CN118185026A - Polymer scale inhibitor based on inulin modified grafting, and preparation method and application thereof - Google Patents
Polymer scale inhibitor based on inulin modified grafting, and preparation method and application thereof Download PDFInfo
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- CN118185026A CN118185026A CN202410351432.0A CN202410351432A CN118185026A CN 118185026 A CN118185026 A CN 118185026A CN 202410351432 A CN202410351432 A CN 202410351432A CN 118185026 A CN118185026 A CN 118185026A
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- inulin
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- polysuccinimide
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- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 title claims abstract description 92
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 73
- 229920001202 Inulin Polymers 0.000 title claims abstract description 65
- 229940029339 inulin Drugs 0.000 title claims abstract description 65
- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 38
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 20
- 230000005764 inhibitory process Effects 0.000 claims abstract description 15
- 238000007112 amidation reaction Methods 0.000 claims abstract description 10
- 238000006467 substitution reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 230000003113 alkalizing effect Effects 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000502 dialysis Methods 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002862 amidating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F5/12—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 containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polymer scale inhibitor based on inulin modification grafting, and a preparation method and application thereof, and belongs to the technical field of high polymer water treatment. The scale inhibitor is prepared by graft polymerization of polysuccinimide monomer and modified inulin monomer, wherein the modified inulin monomer is prepared by substitution reaction of inulin and 2-chloroethylamine in the presence of alkali solution. According to the invention, the inulin is taken as a monomer, amino groups are introduced into a molecular chain of the inulin to obtain a modified inulin monomer, and then the modified inulin monomer and polysuccinimide are subjected to amidation reaction, and the modified inulin monomer is introduced into a molecular chain of the polysuccinimide, so that the prepared polymer scale inhibitor has better chelating ability, and therefore, has better scale inhibition effect. Meanwhile, as the inulin is easy to degrade, the polymer scale inhibitor has good biodegradability and does not pollute the environment.
Description
Technical Field
The invention belongs to the technical field of high molecular water treatment, and particularly relates to a polymer scale inhibitor based on inulin modification grafting, and a preparation method and application thereof.
Background
In the field of water treatment of circulating cooling water systems, sea water desalination devices, secondary oil extraction industrial water and the like, the scaling problem is one of the most main problems of reducing the water and water treatment efficiency, damaging equipment and generating potential safety hazards.
At present, scale control by using a scale inhibitor is the most economical and efficient technical approach. In the field of water treatment, the development of scale inhibitors has undergone 3 stages of phosphorus-containing scale inhibitors, copolymer scale inhibitors and green and environment-friendly scale inhibitors. The phosphorus-containing scale inhibitor is divided into an inorganic phosphorus scale inhibitor and an organic phosphine scale inhibitor, and the inorganic phosphorus-containing scale inhibitor has poor scale inhibition effect; the organic phosphine scale inhibitor has excellent scale inhibition performance and is most widely applied in the field of water treatment. However, with the continuous improvement of environmental awareness, the phosphorus-containing scale inhibitor can be used as a microorganism nutrition source to cause water microorganism breeding, so that water eutrophication and pipe network microorganism corrosion are aggravated, and the use of the phosphorus-containing scale inhibitor is gradually limited. The copolymer scale inhibitor has good scale inhibition performance, but researches show that the copolymer scale inhibitor is difficult to degrade by microorganisms, and long-term accumulation can cause water pollution and harm human health. Therefore, the green and environment-friendly scale inhibitor has become the focus and hot spot of the development of the current water treatment scale inhibitor.
However, the existing green environment-friendly scale inhibitor also has the problems of complex synthesis process, poor scale inhibition capability and the like.
Disclosure of Invention
The invention aims to provide a polymer scale inhibitor based on inulin modification grafting, and a preparation method and application thereof, which are used for solving the problems of complex synthesis process, poor scale inhibition capability and the like of the green environment-friendly scale inhibitor in the prior art.
In a first aspect, the invention provides an inulin-modified grafted polymer scale inhibitor, which is prepared by graft polymerization of polysuccinimide monomers and modified inulin monomers and has a structure shown in the following formula (I):
wherein the modified inulin monomer is prepared by the substitution reaction of inulin and 2-chloroethylamine in the presence of alkali solution, and the substitution degree of the 2-chloroethylamine is 1-2; in the formula (I), the value range of m is 50-60; the value range of n is 2-60.
