CN103834010A - Rosin-based grafted polyaspartic acid and preparation method thereof - Google Patents
Rosin-based grafted polyaspartic acid and preparation method thereof Download PDFInfo
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- CN103834010A CN103834010A CN201410107424.8A CN201410107424A CN103834010A CN 103834010 A CN103834010 A CN 103834010A CN 201410107424 A CN201410107424 A CN 201410107424A CN 103834010 A CN103834010 A CN 103834010A
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- aspartic acid
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Abstract
The invention discloses rosin-based grafted polyaspartic acid and discloses a preparation method and application in water treatment of rosin-based grafted polyaspartic acid. The rosin-based grafted polyaspartic acid has a structure shown in the specification, wherein R is rosin amine dehydrogenation residue and has a structure shown in the specification. The method for preparing the polymer comprises the following steps: (a) performing pyrocondensation polymerization on maleic anhydride and ammonia water to form PSI polysuccinimide; (b) carrying out a grafting reaction between polysuccinimide and rosin amine; (c) finally adding a solution of sodium hydroxide for fully hydrolyzing. The rosin-based grafted polyaspartic acid is green and environment-friendly and has excellent performances in a high-hardness, high-alkalinity, high-PH value and high-concentration factor system.
Description
Technical field
The invention belongs to Water Treatment Chemicals and Application Areas, a kind of rosinyl grafting poly aspartic acid and preparation method thereof is provided.
Background technology
Rosin is a kind of natural resource, has biodegradable, renewable and source is wide, lower-price characteristic.Rosin Amine D is a kind of aliphatic amide being derived by rosin; there is the effect of inhibition, sterilization, algae removal, deinsectization; therefore be widely used and protection and the cleaning and descaling of hardware, wood preservation, aspect pigment, paint, rubber, medicine, papermaking, weaving, application is also very wide.But because solvability in its water is not good, having limited its range of application, rosin Amine D has been carried out to modification and compensate its defect and have very large value, is the direction of rosin applied research.
Patent CN101982460A discloses a kind of Dehydroabieticacyl thiourea derivatives, for negatively charged ion as the identification receptor of phosphate radical, acetate, chloroacetate root, sulfate radical, nitrate radical, chlorion or bromide anion etc.What Wen Shen of Nanjing University etc. has reported the inhibiter of a kind of oil-soluble Rosin-based Imidazoline for metal sour environment.A patent of Beijing Institute of Light Industry discloses a kind of Abietyl quaternary ammonium salt N, N, and the preparation method of N-trimethylammonium-N-rosinyl methyl sulfate ammonium, and introduced its application as sterilization tensio-active agent.
The above-mentioned character of the modification of rosin derivative having been improved to a certain extent to rosin, but all ignored biodegradable environmental issue, increase the decomposition difficulty of original rosin, bring burden to environment.
Summary of the invention
The present invention discloses a kind of rosinyl grafting poly aspartic acid and its preparation method and application, and biodegradable rosin Amine D is grafted to same biodegradable natural poly aspartic acid side group, obtains a kind of water treatment agent with scale inhibitor.The method has not only been improved the water-soluble of rosin Amine D but also has been made this graft copolymer have effect of scale inhibition and inhibition simultaneously.
A kind of rosinyl grafting poly aspartic acid has structure I:
Ⅰ
Wherein R is that rosin Amine D dehydrogenation residue has structure II
Ⅱ
Concrete the present invention implements by following concrete scheme:
(1) maleic anhydride and ammoniacal liquor are joined in reactor and be neutralized into ammonium salt, then mediate thermal polycondensation reaction with kneader high temperature, obtain the gluey polysuccinimide of solid;
(2) gluey above-mentioned gained polysuccinimide and rosin Amine D are dissolved in organic solvent to reacting by heating;
(3) reaction finishes to regulate pH value with sodium hydroxide solution, obtains brown color precipitation, filters the mixed solvent washing with ethanol and water, dries.
Maleic anhydride and NH that above-mentioned steps (1) is described
4h
2the mol ratio of O is 1:1.2 ~ 2.
The described ammoniacal liquor mass concentration of above-mentioned steps (1) is 20 ~ 30%.
The maleic anhydride that above-mentioned steps (1) is described and the neutral temperature of ammoniacal liquor are room temperature.
The temperature that the described maleic anhydride ammonium salt of above-mentioned steps (1) is mediated thermal polycondensation is 160 ~ 250 DEG C; The time of mediating thermal polycondensation is 0.5 ~ 2 hour.
The add-on of the rosin Amine D described in above-mentioned steps (2) is 0.1 ~ 0.8 times of maleic anhydride molar weight.
The described organic solvent of above-mentioned steps (2) is benzene,toluene,xylene.
The rosin Amine D that above-mentioned steps (2) is described and the temperature of reaction of polysuccinimide are 50 ~ 80 DEG C; Reaction times is 0.5 ~ 5 hour.
What above-mentioned steps (3) was described uses sodium hydroxide solution regulation system pH value to 8 ~ 10; In mixed solvent described in step (3), the volume ratio of ethanol and water is 1 ~ 3:1.
