CN109161019A - A kind of preparation method of beta-dicarbonyl compound modified polyaspartic acid - Google Patents
A kind of preparation method of beta-dicarbonyl compound modified polyaspartic acid Download PDFInfo
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- CN109161019A CN109161019A CN201810971820.3A CN201810971820A CN109161019A CN 109161019 A CN109161019 A CN 109161019A CN 201810971820 A CN201810971820 A CN 201810971820A CN 109161019 A CN109161019 A CN 109161019A
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- polysuccinimide
- dicarbonyl compound
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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
- C08G73/1092—Polysuccinimides
Abstract
The invention discloses a kind of preparation methods of beta-dicarbonyl compound modified polyaspartic acid, this method comprises: taking water as a solvent, under the catalysis of sodium hydroxide, polysuccinimide is reacted with beta-dicarbonyl compound, obtains the beta-dicarbonyl compound modified polyaspartic acid.The high-efficient environmental modified polyaspartic acid of scale inhibition can get using method of the invention, with stable, suitable viscosity average molecular weigh, a kind of new approaches are provided for designing and developing for green high-efficient Water Treatment Chemicals, are all had very important significance for developing industry recirculated cooling water technology, raising industrial production utilization rate and alleviation shortage of water resources.
Description
Technical field
The invention belongs to macromolecule treatment function Material Fields, and in particular to a kind of modified poly- day of beta-dicarbonyl compound
The preparation method of aspartic acid.
Background technique
For decades, researchers have carried out a large amount of research work to poly-aspartate (PASP).Current research table
It is bright, as a kind for the treatment of function material, scale inhibition, dispersion and the corrosion inhibition of PASP be widely used at present containing Phosphorus
Water treatment agent is compared to there are still certain gaps, and the more general water treatment agent of price is slightly higher.Therefore, it in order to improve its performance, opens up
Its application range is opened up, the core concept of research is to be designed by modification technology appropriate to material, by the official of Various Functions
It can roll into a ball and be introduced into PASP molecule, realize PASP structure function, performance diversification.Patent CN107602858A is sugared by carboxymethyl
Dehydrating condensation obtains glycosyl acetyl diamines under conditions of phosphoric acid catalyzed with diamines, and L- asparagus fern is added into kneading reactor respectively
Propylhomoserin and phosphoric acid mixing, stirring, heating, obtain polysuccinimide after polymerization, itself and glycosyl acetyl diamine reactant obtain
To polysuccinimide derivative.Two catalyst select phosphoric acid, and not only catalytic effect is general, and will cause unnecessary warp
Ji waste；Patent CN103724625A passes through high-temperature polycondensation, alkaline item using L-Aspartic acid monomer as raw material under certain condition
It is hydrolyzed under part and the subsequent purification steps such as neutralization obtains product.Not only low yield, step are many and diverse for the technique, and scale inhibition effect is not
And traditional phosphorus system antisludging agent；Patent CN104387585A discloses one kind using aspartic acid and lysine as raw material, 915 ±
50MHz, 400~10000W microwave condition under, be added a small amount of catalyst and appropriate organic solvent, radiate 1~30min, synthesis
Intermediate, organic solvent all recycles in gaseous form at this time, and intermediate is eluted through pure water, further alkaline after separating catalyst
Hydrolysis obtains aspartic acid-LYSINE COPOLYMER.In the article that inventor delivers before, C is selected2H5ONa, dehydrated alcohol conduct
The catalysts and solvents of beta-dicarbonyl compound graft modification poly-aspartate, from the point of view of final experimental result, scale-inhibiting properties
It is still to be improved.
Since inorganic salts, corrosive ion and the presence of microorganism, cooling water recycle for a long time in a device in industrial water
It uses, inevitably generates corrosion and scale problems, decline equipment heat-transfer capability, cause the waste of the energy.However, passing
The medicament phosphorus content of system is higher, is unfavorable for the normal development of the ecosystem, the products scale inhibition such as emerging poly-aspartate efficiency is simultaneously
Not as good as traditional medicament.
