CN108947862B - Pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) and preparation method and application thereof - Google Patents
Pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) and preparation method and application thereof Download PDFInfo
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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Abstract
The invention provides a hyperbranched polymer named pentaerythritol tetra ((N, N-bis (2-aminoethyl)) -3-aminopropionate), which has the chemical formula: c [ CH ]2OCOCH2CH2N(CH2CH2NH2)2]4The polymer is a water-soluble hyperbranched polymer with amino end groups and a pentaerythritol core, and can effectively inhibit the formation of silica scale and silicate scale in water. The invention also provides a preparation method of the hyperbranched polymer, which comprises the steps of firstly carrying out primary amino protection on diethylenetriamine, then carrying out addition reaction on the diethylenetriamine and pentaerythritol tetraacrylate, and finally carrying out hydrolysis to remove amino protecting groups to obtain pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate).
Description
Technical Field
The invention belongs to the technical field of industrial water treatment, and relates to control of silica scale such as silicon dioxide and silicate. More particularly, relates to a silica scale inhibitor hyperbranched polymer pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) and a preparation method thereof.
Background
In industrial water treatment systems (e.g., circulating cooling water, boiler water, reverse osmosis, evaporative desalination), raw water usually contains a certain amount of soluble silica, and as the system evaporates or concentrates, silica scale and silicate scale are formed when the concentration exceeds its solubility range, and once the silica scale is formed, it is difficult to remove it, and when water with a high silica content is used, the operation of the cooling system and the reverse osmosis system must be performed at a low efficiency, which results in increased production costs and reduced system efficiency.
In the art, the method for preventing inorganic salt scale (such as calcium carbonate, calcium sulfate, barium sulfate, calcium phosphate, etc.) is to add organic phosphine scale inhibitor or polycarboxylate dispersant, and these traditional organic phosphine scale inhibitor and polymer scale inhibitor dispersant are anionic compounds, and for ionic crystal scale such as CaCO3、CaSO4、BaSO4The formation of the scale inhibitor and the like has strong inhibiting or dispersing effect, but the anionic scale inhibiting and dispersing agent has no remarkable effect on inhibiting the silica scale.
Demadis.K.D. studies show that the entire generation of polyamidoamine (e.g., PAMAM-1.0G, PAMAM-2.0G) dendrimers have good silica scale inhibition (Demadis K.D., A structure/function students as silicon scale growth inhibitors. journal of chemical technology and biotechnology 2005,80: 630-. However, the preparation steps of the PAMAM are complex, and the use cost is high.
Disclosure of Invention
In view of the above, the present invention aims to provide a silica scale inhibitor which has an inhibitory effect on silica and silicate scales and is inexpensive to use.
The silica scale inhibitor provided by the invention is a water-soluble hyperbranched polymer, the chemical name of which is pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate), and the chemical formula of the polymer is as follows: c [ CH ]2OCOCH2CH2N(CH2CH2NH2)2]4(ii) a The structural formula is shown as formula I:
the preparation method of pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) provided by the invention is simple, the solvent can be recycled, the number of byproducts is small, and the cost is low.
In order to achieve the above object, the present invention provides a method for preparing pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) comprising the steps of:
(1) primary amino group protection reaction: under the protection of inert gas, mixing diethylenetriamine and 4-methyl-2-pentanone serving as a primary amino group protective agent, and carrying out dehydration reaction. After the theoretical amount of water is generated, the reaction is finished, and the reaction product is cooled to room temperature to obtain a secondary amine precursor solution which is a product of diethylenetriamine with protected primary amino groups. The reaction equation of the primary amino group protection reaction is shown as formula II:
(2) addition reaction: and (2) mixing pentaerythritol tetraacrylate and 4-methyl-2-pentanone, slowly adding the mixture into the secondary amine precursor solution obtained in the step (1) for addition reaction, and then carrying out reduced pressure distillation to remove 4-methyl-2-pentanone to obtain an addition product. The reaction equation of the addition reaction is shown as formula III:
(3) and (3) hydrolysis reaction: hydrolyzing the addition product and water under the action of an alcohol catalyst to remove a primary amino protecting group, and then distilling under reduced pressure to remove water, the catalyst and an amino protective agent 4-methyl-2-pentanone to obtain pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate). The hydrolysis reaction equation is shown as formula IV:
in the primary amino group protection reaction, the reaction temperature is 70-100 ℃, and the most preferable temperature is 80-90 ℃; the reaction time is 5-10 h, and the most preferable time is 6-8 h.
