CN108559081A - 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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- CN108559081A CN108559081A CN201810424165.XA CN201810424165A CN108559081A CN 108559081 A CN108559081 A CN 108559081A CN 201810424165 A CN201810424165 A CN 201810424165A CN 108559081 A CN108559081 A CN 108559081A
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- aspartic acid
- copolymer
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- lysine copolymer
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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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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
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- 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 detached 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, scale inhibition effect of the copolymer to calcium carbonate and calcium sulfate is improved, copolymer is made to improve 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 synthesis of aspartic acid-LYSINE COPOLYMER
The derivative of method, the copolymer, the aspartic acid-LYSINE COPOLYMER and aspartic acid-LYSINE COPOLYMER derivative
The antisludging agent that can be used as in anti-penetration wastewater disposal technical process uses.
Background technology
With the development of global economy and society, the whole world increasingly increases available freshwater resources demand, and reverse osmosis work
For a kind of water treatment technology of high-quality and high-efficiency, engineer application total amount is continuously increased.In practical applications as raw water is continuous
Concentration, one of the various scale-forming ion concentration also constantly increase, and are finally formed comprising calcium carbonate, calcium sulfate, phosphorus in membrane surface
The pollution layer of the substances such as sour calcium, silica.
In order to alleviate the pollution situation during reverse-osmosis treated, 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
It is in organic solvent, to pass through microwave irradiation synthesis under the auxiliary of catalyst using aspartic acid and lysine as raw material to close object
'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 as a kind of medicament of universality.
Invention content
In view of above-mentioned aspartic acid-LYSINE COPOLYMER synthetic method there are the problem of, the present invention provides a kind of aspartic acid-
The solid phase synthesis process of LYSINE COPOLYMER antisludging agent, solve needed in existing synthetic method a large amount of volatile organic solvents and
The problem of needing more complex special synthesis device.Provide simultaneously a kind of aspartic acid-LYSINE COPOLYMER derivative and its
It is relatively narrow to solve copolymer anti-scale range for preparation method, it is difficult to while there is high scale inhibition to calcium phosphate, calcium carbonate and calcium sulfate etc.
The problem of 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 catalyst is then added into raw material,
2 ~ 5h is reacted under 150 ~ 200 DEG C of reaction temperatures, it is cooling after the completion of reaction, reaction product is dissolved using ultra-pure water, after centrifugation
Take supernatant, 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 react intermediate by organic solvent precipitation method
Body precipitation separation；
（3）Under conditions of pH=9 ~ 12, reaction intermediate is added in ultra-pure water, 0.5 ~ 2h of stirring obtains aspartic acid-and relies
Histidine copolymer.
Further, step（1）In catalyst be 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 is 160 ~ 180 DEG C, and the reaction time is 3 ~ 4h.
Further, step（2）Middle organic solvent is methanol or ethyl alcohol, step（3）Middle pH=10 ~ 11, mixing time be 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) ranging from 0.1 ~ 1, y2/(y1+y2) ranging from 0.1 ~ 1, R be hydrogen, phosphoric acid
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 following steps：
（A1）Aspartic acid-the LYSINE COPOLYMER and reaction monomers are added in all ultra-pure waters, configuration aspartic acid-relies ammonia
The amount ratio of acid copolymer solution, reaction monomers and the substance of aspartic acid-LYSINE COPOLYMER is 0.1 ~ 10:1；
（A2）By step（A1）Gained mixed solution 1 ~ 30h of isothermal reaction under 25 ~ 80 DEG C of reaction temperatures, then pH=2-6's
Under the conditions of, separation reaction product is precipitated by organic solvent precipitation method and is derived to get the aspartic acid-LYSINE COPOLYMER
Object, the reaction monomers are one or more, the phosphate in phosphate, epoxypropyltrimethylchloride chloride and citric acid
Preferably sodium tripolyphosphate.
Further, step（A1）The amount ratio of the substance of middle reaction monomers and aspartic acid-LYSINE COPOLYMER is 0.1 ~
9:1。
Further, step（A2）The middle 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 advantages that：（1）Aspartic acid-LYSINE COPOLYMER is using solid
The mode being combined to synthesizes aspartic acid-LYSINE COPOLYMER under relatively mild reaction condition, is not necessarily to largely wave in the process
Hair property organic solvent and special synthesis device, product purity is high, performance is stable, scale inhibition effect is excellent；（2）By to 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 makes copolymer improve the low scale inhibition effect of calcium phosphate；（3）Either copolymer or derivative can drop
Solution, on environment without influence.
