CN105482117A - Polyaspartic acid/urea graft copolymer as well as preparation method and application thereof - Google Patents
Polyaspartic acid/urea graft copolymer as well as preparation method and application thereof Download PDFInfo
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- CN105482117A CN105482117A CN201610035306.XA CN201610035306A CN105482117A CN 105482117 A CN105482117 A CN 105482117A CN 201610035306 A CN201610035306 A CN 201610035306A CN 105482117 A CN105482117 A CN 105482117A
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to a novel amide group-containing polyaspartic acid derivative, namely, polyaspartic acid/urea graft copolymer. The structure of the polyaspartic acid/urea graft copolymer is as shown in the following formula (I) or (II), wherein the formula (I) or (II) is shown in the description; n is selected from 35-130; the ratio of n to p is 1: (0.01-0.99); the weight average molecular weight of the polyaspartic acid/urea graft copolymer is 4000-15000. The polyaspartic acid derivative provided by the invention is a low-cost, non-toxic, non-phosphorus and biodegradable high-molecular polymer, has excellent chelating and dispersing performance, and has an excellent scale inhibition effect on various scales such as calcium carbonate, calcium sulfate and calcium phosphate. The invention also provides a preparation method for the polyaspartic acid derivative. According to the preparation method, polyaspartic acid is modified through a hydrolytic ring opening manner; meanwhile, the preparation method has the advantages of being simple in production process, low in pollution to environment, excellent in scale inhibition performance of products, and the like; in addition, raw materials are cheap and wide in source; the preparation method is suitable for industrial production.
Description
Technical field
The invention belongs to high molecular polymer field, be specifically related to a kind of novel poly-aspartate derivant, relate more specifically to poly aspartic acid/urea graft copolymer, and preparation method thereof.
Background technology
In recent years, develop rapidly along with industrial, industrial water consumption increases day by day, and wherein water coolant accounts for more than 60% of process water, therefore saves the primary goal that water coolant just becomes Industrial Water Saving.Recycling of water coolant is the most effective way of saving water coolant.But recycling in process at water coolant, the reasons such as temperature raises, raw water quality difference make system contamination, fouling, reduce the heat transfer efficiency of system, add the energy consumption of system.Therefore, recycle in the process of water coolant and be necessary to take certain antiscale, scale inhibition measure.Add the important means that Scale inhibitors is antiscale, scale inhibition, it plays very important effect to preventing precipitation formation.For this reason, how to control the growth of incrustation scale, exploitation environmental protection, efficiently Scale Inhibitors for Water have become the focus of current industrial water conditioning agent research.Scale inhibitors conventional in current water treatment has natural Scale inhibitors, P containing sludge inhibitor, polycarboxylic acid scale inhibitor and novel green scale inhibitor.
Poly aspartic acid, as a kind of novel degradable green Scale inhibitors, has excellent complexing power and dispersing property.But poly aspartic acid chain only has free carboxy, and comprehensive scale-inhibiting properties is bad.Be incorporated in the molecular structure of poly aspartic acid by functional group hydroxyl, carboxylic acid group, sulfonic group, phosphate etc. with scale-inhibiting properties, the object improving poly aspartic acid performance can be reached.Polysuccinimide is the intermediate product preparing poly aspartic acid, and it is the linear polyimide that a kind of activity is very strong, has good reactive behavior, is easily generated the poly-aspartate derivant with functional group side chain by amino open loop.By the method modified synthesis poly-aspartate derivant of hydrolysis of polysuccinimide open loop, reaction process is simple, and temperature of reaction is lower, does not need additionally to add organic solvent and phosphoric acid catalyst.CN102875808A discloses a kind of preparation method containing sulfonic aspartate copolymer, be that intermediate polysuccinimide prepared by raw material with aspartic acid, then 2-aminoethyl sulfonic acid salt and the glutaminate aqueous solution are added in the suspension of polysuccinimide and water simultaneously, solid is separated out with dehydrated alcohol, obtain, containing sulfonic poly-aspartate derivant, improve scale-inhibiting properties.The price comparison of the method raw material aspartic acid is expensive, be unfavorable for industrial production, and sulfonic group has pollution to environment.
Therefore, be necessary that a kind of new green scale inhibitor of exploitation is to overcome the limitation of prior art.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of novel poly-aspartate derivant, has more excellent scale-inhibiting properties than existing poly-aspartate derivant Scale inhibitors.
