CN1288206C - Epoxy resin/montmorillonoid nano-compoiste-material and its preparation method - Google Patents
Epoxy resin/montmorillonoid nano-compoiste-material and its preparation method Download PDFInfo
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- CN1288206C CN1288206C CN 01136947 CN01136947A CN1288206C CN 1288206 C CN1288206 C CN 1288206C CN 01136947 CN01136947 CN 01136947 CN 01136947 A CN01136947 A CN 01136947A CN 1288206 C CN1288206 C CN 1288206C
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Abstract
The present invention relates to an epoxy resin / montmorillonite nanometer composite material and a preparing method thereof. The dimension of a dispersed phase of montmorillonite is from 10 nm to 100 nm. The epoxy resin / montmorillonite nanometer composite material has the components and contents with the following proportion by weight: 100 portions of epoxy resin, 0.5 to 20 portions of intercalation soil, 0.5 to 50 portions of curing agents, 1.0 to 20 portions of accelerating agents, 0.5 to 50 portions of diluting agents and 10.0 to 80.0 portions of solvents. Montmorillonite is organic montmorillonite processed by expanding intercalation. The preparing method comprises the step that the montmorillonite and the epoxy resin carry out a curing reaction under the actions of the curing agents and the accelerating agents to cause the montmorillonite to be dissociated into nanometer particles and to be uniformly dispersed in epoxy resin basal bodies. The method has the advantages of simple operation and easy industrial production. A prepared composite material obviously enhances the mechanical property and the heat resistance.
Description
Technical field of the present invention
The invention belongs to a kind of Resins, epoxy (EP) matrix material and preparation method thereof, particularly a kind of Epoxy Resin nano composite material and preparation method thereof.
Background technology of the present invention
Resins, epoxy (EP) is a kind of thermosetting material, is to use the most general thermosetting resin, this resin to add in the strongthener field to become insoluble infusible thermosetting material after solidifying agent solidifies.Resins, epoxy has good machinery, performance such as electric, chemical, bonding, is widely used in aspects such as tackiness agent, coating, matrix material.In existing method of modifying, adopt rubber-toughened epoxy resin, the strength of materials, rigidity are descended.Adding nano material in Resins, epoxy is a kind of effective method of modifying, the surperficial non-matching atom of nano material is many, increase with Resins, epoxy generation physics or chemically combined possibility, having strengthened particle combines with the interface of matrix, thereby can bear certain load, have the toughness reinforcing possibility of enhancing.In recent years, people are more and more to the research of Resins, epoxy based nano composite material, but the nano material that adopts mostly is nano-metal-oxide, as silicon-dioxide, titanium dioxide; Polynite particular structure and performance have also caused people's attention.The report of having seen Resins, epoxy-Nano composite material of montmorillonite aspect has:
(1) Lv Jiankun, Ke Yucai, QiZongNeng etc. " intercalation polymeric prepares clay/epoxy resin nano composites process medium clay soil and peels off the research of behavior ", polymer journal 2000 (1): 85～89, the document adopts XRD and DSC means to study the peel off behavior of clay in Resins, epoxy, analyzed clay and peeled off relation with the epoxy resin cure degree;
(2) Lv Jiankun, Ke Yucai, QiZongNeng etc. " the formation mechanism and the performance of epoxy/clay nanocomposites ", polymer circular 2000 (2): 18～26, the document has further been reported the microtexture of epoxy/clay nanocomposites, simultaneously to the flexural strength of epoxy clay exfoliated nano-composite, modulus, resistance to impact shock is measured, the result shows, the modulus of matrix material is linear raising with the increase of clay content, and bending strength improves afterwards earlier with the clay content increase and reduces maximum when content 2% (mass percent), it is about 10% that bending strength improves, and content surpasses 3.5% (massfraction) back bending strength and is lower than virgin resin; Shock strength increases when clay content is low, when clay content is 2～3% (massfractions) maximum value is arranged, and improves about 50% than pure epoxy resin.The document is also analyzed the dynamic properties of matrix material by the DMA means, the result shows, the modulus of matrix material improves, but reduces because of the adding of clay makes the second-order transition temperature (Tg) of matrix material, and the drain performance and the virgin resin of matrix material are basic identical.The author has also measured the thermal expansivity and the heat-drawn wire (HDT) of matrix material, the thermal expansivity of matrix material is lower than virgin resin, dimensional stability is better, and clay content is that the heat-drawn wire (HDT) of the matrix material of 2% (massfraction) improves about 15 ℃.
(3) Chen Chunyan, Wang Xia, Jin Shijiu " the compound research of the intercalation of Resins, epoxy and polynite " hi-tech communication 1999 (3): 39～44, this document adopts scorification and solvent supersonic method to prepare the Epoxy Resin intercalation composite material respectively, the author utilizes means such as XRD, SEM, TEM that the matrix material microtexture is characterized, document emphasis is studied the rheological property of matrix material, the result is that the matrix material behind the interpolation clay has had good sag resistance, does not do report for the mechanical property and the thermal characteristics of matrix material.
