CN106543436B - High molecular weight organic amine and maleic anhydride modified polyaspartic acid salts and its preparation method - Google Patents
High molecular weight organic amine and maleic anhydride modified polyaspartic acid salts and its preparation method Download PDFInfo
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Abstract
The invention discloses a kind of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts and its preparation methods, are related to high-molecular compound synthesis technical field.The following steps are included: the preparation of (1) modifying agent: being reacted using organic diamine with maleic anhydride, add alkali, bicarbonate, carbonate or oxide, after reaction plus water is configured to solution, forms homogeneous transparent liquid, as modifying agent；Organic diamine is ethylenediamine, propane diamine, butanediamine, pentanediamine or hexamethylene diamine；The molar ratio of maleic anhydride and organic diamine is 1:1；(2) PSI is placed in flask, distilled water is added, then modifying agent prepared by step (1) is added, the above hydrolysis of room temperature obtains modified polyaspartic acid salt；Wherein, the molar ratio of polysuccinimide PSI and the organic diamine in modifying agent is 1:0.9~1.1.The modified polyaspartic acid molecules of salt amount reaches as high as 40,000 or more, widely used, has the great market competitiveness.
Description
Technical field
The present invention relates to high-molecular compound synthesis technical fields.
Background technique
One kind that poly-aspartate (PASP), which is early 1990s, to be developed by Donlar company, the U.S. is nontoxic and pollution-free,
Biodegradable environmental type water treatment agent, and obtain 1996 annual Presidential Green Chemistry Challenge Awards.Poly- asparagus fern
Propylhomoserin (PASP) is a kind of polyaminoacid with carboxylic side-chain, has chelating and peptizaiton；And it a kind of novel gives birth to
The environmentally friendly high molecular material of object degradation.Natural poly-aspartate is primarily present in the shell of mollusk and snail class
In, it is polymer made of being shunk by the amino and carboxyl of aspartic acid (Aspartic acid, ASP) monomer, with class
It is similar to the amido link structure of protein, can be a kind of environment amenable green polymer with complete biodegradable.Due to poly- day
Containing a large amount of-COOH ,-NHCO- isopolarity group in aspartic acid molecule, there is good hydrophily and water solubility；In addition,
- COOH on side chain is easy to ionize in aqueous solution, is formed carboxyl anion (- COO-), it can occur with different kinds of ions
Complex reaction, making poly-aspartate in aqueous solution has good chemical activity.Peptide bond on its structural backbone is vulnerable to micro- life
The effects of object, fungi and be broken, final catabolite is the water and carbon dioxide of environmental sound.With it is without phosphorus, nontoxic, without public affairs
Evil, the characteristic of fully biodegradable, belong to green chemical, meet environmentally protective requirement.Poly-aspartate can be used as fertilizer
Material synergist is widely used in agricultural, field of forestry, also can be used as anti-incrustation corrosion inhibitor and is widely used in industry cooling recirculated water, anti-
The water treatment fields such as water, oil field reinjection water, metalworking fluid, boiler and steam pipework are permeated, in the row such as papermaking, printing and dyeing, washing
Industry can be used as dispersing agent, it can also be used to field of daily chemicals etc..
PASP synthesis reported in the literature refers mainly to the synthesis of polyaspartic acid salts, wherein poly-aspartate sodium salt study on the synthesis
More, market dosage is also larger.The synthesis step of industrial polyaspartic acid salts is broadly divided into two steps at present: the first step is intermediate
The synthesis of body polysuccinimide (PSI), second step are to prepare poly-aspartate with alkaline matter (such as sodium hydroxide) hydrolysis PSI
Salt.
For raw material angle, there are mainly two types of routes for existing PSI synthesis technology, first is that using ASPARTIC ACID as raw material
Obtaining PSI(through hot polymerization specifically can be using direct thermal polycondensation, acid-catalyzed polycondensation and solution polycondensation etc.), some above technical process
Need high pressure or organic solvent；Second is that anti-as raw material and ammonia donor (such as ammonium hydroxide, ammonia, ammonium carbonate, urea etc.) using maleic anhydride
Ammonium salt should be generated, then obtains PSI through hot polymerization.
