CN102432867B - 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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- CN102432867B CN102432867B CN201110274368.3A CN201110274368A CN102432867B CN 102432867 B CN102432867 B CN 102432867B CN 201110274368 A CN201110274368 A CN 201110274368A CN 102432867 B CN102432867 B CN 102432867B
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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 diversity hyperbranched polymer containing different end group structure and preparation method thereof.
Background technology
Ultrabranching polyamide not only has the character of corresponding linear polyamidoamine, as the character such as fire-resistant, heat-resisting, can make up bad this shortcoming of linear polyamidoamine solvability simultaneously, and because the unformed and low viscosity of hyperbranched polymer structure can be carried out reaction smoothly, so the synthetic and performance study of hyperbranched polymer has caused people's extensive concern.
At present, the synthetic method of hyperbranched polymer is varied, but the hyperbranched polymer of great majority end carboxyl or end amino is all to obtain by modification, causes preparation section complicated, and the by product of introducing increases, and to purification, has brought inconvenience, and productive rate reduces.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of diversity hyperbranched polymer containing different end group structure and preparation method thereof, to realize two kinds of monomers, by differential responses, compare and obtain the hyperbranched polymer that contains different functional end-groups.
To achieve these goals, the technical solution used in the present invention is:
A preparation method who contains the diversity hyperbranched polymer of different end group structure, comprises the following steps:
Step 1: taking tribasic carboxylic acid 10～30mmol, to be dissolved in temperature be in 50～100mL ethanol or ethylene glycol solution of 50～80 ℃;
Step 2: under the condition of nitrogen protection, according to diamines and the tribasic carboxylic acid mol ratio ratio of 1: 4～1: 6, add diamines to make itself and tribasic carboxylic acid stirring reaction 6～10h at 50～80 ℃, make hyperbranched polymer crude product G
1(COOH)
8;
Step 3: the hyperbranched polymer crude product making is obtained to hyperbranched polymer through acetone extract washing and vacuum filtration.
By G
1(COOH)
8according to 1: 8～1: 10 stirring reaction 8～12h at 60～90 ℃ of mol ratio, obtain 1.5 generation Hyperbranched Polymer with Terminal Amido crude product G with diamines
1.5(NH
2)
8.
By G
1.5(NH
2)
8according to 1: 24～1: 30 stirring reaction 12～24h at 60～100 ℃ of mol ratio, obtain two generation hyperbranched polymer crude product G with tribasic carboxylic acid
2(COOH)
48.
In step 2, if according to diamines and the tribasic carboxylic acid mol ratio ratio of 3: 1～6: 1, add diamines that it is reacted with tribasic carboxylic acid, make hyperbranched polymer crude product G
1(NH
2)
3.
By G
1(NH
2)
3according to 1: 9～1: 15 stirring reaction 8～12h at 60～90 ℃ of mol ratio, obtain 1.5 end carboxyl super branched crude product G of generation with tribasic carboxylic acid
1.5(COOH)
18.
By G
1.5(COOH)
18according to 1: 18～1: 24 stirring reaction 12～24h at 60～100 ℃ of mol ratio, obtain two generation hyperbranched polymer crude product G with diamines
2(NH
2)
18.
In described step 1, for obtaining better solute effect and reflection environment, the dewatering agent EDCI that can also to add with tribasic carboxylic acid mol ratio be 1.1: 1, and with tribasic carboxylic acid mol ratio be the condensing agent HOBT of 0.1: 1～1.1: 1.
In described step 3, be to obtain purer product, adopt vacuum filtration to remove the not tribasic carboxylic acid of complete reaction, then with acetone extract ethylene glycol solvent and the not diamines of complete reaction and the water that reacts generation, the repeated multiple times hyperbranched polymer that obtains.
Described tribasic carboxylic acid is nitrilotriacetic acid(NTA), trimesic acid or citric acid, and diamines is quadrol, hexanediamine or Ursol D.
Compared with prior art, the present invention has the following advantages:
Two kinds of monomers prepare relative molecular mass wider distribution according to above-mentioned reaction scheme, low viscous polyfunctional group hyperbranched polymer.The present invention can need to prepare serial hyperbranched polymer according to application: end is amino, end carboxyl, and carboxyl, hydroxyl coexist, and amino, hydroxyl coexists, and amino, carboxyl coexists, and carboxyl, amino, hydroxyl coexist.These series product have a good application prospect.By regulate reacting mol ratio and can obtaining a kind of hyperbranched polymer and have terminal carboxyl(group) and amino active function groups of tribasic carboxylic acid and diamine monomer simultaneously, the relative molecular mass of hyperbranched polymer is 1000～500000.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment mono-
A preparation method who contains the diversity hyperbranched polymer of different end group structure, comprises the steps:
Step 1: taking nitrilotriacetic acid(NTA) 10mmol, to be dissolved in temperature be in the 50mL ethylene glycol solution of 50 ℃, the dewatering agent EDCI that to add with nitrilotriacetic acid(NTA) mol ratio be 1.1: 1, and with the nitrilotriacetic acid(NTA) mol ratio condensing agent HOBT that is 0.8: 1;
Step 2: under the condition of nitrogen protection, according to quadrol and the nitrilotriacetic acid(NTA) mol ratio ratio of 1: 4, add quadrol to make itself and nitrilotriacetic acid(NTA) stirring reaction 8h at 60 ℃, make hyperbranched polymer crude product G
1(COOH)
8;
Step 3: the hyperbranched polymer crude product making is obtained to hyperbranched polymer G through acetone extract washing and vacuum filtration
1(COOH)
8.
