CN102060978B - Pyridine polyether ionic liquid toughened epoxy resin and preparation method thereof - Google Patents
Pyridine polyether ionic liquid toughened epoxy resin and preparation method thereof Download PDFInfo
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- CN102060978B CN102060978B CN2010105656663A CN201010565666A CN102060978B CN 102060978 B CN102060978 B CN 102060978B CN 2010105656663 A CN2010105656663 A CN 2010105656663A CN 201010565666 A CN201010565666 A CN 201010565666A CN 102060978 B CN102060978 B CN 102060978B
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- polyoxyalkylene nonionic
- type polyoxyalkylene
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Abstract
The invention discloses pyridine polyether ionic liquid toughened epoxy resin and a preparation method thereof. Pyridine polyether ionic liquid serving as a toughening agent is added into epoxy resin prepolymer in a mass ratio of (20-60):(80-40). The preparation method comprises the following steps of: mixing the pyridine polyether ionic liquid and the epoxy resin prepolymer, and reacting at the temperature of 80 DEG C for 2 hours with stirring; and adding a curing agent, uniformly stirring, and curing at the temperature of between 120 and 160 DEG C for 5 hours to obtain a finished product. By controlling a certain ratio of the ionic liquid to the epoxy resin, the toughness of the epoxy resin can be enhanced.
Description
One, technical field
The present invention relates to a kind of method for toughening of epoxy resin, epoxy resin that specifically a kind of pyridine type polyoxyalkylene nonionic liquid is toughness reinforcing and preparation method thereof.
Two, background technology
Epoxy resin is used for many industrial circles with forms such as matrix material, tackiness agent, Embedding Materials.Yet its cured article cross-linking density is big, is tridimensional network, and the slip (plastic deformation) of molecular chain is seldom arranged, and the result causes big, the poor toughness of material fragility; And volumetric shrinkage when solidifying, the stress concentration that easy generation is bigger has reduced its over-all properties so to a great extent.
People once adopted a lot of methods to improve its toughness, commonly in epoxy-resin systems, add at present rubber carry out toughness reinforcing, like the acrylonitrile-butadiene copolymer (CTBN) of carboxy blocking, thiorubber etc.
Ionic liquid is the environment-friendly type solvent that a type of rising in recent years has application prospect; It is with non-volatile, stable to water and air, and inorganic, organic cpds and macromolecular material are had good solubility and be widely used in fields such as electrochemistry, organic synthesis, chemical separating, material prepn.Come modified polymer material more and more to receive polymer scholar's concern with ionic liquid.Ionic liquid is incorporated in the organic polymer material, prepares ion liquid modified superpolymer, aspect the raising polymer performance good prospects for application is being arranged.
Pyridine type polyoxyalkylene nonionic liquid has terminal hydroxy group and flexible polyethers long-chain, with pyridine type polyoxyalkylene nonionic liquid the curing system of epoxy resin is carried out study on the modification, and at home and abroad also not seeing at present has report.
Three, summary of the invention
The present invention is the weak point for fear of above-mentioned prior art, and epoxy resin that a kind of toughness is high, the simple pyridine type polyoxyalkylene nonionic of preparation technology liquid is toughness reinforcing and preparation method thereof is provided.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of the epoxy resin that a kind of pyridine type polyoxyalkylene nonionic of the present invention liquid is toughness reinforcing are; Pyridine type polyoxyalkylene nonionic liquid is added in the epoxy prepolymer as toughner, and the mass ratio of said pyridine type polyoxyalkylene nonionic liquid and epoxy prepolymer is 20-60: 80-40;
The general structure of said pyridine type polyoxyalkylene nonionic liquid is:
Negatively charged ion X wherein
-Be Cl
-, Br
-, I
-, Al
2Cl
7 -, BE
4 -, PF
6 -, NO
3 -, NO
2 -, SO
4 2-, CH
3COO
-, SbF
6 -, ZnCl
3 -, SnCl
3 -, N (CF
3SO
2)
-, N (C
2F
5SO
2)
-, N (FSO
2)
2 -, C (CF
3SO
2)
3 -, CF
3CO
2 -, CF
3SO
3 -Or CH
3SO
3 -
The preparing method's of the epoxy resin that a kind of pyridine type polyoxyalkylene nonionic of the present invention liquid is toughness reinforcing characteristics are to operate according to the following steps:
Pyridine type polyoxyalkylene nonionic liquid is mixed with epoxy prepolymer, and 80 ℃ of stirring reactions 2 hours add solidifying agent then and stir, 120-160 ℃ solidified 5 hours finished product;
Said solidifying agent is a quadrol, and addition is 10% of a said epoxy prepolymer quality.