In some embodiments, the molar ratio of inulin to 2-chloroethylamine is 1 (2-4), which may be, for example, 1:2, 1:2.4, 1:2.8, 1:3.2, 1:3.6, 1:4, or other values within this range; the mass ratio of polysuccinimide to inulin is (1-3) 0.5, and may be, for example, 1:0.5, 1.5:0.5, 2:0.5, 2.5:0.5, 3:0.5 or other values within this range.
In a second aspect, the invention provides a preparation method of the polymer scale inhibitor based on inulin modification grafting, which comprises the following steps:
S1, adding inulin into an alkali solution, stirring and dissolving the inulin, and then carrying out alkalization treatment; then dripping 2-chloroethylamine aqueous solution for substitution reaction to obtain modified inulin monomer solution;
S2, providing a polysuccinimide monomer aqueous solution, dropwise adding a modified inulin monomer solution into the polysuccinimide monomer aqueous solution, and carrying out amidation reaction under alkaline conditions to obtain the polymer scale inhibitor.
In the preparation method provided by the invention, the polymer scale inhibitor based on inulin modification grafting is prepared by the reaction shown in the following formulas (1) and (2):
specifically, in the preparation process of the polymer scale inhibitor, the reaction mechanism is as follows: activating inulin in the presence of alkali solution at a certain temperature, reacting hydroxyl on the inulin with NaOH to form-ONa, reacting with chlorine on 2-chloroethylamine as an active site to generate ether bond and NaCl, and introducing amino into inulin molecular chain; as a plurality of carboxyl groups and amide groups exist in the polysuccinimide molecular chain, amidation reaction is carried out between the polysuccinimide molecular chain and the amide groups under alkaline conditions, and finally the inulin molecule is grafted on the polysuccinimide chain, thus obtaining the polymer scale inhibitor.
In some embodiments, in step S1, the alkali solution is an aqueous NaOH solution, the mass concentration of the aqueous NaOH solution is 15%, and the molar ratio of inulin to NaOH is 1 (3-4), which may be, for example, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, 1:4, or other values within this range; the temperature of the alkalizing treatment is 40 to 50℃and may be, for example, 40℃42℃44℃46℃48℃50℃or other values within the range; the time is 40 to 50 minutes, and may be, for example, 40 minutes, 42 minutes, 44 minutes, 46 minutes, 48 minutes, 50 minutes, or other values within the range.
In some embodiments, in step S1, the 2-chloroethylamine aqueous solution is added dropwise for a period of 30; and in the 2-chloroethylamine aqueous solution, the mass ratio of 2-chloroethylamine to water is 1 (0.5-1), for example, may be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1 or other values within the range.
In some embodiments, in step S1, the temperature of the substitution reaction is 50-60 ℃, e.g., may be 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, or other values within this range; the time is 3 to 4 hours, and may be, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, or other values within the range.
In some embodiments, in step S2, the mass ratio of polysuccinimide to water in the aqueous polysuccinimide monomer solution is 1:3.
In some embodiments, in step S2, the time for dropping the modified inulin monomer solution is 30 to 60min, for example, may be 30min, 35min, 40min, 45min, 50min, 55min, 60min or other values within this range; the amidation reaction temperature may be 50 to 70℃and may be, for example, 50℃54℃58℃62℃66℃70℃or other values within the range; the time is 6 to 7 hours, and may be, for example, 6 hours, 6.2 hours, 6.4 hours, 6.6 hours, 6.8 hours, 7 hours or other values within the range.
In some embodiments, in step S2, the pH of the solution is adjusted to 9-11 during the amidation reaction, which may be, for example, 9, 9.4, 9.8, 10, 10.2, 10.6, 11 or other values within this range.
In some embodiments, the method further comprises the step of purifying the polymeric scale inhibitor obtained in step S2.
In some preferred embodiments, the purification comprises passing the polymeric scale inhibitor obtained in step S2 through a 2000Da dialysis membrane and freeze-drying for 48 hours to obtain a purified polymeric scale inhibitor.
In a third aspect, the invention provides the use of the polymer scale inhibitor based on inulin modification grafting in scale inhibition of wastewater.
The beneficial effects of the invention are as follows: compared with the prior art, the modified inulin monomer is obtained by taking inulin as a monomer and introducing amino groups into the molecular chain of the inulin, and the amino groups have higher reactivity compared with hydroxyl groups in the inulin molecules, so that the modified inulin monomer is beneficial to promoting the grafting reaction; then carrying out amidation reaction on the modified inulin monomer and polysuccinimide, and introducing the modified inulin monomer into the polysuccinimide molecular chain, so that the prepared polymer scale inhibitor has better chelating ability, and meanwhile, the polymer scale inhibitor has good biodegradability due to easy degradation of inulin, and no pollution is generated to the environment.