Summary of the invention
For the deficiency of existing poly-aspartate product, the present invention provides a kind of modified poly- asparagus fern ammonia of beta-dicarbonyl compound
The preparation method of acid, to obtain the high-efficient environmental modified polyaspartic acid of scale inhibition.
Present invention technical solution used for the above purpose is as follows:
A kind of preparation method of beta-dicarbonyl compound modified polyaspartic acid, comprising: take water as a solvent, in sodium hydroxide
Catalysis under, polysuccinimide is reacted with beta-dicarbonyl compound, obtains the modified poly- asparagus fern of the beta-dicarbonyl compound
Propylhomoserin.
Preferably, the beta-dicarbonyl compound is formyl acetic acid ethyl ester, ethyl acetoacetate, diethyl malonate or benzene
Formyl acetic acid ethyl ester.
Preferably, the molar ratio of the monomer of the polysuccinimide and beta-dicarbonyl compound, sodium hydroxide is 1:0.5
~1.2:1~2.
Preferably, the temperature of the reaction is 30~40 DEG C, the time 18~for 24 hours.
Preferably, the polysuccinimide is to be made using maleic anhydride as monomer by including the following steps, namely:
(1) in aqueous solvent, maleic anhydride reacts 1.5~2.5h in 60~90 DEG C with ammonium salt, obtains predecessor；
(2) obtained predecessor is warming up to 160~180 DEG C, reacts 1~1.5h, obtains polysuccinimide.
Preferably, the polysuccinimide is purified in the following way: with n,N-Dimethylformamide by poly- amber
The dissolution of amber acid imide filters after stirring 4~6 hours in 40~50 DEG C；Ethyl alcohol is added, 20~40min of precipitating is filtered, filter cake
The polysuccinimide as purified.
Preferably, the ammonium salt is ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, ammonium sulfate or ammonium nitrate.
Preferably, the molar ratio of the maleic anhydride and ammonium salt is 1:1.2~1.5, wherein the mole of ammonium salt is with ammonium root
Ionometer.
The purifying of polysuccinimide (PSI) is that beta-dicarbonyl compound connects skill with PSI open loop and reacts the weight being normally carried out
It ensures.
Such as use C2H5ONa, dehydrated alcohol are as catalyst, solvent, the PASP product viscosity average molecular weigh mistake reacted
Height, water soluble polymer chain is too long, it primarily serves absorption and the effect of bridge formation in the solution, accelerates fine particle in solution
Flocculation sedimentation, dispersibility significantly reduce, cause scale prevention ability to weaken.In contrast, the present invention selects NaOH, water as poly-
The catalysts and solvents that succinimide is reacted with beta-dicarbonyl compound can overcome C2H5ONa, the above-mentioned of dehydrated alcohol lack
It falls into, makes modified PASP product that there is stable, suitable viscosity average molecular weigh, it is ensured that it is with excellent scale-inhibiting properties, and β-two
The degradation mode of carbonyls is divided into acid decomposition and keto-acid is decomposed, and product is nontoxic small molecule.At green high-efficient water
Designing and developing for Physicochemical product provides a kind of new approaches, for developing industry recirculated cooling water technology, improves industrial production benefit
It is all had very important significance with rate and alleviation shortage of water resources.
