CN102432867A - Diversified hyper-branched polymers containing different terminal group structures, and preparation method thereof - Google Patents
Diversified hyper-branched polymers containing different terminal group structures, and preparation method thereof Download PDFInfo
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- CN102432867A CN102432867A CN2011102743683A CN201110274368A CN102432867A CN 102432867 A CN102432867 A CN 102432867A CN 2011102743683 A CN2011102743683 A CN 2011102743683A CN 201110274368 A CN201110274368 A CN 201110274368A CN 102432867 A CN102432867 A CN 102432867A
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Abstract
The invention relates to diversified hyper-branched polymers containing different terminal group structures, and a preparation method thereof. The preparation method comprises steps that: tricarboxylic acid is weighed, and is dissolved in a solution of ethanol or glycol; diamine is added under the protection of nitrogen, such that diamine and tricarboxylic acid are subject to a reaction, wherein the molar ratio of diamine to tricarboxylic acid is 1:4-1:6 or 3:1-6:1; after the reaction, a hyper-branched polymer crude product is obtained; the crude product is subject to acetone extraction and washing, and vacuum filtration, such that a hyper-branched polymer is obtained. With the method provided by the invention, hyper-branched polymers containing different terminal functional groups are prepared by using two monomers with different reaction ratios.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of different end group diversity structure hyperbranched polymer and preparation method thereof that contains.
Background technology
Ultrabranching polyamide not only has the character of corresponding linear polyamidoamine; Like character such as fire-resistant, heat-resisting; Simultaneously can remedy bad this shortcoming of linear polyamidoamine solvability; And because the unformed and LV of hyperbranched polymer structure makes reaction to carry out smoothly, so the synthetic and performance study of hyperbranched polymer has caused people's extensive concern.
At present, the compound method of hyperbranched polymer is varied, but the hyperbranched polymer of great majority end carboxyl or the amino class of end all is to obtain through modification, causes preparation section complicated, and the by product of introducing increases, and has brought inconvenience to purification, and productive rate reduces.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art; The object of the present invention is to provide a kind of different end group diversity structure hyperbranched polymer and preparation method thereof that contains, with realize two kinds of monomers through differential responses than the hyperbranched polymer that obtains containing different functional end-groups.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of preparation method who contains different end group diversity structure hyperbranched polymer may further comprise the steps:
Step 1: taking by weighing tribasic carboxylic acid 10～30mmol, to be dissolved in temperature be in 50～80 ℃ the 50～100mL ethanol or ethylene glycol solution;
Step 2: under the condition of nitrogen protection,, add diamines and make itself and tribasic carboxylic acid, make hyperbranched polymer bullion G at 50～80 ℃ of following stirring reaction 6～10h according to diamines and 1: 4～1: 6 ratio of tribasic carboxylic acid mol ratio
1(COOH)
8
Step 3: the hyperbranched polymer bullion that makes is promptly obtained hyperbranched polymer through acetone extract washing and vacuum filtration.
With G
1(COOH)
8With diamines according to mol ratio 1: 8～1: 10 at 60～90 ℃ of following stirring reaction 8～12h, obtain 1.5 generations amine-terminated hyperbranced fluidized polymer bullion G
1.5(NH
2)
8
With G
1.5(NH
2)
8With tribasic carboxylic acid according to mol ratio 1: 24～1: 30 at 60～100 ℃ of following stirring reaction 12～24h, obtain two generation hyperbranched polymer bullion G
2(COOH)
48
In the step 2,, add diamines itself and tribasic carboxylic acid are reacted, then make hyperbranched polymer bullion G if according to diamines and 3: 1～6: 1 ratio of tribasic carboxylic acid mol ratio
1(NH
2)
3
With G
1(NH
2)
3With tribasic carboxylic acid according to mol ratio 1: 9～1: 15 at 60～90 ℃ of following stirring reaction 8～12h, obtain end carboxyl super branched bullion G of 1.5 generations
1.5(COOH)
18
With G
1.5(COOH)
18With diamines according to mol ratio 1: 18～1: 24 at 60～100 ℃ of following stirring reaction 12～24h, obtain two generation hyperbranched polymer bullion G
2(NH
2)
18
In the said step 1, for obtaining better solute effect and reflection environment, can also add with the tribasic carboxylic acid mol ratio is 1.1: 1 dewatering agent EDCI, and with the tribasic carboxylic acid mol ratio be 0.1: 1～1.1: 1 condensing agent HOBT.
In the said step 3, be to obtain purer product, adopt vacuum filtration to remove the not tribasic carboxylic acid of complete reaction, with acetone extract ethylene glycol solvent and the not diamines of complete reaction and the water that reacts generation, repeated multiple times can get hyperbranched polymer again.
