CN1249177C - Solid phase intercalation preparation method of nano montmorillonite and its prepared nano montmorillonite base material - Google Patents
Solid phase intercalation preparation method of nano montmorillonite and its prepared nano montmorillonite base material Download PDFInfo
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- CN1249177C CN1249177C CN 200410015775 CN200410015775A CN1249177C CN 1249177 C CN1249177 C CN 1249177C CN 200410015775 CN200410015775 CN 200410015775 CN 200410015775 A CN200410015775 A CN 200410015775A CN 1249177 C CN1249177 C CN 1249177C
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- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 54
- 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 title claims abstract description 38
- 238000009830 intercalation Methods 0.000 title claims abstract description 18
- 230000002687 intercalation Effects 0.000 title claims abstract description 18
- 239000007790 solid phase Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000000463 material Substances 0.000 title abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 150000002118 epoxides Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 239000004417 polycarbonate Substances 0.000 abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 229920000515 polycarbonate Polymers 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 23
- 238000002441 X-ray diffraction Methods 0.000 description 18
- -1 organo montmorillonite Chemical compound 0.000 description 15
- 239000013078 crystal Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 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 7
- 150000002500 ions Chemical class 0.000 description 7
- 150000002892 organic cations Chemical group 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 238000005341 cation exchange Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 150000001767 cationic compounds Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 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 3
- 229910001411 inorganic cation Inorganic materials 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000138 intercalating agent Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WNBGYVXHFTYOBY-UHFFFAOYSA-N benzyl-dimethyl-tetradecylazanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 WNBGYVXHFTYOBY-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229960000800 cetrimonium bromide Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 239000002355 dual-layer Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention discloses a method for preparing the solid-phase intercalation of nanometer montmorillonite. After epoxy compounds and purified montmorillonite are uniformly mixed, a mixture of the epoxy compounds and the purified montmorillonite is sheared and refined in high strength by double rollers, double screw rods or a banbury mixer at the temperature of 150 to 200 DEG C so that the intercalation and the stripping of the montmorillonite are directly completed, and the montmorillonite is cured into a stripped type nanometer montmorillonite parent material in a compact powder form . The parent material comprises, in weight percentages, 65 to 75% of montmorillonite and 25 to 35% of epoxy compound. The method has the advantages of simplicity and low cost. The parent material prepared by the method has high montmorillonite content, and distance among montmorillonite layers is 3.5 nm to 10.0 nm. The parent material can be used as modified materials of general plastics, such as polyvinyl chloride and polyolefin, and engineering plastics, such as polycarbonate.
Description
Technical field
The invention belongs to technical field of composite materials, specifically relate to a kind of technology of preparing of the nano imvite that can be used for plastics and the nano montmorillonite masterbatch of this method preparation thereof.
Background technology
1. polynite treatment technology present situation
Polynite or title wilkinite, its theoretical construct formula is: Na
x(H
2O)
4{ (Al
2-xMg
x) [Si
4O
10] (OH)
2.Polynite belongs to the clay mineral of 2: 1 configuration 3-tier architectures, its structure cell is made up of 1 layer of alumina octahedral of 2 layers of silicon-oxy tetrahedron therebetween, and tetrahedron relies on common Sauerstoffatom to link with octahedra, forms thick 0.96nm, the accurate two-dimentional wafer of about 100～1000 high-sequentials of flakiness ratio, the structure cell parallel stacked.Isomorphous substitution phenomenon in the polynite is very general, the Si in the lattice
4+, Al
3+Easily by other low price ionic replacement, the unit crystal layer has more negative charge, can adsorb the equivalent positively charged ion.The positively charged ion that may exist between crystal layer has Mg
2+, Ca
2+, Na
+, K
+, H
+And Li
+Deng.Positively charged ion in the polynite crystal layer all has commutative performance, can be by other organic or inorganic cationic exchange, and tradable positively charged ion amount is called cation exchange capacity (CEC) in the polynite crystal layer.
Kind, content according to exchangeable cation between the polynite crystal layer are divided into sodium-based montmorillonite, calcium-base montmorillonite and natural bleaching soil with natural montmorillonite.If when common a certain ionic exchange capacity accounts for the total exchange capacity of polynite over half, then be referred to as the polynite of this radical ion, as sodium-based montmorillonite, calcium-base montmorillonite, natural bleaching soil then is to be H with the exchange cation
+, Al
3+Determine.The physicochemical property of polynite and Technology depend primarily on its contained exchangeable cation kind and content, so must carry out water to natural montmorillonite purifies, improve the cation exchange capacity of polynite, the polynite cation exchange capacity that is applicable to composite modification is the purification polynite of 80～130mmol/100g.