Drawings
FIG. 1 is an infrared spectrum of a polymer scale inhibitor prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The experimental methods for which specific conditions are not specified in the examples are generally commercially available according to conventional conditions and those described in handbooks, or according to conditions recommended by the manufacturer, using general-purpose equipment, materials, reagents, etc., unless otherwise specified.
Example 1
A preparation method of a polymer scale inhibitor based on inulin modification grafting comprises the following steps:
S1, adding inulin and 15% NaOH aqueous solution in mass concentration into a three-neck flask provided with a thermometer and a stirrer device, stirring and dissolving at 40 ℃, alkalizing for 40min, and then dropwise adding 2-chloroethylamine aqueous solution for 30min; wherein the molar ratio of the inulin to the NaOH is 1:4, the molar ratio of the inulin to the 2-chloroethylamine is 1:4, and in the 2-chloroethylamine aqueous solution, the mass of deionized water is equal to the mass of the 2-chloroethylamine; after the dripping is finished, the temperature is regulated to 50 ℃, the timing is carried out after the temperature reaches the designated temperature, and the modified inulin monomer solution (IN-CEA) is obtained after the reaction for 4 hours;
S2, adding Polysuccinimide (PSI) and deionized water into a three-neck flask provided with a thermometer and a stirrer device, stirring and heating to 50 ℃; wherein the mass ratio of polysuccinimide to inulin is 3:0.5, and the mass ratio of polysuccinimide to deionized water is 1:3; dropwise adding the modified inulin monomer solution prepared in the step S1 into a three-neck flask for 30min, heating to 60 ℃ after the dropwise adding, adjusting the pH value to 9-11, and reacting for 6h; and cooling to room temperature after the reaction is finished to obtain brown polymer scale inhibitor solution, cooling and weighing, passing through a 2000Da dialysis membrane, and freeze-drying for 48 hours to obtain the purified polymer scale inhibitor.
The polymer scale inhibitor prepared in this example was subjected to infrared test, and the results are shown in fig. 1.
As can be seen from FIG. 1, there are 3400cm-1、2973.96cm-1、2360.82cm-1、2304.04cm-1、1650cm-1、1590cm-1、1400cm-1、1250cm-1、1050cm-1、667cm-1 characteristic peaks, wherein 3400cm -1 is an amino peak in an amide group and an hydroxyl peak in inulin, 2973.96cm -1 is a stretching vibration of methyl and methylene in a molecule, 2360.82cm -1 and 2304.04cm -1 are caused by 2-chloroethylamine of which the residual part is not completely reacted in the product, 1650cm -1 and 667cm -1 are caused by a C=O stretching vibration peak in the molecule, 1590cm -1 is an N-H characteristic peak, 1400cm -1 is a stretching vibration absorption peak after C-N and C=O bond in an amide group are connected, indicating that an amide group is formed in the molecule, 1250cm -1 is a deforming vibration of an amine group, and 1050cm -1 is a stretching vibration of C-OH in inulin.
Example 2
A preparation method of a polymer scale inhibitor based on inulin modification grafting comprises the following steps:
S1, adding inulin and 15% NaOH aqueous solution in mass concentration into a three-neck flask provided with a thermometer and a stirrer device, stirring and dissolving at 50 ℃, alkalizing for 40min, and then dropwise adding 2-chloroethylamine aqueous solution for 30min; wherein the molar ratio of the inulin to the NaOH is 1:4, the molar ratio of the inulin to the 2-chloroethylamine is 1:2, and in the 2-chloroethylamine aqueous solution, the mass of deionized water is equal to the mass of the 2-chloroethylamine; after the dripping is finished, the temperature is regulated to 50 ℃, the timing is carried out after the temperature reaches the designated temperature, and the modified inulin monomer solution (IN-CEA) is obtained after the reaction for 4 hours;
S2, adding Polysuccinimide (PSI) and deionized water into a three-neck flask provided with a thermometer and a stirrer device, stirring and heating to 50 ℃; wherein the mass ratio of polysuccinimide to inulin is 2:0.5, and the mass ratio of polysuccinimide to deionized water is 1:3; dropwise adding the modified inulin monomer solution prepared in the step S1 into a three-neck flask for 60min, heating to 70 ℃ after the dropwise adding, adjusting the pH value to 9-11, and reacting for 7h; and cooling to room temperature after the reaction is finished to obtain brown polymer scale inhibitor solution, cooling and weighing, passing through a 2000Da dialysis membrane, and freeze-drying for 48 hours to obtain the purified polymer scale inhibitor.