By above-mentioned G
1(COOH)
8according to 1: 8 stirring reaction 12h at 60 ℃ of mol ratio, obtain 1.5 generation Hyperbranched Polymer with Terminal Amido crude product G with quadrol
1.5(NH
2)
8;
Again by G
1.5(NH
2)
8according to 1: 24 stirring reaction 24h at 60 ℃ of mol ratio, obtain two generation hyperbranched polymer crude product G with nitrilotriacetic acid(NTA)
2(COOH)
48.
Embodiment bis-
A preparation method who contains the diversity hyperbranched polymer of different end group structure, comprises the steps:
Step 1: taking citric acid 30mmol, to be dissolved in temperature be in the 50mL ethanolic soln of 50 ℃, the dewatering agent EDCI that to add with citric acid mol ratio be 1.1: 1, and with the condensing agent HOBT activation that is 1: 1 of citric acid mol ratio;
Step 2: under the condition of nitrogen protection, according to quadrol and the citric acid mol ratio ratio of 4: 1, add quadrol to make itself and citric acid stirring reaction 6h at 50 ℃, make hyperbranched polymer crude product G
1(NH
2)
3;
Step 3: the hyperbranched polymer crude product making is obtained to hyperbranched polymer G through acetone extract washing and vacuum filtration
1(NH
2)
3.
By above-mentioned G
1(NH
2)
3according to 1: 9 stirring reaction 8h at 60 ℃ of mol ratio, obtain 1.5 end carboxyl super branched crude product G of generation with citric acid
1.5(COOH)
18.
Again by G
1.5(COOH)
18according to 1: 24 stirring reaction 24h at 100 ℃ of mol ratio, obtain two generation hyperbranched polymer crude product G with quadrol
2(NH
2)
18.
Embodiment tri-
A preparation method who contains the diversity hyperbranched polymer of different end group structure, comprises the steps:
Step 1: taking nitrilotriacetic acid(NTA) 10mmol, to be dissolved in temperature be in the 100mL ethylene glycol solution of 50 ℃, the dewatering agent EDCI that to add with nitrilotriacetic acid(NTA) mol ratio be 1.1: 1, and with the condensing agent HOBT activation that is 0.1: 1 of nitrilotriacetic acid(NTA) mol ratio;
Step 2: under the condition of nitrogen protection, according to quadrol and the nitrilotriacetic acid(NTA) mol ratio ratio of 3: 1, add quadrol to make itself and nitrilotriacetic acid(NTA) stirring reaction 6h at 50 ℃, make hyperbranched polymer crude product G
1(NH
2)
3;
Step 3: the hyperbranched polymer crude product making is obtained to hyperbranched polymer G through acetone extract washing and vacuum filtration
1(NH
2)
3.
By above-mentioned G
1(NH
2)
3according to 1: 15 stirring reaction 8h at 90 ℃ of mol ratio, obtain 1.5 end carboxyl super branched crude product G of generation with nitrilotriacetic acid(NTA)
1.5(COOH)
18.
Again by G
1.5(COOH)
18according to 1: 18 stirring reaction 12h at 60 ℃ of mol ratio, obtain two generation hyperbranched polymer crude product G with quadrol
2(NH
2)
18.
Embodiment tetra-
A preparation method who contains the diversity hyperbranched polymer of different end group structure, comprises the steps:
Step 1: taking nitrilotriacetic acid(NTA) 30mmol, to be dissolved in temperature be in the 100mL ethylene glycol solution of 80 ℃, the dewatering agent EDCI that to add with nitrilotriacetic acid(NTA) mol ratio be 1.1: 1, and with the condensing agent HOBT activation that is 1: 1 of nitrilotriacetic acid(NTA) mol ratio;
Step 2: under the condition of nitrogen protection, according to quadrol and the nitrilotriacetic acid(NTA) mol ratio ratio of 6: 1, add quadrol to make itself and nitrilotriacetic acid(NTA) stirring reaction 10h at 80 ℃, make hyperbranched polymer crude product G
1(NH
2)
3;
Step 3: the hyperbranched polymer crude product making is obtained to hyperbranched polymer G through acetone extract washing and vacuum filtration
1(NH
2)
3.
By above-mentioned G
1(NH
2)
3according to 1: 10 stirring reaction 10h at 80 ℃ of mol ratio, obtain 1.5 end carboxyl super branched crude product G of generation with nitrilotriacetic acid(NTA)
1.5(COOH)
18.
Again by G
1.5(COOH)
18according to 1: 20 stirring reaction 20h at 80 ℃ of mol ratio, obtain two generation hyperbranched polymer crude product G with quadrol
2(NH
2)
18.