(4) P.Kelly, A.Akelah, S.Qutubuddin, A.Moet " Reduction of ResidualStress in Montmorillonite/Epoxy Compounds ", J.Mater.Sci.29 (1994): 2274～2280, utilize wide-angle x-ray diffraction and small angle X ray scattering method that the microtexture of matrix material is studied in the literary composition, the result is clay fine dispersion in epoxy resin-base, and the lattice spacing of matrix material medium clay soil has had raising; The author also utilizes the DSC means to measure the second-order transition temperature of matrix material, and the result is that the second-order transition temperature of matrix material increases than virgin resin; Test result to the maximum residual stress of matrix material shows that the unrelieved stress of matrix material reduces nearly 60% than virgin resin; Dynamic properties (DMA) test result shows that the dynamic storage modulus of matrix material increases than virgin resin.
(5) Muhs.Wang and Thomas J.Pinnavaia " Clay-Polymer Nanocomposites Formedfrom Acidic Derivatives of Montmorillonite and an Epoxy Resin ", Chem.Mater.1994,6:468～474, the document has been studied clay with the XRD means and has well been peeled off into monolithic layer and be dispersed in the resin matrix at epoxy resin-base, and this phenomenon has obtained checking in the TEM photo; Verified that with the DSC means polymerization reaction heat of matrix material reduces with the clay content increase, has not had the description of mechanical property and thermal characteristics aspect in the literary composition.
(6) Andre Lee and Joseph D.Lichtenhan " Thermal and ViscoelasticProperty of Epoxy-clay and Hybrid Inorganic-Organic Epoxy Nanocomposites ", J.Appli.Polym.Sci.1999,73:1993-2001, the document is studied the thermal characteristics and the visco-elasticity of epoxy resin/clay matrix material, wherein the second-order transition temperature of epoxy resin/clay matrix material (Tg) there is no obvious difference with virgin resin, the creep resistance of matrix material improves, the Micro-Structure Analysis result shows, clay is peeled off in epoxy resin-base, and the clay lattice spacing is greater than 100nm.
(7) Carsten Zilg, Rolf M ü lhaupt, J ü rgen Finter " Morphology andtoughness/stiffness balance of nanocomposites based upon anhydride-curedepoxy resins and layered silicates ", Macromol.Chem.Phys.1999,200:661-670, the document has been studied a series of Resins, epoxy/laminated nm-silicate composite materials that use the anhydride curing agent preparation, the Micro-Structure Analysis of matrix material shows, the silicate plate interlamellar spacing does not surpass 10nm, the second-order transition temperature of matrix material decreases, but its rigidity does not reduce, wherein with the Young's modulus of the matrix material of synthetic fluorine mica preparation with represent the tough equilibrated stress strength factor K of material
ICAll the increase with silicate content increases, but simultaneously, the tensile strength of matrix material descends.
(8) T.J.Pinnavaia etal. " Flexible Resin-clay composite:Method ofPreparation and Use " US Patent, 5,801,216. (1998), Carsten Zilg, RolfM ü lhaupt, J ü rgen Finter " Morphology and toughness/stiffness balance ofnanocomposites based upon anhydride-cured epoxy resins and layeredsilicates ", Macromol.Chem.Phys.1999,200:661-670, this patent adopts several different Resins, epoxy and organic clay to prepare epoxy resin/clay intercal type or leafing type matrix material, and pass through XRD, the TEM means have been tested the microtexture of matrix material, for leafing type epoxy resin/clay matrix material, the X-ray diffraction peak of clay disappears, and promptly clay has reached exfoliated state in epoxy resin-base.The tensile strength and the tensile modulus of the matrix material that the clay of handling with octadecylamine that wherein relates to prepares all have raising than virgin resin, increase with clay content and to be linear and to increase, wherein clay content is that the tensile strength and the stretch-proof modulus of the matrix material of 15% (massfraction) increased nearly 10 times.
Technology contents of the present invention
Technical problem to be solved by this invention is to overcome weak point of the prior art, and a kind of Epoxy Resin nano composite material and preparation method thereof is provided.The epoxy resin composite material of this method preparation can improve the mechanical property and the resistance toheat of polymeric matrix.
Technical solution of the present invention is as follows:
Polynite disperse phase yardstick is 10～100nm in the Epoxy Resin nano composite material of the present invention, its component and content following (weight part):
Resins, epoxy 100
Intercalation soil 0.5～20
Solidifying agent 0.5～70
Promotor 1.0～20
Thinner 0.5～50
Solvent 10.0～80.0
Intercalation soil in the Epoxy Resin nano composite material component of the present invention is the organo montmorillonite through the processing of intercalation expansionization, and intercalation soil sheet interlayer spacing is 15～25 , its component and content following (weight part):
Polynite 0.5～20
Intercalator 0.12～18.00
Protonating agent 0.02～5.00
Resins, epoxy in the Epoxy Resin nano composite material component of the present invention be bisphenol A epoxide resin (being the dihydroxyphenyl propane glycidyl ether) (E-51), it is by epoxy chloropropane and diphenylol propane polycondensation and get.
Solidifying agent in the Epoxy Resin nano composite material component of the present invention is low molecular polyamides (203#) or liquid methyl tetrahydrochysene acid anhydrides (BH-550).