In the primary amino group protection reaction, 4-methyl-2-pentanone is not only an amino protective agent but also a reaction solvent, and the molar ratio of the 4-methyl-2-pentanone to diethylenetriamine is more than 3, preferably 4-8: 1.
In the addition reaction, the reaction temperature is 20-50 ℃, and preferably 25-40 ℃; the reaction time is 16-48 h, preferably 20-30 h.
In the addition reaction, 4-methyl-2-pentanone is a reaction solvent, and the mass ratio of the 4-methyl-2-pentanone to pentaerythritol tetraacrylate is 0.1-10: 1, and the preferable ratio is 0.5-1: 1.
In the addition reaction, the mass ratio of the secondary amine precursor to the pentaerythritol tetraacrylate is (4.0-4.1): 1.
In the hydrolysis reaction, the reaction temperature is 50-100 ℃, and preferably 70-90 ℃; the reaction time is 5-10 h, preferably 6-8 h.
In the hydrolysis reaction, the alcohol catalyst is isopropanol, isobutanol, isoamylol, isohexanol and the like, and the amount of the catalyst is 1-50% of the mass of the addition product, preferably 5-10%.
In the amino protection reaction and the hydrolysis reaction, the reduced pressure distillation temperature is 70-100 ℃, and preferably 80-90 ℃; the time is 5-10 h, preferably 6-8 h.
The invention provides application of pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) prepared by the preparation method in the scheme or application of pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) prepared by the preparation method in the scheme in inhibiting silica scale.
The pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) provided by the invention is a hyperbranched polymer with terminal amino groups and a pentaerythritol core, and the terminal amino groups (-NH) in the structure2) The material can be protonated under the condition of industrial water treatment (pH 6-9) so as to have positive charge (-NH)3 +) Can generate electrostatic attraction with silicon dioxide monomers, oligomers and deprotonated silanol groups with negative charges in the solution, thereby blocking the polymerization reaction of soluble silicon dioxide in water, increasing the solubility of the soluble silicon dioxide, achieving the effect of inhibiting the formation of silica scale, and having wide application prospect in the aspect of inhibiting the silica scale.
The results of examples show that pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) provided by the present invention was used as a silica scale inhibitor, and the concentration of pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) was 30 mg.L-1In the case of the filtrate, the soluble SiO in the filtrate is obtained after 72 hours2The content of (A) can reach 363 mg.L-1When PAMAM-0G is used as the silica scale inhibitor, the amount of the soluble SiO in the filtrate after 72h is the same2Has a content of 247 mg.L-1(ii) a Therefore, the pentaerythritol tetra ((N, N-bis (2-aminoethyl)) -3-aminopropionate) provided by the invention has excellent effect of inhibiting silicon dioxide scale deposition, and the effect is better than that of polyamide-amine.
The invention provides a preparation method of pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) in the scheme, firstly, the primary amino group protection is carried out on diethylenetriamine, then, the addition reaction is carried out on the diethylenetriamine and pentaerythritol tetraacrylate, and finally, the primary amino group removal protection is carried out, so that the pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) is obtained. The preparation method provided by the invention has the advantages of simple steps and low cost.
Detailed Description
The pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) and the preparation method and use thereof according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Since the primary amino group protection is a dehydration reaction, in the examples, a device having a water separator is used to perform the dehydration reaction, and the generated water is introduced into the water separator to accelerate the dehydration reaction. When the weight of the water in the water separator reaches the theoretical dehydration weight, the primary amino group protection reaction is finished.
