CN101250265A - Method for synthesizing polysuccinimide and polysuccinimide copolymer - Google Patents
Method for synthesizing polysuccinimide and polysuccinimide copolymer Download PDFInfo
- Publication number
- CN101250265A CN101250265A CNA2008103005957A CN200810300595A CN101250265A CN 101250265 A CN101250265 A CN 101250265A CN A2008103005957 A CNA2008103005957 A CN A2008103005957A CN 200810300595 A CN200810300595 A CN 200810300595A CN 101250265 A CN101250265 A CN 101250265A
- Authority
- CN
- China
- Prior art keywords
- acid
- polysuccinimide
- copolymer
- 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
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyamides (AREA)
Abstract
The invention discloses poly succinimide and a synthetic process for copolymer of poly succinimide. The process uses aspartic acid, maleic acid monoammonium glycyrrhizinate or fumaric acid monoammonium glycyrrhizinate, or mixture of other amino acid as raw material, uses acid compound as catalyst, polymerizes and synthesizes poly succinimide and copolymer of poly succinimide. The acid compound catalyst of the invention is water treatment chemicals, the poly succinimide and copolymer of poly succinimide which is synthesized is mainly used for water treatment.
Description
(1) technical field
The present invention relates to the synthetic method of polysuccinimide (claiming polysuccinimide again) and copolymers of polysuccinimide, this method is with aspartic acid, maleic acid mono-ammonium or FUMARIC ACID TECH GRADE mono-ammonium, or and other amino acid whose mixture be raw material, acidic cpd is a catalyzer, in reactor, polysuccinimide or polysuccinimide amino acid copolymer are synthesized in polymerization together.Polysuccinimide of the present invention or polysuccinimide amino acid copolymer are mainly used in water treatment, and the acidic cpd catalyzer also is a Water Treatment Chemicals.Belong to macromolecule chemical industry and water-treatment technology field.
(2) background technology
Polysuccinimide and copolymers of polysuccinimide are the intermediates of producing poly-aspartic-acid and polyaspartic acid copolymer.
Poly-aspartic-acid and polyaspartic acid copolymer are the friendly type bioabsorbable polymer materials of a kind of novel environmental, and a kind of water soluble amino acid polymer with hydroxy-acid group has the very easily characteristic of degraded.The poly-aspartic-acid series product can be widely used in fields such as water conditioner, washing composition, makeup, fungistat, dispersion agent, sequestrant, process hides, pharmacy, hydrogel, be a kind of purposes very widely, the environmentally friendly chemical of nontoxic, pollution-free, easy degraded.
Synthetic a few days ago polysuccinimide and copolymers of polysuccinimide adopt phosphoric acid or sulfuric acid, or their acid-salt is a catalyzer.
The preparation method of U.S. Pat 4839461 poly-succinimides in the water-soluble solution of maleic anhydride, by dropping ammonia, changes the amine salt of toxilic acid into, and the direct heat polycondensation is poly-succinimide under 125 ℃ then～145 ℃ the temperature.US5296578 brings up to 220 ℃～260 ℃ with the temperature of thermal polycondensation in the above-mentioned reaction, to improve the productive rate of poly-succinimide.US 5714558 is a medium with water or organic solvent in pressurized vessel, adds maleic anhydride and gaseous ammonia, is warming up to 130 ℃～300 ℃, react 5 minutes～5 hours, generates to gather succinimide.The mass treatment that technological process produces is difficulty very, and equipment requirements is high.
JP 0931196 (1997) is to be raw material with the aspartic acid, is reactor with horizontal mixing roll, under an acidic catalyst (being mainly phosphoric acid) existence condition, prepares polysuccinimide in 150～300 ℃ of polymerizations.The catalyzer add-on is 0.01～0.3 (mol ratio) of raw material total amount.