Said tribasic carboxylic acid is nitrilotriacetic acid(NTA), trimesic acid or Hydrocerol A, and diamines is quadrol, hexanediamine or Ursol D.
Compared with prior art, the present invention has the following advantages:
Two kinds of monomers prepare the relative molecular mass wider distribution according to above-mentioned reaction scheme, low viscous polyfunctional group hyperbranched polymer.The present invention can prepare serial dissaving polymer based on application need: end is amino, end carboxyl, carboxyl, hydroxyl coexistence, amino, hydroxyl coexistence, amino, carboxyl coexistence, carboxyl, amino, hydroxyl coexistence.These series product have a good application prospect.Can obtain a kind of hyperbranched polymer through the reaction mol ratio of regulating tribasic carboxylic acid and diamine monomer and have terminal carboxyl(group) and amino active function groups simultaneously, the relative molecular mass of hyperbranched polymer is 1000～500000.
Embodiment
Below in conjunction with embodiment the present invention is explained further details.
Embodiment one
A kind of preparation method who contains different end group diversity structure hyperbranched polymer comprises the steps:
Step 1: taking by weighing nitrilotriacetic acid(NTA) 10mmol, to be dissolved in temperature be in 50 ℃ the 50mL ethylene glycol solution, and adding with the nitrilotriacetic acid(NTA) mol ratio is 1.1: 1 dewatering agent EDCI, and with the nitrilotriacetic acid(NTA) mol ratio be 0.8: 1 condensing agent HOBT;
Step 2: under the condition of nitrogen protection,, add quadrol and make itself and nitrilotriacetic acid(NTA), make hyperbranched polymer bullion G at 60 ℃ of following stirring reaction 8h according to quadrol and 1: 4 ratio of nitrilotriacetic acid(NTA) mol ratio
1(COOH)
8
Step 3: the hyperbranched polymer bullion that makes is promptly obtained hyperbranched polymer G through acetone extract washing and vacuum filtration
1(COOH)
8
With above-mentioned G
1(COOH)
8With quadrol according to mol ratio 1: 8 at 60 ℃ of following stirring reaction 12h, obtain 1.5 generations amine-terminated hyperbranced fluidized polymer bullion G
1.5(NH
2)
8
Again with G
1.5(NH
2)
8With nitrilotriacetic acid(NTA) according to mol ratio 1: 24 at 60 ℃ of following stirring reaction 24h, obtain two generation hyperbranched polymer bullion G
2(COOH)
48
Embodiment two
A kind of preparation method who contains different end group diversity structure hyperbranched polymer comprises the steps:
Step 1: taking by weighing Hydrocerol A 30mmol, to be dissolved in temperature be in 50 ℃ the 50mL ethanolic soln, and adding with the Hydrocerol A mol ratio is 1.1: 1 dewatering agent EDCI, and with the Hydrocerol A mol ratio be 1: 1 condensing agent HOBT activation;
Step 2: under the condition of nitrogen protection,, add quadrol and make itself and Hydrocerol A, make hyperbranched polymer bullion G at 50 ℃ of following stirring reaction 6h according to quadrol and 4: 1 ratio of Hydrocerol A mol ratio
1(NH
2)
3
Step 3: the hyperbranched polymer bullion that makes is promptly obtained hyperbranched polymer G through acetone extract washing and vacuum filtration
1(NH
2)
3
With above-mentioned G
1(NH
2)
3With Hydrocerol A according to mol ratio 1: 9 at 60 ℃ of following stirring reaction 8h, obtain end carboxyl super branched bullion G of 1.5 generations
1.5(COOH)
18
Again with G
1.5(COOH)
18With quadrol according to mol ratio 1: 24 at 100 ℃ of following stirring reaction 24h, obtain two generation hyperbranched polymer bullion G
2(NH
2)
18
Embodiment three
A kind of preparation method who contains different end group diversity structure hyperbranched polymer comprises the steps:
Step 1: taking by weighing nitrilotriacetic acid(NTA) 10mmol, to be dissolved in temperature be in 50 ℃ the 100mL ethylene glycol solution, and adding with the nitrilotriacetic acid(NTA) mol ratio is 1.1: 1 dewatering agent EDCI, and with the nitrilotriacetic acid(NTA) mol ratio be 0.1: 1 condensing agent HOBT activation;