It is the method for producing PSI and mainly using industrial at present, hydrolysis by the direct thermal polycondensation of raw material of ASPARTIC ACID
The commodity PASP molecular weight obtained afterwards is typically in the range of between 6000 ~ 8000；Sour (such as phosphoric acid) catalyzed polycondensation although it is available more
High molecular weight PSI, but the problems such as there are reaction masses easily to agglomerate, material uneven heating is even, it causes product stability poor, polymerize
Object molecular weight distribution is widened, and causes industrialization cost too high to the more demanding of industrial equipment；Solution polycondensation is generally used
To organic solvent (such as formamide, dimethyl sulfoxide, sulfolane), since easy to pollute and aftertreatment technology is cumbersome, energy consumption is high, if
The standby reasons such as cost and cost of labor height are also difficult to compete with other low cost process.Using maleic anhydride as raw material and ammonia donor
It is another main technique industrially taken that hot polymerization, which prepares PSI, after (such as ammonium hydroxide) reaction, and the commodity PASP obtained after hydrolysis divides
Son amount is between 4000-6000, although molecular weight is lower, cost is relatively low compared with ASPARTIC ACID is raw material, has
Certain competitiveness is also a common industrialized preparing process at present.
But the polyaspartic acid salts molecular weight of both the above technique production is smaller, wants far from widely application is met
It asks, there is research trial microwave method to improve molecular weight, but organic solvent need to be used, molecular weight increases limited and industrialization difficulty
It is larger.According to the literature, macromolecule poly-aspartate/salt performance is apparently higher than poly-aspartate/salt of low molecular weight, when
After molecular weight increases, its scale inhibition performance and corrosion inhibition are significantly improved when being sustained for water process and metal, are increased for agricultural fertilizer
Its effect of increasing production is higher when imitating agent.
The industrialized production polyaspartic acid salts bottleneck relatively low there are molecular weight at present.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high molecular weight organic amines and maleic anhydride modified poly- asparagus fern ammonia
Hydrochlorate and its preparation method, which is can the high organic amine of industrialized production molecular weight and maleic anhydride modified poly-
Aspartic acid product salt, reaction are not required to organic solvent, are not required to improve existing industrial equipment, can be produced under normal pressure,
Modified polyaspartic acid product salt molecular weight produced reaches as high as 40,000 or more, and purposes is more extensive, and price and existing production
Product remain basically stable, and have the great market competitiveness.
In order to solve the above technical problems, the technical solution used in the present invention is:
A kind of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, general structure are as follows:
Wherein, i=2,3,4,5 or 6；M is Na, K, Ca etc.；N and m is element length.
Unmodified poly-aspartic-acid structure are as follows:
Wherein, M Na, K, Ca etc.；N and m is element length.
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) preparation of modifying agent: being reacted with maleic anhydride using organic diamine, add alkali, bicarbonate, carbonate or
Oxide, after reaction plus water is configured to solution, forms homogeneous transparent liquid, as modifying agent；Wherein, organic diamine is second
Diamines, propane diamine, butanediamine, pentanediamine or hexamethylene diamine；The molar ratio of maleic anhydride and organic diamine is 1:1；
(2) polysuccinimide PSI is placed in flask, distilled water is added, then by modifying agent prepared by step (1)
It is added, the above hydrolysis of room temperature obtains modified polyaspartic acid salt；Wherein, polysuccinimide PSI and having in modifying agent
The molar ratio of machine diamines is 1:0.9~1.1.
Preferably, in step (1), organic diamine is ethylenediamine；Reaction time is 0.5h or more.
Preferably, in step (1), alkali NaOH, KOH or Ca (OH)2；Bicarbonate is NaHCO3、KHCO3Or Ca
(HCO3)2；Carbonate is Na2CO3、K2CO3Or CaCO3；Oxide is Na2O、K2O or CaO.
It is further preferred that in step (1), maleic anhydride and NaOH, KOH, NaHCO3Or KHCO3Molar ratio be 1:
0.8-1.2。
Still more preferably, in step (1), maleic anhydride and NaOH, KOH, NaHCO3Or KHCO3Molar ratio be 1:
1。
It is further preferred that in step (1), maleic anhydride and Ca (OH)2、Na2CO3、K2CO3、Ca(HCO3)2、CaCO3、
Na2O、K2The molar ratio of O or CaO is 1:0.4-0.6.