The influence of different catalysts and solvent to beta-dicarbonyl compound modified polyaspartic acid performance
This part is to make further details of elaboration to catalysts and solvents (NaOH, water) selected in invention, is deeply cutd open
Analysis and catalyst selected before inventor, solvent (C2H5ONa, dehydrated alcohol) between difference.By a large amount of experimental study
Show: selecting the catalysts and solvents of NaOH, water as poly-aspartate (PASP) graft reaction, the product being finally modified can be made
Possess 100% scale inhibition performance and higher corrosion inhibition, and C2H5Such effect is but not achieved in ONa, dehydrated alcohol.It connects down
This will be described in detail from three Protonation effect, three-dimensional effect and solvation effect angles:
The reaction mechanism of 1 two groups of catalyst, solvent
It is as shown in Figure 1 using the reaction mechanism of NaOH, water as catalyst, solvent；
With C2H5ONa, dehydrated alcohol are as shown in Figure 2 as the reaction mechanism of catalyst, solvent；
Wherein, n1=n2=n3, α2< < α1< α3, β2< < β1< β3, α1+β1< n1, α2+β2< n2, α3+β3< n3, respectively
Next a quantitative relation can be discussed in detail.
The parsing of 2 reaction mechanisms
2.1 solvation effect
In anhydrous ethanol solvent, ethyl alcohol can't be ionized, and there's almost no Hydrogen Proton in solution, thus only sodium ion,
Alcoxyl anion, β anion (beta-dicarbonyl compound anion) constitute solution charge balance, therefore N atom combines in Fig. 2
Be not H proton, but sodium ion；Similarly ester group will not resolve into carboxylic acid group, ester point in final modified product
Solution is that solution can provide water for it for an important prerequisite condition of carboxylic acid and alcohol, it can thus be appreciated that the monomer molecule of ethanol system
Amount is more much bigger than aqueous systems, this is also one of the reason of last modified product viscosity average molecular weigh is higher than normal value (to glue and divide equally
Son amount excessively high causes product scale-inhibiting properties to be substantially reduced), and NaOH, water system in then on the contrary, and due to hydroxyl
The presence of ion has small part polysuccinimide with it and side reaction generation PASP occurs, therefore there are α2< < α1< α3, β2
< < β1< β3Such quantitative relation.
2.2 Protonation effect
Since there is no Hydrogen Proton and hydroxide ions in dehydrated alcohol, so when sodium ethoxide is as catalyst, finally
Without effectively closing end group, (X, Y may be alkoxy, sodium ion, and dehydrated alcohol system intermediate ion mobility to modified product
It is poor), i.e. α1+β1< α3+β3, cause viscosity average molecular weigh to be higher than normal value, water soluble polymer chain is too long, in the solution mainly
Play absorption and build bridge, accelerate the flocculation sedimentation of fine particle in solution, dispersibility significantly reduces, and causes scale inhibition energy
Power weakens；And NaOH, aqueous systems have stronger terminal end capping groups (H- ,-OH), control to a certain extent polymer-modified
Adhesive aggregation molecular weight makes it have excellent scale inhibition, corrosion inhibition.However, pH value should be controlled in the synthesis process, avoid protonating
Degree is excessively high and by-product PASP (α occurs2+β2< < α1+β1)。
2.3 three-dimensional effect
Three-dimensional effect is built upon solvation effect, on Protonation effect, due to different solvent and catalyst system
Reaction process is affected, final products is made to possess different water-soluble long-chains and different space structures.Detailed construction is as schemed
1, shown in 2.
Three effects complement each other, most importantly solvation effect, followed by Protonation effect and three-dimensional effect.
