CN103819669A - Method for modifying composite polyaspartic acid - Google Patents
Method for modifying composite polyaspartic acid Download PDFInfo
- Publication number
- CN103819669A CN103819669A CN201210464165.5A CN201210464165A CN103819669A CN 103819669 A CN103819669 A CN 103819669A CN 201210464165 A CN201210464165 A CN 201210464165A CN 103819669 A CN103819669 A CN 103819669A
- Authority
- CN
- China
- Prior art keywords
- aspartic acid
- polysuccinimide
- modifying
- maleic anhydride
- poly aspartic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 42
- 229920000805 Polyaspartic acid Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title abstract 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229960005261 aspartic acid Drugs 0.000 claims abstract description 13
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims abstract description 11
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 abstract description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 3
- 239000000908 ammonium hydroxide Substances 0.000 abstract 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241001677188 Coccus viridis Species 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 102100035024 Carboxypeptidase B Human genes 0.000 description 1
- 101000946524 Homo sapiens Carboxypeptidase B Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002977 biomimetic material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyamides (AREA)
Abstract
The invention provides a method for modifying composite polyaspartic acid. Maleic anhydride is used as a raw material, ammonium hydroxide is dropwise added into the water solution of the maleic anhydride, and polysuccinimide is obtained after agitating for reaction is carried out for 0.5-1 h under a water bath condition with the temperature of 150 DEG C. The composite polyaspartic acid is obtained through the reaction of L-aspartic acid/L-aspartate, and the polysuccinimide. The molar ratio of the polysuccinimide to the L-aspartic acid/the L-aspartate is 1:(0.5-2); the polysuccinimide and the L-aspartic acid/the L-aspartate react under the condition of 80-380 DEG C for 0.5-2 h; the molar ratio of the maleic anhydride to the ammonium hydroxide is 1:(0.5-1.2), and the ammonium hydroxide is counted by NH3. The composite polyaspartic acid provided by the invention has excellent scale inhibition performance to calcium sulfate and barium sulphate.
Description
Technical field
The present invention relates to a kind of method of modifying of poly aspartic acid, relate in particular to a kind of method of aspartic acid modified polyaspartic acid.
Background technology
Poly aspartic acid (Polyaspartic acid) is a kind of aminoacid polymers, has excellent enough performances, and the peptide bond on its mechanism's main chain is subject to microbial process and ruptures simultaneously, belongs to readily biodegradable material.Poly aspartic acid is inspired and a kind of green scale inhibitor of succeeding in developing by marine animal metabolic process, be specially adapted to suppress the one-tenth dirt of calcium carbonate in water coolant, feedwater and reverse osmosis membrane processing etc., can prevent dirty blocking pipe and stratum, improve thermo-efficiency, stop corrosion of metal.Poly aspartic acid has linear polyimide amine structure, is the amino peptide connecting, the amido link structure of analogous protein, and molecular chain has α type and β type, has good biocompatibility, can quick and complete degraded in environment, can not exert an influence to environment.Poly aspartic acid, is called for short PASP, and its manufacturing process is clean, is generally acknowledged green scale inhibitor and the renewal product of water conditioner.
Owing to containing a large amount of-COOH ,-NHCO-isopolarity group in poly aspartic acid molecule, and in the each structural unit of poly aspartic acid, have 4 Sauerstoffatoms and 1 nitrogen-atoms, oxygen and nitrogen-atoms very easily form hydrogen bond with water molecules, make it have good wetting ability and water-soluble; In addition, on side chain-COOH in the aqueous solution, be easy to ionization, form carboxyl negative ion (COO-), it can with different kinds of ions generation complex reaction, make poly aspartic acid in the aqueous solution, there is good chemically reactive.But because functional group's kind in poly aspartic acid molecule is single, cause its performance single, application is restricted.In order to improve the performance of poly aspartic acid, widen its Application Areas, recent domestic has carried out a large amount of research to the modification of poly aspartic acid.
Environment friendly and the biodegradable of poly aspartic acid have been kept through the poly aspartic acid of modification; Meanwhile, owing to having introduced other active group in molecule, can be used as the uses such as water conditioner, biomimetic material and pharmaceutical carrier, widened its Application Areas.But, as a kind of novel biodegradable macromolecular material, want to have widely the not Biodegradable material of applying, having more the market competitiveness, replace current use, also need further to optimize synthesis condition, improve synthetic method, explore new method of modifying, further to improve its use properties, expand its Application Areas.In a word, environmentally friendly poly-aspartate derivant will become new study hotspot.
