CN100451068C - Epoxy/layersilicate hano composite material, and its preparing method - Google Patents
Epoxy/layersilicate hano composite material, and its preparing method Download PDFInfo
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Abstract
This invention is related to nanocomposite technique specifically involving a kind of epoxy/lamellar silicate nanocomposite and its preparation method. The components of the said composite and their contents by weight are as follows: epoxy resin, 100 portions; aliphatic amine, 0.001-10 portions; silicate, 0.5-50 portions; the firming agent, 10-100 portions. The said preparation methods are as follows: 1) intercalating process of the lamellar silicate; 2) adding the lamellar silicate processed by intercalation into epoxy resin under agitating conditions and reacting for 10-60 minutes at 600-100DEG C; 3) adding the firming agent to epoxy resin which contains the said lamellar silicate processed by intercalation and then solidifying them for 5 minutes to 7 days at 10-120DEG C. The invention can obtain the exfoliated desquamated epoxy/lamellar silicate nanocomposite by solidification at room temperature. The dissociated lamina of montmorillonite in the obtained nanocomposite disperses more uniformly in the said composite and fully displays its function to consolidate the parent material.
Description
Technical field
The present invention relates to the nano composite material technology, be specially a kind of epoxy/laminated nm-silicate composite material and preparation method thereof.
Background technology
The Okada in Japan Toyota research centre develops nylon 6/ clay composite material (Okada A.KawasumiM.Kojima Y.et al.Polymer Preprint.1987,28:447), compare with pure nylon, heat-drawn wire has improved about 100 ℃, modulus in flexure is enhanced about more than once, and flexural strength has improved 63% approximately.After this people develop polyolefine/clay, urethane/clay, nano composite material of epoxy resin/clay again.Composite nano polymer/clay material is owing to have good performance, thereby extremely people pay close attention to.
Chinese patent application CN1250064 (open day: 2000.04.12, applicant: disclose a kind of preparation method of Epoxy Resin intercalation composite material Institute of Chemistry, Academia Sinica), a kind of method for preparing the Epoxy Resin intercalation composite material is provided.Make aliphatic amide enter the sheet interlayer of clay by cation exchange reaction,, just Resins, epoxy, tertiary amine solidifying agent intercalation can be entered interlayer without medium swelling or ultra-sonic dispersion.Form montmorillonite-based nano dispersive intercalation composite material after the epoxy resin cure.The aliphatic amide that uses is CH
3(CH
2)
nNR
3 +, solidifying agent is a dimethyl benzyl amine, containing the Resins, epoxy of polynite and the condition of cure of solidifying agent is 60-100 ℃.Its shortcoming is the solidification value height, and temperature is lower than 60 ℃ and is difficult to solidify.So almost can not form exfoliated nano-composite being lower than under 60 ℃ of conditions.
Chinese patent CN1250790 (open day: 2000.04.19, applicant: disclose a kind of Antiflowing epoxy resin/mentmorillonite compound and preparation method thereof Institute of Chemistry, Academia Sinica), the present invention is a kind of Antiflowing epoxy resin/mentmorillonite compound, comprises Resins, epoxy, solidifying agent and the polynite that organises.This mixture has good sag resistance, and the resin system hot setting does not trickle.Add imvite modified dose and not only do not lose system mechanics and thermal property, even the mechanics of system and thermal property are slightly improved.Solidifying agent is an aromatic amine curing agent, 4,4 '-diamino ditane (DDM).Fatty amine salt or ammonium salt have CH
3(CH
2)
nNR
3 +, n=5-20.Contain the Resins, epoxy of polynite and solidifying agent 60-100 ℃ of curing, to intercalation type nano composite material.The Epoxy Resin system of being invented can not form exfoliated nano-composite.
The mixture that In-Joo Chin etc. utilizes the polynite that EPON 828 and mphenylenediamine solidifying agent and aliphatic amide handle is 80 ℃ of reactions after 2 hours, peeled off [In-Joo Chin in 2 hours 135 ℃ of reactions again, ThomasThurn-Albrecht, Ho-Cheol Kim, Thomas P.Russell, Jing Wang, On exfoliation ofmontmorillonite inexpoxy, 2001,42:5947-5952].
