CN101538399A - Damping type epoxy resin material and preparation method thereof - Google Patents
Damping type epoxy resin material and preparation method thereof Download PDFInfo
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- CN101538399A CN101538399A CN200910049413A CN200910049413A CN101538399A CN 101538399 A CN101538399 A CN 101538399A CN 200910049413 A CN200910049413 A CN 200910049413A CN 200910049413 A CN200910049413 A CN 200910049413A CN 101538399 A CN101538399 A CN 101538399A
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Abstract
The invention relates to a damping type epoxy resin material prepared by adding hindered phenol type or hindered amine type organic micromolecule compound to epoxide resin and a preparation method of the material. In the invention, the epoxide resin, firming agent, addition agent and hindered phenol type or hindered amine type organic micromolecule compound are simply mixed, curing is carried out on the mixture to prepare the epoxide resin material with obviously improved damping property. The epoxide resin prepared by the method of the invention is a pollution-free and environmentally-friendly material featuring simple processing, low cost, thus overcoming the defects of the prior art.
Description
Technical field:
The present invention relates to a kind of epoxide resin material, relate in particular to damping type epoxy resin material by in Resins, epoxy, adding the organic micromolecule compound preparation and preparation method thereof through modification.
Background technology:
Resins, epoxy because of its good physical mechanical and electrical insulation capability, with the adhesiveproperties of various materials, with and use the handiness of technology to be widely used in coating, matrix material, casting material, sizing agent, moulding material and injecting forming material.Though but common Resins, epoxy has excellent physical and mechanical properties, but owing to complicated poor weather environment such as high-altitude, superaltitude even space environment, some special construction can cause violent vibration to amplification and other mechanical means that runs up of vibration, and then cause the structural failure of the out of control even framework of intraware, so ordinary epoxy resin is difficult to use widely as structural part, thereby the maximum that has limited its potential performance is brought into play.On the other hand, along with developing rapidly of spationautics, also more and more higher to the loss effect of external vibration energy during as the mechanical means structural part to Resins, epoxy.
Damping material is a kind of type material that developed recently gets up, and can prevent or alleviate the destruction of mechanical vibration to parts.The superpolymer damping material is a kind of functional materials that can effectively absorb vibrational energy, is mainly used in fields such as military affairs, space flight in early days, and along with the pay attention to day by day of people to environmental protection, beginning is used for civilian in a large number, develops very rapid.Polymer damping material generally shows best damping capacity in the glass transition zone, can partly change the mechanical energy that absorbs or acoustic energy into heat energy and dissipate.But Resins, epoxy is higher as its second-order transition temperature of polymkeric substance (Tg), about 50 ℃ of the common deficiencies of scope of and dissipation factor (tan δ)＞more than 0.1.Therefore domestic and international many researchists are devoted to obtain well behaved damping material by Resins, epoxy is carried out modification.Traditional method of modifying all is to adopt materials such as adding rubber or elastomerics to carry out blend, and is not obvious but these methods all exist as the damping improvement, the process complexity, and consistency is poor, cost height, the shortcoming of contaminate environment.
Summary of the invention:
At the defective of prior art, the present invention proposes a kind of new damping type epoxy resin material.A kind of simple, that cost is low, pollution-free, damping capacity obviously improves epoxide resin material and preparation method thereof of processing is provided, overcomes deficiency of the prior art.
Design of the present invention is as follows:
Have the carbon-oxygen bond after a large amount of epoxide group open loops behind the epoxy resin cure on the main chain, the Sauerstoffatom in these carbon-oxygen bonds can with the compound formation interaction of hydrogen bond that contains groups such as hydroxyl, phenolic hydroxyl group and amido.The hydrogen bond energy waste of caused energy waste during of dissociating much larger than the superpolymer glass transition, by dissociating and bonding action of carbon-oxygen bond and hydroxyl, phenolic hydroxyl group and the formed hydrogen bond of amido, can realize energy waste to external vibration, reach the effect of damping shock absorption, improved the damping capacity of used Resins, epoxy thus, made it as structural part the time, also have good damping performance.