Example 1
(1) 41.20g (0.40mol) of diethylenetriamine and 170.00g (1.70mol) of 4-methyl-2-pentanone are respectively added into a round-bottom flask with a water separator, the round-bottom flask is heated to 90 ℃ under the protection of nitrogen, the moisture at the lower layer in the water separator is continuously removed, the round-bottom flask is weighed, after 8 hours, the weight of the collected moisture is about 14.4g, the reaction is finished, and the reaction liquid is cooled to room temperature to obtain a primary amino group protected secondary amine precursor solution;
(2) slowly adding 70.40g (50%, 0.10mol) of a 4-methyl-2-pentanone solution of pentaerythritol tetraacrylate into the reaction solution in the step (1), reacting at 25 ℃ for 24 hours, heating to 80 ℃, and distilling under reduced pressure to remove the solvent 4-methyl-2-pentanone to obtain a light yellow viscous addition product;
(3) adding 280g of deionized water and 7.5g of isopropanol into the addition product obtained in the step (2), heating to 70 ℃, carrying out hydrolysis reaction for 7 hours, and then carrying out reduced pressure distillation at 70 ℃ to remove water, isopropanol and 4-methyl-2-pentanone to obtain 76.10g of light amber hyperbranched polymer pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate).
Preparation of the resulting hyperbranched polymer pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate)13C nuclear magnetic resonance spectroscopy (D)2O) has the following chemical shifts: 31.29, 36.53, 39.91, 53.62, 58.16, 62.72, 181.61 ppm; this result indicates that the product obtained in this example is indeed pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate).
Example 2
(1) Adding 41.20g (0.40mol) of diethylenetriamine and 200.0g (2.00mol) of 4-methyl-2-pentanone into a round-bottom flask with a water separator respectively, heating to 80 ℃ under the protection of nitrogen, continuously removing the water on the lower layer in the water separator, weighing, collecting the water with the weight of about 14.40g after 7 hours, indicating that the reaction is finished, and cooling the reaction liquid to room temperature to obtain a primary amino protected secondary amine precursor solution;
(2) slowly adding 58.67g (60%, 0.10mol) of a 4-methyl-2-pentanone solution of pentaerythritol tetraacrylate into the reaction solution in the step (1), reacting at 35 ℃ for 20 hours, heating to 70 ℃, and distilling under reduced pressure to remove the solvent 4-methyl-2-pentanone to obtain a light yellow viscous addition product;
(3) adding 280g of deionized water and 10.0g of isopropanol into the addition product obtained in the step (2), heating to 50 ℃, carrying out hydrolysis reaction for 8 hours, and then carrying out reduced pressure distillation at 80 ℃ to remove water, isopropanol and 4-methyl-2-pentanone to obtain 75.92g of light amber hyperbranched polymer pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate).
Preparation of the resulting hyperbranched polymer pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate)13C nuclear magnetic resonance spectroscopy (D)2O) has the following chemical shifts: 31.22, 36.25, 39.88, 53.65, 58.20, 62.69, 181.77 ppm; this result indicates that the product obtained in this example is indeed pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate).
Example 3
(1) Respectively adding 42.23g (0.41mol) of diethylenetriamine and 250.0g (2.50mol) of 4-methyl-2-pentanone into a round-bottom flask with a water separator, heating to 70 ℃ under the protection of nitrogen, continuously removing the water on the lower layer in the water separator, weighing, collecting the water with the weight of about 14.40g after 6 hours, indicating that the reaction is finished, and cooling the reaction liquid to room temperature to obtain a primary amino group protected secondary amine precursor;
(2) slowly adding 50.29g (70%, 0.10mol) of a 4-methyl-2-pentanone solution of pentaerythritol tetraacrylate into the reaction solution in the step (1), reacting at 50 ℃ for 36 hours, heating to 90 ℃, and distilling under reduced pressure to remove the solvent 4-methyl-2-pentanone to obtain a light yellow viscous addition product;
(3) adding 280g of deionized water and 15.0g of isopropanol into the addition product obtained in the step (2), heating to 80 ℃, carrying out hydrolysis reaction for 5 hours, and then carrying out reduced pressure distillation at 90 ℃ to remove water, isopropanol and 4-methyl-2-pentanone to obtain 76.15g of light amber hyperbranched polymer pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate).