The preparing method's of the epoxy resin that a kind of pyridine type polyoxyalkylene nonionic of the present invention liquid is toughness reinforcing characteristics also are: said curing is to be incubated 1 hour down at 120 ℃, 140 ℃ of insulations 2 hours, is warming up to 160 ℃ of insulations 2 hours then.
The ionic liquid that the present invention uses has flexible chain and polyether group simultaneously.Toughness reinforcing mechanism is to contain a large amount of polyether soft segments in the pyridine type polyoxyalkylene nonionic liquid; When solidifying with epoxy resin; Can increase the flexibility of curing cross-linked network; Alleviate stress concentration to a certain extent, improved the plastic deformation ability of curing system, so the toughness of curing system is significantly improved.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, the cost of material of the present invention's use is cheap, and reaction is simple, and mild condition is easy to control, is convenient to industrialization.
2, the present invention can obtain the very strong epoxy resin of toughening effect through controlling the certain ionic liquid and the ratio of epoxy resin.When pyridine type polyoxyalkylene nonionic liquid and epoxy resin mass ratio are 20: 80,40: 60,60: 40; The shock strength of curing system has improved 58%, 160%, 340% respectively than pure epoxy resin; Wherein ionic liquid and epoxy resin mass ratio are 60: 40 o'clock; Although batten thickness reaches 6mm, can be arbitrarily crooked, demonstrate tangible caoutchouc elasticity; Wherein pyridine type polyoxyalkylene nonionic liquid and epoxy resin mass ratio are that the toughness of 20: 80 o'clock curing systems is greatly improved, and Strength Changes is little.
Four, embodiment
Embodiment 1:
Present embodiment is that pyridine type polyoxyalkylene nonionic liquid is mixed with epoxy prepolymer, 80 ℃ of stirring reactions 2 hours, and it is thick that reaction back system becomes black; Add quadrol then and stir; Be incubated 1h down at 120 ℃,, be warming up to 160 ℃ of insulation 2h then and get finished product at 140 ℃ of insulation 2h;
Wherein the mass ratio of pyridine type polyoxyalkylene nonionic liquid and epoxy prepolymer is 20: 80, and the consumption of quadrol is 10% of an epoxy prepolymer quality.
Pyridine type polyoxyalkylene nonionic liquid prepares with following method in the present embodiment:
The 40g Hydrin is dissolved in the 50mL toluene, stirs the pyridine that adds 68mL down, 50 ℃ of following stirring reactions 10 hours; Add the 50mL ether after being cooled to room temperature; Solvent and low-boiling-point organic compound are removed in underpressure distillation 3 hours under 90 ℃, 0.1MPa then, negatively charged ion be Cl
-Pyridine type polyoxyalkylene nonionic liquid, structural formula is following:
Embodiment 2:
The preparation method of present embodiment is with embodiment 1, and the mass ratio of different is pyridine type polyoxyalkylene nonionic liquid and epoxy prepolymer is 40: 60, and used pyridine type polyoxyalkylene nonionic liquid is that negatively charged ion is PF
6 -Pyridine type polyoxyalkylene nonionic liquid.
Pyridine type polyoxyalkylene nonionic liquid prepares with following method in the present embodiment:
The 40g Hydrin is dissolved in the 50mL toluene, stirs the pyridine that adds 68mL down, 50 ℃ of following stirring reactions 10 hours; Add the 50mL ether after being cooled to room temperature; Solvent and low-boiling-point organic compound are removed in underpressure distillation 3 hours under 90 ℃, 0.1MPa then, negatively charged ion be Cl
-Pyridine type polyoxyalkylene nonionic liquid.