The present invention is by following technology
Organic micromolecule compound modification scheme realizes:
A kind of damping type epoxy resin material is characterized in that, the ratio of weight and number of described material is as follows:
Glycidyl amine type epoxy resin: 100 parts
Damping modification agent: 2～150 parts
Polyamine curing agent: 10～12 parts,
Wherein, described glycidyl amine type epoxy resin is 4,4 '-diaminodiphenylmethane Resins, epoxy (AG-80) or p-aminophenol Resins, epoxy (AFG-90),
The damping modification agent is hindered phenol compound or hindered amine compound,
Described polyamine curing agent is for being selected from diethylenetriamine (DETA), triethylene tetramine (TETA), a kind of in tetraethylene pentamine (TEPA), the diamino diphenyl sulfone (DDS).
Above-mentioned hindered phenol compound preferred 3,9-two { 1,1-dimethyl-2[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl }-2,4,6,8-four oxa-volution (5,5) undecane (trade(brand)names: A0-80), or four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (trade(brand)name: A0-60).
The preferred N of above-mentioned hindered amine compound, N '-two-(2,2,6,6-tetramethyl--4-piperidyl)-1,6-hexanediamine or 1,2,3,4-ethylene-dimalonic acid four (2,2,6,6-tetramethyl--4-piperidyl) ester (trade(brand)name: LA-57).
The present invention also provides a kind of preparation method of described damping type epoxy resin material, it is characterized in that, be matrix with the glycidyl amine type epoxy resin, is the damping modification agent with hindered phenol compound or hindered amine compound, with the polyamine compounds is solidifying agent, prepares by following steps:
1, will pour in the beaker after the raw material weighing according to the above ratio, add 75～80 parts of acetone as solvent;
2, blend under the effect of magnetic stirring apparatus, agitator speed 100～150rpm, the blend time is 60～120min, to presenting orange or amber settled solution, does not have suspension or precipitation;
3, the solution of step 2 gained is poured in the distilling flask, at pressure is under 0.6～0.8 normal atmosphere, bath temperature is under 50～55 ℃ acetone slowly to be steamed, (acetone that steams can be recycled, reducing cost and environmental pollution) remaining liq vacuumizes in baking oven and is heating and curing in the matrass, promptly gets described damping type epoxy resin material.
Beneficial effect
Damping type epoxy resin material, at the inner damping imparting agent that adds of resin matrix, under the situation that mechanics and physical properties to its matrix do not have considerable influence, its use range is widened significantly, the purpose of the damping capacity of matrix material after reaching effective and improving epoxy resin-base, solidify part and add fiber.The method that the present invention adopts also can be regulated and control the damping capacity of matrix material by regulating the damping modification dosage that adds, and has simple and easy to doly, and cost is low, pollutes little characteristics.
Description of drawings:
The dynamic mechanical analysis test collection of illustrative plates of Fig. 1 Resins, epoxy AG-80;
The dynamic mechanical analysis test collection of illustrative plates of Fig. 2 AG-80/A0-80=100/100;
The dynamic mechanical analysis test collection of illustrative plates of Fig. 3 AG-80/A0-60=100/100;
The dynamic mechanical analysis test collection of illustrative plates of Fig. 4 AG-80/A0-80/A0-60=100/50/50;
The dynamic mechanical analysis test collection of illustrative plates of Fig. 5 AG-80/LA-57=100/80;
The dynamic mechanical analysis test collection of illustrative plates of Fig. 6 AFG-90/A0-80=100/50;
The dynamic mechanical analysis test collection of illustrative plates of Fig. 7 AFG-90/A0-60=100/55;
Fig. 8 carbon fiber strengthens the dynamic mechanical analysis test collection of illustrative plates of AG-80/A0-80=100/60;
Embodiment:
The present invention is further elaborated by following examples and accompanying drawing now, but do not limit the scope of the invention.
Adopt dynamic mechanical analysis instrument (DMA) that the damping material of the following example preparation is carried out dynamic mechanical analysis.Test condition: frequency 10Hz, temperature-50 ℃～200 ℃, 3 ℃/min of temperature rise rate adopts drawing die.