Embodiment five
A preparation method who contains the diversity hyperbranched polymer of different end group structure, comprises the steps:
Step 1: taking citric acid 20mmol, to be dissolved in temperature be in the 80mL ethanolic soln of 50 ℃, the dewatering agent EDCI that to add with citric acid mol ratio be 1.1: 1, and with the condensing agent HOBT activation that is 1: 1 of citric acid mol ratio;
Step 2: under the condition of nitrogen protection, according to quadrol and the citric acid mol ratio ratio of 1: 6, add quadrol to make itself and citric acid stirring reaction 8h at 60 ℃, make hyperbranched polymer crude product G
1(COOH)
8;
Step 3: the hyperbranched polymer crude product making is obtained to hyperbranched polymer G through acetone extract washing and vacuum filtration
1(COOH)
8.
By above-mentioned G
1(COOH)
8according to 1: 9 stirring reaction 10h at 80 ℃ of mol ratio, obtain 1.5 generation Hyperbranched Polymer with Terminal Amido crude product G with quadrol
1.5(NH
2)
8.
Again by G
1.5(NH
2)
8according to 1: 25 stirring reaction 20h at 80 ℃ of mol ratio, obtain two generation hyperbranched polymer crude product G with citric acid
2(COOH)
48.
Embodiment six
Be with the difference of embodiment mono-, with trimesic acid, substitute nitrilotriacetic acid(NTA), make semiaromatic type hyperbranched polymer, and make lard type hyperbranched polymer while reacting with nitrilotriacetic acid(NTA).
Embodiment seven
Be with the difference of embodiment mono-, with hexanediamine, substitute quadrol, make product chain length elongated, structure is more stable.
Embodiment eight
Be with the difference of embodiment mono-, with Ursol D, substitute quadrol, trimesic acid substitutes nitrilotriacetic acid(NTA), and making product is fragrant hyperbranched polymer.
In the present invention, take nitrilotriacetic acid(NTA) and reacting ethylenediamine as example, its reaction equation is as follows:
Wherein, R represents group (CH
2cH
2).
Claims (4)
1. contain a preparation method for the diversity hyperbranched polymer of different end group structure, it is characterized in that, comprise the following steps:
Step 1: taking tribasic carboxylic acid 10～30mmol, to be dissolved in temperature be that in 50～100mL ethanol or ethylene glycol solution of 50～80 ℃, described tribasic carboxylic acid is nitrilotriacetic acid(NTA), trimesic acid or citric acid, and diamines is quadrol or hexanediamine;
Step 2: under the condition of nitrogen protection, according to the ratio of diamines and tribasic carboxylic acid mol ratio 1 ︰ 4～1 ︰ 6, add diamines to make itself and tribasic carboxylic acid stirring reaction 6～10h at 50～80 ℃, make hyperbranched polymer crude product G
1(COOH)
8; By G
1(COOH)
8according to mol ratio 1 ︰ 8～1 ︰ 10 stirring reaction 8～12h at 60～90 ℃, obtain 1.5 generation Hyperbranched Polymer with Terminal Amido crude product G with diamines
1.5(NH
2)
8; By G
1.5(NH
2)
8according to mol ratio 1:24～1:30 stirring reaction 12～24h at 60～100 ℃, obtain two generation hyperbranched polymer crude product G with tribasic carboxylic acid
2(COOH)
48;
Step 3: by make two generation hyperbranched polymer crude product through acetone extract washing and vacuum filtration, obtain hyperbranched polymer.
2. the preparation method of the diversity hyperbranched polymer containing different end group structure according to claim 1, it is characterized in that, in described step 2, according to the ratio of diamines and tribasic carboxylic acid mol ratio 3 ︰ 1～6 ︰ 1, add diamines that it is reacted with tribasic carboxylic acid, make hyperbranched polymer crude product G
1(NH
2)
3; By G
1(NH
2)
3according to mol ratio 1 ︰ 9～1 ︰ 15 stirring reaction 8～12h at 60～90 ℃, obtain 1.5 end carboxyl super branched crude product G of generation with tribasic carboxylic acid
1.5(COOH)
18; By G
1.5(COOH)
18according to mol ratio 1 ︰ 18～1 ︰ 24 stirring reaction 12～24h at 60～100 ℃, obtain two generation hyperbranched polymer crude product G with diamines
2(NH
2)
18.
3. the preparation method of the diversity hyperbranched polymer containing different end group structure according to claim 1 and 2, it is characterized in that, in described step 1, the dewatering agent EDCI that also to add with tribasic carboxylic acid mol ratio be 1.1:1, and with the tribasic carboxylic acid mol ratio condensing agent HOBT that is 0.1:1～1.1:1.
4. the preparation method of the diversity hyperbranched polymer containing different end group structure according to claim 1 and 2, it is characterized in that, in described step 3, adopt vacuum filtration to remove the not tribasic carboxylic acid of complete reaction, use acetone extract ethylene glycol solvent and the not diamines of complete reaction and the water of reaction generation again, the repeated multiple times hyperbranched polymer that obtains.
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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 |
-
2011
- 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 |
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