Promotor in the Epoxy Resin nano composite material component of the present invention is 2,4,6-three (dimethylamino methyl) phenol (DMP-30) or benzyldimethylamine (BDMA).
Thinner in the Epoxy Resin nano composite material component of the present invention is a n-butyl glycidyl ether.
Solvent in the Epoxy Resin nano composite material component of the present invention is dimethylbenzene (DMB) or N, N '-dimethyl formamide (DMF).
Polynite raw material particle size during intercalation of the present invention local soil type divides is 30～80 μ m, and the cationic exchange total volume is 40～200mmol/100g, and montmorillonite layer thickness is 10 , and the cheating engaging layer spacing is 2～5 .
Intercalator during intercalation of the present invention local soil type divides is n-octyl amine, n-Decylamine, hexanediamine, amino dodecane, cetylamine, stearylamine, cetyl trimethylammonium bromide, acrylamide, dihydroxy ethyl methyl octadecyl bromination amine or its mixture.
Protonating agent during intercalation of the present invention local soil type divides is a protonic acid, as sulfuric acid, phosphoric acid, sulfonic acid, hydrochloric acid, acetic acid.
The method steps of Epoxy Resin nano composite material preparation of the present invention is as follows:
(1) pre-treatment of polynite:
A certain amount of original polynite is scattered in (massfraction of polynite is less than 5 percent) in the deionized water, and violent stirring makes polynite thoroughly disperse to form suspension, behind the sedimentation certain hour, gets the upper strata and is used for organically-modified.
(2) organically-modified (preparation of intercalation soil) of polynite:
A, elder generation stir pretreated polynite in the dispersion medium high speed, form stable suspensoid, and temperature of reaction is controlled at 50～90 ℃;
B, intercalator and protonating agent are added in the above-mentioned suspensoid, stir again and make it fully expanded, kept 4～24 hours, form suspension;
C, above-mentioned suspension is separated with supercentrifuge, then for several times with ethanol-water solution washing solid phase, to AgNO with 0.1M
3Do not contain CL in the solution check washing lotion
-Till;
Make intercalation soil after d, the vacuum-drying, its grinding and sieving is standby;
(3) preparation Epoxy Resin nano composite material
The infiltration of a, Resins, epoxy and polynite
Adopt direct intercalation compounding: Resins, epoxy is joined in the polymerization reactor, stirring also is warming up to 40 ℃～80 ℃, adds intercalation soil constant temperature high-speed stirring 10～60 minutes, makes the two thorough mixing even, ultra-sonic dispersion is 5～30 minutes again, makes epoxy resin prepolymer-montmorillonite Composite system;
The curing of b, epoxy resin prepolymer-montmorillonite composite
After above-mentioned gained epoxy resin prepolymer-montmorillonite composite is cooled to 30 ℃～60 ℃, in reactor, add thinner, solidifying agent, with above-mentioned system thorough mixing, closed system, it is 0.1MPa that the maintenance system temperature is evacuated to vacuum tightness while stirring at 40～50 ℃, remove the bubble in the system, stop after 30 minutes stirring and vacuumizing;
C, reactant is poured into mould, solidified under the room temperature 2～5 hours, solidified 2～16 hours down at 50 ℃～150 ℃ again, can make the Epoxy Resin nano composite material.
In the infiltration method of Resins, epoxy and polynite, also can adopt the solution intercalation composite algorithm: be scattered in Resins, epoxy and polynite in the reactor in proportion with solvent, stirred at a certain temperature 1～2 hour, ultra-sonic dispersion is 5～30 minutes again, solvent is removed in underpressure distillation, last vacuum defoamation makes epoxy resin prepolymer-montmorillonite Composite system.
Epoxy Resin nano composite material of the present invention is to prepare by the direct graft process of epoxy resin prepolymer or solution intercalation method.The direct graft process of Resins, epoxy is made intercalation soil after being meant the polynite elder generation process intercalation of intercalator, then itself and epoxy resin prepolymer is carried out thorough mixing, adds the webbed build macromolecular structure of solidifying agent and promotor curing cross-linked again.Intercalation soil (polynite after the processing) is dissociated into the nanometer lamella and is dispersed in the epoxy resin-base in curing reaction, thereby obtains the Epoxy Resin nano composite material.The solution intercalation method of Resins, epoxy is meant with organic solvent dissolves Resins, epoxy earlier, adds intercalation soil thorough mixing then, and system removes solvent afterwards, adds the webbed build macromolecular structure of solidifying agent and promotor curing cross-linked again.Intercalation soil at first in solution with the Resins, epoxy thorough mixing, in curing reaction, be dissociated into the nanometer lamella then and be dispersed in the epoxy resin-base, thereby obtain the Epoxy Resin nano composite material.Wherein used Resins, epoxy is a kind of bisphenol A type epoxy resin (being the dihydroxyphenyl propane glycidyl ether), and it is by epoxy chloropropane and diphenylol propane polycondensation and get, and its structural formula is as follows:
Polynite during intercalation local soil type divides is class mineral, and major ingredient is for containing the layered silicate of 80%-95% polynite (Mont).Polynite is multiple layer mineral, its unit cell be by add in the middle of two drift angles Si-O tetrahedron inwardly a slice Al (O, OH) the octahedra composition rely on shared Sauerstoffatom to be connected between tetrahedron and the octahedron, continuous between the structure cell for the oxygen layer.The lamellar spacing of polynite is 1.0nm.The lamella internal surface has negative charge, and its specific surface area is 200～800m
2/ g, interlayer cation are Na
+, Ca
2+, Mg
2+, or Al
3+Deng genus interchangeability positively charged ion.After adopting organic amine (ammonium) salt quasi-molecule and montmorillonite polynite to carry out ion exchange reaction, the polynite interfloor distance is widened, be easy to the sheet interlayer that epoxy resin prepolymer is inserted into polynite.Selected polynite thereby the cationic exchange total volume (CEC) that should have are 40～200mmol/100g.The polynite raw material particle size is at 30～80 μ m, and montmorillonite layer thickness is 10 , and the cheating engaging layer spacing is 2～5 .Intercalation soil sheet interlayer spacing behind intercalation polymeric is increased to 25～50 , and the montmorillonite layer spacing is bigger, and performance of composites better.