Still more preferably, in step (1), maleic anhydride and Ca (OH)2、Na2CO3、K2CO3、Ca(HCO3)2、CaCO3、
Na2O、K2The molar ratio of O or CaO is 1:0.5.
Preferably, in step (2), hydrolysising reacting temperature is room temperature~100 DEG C, and the reaction time is no less than 1h.
Preferably, there are two types of the preparation methods of polysuccinimide PSI:Using aspartic acid as raw material, directly heat de-
Water prepares PSI；Alternatively,In flask, using maleic anhydride, maleic acid or fumaric acid as raw material, ammonia is added and is prepared for precursor reactant
Intermediate is heated polymerization preparation PSI after reaction by intermediate；
WithWhen kind method preparation PSI, aspartic acid is L-Aspartic acid, D-Asp and/or D, L- asparagus fern ammonia
Acid；Reaction time is no less than 2h, and reaction temperature is not less than 160 DEG C；The factors such as considering cost are mainly with L-Aspartic acid
Raw material；
WithWhen kind of method preparation PSI, ammonia donor be ammonium hydroxide, ammonia, ammonium hydrogen carbonate, ammonium carbonate, urea, ammonium chloride or
Ammonium nitrate；The molar ratio of maleic anhydride, maleic acid or fumaric acid and ammonia donor is between 1:0.8 to 1:1.2；Intermediate preparation
When, control reacting liquid temperature is not higher than 80 DEG C, and the reaction time is no less than 0.5h；When heating polymerization preparation PSI, the reaction time is many
In 1h, reaction temperature is not less than 160 DEG C；The factors such as considering cost, mainly using maleic anhydride and ammonium hydroxide as raw material.
It is further preferred that the molar ratio of maleic anhydride, maleic acid or fumaric acid and ammonia donor is 1:1 ~ 1.2.More into one
Step is preferred, and the molar ratio of maleic anhydride, maleic acid or fumaric acid and ammonia donor is 1:1 ~ 1.1.
The polyaspartic acid salts molecular weight of industrial production synthesis at present is between 2000 ~ 8000, and organic amine and maleic acid
Polyaspartic acid salts molecular weight after anhydride modification reaches as high as 40000 or more, and molecular weight greatly improves.This reaction does not have to pressurization,
It without organic solvent, can be produced using existing equipment, not have to carry out equipment investment, reaction process is easy to control, will not generate
Other pollutions, and similar modified polyaspartic acid salt (such as sodium salt) product price and existing poly-aspartate sodium salt production cost base
This maintains an equal level, and has great economic benefit and social value.
Modifying agent can provide the amino group (- NH that long-chain has alkalinity2), for the ring-opening reaction of PSI, effect is suitable
Alkali in the poly- day synthesis of tradition.Structure of modifier is as follows:
Wherein, i=2,3,4,5 or 6；M is Na, K or Ca.
The beneficial effects of adopting the technical scheme are that
(1) organic amine of the invention and the polyaspartic acid salts molecular weight of maleic anhydride modified synthesis are bigger, reach as high as
40000 or more, functional stronger, the scope of application is wider；
(2) compared with traditional polyaspartic acid salts, the backbone of modifying agent makes modified polyaspartic acid salinity of the present invention
Long-chain-the COOH contained in son is easy to ionize in aqueous solution, forms carboxyl anion (- COO-), chemical activity is high, more
Chelation easily occurs with different kinds of ions, purposes is wider；
(3) present invention breaches the simple bottleneck for using basic hydrolysis PSI compared with traditional handicraft, and in addition to alkali, gold may be selected
Belong to carbonate, bicarbonate and the oxide of ion, production cost is lower than or maintains an equal level substantially with prior art, and available
Existing equipment production has the great market competitiveness, profit and social benefit are more obvious without being invested again.
Specific embodiment
Below with reference to embodiment, the invention will be further described." part " used in the following embodiment is molar part
Number.All reactions in flask can be substituted in industrialized production with reaction kettle in embodiment；Reaction in an oven is in work
Available disk dry reaction device, mixer and kneader substitution in the production of industry metaplasia；Griding reaction can use mixer in industrialized production
It is substituted with kneader.