Resin Epon 828 such as X.Kornman, Jeffamine D-230 (Huntsman Corporation) solidifying agent, two kinds of alicyclic ring polyamines, 75 ℃ of curing reactions 3 hours, obtain exfoliated epoxy/clay composite material [X.Kornmann, H.Lindberg, L.A.Berglund, Synthesis of epoxy-clay nanocomposites.Influence of the nature of the curing agent on structure.Polymer, 2001,42,4493-4499].
The E51/ organo montmorillonite of Song Chunfang preparation is used diethylenetriamine, and ' diaminodiphenylmethane, three [(dimethylamino) methyl] solidified 3 hours at 80 ℃ or 90 ℃ modified amine, 4,4, obtained exfoliated material.[Song Chunfang, Lin Weiwei, Wang Qi, Feng Linxian, Li Qiang, solidifying agent type and condition of cure are peeled off the influence of behavior to epoxy/clay nanocomposites intercalation, matrix material journal, 2003,20 (2): 30]
Lv Jiankun utilizes E51 Resins, epoxy, organic modification montmonrillonite, when solidifying agent is DDM, condition of cure is 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃ of reactions only formed intercalation type nano composite material in 2 hours, when solidifying agent is MeTHPA, condition of cure is 80 ℃, 120 ℃, 160 ℃, 200 ℃ of 2h can form exfoliated material [L ü Jiankun, Ke Yucai, Qi Zongneng, Yi Xiaosu, Study on intercalation andexfoliation behavior of organoclay in epoxy resin, J Polym Sci, Part B, 2001, Vol.39:115-120].
By above document as can be seen, the exfoliated investigator of being wishes the composite nano polymer/clay material that obtains.Because in the exfoliated nano-composite, clay is peeled off into tiny lamella, disperse more even, more favourable to the mechanical property, thermal characteristics, the anti-gas osmosising that improve matrix material, form intercalation type nano composite material more relatively easily, form difficulty of exfoliated nano-composite,, promptly selecting suitable intercalator, solidifying agent to utilize higher temperature just can finish stripping process because it often needs bigger energy to overcome Van der Waals force between the clay adjacent sheets.
Summary of the invention
The present invention has overcome the high and difficult two big shortcomings that form exfoliated nano-composite of the curing reaction temperature that exists in the prior art, and provides a kind of can curing under normal temperature condition to obtain exfoliated epoxy/laminated nm-silicate composite material and preparation method thereof.Therefore dissociated montmorillonite layer disperses more evenly in nano composite material in the nano composite material that is obtained, and gives full play to the effect of reinforcement body material.
Technical scheme of the present invention is:
A kind of epoxy/laminated nm-silicate composite material, described nano composite material comprise following component and content (weight part):
Resins, epoxy 100;
Aliphatic amide 0.001-10;
Layered silicate 0.5-50;
Solidifying agent 10-100;
Described layered silicate is the layered silicate through intercalation processing, and its particle diameter is 200 orders-2000 orders.
Resins, epoxy comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, bisphenol-s epoxy resin, the methylol bisphenol A type epoxy resin, bisphenol-A epoxy resin, organic-silicon-modified bisphenol A type epoxy resin, organic titanium modified bisphenol A type Resins, epoxy, modified nylon Resins, epoxy, fluorinated epoxy resin, line style phenol formaldehyde (PF) Resins, epoxy, ortho-cresol formaldehyde Resins, epoxy, aliphatic glycidyl ether Resins, epoxy, glycidyl ester type epoxy resin, one of glycidyl amine type epoxy resin.
Solidifying agent is phenol aldehyde modified amine, contains phenolic hydroxyl group and amine reactive hydrogen in this solidifying agent molecule, has strengthened the reactive behavior of solidifying agent greatly, has improved curing reaction speed amino and epoxy group(ing), very easily forms the height cross-linked network.Commercially available solidifying agent such as JA-1,701,702,703,703-A, T31 etc. all belong to phenol aldehyde modified amine category at present.Phenolic aldehyde amine also claims phenolic aldehyde amine or mannich base in China.
Layered silicate material can be natural or synthetical, is one of vermiculite, wilkinite, polynite, kaolin, sepiolite or mixture.
The structure of aliphatic amide: CH
3(CH
2)
nNH
2, n=5～17 wherein.