Polynite content is 0.5～20 (weight part) in the present invention, and when content is lower than 0.5 part, polynite is not enough to produce enough enhancements and thermotolerance; When content surpasses 20 parts, the mechanical property of matrix material descends on the contrary, and the transparency of matrix material also obviously descends simultaneously.
The present invention compared with prior art has following advantage:
1, direct intercalation technique provided by the invention is at first intercalator to be inserted into accurate two-dimentional silicate montmorillonite material lamella chien shih montmorillonite layer to strut, and then rely on macromolecular chain macromolecular chain to be inserted into the silicate plate interlayer and lamella is dissociated with the interaction between the intercalator organic group, thereby polynite reaches the homodisperse of nanoscale, forms nano composite polymer-montmorillonoid material.Compare with changing processing condition, the present invention is simple to operate, is easy to suitability for industrialized production, and performance improves a lot.
2, solution intercalation technology provided by the invention is at first intercalator to be inserted into accurate two-dimentional silicate montmorillonite material lamella chien shih montmorillonite layer to strut, then intercalation soil is fully disperseed with Resins, epoxy in solution, then rely on macromolecular chain macromolecular chain to be inserted into the silicate plate interlayer and lamella is dissociated with the interaction between the intercalator organic group, thereby polynite reaches the homodisperse of nanoscale, forms nano composite polymer-montmorillonoid material.Compare with changing processing condition, the present invention is simple to operate, is easy to suitability for industrialized production, and performance improves a lot.、
3, the Epoxy Resin nano composite material of the present invention's preparation, be dispersed in polynite in the epoxy resin-base with 10～100nm yardstick, has very large interfacial area, very strong interaction is arranged between inorganic phase and polymeric matrix, can give full play to the rigidity and the resistance toheat of inorganics, and the thermotolerance of gained matrix material and resistance to impact shock there is more obviously raising than virgin resin.Sample testing is the result show: the matrix material that obtains as the direct graft process of solidifying agent with low molecular polyamides 203#, its resistance to impact shock has improved 154%, and tensile strength has improved 17.7%, the heat decomposition temperature of matrix material has improved 10.4 ℃, and heat-drawn wire (HDT) has improved 9.6 ℃.The matrix material of making solidifying agent with 203# equally and adopting the solution intercalation method to prepare, its resistance to impact shock has improved 192%, and heat-drawn wire improves 20 ℃.And be the matrix material that solidifying agent adopts direct graft process to obtain with methyl tetrahydrochysene acid anhydrides BH-550, its resistance to impact shock has improved 87.8%, and tensile strength has improved 20.9%, and the heat decomposition temperature of matrix material has improved 24.7 ℃, and heat-drawn wire (HDT) has improved 8.7 ℃.The adding of this explanation polynite has realized that the enhancing of matrix material is toughness reinforcing, and the thermostability of matrix material has clear improvement simultaneously.
The drawing of accompanying drawing is described as follows
Fig. 1 is a montmorillonite XRD diffraction spectrogram
A1 is original polynite among the figure, and a2 is a modified montmorillonoid, and a3 is that Resins, epoxy soaks into polynite, and a4 is the Epoxy Resin matrix material.
The specific embodiment of the present invention is as follows:
Embodiment 1:
(1) takes off native pre-treatment
The original polynite of 150 grams is scattered in (massfraction of polynite is less than 5 percent) in the deionized water, and violent stirring makes polynite thoroughly disperse to form suspension, behind the sedimentation certain hour, gets the upper strata and is used for organically-modified.
(2) organically-modified (preparation of intercalation soil) of polynite:
A, the ethanolic soln high speed that earlier pretreated polynite 15 is restrained at 600 parts stir, and form stable suspensoid, and temperature of reaction is controlled at 50 ℃;
B, intercalator cetylamine 6 gram and protonating agent concentrated hydrochloric acid are added in the above-mentioned suspensoids for 2.8 milliliters, stir again and make it fully expanded, kept 12 hours, form suspension;
C, above-mentioned suspension is separated with supercentrifuge, then for several times with ethanol-water solution washing solid phase, to AgNO with 0.1M
3Do not contain CL in the solution check washing lotion
-Till;
Make intercalation soil after d, the vacuum-drying, its grinding and sieving is standby.