Step 2: under the condition of nitrogen protection,, add quadrol and make itself and nitrilotriacetic acid(NTA), make hyperbranched polymer bullion G at 50 ℃ of following stirring reaction 6h according to quadrol and 3: 1 ratio of nitrilotriacetic acid(NTA) mol ratio
1(NH
2)
3
Step 3: the hyperbranched polymer bullion that makes is promptly obtained hyperbranched polymer G through acetone extract washing and vacuum filtration
1(NH
2)
3
With above-mentioned G
1(NH
2)
3With nitrilotriacetic acid(NTA) according to mol ratio 1: 15 at 90 ℃ of following stirring reaction 8h, obtain end carboxyl super branched bullion G of 1.5 generations
1.5(COOH)
18
Again with G
1.5(COOH)
18With quadrol according to mol ratio 1: 18 at 60 ℃ of following stirring reaction 12h, obtain two generation hyperbranched polymer bullion G
2(NH
2)
18
Embodiment four
A kind of preparation method who contains different end group diversity structure hyperbranched polymer comprises the steps:
Step 1: taking by weighing nitrilotriacetic acid(NTA) 30mmol, to be dissolved in temperature be in 80 ℃ the 100mL ethylene glycol solution, and adding with the nitrilotriacetic acid(NTA) mol ratio is 1.1: 1 dewatering agent EDCI, and with the nitrilotriacetic acid(NTA) mol ratio be 1: 1 condensing agent HOBT activation;
Step 2: under the condition of nitrogen protection,, add quadrol and make itself and nitrilotriacetic acid(NTA), make hyperbranched polymer bullion G at 80 ℃ of following stirring reaction 10h according to quadrol and 6: 1 ratio of nitrilotriacetic acid(NTA) mol ratio
1(NH
2)
3
Step 3: the hyperbranched polymer bullion that makes is promptly obtained hyperbranched polymer G through acetone extract washing and vacuum filtration
1(NH
2)
3
With above-mentioned G
1(NH
2)
3With nitrilotriacetic acid(NTA) according to mol ratio 1: 10 at 80 ℃ of following stirring reaction 10h, obtain end carboxyl super branched bullion G of 1.5 generations
1.5(COOH)
18
Again with G
1.5(COOH)
18With quadrol according to mol ratio 1: 20 at 80 ℃ of following stirring reaction 20h, obtain two generation hyperbranched polymer bullion G
2(NH
2)
18
Embodiment five
A kind of preparation method who contains different end group diversity structure hyperbranched polymer comprises the steps:
Step 1: taking by weighing Hydrocerol A 20mmol, to be dissolved in temperature be in 50 ℃ the 80mL ethanolic soln, and adding with the Hydrocerol A mol ratio is 1.1: 1 dewatering agent EDCI, and with the Hydrocerol A mol ratio be 1: 1 condensing agent HOBT activation;
Step 2: under the condition of nitrogen protection,, add quadrol and make itself and Hydrocerol A, make hyperbranched polymer bullion G at 60 ℃ of following stirring reaction 8h according to quadrol and 1: 6 ratio of Hydrocerol A mol ratio
1(COOH)
8
Step 3: the hyperbranched polymer bullion that makes is promptly obtained hyperbranched polymer G through acetone extract washing and vacuum filtration
1(COOH)
8
With above-mentioned G
1(COOH)
8With quadrol according to mol ratio 1: 9 at 80 ℃ of following stirring reaction 10h, obtain 1.5 generations amine-terminated hyperbranced fluidized polymer bullion G
1.5(NH
2)
8
Again with G
1.5(NH
2)
8With Hydrocerol A according to mol ratio 1: 25 at 80 ℃ of following stirring reaction 20h, obtain two generation hyperbranched polymer bullion G
2(COOH)
48
Embodiment six
Be with the difference of embodiment one, substitute nitrilotriacetic acid(NTA), make semiaromatic type hyperbranched polymer, and make the lard type hyperbranched polymer when reacting with nitrilotriacetic acid(NTA) with trimesic acid.
Embodiment seven
Be that with the difference of embodiment one substitute quadrol with hexanediamine, it is elongated to make the product chain length, structure is more stable.
Embodiment eight
Be that with the difference of embodiment one substitute quadrol with Ursol D, trimesic acid substitutes nitrilotriacetic acid(NTA), making product is the fragrant hyperbranched polymer.
Among the present invention, be example with nitrilotriacetic acid(NTA) and reacting ethylenediamine, its reaction equation is following:
Wherein, R representes group (CH
2CH
2).
