CN108559081B - A kind of aspartic acid-LYSINE COPOLYMER and its derivative - Google Patents
A kind of aspartic acid-LYSINE COPOLYMER and its derivative Download PDFInfo
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- CN108559081B CN108559081B CN201810424165.XA CN201810424165A CN108559081B CN 108559081 B CN108559081 B CN 108559081B CN 201810424165 A CN201810424165 A CN 201810424165A CN 108559081 B CN108559081 B CN 108559081B
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- aspartic acid
- lysine
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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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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a kind of aspartic acid-LYSINE COPOLYMER and its derivatives, first under the effect of the catalyst by aspartic acid and lysine, reaction intermediate is obtained by solid phase synthesis process, then reaction intermediate is separated by organic solvent, finally hydrolysis obtains aspartic acid-LYSINE COPOLYMER under alkaline condition, this method mild condition, and avoid using a large amount of organic solvent, it is environmental-friendly.Phosphate group, citrate group or oxygen propyl group trimethyl ammonia chloride ammonium group are grafted on the amino of copolymer lysine monomer free simultaneously, prepare the copolymer derivative with a variety of scale inhibition groups, copolymer is improved to the scale inhibition effect of calcium carbonate and calcium sulfate, improves copolymer to the low scale inhibition effect of calcium phosphate.
Description
Technical field
The present invention relates to field of polymer material preparing technology, and in particular to a kind of aspartic acid-LYSINE COPOLYMER
The derivative of synthetic method, the copolymer, the aspartic acid-LYSINE COPOLYMER and aspartic acid-LYSINE COPOLYMER spread out
Biology can be used as the antisludging agent in anti-penetration wastewater disposal technical process and use.
Background technique
With the development of global economy and society, the whole world increasingly increases available freshwater resources demand, and reverse osmosis
Water treatment technology as a kind of high-quality and high-efficiency thoroughly, engineer application total amount are continuously increased.In practical applications with raw water quilt
Constantly concentration, one of the various scale-forming ion concentration also constantly increase, and finally being formed in membrane surface includes calcium carbonate, sulfuric acid
The pollution layer of the substances such as calcium, calcium phosphate, silica.
In order to alleviate the pollution situation during reverse osmosis treatment, need to add antisludging agent to slow down this trend.Now,
With the continuous improvement of the environment amenable requirement of people, the greenization of water treatment agent has become the mainstream of its development.Especially
It is with the antisludging agent of polyaminoacid class, because its scale inhibition effect is preferable, is readily biodegradable and the advantages that raw material green is easy to get,
As research hotspot in recent years.
Chinese patent CN104387585A discloses a kind of aspartic acid-LYSINE COPOLYMER and its synthetic method, the change
Closing object is in organic solvent, to pass through microwave irradiation synthesis under the auxiliary of catalyst using aspartic acid and lysine as raw material
's.This method haves the advantages that reaction speed is fast, but it needs in the synthesis process using a large amount of volatile organic solvents and needs
Want more complex special synthesis device.In addition, experimental studies have found that, aspartic acid-LYSINE COPOLYMER imitates calcium phosphate scale inhibition
Fruit is bad, it is difficult to the medicament as a kind of universality.
Summary of the invention
In view of above-mentioned aspartic acid-LYSINE COPOLYMER synthetic method there are the problem of, the present invention provides a kind of asparagus fern
Propylhomoserin-LYSINE COPOLYMER antisludging agent solid phase synthesis process, solves and needs a large amount of volatility organic in existing synthetic method
Solvent and the problem of need more complex special synthesis device.It is derivative that a kind of aspartic acid-LYSINE COPOLYMER is provided simultaneously
It is relatively narrow to solve copolymer anti-scale range for object and preparation method thereof, it is difficult to while having to calcium phosphate, calcium carbonate and calcium sulfate etc.
The problem of high scale inhibition effect.