(3) preparation Epoxy Resin nano composite material
A, the Resins, epoxy E-51 that gets 70g join in the polymerization reactor, stir and be warming up to 70 ℃, add the intercalation soil constant temperature high-speed stirring 30 minutes of 1.0g, and then ultra-sonic dispersion 15 minutes, make the two thorough mixing even;
B, be cooled to 40 ℃ after, in reactor, add 8 milliliters of thinner 669#, solidifying agent low molecular polyamides 203#30g, with above-mentioned system thorough mixing, closed system, it is 0.1MPa that the maintenance system temperature is evacuated to vacuum tightness while stirring at 40～50 ℃, remove the bubble in the system, stop after 30 minutes stirring and vacuum;
C, reactant is poured into mould, solidified 2 hours under the room temperature, solidified 12 hours down at 80 ℃ again, can make the Epoxy Resin nano composite material.
The polynite disperse phase is dispersed in the epoxy resin-base with 10～100nm yardstick after tested.The structure of gained matrix material and performance see Table 1, table 2.
Embodiment 2～5 preparation methods are identical with embodiment 1, and wherein the consumption of intercalation soil is respectively 3g, 5g, 7g, 10g, and solidifying agent is also identical with embodiment 1 with the thinner consumption.The structure of matrix material and performance see Table 1, table 2.
Embodiment 6:
(1) pre-treatment of polynite
The original polynite of 100 grams is scattered in (massfraction of polynite is less than 5 percent) in the deionized water, and violent stirring makes polynite thoroughly disperse to form suspension, behind the sedimentation certain hour, gets the upper strata and is used for organically-modified.
(2) organically-modified (preparation of intercalation soil) of polynite:
A, the ethanolic soln high speed that earlier pretreated polynite 20 is restrained at 700 parts stir, and form stable suspensoid, and temperature of reaction is controlled at 60 ℃;
B, intercalator cetylamine 7.8 gram and protonating agent concentrated hydrochloric acid are added in the above-mentioned suspensoids for 3.5 milliliters, stir again and make it fully expanded, kept 12 hours, form suspension;
C, above-mentioned suspension is separated with supercentrifuge, then for several times with ethanol-water solution washing solid phase, to AgNO with 0.1M
3Do not contain CL in the solution check washing lotion
-Till;
Make intercalation soil after d, the vacuum-drying, its grinding and sieving is standby.
(3) preparation Epoxy Resin nano composite material
A, the Resins, epoxy E-51 that gets 67g join in the polymerization reactor, stir and be warming up to 70 ℃, add the intercalation soil constant temperature high-speed stirring 30 minutes of 1.0g, and then ultra-sonic dispersion 10 minutes, make the two thorough mixing even;
B, be cooled to 40 ℃ after, in reactor, add solidifying agent low molecular polyamides 203#33g, with above-mentioned system thorough mixing, closed system, it is 0.1MPa that the maintenance system temperature is evacuated to vacuum tightness while stirring at 40～50 ℃, remove the bubble in the system, stop after 30 minutes stirring and vacuum;
C, reactant is poured into mould, solidified 2 hours under the room temperature, solidified 12 hours down at 80 ℃ again, can make the Epoxy Resin nano composite material.
The polynite disperse phase is dispersed in the epoxy resin-base with 10～100nm yardstick after tested.The structure of gained matrix material and performance see Table 1, table 2.
Embodiment 7～10 preparation methods are identical with embodiment 6, and wherein the consumption of intercalation soil is respectively 3g, 5g, 7g, 10g, and hardener dose is also identical with embodiment 6.The structure of matrix material and performance see Table 1, table 2.
Embodiment 11:
(1) pre-treatment of polynite is identical with embodiment 1
(2) organically-modified (preparation of intercalation soil) of polynite;
A, the ethanolic soln high speed that earlier pretreated polynite 18 is restrained at 650 parts stir, and form stable suspensoid, and temperature of reaction is controlled at 65 ℃;
B, intercalator dihydroxy ethyl methyl octadecyl ammonium chloride 9.8 gram is added in the above-mentioned suspensoid, stir again and make it fully expanded, kept 12 hours, form suspension;
C, above-mentioned suspension is separated with supercentrifuge, then for several times with ethanol-water solution washing solid phase, to AgNO with 0.1M
3Do not contain CL in the solution check washing lotion
-Till;
Make intercalation soil after d, the vacuum-drying, its grinding and sieving is standby.
(3) preparation Epoxy Resin nano composite material
A, the Resins, epoxy E-51 that gets 80g join in the polymerization reactor, stir and be warming up to 70 ℃, add the intercalation soil constant temperature high-speed stirring 30 minutes of 1.0g, and then ultra-sonic dispersion 10 minutes, make the two thorough mixing even;
B, be cooled to 40 ℃ after, in reactor, add liquid methyl tetrahydrochysene acid anhydrides 20g of solidifying agent and promotor 2,4,6 three (dimethylamino methyl) phenol (DMP-30) 2g, with above-mentioned system thorough mixing, closed system, it is 0.1MPa that the maintenance system temperature is evacuated to vacuum tightness while stirring at 40～50 ℃, remove the bubble in the system, stop after 30 minutes stirring and vacuum;
C, reactant is poured into mould, solidified 2 hours under the room temperature, solidify down at 85 ℃ again and solidified 2 hours down in 2 hours and 145 ℃, can make the Epoxy Resin nano composite material.