Claims (10)
1. a preparation method who contains different end group diversity structure hyperbranched polymer is characterized in that, may further comprise the steps:
Step 1: taking by weighing tribasic carboxylic acid 10～30mmol, to be dissolved in temperature be in 50～80 ℃ the 50～100mL ethanol or ethylene glycol solution;
Step 2: under the condition of nitrogen protection,, add diamines and make itself and tribasic carboxylic acid, make hyperbranched polymer bullion G at 50～80 ℃ of following stirring reaction 6～10h according to diamines and 1: 4～1: 6 ratio of tribasic carboxylic acid mol ratio
1(COOH)
8
Step 3: the hyperbranched polymer bullion that makes is promptly obtained hyperbranched polymer through acetone extract washing and vacuum filtration.
2. the preparation method who contains different end group diversity structure hyperbranched polymer according to claim 1 is characterized in that, with G
1(COOH)
8With diamines according to mol ratio 1: 8～1: 10 at 60～90 ℃ of following stirring reaction 8～12h, obtain 1.5 generations amine-terminated hyperbranced fluidized polymer bullion G
1.5(NH
2)
8
3. the preparation method who contains different end group diversity structure hyperbranched polymer according to claim 2 is characterized in that, with G
1.5(NH
2)
8With tribasic carboxylic acid according to mol ratio 1: 24～1: 30 at 60～100 ℃ of following stirring reaction 12～24h, obtain two generation hyperbranched polymer bullion G
2(COOH)
48
4. the preparation method who contains different end group diversity structure hyperbranched polymer according to claim 1; It is characterized in that, in the said step 2, according to diamines and 3: 1～6: 1 ratio of tribasic carboxylic acid mol ratio; Add diamines itself and tribasic carboxylic acid are reacted, make hyperbranched polymer bullion G
1(NH
2)
3
5. the preparation method who contains different end group diversity structure hyperbranched polymer according to claim 4 is characterized in that, with G
1(NH
2)
3With tribasic carboxylic acid according to mol ratio 1: 9～1: 15 at 60～90 ℃ of following stirring reaction 8～12h, obtain end carboxyl super branched bullion G of 1.5 generations
1.5(COOH)
18
6. the preparation method who contains different end group diversity structure hyperbranched polymer according to claim 5 is characterized in that, with G
1.5(COOH)
18With diamines according to mol ratio 1: 18～1: 24 at 60～100 ℃ of following stirring reaction 12～24h, obtain two generation hyperbranched polymer bullion G
2(NH
2)
18
7. according to claim 1 or the 4 described preparing methods that contain different end group diversity structure hyperbranched polymer; It is characterized in that; In the said step 1; Also adding with the tribasic carboxylic acid mol ratio is 1.1: 1 dewatering agent EDCI, and with the tribasic carboxylic acid mol ratio be 0.1: 1～1.1: 1 condensing agent HOBT.
8. according to claim 1 or the 4 described preparing methods that contain different end group diversity structure hyperbranched polymer; It is characterized in that; In the said step 3; Adopt vacuum filtration to remove the not tribasic carboxylic acid of complete reaction, with acetone extract ethylene glycol solvent and the not diamines of complete reaction and the water that reacts generation, repeated multiple times can get hyperbranched polymer again.
9. according to the described preparation method who contains different end group diversity structure hyperbranched polymer of the arbitrary claim of claim 1 to 6, it is characterized in that said tribasic carboxylic acid is nitrilotriacetic acid(NTA), trimesic acid or Hydrocerol A, diamines is quadrol or hexanediamine.
10. one kind contains different end group diversity structure hyperbranched polymer, it is characterized in that, it is prepared from the described method of claim 1.
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Cited By (1)
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|---|---|---|---|---|
| CN113912530A (en) * | 2021-11-10 | 2022-01-11 | 山东汇海医药化工有限公司 | Treatment method of 4-AA intermediate waste liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514764A (en) * | 1990-11-19 | 1996-05-07 | Cornell Research Foundation, Inc. | Hyperbranched polyesters and polyamides |
| CN101323662A (en) * | 2008-07-24 | 2008-12-17 | 绍兴文理学院 | Biodegradable hyper branched aliphatic polyamide fiber daiamid and preparation thereof |
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- 2011-09-16 CN CN201110274368.3A patent/CN102432867B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514764A (en) * | 1990-11-19 | 1996-05-07 | Cornell Research Foundation, Inc. | Hyperbranched polyesters and polyamides |
| CN101323662A (en) * | 2008-07-24 | 2008-12-17 | 绍兴文理学院 | Biodegradable hyper branched aliphatic polyamide fiber daiamid and preparation thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912530A (en) * | 2021-11-10 | 2022-01-11 | 山东汇海医药化工有限公司 | Treatment method of 4-AA intermediate waste liquid |
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