Embodiment 1
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of maleic anhydride and 0.9 part of ammonia (ammonia donor is 25 % ammonium hydroxide of mass percent) are added to burning
In bottle, 60 DEG C are reacted 0.5 hour, are transferred in 180 DEG C of baking ovens, are polymerize 4 hours, are obtained PSI；
(2) preparation of modifying agent: being first added 1 part of ethylenediamine in mortar, adds 1 part of maleic anhydride, and grinding 0.5 is small
When, 0.9 part of NaOH solid is added, continues grinding 0.5 hour, 10 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 12 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, controls 80 DEG C of temperature reactions 1 hour to get modified polyaspartic acid sodium salt.
Embodiment 2
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of maleic anhydride and 1 part of ammonia (ammonia donor is ammonium nitrate) being added in flask, are added 15 parts
Distilled water, 50 DEG C are reacted 1 hour, are transferred in 200 DEG C of baking ovens, polyase 13 hour, are obtained PSI；
(2) preparation of modifying agent: being first added 1 part of butanediamine in mortar, adds 1 part of maleic anhydride, and grinding 0.5 is small
When, 0.9 part of KHCO is added3Solid continues grinding 1 hour, 11 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 12 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, control temperature 60 C reacts 6 hours to get modified polyaspartic acid sylvite.
Embodiment 3
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of maleic acid and 1 part of ammonia (ammonia donor is ammonia) being added in flask, 4 parts of distillations are added
Water, 40 DEG C are reacted 0.5 hour, are transferred in 220 DEG C of baking ovens, are polymerize 5 hours, are obtained PSI；
(2) preparation of modifying agent: being first added 1 part of hexamethylene diamine in mortar, adds 1 part of maleic anhydride, grinds 1 hour,
0.55 part of CaCO is added3Solid powder continues grinding 1 hour, 12 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 14 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, control temperature 70 C reacts 8 hours to get modified polyaspartic acid calcium salt.
Embodiment 4
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of L-Aspartic acid being placed in baking oven, 220 DEG C polymerize 4 hours, obtain PSI；
(2) preparation of modifying agent: being first added 1 part of propane diamine in mortar, adds 1 part of maleic anhydride, and grinding 0.5 is small
When, 1.1 parts of NaHCO are added3Solid continues grinding 1 hour, 10 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 13 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, control temperature 70 C reacts 4 hours to get modified polyaspartic acid sodium salt.
Embodiment 5
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of L-Aspartic acid being placed in baking oven, 220 DEG C polymerize 10 hours, obtain PSI；
(2) preparation of modifying agent: being first added 0.9 part of pentanediamine in mortar, adds 0.9 part of maleic anhydride, and grinding 1 is small
When, 1 part of KOH solid is added, continues grinding 0.5 hour, 14 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 12 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, controls 40 DEG C of temperature reactions 8 hours to get modified polyaspartic acid sylvite.
Embodiment 6
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of D-Asp being placed in baking oven, 180 DEG C polymerize 8 hours, obtain PSI；
(2) preparation of modifying agent: being first added 1.1 parts of ethylenediamines in mortar, adds 1.1 parts of maleic anhydrides, grinding 0.5
Hour, 0.55 part of CaO solid powder is added, continues grinding 1 hour, 12 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 10 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, control temperature 50 C reacts 10 hours to get modified polyaspartic acid calcium
Salt.
Embodiment 7
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of fumaric acid and 1.1 parts of ammonia (ammonia donor is ammonium carbonate) being added in flask, are added 10 parts
Distilled water, 80 DEG C are reacted 1 hour, are transferred in 220 DEG C of baking ovens, are polymerize 5 hours, are obtained PSI；
(2) preparation of modifying agent: being first added 1 part of pentanediamine in mortar, adds 1 part of maleic anhydride, grinds 1 hour,
0.5 part of Na is added2CO3Solid continues grinding 1 hour, 12 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 13 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, control temperature 60 C reacts 6 hours to get modified polyaspartic acid sodium salt.