Description of the drawings
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 implementation mode
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 is 7 according to mass ratio with lysine:3, take mixture material to amount to 10g, through evaporating recrystallization method recrystallization
Afterwards, according to phosphoric acid solution and mixture quality than 0.4：The phosphoric acid solution that mass fraction is 85% is added in 1 ratio, is uniformly mixed
It is placed in culture dish, heats 4h at 160 DEG C in Muffle furnace.After intermediate cooling, ultra-pure water 50ml is taken to dissolve 20min,
Then midbody solution centrifugation is taken into supernatant.Supernatant pH value is adjusted to 4, in 400ml methanol in Precipitation
Mesosome.Then, intermediate is hydrolyzed to 1h under conditions of pH=11 up to target product.
After tested, product is in a concentration of 10mg L-1, under conditions of national standard GB/T6632-2008, i.e., in calcium ion
A concentration of 600 mg L-1（With calcium carbonate）, bicarbonate ion concentration be 1200 mg L-1（With calcium carbonate）, 80 DEG C add
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 is 0.1 according to mass ratio with lysine:1, it takes mixture material to amount to 10g, is tied again through evaporating recrystallization method
After crystalline substance, according to phosphoric acid solution and mixture quality than 0.1：The phosphoric acid solution that mass fraction is 85% is added in 1 ratio, and mixing is equal
It is even to be placed in culture dish, 5h is heated at 150 DEG C in Muffle furnace.After intermediate cooling, ultra-pure water 50ml is taken to dissolve
Then midbody solution centrifugation 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 is 10 according to mass ratio with lysine:1, take mixture material to amount to 10g, through evaporating recrystallization method recrystallization
Afterwards, according to sodium dihydrogen phosphate and mixture quality than 0.5：Sodium dihydrogen phosphate is added in 1 ratio, is uniformly mixed and is placed on culture dish
In, 2h is heated at 200 DEG C in Muffle furnace.After intermediate cooling, ultra-pure water 50ml is taken to dissolve 20min, then by intermediate
Solution centrifugation takes supernatant.Supernatant pH value is adjusted to 6, the Precipitation intermediate in 400ml ethyl alcohol.Then, will
Intermediate hydrolyzes 1h up to target product under conditions of pH=12.
Embodiment 4：
Example 1 prepares aspartic acid-LYSINE COPOLYMER 0.86g, and sodium tripolyphosphate 3.65g is dissolved in 17.2ml ultra-pure waters
In, it is reacted 12 hours in 40 DEG C after stirring evenly, solution ph after reaction is adjusted to 4, separation is precipitated in 400ml ethyl alcohol,
Up to aspartic acid-LYSINE COPOLYMER derivative of 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 ultra-pure waters, stirring
It is reacted 12 hours in 60 DEG C after uniformly, solution ph after reaction is adjusted to 4, precipitation separation is to get grafting in 400ml ethyl alcohol
The aspartic acid of citric acid group-LYSINE COPOLYMER derivative, is denoted as PAL/CA.
Embodiment 6：
Example 1 prepares aspartic acid-LYSINE COPOLYMER 2g, and epoxypropyltrimethylchloride chloride 5g is dissolved in 40ml ultra-pure waters
In, it is reacted 4 hours in 80 DEG C after stirring evenly, solution ph after reaction is adjusted to 4, separation is precipitated in 400ml ethyl alcohol, i.e.,
It must be grafted aspartic acid-LYSINE COPOLYMER derivative of oxygen propyl group trimethyl ammonium chloride, be denoted as PAL/GTA.
Embodiment 7：
Example 2 prepares aspartic acid-LYSINE COPOLYMER 0.86g, and sodium tripolyphosphate 0.086g is dissolved in 17.2ml ultra-pure waters
In, it is reacted 30 hours in 25 DEG C after stirring evenly, solution ph after reaction is adjusted to 6, separation is precipitated in 400ml ethyl alcohol,
Up to aspartic acid-LYSINE COPOLYMER derivative of grafting phosphate group.
Embodiment 8：
Example 2 prepares aspartic acid-LYSINE COPOLYMER 0.86g, and sodium tripolyphosphate 7.74g is dissolved in 17.2ml ultra-pure waters
In, it is reacted 12 hours in 35 DEG C after stirring evenly, solution ph after reaction is adjusted to 2, separation is precipitated in 400ml methanol,
Up to aspartic acid-LYSINE COPOLYMER derivative of grafting phosphate group.