The polynite disperse phase is dispersed in the epoxy resin-base with 10～100nm yardstick after tested.The structure of gained matrix material and performance see Table 1, table 2.
Embodiment 12～15 preparation methods are identical with embodiment 11, and wherein the consumption of intercalation soil is respectively 3g, 5g, 7g, 10g, and hardener dose is also identical with embodiment 11 with accelerator level.The structure of matrix material and performance see Table 1, table 2.
Table 1: the microtexture and the mechanical property of direct graft process Epoxy Resin nano composite material
| Embodiment | Intercalation soil consumption (gram) | The lattice spacing of polynite (nm) | Resistance to impact shock (the KJ/m of matrix material 2) | The tensile strength of matrix material (mpa) |
| 1 | 1 | ≥8.824 | 7.48 | 45.30 |
| 2 | 3 | The same | 8.78 | 46.80 |
| 3 | 5 | The same | 10.43 | 52.95 |
| 4 | 7 | The same | 8.47 | 45.70 |
| 5 | 10 | The same | 6.25 | - |
| 6 | 1 | The same | 6.67 | 63.20 |
| 7 | 3 | The same | 7.25 | 63.52 |
| 8 | 5 | The same | 9.88 | 64.77 |
| 9 | 7 | The same | 6.69 | 57.42 |
| 10 | 10 | The same | 6.48 | - |
| 11 | 1 | The same | 6.81 | 47.20 |
| 12 | 3 | The same | 7.40 | 50.28 |
| 13 | 5 | The same | 6.51 | 44.38 |
| 14 | 7 | The same | 4.78 | 43.28 |
| 15 | 10 | The same | - | - |
The result of matrix material microtexture shows in the table 1, and the spacing of polynite improves a lot in the gained Epoxy Resin nano composite material, and the polynite disperse phase is dispersed in the epoxy resin-base with the lattice spacing greater than 8.824nm.
The mechanical property result of matrix material shows in the table 1, adds a small amount of organo montmorillonite, and matrix material can be realized strengthening toughness reinforcing simultaneously.Wherein the resistance to impact shock with the virgin resin of thinner 669# and solidifying agent low molecular polyamides 203# preparation is 4.52KJ/m
2, tensile strength is 40.26MPa, wherein polynite content is that the resistance to impact shock of the matrix material of 5% (massfraction) has improved 131% than virgin resin, tensile strength has improved 31.5%; Only the resistance to impact shock of the virgin resin for preparing with solidifying agent low molecular polyamides 203# is 3.89KJ/m
2, tensile strength is 55.05MPa, wherein polynite content is that the resistance to impact shock of the matrix material of 5% (massfraction) has improved 154% than virgin resin, tensile strength has improved 17.7%; Resistance to impact shock with the virgin resin of liquid methyl tetrahydrochysene acid anhydrides of solidifying agent and promotor 2,4,6 three (dimethylamino methyl) phenol DMP-30 preparation is 3.94KJ/m
2, tensile strength is 41.6MPa, wherein polynite content is the matrix material of 3% (massfraction), its resistance to impact shock has improved 88% than virgin resin, tensile strength has improved nearly 21%.
Table 2 is the resistance toheat of graft process Epoxy Resin nano composite material directly
| Embodiment | Intercalation soil consumption (g) | Heat-drawn wire HDT (℃) | Embodiment | Intercalation soil consumption (g) | Heat-drawn wire HDT (℃) |
| 1 | 1 | 34.7 | 8 | 5 | 58.4 |
| 2 | 3 | 38.3 | 9 | 7 | 54.8 |
| 3 | 5 | 42.7 | 10 | ||
| 4 | 7 | 34.9 | 11 | 1 | 130.3 |
| 5 | 12 | 3 | 131.7 | ||
| 6 | 1 | 49.2 | 13 | 5 | 132.3 |
| 7 | 3 | 53.3 | 14 | 7 | 130.5 |
Annotate: the heat-drawn wire (HDT) of the virgin resin for preparing with reactive thinner n-butyl glycidyl ether and solidifying agent low molecular polyamides 203# is 31.7 ℃, only the heat-drawn wire (HDT) of the virgin resin for preparing with solidifying agent 203# is 48.6 ℃, and is 124.1 ℃ with the heat-drawn wire (HDT) of the virgin resin of the preparation of anhydride curing agent BH-550.
The result of table 2 shows that the resistance toheat of gained Epoxy Resin nano composite material all has raising in various degree.Wherein in the matrix material with thinner 669# and solidifying agent low molecular polyamides 203# preparation, heat-drawn wire (HDT) than virgin resin when polynite content is 5% (massfraction) has improved 11 ℃, only in the matrix material with solidifying agent 203# preparation, improve 9.8 ℃ than the heat-drawn wire (HDT) of virgin resin when polynite content is 5% (massfraction), and when polynite content is 5% (massfraction) in the matrix material of the preparation of anhydride curing agent BH-550 than 8.2 ℃ of heat-drawn wire (HDT) raisings of virgin resin.