With the gained negatively charged ion is Cl
-Pyridine type polyoxyalkylene nonionic liquid be dissolved in the methyl-sulphoxide, the back that stirs adds sodium hexafluoro phosphate, in 50 ℃ of reactions 24 hours, carries out anionresin; Leave standstill and remove by filter sodium-chlor after ion exchange reaction finishes, underpressure distillation 3 hours under 90 ℃, 0.1MPa then, negatively charged ion be PF
6 -Pyridine type polyoxyalkylene nonionic liquid, structural formula is following:
Embodiment 3:
The preparation method of present embodiment is with embodiment 1, and the mass ratio of different is pyridine type polyoxyalkylene nonionic liquid and epoxy prepolymer is 60: 40, and used pyridine type polyoxyalkylene nonionic liquid is that negatively charged ion is BF
4 -Pyridine type polyoxyalkylene nonionic liquid.
Pyridine type polyoxyalkylene nonionic liquid prepares with following method in the present embodiment:
The 40g Hydrin is dissolved in the 50mL toluene, stirs the pyridine that adds 68mL down, 50 ℃ of following stirring reactions 10 hours; Add the 50mL ether after being cooled to room temperature; Solvent and low-boiling-point organic compound are removed in underpressure distillation 3 hours under 90 ℃, 0.1MPa then, negatively charged ion be Cl
-Pyridine type polyoxyalkylene nonionic liquid.
It is Cl that gained is got negatively charged ion
-Pyridine type polyoxyalkylene nonionic liquid be dissolved in the methyl-sulphoxide, the back that stirs adds sodium tetrafluoroborate, in 50-80 ℃ of reaction 5-7 hour, carries out anionresin; Leave standstill and remove by filter sodium-chlor after ion exchange reaction finishes, underpressure distillation 3 hours under 90 ℃, 0.1MPa then, negatively charged ion be BF
4 -Pyridine type polyoxyalkylene nonionic liquid, structural formula is following:
The epoxy resin toughened mechanical property of pyridine type polyoxyalkylene nonionic liquid of embodiment 1-3 preparation is seen table 1; Can know by table 1; When pyridine type polyoxyalkylene nonionic liquid and epoxy resin mass ratio were 20: 80, the shock strength of curing system had improved 58% than pure epoxy resin; When pyridine type polyoxyalkylene nonionic liquid and epoxy resin mass ratio were 40: 60, the shock strength of curing system had improved 160% than pure epoxy resin; When pyridine type polyoxyalkylene nonionic liquid and epoxy resin mass ratio were 60: 40, the shock strength of curing system had improved 340% than pure epoxy resin, although batten thickness reaches 6mm, can be arbitrarily crooked, and demonstrate tangible caoutchouc elasticity.
Table 1 is the pyridine type polyoxyalkylene nonionic liquid of different mass ratio and the mechanical property of epoxy resin solidifying system
| Group | 1 | 2 | 3 | 4 |
| PPIL∶EP | 0∶100 | 20∶80 | 40∶60 | 60∶40 |
| Simple beam impact strength/KJm -2 | 2.13 | 3.37 | 5.54 | 9.39 |
| Flexural strength/MPa | 72.34 | 58.25 | 18.38 | 3.58 |
| Tensile strength/MPa | 45.53 | 55.18 | 18.79 | 16.34 |
| Tension fracture elongation rate/% | 12.73 | 19.29 | 23.02 | 25.58 |
Claims (3)
1. toughness reinforcing epoxy resin of pyridine type polyoxyalkylene nonionic liquid; It is characterized in that; Pyridine type polyoxyalkylene nonionic liquid added in the epoxy prepolymer as toughner and add to obtaining after curing agent ethylene diamine solidifies, the mass ratio of said pyridine type polyoxyalkylene nonionic liquid and epoxy prepolymer is 20-60: 80-40;
The structural formula of said pyridine type polyoxyalkylene nonionic liquid is:
Said
is dissolved in the 40g Hydrin in the 50mL toluene; Stir the pyridine that adds 68mL down; 50 ℃ of following stirring reactions 10 hours; Add the 50mL ether after being cooled to room temperature; The pyridine type polyoxyalkylene nonionic liquid that obtains behind solvent and the low-boiling-point organic compound is removed in underpressure distillation 3 hours under 90 ℃, 0.1MPa then;