It is raw material that US 5830985 (1998) (preparation of poly-aspartic-acid) discloses with the aspartic acid, is reactor with the fluidized bed dryer, with CO
2Or N
2Be carrier gas, an acidic catalyst (being mainly phosphoric acid) exists down, prepares polysuccinimide 150～200 ℃ of polymerizations, and molecular weight is 800～100000.Reactor belongs to fluidizing reactor, carries out owing to be reflected under the fluidized state, and raw material particle size is had harsh requirement, and Controlling System is had relatively high expectations, and control of process condition is difficulty, realizes difficulty of industrialization.
The catalyzer of CN1267673 is an alkali metal salt and the ammonium salt of sulfuric acid and phosphoric acid.
The catalyzer of CN1123588 is a phosphoric acid.
The ammonium salt of the initiator sulfuric acid of CN1279085, CN1279086, phosphoric acid, carbonic acid or hydrogen sodium salt.
The catalyzer of CN1860900 is phosphoric acid, sulfuric acid, polyphosphoric acid.
Vitriol, phosphoric acid salt, carbonate enter and easily generate calcium sulfate, calcium phosphate, precipitation of calcium carbonate in the water, worsen water quality.
The object of the present invention is to provide a kind of sulfuric acid, phosphoric acid, vitriol, phosphoric acid salt, carbonate synthetic technology of not adopting, polymerization prepares the method for polysuccinimide and copolymers of polysuccinimide.
(3) summary of the invention
Technical scheme of the present invention is: adopting the acidic cpd in the Water Treatment Chemicals is catalyzer.
The acidic cpd catalyzer is solid, solid salt or the aqueous solution of following substances, also can be two kinds or several mixed states.The concentrated acid compound is an Amino Trimethylene Phosphonic Acid; hydroxy ethylene diphosphonic acid; the ethylene diamine tetramethylene phosphonic acid; the hexamethylene-diamine tetramethylene phosphonic acid; diethylenetriamine pentamethylenophosphonic acid(DTPP); the 2-HPAA; 2-phosphinylidyne butane 1; 2, the 4-tricarboxylic acid; polyacrylic acid; the phosphono polyacrylic acid; polymethyl acrylic acid; polymaleic acid; poly aspartic acid; the aspartic acid multipolymer; poly-epoxy succinic acid; vinylformic acid-copolymer-maleic anhydride; vinylformic acid-itaconic acid copolymer; the acrylic acid-ethylene sulfonic acid copolymer; styrene sulfonic acid-copolymer-maleic anhydride.
These acidic cpds were exactly scale inhibition, the inhibiter of Water Treatment Chemicals originally.Product performance are obviously improved.
(4) embodiment
Embodiments of the present invention are such:
Adopting aspartic acid, maleic acid mono-ammonium or FUMARIC ACID TECH GRADE mono-ammonium is raw material.At first with aspartic acid, maleic acid mono-ammonium or FUMARIC ACID TECH GRADE mono-ammonium and solid acid phosphate cpd catalyzer uniform mixing.The catalyzer add-on is 0.01～0.45 with the raw materials quality ratio.
The invention will be further described (but therefore not limiting claim protection domain of the present invention) below in conjunction with embodiment.
Embodiment one:
The mixture that in thermal glass dish or poly fourfluoroplastics dish, adds 100 gram L-aspartic acids and catalyzer 50% Amino Trimethylene Phosphonic Acid.50% Amino Trimethylene Phosphonic Acid add-on is 10% of a L-aspartic acid.Put mixture into the light wave microwave reactor, use light wave heated mixt 2 minutes earlier, use 800W 2450MHz microwave heating polymerization 6min then, make solid polysuccinimide 84 grams.The mean number average molecular weight is 3500.
Embodiment two:
The light wave microwave reactor is put in the vacuum environment, after the microwave heating of unlatching light wave, vacuumizes again.