Embodiment 8
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of maleic anhydride and 1.1 parts of ammonia (ammonia donor is urea) being added in flask, 6 parts of steamings are added
Distilled water, 50 DEG C are reacted 1 hour, are transferred in 180 DEG C of baking ovens, are polymerize 1 hour, are obtained PSI；
(2) preparation of modifying agent: being first added 1 part of ethylenediamine in mortar, adds 1 part of maleic anhydride, and grinding 0.5 is small
When, 0.5 part of Ca (OH) is added2Solid continues grinding 1 hour, 11 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 10 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, controls 30 DEG C of temperature reactions 10 hours to get modified polyaspartic acid calcium
Salt.
Embodiment 9
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: by 1 part of D, L-Aspartic acid is placed in baking oven, and 240 DEG C polymerize 6 hours, obtains PSI；
(2) preparation of modifying agent: being first added 1 part of pentanediamine in mortar, adds 1 part of maleic anhydride, grinds 1 hour,
0.45 part of K is added2CO3Solid continues grinding 1 hour, 12 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 12 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, control temperature 45 C reacts 5 hours to get modified polyaspartic acid sylvite.
Embodiment 10
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of maleic anhydride and 1 part of ammonia (ammonia donor is ammonium chloride) being added in flask, are added 11 parts
Distilled water, 60 DEG C are reacted 1 hour, are transferred in 200 DEG C of baking ovens, are polymerize 2 hours, are obtained PSI；
(2) preparation of modifying agent: being first added 1 part of ethylenediamine in mortar, adds 1 part of maleic anhydride, and grinding 0.5 is small
When, 0.5 part of Na is added2CO3Solid continues grinding 1 hour, 12 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) being placed in flask, 8 parts of distilled water are added, so
Modifying agent prepared by step (2) is added afterwards, control temperature 70 C reacts 3 hours to get modified polyaspartic acid sodium salt.
Embodiment 11
The preparation method of high molecular weight organic amine and maleic anhydride modified polyaspartic acid salts, comprising the following steps:
(1) prepared by PSI: 1 part of maleic anhydride and 1 part of ammonia (ammonia donor is ammonium hydrogen carbonate) being added in flask, are added 10
Part distilled water, 60 DEG C are reacted 1 hour, are transferred in 220 DEG C of baking ovens, polyase 13 hour, are obtained PSI；
(2) preparation of modifying agent: being first added 1 part of propane diamine in mortar, adds 1 part of maleic anhydride, and grinding 0.5 is small
When, 0.5 part of Ca (HCO is added3)2Solid continues grinding 1 hour, 10 parts of distilled water is added and stir evenly transparent liquid；
(3) modified polyaspartic acid salt synthesizes: PSI prepared by step (1) is placed in flask, 12 parts of distilled water are added,
Then modifying agent prepared by step (2) is added, control temperature 60 C reacts 8 hours to get modified polyaspartic acid calcium salt.
Comparative example 1
Using maleic anhydride as the synthesis of starting material sodium polyaspartate
1 part of maleic anhydride and 1 part of ammonia (ammonia donor is 25 % ammonium hydroxide of mass percent) are added in flask, 60 DEG C of reactions
It 0.5 hour, is transferred in 220 DEG C of baking ovens, polymerize 8 hours, obtain PSI；Prepared PSI is placed in flask, 17 parts of steamings are added
Distilled water, is added 1 part of sodium hydroxide, and control temperature 70 C reacts 1 hour to get poly-aspartate sodium salt.
Comparative example 2
Using L-Aspartic acid as the synthesis of raw material sodium polyaspartate
1 part of L-Aspartic acid is placed in baking oven, 220 DEG C polymerize 8 hours, obtain PSI；Prepared PSI is placed in flask
In, 17 parts of distilled water are added, 1 part of sodium hydroxide is added, control temperature 70 C reacts 1 hour to get poly-aspartate sodium salt.
According to the molecular weight of polyaspartic acid salts HG/T 3822-2006 standard test embodiment 1-11 and comparative example 1-2.
Claims (10)
1. a kind of organic amine and maleic anhydride modified high molecular weight polyasparagic acid salt, it is characterised in that: its general structure is such as
Under:
Wherein, i=2,3,4,5 or 6；M is Na, K or Ca；N and m is element length.