Another object of the present invention is: provide a kind of method preparing described poly-aspartate derivant, has low cost and the advantage of environmental protection.
Another object of the present invention is: provide the described application of poly-aspartate derivant in the fields such as water treatment, medicine, agricultural, daily use chemicals.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
First, provide a kind of poly-aspartate derivant, it is the poly aspartic acid/urea graft copolymer (PASP/Urea) of amide-containing, and its structure is as shown in the formula shown in (I) or (II):
In formula (I) or (II): described n gets 35-130; N:p=1:0.01-1:0.99.
The preferred poly-aspartate derivant of the present invention, its weight-average molecular weight is 4000-15000.
The preferred poly-aspartate derivant of the present invention, is prepared by following methods: first obtain ethyl maleate with maleic anhydride and ethanol synthesis; The ethyl maleate obtained is obtained by reacting ethyl maleate ammonium salt solution with ammoniacal liquor again; Ethyl maleate ammonium salt carries out polycondensation and obtains polysuccinimide (PSI) under polar solvent effect; Finally in PSI suspension liquid, add the basic solution being dissolved with urea, carry out ammonia solution graft reaction 4-48h in a heated condition, reaction terminates adjust ph to neutral, obtains poly aspartic acid of the present invention/urea graft copolymer.
In addition, the present invention also provides a kind of method preparing described poly-aspartate derivant, is first to obtain ethyl maleate with maleic anhydride and ethanol synthesis; The ethyl maleate obtained is obtained by reacting ethyl maleate ammonium salt solution with ammoniacal liquor again; Ethyl maleate ammonium salt carries out polycondensation and obtains polysuccinimide (PSI) under polar solvent effect; Finally in PSI suspension liquid, add the basic solution being dissolved with urea, carry out ammonia solution graft reaction 4-48h in a heated condition, reaction terminates adjust ph to neutral, obtains poly aspartic acid of the present invention/urea graft copolymer,
Synthetic route is as follows substantially for it:
The present invention preferably prepares the method for described poly-aspartate derivant, and concrete steps comprise:
(1) maleic anhydride and ethanol react 1.5 ~ 3h with the mol ratio of 1:1.1-1:1.5 at 50 ~ 80 DEG C, obtain ethyl maleate;
(2) add ammoniacal liquor in the ethyl maleate solution obtained to (1), the mol ratio of maleic anhydride monoethylester and ammoniacal liquor is 1:1.1-1:2.0, reacts 2-5h and obtain ethyl maleate ammonium salt solution under room temperature;
(3) polar solvent containing nitrogen methyl-2-pyrrolidone is added in the ethyl maleate ammonium salt solution obtained to (2), polycondensation 4-10h is carried out at 150-220 DEG C of temperature, react rear cooling and solution has slowly been joined in dehydrated alcohol, having obtained the polysuccinimide of purifying;
(4) polysuccinimide that step (3) obtains is prepared into suspension liquid, the mixing solutions again urea being dissolved in the formation of highly basic solvent is slowly added drop-wise in described suspension liquid, the mol ratio of polysuccinimide and urea is made to be 1:0.01-1:0.99, at 50 DEG C, ammonia solution graft reaction 4-48h is carried out in heating, reaction terminates adjust ph to neutral, obtains brown precipitate and is poly aspartic acid of the present invention/urea graft copolymer.
The present invention is preferably prepared in the method for described poly-aspartate derivant further, and the maleic anhydride described in step (1) and the mol ratio of ethanol are 1:1.2.
The present invention preferably prepares in the method for described poly-aspartate derivant, and the polar solvent containing nitrogen methyl-2-pyrrolidone described in step (3) is selected from: nitrogen methyl-2-pyrrolidone, or the mixed solvent of nitrogen methyl-2-pyrrolidone and tetramethylene sulfone; In preferred scheme, in described mixing solutions, the mass ratio of nitrogen methyl-2-pyrrolidone and tetramethylene sulfone is 2:1-1:2; In most preferably described mixing solutions, the mass ratio of nitrogen methyl-2-pyrrolidone and tetramethylene sulfone is 1:1.
The present invention preferably prepares in the method for described poly-aspartate derivant, and the polycondensation reaction time described in step (3) is 6-8h.