3 reaction mechanism differences are described in detail
Firstly, beta-dicarbonyl compound is in NaOH (or C2H5ONa β anion, β anion attack PSI are formed under the action of)
In C=O bond, be transferred to original negative electrical charge on the oxygen atom in the carbon oxygen singly-bound newly formed, at this time beta-dicarbonyl
It closes object and is already connected to PSI, the negative electrical charge of carbon oxygen singly-bound, which is moved back, at the same time forces original carbonnitrogen bond to be broken, and negative electrical charge is transferred to
On nitrogen-atoms, thus difference also embodies, and since dehydrated alcohol system Hydrogen Proton content is very little, nitrogen anion can only connect work
The poor sodium ion of dynamic property constitutes charge balance, and aqueous systems are then rich in Hydrogen Proton, enough in conjunction with nitrogen anion；
Carried out simultaneously in aqueous systems there are also the side reaction for generating PASP, can will by adjusting the operating technologies such as pH value
This extent of reaction minimizes, i.e., hydroxyl substituted beta anion carries out necleophilic reaction, forms by-product；
Another important difference is end-block effect, and effective blocking groups such as hydrogen-based, hydroxyl are rich in aqueous systems,
The reaction chain length to regroup is controlled, makes viscosity average molecular weigh in normal value (1.0 × 104) within, and dehydrated alcohol system
Then different, the convergence of the degree of polymerization is more difficult, lacks effective terminal end capping groups, result α1+β1< α3+β3；
Ester hydrolysis reaction can occur along with preliminarily forming for modified product, in aqueous systems, so that final product contains
There is carboxyl, and dehydrated alcohol system ester group will not hydrolyze, and lack the condition that ester hydrolysis reaction occurs, final ester group is retained；
The bad major reason of dehydrated alcohol system scale inhibition, corrosion inhibition is exactly that its viscosity average molecular weigh is higher than normal value (1.0
×104), product dispersion performance is poor, lays particular emphasis on flocculant, and this system is further improved, therefore present invention selection NaOH,
Catalysts and solvents of the water as graft reaction.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is using NaOH, water as catalyst, solvent, the reaction mechanism of beta-dicarbonyl compound and PSI；
Fig. 2 is with C2H5ONa, dehydrated alcohol are as catalyst, solvent, the reaction mechanism of beta-dicarbonyl compound and PSI.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1
Claim 9.8g maleic anhydride to be dissolved in 20ml distilled water under the conditions of 60 DEG C, 5.76g carbonic acid is added portionwise into ice-water bath
Ammonium is warming up to 70 DEG C after dissolution, amination hydrolyzes 2.5h, obtains white pasty masses maleimide.It is warming up to 165 DEG C again, height
Polycondensation reaction 1.5h is warmed, unpurified orange-yellow brittle solid PSI is obtained.
Above-mentioned 15.0g PSI is weighed, is made it dissolve with 60ml n,N-Dimethylformamide (DMF), in 40 DEG C of thermostatted water
It stirs 4 hours, is filtered, waste in bath, dehydrated alcohol, precipitating 30min is added, then filtered with Buchner funnel, filter cake is
The PSI of purifying, filtrate recycling.
The formyl acetic acid ethyl ester (EHA) and 4.8g NaOH for weighing 10.4g are added in 141ml water, are added after reacting 30min
Enter 9.7g purifying PSI, then 40 DEG C react 18 hours, after obtain red tan solution.With 4mol/L hydrochloric acid by system
PH value is adjusted to 5.8, is purified with the dehydrated alcohol of 5 times of volumes, stirs to get rufous viscous solid, it is modified that brown is obtained after dry
Poly-aspartate (EHA-PASP) recycles supernatant.
Embodiment 2
Claim 9.8g maleic anhydride to be dissolved in 20ml distilled water under the conditions of 60 DEG C, 6.72g carbonic acid is added portionwise into ice-water bath
Ammonium is warming up to 80 DEG C after dissolution, amination hydrolyzes 2.0h, obtains white pasty masses maleimide.It is warming up to 165 DEG C again, height
Polycondensation reaction 1.5h is warmed, unpurified orange-yellow brittle solid PSI is obtained.
Above-mentioned 15.0g PSI is weighed, is made it dissolve with 60ml n,N-Dimethylformamide (DMF), in 40 DEG C of thermostatted water
It stirs 4 hours, is filtered, waste in bath, dehydrated alcohol, precipitating 30min is added, then filtered with Buchner funnel, filter cake is
The PSI of purifying, filtrate recycling.