The present invention also provides the preparation method of above-mentioned epoxy/laminated nm-silicate composite material, and its process is as follows:
1) intercalation processing of layered silicate
The layered silicate powder is mixed with the aqueous solution that concentration expressed in percentage by weight is 0.5-30%, and the preparation concentration expressed in percentage by weight is the CH of 1-20% in another container again
3(CH
2)
nNH
2Or CH
3(CH
2)
nNH
3The X aqueous solution, n=5-17 wherein, X is a halogens; Two kinds of solution are mixed the back 50-90 ℃ of reaction 20 minutes-48 hours.Centrifuging is to filtrate 0.1N AgNO
3Check till the no white precipitate.After the product drying, be ground to 200 orders-2000 purpose particle.
2) layered silicate of above-mentioned intercalation processing joined in the Resins, epoxy under whipped state, 0-100 ℃ of reaction 10 minutes-60 minutes.Stirring can be used general mixing and dispersing device, as high speed dispersor etc.
3) Resins, epoxy that contains the layered silicate of intercalation processing adds solidifying agent, solidifies 5 minutes-7 days at 10 ℃-120 ℃.
In the described step 1), the reaction times is preferably 8-24 hour.
In the described step 3), curing reaction temperature is preferably 15-40 ℃, and the curing reaction time is preferably 0.5-24 hour.
Advantage of the present invention is as follows:
1, normal temperature solidified.The present invention can be solidified under normal temperature condition and obtained exfoliated epoxy/laminated nm-silicate composite material, dissociated montmorillonite layer disperses more even in nano composite material in the nano composite material that is obtained, be painted on substrate material surface, give full play to the effect of strengthening body material.
2, layered silicate of the present invention can be peeled off in the ambient cure process.
3, the present invention is solidified at ambient temperature at this nano composite material laminate silicate and can be formed exfoliated nano-composite, thereby has improved the performances such as mechanics of material.
Embodiment
Unless outside specializing among the present invention, related ratio all is weight percentage or weight ratio.
Testing method: test stratiform silicates surface-layer spacing with D/max-rA type X-ray diffractometer, test condition: CuK α radiation, the monochromatization of diffracted beam graphite monochromator, tube voltage 50kV, tube current 100mA.
Comparative example 1
To join in the 90g E51 Resins, epoxy less than the original montmorillonoid soil 10g through any processing, 70 ℃ of heating are 30 minutes under abundant whipped state, add 20g T31 modified amine then, mix the back in 30 ℃ of dryings 12 hours.Measuring polynite surface layer spacing is 1.26nm.
Comparative example 2-5
The 5g polynite is added water 95g, be mixed with 5% the aqueous solution; Claim the 2g cetylamine again, preparation contains the aqueous solution of 10% cetylamine, and two kinds of solution are mixed the back 70 ℃ of reactions 8 hours.Centrifuging is to filtrate 0.1NAgNO
3Check till the no white precipitate.After the product drying, be ground to 200 purpose particles.
The polynite 5g of intercalation processing joined under whipped state in the 100g E51 Resins, epoxy, 70 ℃ of reactions 30 minutes.
The Resins, epoxy that contains the polynite of intercalation processing adds 10g solidifying agent diethylenetriamine, solidify 20 hours, 40 ℃ at 30 ℃ and solidify 6 hours, 80 ℃ and solidify 2 hours, 120 ℃ and solidified 1 hour, corresponding comparative example is 2, comparative example 3, comparative example 4, comparative example 5.Measure comparative example and be 2, the polynite surface layer spacing of comparative example 3, comparative example 4, comparative example 5 is 3.37nm.
Embodiment 1-4
The 5g polynite is added water 95g, be mixed with 5% the aqueous solution; Claim the 2g cetylamine again, preparation contains the aqueous solution of 10% cetylamine, and two kinds of solution are mixed the back 70 ℃ of reactions 8 hours.Centrifuging is to filtrate 0.1NAgNO
3Check till the no white precipitate.After the product drying, be ground to 200 purpose particles.
The polynite 5g of intercalation processing (wherein cetylamine content is 20%) is as stated above joined under whipped state in the 100gE51 Resins, epoxy, 70 ℃ of reactions 30 minutes.