The present invention preferably prepares in the method for described poly-aspartate derivant, and the polycondensation temperature described in step (3) is 180 ~ 200 DEG C.
The present invention preferably prepares in the method for described poly-aspartate derivant, and the highly basic described in step (4) is selected from one or more the mixed solvent in sodium hydroxide, potassium hydroxide, sodium ethylate, cesium hydroxide or sodium cyanide.
The present invention is preferably prepared in the method for described poly-aspartate derivant further, the mixing solutions that urea described in step (4) is dissolved in the formation of highly basic solvent is the mixing solutions that urea is dissolved in sodium ethylate formation, and wherein the mol ratio of urea and sodium ethylate is 1:1.0-1:2.0.
The present invention preferably prepares in the method for described poly-aspartate derivant, after obtaining brown precipitate described in step (4), and further vacuum-drying 10-24h.
The present invention preferably prepares in the method for described poly-aspartate derivant, and it is polysuccinimide is dissolved in ethanol, DMF or water equal solvent to form suspension liquid that the polysuccinimide described in step (4) is prepared into suspension liquid; In preferred method, polysuccinimide is dissolved in ethanol and forms suspension liquid.
The present invention preferably prepares in the method for described poly-aspartate derivant, and in the poly aspartic acid that step (4) obtains/urea graft copolymer, the percentage of grafting of urea is 1%-99%.
Finally, the present invention also provides the application in the antiscale of described poly-aspartate derivant at water or scale inhibition; Especially the application in the antiscale of process water comprising the fields such as water treatment, medicine, agricultural, daily use chemicals or scale inhibition.
Compared with prior art, the invention provides a kind of novel poly-aspartate derivant, i.e. poly aspartic acid/urea graft copolymer, this compound is a kind of nontoxic, not phosphorous, degradable high molecular polymer, amide group is introduced in its molecular chain, enhance its anticorrosion-antiscaling property and dispersing property, overcome the deficiency of existing poly aspartic acid on resistance calcium phosphate scale and dispersiveness; For multiple dirts such as calcium carbonate, calcium sulfate and calcium phosphate, all there is excellent scale inhibition effect.
The present invention also provides the preparation method of described poly aspartic acid/urea graft copolymer, by the method for hydrolysis, modification is carried out to poly aspartic acid, have that production technique is simple, environmental pollution is little, many-sided advantage of product scale-inhibiting properties excellence simultaneously, and raw material is cheap, wide material sources, are suitable for industrial production.
Embodiment
Preparation embodiment 1
Take 9.8g maleic anhydride, 5.5g dehydrated alcohol adds in there-necked flask, reacts 2.5h and obtains colourless solution, be cooled to room temperature, obtain ethyl maleate under 60 DEG C of temperature condition.
Preparation embodiment 2
Take 9.8g maleic anhydride, 5.5g dehydrated alcohol adds in there-necked flask, reacts 2.5h and obtains colourless solution, be cooled to room temperature under 60 DEG C of temperature condition.In there-necked flask, add 8.9g25% ammoniacal liquor, react 3h under room temperature and obtain pale yellow solution ammonium salt solution.
Preparation embodiment 3
Join in there-necked flask by 9.8g maleic anhydride and 5.53g ethanol, react under 60 DEG C of temperature condition, along with the carrying out of reaction, dissolution of solid, after 2.5h, stopped reaction obtains colourless ethyl maleate solution, is cooled to room temperature.In there-necked flask, add 8.9g25% ammoniacal liquor room temperature reaction 3h with constant pressure funnel and obtain light yellow ammonium salt solution.Add in flask by 15g tetramethylene sulfone and nitrogen methyl-2-pyrrolidone (1:1) mixed solvent, adularescent muddiness occurs, at N
2protection, mechanical stirring, carries out thermal polycondensation under point water condition, reacts 6h at 180 DEG C.Along with the rising of temperature of reaction, muddy to disappear, when temperature is greater than 150 DEG C, solution starts to become orange, and color is constantly deepened, and finally obtains the solution that brown is sticky.Slowly be added to while hot in dehydrated alcohol by solution, tan precipitate is separated out, and carry out suction filtration, drying obtains 9.4g polysuccinimide.