Compared with prior art excellent beneficial feature of the present invention is: the compounds of this invention rosin grafting poly aspartic acid has improved rosin Amine D has water-solublely expanded its application in water treatment field; Rosin grafting poly aspartic acid has the double effects of scale inhibition and inhibition simultaneously, and its rust inhibition is better than benzotriazole in the rosin Amine D content situation identical with benzotriazole amount; This compound has nontoxic, totally biodegradable, and its application can not cause burden to environment, is a kind of green product of safety and environmental protection.
Embodiment
Embodiment 1
A kind of rosinyl grafting poly aspartic acid has structure
In its Chinese style, R is
This compound is used for the water treatment field such as hardware pickling, recirculated cooling water, feedwater as a kind of corrosion-mitigation scale-inhibition base.
This compound rosinyl grafting poly aspartic acid is prepared by following concrete technology:
(1) by maleic anhydride and 25% ammoniacal liquor according to maleic anhydride and NH
4h
2the mol ratio of O is that the ratio of 1:1.5 joins in reactor, and normal temperature is neutralized into ammonium salt, then mediates thermal polycondensation reaction 1 hour with 210 DEG C of kneaders, obtains the gluey polysuccinimide of solid;
(2) rosin Amine D of 0.5 times of maleic anhydride molar weight and the gluey polysuccinimide of (1) step reaction gained are dissolved in toluene, are heated to 60 DEG C of reactions 2.5 hours;
(3) reaction finishes to regulate pH value to 10 with sodium hydroxide solution, obtains brown color precipitation, filters the mixed solvent washing of the ethanol that is 2:1 by volume ratio and water, dries.
Embodiment 2
A kind of rosinyl grafting poly aspartic acid has structure
In its Chinese style, R is
This compound is used for the water treatment field such as hardware pickling, recirculated cooling water, feedwater as a kind of corrosion-mitigation scale-inhibition base.
This compound rosinyl grafting poly aspartic acid is prepared by following concrete technology:
(1) by maleic anhydride and 20% ammoniacal liquor according to maleic anhydride and NH
4h
2the mol ratio of O is that the ratio of 1:1.2 joins in reactor, and normal temperature is neutralized into ammonium salt, then mediates thermal polycondensation reaction 0.5 hour with 240 DEG C of kneaders, obtains the gluey polysuccinimide of solid;
(2) rosin Amine D of 0.7 times of maleic anhydride molar weight and the gluey polysuccinimide of (1) step reaction gained are dissolved in toluene, are heated to 55 DEG C of reactions 3 hours;
(3) reaction finishes to regulate pH value to 9 with sodium hydroxide solution, obtains brown color precipitation, filters the mixed solvent washing of the ethanol that is 2:1 by volume ratio and water, dries.
Embodiment 3
A kind of rosinyl grafting poly aspartic acid has structure
In its Chinese style, R is
This compound is used for the water treatment field such as hardware pickling, recirculated cooling water, feedwater as a kind of corrosion-mitigation scale-inhibition base.
This compound rosinyl grafting poly aspartic acid is prepared by following concrete technology:
(1) by maleic anhydride and 25% ammoniacal liquor according to maleic anhydride and NH
4h
2the mol ratio of O is that the ratio of 1:1.5 joins in reactor, and normal temperature is neutralized into ammonium salt, then mediates thermal polycondensation reaction 2 hours with 180 DEG C of kneaders, obtains the gluey polysuccinimide of solid;
(2) rosin Amine D of 0.2 times of maleic anhydride molar weight and the gluey polysuccinimide of (1) step reaction gained are dissolved in toluene, are heated to 75 DEG C of reactions 1 hour;
(3) reaction finishes to regulate pH value to 10 with sodium hydroxide solution, obtains brown color precipitation, filters the mixed solvent washing of the ethanol that is 1:1 by volume ratio and water, dries.
Embodiment 4
A kind of rosinyl grafting poly aspartic acid has structure
In its Chinese style, R is
This compound is used for the water treatment field such as hardware pickling, recirculated cooling water, feedwater as a kind of corrosion-mitigation scale-inhibition base.
This compound rosinyl grafting poly aspartic acid is prepared by following concrete technology:
(1) by maleic anhydride and 30% ammoniacal liquor according to maleic anhydride and NH
4h
2the mol ratio of O is that the ratio of 1:1.8 joins in reactor, and normal temperature is neutralized into ammonium salt, then mediates thermal polycondensation reaction 1 hour with 170 DEG C of kneaders, obtains the gluey polysuccinimide of solid;
(2) rosin Amine D of 0.8 times of maleic anhydride molar weight and the gluey polysuccinimide of (1) step reaction gained are dissolved in toluene, are heated to 50 DEG C of reactions 4 hours;
(3) reaction finishes to regulate pH value to 8 with sodium hydroxide solution, obtains brown color precipitation, filters the mixed solvent washing of the ethanol that is 3:1 by volume ratio and water, dries.