The Resins, epoxy that contains the polynite of intercalation processing adds 30g solidifying agent T31, solidify 20 hours, 40 ℃ at 30 ℃ and solidify 2 hours, 120 ℃ curing of 6 hours, 80 ℃ curing 1 hour, corresponding embodiment is embodiment 1, embodiment 2, embodiment 3, embodiment 4.Measure at the x-ray diffraction instrument and not find that peak position exists, show that the polynite in the nano composite material of embodiment 1, embodiment 2, embodiment 3, the preparation of embodiment 4 methods takes place to peel off fully.
Embodiment 5-7
The 5g polynite is added water 95g, be mixed with 5% the aqueous solution; Claim the 10g octadecyl ammonium chloride again, preparation contains the aqueous solution of 10% octadecyl ammonium chloride, and two kinds of solution are mixed the back 70 ℃ of reactions 8 hours.Centrifuging is to filtrate 0.1NAgNO
3Check till the no white precipitate.After the product drying, be ground to 200 purpose particles.
The polynite 5g of intercalation processing (wherein stearylamine content is 25%) is as stated above joined under whipped state in the 100g E51 Resins, epoxy, 80 ℃ of reactions 1 hour.The Resins, epoxy that contains the polynite of intercalation processing adds 15g solidifying agent 701,40g solidifying agent 701,70g solidifying agent 701, and corresponding embodiment is embodiment 5, embodiment 6, embodiment 7.Solidified 12 hours at 30 ℃ then.Measure at the x-ray diffraction instrument and not find that peak position exists, show that the polynite in the nano composite material of embodiment 5, embodiment 6, the preparation of embodiment 7 methods takes place to peel off fully.
Embodiment 8-10
The preparation method of the polynite of intercalation processing is with embodiment 5.Polynite 1g, 10g, the 35g of intercalation processing are joined under whipped state in the 100g E44 Resins, epoxy, 70 ℃ of reactions 30 minutes.The Resins, epoxy that contains the polynite of intercalation processing adds 30g solidifying agent 726, and corresponding embodiment is embodiment 8, embodiment 9, embodiment 10.Solidified 4 hours at 60 ℃ then.Measure at the x-ray diffraction instrument and not find that peak position exists, show that the polynite in the nano composite material of embodiment 8, embodiment 9, the preparation of embodiment 10 methods takes place to peel off fully.
Embodiment 11-13
Preparation polynite content is 1%, 10%, 30% the aqueous solution (wherein polynite add-on is respectively 1g, 10g, 30g); Preparation contains the aqueous solution (wherein the stearylamine add-on is 10g) of 10% stearylamine again, 1%, 10%, the 30% polynite aqueous solution is mixed with 10% stearylamine solution respectively, and 90 ℃ of reactions 24 hours.Centrifuging is to filtrate 0.1NAgNO
3Check till the no white precipitate.After the product drying, be ground to 200 purpose particles.
In order the polynite 5g (wherein the content of stearylamine is respectively 26%, 24.4%, 23%) of the intercalation processing of above-mentioned different polynite prepared at concentrations is joined under whipped state in the 100g E51 Resins, epoxy respectively, and 70 ℃ of reactions 30 minutes.The Resins, epoxy that will contain the polynite of intercalation processing respectively in order adds 40g solidifying agent 701, and corresponding embodiment is embodiment 11, embodiment 12, embodiment 13.Solidified 7 days at 30 ℃ then.Measure at the x-ray diffraction instrument and not find that peak position exists, show that the polynite in the nano composite material of embodiment 11, embodiment 12, the preparation of embodiment 13 methods takes place to peel off fully.
Embodiment 14-16
The preparation bentonite content is 15% the aqueous solution (wherein the wilkinite add-on is 15g); Preparation contains the aqueous solution (wherein the stearylamine add-on is respectively 1g, 10g, 20g) of 1%, 10%, 20% stearylamine again, with bentonite solution respectively with the aqueous solution of 1%, 10%, 20% stearylamine, and 55 ℃ of reactions 45 hours.Centrifuging is to filtrate 0.1N AgNO
3Check till the no white precipitate.After the product drying, be ground to 200 purpose particles.