Preparation embodiment 4
Join in there-necked flask by 9.8g maleic anhydride and 5.6g ethanol, react under 60 DEG C of temperature condition, along with the carrying out of reaction, dissolution of solid, after 2.5h, stopped reaction obtains colourless ethyl maleate solution, is cooled to room temperature.In there-necked flask, add 8.9g25% ammoniacal liquor room temperature reaction 3h with constant pressure funnel and obtain light yellow ammonium salt solution.Add in flask by 15g tetramethylene sulfone and nitrogen methyl-2-pyrrolidone (1:1) mixed solvent, adularescent muddiness occurs, at N
2protection, mechanical stirring, carries out thermal polycondensation under point water condition, reacts 6h at 180 DEG C.Along with the rising of temperature of reaction, muddy to disappear, when temperature is greater than 150 DEG C, solution starts to become orange, and color is constantly deepened, and finally obtains the solution that brown is sticky.Be cooled to 50 DEG C, the sodium hydroxide solution adding 18% in polysuccinimide system regulates pH to 8-9, after reacting 1 hour, carry out separatory and obtain poly aspartic acid aqueous phase solution, use salt acid for adjusting pH to 3 again, be poured in the alcohol solvent of stirring, separate out solid.Then suction filtration, washing with alcohol 3 times, 55.0 DEG C of vacuum-drying 5h obtain off-white or buff white solid, are poly aspartic acid.According to the display of gpc analysis result, the weight-average molecular weight of poly aspartic acid is 7130.
Preparation embodiment 5
Join in there-necked flask by 19.6g maleic anhydride and 11.1g ethanol, react under 60 DEG C of temperature condition, along with the carrying out of reaction, dissolution of solid, after 2.5h, stopped reaction obtains colourless ethyl maleate solution, is cooled to room temperature.In there-necked flask, add 16.2g ammoniacal liquor room temperature reaction 3h with constant pressure funnel and obtain light yellow ammonium salt solution.Add in flask by 30g tetramethylene sulfone and nitrogen methyl-2-pyrrolidone (1:1) mixed solvent, adularescent muddiness occurs, at N
2protection, mechanical stirring, carries out thermal polycondensation under point water condition, reacts 6h at 180 DEG C.Along with the rising of temperature of reaction, muddy to disappear, when temperature is greater than 150 DEG C, solution starts to become orange, and color is constantly deepened, and finally obtains the solution that brown is sticky.Slowly be added to while hot in dehydrated alcohol by solution, tan precipitate is separated out, and carry out suction filtration, drying obtains polysuccinimide.Get 1g polysuccinimide and ethanol to join in flask and form suspension liquid, again the alcohol sodium solution of 0.3g urea is slowly added drop-wise in suspension liquid, at 50 DEG C, ammonolysis reaction 10h is carried out in heating, with salt acid for adjusting pH value to neutral, reaction terminates brown precipitate and separates out, suction filtration, vacuum-drying, obtain 1.2g poly aspartic acid/urea graft copolymer.According to the display of gpc analysis result, the weight-average molecular weight of multipolymer is 9049.
Preparation embodiment 6
Join in there-necked flask by 19.6g maleic anhydride and 12.0g ethanol, react under 60 DEG C of temperature condition, along with the carrying out of reaction, dissolution of solid, after 2.5h, stopped reaction obtains colourless ethyl maleate solution, is cooled to room temperature.In there-necked flask, add 11.7g ammoniacal liquor room temperature reaction 3h with constant pressure funnel and obtain light yellow ammonium salt solution.Add in flask by 30g tetramethylene sulfone and nitrogen methyl-2-pyrrolidone (1:1.5) mixed solvent, adularescent muddiness occurs, at N
2protection, mechanical stirring, carries out thermal polycondensation under point water condition, reacts 7h at 190 DEG C.Along with the rising of temperature of reaction, muddy to disappear, when temperature is greater than 150 DEG C, solution starts to become orange, and color is constantly deepened, and finally obtains the solution that brown is sticky.Slowly be added to while hot in dehydrated alcohol by solution, tan precipitate is separated out, and carry out suction filtration, drying obtains polysuccinimide.Get 1.9g polysuccinimide and ethanol to join in flask and form suspension liquid, again the alcohol sodium solution of 0.7g urea is slowly added drop-wise in suspension liquid, at 50 DEG C, ammonolysis reaction 10h is carried out in heating, with salt acid for adjusting pH value to neutral, reaction terminates brown precipitate and separates out, suction filtration, vacuum-drying, obtain 2.5g poly aspartic acid/urea graft copolymer.According to the display of gpc analysis result, the weight-average molecular weight of multipolymer is 11300.