Claims (10)
1. a rosinyl grafting poly aspartic acid has structure I:
Ⅰ
Wherein R is that rosin Amine D dehydrogenation residue has structure II
Ⅱ。
2. a method of preparing rosinyl grafting poly aspartic acid described in claim 1, it comprises the steps:
Maleic anhydride and ammoniacal liquor are joined in reactor and is neutralized into ammonium salt, then mediate thermal polycondensation reaction with kneader high temperature, obtain the gluey polysuccinimide of solid;
Gluey above-mentioned gained polysuccinimide and rosin Amine D are dissolved in organic solvent to reacting by heating;
Reaction finishes to regulate pH value with sodium hydroxide solution, obtains brown color precipitation, filters the mixed solvent washing with ethanol and water, dries.
3. a kind of preparation method of rosinyl grafting poly aspartic acid according to claim 2, is characterized in that: maleic anhydride and NH that step (1) is described
4h
2the mol ratio of O is 1:1.2 ~ 2.
4. a kind of preparation method of rosinyl grafting poly aspartic acid according to claim 2, is characterized in that: the described ammoniacal liquor mass concentration of step (1) is 20 ~ 30%.
5. a kind of preparation method of rosinyl grafting poly aspartic acid according to claim 2, is characterized in that: the maleic anhydride that step (1) is described and the neutral temperature of ammoniacal liquor are room temperature.
6. a kind of preparation method of rosinyl grafting poly aspartic acid according to claim 2, is characterized in that: the temperature that the described maleic anhydride ammonium salt of step (1) is mediated thermal polycondensation is 160 ~ 250 DEG C; The time of mediating thermal polycondensation is 0.5 ~ 2 hour.
7. a kind of preparation method of rosinyl grafting poly aspartic acid according to claim 2, is characterized in that: the add-on of the described rosin Amine D of step (2) is 0.1 ~ 0.8 times of maleic anhydride molar weight.
8. a kind of preparation method of rosinyl grafting poly aspartic acid according to claim 2, is characterized in that: the described organic solvent of step (2) is benzene,toluene,xylene.
9. a kind of preparation method of rosinyl grafting poly aspartic acid according to claim 2, is characterized in that: the rosin Amine D that step (2) is described and the temperature of reaction of polysuccinimide are 50 ~ 80 DEG C; Reaction times is 0.5 ~ 5 hour.
10. a kind of preparation method of rosinyl grafting poly aspartic acid according to claim 2, is characterized in that: step (3) described with sodium hydroxide solution regulation system pH value to 8 ~ 10; In mixed solvent described in step (3), the volume ratio of ethanol and water is 1 ~ 3:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804187A (en) * | 2015-04-24 | 2015-07-29 | 厦门双瑞船舶涂料有限公司 | Preparation method of multifunctional group bionic mussel adhesive protein polymer |
| CN106336024A (en) * | 2016-10-17 | 2017-01-18 | 山东泰和水处理科技股份有限公司 | Isophorone diamine tetramethylene phosphonic acid or sodium salt thereof, preparation method and application |
| CN111217961A (en) * | 2020-04-07 | 2020-06-02 | 山东新港化工有限公司 | Water-soluble pour point depressant for crude oil and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1085072A2 (en) * | 1999-09-15 | 2001-03-21 | Bayer Ag | Low-emission biodegradable adhesive |
| 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 |
-
2014
- 2014-03-21 CN CN201410107424.8A patent/CN103834010B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1085072A2 (en) * | 1999-09-15 | 2001-03-21 | Bayer Ag | Low-emission biodegradable adhesive |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 张光华: "《水处理化学品》", 31 January 2005, 北京：化学工业出版社, article "070202 松香胺 rosin amine", pages: 542-543 * |
| 李东光: "《工业水处理阻垢剂配方与制备200例》", 30 June 2012, 北京：化学工业出版社, article ""阻垢剂聚天冬氨酸合成物"", pages: 99-100 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804187A (en) * | 2015-04-24 | 2015-07-29 | 厦门双瑞船舶涂料有限公司 | Preparation method of multifunctional group bionic mussel adhesive protein polymer |
| CN104804187B (en) * | 2015-04-24 | 2017-02-01 | 厦门双瑞船舶涂料有限公司 | Preparation method of multifunctional group bionic mussel adhesive protein polymer |
| CN106336024A (en) * | 2016-10-17 | 2017-01-18 | 山东泰和水处理科技股份有限公司 | Isophorone diamine tetramethylene phosphonic acid or sodium salt thereof, preparation method and application |
| CN106336024B (en) * | 2016-10-17 | 2019-10-25 | 山东泰和水处理科技股份有限公司 | Four methylenephosphonic acid of isophorone diamine or its sodium salt and preparation method and application |
| CN111217961A (en) * | 2020-04-07 | 2020-06-02 | 山东新港化工有限公司 | Water-soluble pour point depressant for crude oil and preparation method and application thereof |
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Address after: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Applicant after: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. Address before: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Applicant before: SHANDONG TAIHE WATER TREATMENT Co.,Ltd. |
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Address after: No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province 277100 Patentee after: Shandong Taihe Technology Co.,Ltd. Address before: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Patentee before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |