CN101838439A - Nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin and production method thereof - Google Patents
Nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin and production method thereof Download PDFInfo
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- CN101838439A CN101838439A CN200910108785A CN200910108785A CN101838439A CN 101838439 A CN101838439 A CN 101838439A CN 200910108785 A CN200910108785 A CN 200910108785A CN 200910108785 A CN200910108785 A CN 200910108785A CN 101838439 A CN101838439 A CN 101838439A
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- butadiene rubber
- acrylonitrile butadiene
- epoxy resin
- carboxylic acrylonitrile
- nanometer carboxylic
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Abstract
The invention provides nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin, aiming at providing nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin which has high rigidity, tenacity and thermal endurance and can not lower the other properties thereof. The epoxy resin comprises the following components by weight percent: 8-15% of nanometer carboxylic acrylonitrile butadiene rubber, 72-80% of epoxy resin, 3-4% of dispersing agent, 3-5% of coupling agent, 1.5-2% of accelerator, 1.5-2% of defoamer and 1-2% of flatting agent. The epoxy resin is prepared by the method comprising the following steps: mixing the nanometer carboxylic acrylonitrile butadiene rubber and dispersing agent; activating the mixture and carrying out temperature control, speed regulation and anchor mixing; mixing the mixture with the other components, and presoaking; and then obtaining the epoxy resin by carrying out the three working procedures, namely coarse grinding, fine grinding and refined grinding.
Description
Technical field
The present invention relates to a kind of modified epoxy and production method thereof, refer to a kind of nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin and production method thereof especially.
Background technology
Resins, epoxy (hereinafter to be referred as EP) is meant the organic high molecular compound that contains two or more epoxide groups in the molecule, and its structure is to be feature to contain active epoxide group in the molecular chain.This makes them form insoluble, the infusible cancellated superpolymer of three-dimensional that has with polytype solidifying agent generation crosslinking reaction, and characteristic becomes most widely used resin system in more modern type materials thus.General EP as thermosetting resin because series of physical and chemical properties such as intensity height, corrosion-resistant, anti-aging, in light weight, easy processing, more and more widely be applied to glue class base-material, every field such as sealed insulation, the vehicles, building structure, fiber composite, military project aviation are one of important materials of industry now.Simultaneously, common general EP self but has very big defective, have very high rigidity though mainly show highly cross-linked back, solidify that toughness low fragility in back is big, fragility is bigger under the low temperature, also all there are some drawbacks in its shock strength, fatigue property, resistance toheat simultaneously.For example produce cracking after applying electronic electrician's the casting thing demoulding and scrap; National reservoir dam is owing to be subjected to earth movement and expand with heat and contract with cold to wait to influence table and know from experience and produce the crack, after EP casting reparation, owing to 2～3 years only in poor toughness work-ing life, caused the significant wastage of national manpower, financial resources.Because therefore these drawbacks that general EP exists are subjected to very big restriction in many Application Areass.In order to satisfy the requirement stricter, harsh of current each industry and new and high technology, must solve the above-mentioned defective of EP to material.General EP being carried out tough-increased and reinforced modification improve its integrated performance index, is an important topic of current epoxy industry.At present, the domestic and international toughness reinforcing multiple mode that has is mentioned in the trial-production charter, and the initial stage adopts the carboxylate of long molecular chain toughness reinforcing, though it can reduce string stress and the initial stage does not ftracture, because these long molecular chain carboxylates are free on and do not produce crosslinked action between the solidified Resins, epoxy.As time goes on can produce by interior transport phenomena outwardly, cause embrittlement cracking at last and lost efficacy.The employing resinous blending is also arranged mid-term, and the means of rubber blending are carried out toughening modifying to EP, and also because many reason effects are not clearly, and complex process, quality are unstable even factor such as cost an arm and a leg and hinder its development.The more method for toughening of current employing has: method of the method for the method of the toughness reinforcing EP of island structure, the toughness reinforcing EP of interpenetrating(polymer)networks, method, polar rubber such as thiorubber with nano inorganic particle toughening EP, end carboxyl butyronitrile or the toughness reinforcing EP of hydroxy'terminated butadiene nitrile rubber or the like.Some rests on laboratory stage (as: method of the toughness reinforcing EP of interpenetrating(polymer)networks) in these methods, though some toughening effect is pretty good, but some good performance characteristics of having sacrificed EP again are (as: after adding island structure toughness reinforcing, shock-resistant toughness reinforcing effect obviously improves, but reduce heat-drawn wire and made it to have lost competitive power, it is obvious and for example to add the toughness reinforcing certain effect of EP of polar rubber such as thiorubber blending, but heat-drawn wire is descended, and cost an arm and a leg, end carboxyl butyronitrile or hydroxy'terminated butadiene nitrile rubber price are on the hundreds of unit per kilogram price such to several thousand yuan of per kilograms), common product is difficult to adopt.Nano inorganic particle toughening EP is nearest research focus, but rest on the experimental phase mostly from existing document, tracing it to its cause is that nano inoganic particle and common bisphenol A epoxide resin intermiscibility are bad, employing too complicated as the intercalation technique scheme, and fund input is big and quality stability is poor.
Summary of the invention
Shortcoming at the market requirement and prior art, the object of the present invention is to provide a kind of have high rigidity, high tenacity and high temperature tolerance, Resins, epoxy and production method thereof that other performance is reduced, promptly a kind of nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin and production method thereof.
The technical solution adopted for the present invention to solve the technical problems is: a kind of nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin, it is characterized in that comprising the component of following weight percent: nanometer carboxylic acrylonitrile butadiene rubber 8-15%, Resins, epoxy 72-80%, dispersion agent 3-4%, coupling agent (claiming surface treatment agent again) 3-5%, promotor 1.5-2%, defoamer 1.5-2%, flow agent 1-2%, total component and be 100%.
In an embodiment of the present invention, the Resins, epoxy of employing is E-51 or E-44, and weight part in use is identical.
Nano material (claims ultrafine particulate again, ultrafine powder) is a kind of typical systems that is in atom a small bundle of straw, etc. for silkworms to spin cocoons on and objective object boundary transitional region, its structure both had been different from the body block of material, also be different from single atom, its special structure makes it have surface effects, volume effect, quantum tunneling effect or the like, have a series of novel physical and chemical property, in an embodiment of the present invention, nanometer carboxylic acrylonitrile butadiene rubber adopts nanometer carboxylic acrylonitrile butadiene rubber VP-501.
In an embodiment of the present invention, dispersion agent is a methyldiphenyl sodium sulfate, dispersant adsorption is in EP liquid---nanometer carboxylic acrylonitrile butadiene rubber VP-501 solid interface, can significantly reduce interfacial free energy, and cause pressed powder rubber to be distributed among the EP of liquid equably and make it and do not assembling.We adopt the methyldiphenyl sodium sulphate as dispersion agent, after testing the proof, use this dispersion agent not only to strengthen the dispersion effect of nanoparticle, effectively chelating the interface combination of material.
Coupling agent (claiming surface treatment agent again), be by chemistry and (or) physical action with two kinds of nature differences very big be difficult for the material that bonded material mortise is got up originally.It not only makes filled polymers closely link to each other and reaches excellent mechanical intensity, and filler obviously reduces through the diameter of the processing polymkeric substance of coupling agent, and the dispersiveness of filler in polymkeric substance, the flowability of material are improved.In an embodiment of the present invention, coupling agent (claiming surface treatment agent again) is sec.-propyl three isostearoyl base phthalic acid esters.Coupling agent sec.-propyl three isostearoyl base phthalic acid esters can also effectively improve the effect of mechanical property, apparent mass and the processing characteristics of modification EP derived product.
So-called promotor is meant that the EP that can make after the modification strengthens physical strength with the fused back of solidifying agent, increases solidification effect, promotes the material of its curing response speed.In an embodiment of the present invention, promotor is trolamine.
Because shear material high-speed stirring and high speed rotating are powerful in process of production, the air a large amount of in this process are formed countless small bubbles by winding up in material, during use deaeration not thorough, so behind the material curing molding, can produce cellular porosity.To this, in component, added defoamer, eliminated the bubble of product.The defoamer that uses in the present invention is dimethyl siloxane.
It is higher to solve the EP oneself viscosity also to add flow agent in the component prescription, behind the adding VP-501, and the problem that viscosity increases.The flow agent that uses in the present invention is the poly-hydroxy organo-siloxane.
The invention has the beneficial effects as follows: can make EP have high rigidity, high tenacity and high temperature tolerance, other performance is reduced, make the Resins, epoxy shock strength increase substantially (be common EP cured article 2～3 times), other performance index such as EP heat-drawn wire, second-order transition temperature are gone up not down, and product is nontoxic, harmless, nonflammable, long quality-guarantee period, production process does not produce waste water,waste gas and industrial residue, technical difficulty is little, cost of investment is low, the construction period is short, almost do not have the environmental protection problem, be real environmentfriendly products.
Embodiment
Accompanying drawing is a production process reference drawing of the present invention, and the production method of a kind of nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of the present invention is as follows:
The first step:, carry out temperature control speed governing anchor formula after activated and stir pre-dispersed with nanometer carboxylic acrylonitrile butadiene rubber in the component and dispersant.30～40 ℃ of temperature controls, mixing speed per minute 800～1000 changes two minutes time.
Second step: with the material after the first step in the component ratio add Resins, epoxy and coupling agent, defoamer, flow agent, that promotor is carried out preimpregnation is molten.
The 3rd step: the material of the second step preimpregnation after molten ground rough segmentation loose.
The 4th step: grind finely divided to the material after the 3rd step.
The 5th step: the material after the 4th step is carried out the slurry formula stir fine dispersion, make finished product.
Nanoparticle stirs dispersion through once high, and the secondary vigor is sheared and disperseed an average rate dispersed with stirring, under the effect of external force, agglomeration disappears, and has reached dispersion effect, in physics dispersive process, also add chemical dispersant simultaneously, further optimized dispersion effect.
Grind the diffusing S90 of use of rough segmentation three-roller in the 3rd step of the present invention; The 4th step was ground finely divided use S60 three-roller.
In the first embodiment of the present invention, (be called for short example one), adopt following component proportioning:
Nanometer carboxylic acrylonitrile butadiene rubber 8-12%, Resins, epoxy 75-80%, methyldiphenyl sodium sulfate 3-4%, sec.-propyl three isostearoyl base phthalic acid ester 3-5%, trolamine 1.5-2%, dimethyl siloxane 1.5-2%, poly-hydroxy organo-siloxane 1-2%, total component and be 100%.
In the second embodiment of the present invention, (be called for short example two), adopt following component proportioning:
Nanometer carboxylic acrylonitrile butadiene rubber 12-15%, Resins, epoxy 72-76%, methyldiphenyl sodium sulfate 3-4%, sec.-propyl three isostearoyl base phthalic acid ester 3-5%, trolamine 1.5-2%, dimethyl siloxane 1.5-2%, poly-hydroxy organo-siloxane 1-2%, total component and be 100%.
In the third embodiment of the present invention, (be called for short example three), adopt following component proportioning:
Nanometer carboxylic acrylonitrile butadiene rubber 12%, Resins, epoxy 76%, methyldiphenyl sodium sulfate 3%, sec.-propyl three isostearoyl base phthalic acid esters 3%, trolamine 2%, dimethyl siloxane 2%, poly-hydroxy organo-siloxane 2%.
The nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of three embodiment and prior art Resins, epoxy performance synopsis are as follows:
Claims (9)
1. nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin is characterized in that comprising the component of following weight percent: nanometer carboxylic acrylonitrile butadiene rubber 8-15%, Resins, epoxy 72-80%, dispersion agent 3-4%, coupling agent 3-5%, promotor 1.5-2%, defoamer 1.5-2%, flow agent 1-2%.
2. according to the nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of claim 1, it is characterized in that: described Resins, epoxy is E-51 or E-44.
3. according to the nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of claim 1, it is characterized in that: described nanometer carboxylic acrylonitrile butadiene rubber is nanometer carboxylic acrylonitrile butadiene rubber VP-501.
4. according to the nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of claim 1, it is characterized in that: described dispersion agent is a methyldiphenyl sodium sulfate.
5. according to the nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of claim 1, it is characterized in that: described coupling agent is sec.-propyl three isostearoyl base phthalic acid esters.
6. according to the nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of claim 1, it is characterized in that: described promotor is trolamine.
7. according to the nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of claim 1, it is characterized in that: described defoamer is a dimethyl siloxane.
8. according to the nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of claim 1, it is characterized in that: described flow agent is the poly-hydroxy organo-siloxane.
9. according to the working system of the nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin of claim 1, it is characterized in that:
The first step:, carry out temperature control speed governing anchor formula after activated and stir pre-dispersed with nanometer carboxylic acrylonitrile butadiene rubber in the component and dispersant.30～40 ℃ of temperature controls, mixing speed per minute 800～1000 changes two minutes time.
Second step: with the material after the first step in the component ratio add Resins, epoxy and coupling agent, defoamer, flow agent, that promotor is carried out preimpregnation is molten.
The 3rd step: the material of the second step preimpregnation after molten ground rough segmentation loose.
The 4th step: grind finely divided to the material after the 3rd step.
The 5th step: the material after the 4th step is carried out the slurry formula stir fine dispersion, make finished product.
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| CN200910108785A CN101838439A (en) | 2009-07-20 | 2009-07-20 | Nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin and production method thereof |
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| CN200910108785A CN101838439A (en) | 2009-07-20 | 2009-07-20 | Nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin and production method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453458A (en) * | 2010-10-28 | 2012-05-16 | 长沙把兄弟胶粘剂有限公司 | Nano rubber modified room temperature cured high temperature resistant structure adhesive |
| CN104725776A (en) * | 2013-12-19 | 2015-06-24 | 徐唱 | Hydantoin type epoxy resin toughening agent and preparation method thereof |
| CN104725782A (en) * | 2013-12-19 | 2015-06-24 | 徐唱 | Nanometer rubber epoxy resin toughening agent and preparation method thereof |
-
2009
- 2009-07-20 CN CN200910108785A patent/CN101838439A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453458A (en) * | 2010-10-28 | 2012-05-16 | 长沙把兄弟胶粘剂有限公司 | Nano rubber modified room temperature cured high temperature resistant structure adhesive |
| CN102453458B (en) * | 2010-10-28 | 2013-06-12 | 长沙把兄弟胶粘剂有限公司 | Nano rubber modified room temperature cured high temperature resistant structure adhesive |
| CN104725776A (en) * | 2013-12-19 | 2015-06-24 | 徐唱 | Hydantoin type epoxy resin toughening agent and preparation method thereof |
| CN104725782A (en) * | 2013-12-19 | 2015-06-24 | 徐唱 | Nanometer rubber epoxy resin toughening agent and preparation method thereof |
| CN104725782B (en) * | 2013-12-19 | 2017-11-28 | 李发凯 | A kind of nano-rubber epoxy resin toughener and preparation method thereof |
| CN104725776B (en) * | 2013-12-19 | 2017-12-01 | 李发凯 | A kind of glycolylurea type epoxy resin toughener and preparation method thereof |
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Open date: 20100922 |