The ethyl acetoacetate (EAA) and 6.0g NaOH for weighing 11.7g are added in 155ml water, are added after reacting 35min
Enter 9.7g purifying PSI, then 35 DEG C react 20 hours, after obtain red tan solution.With 4mol/L hydrochloric acid by system
PH value is adjusted to 5.8, is purified with the dehydrated alcohol of 5 times of volumes, stirs to get rufous viscous solid, it is modified that brown is obtained after dry
Poly-aspartate (EAA-PASP) recycles supernatant.
Embodiment 3
Claim 9.8g maleic anhydride to be dissolved in 20ml distilled water under the conditions of 60 DEG C, 6.72g carbonic acid is added portionwise into ice-water bath
Ammonium is warming up to 85 DEG C after dissolution, amination hydrolyzes 1.5h, obtains white pasty masses maleimide.It is warming up to 170 DEG C again, height
Polycondensation reaction 1.2h is warmed, unpurified orange-yellow brittle solid PSI is obtained.
Above-mentioned 15.0g PSI is weighed, is made it dissolve with 60ml n,N-Dimethylformamide (DMF), in 40 DEG C of thermostatted water
It stirs 4 hours, is filtered, waste in bath, dehydrated alcohol, precipitating 30min is added, then filtered with Buchner funnel, filter cake is
The PSI of purifying, filtrate recycling.
The diethyl malonate (DEM) and 6.4g NaOH for weighing 12.8g are added in 164ml water, are added after reacting 40min
Enter 9.7g purifying PSI, then 34 DEG C react 20 hours, after obtain red tan solution.With 4mol/L hydrochloric acid by system
PH value is adjusted to 6, is purified with the dehydrated alcohol of 5 times of volumes, stirs to get rufous viscous solid, and it is modified poly- that brown is obtained after dry
Aspartic acid (DEM-PASP) recycles supernatant.
Embodiment 4
Claim 9.8g maleic anhydride to be dissolved in 20ml distilled water under the conditions of 60 DEG C, 6.72g carbonic acid is added portionwise into ice-water bath
Ammonium is warming up to 90 DEG C after dissolution, amination hydrolyzes 1.5h, obtains white pasty masses maleimide.It is warming up to 180 DEG C again, height
Polycondensation reaction 1.0h is warmed, unpurified orange-yellow brittle solid PSI is obtained.
Above-mentioned 15.0g PSI is weighed, is made it dissolve with 60ml n,N-Dimethylformamide (DMF), in 40 DEG C of thermostatted water
It stirs 4 hours, is filtered, waste in bath, dehydrated alcohol, precipitating 30min is added, then filtered with Buchner funnel, filter cake is
The PSI of purifying, filtrate recycling.
The ethyl benzoylacetate (EBA) and 8g NaOH for weighing 15.2g are added in 186ml water, are added after reacting 50min
Enter 9.7g purifying PSI, then 30 DEG C react 24 hours, after obtain red tan solution.With 4mol/L hydrochloric acid by system
PH value is adjusted to 6, is purified with the dehydrated alcohol of 5 times of volumes, stirs to get rufous viscous solid, and it is modified poly- that brown is obtained after dry
Aspartic acid (EBA-PASP) recycles supernatant.
Embodiment 5
Claim 9.8g maleic anhydride to be dissolved in 20ml distilled water under the conditions of 60 DEG C, 5.76g carbonic acid is added portionwise into ice-water bath
Ammonium is warming up to 80 DEG C after dissolution, amination hydrolyzes 2.0h, obtains white pasty masses maleimide.It is warming up to 165 DEG C again, height
Polycondensation reaction 1.5h is warmed, unpurified orange-yellow brittle solid PSI is obtained.
Above-mentioned 15.0g PSI is weighed, is made it dissolve with 60ml n,N-Dimethylformamide (DMF), in 40 DEG C of thermostatted water
It stirs 4 hours, is filtered, waste in bath, dehydrated alcohol, precipitating 30min is added, then filtered with Buchner funnel, filter cake is
The PSI of purifying, filtrate recycling.
