CN1569922A - Asparagic acid possessing phosphinic group, its preparation method and uses in water processing - Google Patents
Asparagic acid possessing phosphinic group, its preparation method and uses in water processing Download PDFInfo
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- CN1569922A CN1569922A CN 03150354 CN03150354A CN1569922A CN 1569922 A CN1569922 A CN 1569922A CN 03150354 CN03150354 CN 03150354 CN 03150354 A CN03150354 A CN 03150354A CN 1569922 A CN1569922 A CN 1569922A
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- aspartic acid
- poly aspartic
- phosphonate group
- phosphorus trichloride
- formaldehyde
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Abstract
The invention discloses an asparagic acid possessing phosphinic group, its preparation method and uses in water processing by using asparagic acid phsophorus trichloride, formaldehyde and water as raw material, wherein the asparagic acid has fine CaCO3 and Ca3(PO4)2 scale resistant function.
Description
Technical field
The present invention relates to contain phosphonate group poly aspartic acid, its preparation method and the application in water treatment thereof, promptly in a molecule, contain water quality stabilizer, its preparation method and the application in water treatment thereof of amido linkage, carboxyl and three functional groups of phosphonate group simultaneously.
Background technology
In recirculating cooling water system, mainly exist fouling, corrosion and microorganism to endanger three aspect problems.And anti-locking system fouling and corrosion most convenient and effective means are to add corrosion inhibiting and descaling agent in recirculated cooling water.The at present domestic prescription that is usually used in the recirculated cooling water processing mostly is phosphorus line formulation, its host is the corrosion inhibiting and descaling agent that contains phosphonate group, they mainly comprise: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), phosphono-containing butane-1,2,4-tricarboxylic acid (PBTCA), 2-hydroxyl phosphino-acetate (HPA) etc.Along with production-scale continuous expansion, the process water problem becomes the principal element of restriction production development gradually.Except that national macro adjustments and controls, reasonable disposition to water resources, the reuse in recirculating cooling water system of the raising of recirculating cooling water system cycles of concentration and sewage is two main paties of enterprises water saving, and the smooth implementation of these two kinds water saving schemes must be based upon on the basis of water conditioning.Therefore developing new and effective water quality stabilizer becomes the key that addresses the above problem.
CN1398799A, CN1341676A, CN1146210A, US5116513, US5152902, US5284512 and US5391764 disclose poly aspartic acid and preparation method thereof, and its shortcoming is the resistance CaCO of prepared poly aspartic acid
3, Ca
3(PO
4)
2Dirty and stable zinc salt poor performance.
Summary of the invention
The object of the present invention is to provide a kind of phosphonate group poly aspartic acid that contains.Its characteristics are to contain simultaneously in the molecule amido linkage, carboxyl and three sense groups of phosphonate group, make it not only have good resistance CaCO
3With resistance Ca
3(PO
4)
2The dirt function also has Zn in certain stabilize water
2+Ability and corrosion inhibition and other composite reagent, have synergistic effect preferably.
Another object of the present invention is to provide a kind of preparation method who contains the phosphonate group poly aspartic acid.
A further object of the present invention is and will contains the water treatment that the phosphonate group poly aspartic acid is used for industrial circulating cooling water.
The invention provides a kind of phosphonate group poly aspartic acid that contains, its general formula is:
R wherein
1, R
2, R
3And R
4Be H or CH independently
2-PO
3H
2, poly aspartic acid (R
1, R
2, R
3And R
4When being H) molecular weight be 2000-20000, be preferably 3000-5000, most preferably be 4000-5000, with PO
4The content of meter organic phosphine is at least 2 weight %.
H in the poly aspartic acid on the nitrogen is by CH
2-PO
3H
2What replace is many more, and the content of organic phosphine is high more, and its scale-inhibiting properties is good more, but the content of organic phosphine can unrestrictedly not increase, its maximum be in the poly aspartic acid H on the nitrogen all by CH
2-PO
3H
2Replace, organic phosphine content of the present invention is with PO
4Meter is preferably 2 weight %-11 weight %, 5 weight %-11 weight % more preferably.