To achieve the goals above, a kind of aspartic acid-LYSINE COPOLYMER of the present invention, is prepared using following steps:
(1) using aspartic acid and lysine as raw material, raw material is uniformly mixed, suitable catalysis is then added into raw material
2 ~ 5h is reacted in agent under 150 ~ 200 DEG C of reaction temperatures, after the reaction was completed, cooling, is dissolved reaction product using ultrapure water, from
Supernatant is taken after the heart, wherein the mass ratio of aspartic acid and lysine is 0.1 ~ 10:1；
(2) supernatant is added in organic solvent, under conditions of pH=2 ~ 6, will be reacted by organic solvent precipitation method
Intermediate precipitation and separation；
(3) under conditions of pH=9 ~ 12, reaction intermediate is added in ultrapure water, 0.5 ~ 2h of stirring obtains asparagus fern ammonia
Acid-LYSINE COPOLYMER.
Further, the catalyst in step (1) is 85% phosphoric acid solution, the mass ratio of catalyst and raw material is 0.1 ~
0.5:1；Preferably, the mass ratio of aspartic acid and lysine is 0.1 ~ 9:1, the mass ratio of catalyst and raw material is 0.15 ~
0.4:1, reaction temperature are 160 ~ 180 DEG C, and the reaction time is 3 ~ 4h.
Further, organic solvent is methanol or ethyl alcohol in step (2), pH=10 ~ 11 in step (3), mixing time is 1 ~
1.5h。
A kind of aspartic acid-LYSINE COPOLYMER derivative of the present invention, structural formula are
In formula: (x1+x2)/( x1+x2+y1+y2) range be 0.1 ~ 1, y2/(y1+y2) range be 0.1 ~ 1, R be hydrogen,
Phosphate group, citrate group or oxygen propyl group trimethyl ammonia chloride ammonium group.
A kind of preparation method of aspartic acid-LYSINE COPOLYMER derivative, specifically includes the following steps:
(A1) aspartic acid-LYSINE COPOLYMER and reaction monomers are added in all ultrapure waters, configure aspartic acid-
LYSINE COPOLYMER solution, reaction monomers and aspartic acid-LYSINE COPOLYMER the mass ratio of the material are 0.1 ~ 10:1；
(A2) by mixed solution 1 ~ 30h of isothermal reaction under 25 ~ 80 DEG C of reaction temperatures obtained by step (A1), then pH=
Under conditions of 2-6, by organic solvent precipitation method precipitation and separation reaction product to get the aspartic acid-LYSINE COPOLYMER
Derivative, the reaction monomers are one of phosphate, epoxypropyltrimethylchloride chloride and citric acid or a variety of, the phosphorus
Hydrochlorate is preferably sodium tripolyphosphate.
Further, in step (A1) reaction monomers and aspartic acid-LYSINE COPOLYMER the mass ratio of the material be 0.1 ~
9:1。
Further, in step (A2) reaction time be 2 ~ for 24 hours, reaction temperature be 35 ~ 60 DEG C, organic solvent be methanol or
Ethyl alcohol.
Further, the aspartic acid-LYSINE COPOLYMER and its derivative can be used as antisludging agent use.
Compared with prior art, the invention has the following advantages: (1) aspartic acid-LYSINE COPOLYMER is using solid
The mode being combined to synthesizes aspartic acid-LYSINE COPOLYMER under relatively mild reaction condition, in the process without largely waving
Hair property organic solvent and special synthesis device, product purity is high, performance is stable, scale inhibition effect is excellent；(2) by copolymer into
Row is modified, and phosphate group, citrate group or oxygen propyl group trimethyl ammonia chloride ammonium group are grafted to copolymer lysine monomer
On free amino, by the complex role between a variety of scale inhibition groups, resistance of the copolymer to calcium carbonate and calcium sulfate is improved
Dirty effect improves copolymer to the low scale inhibition effect of calcium phosphate；(3) either copolymer or derivative can drop
Solution, on environment without influence.
Detailed description of the invention
Fig. 1 is calcium carbonate crystal scanning electron microscope (SEM) photograph.
Fig. 2 is that the calcium carbonate crystal scanning electron microscope (SEM) photograph formed after PAL is added.