The mixture that in thermal glass dish or poly fourfluoroplastics dish, adds 200 gram L-aspartic acids and catalyzer 48% polymaleic acid.48% polymaleic acid add-on is 20% of a L-aspartic acid.Put mixture into the light wave microwave reactor, use light wave heated mixt 2 minutes earlier, after 800W 2450MHz microwave heating time is set to 12min then, begin to vacuumize, vacuum tightness is-0.05MPa.Make fluffy solid polysuccinimide 159 grams of foaming shape withered yellow.The mean number average molecular weight is 12000.
Embodiment three:
The mixture that in thermal glass dish or poly fourfluoroplastics dish, adds 200 gram maleic acid list ammoniums and catalyzer hydroxy ethylene diphosphonic acid.50% hydroxy ethylene diphosphonic acid add-on is 10% of a maleic acid list ammonium.Put mixture into the light wave microwave reactor, use light wave heated mixt 2 minutes earlier, use 800W 2450MHz microwave heating 8min then, make solid polysuccinimide 145 grams.The mean number average molecular weight is 4500.
Embodiment four:
The mixture that in thermal glass dish or poly fourfluoroplastics dish, adds 200 gram maleic acid list ammoniums and catalyzer vinylformic acid-copolymer-maleic anhydride.30% vinylformic acid-copolymer-maleic anhydride add-on is 20% of a maleic acid list ammonium.Put mixture into the light wave microwave reactor, use light wave heated mixt 2 minutes earlier, with 800W 2450MHz heating heating 15min, make solid polysuccinimide 135 grams then.The mean number average molecular weight is 5000.
Claims (1)
1. the synthetic method of polysuccinimide and copolymers of polysuccinimide, it is characterized in that: with aspartic acid, maleic acid mono-ammonium or FUMARIC ACID TECH GRADE mono-ammonium, or and other amino acid whose mixture be raw material, acidic cpd is a catalyzer, together at synthetic polysuccinimide of reactor internal heating polymerization or copolymers of polysuccinimide.The acidic cpd catalyzer is solid, solid salt or the aqueous solution of following substances, also can be two kinds or several mixed states.The concentrated acid compound is an Amino Trimethylene Phosphonic Acid; hydroxy ethylene diphosphonic acid; the ethylene diamine tetramethylene phosphonic acid; the hexamethylene-diamine tetramethylene phosphonic acid; diethylenetriamine pentamethylenophosphonic acid(DTPP); the 2-HPAA; 2-phosphinylidyne butane 1; 2, the 4-tricarboxylic acid; polyacrylic acid; the phosphono polyacrylic acid; polymethyl acrylic acid; polymaleic acid; poly aspartic acid; the aspartic acid multipolymer; poly-epoxy succinic acid; vinylformic acid-copolymer-maleic anhydride; vinylformic acid-itaconic acid copolymer; the acrylic acid-ethylene sulfonic acid copolymer; styrene sulfonic acid-copolymer-maleic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008103005957A CN101250265A (en) | 2008-03-17 | 2008-03-17 | Method for synthesizing polysuccinimide and polysuccinimide copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008103005957A CN101250265A (en) | 2008-03-17 | 2008-03-17 | Method for synthesizing polysuccinimide and polysuccinimide copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101250265A true CN101250265A (en) | 2008-08-27 |
Family
ID=39953881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008103005957A Pending CN101250265A (en) | 2008-03-17 | 2008-03-17 | Method for synthesizing polysuccinimide and polysuccinimide copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101250265A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768268A (en) * | 2010-02-11 | 2010-07-07 | 山东省泰和水处理有限公司 | Method for preparing polyaspartic acid by crystal condensation |
| CN101580311B (en) * | 2009-06-24 | 2012-02-29 | 安徽省蓝天化工有限公司 | Polymaleic acid boiler scale-inhibition corrosion inhibitor |