When the present invention contained the phosphonate group poly aspartic acid in preparation, can adopt with poly aspartic acid, phosphorus trichloride, formaldehyde and water was feedstock production, and also can adopt poly aspartic acid, phosphorous acid, formaldehyde and water is feedstock production.
The invention provides the above-mentioned a kind of preparation method who contains the phosphonate group poly aspartic acid, be included in and in the poly aspartic acid aqueous solution, add formaldehyde and water under 10-30 ℃, controlled temperature is not higher than 50 ℃, drip phosphorus trichloride, treat to be warming up to again after phosphorus trichloride adds 60-110 ℃, preferred 80-100 ℃, and under 60-110 ℃, preferred 80-100 ℃, reacted 1-4 hour, obtain containing the phosphonate group poly aspartic acid; Perhaps control the poly aspartic acid aqueous temperature and be not higher than 50 ℃, drip phosphorus trichloride, treat to be warming up to again after phosphorus trichloride adds 60-110 ℃, preferred 80-100 ℃, drip formaldehyde, treat formaldehyde dropwise the back 60-110 ℃, preferred 80-100 ℃ following insulation reaction 1-4 hour, obtain containing the phosphonate group poly aspartic acid.Wherein the weight ratio of poly aspartic acid and phosphorus trichloride is: poly aspartic acid/phosphorus trichloride=15/ (3-18); The mol ratio of phosphorus trichloride and formaldehyde is: phosphorus trichloride/formaldehyde=1/ (1-1.1).
The present invention also provides the above-mentioned another kind of preparation method who contains the phosphonate group poly aspartic acid, be included in and in the poly aspartic acid aqueous solution, add formaldehyde, phosphorous acid and water under 10-30 ℃, controlled temperature is not higher than 50 ℃, drip concentrated hydrochloric acid, treat to be warming up to 60-110 ℃ again after concentrated hydrochloric acid adds, to be preferably 80-100 ℃, and 60-110 ℃, be preferably 80-100 ℃ of down reaction 1-4 hour, obtain containing the phosphonate group poly aspartic acid.Wherein the weight ratio of poly aspartic acid and phosphorous acid is: poly aspartic acid/phosphorous acid=15/ (2-11); The mol ratio of phosphorous acid and formaldehyde is: phosphorous acid/formaldehyde=1/ (1-1.1).
The purpose that concentrated hydrochloric acid adds is to carry out in order to make to be reflected under the acidic conditions, and its consumption is had no particular limits, and the mol ratio of preferred hydrogenchloride of its add-on and poly aspartic acid is 0.5-2 for well.
Above-mentioned preparation method's synthetic route is simple.Institute's synthetic contains phosphonate group poly aspartic acid water quality stabilizer and has good resistance CaCO
3With resistance Ca
3(PO
4)
2The dirt performance also has Zn in certain stabilize water
2+Ability and corrosion inhibition and other composite reagent, have synergistic effect preferably, therefore can be used as dirt dispersion agent and be widely used in during recirculated cooling water handles.Exploitation of the present invention, promotion and application have bigger economic benefit and social benefit.
Embodiment
Following embodiment will help to illustrate the present invention, but not limit to its scope.