Have the physical significance of related parameter as follows with dynamic mechanical analysis instrument DMA:
Tanδ＝E”/E’
Tan δ---dissipation factor
E "---out-of-phase modulus
E '---storage modulus
Embodiment 1
Taking by weighing 100 parts of Resins, epoxy AG-80,100 parts of hindered phenol AO-80 and 12 parts of solidifying agent DETA places beaker to add 80 parts of acetone to carry out under the magnetic stirring apparatus effect till the about 1h of blend clarifies to solution, then at 0.8 normal atmosphere, under 50 ℃ acetone is slowly steamed, surplus solution is poured into and is vacuumized under the environment in the mould in baking oven, 80 ℃ of heating 30min, 100 ℃ of heating 60min, 120 ℃ of heating 4h make sample, adopt the dynamic mechanical analysis instrument that it is analyzed.Adopt the dynamic mechanical test analysis collection of illustrative plates of the AG-80 Resins, epoxy of this prescription to see Fig. 2.As shown in Figure 2, the dissipation factor peak value of this matrix material is 0.18 and 0.45, and the peak value corresponding temperature is 24 ℃ and 97 ℃; Dissipation factor is 15 ℃-125 ℃ greater than 0.1 temperature range.
Embodiment 2
Taking by weighing 100 parts of Resins, epoxy AG-80,100 parts of hindered phenol AO-60 and 12 parts of solidifying agent DETA places beaker to add 80 parts of acetone to carry out under the magnetic stirring apparatus effect till the about 1.2h of blend clarifies to solution, then at 0.8 normal atmosphere, under 50 ℃ acetone is slowly steamed, surplus solution is poured into and is vacuumized under the environment in the mould in baking oven, 80 ℃ of heating 30min, 100 ℃ of heating 60min, 120 ℃ of heating 4h make sample, adopt the dynamic mechanical analysis instrument that it is analyzed.Adopt the dynamic mechanical test analysis collection of illustrative plates of the AG-80 Resins, epoxy of this prescription to see Fig. 3.As shown in Figure 3, the dissipation factor peak value of this matrix material is 0.13 and 0.35, and the peak value corresponding temperature is 25 ℃ and 95 ℃; Dissipation factor is 25 ℃-122 ℃ greater than 0.1 temperature range.
Embodiment 3
Taking by weighing 100 parts of Resins, epoxy AG-80,50 parts of hindered phenol AO-60,50 parts of hindered phenol AO-80 and 12 parts of solidifying agent DETA places beaker to add 80 parts of acetone to carry out under the magnetic stirring apparatus effect till the about 1.2h of blend clarifies to solution, then at 0.8 normal atmosphere, under 50 ℃ acetone is slowly steamed, surplus solution is poured into and is vacuumized under the environment in the mould in baking oven, 80 ℃ of heating 30min, 100 ℃ of heating 60min, 120 ℃ of heating 4h make sample, adopt the dynamic mechanical analysis instrument that it is analyzed.Adopt the dynamic mechanical test analysis collection of illustrative plates of the AG-80 Resins, epoxy of this prescription to see Fig. 4.As shown in Figure 4, the dissipation factor peak value of this matrix material is 0.15 and 0.35, and the peak value corresponding temperature is 0 ℃ and 95 ℃; Dissipation factor is-20 ℃-128 ℃ greater than 0.1 temperature range.
Embodiment 4
Taking by weighing 100 parts of Resins, epoxy AG-80,80 parts of hindered amine LA-57 and 12 parts of solidifying agent DETA places beaker to add 100 parts of acetone to carry out under the magnetic stirring apparatus effect till the about 1.2h of blend clarifies to solution, then at 0.8 normal atmosphere, under 50 ℃ acetone is slowly steamed, surplus solution is poured into and is vacuumized under the environment in the mould in baking oven, 80 ℃ of heating 30min, 100 ℃ of heating 60min, 120 ℃ of heating 4h make sample, adopt the dynamic mechanical analysis instrument that it is analyzed.Adopt the dynamic mechanical test analysis collection of illustrative plates of the AG-80 Resins, epoxy of this prescription to see Fig. 5.As shown in Figure 5, the dissipation factor peak value of this matrix material is 0.08 and 0.37, and the peak value corresponding temperature is 20 ℃ and 100 ℃; Dissipation factor is 50 ℃-125 ℃ greater than 0.1 temperature range.