Embodiment 16:
(1) preprocessing process of polynite is identical with embodiment 1.
(2) organically-modified (preparation of intercalation soil) of polynite:
A, the aqueous ethanolic solution high speed that earlier pretreated polynite 15 is restrained at 500 parts stir, and form stable suspensoid, and temperature of reaction is controlled at 70 ℃;
B, intercalator hexanediamine 0.8 gram and protonating agent concentrated hydrochloric acid 3ml add in the above-mentioned suspensoid, stir to make it fully expanded again, keep 8 hours, form suspension;
C, above-mentioned suspension is separated with supercentrifuge, then for several times with ethanol-water solution washing solid phase, to AgNO with 0.1M
3Solution check washing lotion does not contain CL
-Till;
Make intercalation soil after d, the vacuum-drying, its grinding and sieving is standby.
(3) preparation Epoxy Resin nano composite material:
A, get 100 gram Resins, epoxy E-51 and join in the polymerization reactor, add solvent dimethyl formamide (DMF) 20 grams then, stirring also is warming up to 80 ℃, adds intercalation soil 4.5 gram constant temperature high-speed stirring after 50 minutes, makes polynite and Resins, epoxy thorough mixing even;
B, to be evacuated to vacuum tightness be 0.09MPa, stirring down, heating removes solvent dimethyl formamide (DMF), temperature is controlled at below 156 ℃, reduce the temperature to room temperature then and add solidifying agent low molecular polyamides-203#50 gram again, stir about 20 minutes of vacuum defoamation down, stop afterwards stirring and vacuum;
C, reactant is poured in the mould of preheating in advance, at room temperature solidify after 2 hours and solidified 4-5 hour down at 150 ℃ again, can make the Epoxy Resin nano composite material.
The composition of embodiment 17,18 preparation methods and matrix material is substantially the same manner as Example 16, and just polynite content is respectively 5% (massfraction) and 7% (massfraction)
After tested, the polynite of matrix material is dispersed in the epoxy resin-base with the lattice spacing greater than 8.824nm among the embodiment 16,17,18, and the resistance toheat and the mechanical property of gained matrix material see Table 3.
Table 3 solvent graft process prepares the resistance toheat and the shock resistance of matrix material
| Polynite content (%) | 0 | 3 | 5 | 7 |
| Heat-drawn wire (HDT) ℃ | 41.5 | 61.5 | 56.5 | 55 |
| Resistance to impact shock (KJ/m 2) | 3.00 | 8.77 | 6.26 | 3.09 |
Table 3 is the result show, the resistance toheat of the Epoxy Resin nano composite material of employing solvent method preparation and resistance to impact shock all have raising in various degree, when wherein organo montmorillonite content is 3% (massfraction), the heat-drawn wire of matrix material (HDT) has improved 20 ℃, and its resistance to impact shock has improved 192%.
In the preparation process of whole Epoxy Resin nano composite material, the spacing of polynite is increasing gradually, the XRD test result as shown in Figure 1, its result shows: the spacing of original sodium-based montmorillonite is 1.228nm; Cetylamine montmorillonite modified spacing can reach 2.177nm, and as seen existing a considerable amount of organic cations enter between cheating engaging layer; Organo montmorillonite spacing after E-51 soaks into can reach 3.649nm, E-51 before curing intercalation enter between cheating engaging layer; Behind the composite material solidification, the crystal layer diffraction peak of polynite disappears, and illustrates that in solidification process the further intercalation of Resins, epoxy enters between cheating engaging layer, and the polynite crystal layer is strutted, and it is evenly spread in the epoxy resin-base with the nano level yardstick.