Fig. 3 is that the calcium carbonate crystal scanning electron microscope (SEM) photograph formed after PAL/STP is added.
Fig. 4 is that the calcium carbonate crystal scanning electron microscope (SEM) photograph formed after PAL/CA is added.
Fig. 5 is that the calcium carbonate crystal scanning electron microscope (SEM) photograph formed after PAL/GTA is added.
Specific embodiment
Below by specific embodiment, the present invention will be described in detail, but embodiment is not limit the scope of the invention.
Embodiment 1:
Aspartic acid and lysine are 7:3 according to mass ratio, and mixture material is taken amount to 10g, through evaporation recrystallization method weight
After crystallization, the phosphoric acid solution that mass fraction is 85%, mixing is added according to the ratio of phosphoric acid solution and mixture quality ratio 0.4:1
It is uniformly placed in culture dish, in 160 DEG C of heating 4h in Muffle furnace.After intermediate is cooling, ultrapure water 50ml is taken to dissolve
Then midbody solution centrifuge separation is taken supernatant by 20min.Supernatant pH value is adjusted to 4, is precipitated in 400ml methanol
Intermediate is precipitated.Then, intermediate is hydrolyzed to 1h under conditions of pH=11 up to target product.
After tested, product is when concentration is 10mg L-1, under conditions of Yu Guobiao GB/T6632-2008, i.e., in calcium ion
Concentration is 600 mg L-1(with calcium carbonate), bicarbonate ion concentration be 1200 mg L-1(with calcium carbonate), 80 DEG C plus
Scale inhibition performance is 57.4% under conditions of heat 10 hours.The business antisludging agent of sample scale inhibition performance under same concentration is 51.2% as a comparison.
Embodiment 2:
Aspartic acid and lysine are 0.1:1 according to mass ratio, and mixture material is taken amount to 10g, through evaporation recrystallization method
After recrystallization, the phosphoric acid solution that mass fraction is 85% is added according to the ratio of phosphoric acid solution and mixture quality ratio 0.1:1, mixes
Conjunction is uniformly placed in culture dish, in 150 DEG C of heating 5h in Muffle furnace.After intermediate is cooling, ultrapure water 50ml is taken to dissolve
Then midbody solution centrifuge separation is taken supernatant by 20min.Supernatant pH value is adjusted to 2, is precipitated in 400ml methanol
Intermediate is precipitated.Then, intermediate is hydrolyzed to 1h under conditions of pH=9 up to target product.
Embodiment 3:
Aspartic acid and lysine are 10:1 according to mass ratio, and mixture material is taken amount to 10g, through evaporation recrystallization method weight
After crystallization, sodium dihydrogen phosphate is added according to the ratio of sodium dihydrogen phosphate and mixture quality ratio 0.5:1, is uniformly mixed and is placed on training
It supports in ware, in 200 DEG C of heating 2h in Muffle furnace.After intermediate is cooling, ultrapure water 50ml is taken to dissolve 20min, then will in
Between liquid solution centrifuge separation take supernatant.Supernatant pH value is adjusted to 6, the Precipitation intermediate in 400ml ethyl alcohol.With
Afterwards, intermediate is hydrolyzed to 1h under conditions of pH=12 up to target product.
Embodiment 4:
Example 1 prepares aspartic acid-LYSINE COPOLYMER 0.86g, and it is ultrapure that sodium tripolyphosphate 3.65g is dissolved in 17.2ml
In water, is reacted 12 hours in 40 DEG C after mixing evenly, solution ph after reaction is adjusted to 4, the precipitating point in 400ml ethyl alcohol
From aspartic acid-LYSINE COPOLYMER derivative to get grafting phosphate group, it is denoted as PAL/STP.
Embodiment 5:
Example 1 prepares aspartic acid-LYSINE COPOLYMER 0.8g, and citric acid 1.935g is dissolved in 16ml ultrapure water,
After mixing evenly in 60 DEG C react 12 hours, solution ph after reaction is adjusted to 4, in 400ml ethyl alcohol precipitation and separation to get
It is grafted aspartic acid-LYSINE COPOLYMER derivative of citric acid group, is denoted as PAL/CA.