EBA the and 4.8g NaOH for weighing 10.4g is added in 141ml water, and 9.7g purifying is added after reacting 30min
PSI, then react 18 hours, after obtain red tan solution.The pH value of product is adjusted to 5.8 with 4mol/L hydrochloric acid, with 5 times of bodies
Long-pending dehydrated alcohol purifying, stirs to get rufous viscous solid, obtains brown modified polyaspartic acid (EBA- after dry
PASP), supernatant is recycled.
Using static scale inhibition method (referring to GB/T16632-2008 " measurement-tosca of water treatment agent scale-inhibiting properties
Method ") to three kinds of modified polyaspartic acids (EHA-PASP, DEM-PASP and EBA-PASP) different dosages, scale inhibition temperature,
Scale inhibition time, Ca2+Scale-inhibiting properties (predominantly CaCO under the conditions of concentration etc.3Dirt) it is studied, as a result as follows:
(1) EHA-PASP drug concentration be 8mg/L, 6~10h of scale inhibition time, scale inhibition temperature 40~
80 DEG C, Ca2+Scale inhibition performance is 100% when 50~250mg/L of concentration；
(2) EAA-PASP drug concentration be 8mg/L, 6~10h of scale inhibition time, 40~80 DEG C of scale inhibition temperature, Ca2+Concentration
Scale inhibition performance is 100% when 50~250mg/L；
(3) DEM-PASP drug concentration be 10mg/L, 6~8h of scale inhibition time, 40~75 DEG C of scale inhibition temperature, Ca2+Concentration
Scale inhibition performance is 100% when 50~150mg/L；
(4) EBA-PASP drug concentration be 8mg/L, 6~10h of scale inhibition time, 40~80 DEG C of scale inhibition temperature, Ca2+Concentration
Scale inhibition performance is 100% when 50~250mg/L.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (9)
1. a kind of preparation method of beta-dicarbonyl compound modified polyaspartic acid, comprising: take water as a solvent, in sodium hydroxide
Under catalysis, polysuccinimide is reacted with beta-dicarbonyl compound, obtains the modified poly- asparagus fern ammonia of the beta-dicarbonyl compound
Acid.
2. preparation method according to claim 1, it is characterised in that: the beta-dicarbonyl compound is formyl acetic acid second
Ester, ethyl acetoacetate, diethyl malonate or ethyl benzoylacetate.
3. preparation method according to claim 1, it is characterised in that: the monomer and beta-dicarbonyl of the polysuccinimide
Compound, sodium hydroxide molar ratio be 1:0.5~1.2:1~2.
4. preparation method according to claim 1 or 2 or 3, it is characterised in that: the temperature of the reaction is 30~40 DEG C,
Time 18~for 24 hours.
5. preparation method according to claim 1, it is characterised in that: it is single that the polysuccinimide, which is with maleic anhydride,
Body is made by including the following steps, namely:
(1) in aqueous solvent, maleic anhydride reacts 1.5~2.5h in 60~90 DEG C with ammonium salt, obtains predecessor；
(2) obtained predecessor is warming up to 160~180 DEG C, reacts 1~1.5h, obtains polysuccinimide.
6. preparation method according to claim 1 or 5, it is characterised in that: the polysuccinimide is in the following way
It is purified: being dissolved polysuccinimide with n,N-Dimethylformamide, filtered after being stirred 4~6 hours in 40~50 DEG C；Again
Ethyl alcohol is added, 20~40min of precipitating is filtered, and filter cake is the polysuccinimide purified.
7. preparation method according to claim 5, it is characterised in that: the ammonium salt is ammonium carbonate, ammonium hydrogen carbonate, chlorination
Ammonium, ammonium sulfate or ammonium nitrate.
8. preparation method according to claim 5, it is characterised in that: the molar ratio of the maleic anhydride and ammonium salt is 1:
1.2~1.5, wherein the mole of ammonium salt is in terms of ammonium ion.
9. the beta-dicarbonyl compound modified polyaspartic acid being prepared according to any preparation method of claim 1-8.
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