The assessment of performance method that contains the phosphonate group poly aspartic acid of following embodiment gained is as follows:
Resistance calcium carbonate scale performance is got distilled water, is mixed with Ca
2+Concentration is 250mgL
-1(with CaCO
3Meter, as follows), basicity is 250mgL
-1(with CaCO
3Meter, as follows) test water, add 8mgL
-1The medicament of (in effective concentration), evaporation concentration in 80 ± 1 ℃ of waters bath with thermostatic control to 2 times of cycles of concentration, remains Ca in the sampling analysis water
2+Concentration, make blank sample simultaneously, and calculate scale inhibition performance.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0)/(2C
1-C
0) * 100%
C: actual measurement Ca
2+Concentration
C
0: the Ca of blank sample
2+Concentration
C
1: the Ca in the former water
2+Concentration
Resistance calcium phosphate scale performance is got distilled water and is added a certain amount of calcium ion, preparation Ca
2+Concentration is 250mgL
-1, PO
4 3-Concentration is 5mgL
-1Test water, add 8mgL
-1Medicament, in 80 ± 1 ℃ of waters bath with thermostatic control, left standstill 10 hours, make blank sample simultaneously, and remain PO in the sampling analysis water
4 3-Concentration, and calculate scale inhibition performance.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) * 100%
C: actual measurement PO
4 3-Concentration
C
0: PO in the blank sample
4 3-Concentration
C
1: PO in the former water
4 3-Concentration
Stablize the zinc salt performance and get distilled water preparation Ca
2+Concentration is 250mgL
-1, basicity is 250mgL
-1And Zn
2+Be 5mgL
-1Test water, add 8mgL
-1Medicament, in 80 ± 1 ℃ of waters bath with thermostatic control, left standstill 10 hours, remain Zn in the sampling analysis water
2+Concentration, make blank sample simultaneously, and calculate resistance zinc rate.
Resistance zinc rate calculation formula is: resistance zinc rate=(C-C
0)/(C
1-C
0) * 100%
C: actual measurement Zn
2+Concentration
C
0: the Zn of blank sample
2+Concentration
C
1: the Zn in the former water
2+Concentration
Resistance zinc rate is high more, and the stability of zinc salt in water is good more, and it is good more to illustrate that medicament is stablized the performance of zinc salt.
Corrosion inhibition is fixed on the test piece of 20# qualitative carbon steel on the lacing film instrument, puts into the Beijing Miyun Reservoir tap water that is added with medicament, and 40 ± 1 ℃ of steady temperatures keep rotating speed 75rpm rotation 72 hours, and the weight of test piece is calculated average corrosion rate before and after the record test.
The average corrosion rate calculation formula is: F=C * Δ W/A * T * ρ
C: computational constant, when being unit with mm/a (millimeter/year), C=8.76 * 10
7
Δ W: the corrosion weight loss of test specimen (gram)
A: the area of test specimen (centimetre
2)
T: the corrosion test time (hour)
ρ: the density (kilogram/rice of material for test
3)
The measuring method total phosphorus of phosphorus, positive phosphorus, phosphorous measuring method are with reference to total phosphorus, positive phosphorus, phosphorous measuring method among " People's Republic of China's specialized standard " ZB G 71002～71004-89.
Organic phosphine Determination on content formula is: X
2=X
1* 3.067-X
3* 1.203-X
4
X
1: total phosphorous (in P);
X
2: organic phosphine content is (with PO
4Meter);
3.067: the coefficient that becomes the phosphate radical quality by the phosphorus mass conversion;
X
3: inferior phosphorus content is (with PO
3Meter);
1.203: the coefficient that is converted into phosphate radical by orthophosphite;
X
4: positive phosphorus content is (with PO
4Meter).
Embodiment 1
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 70 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 8.2%.
Embodiment 2
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 105 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 7.3%.
Embodiment 3
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃ and insulation reaction 4 hours, cool off product.The organic phosphine content of product is 9.5%.
Embodiment 4
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 9.4%.
Embodiment 5
(the too bright chemical engineering industry in Shanxi company limited produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 8000-18000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 9.4%.
Embodiment 6
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃, drip formalin 26.6g (effective constituent is by 36%), treat that formalin dropwises back insulation reaction 2 hours under 90 ± 2 ℃ of temperature, cool off product.The organic phosphine content of product is 10.1%.
Embodiment 7
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 167ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) and phosphorous acid 26.9g (effective constituent is by 97%) down in room temperature (20 ℃).Below 50 ℃, drip concentrated hydrochloric acid 11.7g with the cooling bath control reaction temperature.Treat that concentrated hydrochloric acid dropwises, be warming up to 90 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 9.3%.
Embodiment 8
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Below 50 ℃, drip phosphorus trichloride 27.1g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃, drip formalin 16.5g (effective constituent is by 36%), treat that formalin dropwises back insulation reaction 2 hours under 90 ± 2 ℃ of temperature, cool off product.The organic phosphine content of product is 6.4%.
Embodiment 9
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Below 50 ℃, drip phosphorus trichloride 13.5g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃, drip formalin 8.2g (effective constituent is by 36%), treat that formalin dropwises back insulation reaction 2 hours under 90 ± 2 ℃ of temperature, cool off product.The organic phosphine content of product is 3.5%.
Comparative Examples 1
The poly aspartic acid that Chang Mao Biochemical Engineering Co produces (content: 40%, molecular weight: 4000-5000).
Comparative Examples 2
The poly aspartic acid that Shanxi too bright chemical engineering industry company limited produces (content: 40%, molecular weight: 8000-18000).
The scale-inhibiting properties of embodiment and Comparative Examples sees the following form 1.
Table 1
Embodiment calcium phosphate scale inhibition performance/% resistance zinc rate/% lime carbonate scale inhibition performance/%
1 78.8 19.4 90.0
2 65.4 12.8 74.7
3 87.9 30.5 97.2
4 86.8 29.2 97.3
5 80.9 21.6 92.3
6 90.5 32.8 99.6
7 86.1 27.0 96.8
8 76.2 19.6 87.4
9 44.3 12.3 66.5
Comparative Examples 1 20.6 3.5 40.9
Comparative Examples 2 15.2 0 32.9
The corrosion inhibition of embodiment and Comparative Examples sees the following form 2.
Table 2
Adding medicine concentration/the mg.L of institute
-1Corrosion speed/mm.a
-1
Embodiment 4 20 0.324
Embodiment 6 20 0.305
Embodiment 7 20 0.346
Embodiment 9 20 0.457
Comparative Examples 1 20 0.758
Embodiment 4+HEDP+Zn
2+8+,4+2 0.018
Embodiment 6+HEDP+Zn
2+8+,4+2 0.016
Embodiment 7+HEDP+Zn
2+8+,4+2 0.019
Embodiment 9+HEDP+Zn
2+8+,4+2 0.059
Comparative Examples 1+HEDP+Zn
2+8+,4+2 0.102
Blank 0.932
Claims (10)
1. one kind contains the phosphonate group poly aspartic acid, and its general formula is:
R wherein
1, R
2, R
3And R
4Be H or CH independently
2-PO
3H
2, the molecular weight of poly aspartic acid is 2000-20000, with PO
4The content of meter organic phosphine is at least 2 weight %.
2. the phosphonate group poly aspartic acid that contains according to claim 1 is characterized in that with PO
4The content of meter organic phosphine is 2 weight %-11 weight %, is preferably 5 weight %-11 weight %.
3. the phosphonate group poly aspartic acid that contains according to claim 1 is characterized in that the molecular weight of poly aspartic acid is 3000-5000, is preferably 4000-5000.
4. each described preparation method who contains the phosphonate group poly aspartic acid of claim 1-3, be included in and in the poly aspartic acid aqueous solution, add formaldehyde and water under 10-30 ℃, controlled temperature is not higher than 50 ℃, drip phosphorus trichloride, treat to be warming up to 60-110 ℃ again after phosphorus trichloride adds, and under 60-110 ℃, reacted 1-4 hour, obtain containing the phosphonate group poly aspartic acid; Perhaps control the poly aspartic acid aqueous temperature and be not higher than 50 ℃, drip phosphorus trichloride, treat to be warming up to 60-110 ℃ again after phosphorus trichloride adds, drip formaldehyde, treat that formaldehyde dropwised the back at 60-110 ℃ of following insulation reaction 1-4 hour, obtained containing the phosphonate group poly aspartic acid.
5. the preparation method who contains the phosphonate group poly aspartic acid according to claim 4 is characterized in that the weight ratio of poly aspartic acid and phosphorus trichloride is: poly aspartic acid/phosphorus trichloride=15/ (3-18); The mol ratio of phosphorus trichloride and formaldehyde is: phosphorus trichloride/formaldehyde=1/ (1-1.1).
6. according to claim 4 or the 5 described preparation methods that contain the phosphonate group poly aspartic acid, it is characterized in that described temperature of reaction is 80-100 ℃.
7. each described preparation method who contains the phosphonate group poly aspartic acid of claim 1-3, be included in and in the poly aspartic acid aqueous solution, add formaldehyde, phosphorous acid and water under 10-30 ℃, controlled temperature is not higher than 50 ℃, drip concentrated hydrochloric acid, treat to be warming up to 60-110 ℃ again after concentrated hydrochloric acid adds, and under 60-110 ℃, reacted 1-4 hour, obtain containing the phosphonate group poly aspartic acid.
8. the preparation method who contains the phosphonate group poly aspartic acid according to claim 7 is characterized in that the weight ratio of poly aspartic acid and phosphorous acid is: poly aspartic acid/phosphorous acid=15/ (2-11); The mol ratio of phosphorous acid and formaldehyde is: phosphorous acid/formaldehyde=1/ (1-1.1).
9. according to claim 7 or the 8 described preparation methods that contain the phosphonate group poly aspartic acid, it is characterized in that described temperature of reaction is 80-100 ℃.
Claim 1-3 each describedly contain the application of phosphonate group poly aspartic acid aspect water treatment.
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|---|---|---|---|
| CN 03150354 CN1277864C (en) | 2003-07-25 | 2003-07-25 | Asparagic acid possessing phosphinic group, its preparation method and uses in water processing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150354 CN1277864C (en) | 2003-07-25 | 2003-07-25 | Asparagic acid possessing phosphinic group, its preparation method and uses in water processing |
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| Publication Number | Publication Date |
|---|---|
| CN1569922A true CN1569922A (en) | 2005-01-26 |
| CN1277864C CN1277864C (en) | 2006-10-04 |
Family
ID=34472700
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241702A (en) * | 2011-04-27 | 2011-11-16 | 河南清水源科技股份有限公司 | Poly 4-amino dimethylene phosphonic acid 2-butenoic acid and production process thereof |
| CN104397026A (en) * | 2014-11-25 | 2015-03-11 | 苏州佑君环境科技有限公司 | Water-treated potassium ferrate sterilizing agent and preparation method thereof |
| CN105293661A (en) * | 2015-11-09 | 2016-02-03 | 淄博鲁瑞精细化工有限公司 | Chloridion-free organic phosphine chelating agent and preparation method thereof |
| CN107720984A (en) * | 2017-10-17 | 2018-02-23 | 高产明 | A kind of preparation method of the low-phosphorous water quality stabilizer of efficient scale corrosion inhibition type |
| CN108373536A (en) * | 2018-05-22 | 2018-08-07 | 河北工业大学 | A kind of synthetic method and application with schiff base structure modified polyaspartic acid |
-
2003
- 2003-07-25 CN CN 03150354 patent/CN1277864C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241702A (en) * | 2011-04-27 | 2011-11-16 | 河南清水源科技股份有限公司 | Poly 4-amino dimethylene phosphonic acid 2-butenoic acid and production process thereof |
| CN102241702B (en) * | 2011-04-27 | 2014-04-30 | 河南清水源科技股份有限公司 | Poly 4-amino dimethylene phosphonic acid 2-butenoic acid and production process thereof |
| CN104397026A (en) * | 2014-11-25 | 2015-03-11 | 苏州佑君环境科技有限公司 | Water-treated potassium ferrate sterilizing agent and preparation method thereof |
| CN105293661A (en) * | 2015-11-09 | 2016-02-03 | 淄博鲁瑞精细化工有限公司 | Chloridion-free organic phosphine chelating agent and preparation method thereof |
| CN107720984A (en) * | 2017-10-17 | 2018-02-23 | 高产明 | A kind of preparation method of the low-phosphorous water quality stabilizer of efficient scale corrosion inhibition type |
| CN108373536A (en) * | 2018-05-22 | 2018-08-07 | 河北工业大学 | A kind of synthetic method and application with schiff base structure modified polyaspartic acid |
| CN108373536B (en) * | 2018-05-22 | 2020-04-14 | 河北工业大学 | Synthesis method and application of modified polyaspartic acid with Schiff base structure |
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| Publication number | Publication date |
|---|---|
| CN1277864C (en) | 2006-10-04 |
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