Embodiment 6:
Example 1 prepares aspartic acid-LYSINE COPOLYMER 2g, and it is super that epoxypropyltrimethylchloride chloride 5g is dissolved in 40ml
In pure water, is reacted 4 hours in 80 DEG C after mixing evenly, solution ph after reaction is adjusted to 4, the precipitating point in 400ml ethyl alcohol
From aspartic acid-LYSINE COPOLYMER derivative to get grafting oxygen propyl group trimethyl ammonium chloride, it is denoted as PAL/GTA.
Embodiment 7:
Example 2 prepares aspartic acid-LYSINE COPOLYMER 0.86g, and it is super that sodium tripolyphosphate 0.086g is dissolved in 17.2ml
In pure water, is reacted 30 hours in 25 DEG C after mixing evenly, solution ph after reaction is adjusted to 6, the precipitating point in 400ml ethyl alcohol
From aspartic acid-LYSINE COPOLYMER derivative to get grafting phosphate group.
Embodiment 8:
Example 2 prepares aspartic acid-LYSINE COPOLYMER 0.86g, and it is ultrapure that sodium tripolyphosphate 7.74g is dissolved in 17.2ml
In water, is reacted 12 hours in 35 DEG C after mixing evenly, solution ph after reaction is adjusted to 2, the precipitating point in 400ml methanol
From aspartic acid-LYSINE COPOLYMER derivative to get grafting phosphate group.
Embodiment 9:
Example 1 prepares aspartic acid-LYSINE COPOLYMER 2g, epoxypropyltrimethylchloride chloride 2g, tripolyphosphate
Sodium 1.65g and citric acid 1.935g are dissolved in 40ml ultrapure water, are reacted 4 hours in 80 DEG C after mixing evenly, by solution after reaction
PH value is adjusted to 4, and precipitation and separation is in 400ml ethyl alcohol to get containing there are three types of the aspartic acid of group-LYSINE COPOLYMERs to derive
Object.
Under conditions of additive amount is 5mg/L, antisludging agent and certain business prepared by embodiment 1,4,5 and 6 is measured respectively
Antisludging agent is to the scale inhibition performance of calcium carbonate, calcium phosphate and calcium sulfate, shown in table specific as follows.Simultaneously by measurement calcium sulphate crystal
Antisludging agent and the figure of the SEM without adding antisludging agent prepared by embodiment 1,4,5 and 6 is added.Experimental result can be seen that preparation
Antisludging agent is that the formation of calcium carbonate crystal has destruction.
| Calcium carbonate | Calcium phosphate | Calcium sulfate | |
| PAL | 82.7% | 12.3% | 47.7% |
| PAL/STP | 91.6% | 23.5% | 65.2% |
| PAL/CA | 75.6% | 28.7% | 50.1% |
| PAL/GTA | 54.1% | 34.8% | 48.2% |
| Business antisludging agent | 80.7% | —— | —— |
Claims (7)
1. a kind of derivative of aspartic acid-LYSINE COPOLYMER, which is characterized in that structural formula is
In formula: (x1+x2)/(x1+x2+y1+y2) range be 0.1~1, y2/(y1+y2) range be 0.1~1, R be phosphate
Group, citrate group or oxygen propyl group trimethyl ammonia chloride ammonium group.
2. aspartic acid-LYSINE COPOLYMER derivative according to claim 1, which is characterized in that the copolymer spreads out
Biology is prepared using following methods:
(A1) aspartic acid-LYSINE COPOLYMER and reaction monomers are added in ultrapure water, prepare aspartic acid-and relies ammonia
Acid copolymer solution, reaction monomers and aspartic acid-LYSINE COPOLYMER the mass ratio of the material are 0.1~10:1；
(A2) by mixed solution 1~30h of isothermal reaction under 25~80 DEG C of reaction temperatures obtained by step (A1), then in pH=2-
Under conditions of 6, by organic solvent precipitation method precipitation and separation reaction product to get the aspartic acid-LYSINE COPOLYMER
Derivative, the reaction monomers are one of phosphate, epoxypropyltrimethylchloride chloride and citric acid or a variety of.