Preparation embodiment 7
Join in there-necked flask by 19.6g maleic anhydride and 12.9g ethanol, react under 60 DEG C of temperature condition, along with the carrying out of reaction, dissolution of solid, after 2.5h, stopped reaction obtains colourless ethyl maleate solution, is cooled to room temperature.In there-necked flask, add 19.6g ammoniacal liquor room temperature reaction 3h with constant pressure funnel and obtain light yellow ammonium salt solution.Add in flask by 30g tetramethylene sulfone and nitrogen methyl-2-pyrrolidone (1:2) mixed solvent, adularescent muddiness occurs, at N
2protection, mechanical stirring, carries out thermal polycondensation under point water condition, reacts 8h at 200 DEG C.Along with the rising of temperature of reaction, muddy to disappear, when temperature is greater than 150 DEG C, solution starts to become orange, and color is constantly deepened, and finally obtains the solution that brown is sticky.Slowly be added to while hot in dehydrated alcohol by solution, tan precipitate is separated out, and carry out suction filtration, drying obtains polysuccinimide.Get 2.9g polysuccinimide and ethanol to join in flask and form suspension liquid, again the alcohol sodium solution of 1.3g urea is slowly added drop-wise in suspension liquid, at 50 DEG C, ammonolysis reaction 10h is carried out in heating, with salt acid for adjusting pH value to neutral, reaction terminates brown precipitate and separates out, suction filtration, vacuum-drying, obtain 4.1g poly aspartic acid/urea graft copolymer.According to the display of gpc analysis result, the weight-average molecular weight of multipolymer is 10650.
Preparation embodiment 8
Join in there-necked flask by 19.6g maleic anhydride and 13.8g ethanol, react under 60 DEG C of temperature condition, along with the carrying out of reaction, dissolution of solid, after 2.5h, stopped reaction obtains colourless ethyl maleate solution, is cooled to room temperature.In there-necked flask, add 20.4g ammoniacal liquor room temperature reaction 3h with constant pressure funnel and obtain light yellow ammonium salt solution.Add in flask by 30g tetramethylene sulfone and nitrogen methyl-2-pyrrolidone (1:1) mixed solvent, adularescent muddiness occurs, at N
2protection, mechanical stirring, carries out thermal polycondensation under point water condition, reacts 9h at 170 DEG C.Along with the rising of temperature of reaction, muddy to disappear, when temperature is greater than 150 DEG C, solution starts to become orange, and color is constantly deepened, and finally obtains the solution that brown is sticky.Slowly be added to while hot in dehydrated alcohol by solution, tan precipitate is separated out, and carry out suction filtration, drying obtains polysuccinimide.Get 3.9g polysuccinimide and ethanol to join in flask and form suspension liquid, again the alcohol sodium solution of 1.9g urea is slowly added drop-wise in suspension liquid, at 50 DEG C, ammonolysis reaction 10h is carried out in heating, with salt acid for adjusting pH value to neutral, reaction terminates brown precipitate and separates out, suction filtration, vacuum-drying, obtain 5.3g poly aspartic acid/urea graft copolymer.According to the display of gpc analysis result, the weight-average molecular weight of multipolymer is 13000.
Application Example 1
Get the contrast experiment that poly aspartic acid/urea graft copolymer that the preparation poly aspartic acid prepared of embodiment 4 and preparation embodiment 5-8 prepare carries out scale-inhibiting properties, according to the mensuration of GB/T16632-2008 water treatment scale performance, assess poly aspartic acid of the present invention/urea graft copolymer to the impact of calcium carbonate scale-inhibiting properties.Configuration water sample: the starting point concentration of calcium ion is 240mg/L, and the concentration of bicarbonate ion is 732mg/L, and pH value is 9 and ignores the change of pH value, heats 10h in 80 DEG C of waters bath with thermostatic control.When concentration is 4mg/L, poly aspartic acid prepared by preparation embodiment 4 is 28% to the scale inhibition performance of calcium carbonate; And prepare poly aspartic acid/urea graft copolymer prepared by embodiment 5-8 under same concentration to the scale inhibition performance of calcium carbonate all more than 60%, illustrate that poly aspartic acid of the present invention/urea graft copolymer has than poly aspartic acid better resistance calcium carbonate performance.
Application Example 2
Get the graft copolymer prepared of preparation embodiment 5-8 and carry out scale-inhibiting properties experiment, assess poly aspartic acid of the present invention/urea graft copolymer to the impact of calcium sulfate scale-inhibiting properties.Configuration water sample: the starting point concentration of calcium ion and sulfate ion is 6800mg/L, and pH value is 9 and ignores the change of pH value, heats 10h in 80 DEG C of waters bath with thermostatic control.When concentration is 6mg/L, the poly aspartic acid/scale inhibition performance of urea graft copolymer to calcium sulfate that preparation embodiment 5-8 prepares is 100%, illustrates that poly aspartic acid of the present invention/urea graft copolymer has outstanding resistance calcium sulfate performance.
Application Example 3
Get the graft copolymer prepared of preparation embodiment 5-8 and carry out scale-inhibiting properties experiment, assess poly aspartic acid of the present invention/urea graft copolymer to the impact of calcium phosphate scale-inhibiting properties.Configuration water sample: the starting point concentration of calcium ion is 250mg/L, and the concentration of phosphate anion is 10mg/L, and pH value is 9 and ignores the change of pH value, heats 10h in 80 DEG C of waters bath with thermostatic control.When concentration is 8mg/L, poly aspartic acid/urea graft copolymer that preparation embodiment 5-8 prepares all higher than 85%, illustrates that poly aspartic acid of the present invention/urea graft copolymer has outstanding resistance calcium phosphate performance to the scale inhibition performance of calcium phosphate.
Claims (10)
1. a poly-aspartate derivant, is characterized in that, it is the poly aspartic acid/urea graft copolymer of amide-containing, and its structure is as shown in the formula shown in (I) or (II):
In formula (I) or (II): described n gets 35-130; N:p=1:0.01-1:0.99.
2. poly-aspartate derivant as claimed in claim 1, it is characterized in that, it is prepared by following methods: first obtain ethyl maleate with maleic anhydride and ethanol synthesis; The ethyl maleate obtained is obtained by reacting ethyl maleate ammonium salt solution with ammoniacal liquor again; Ethyl maleate ammonium salt carries out polycondensation and obtains polysuccinimide (PSI) under polar solvent effect; Finally in PSI suspension liquid, add the basic solution being dissolved with urea, carry out ammonia solution graft reaction 4-48h in a heated condition, reaction terminates adjust ph to neutral, obtains described poly aspartic acid/urea graft copolymer.
3. prepare a method for poly-aspartate derivant described in claim 1, it is characterized in that: first obtain ethyl maleate with maleic anhydride and ethanol synthesis; The ethyl maleate obtained is obtained by reacting ethyl maleate ammonium salt solution with ammoniacal liquor again; Ethyl maleate ammonium salt carries out polycondensation and obtains polysuccinimide (PSI) under polar solvent effect; Finally in PSI suspension liquid, add the basic solution being dissolved with urea, carry out ammonolysis reaction 4-48h in a heated condition, reaction terminates adjust ph to neutral, obtains described poly aspartic acid/urea graft copolymer.
4. method according to claim 3, is characterized in that, comprises the following steps:
(1) maleic anhydride and ethanol react 1.5 ~ 3h with the mol ratio of 1:1.1-1:1.5 at 50 ~ 80 DEG C, obtain ethyl maleate;
(2) add ammoniacal liquor in the ethyl maleate solution obtained to (1), the mol ratio of ethyl maleate and ammoniacal liquor is 1:1.1-1:2.0, reacts 2-5h and obtain ethyl maleate ammonium salt solution under room temperature;
(3) polar solvent containing nitrogen methyl-2-pyrrolidone is added in the ethyl maleate ammonium salt solution obtained to (2), polycondensation 4-10h is carried out at 150-220 DEG C of temperature, react rear cooling and solution has slowly been joined in dehydrated alcohol, having obtained the polysuccinimide of purifying;
(4) polysuccinimide that step (3) obtains is prepared into suspension liquid, the mixing solutions again urea being dissolved in the formation of highly basic solvent is slowly added drop-wise in described suspension liquid, the mol ratio of polysuccinimide and urea is made to be 1:0.01-1:0.99, at 50 DEG C, ammonia solution graft reaction 4-48h is carried out in heating, reaction terminates adjust ph to neutral, obtains brown precipitate and is described poly aspartic acid/urea graft copolymer.
5. method according to claim 4, is characterized in that: the polar solvent containing nitrogen methyl-2-pyrrolidone described in step (3) is selected from: nitrogen methylpyrrolidone solution, or the mixing solutions of nitrogen methyl-2-pyrrolidone and tetramethylene sulfone; In preferred scheme, in described mixing solutions, the mass ratio of nitrogen methyl-2-pyrrolidone and tetramethylene sulfone is 2:1-1:2; More preferably in described mixing solutions, the mass ratio of nitrogen methyl-2-pyrrolidone and tetramethylene sulfone is 1:1.
6. method according to claim 4, is characterized in that: the polycondensation reaction time described in step (3) is 6-8h; Described polycondensation temperature is 180 ~ 200 DEG C.
7. method according to claim 4, is characterized in that: the highly basic solvent described in step (4) is selected from a kind of solution in sodium hydroxide, potassium hydroxide, sodium ethylate, cesium hydroxide or sodium cyanide or two or more mixing solutionss.
8. method according to claim 4, is characterized in that: the mixing solutions that the urea described in step (4) is dissolved in the formation of highly basic solvent is the mixing solutions that urea is dissolved in sodium ethylate formation, and wherein the mol ratio of urea and sodium ethylate is 1:1.0-1:2.0.
9. method according to claim 4, is characterized in that: it is polysuccinimide is dissolved in ethanol, DMF or water to form suspension liquid that the polysuccinimide described in step (4) is prepared into suspension liquid; Preferably polysuccinimide is dissolved in ethanol and forms suspension liquid.
10. the application of poly-aspartate derivant according to claim 1 in the antiscale or scale inhibition of water, is characterized in that: the antiscale of described water or scale inhibition comprise water treatment, medicine, agricultural, the antiscale of process water of household chemicals field or scale inhibition.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN108059713A (en) * | 2018-01-02 | 2018-05-22 | 厦门双瑞船舶涂料有限公司 | The aqueous epoxy curing agent and preparation method of a kind of functional group containing DOPA |
| CN112246232A (en) * | 2020-10-16 | 2021-01-22 | 李艳艳 | Polyaspartic acid modified cellulose aerogel and preparation method thereof |
| CN113527679A (en) * | 2020-04-15 | 2021-10-22 | 中国石油化工股份有限公司 | Polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer and application thereof |
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| CN106007015A (en) * | 2016-07-26 | 2016-10-12 | 青岛辰达生物科技有限公司 | Polyaspartic acid for water treatment scale inhibitor, as well as preparation method and application of polyaspartic acid |
| CN106007015B (en) * | 2016-07-26 | 2018-11-20 | 泉州市春川贸易有限公司 | A kind of poly-aspartate and its preparation method and application for Scale Inhibitors for Water |
| CN108059713A (en) * | 2018-01-02 | 2018-05-22 | 厦门双瑞船舶涂料有限公司 | The aqueous epoxy curing agent and preparation method of a kind of functional group containing DOPA |
| CN113527679A (en) * | 2020-04-15 | 2021-10-22 | 中国石油化工股份有限公司 | Polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer and application thereof |
| CN113527679B (en) * | 2020-04-15 | 2023-03-31 | 中国石油化工股份有限公司 | Polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer and application thereof |
| CN112246232A (en) * | 2020-10-16 | 2021-01-22 | 李艳艳 | Polyaspartic acid modified cellulose aerogel and preparation method thereof |
| CN114956898A (en) * | 2022-06-30 | 2022-08-30 | 河北协同化学有限公司 | Nitrogen-fixing fertilizer-maintaining synergist, self-assembly nitrogen-containing fertilizer containing nitrogen-fixing fertilizer-maintaining synergist and preparation method of self-assembly nitrogen-containing fertilizer |
| CN114956898B (en) * | 2022-06-30 | 2023-10-13 | 河北协同化学有限公司 | Nitrogen fixation fertilizer retention synergist, self-assembled nitrogen-containing fertilizer containing nitrogen fixation fertilizer retention synergist and preparation method |
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