Claims (7)
1. Epoxy Resin nano composite material, it is characterized in that: polynite disperse phase yardstick is 10-100nm in the matrix material, it is as follows that raw materials used component and weight are formed umber:
Resins, epoxy 100
Intercalation soil 0.5～20
Solidifying agent 0.5～70
Used intercalation soil is to be made by the organically-modified of polynite, and solidifying agent is low molecular polyamides 203# or liquid methyl tetrahydrochysene acid anhydrides;
Matrix material is made through following steps by above raw material:
(1) polynite is carried out pre-treatment earlier before organically-modified
Massfraction is scattered in the deionized water less than 5 percent original polynite, and violent stirring makes polynite thoroughly disperse to form suspension, behind the sedimentation certain hour, gets the upper strata polynite and is used for organically-modified;
(2) the organically-modified preparation intercalation soil of polynite
A. earlier pretreated polynite is stirred in the dispersion medium high speed, form stable suspensoid, temperature of reaction is controlled at 50～90 ℃;
B. intercalator and protonating agent are added in the above-mentioned suspensoid, stir again and make it fully expanded, kept 4～24 hours, form suspension;
C. above-mentioned suspension is separated with supercentrifuge, then for several times with ethanol-water solution washing solid phase, to AgNO with 0.1M
3Do not contain CL in the solution check washing lotion
-Till;
D. make intercalation soil after the vacuum-drying, its grinding and sieving is standby;
(3) preparation Epoxy Resin nano composite material
A. the infiltration of Resins, epoxy and polynite
Adopt direct intercalation compounding: extracting epoxy resin joins in the polymerization reactor, stirring also is warming up to 40 ℃～80 ℃, adds intercalation soil constant temperature high-speed stirring 10～60 minutes, makes the two thorough mixing even, ultra-sonic dispersion is 5～30 minutes again, makes epoxy resin prepolymer-montmorillonite Composite system;
B. the curing of epoxy resin prepolymer-montmorillonite composite
After above-mentioned gained epoxy resin prepolymer-montmorillonite composite is cooled to 30 ℃～60 ℃, in reactor, add solidifying agent, with above-mentioned system thorough mixing, closed system, the maintenance system temperature is at 40 ℃～50 ℃, being evacuated to vacuum tightness while stirring is 0.1MPa, removes the bubble in the system, stops after 30 minutes stirring and vacuumizing;
C. reactant is poured into mould, solidified under the room temperature 2～5 hours, solidified 2～16 hours down at 50 ℃～150 ℃ again, can make the Epoxy Resin nano composite material;
Intercalator during described intercalation local soil type divides is hexanediamine, n-octyl amine, n-Decylamine, amino dodecane, dihydroxy ethyl methyl octadecyl bromination amine or its mixture, and solidifying agent is low molecular polyamides 203# or liquid methyl tetrahydrochysene acid anhydrides.
2, according to the described Epoxy Resin nano composite material of claim 1, it is characterized in that raw materials used component also comprises promotor, promotor is 2,4,6-three (dimethylamino methyl) phenol or benzyldimethylamine, it is 1.0～20 that its weight is formed umber.
3, according to the described Epoxy Resin nano composite material of claim 1, it is characterized in that raw materials used component also comprises thinner, thinner is a n-butyl glycidyl ether, it is 0.5～50 that its weight is formed umber.
4. according to arbitrary described Epoxy Resin nano composite material in the claim 1～3, it is characterized in that: the Resins, epoxy in the matrix material component is bisphenol A type epoxy resin, i.e. the bisphenol A-type glycidyl ether.
5. as the preparation method of the said Epoxy Resin nano composite material of claim 1, it is characterized in that:
(1) polynite is carried out pre-treatment earlier before organically-modified
Massfraction is scattered in the deionized water less than 5 percent original polynite, and violent stirring makes polynite thoroughly disperse to form suspension, behind the sedimentation certain hour, gets the upper strata polynite and is used for organically-modified;
(2) the organically-modified preparation intercalation soil of polynite
A. earlier pretreated polynite is stirred in the dispersion medium high speed, form stable suspensoid, temperature of reaction is controlled at 50～90 ℃;
B. intercalator and protonating agent are added in the above-mentioned suspensoid, stir again and make it fully expanded, kept 4～24 hours, form suspension;
C. above-mentioned suspension is separated with supercentrifuge, then for several times with ethanol-water solution washing solid phase, to AgNO with 0.1M
3Do not contain CL in the solution check washing lotion
-Till;
D. make intercalation soil after the vacuum-drying, its grinding and sieving is standby;
(3) preparation Epoxy Resin nano composite material
A. the infiltration of Resins, epoxy and polynite
Adopt direct intercalation compounding: extracting epoxy resin joins in the polymerization reactor, stirring also is warming up to 40 ℃～80 ℃, adds intercalation soil constant temperature high-speed stirring 10～60 minutes, makes the two thorough mixing even, ultra-sonic dispersion is 5～30 minutes again, makes epoxy resin prepolymer-montmorillonite Composite system;
B. the curing of epoxy resin prepolymer-montmorillonite composite
After above-mentioned gained epoxy resin prepolymer-montmorillonite composite is cooled to 30 ℃～60 ℃, in reactor, add solidifying agent, with above-mentioned system thorough mixing, closed system, the maintenance system temperature is at 40 ℃～50 ℃, being evacuated to vacuum tightness while stirring is 0.1MPa, removes the bubble in the system, stops after 30 minutes stirring and vacuumizing;
C. reactant is poured into mould, solidified under the room temperature 2～5 hours, solidified 2～16 hours down at 50 ℃～150 ℃ again, can make the Epoxy Resin nano composite material;
Intercalator during described intercalation local soil type divides is hexanediamine, n-octyl amine, n-Decylamine, amino dodecane, dihydroxy ethyl methyl octadecyl bromination amine or its mixture, and solidifying agent is low molecular polyamides 203# or liquid methyl tetrahydrochysene acid anhydrides.
6, preparation method as the said Epoxy Resin nano composite material of claim 5, it is characterized in that: also add thinner in the step b in (3) preparation Epoxy Resin nano composite material when reactor adds solidifying agent, thinner is a n-butyl glycidyl ether.
7, preparation method as the said Epoxy Resin nano composite material of claim 5, it is characterized in that: when reactor adds solidifying agent, also add promotor in the step b in (3) preparation Epoxy Resin nano composite material, promotor is 2,4,6-three (dimethylamino methyl) phenol or benzyldimethylamine.
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