Embodiment 9：
Example 1 prepares aspartic acid-LYSINE COPOLYMER 2g, epoxypropyltrimethylchloride chloride 2g, sodium tripolyphosphate
1.65g and citric acid 1.935g are dissolved in 40ml ultra-pure waters, are reacted 4 hours in 80 DEG C after stirring evenly, by pH value of solution after reaction
Value is adjusted to 4, and precipitation separation is to get containing there are three types of the aspartic acid of group-LYSINE COPOLYMERs to derive in 400ml ethyl alcohol
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 measuring in calcium sulphate crystal
Antisludging agent and the SEM figures without adding antisludging agent prepared by embodiment 1,4,5 and 6 is added.Experimental result can be seen that preparation
Antisludging agent, which is 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 (8)
1. a kind of aspartic acid-LYSINE COPOLYMER, which is characterized in that 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 cooling after the completion of reaction, reaction product is dissolved using ultra-pure water, after centrifugation
Take supernatant, 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 react intermediate by organic solvent precipitation method
Body precipitation separation；
（3）Under conditions of pH=9 ~ 12, reaction intermediate is added in ultra-pure water, 0.5 ~ 2h of stirring obtains aspartic acid-and relies
Histidine copolymer.
2. aspartic acid-LYSINE COPOLYMER according to claim 1, which is characterized in that step（1）In catalyst be
The mass ratio of 85% phosphoric acid solution, catalyst and raw material is 0.1 ~ 0.5：1, step（2）Middle organic solvent is methanol or ethyl alcohol, step
Suddenly（3）Middle pH=10 ~ 11, mixing time are 1 ~ 1.5h.
3. aspartic acid-LYSINE COPOLYMER according to claim 2, which is characterized in that aspartic acid and lysine
Mass ratio is 0.1 ~ 9:1, the mass ratio of catalyst and raw material is 0.15 ~ 0.4：1, reaction temperature is 160 ~ 180 DEG C, when reaction
Between be 3 ~ 4h.
4. a kind of claim 1-3 any one of them aspartic acid-LYSINE COPOLYMER derivative, which is characterized in that structure
Formula is
In formula：(x1+x2)/( x1+x2+y1+y2) ranging from 0.1 ~ 1, y2/(y1+y2) ranging from 0.1 ~ 1, R be hydrogen, phosphoric acid
Group, citrate group or oxygen propyl group trimethyl ammonia chloride ammonium group.
5. aspartic acid-LYSINE COPOLYMER derivative according to claim 4, which is characterized in that the copolymer derives
Object is prepared using following methods：
（A1）Aspartic acid-the LYSINE COPOLYMER and reaction monomers are added in all ultra-pure waters, configuration aspartic acid-relies ammonia
The amount ratio of acid copolymer solution, reaction monomers and the substance of aspartic acid-LYSINE COPOLYMER is 0.1 ~ 10:1；
（A2）By step（A1）Gained mixed solution 1 ~ 30h of isothermal reaction under 25 ~ 80 DEG C of reaction temperatures, then pH=2-6's
Under the conditions of, separation reaction product is precipitated by organic solvent precipitation method and is derived to get the aspartic acid-LYSINE COPOLYMER
Object, the reaction monomers are one or more in phosphate, epoxypropyltrimethylchloride chloride and citric acid.
6. aspartic acid-LYSINE COPOLYMER derivative according to claim 5, which is characterized in that step（A1）Middle reaction
The amount ratio of monomer and the substance of aspartic acid-LYSINE COPOLYMER is 0.1 ~ 9:1.
7. aspartic acid-LYSINE COPOLYMER derivative according to claim 6, which is characterized in that step（A2）Middle reaction
Time be 2 ~ for 24 hours, reaction temperature be 35 ~ 60 DEG C, organic solvent be methanol or ethyl alcohol.
8. aspartic acid-LYSINE COPOLYMER derivative according to claim 7, which is characterized in that the aspartic acid-relies
Histidine copolymer and its derivative can be used as antisludging agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114456364A (en) * | 2022-02-18 | 2022-05-10 | 自然资源部第二海洋研究所 | Synthetic method and application of glycolic acid polymer and derivative 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114456364A (en) * | 2022-02-18 | 2022-05-10 | 自然资源部第二海洋研究所 | Synthetic method and application of glycolic acid polymer and derivative 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 |
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