| CN104292460A (en) * | 2014-10-23 | 2015-01-21 | 华北电力大学（保定） | Aspartic acid-itaconic acid copolymer and synthetic method thereof |
| CN105060515A (en) * | 2015-06-30 | 2015-11-18 | 苏州佑君环境科技有限公司 | Scale inhibitor for preventing deposition of barium and strontium scales, and preparation method thereof |
-
2008
- 2008-03-17 CN CNA2008103005957A patent/CN101250265A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580311B (en) * | 2009-06-24 | 2012-02-29 | 安徽省蓝天化工有限公司 | Polymaleic acid boiler scale-inhibition corrosion inhibitor |
| CN101768268A (en) * | 2010-02-11 | 2010-07-07 | 山东省泰和水处理有限公司 | Method for preparing polyaspartic acid by crystal condensation |
| CN101768268B (en) * | 2010-02-11 | 2012-06-13 | 山东省泰和水处理有限公司 | Method for preparing polyaspartic acid by crystal condensation |
| CN104292460A (en) * | 2014-10-23 | 2015-01-21 | 华北电力大学（保定） | Aspartic acid-itaconic acid copolymer and synthetic method thereof |
| CN104292460B (en) * | 2014-10-23 | 2017-07-04 | 华北电力大学（保定） | Aspartic acid itaconic acid copolymer and its synthetic method |
| CN105060515A (en) * | 2015-06-30 | 2015-11-18 | 苏州佑君环境科技有限公司 | Scale inhibitor for preventing deposition of barium and strontium scales, and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3059218B1 (en) | Fertilizer compositions including polyanionic polymers | |
| US5478919A (en) | Aspartic acid copolymers and their preparation | |
| US5116513A (en) | Polyaspartic acid as a calcium sulfate and a barium sulfate inhibitor | |
| CN101575413B (en) | Method for synthesizing green scale inhibitor poly-asparagic acid through microwaves | |
| DE4221875A1 (en) | Modified polyaspartic acids, process for their preparation and their use | |
| CN101250265A (en) | Method for synthesizing polysuccinimide and polysuccinimide copolymer | |
| CN102174197B (en) | Microwave synthesis method for hydroxyl modified polyaspartic acid | |
| CN102153749B (en) | Microwave synthesis method for sulfonic group modified polyaspartic acid | |
| CN105482117A (en) | Polyaspartic acid/urea graft copolymer as well as preparation method and application thereof | |
| Kumar | Polyaspartic acid–A versatile green chemical | |
| CN100478288C (en) | Biodegradable composite corrosion and scale inhibitor and method for preparing same | |
| CN105439299A (en) | Method for preparing hyperbranched polyethyleneimine copolymer water treatment agent and application of hyperbranched polyethyleneimine copolymer water treatment agent | |
| CN109019887A (en) | A kind of environmental Water Treatment Chemicals having both inhibition, scale-inhibiting properties | |
| CN100509883C (en) | Production method of polychlorotrifluoroethylene for electrostatic spraying | |
| CN100369954C (en) | Aspartate copolymer and method for preparing same | |
| CN104530428A (en) | Preparation method of modified polyaspartic acid copolymer | |
| JPH11505276A (en) | Method for producing polymers having succinyl repeating units | |
| CN101348567A (en) | Synthetic method of poly(succinimide) and poly(succinimide) copolymer | |
| CN101293945B (en) | Method for preparing modified poly-epoxy succinic acid derivative | |
| WO2001098394A1 (en) | A process for production of polyasparagine and the high nitrogen content polymer formed thereby | |
| US5939522A (en) | Production of polysuccinimide and polyaspartate in thioether solvents | |
| CN1611526A (en) | Wet synthesis of poly aminosuccinic acid by microwave chemical technique | |
| US5688904A (en) | Polyaspartic acid catalysis | |
| US5449748A (en) | Preparation of anhydropolyamino acids at temperatures of 350° C. or above | |
| CN103724625A (en) | New process for synthesizing polyaspartic acid through L-asparaginic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080827 |