Example 3
A preparation method of a polymer scale inhibitor based on inulin modification grafting comprises the following steps:
S1, adding inulin and 15% NaOH aqueous solution in mass concentration into a three-neck flask provided with a thermometer and a stirrer device, stirring and dissolving at 40 ℃, alkalizing for 50min, and then dropwise adding 2-chloroethylamine aqueous solution for 30min; wherein the molar ratio of the inulin to the NaOH is 1:3, the molar ratio of the inulin to the 2-chloroethylamine is 1:4, and in the 2-chloroethylamine aqueous solution, the mass of deionized water is equal to the mass of the 2-chloroethylamine; after the dripping is completed, the temperature of the water bath kettle is regulated to 60 ℃, timing is carried out after the temperature reaches the designated temperature, and the modified inulin monomer solution (IN-CEA) is obtained after 3 hours of reaction.
S2, adding Polysuccinimide (PSI) and deionized water into a three-neck flask provided with a thermometer and a stirrer device, stirring and heating to 50 ℃; wherein the mass ratio of polysuccinimide to inulin is 1:0.5, and the mass ratio of polysuccinimide to deionized water is 1:3; dropwise adding the modified inulin monomer solution prepared in the step S1 into a three-neck flask for 30min, heating to 60 ℃ after the dropwise adding, adjusting the pH value to 9-11, and reacting for 6h; and cooling to room temperature after the reaction is finished to obtain brown polymer scale inhibitor solution, cooling and weighing, passing through a 2000Da dialysis membrane, and freeze-drying for 48 hours to obtain the purified polymer scale inhibitor.
Example 4
A preparation method of a polymer scale inhibitor based on inulin modification grafting comprises the following steps:
s1, adding inulin and 15% NaOH aqueous solution in mass concentration into a three-neck flask provided with a thermometer and a stirrer device, stirring and dissolving at 50 ℃, alkalizing for 50min, and then dropwise adding 2-chloroethylamine aqueous solution for 30min; wherein the molar ratio of the inulin to the NaOH is 1:3, the molar ratio of the inulin to the 2-chloroethylamine is 1:2, and in the 2-chloroethylamine aqueous solution, the mass of deionized water is equal to the mass of the 2-chloroethylamine; after the dripping is finished, the temperature is adjusted to 60 ℃, timing is carried out after the temperature reaches the designated temperature, and the modified inulin monomer solution (IN-CEA) is obtained after 3 hours of reaction;
S2, adding Polysuccinimide (PSI) and deionized water into a three-neck flask provided with a thermometer and a stirrer device, stirring and heating to 50 ℃; wherein the mass ratio of polysuccinimide to inulin is 1.5:0.5, and the mass ratio of polysuccinimide to deionized water is 1:3; dropwise adding the modified inulin monomer solution prepared in the step S1 into a three-neck flask for 60min, heating to 70 ℃ after the dropwise adding, adjusting the pH value to 9-11, and reacting for 7h; and cooling to room temperature after the reaction is finished to obtain brown polymer scale inhibitor solution, cooling and weighing, passing through a 2000Da dialysis membrane, and freeze-drying for 48 hours to obtain the purified polymer scale inhibitor.
Comparative example
The polysuccinimide equivalent to that in example 1 was taken and used directly as a polymer scale inhibitor without grafting treatment.
Evaluation of Scale inhibition Property
The polymer products prepared in examples 1 to 4 and comparative example were tested for the scale inhibition properties of barium sulfate by the following specific test methods:
Accurately weighing the 0.5g scale inhibitor respectively, dissolving with a small amount of pure water, transferring into a 250mL volumetric flask, and diluting to scale to obtain a scale inhibitor solution; 200mL of deionized water is taken in a 250mL volumetric flask, and a pre-prepared BaCl 2 solution is added to enable the content of Ba 2+ to be 2.8 mg.mL -1; accurately adding 2.50mL and 3.75mL of scale inhibitor solution respectively, standing for 10min, and adding a prepared Na 2SO4 solution while shaking to ensure that the SO 4 2- content is 2.06 mg/mL -1; adding deionized water to dilute the mixture to a scale, putting the mixture into a triangular flask with a grinding mouth, putting the triangular flask into a water bath with the temperature of 50+/-1 ℃ for constant temperature for half an hour, and standing the flask for 24 hours.
