aqueous solution of the polyether macromonomer compound and the aqueous solution of the initiator are added to the reaction solution after heating, and the addition time is 0.5~2h.

6. The preparation method according to claim 1, characterized in that, The initiator in the polymerization reaction is at least one of ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyronitrile, tert-butyl peroxide, and diacyl peroxide.

7. A composition containing a four-armed star-shaped polymer with a polyoxyethylene structure, characterized in that, The composition comprises a polymer prepared by any one of the preparation methods described in claims 1 to 6, and a corrosion and scale inhibitor.

8. The composition according to claim 7, characterized in that, The corrosion and scale inhibitor includes: Polyepoxysuccinic acid and / or polyepoxysuccinate, sodium gluconate, inorganic zinc salts and citric acid.

9. The composition according to claim 8, characterized in that, The composition also includes water. The composition was prepared in 100 parts by weight, and the formulations of each component were as follows: 0.1 to 15 parts of a four-armed star-shaped polymer containing a polyoxyethylene structure; 0.1 to 10 parts of polyepoxysuccinic acid and / or polyepoxysuccinate; Sodium gluconate 0.1-5 parts; Inorganic zinc salt 0.1~5 parts; Citric acid 0.1~5 parts; Water is the remainder.

10. The composition according to claim 9, characterized in that, The inorganic zinc salt is at least one of zinc sulfate, zinc chloride, and zinc nitrate.

11. The use of a polymer prepared by any one of claims 1 to 6 in cleaning.

12. The use of a polymer prepared by any one of the preparation methods described in claims 1 to 6 in defoaming.

13. The use of a polymer prepared by any one of the preparation methods of claims 1 to 6 in scale inhibition.

14. The application of the composition of claim 7 in corrosion and scale inhibition.

Images