2. the preparation method of organic amine as described in claim 1 and maleic anhydride modified high molecular weight polyasparagic acid salt, special
Sign is, comprising the following steps:
(1) it the preparation of modifying agent: is reacted using organic diamine with maleic anhydride, adds alkali, bicarbonate, carbonate or oxidation
Object, after reaction plus water is configured to solution, forms homogeneous transparent liquid, as modifying agent；Wherein, organic diamine is second two
Amine, propane diamine, butanediamine, pentanediamine or hexamethylene diamine；The molar ratio of maleic anhydride and organic diamine is 1:1；
(2) polysuccinimide PSI is placed in flask, distilled water is added, then adds modifying agent prepared by step (1)
Enter, the above hydrolysis of room temperature obtains modified polyaspartic acid salt；Wherein, polysuccinimide PSI with it is organic in modifying agent
The molar ratio of diamines is 1:0.9~1.1.
3. the preparation method of organic amine according to claim 2 and maleic anhydride modified high molecular weight polyasparagic acid salt,
Be characterized in that: in step (1), organic diamine is ethylenediamine；Reaction time is 0.5h or more.
4. the preparation method of organic amine according to claim 2 and maleic anhydride modified high molecular weight polyasparagic acid salt,
It is characterized in that: in step (1), alkali NaOH, KOH or Ca (OH)2；Bicarbonate is NaHCO3、KHCO3Or Ca (HCO3)2；Carbonic acid
Salt is Na2CO3、K2CO3Or CaCO3；Oxide is Na2O、K2O or CaO.
5. the preparation method of organic amine according to claim 4 and maleic anhydride modified high molecular weight polyasparagic acid salt,
It is characterized in that: in step (1), maleic anhydride and NaOH, KOH, NaHCO3Or KHCO3Molar ratio be 1:0.8-1.2.
6. the preparation method of organic amine according to claim 5 and maleic anhydride modified high molecular weight polyasparagic acid salt,
It is characterized in that: in step (1), maleic anhydride and NaOH, KOH, NaHCO3Or KHCO3Molar ratio be 1:1.
7. the preparation method of organic amine according to claim 4 and maleic anhydride modified high molecular weight polyasparagic acid salt,
It is characterized in that: in step (1), maleic anhydride and Ca (OH)2、Na2CO3、K2CO3、Ca(HCO3)2、CaCO3、Na2O、K2O or CaO
Molar ratio be 1:0.4-0.6.
8. the preparation method of organic amine according to claim 7 and maleic anhydride modified high molecular weight polyasparagic acid salt,
It is characterized in that: in step (1), maleic anhydride and Ca (OH)2、Na2CO3、K2CO3、Ca(HCO3)2、CaCO3、Na2O、K2O or CaO
Molar ratio be 1:0.5.
9. the preparation method of organic amine according to claim 2 and maleic anhydride modified high molecular weight polyasparagic acid salt,
Be characterized in that: in step (2), hydrolysising reacting temperature is room temperature~100 DEG C, and the reaction time is no less than 1h.
10. the preparation method of organic amine according to claim 2 and maleic anhydride modified high molecular weight polyasparagic acid salt,
It is characterized in that:
There are two types of the preparation methods of polysuccinimide PSI: 1. using aspartic acid as raw material, directly heating dehydration preparation PSI；Or
Person, using maleic anhydride, maleic acid or fumaric acid as raw material, is added ammonia for precursor reactant and prepares intermediate, reaction knot 2. in flask
Intermediate is heated into polymerization preparation PSI after beam；
With the 1. kind method preparation PSI when, aspartic acid is L-Aspartic acid, D-Asp and/or D, L-Aspartic acid；Instead
No less than 2h, reaction temperature are not less than 160 DEG C between seasonable；
With the 2. kind method preparation PSI when, ammonia donor is ammonium hydroxide, ammonia, ammonium hydrogen carbonate, ammonium carbonate, urea, ammonium chloride or nitric acid
Ammonium；The molar ratio of maleic anhydride, maleic acid or fumaric acid and ammonia donor is between 1:0.8 to 1:1.2；When prepared by intermediate,
It controls reacting liquid temperature and is not higher than 80 DEG C, the reaction time is no less than 0.5h；When heating polymerization preparation PSI, the reaction time is no less than
1h, reaction temperature are not less than 160 DEG C.
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