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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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000009830 intercalation Methods 0.000 claims abstract description 67
- 230000002687 intercalation Effects 0.000 claims abstract description 67
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 60
- 239000002114 nanocomposite Substances 0.000 claims abstract description 56
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 239000002689 soil Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract 5
- 238000003756 stirring Methods 0.000 claims description 43
- 239000000725 suspension Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 4
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002612 dispersion medium Substances 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims 7
- 230000004048 modification Effects 0.000 claims 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims 4
- 239000000243 solution Substances 0.000 claims 4
- LPLKJLLIRPEGHK-UHFFFAOYSA-N 2,2-dihydroxyethyl-methyl-octadecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[NH+](C)CC(O)O LPLKJLLIRPEGHK-UHFFFAOYSA-N 0.000 claims 2
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 72
- 239000002904 solvent Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 55
- 239000011347 resin Substances 0.000 description 55
- 239000004593 Epoxy Substances 0.000 description 48
- 239000004927 clay Substances 0.000 description 32
- 230000035939 shock Effects 0.000 description 17
- 239000010410 layer Substances 0.000 description 14
- 239000000138 intercalating agent Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 241000446313 Lamella Species 0.000 description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 238000010010 raising Methods 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 6
- 101710134784 Agnoprotein Proteins 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- -1 organo montmorillonite Chemical compound 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- BCCCOWCNUIXWBW-UHFFFAOYSA-N [Cl-].OC(CCCCCCCCCCCCCCCCC)([NH+](C)CC)O Chemical compound [Cl-].OC(CCCCCCCCCCCCCCCCC)([NH+](C)CC)O BCCCOWCNUIXWBW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WSNJABVSHLCCOX-UHFFFAOYSA-J trilithium;trimagnesium;trisodium;dioxido(oxo)silane;tetrafluoride Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WSNJABVSHLCCOX-UHFFFAOYSA-J 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
一种环氧树脂/蒙脱土纳米复合材料及其制备方法，其蒙脱土分散相尺度为10～100nm，其组分和含量是(重量份)：环氧树脂100、插层土0.5～20、固化剂0.5～50、促进剂1.0～20、稀释剂0.5～50、溶剂10.0～80.0；其中蒙脱土为经插层膨胀化处理的有机蒙脱土。其制备方法是将蒙脱土与环氧树脂在固化剂和促进剂的作用下进行固化反应，使其蒙脱土解离成纳米粒子并均匀分散于环氧树脂基体中而制得。该方法操作简单，易于工业化生产。制得的复合材料力学性能和耐热性能明显提高。An epoxy resin/montmorillonite nanocomposite material and a preparation method thereof, the montmorillonite dispersed phase scale is 10-100nm, and its components and content are (parts by weight): 100 parts by weight of epoxy resin, 0.5-0.50 nm of intercalation soil 20. Curing agent 0.5-50, accelerator 1.0-20, diluent 0.5-50, solvent 10.0-80.0; wherein montmorillonite is organic montmorillonite treated by intercalation expansion. The preparation method is to carry out curing reaction between montmorillonite and epoxy resin under the action of curing agent and accelerator, so that the montmorillonite is dissociated into nano particles and uniformly dispersed in the epoxy resin matrix. The method is simple to operate and easy to industrialized production. The mechanical properties and heat resistance of the prepared composite material are obviously improved.
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)
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