After the reaction was completed, the solution was cooled to room temperature and filtered with quantitative filter paper. The filtrate of BaSO 4 was titrated with ethylenediamine tetraacetic acid (EDTA) standard solution to determine the concentration of Ba 2+. The test results are shown in table 1:
TABLE 1 scale inhibition test results of scale inhibitors prepared in examples 1 to 3 and comparative example
| Sequence number | Dosage of scale inhibitor (mg/L) | Barium sulfate scale inhibition rate |
| Example 1 | 30 | 93.62％ |
| Example 2 | 30 | 85.55％ |
| Example 3 | 30 | 67.85％ |
| Example 4 | 30 | 77.91％ |
| Comparative example | 30 | 52.89％ |
As can be seen from the results in Table 1, compared with the low scale inhibition performance of the scale inhibitor containing polysuccinimide only in the comparative example, the polymer scale inhibitor prepared by using inulin, 2-chloroethylamine and polysuccinimide as raw materials and adopting an NaOH activation type initiation system and amidating through aqueous solution has good scale inhibition effect on barium sulfate, and the scale inhibition rate on barium sulfate can reach 67% -93% when the dosage of the scale inhibitor is 30 mg/L.
It should be noted that, the foregoing embodiments all belong to the same inventive concept, and the descriptions of the embodiments have emphasis, and where the descriptions of the individual embodiments are not exhaustive, reference may be made to the descriptions of the other embodiments.
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The polymer scale inhibitor based on inulin modified grafting is characterized in that the polymer scale inhibitor is obtained by graft polymerization of polysuccinimide monomer and modified inulin monomer, and has a structure shown in the following formula (I):
wherein the modified inulin monomer is prepared by substitution reaction of inulin and 2-chloroethylamine in the presence of alkali solution, and the substitution degree of the 2-chloroethylamine is 1-2;
in the formula (I), the value range of m is 50-60; the value range of n is 2-60.
2. The polymer scale inhibitor based on inulin modification and grafting according to claim 1, wherein the molar ratio of inulin to 2-chloroethylamine is 1 (2-4), and the mass ratio of polysuccinimide to inulin is 1-3:0.5.
3. The method for preparing the polymer scale inhibitor based on inulin modification grafting according to claim 1 or 2, which is characterized by comprising the following steps:
S1, adding inulin into an alkali solution, stirring and dissolving the inulin, and then carrying out alkalization treatment; then dripping 2-chloroethylamine aqueous solution for substitution reaction to obtain modified inulin monomer solution;
s2, providing a polysuccinimide monomer aqueous solution, dropwise adding the modified inulin monomer solution into the polysuccinimide monomer aqueous solution, and carrying out amidation reaction under alkaline conditions to obtain the polymer scale inhibitor.
4. The method for preparing a polymer scale inhibitor based on inulin modification grafting according to claim 3, wherein in step S1, the alkali solution is an aqueous NaOH solution, the mass concentration of the aqueous NaOH solution is 15%, and the molar ratio of the inulin to the NaOH is 1 (3-4); the temperature of the alkalization treatment is 40-50 ℃ and the time is 40-50 min.
5. The method for preparing a polymer scale inhibitor based on inulin modification grafting according to claim 3, wherein in step S1, the time for dropping the 2-chloroethylamine aqueous solution is 30min; and in the 2-chloroethylamine aqueous solution, the mass ratio of the 2-chloroethylamine to water is 1 (0.5-1).
6. The method for preparing a polymer scale inhibitor based on inulin modification grafting according to claim 3, wherein in step S1, the temperature of the substitution reaction is 50-60 ℃ for 3-4 hours.
7. The method for preparing a polymer scale inhibitor based on inulin modification grafting according to claim 3, wherein in step S2, the mass ratio of polysuccinimide to water in the polysuccinimide monomer aqueous solution is 1:3.
8. The method for preparing a polymer scale inhibitor based on inulin modification grafting according to claim 3, wherein in step S2, the time for dropping the modified inulin monomer solution is 30-60 min; the amidation reaction temperature is 50-70 deg.c and the amidation reaction time is 6-7 hr.
9. The method for preparing a polymer scale inhibitor based on inulin modification grafting according to claim 3, wherein in step S2, the pH of the solution is adjusted to 9-11 during the amidation reaction.
10. Use of the polymer scale inhibitor based on inulin modification grafting according to claim 1 for scale inhibition of wastewater.
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