Difference joined the wilkinite 5g (wherein the content of stearylamine is respectively 20.8%, 19%, 18%) of above-mentioned three kinds of different stearylamine prepared at concentrations in the 100g E51 Resins, epoxy in order under whipped state, 70 ℃ of reactions 30 minutes.Add 40g solidifying agent JA-1 respectively at the bentonitic Resins, epoxy that contains intercalation processing in order respectively again, corresponding embodiment is embodiment 14, embodiment 15, embodiment 16.Solidified 48 hours at 70 ℃ then.Measure at the x-ray diffraction instrument and not find that peak position exists, show that the polynite in the nano composite material of embodiment 14, embodiment 15, the preparation of embodiment 16 methods takes place to peel off fully.
Claims (7)
1, a kind of epoxy/laminated nm-silicate composite material is characterized in that by weight, and described nano composite material comprises following component and content:
Resins, epoxy 100;
Layered silicate 0.5-50;
Solidifying agent 10-100;
Described solidifying agent is phenol aldehyde modified amine, and described layered silicate is the layered silicate through the aliphatic amide intercalation processing, and its particle diameter is 200 orders-2000 orders, and the consumption of aliphatic amide is the 0.001-10 weight part.
2, epoxy/laminated nm-silicate composite material according to claim 1 is characterized in that: described laminar silicic acid salts contg is 1-25 part.
3, epoxy/laminated nm-silicate composite material according to claim 1 is characterized in that: described Resins, epoxy is bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, bisphenol-s epoxy resin, the methylol bisphenol A type epoxy resin, bisphenol-A epoxy resin, organic-silicon-modified bisphenol A type epoxy resin, organic titanium modified bisphenol A type Resins, epoxy, modified nylon Resins, epoxy, fluorinated epoxy resin, line style phenol formaldehyde (PF) Resins, epoxy, ortho-cresol formaldehyde Resins, epoxy, aliphatic glycidyl ether Resins, epoxy, glycidyl ester type epoxy resin, one of glycidyl amine type epoxy resin.
4, epoxy/laminated nm-silicate composite material according to claim 1 is characterized in that: the structure of described aliphatic amide: CH
3(CH
2)
nNH
2, n=5～17 wherein.
5, epoxy/laminated nm-silicate composite material according to claim 1 is characterized in that: described layered silicate is one of vermiculite, wilkinite, polynite, kaolin, sepiolite or mixture.
6, the preparation method of epoxy/laminated nm-silicate composite material according to claim 1 is characterized in that carrying out with step in the following order:
1) intercalation processing of layered silicate
The layered silicate powder is mixed with the aqueous solution that concentration expressed in percentage by weight is 0.5-30%, and the preparation concentration expressed in percentage by weight is the CH of 1-20% in another container again
3(CH
2)
nNH
2Or CH
3(CH
2)
nNH
3The X aqueous solution, n=5-17 wherein, X is a halogens; After two kinds of solution mixing, 50-90 ℃ of reaction 20 minutes-48 hours, centrifuging was to filtrate 0.1N AgNO
3Check till the no white precipitate, after the product drying, be ground to particle diameter 200 orders-2000 purpose particle;
2) layered silicate of above-mentioned intercalation processing joined in the Resins, epoxy under whipped state, 60-100 ℃ of reaction 10 minutes-60 minutes;
3) Resins, epoxy that contains the layered silicate of intercalation processing adds solidifying agent, and curing reaction temperature is 15-40 ℃, and the curing reaction time is 0.5-24 hour, solidify to form epoxy/laminated nm-silicate composite material.
7, the preparation method of epoxy/laminated nm-silicate composite material according to claim 6 is characterized in that: in the described step 1), the reaction times is 8-24 hour.
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| CN101864148A (en) * | 2010-07-13 | 2010-10-20 | 哈尔滨工业大学 | Method for modifying epoxy resins and method for preparing carbon fiber composite by applying modified epoxy resins |
| CN102153836B (en) * | 2011-03-28 | 2012-07-04 | 宁波大学 | Ionic liquid layered silicate/epoxide resin nano composite material and preparation method of ionic liquid layered silicate/epoxide resin nano composite material |
| CN102670242B (en) * | 2011-04-07 | 2014-05-28 | 南京大学 | Ultrasonic focusing transducer |
| CN106398115A (en) * | 2016-08-27 | 2017-02-15 | 安徽天瞳智能科技有限公司 | Good thermal stability epoxy resin composition for circuit board substrate |
| CN106280269A (en) * | 2016-08-27 | 2017-01-04 | 安徽天瞳智能科技有限公司 | A kind of good toughness excellent in mechanical performance composition epoxy resin |
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