Said
is dissolved in the 40g Hydrin in the 50mL toluene; Stir the pyridine that adds 68mL down; 50 ℃ of following stirring reactions 10 hours; Add the 50mL ether after being cooled to room temperature; Underpressure distillation 3 hours under 90 ℃, 0.1MPa then is dissolved in the methyl-sulphoxide after removing solvent and low-boiling-point organic compound, and back adding sodium hexafluoro phosphate stirs; In 50 ℃ of reactions 24 hours, carry out anionresin; After finishing, ion exchange reaction leaves standstill and removes by filter sodium-chlor, the pyridine type polyoxyalkylene nonionic liquid that underpressure distillation obtained after 3 hours under 90 ℃, 0.1MPa then;
Said
is dissolved in the 40g Hydrin in the 50mL toluene; Stir the pyridine that adds 68mL down; 50 ℃ of following stirring reactions 10 hours; Add the 50mL ether after being cooled to room temperature; Underpressure distillation 3 hours under 90 ℃, 0.1MPa then is dissolved in the methyl-sulphoxide after removing solvent and low-boiling-point organic compound, and back adding sodium tetrafluoroborate stirs; In 50-80 ℃ of reaction 5-7 hour, carry out anionresin; After finishing, ion exchange reaction leaves standstill and removes by filter sodium-chlor, underpressure distillation 3 hours under 90 ℃, 0.1MPa then, the pyridine type polyoxyalkylene nonionic liquid that obtains.
2. method for preparing the toughness reinforcing epoxy resin of the described pyridine type polyoxyalkylene nonionic of claim 1 liquid is characterized in that operating according to the following steps:
Pyridine type polyoxyalkylene nonionic liquid is mixed with epoxy prepolymer, and 80 ℃ of stirring reactions 2 hours add solidifying agent then and stir, 120-160 ℃ solidified 5 hours finished product;
Said solidifying agent is a quadrol, and addition is 10% of a said epoxy prepolymer quality.
3. method according to claim 2 is characterized in that: said curing is to be incubated 1 hour down at 120 ℃, 140 ℃ of insulations 2 hours, is warming up to 160 ℃ of insulations 2 hours then.
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| CN2010105656663A CN102060978B (en) | 2010-11-29 | 2010-11-29 | Pyridine polyether ionic liquid toughened epoxy resin and preparation method thereof |
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| CN102060978B true CN102060978B (en) | 2012-06-13 |
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| CN104707652B (en) * | 2014-11-21 | 2017-11-24 | 沈阳工业大学 | A kind of end carboxyl polyoxyalkylene nonionic liquid catalyst and preparation method thereof |
| CN105968726B (en) * | 2016-07-12 | 2017-11-28 | 四川大学 | Epoxy resin with double cross-linked network structures and preparation method thereof |
| CN113903520B (en) * | 2021-10-09 | 2024-04-09 | 趵突泉电缆集团有限公司 | High-conductivity high-voltage electric transmission special cable |
| CN116813917A (en) * | 2022-10-31 | 2023-09-29 | 张燕 | Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225160A (en) * | 2008-02-21 | 2008-07-23 | 河南科技大学 | Method for preparing epoxy propyl ionic liquid and polyether-type macroion liquid |
| CN101376707A (en) * | 2008-10-07 | 2009-03-04 | 青岛科技大学 | Method for synthesizing polyether type high polymer quaternary ammonium salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225160A (en) * | 2008-02-21 | 2008-07-23 | 河南科技大学 | Method for preparing epoxy propyl ionic liquid and polyether-type macroion liquid |
| CN101376707A (en) * | 2008-10-07 | 2009-03-04 | 青岛科技大学 | Method for synthesizing polyether type high polymer quaternary ammonium salt |
Non-Patent Citations (1)
| Title |
|---|
| 石可瑜等.聚醚扩链脲增韧环氧树脂体系的冲击性能及其断裂面形态结构.《应用化学》.2002,第19卷(第7期),p625-628. * |
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