Preparation of the resulting hyperbranched polymer pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate)13C nuclear magnetic resonance spectroscopy (D)2O) has the following chemical shifts: 31.03, 35.89, 39.38, 53.76, 58.59, 62.86, 180.09 ppm; this result indicates that the product obtained in this example is indeed pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate).
Example 4
Polyamidoamine PAMAM-0G, available from Sigma aldrich (shanghai) trade ltd (Sigma-aldrich (shanghai) Trading co.ltd.), was 20% methanol solution. 100G of a 20% active PAMAM-0G methanol solution was evaporated at 50 ℃ using a vacuum rotary evaporator to remove the methanol, yielding 20G of a viscous PAMAM-0G.
The PAMAM-0G and pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) prepared in example 1 were subjected to static silica stability tests as follows:
500mL of the solution was prepared in a polyethylene plastic bottle with a mass concentration of 500 mg.L-1(with SiO)2Meter) of sodium silicate solution, adding PAMAM-0G and pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate), adjusting pH to 7.5 +/-0.1 with hydrochloric acid and sodium hydroxide solution, covering a bottle cap, placing in a constant-temperature water bath at 25 ℃, periodically taking part of the solution, filtering with a 0.22 mu m filter membrane, and measuring soluble SiO in the filtrate2The content of (A); soluble SiO2Content is according toAnd the method in the determination of silicon in boiler water (GB/T12149-2007); blank experiments were also performed. The results are shown in Table 1.
TABLE 1SiO2Stability experiments (starting SiO)2＝500mg·L-1，pH＝7.5，25℃)
As can be seen from the experimental results of Table 1, the concentration of pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) was 50 mg.L-1In the case of the filtrate, the soluble SiO in the filtrate is obtained after 72 hours2The content of (A) can reach 422 mg.L-1Under the condition of the same addition amount of the medicament, the silica scale inhibition effect of pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) is better than that of PAMAM-0G; therefore, the pentaerythritol tetra ((N, N-bis (2-aminoethyl)) -3-aminopropionate) provided by the invention has excellent effect of inhibiting silicon dioxide scale deposition, and the effect is better than that of polyamide-amine.
Example 5
The PAMAM-0G of example 4 and pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) prepared in example 1 were subjected to static silica stability experiments in the presence of calcium ions, according to the following experimental methods:
500mL of the mixture was prepared in a polyethylene plastic bottle with a mass concentration of 300 mg.L-1(with SiO)2Metering) sodium silicate solution, and adding a certain amount of silica scale inhibitor; then using HCl and NaOH to make pH of the solution be 9.0 +/-0.1, adding a certain volume of calcium chloride solution to make calcium concentration be 300 mg.L-1Then, the pH of the solution was adjusted to 9.0. + -. 0.1 with HCl and NaOH. Covering with bottle cap, placing in 25 deg.C constant temperature water bath, periodically collecting partial solution, filtering with 0.22 μm filter membrane, and measuring soluble SiO in the filtrate2The content of (A); soluble SiO2The content was measured by the method described in "determination of silicon in Industrial circulating Cooling Water and boiler Water (GB/T12149-2007"), and a blank experiment was carried out. The results are shown in Table 2.
TABLE 2SiO2Results of stability experiments(starting SiO)2＝300mg·L-1，Ca＝300mg·L-1，pH＝9.0)
As can be seen from the data in Table 2, the pentaerythritol tetrakis ((N, N-bis (2-aminoethyl)) -3-aminopropionate) provided by the invention still has excellent effect of inhibiting the deposition of silica and silicate scales in the presence of calcium ions, and the scale inhibition effect is better than that of polyamide-amine 0G.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. The application of pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) as a silica scale inhibitor is characterized by being applied to inhibiting the generation of silica and silicate silica scales in industrial water treatment; the pentaerythritol tetra ((N, N-di (2-aminoethyl)) -3-aminopropionate) is a water-soluble hyperbranched polymer with a chemical formula of C [ CH ]2OCOCH2CH2N(CH2CH2NH2)2]4The structural formula is shown as formula I:
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