3. aspartic acid-LYSINE COPOLYMER derivative according to claim 2, which is characterized in that anti-in step (A1)
It answers monomer and aspartic acid-LYSINE COPOLYMER the mass ratio of the material is 0.1~9:1；In step (A2) reaction time be 2~
For 24 hours, reaction temperature is 35~60 DEG C, and organic solvent is methanol or ethyl alcohol.
4. purposes of aspartic acid-LYSINE COPOLYMER derivative as antisludging agent described in a kind of claim 3.
5. the derivative of aspartic acid-LYSINE COPOLYMER according to claim 1-3, which is characterized in that institute
Aspartic acid-LYSINE COPOLYMER is stated, is prepared using following steps:
(1) using aspartic acid and lysine as raw material, raw material is uniformly mixed, suitable catalyst is then added into raw material,
2~5h is reacted under 150~200 DEG C of reaction temperatures, it is after the reaction was completed, cooling, reaction product is dissolved using ultrapure water, is centrifuged
After take supernatant, wherein the mass ratio of aspartic acid and lysine be 0.1~10:1；
(2) supernatant is added in organic solvent, it, will be in reaction by organic solvent precipitation method under conditions of pH=2~6
Mesosome precipitation and separation；
(3) under conditions of pH=9~12, reaction intermediate is added in ultrapure water, 0.5~2h of stirring obtains asparagus fern ammonia
Acid-LYSINE COPOLYMER.
6. the derivative of aspartic acid-LYSINE COPOLYMER according to claim 5, which is characterized in that in step (1)
Catalyst is 85% phosphoric acid solution, and the mass ratio of catalyst and raw material is 0.1~0.5:1, and organic solvent is methanol in step (2)
Or ethyl alcohol, pH=10~11 in step (3), mixing time are 1~1.5h.
7. the derivative of aspartic acid-LYSINE COPOLYMER according to claim 6, which is characterized in that aspartic acid with
The mass ratio of lysine is 0.1~9:1, and the mass ratio of catalyst and raw material is 0.15~0.4:1, reaction temperature is 160~
180 DEG C, the reaction time is 3~4h.
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| CN110950441A (en) * | 2019-11-29 | 2020-04-03 | 上海应用技术大学 | Green scale inhibitor copolymer and preparation method and application thereof |
| CN114456364B (en) * | 2022-02-18 | 2023-06-02 | 自然资源部第二海洋研究所 | Synthesis method and application of glycolic acid polymer and derivatives thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590260A (en) * | 1984-03-28 | 1986-05-20 | Fuso Chemical Co., Ltd. | Method for producing copoly(amino acid) |
| US5284936A (en) * | 1991-03-29 | 1994-02-08 | University Of South Alabama | Polyamino acid superabsorbents |
| CN103819671A (en) * | 2012-11-16 | 2014-05-28 | 邹金娥 | Preparation method of polyaspartic acid copolymer |
| CN104387585A (en) * | 2014-10-23 | 2015-03-04 | 华北电力大学（保定） | Aspartic acid-lysine copolymer and synthetic method thereof |
-
2018
- 2018-05-07 CN CN201810424165.XA patent/CN108559081B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590260A (en) * | 1984-03-28 | 1986-05-20 | Fuso Chemical Co., Ltd. | Method for producing copoly(amino acid) |
| US5284936A (en) * | 1991-03-29 | 1994-02-08 | University Of South Alabama | Polyamino acid superabsorbents |
| CN103819671A (en) * | 2012-11-16 | 2014-05-28 | 邹金娥 | Preparation method of polyaspartic acid copolymer |
| CN104387585A (en) * | 2014-10-23 | 2015-03-04 | 华北电力大学（保定） | Aspartic acid-lysine copolymer and synthetic method thereof |
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