Summary of the invention
The object of the present invention is to provide a kind of method of modifying of compound poly aspartic acid, can enrich the functional group's kind in poly aspartic acid structure, improve its scale-inhibiting properties.
For achieving the above object, the present invention adopts following technical scheme:
A method of modifying for compound poly aspartic acid take maleic anhydride as raw material, drips ammoniacal liquor in its aqueous solution, and stirring reaction 0.5 ~ 1h under 150 ℃ of conditions of water-bath, obtains polysuccinimide; React with polysuccinimide and obtain compound poly aspartic acid with L-Aspartic acid or L-Aspartic acid salt again.
In preferred scheme, the mol ratio of described polysuccinimide and L-Aspartic acid or L-Aspartic acid salt is 1:0.5 ~ 2.
In preferred scheme, described polysuccinimide is 80 ~ 380 ℃ with the reaction conditions of L-Aspartic acid or L-Aspartic acid salt and reacts 0.5 ~ 2h.
In further preferred scheme, the mol ratio of described maleic anhydride and ammoniacal liquor is 1:0.5 ~ 1.2, and described ammoniacal liquor is with NH
3meter.
Method of modifying provided by the invention has synthesized the poly aspartic acid take aspartic acid as side chain.Compound poly aspartic acid prepared by the present invention, has better scale-inhibiting properties.Compared with simple poly aspartic acid, its scale inhibition performance has improved more than 20%.
Than prior art, the present invention has following beneficial effect:
(1) technological process is simple, and resultant velocity is fast, and productive rate is high;
(2) the compound poly aspartic acid that prepared by method provided by the invention is not phosphorous;
(3) the compound poly aspartic acid that prepared by method provided by the invention has good biodegradability;
(4) the compound poly aspartic acid that prepared by method provided by the invention is due to phosphorous, can greatly reduce the biological pollution of reverse osmosis membrane and reverse osmosis system and the bacterium problem that exceeds standard;
(5) the scale-inhibiting properties excellence of the compound poly aspartic acid that prepared by method provided by the invention to calcium sulfate and barium sulfate.
Embodiment
The following examples can make the present invention of those of ordinary skill in the art's comprehend, but do not limit the present invention in any way.
Embodiment 1
A method of modifying for compound poly aspartic acid, comprises the following steps:
(1) 1:1 drips ammoniacal liquor (with NH in the aqueous solution of maleic anhydride in molar ratio
3meter), stirring reaction 1h under 150 ℃ of conditions of water-bath, obtains polysuccinimide;
(2) polysuccinimide of preparing with L-Aspartic acid and step (1) again, 0.5:1 in molar ratio, in 300 ℃ of reaction 0.5h, obtains compound poly aspartic acid.
Embodiment 2
A method of modifying for compound poly aspartic acid, comprises the following steps:
(1) 1:0.6 drips ammoniacal liquor (with NH in the aqueous solution of maleic anhydride in molar ratio
3meter), stirring reaction 0.5h under 150 ℃ of conditions of water-bath, obtains polysuccinimide;
(2) polysuccinimide of preparing with L-Aspartic acid and step (1) again, 1:1 in molar ratio, in 100 ℃ of reaction 1h, obtains compound poly aspartic acid.
Embodiment 3
A method of modifying for compound poly aspartic acid, comprises the following steps:
(1) 1:1.2 drips ammoniacal liquor (with NH in the aqueous solution of maleic anhydride in molar ratio
3meter), stirring reaction 0.8h under 150 ℃ of conditions of water-bath, obtains polysuccinimide;
(2) polysuccinimide of preparing with L-Aspartic acid salt and step (1) again, 2:1 in molar ratio, in 200 ℃ of reaction 2h, obtains compound poly aspartic acid.
Embodiment 4
A method of modifying for compound poly aspartic acid, comprises the following steps:
(1) 1:0.8 drips ammoniacal liquor (with NH in the aqueous solution of maleic anhydride in molar ratio
3meter), stirring reaction 1h under 150 ℃ of conditions of water-bath, obtains polysuccinimide;
(2) polysuccinimide of preparing with L-Aspartic acid salt and step (1) again, 1.5:1 in molar ratio, in 350 ℃ of reaction 1.5h, obtains compound poly aspartic acid.