Embodiment 5
Taking by weighing 100 parts of Resins, epoxy AFG-90,50 parts of hindered phenol AO-80 and 30 parts of solidifying agent DDS places beaker to add 90 parts of acetone to carry out under the magnetic stirring apparatus effect till the about 1h of blend clarifies to solution, then at 0.8 normal atmosphere, under 50 ℃ acetone is slowly steamed, surplus solution is poured into and is vacuumized under the environment in the mould in baking oven, 85 ℃ of heating 50min, 100 ℃ of heating 90min, 120 ℃ of heating 4h make sample, adopt the dynamic mechanical analysis instrument that it is analyzed.Adopt the dynamic mechanical test analysis collection of illustrative plates of the AFG-90 Resins, epoxy of this prescription to see Fig. 6.As shown in Figure 6, the dissipation factor peak value of this matrix material is 0.15 and 0.23, and the peak value corresponding temperature is 47 ℃ and 150 ℃; Dissipation factor is 25 ℃-180 ℃ greater than 0.1 temperature range.
Embodiment 6
Taking by weighing 100 parts of Resins, epoxy AFG-90,55 parts of hindered phenol AO-60 and 30 parts of solidifying agent DDS places beaker to add 90 parts of acetone to carry out under the magnetic stirring apparatus effect till the about 1.2h of blend clarifies to solution, then at 0.8 normal atmosphere, under 50 ℃ acetone is slowly steamed, surplus solution is poured into and is vacuumized under the environment in the mould in baking oven, 85 ℃ of heating 50min, 100 ℃ of heating 90min, 120 ℃ of heating 4h make sample, adopt the dynamic mechanical analysis instrument that it is analyzed.Adopt the dynamic mechanical test analysis collection of illustrative plates of the AFG-90 Resins, epoxy of this prescription to see Fig. 7.As shown in Figure 7, the dissipation factor peak value of this matrix material is 0.13 and 0.36, and the peak value corresponding temperature is 53 ℃ and 125 ℃; Dissipation factor is 50 ℃-153 ℃ greater than 0.1 temperature range.
Embodiment 7
Taking by weighing 100 parts of Resins, epoxy AG-80,60 parts of hindered phenol AO-80 and 30 parts of solidifying agent DDS places beaker to add 80 parts of acetone to carry out under the magnetic stirring apparatus effect till the about 1h of blend clarifies to solution, then at 0.8 normal atmosphere, under 50 ℃ acetone is slowly steamed, surplus solution is by joining glue, arranging, spread layer and mold pressing and T-300 type carbon fiber make fibre-reinforced epoxy resin composite material (wherein the volume parts of fibre fractionation is about 0.1).Condition of cure: 80 ℃ of heating 30min, 100 ℃ of heating 90min, 120 ℃ of heating 4h make sample, adopt the dynamic mechanical analysis instrument that it is analyzed.Adopt the dynamic mechanical test analysis collection of illustrative plates of the fiber reinforcement AG-80 Resins, epoxy of this prescription to see Fig. 8.As shown in Figure 8, the dissipation factor peak value of this matrix material is 0.07 and 0.1, and the peak value corresponding temperature is 50 ℃ and 75 ℃; Dissipation factor is 45 ℃-85 ℃ greater than 0.05 temperature range.
The result of experimental example show by in glycidyl amine type epoxy resin, add hindered phenol, hindered amine etc. can with the epoxy bond organic micromolecule compound that forms hydrogen bond can effectively improve the damping capacity of epoxide resin material, and damping capacity can also be regulated by the kind and the addition of micromolecular compound.
It is clear, simple to operate that the result of embodiment shows that also this preparation method has principle, and cost is low, pollutes little characteristics.
Claims (4)
1, a kind of damping type epoxy resin material is characterized in that, the ratio of weight and number of described material is as follows:
Glycidyl amine type epoxy resin: 100 parts
Damping modification agent: 2～150 parts
Polyamine curing agent: 10～12 parts,
Wherein, described glycidyl amine type epoxy resin is 4,4 '-diaminodiphenylmethane Resins, epoxy or p-aminophenol Resins, epoxy,
The damping modification agent is hindered phenol compound or hindered amine compound,
Described polyamine curing agent is to be selected from a kind of in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, the diamino diphenyl sulfone.