Claims (4)
1. a method of modifying for compound poly aspartic acid, is characterized in that: take maleic anhydride as raw material, in its aqueous solution, drip ammoniacal liquor, stirring reaction 0.5 ~ 1h under 150 ℃ of conditions of water-bath, obtains polysuccinimide; React with polysuccinimide and obtain compound poly aspartic acid with L-Aspartic acid or L-Aspartic acid salt again.
2. method of modifying according to claim 1, is characterized in that: the mol ratio of described polysuccinimide and L-Aspartic acid or L-Aspartic acid salt is 1:0.5 ~ 2.
3. method of modifying according to claim 2, is characterized in that: described polysuccinimide is 80 ~ 380 ℃ with the reaction conditions of L-Aspartic acid or L-Aspartic acid salt and reacts 0.5 ~ 2h.
4. according to the method for modifying described in any one claim in claim 1 ~ 3, it is characterized in that: the mol ratio of described maleic anhydride and ammoniacal liquor is 1:0.5 ~ 1.2, and described ammoniacal liquor is with NH
3meter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210464165.5A CN103819669A (en) | 2012-11-16 | 2012-11-16 | Method for modifying composite polyaspartic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210464165.5A CN103819669A (en) | 2012-11-16 | 2012-11-16 | Method for modifying composite polyaspartic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103819669A true CN103819669A (en) | 2014-05-28 |
Family
ID=50754984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210464165.5A Pending CN103819669A (en) | 2012-11-16 | 2012-11-16 | Method for modifying composite polyaspartic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103819669A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171316A (en) * | 2018-11-13 | 2020-05-19 | 中国科学院大连化学物理研究所 | Method for synthesizing polysuccinimide by adopting catalytic system |
| CN111286026A (en) * | 2018-12-10 | 2020-06-16 | 中国科学院大连化学物理研究所 | A kind of method for synthesizing polyaspartic acid by catalytic system |
| WO2025103113A1 (en) * | 2023-11-16 | 2025-05-22 | 中国石油天然气股份有限公司 | Phosphorus-free pre-filming agent and preparation method therefor, and pre-filming method for water-cooled heat exchanger |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839461A (en) * | 1986-08-07 | 1989-06-13 | Bayer Aktiengesellschaft | Polyaspartic acid from maleic acid and ammonia |
| US5296578A (en) * | 1992-09-18 | 1994-03-22 | Donlar Corporation | Production of polysuccinimide and polyaspartic acid from maleic anhydride and ammonia |
| CN1398799A (en) * | 2002-04-18 | 2003-02-26 | 同济大学 | Prepn of polyasparagic acid as environment protecting scale inhibitor |
| CN102146161A (en) * | 2010-02-05 | 2011-08-10 | 湖州欣和环境科技有限公司 | Polyaspartic acid complex for scale inhibitor |
-
2012
- 2012-11-16 CN CN201210464165.5A patent/CN103819669A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839461A (en) * | 1986-08-07 | 1989-06-13 | Bayer Aktiengesellschaft | Polyaspartic acid from maleic acid and ammonia |
| US5296578A (en) * | 1992-09-18 | 1994-03-22 | Donlar Corporation | Production of polysuccinimide and polyaspartic acid from maleic anhydride and ammonia |
| CN1398799A (en) * | 2002-04-18 | 2003-02-26 | 同济大学 | Prepn of polyasparagic acid as environment protecting scale inhibitor |
| CN102146161A (en) * | 2010-02-05 | 2011-08-10 | 湖州欣和环境科技有限公司 | Polyaspartic acid complex for scale inhibitor |
Non-Patent Citations (2)
| Title |
|---|
| 张立珠等: "《水处理剂——配方•制备•应用》", 31 January 2011, 化学工业出版社 * |
| 高玉华: "聚天冬氨酸衍生物的合成及其性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171316A (en) * | 2018-11-13 | 2020-05-19 | 中国科学院大连化学物理研究所 | Method for synthesizing polysuccinimide by adopting catalytic system |
| CN111286026A (en) * | 2018-12-10 | 2020-06-16 | 中国科学院大连化学物理研究所 | A kind of method for synthesizing polyaspartic acid by catalytic system |
| WO2025103113A1 (en) * | 2023-11-16 | 2025-05-22 | 中国石油天然气股份有限公司 | Phosphorus-free pre-filming agent and preparation method therefor, and pre-filming method for water-cooled heat exchanger |
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Application publication date: 20140528 |
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