2, damping type epoxy resin material as claimed in claim 1, it is characterized in that, said hindered phenol compound is 3,9-pair 1,1-dimethyl-2[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] and ethyl }-2,4,6,8-four oxa-volution (5,5) undecanes), or four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
3, damping type epoxy resin material as claimed in claim 1 is characterized in that, said hindered amine compound is N, N '-two-(2,2,6,6-tetramethyl--4-piperidyl)-1,6-hexanediamine or 1,2,3,4-ethylene-dimalonic acid four (2,2,6,6-tetramethyl--4-piperidyl) ester.
4, a kind of preparation method of damping type epoxy resin material as claimed in claim 1, it is characterized in that, be matrix with the glycidyl amine type epoxy resin, is the damping modification agent with hindered phenol compound or hindered amine compound, with the polyamine compounds is solidifying agent, prepares by following steps:
1) described material is poured in the beaker after by described ratio of weight and number weighing, added 75～80 parts of acetone as solvent;
2) blend under the effect of magnetic stirring apparatus, agitator speed 100～150rpm, the blend time is 60～120min, to presenting orange or amber settled solution, does not have suspension or precipitation;
3) with step 2) solution of gained pours in the distilling flask, under 0.6～0.8 normal atmosphere, under 50～55 ℃ of the bath temperatures acetone slowly steamed, and remaining liq vacuumizes in baking oven and is heating and curing in the matrass, promptly gets described damping type epoxy resin material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234408A (en) * | 2010-04-29 | 2011-11-09 | 台耀科技股份有限公司 | Epoxy resin composition and prepreg material and printed circuit board prepared from same |
| US20110291260A1 (en) * | 2010-05-26 | 2011-12-01 | Hitachi Chemical Company, Ltd. | Semiconductor encapsulation adhesive composition, semiconductor encapsulation film-like adhesive, method for producing semiconductor device and semiconductor device |
| CN110028774A (en) * | 2019-01-31 | 2019-07-19 | 重庆文理学院 | A kind of damping material and preparation method thereof |
| CN111548721A (en) * | 2020-06-12 | 2020-08-18 | 青岛爱尔家佳新材料股份有限公司 | Sprayable damping coating for ships and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265475B1 (en) * | 1998-07-30 | 2001-07-24 | Tokai Rubber Industries, Ltd. | High damping material composition |
| CN1263909A (en) * | 2000-03-14 | 2000-08-23 | 复旦大学 | Polyetherimide modified epoxy resin |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9129898B2 (en) | 2007-10-22 | 2015-09-08 | Hitachi Chemical Company, Ltd. | Semiconductor encapsulation adhesive composition, semiconductor encapsulation film-like adhesive, method for producing semiconductor device and semiconductor device |
| CN102234408A (en) * | 2010-04-29 | 2011-11-09 | 台耀科技股份有限公司 | Epoxy resin composition and prepreg material and printed circuit board prepared from same |
| US20110291260A1 (en) * | 2010-05-26 | 2011-12-01 | Hitachi Chemical Company, Ltd. | Semiconductor encapsulation adhesive composition, semiconductor encapsulation film-like adhesive, method for producing semiconductor device and semiconductor device |
| US9024455B2 (en) * | 2010-05-26 | 2015-05-05 | Hitachi Chemical Company, Ltd. | Semiconductor encapsulation adhesive composition, semiconductor encapsulation film-like adhesive, method for producing semiconductor device and semiconductor device |
| CN110028774A (en) * | 2019-01-31 | 2019-07-19 | 重庆文理学院 | A kind of damping material and preparation method thereof |
| CN110028774B (en) * | 2019-01-31 | 2021-03-30 | 重庆文理学院 | Damping material and preparation method thereof |
| CN111548721A (en) * | 2020-06-12 | 2020-08-18 | 青岛爱尔家佳新材料股份有限公司 | Sprayable damping coating for ships and preparation method thereof |
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