With a large amount of inorganic cations, organism is exophilicity between the polynite crystal layer.Because inorganic cation has commutative performance, available organic cation exchange inorganic cation makes organ-mmt.Organic montmorillonoid with as the organic polymer or the organic low molecular compounds of intercalator good affinity is arranged, promptly organic compound can more easily insert the interlayer of organo montmorillonite.Organic cation exchange material commonly used is a long-chain fat alkane quaternary ammonium salt, as quaternary ammonium salts such as hexadecyl, octadecyl, two octadecyls.After polynite was handled through organising, interlamellar spacing increased, and X-ray diffraction (XRD) is analyzed, and interlamellar spacing can increase to more than the 1.5nm.The latest developments of " Chinese non-metallic mineral industry guide " the 6th phase of calendar year 2001 " wilkinite organises, nano combined research and utilize progress " a series of organobentonite nano composite material of literary composition report research, wherein introduce (Proceedings of the AmericanSociety for Composites such as Lan, 1996) systematically studied Resins, epoxy-polynite system, utilize hydro-thermal synthetic method, adopt different chain length alkylamine positively charged ion [CH
3(CH
2)
nNH
+ 3 n＞8] and the polynite mineral with different surfaces electric density synthesized the organo montmorillonite of modified montmorillonite interlayer surface.Introduced in " environmental science " 2000 the 7th phases " performance of male-female ion organobentonite Adsorption of Aniline in Water, phenol " literary composition with sodium lauryl sulphate and mixed with long carbochain cats product cetrimonium bromide, bromination tetradecyl benzyl dimethyl ammonium, octadecyl trimethyl ammonium bromide respectively, made a series of male-female ion organo montmorillonites.
The applicant is 03137638.X at number of patent application, name is called in the patent application of " masterbatch of a kind of high organo montmorillonite content and preparation method thereof " and has proposed to utilize epoxy oligomer modified quaternary ammonium salt organo montmorillonite, the masterbatch of the high organo montmorillonite content of preparation intercal type.According to the loading capacity of polynite, different organic cations and different treatment processs, organic cation has different arrangement modes between the polynite crystal layer, mainly contain: monolayer alignment, dual layer arrangement and tiltedly upright the arrangement.
Polynite through organising and handling, because the bigger organic cation of volume has exchanged original metallic cation, interlamellar spacing increases, and is covered by organic cation because of sheet surfaces simultaneously, the wetting ability of polynite becomes lipophilicity.When organic montmorillonoid and monomer or mixed with polymers, the laminate structure of polynite and transport property thereof and expansile characteristics, monomer and polymer molecule further swell the cheating engaging layer spacing between the interlayer migration and interposed layer of organo montmorillonite, obtain intercalation composite material.
The intercalation object enters polynite, and the result makes polynite primary particle size be stripped from into nanoscale from micro-meter scale, and is dispersed in the polymeric matrix, realizes compound on nanoscale of polymkeric substance and montmorillonite layer.Polynite is peeled off and homodisperse is the key that the montmorillonite intercalation method prepares nano composite material, at present the preparation of widespread use have a nylon/montmorillonoid thermoplasticity nano composite plastics of high strength, high-modulus, high heat distortion temperature and excellent barrier properties.The research that utilizes the intercalation method to prepare polynite/thermoset ting resin composite also receives publicity in recent years, and wherein compound with Epoxy Resin, unsaturated polyester/montmorillonite Composite is typical case's representative.The direct graft process of polymkeric substance can obtain good intercalation effect, reaches polynite and fully is dispersed in purpose in the matrix with the nano level lamella; Solution intercalation is restricted because of the organic solvent that is difficult to find polymkeric substance to be fit to.The Qiao Fang of the Chinese Academy of Sciences etc. introduce in " polymer circular " 1997 the 3rd phases " preparation of polyamide-clay matrix material, structural characterization and performance study " literary composition and utilize polymeric amide and polynite to prepare the polyamide/montmorillonite nano composite material, and polynite is dispersed in the polyamide substrate with nanoscale.Chinese Academy of Sciences's chemistry place patent publication No. is CN1289786A, and the patent application of " a kind of in-situ inserted polymerization process for preparing of nm-class montmorillonite filled polyolefine " that name is called discloses the method that a kind of in-situ inserted polymerization is equipped with the direct filled polyolefin of nano imvite.Patent publication No. is CN1374346A, and the application for a patent for invention that name is called " a kind of compound containing nano montmorillonoid and preparation method thereof " discloses the preparation method of a kind of nano imvite/Aethoxy Sklerol or polyalcohols fat complexes.At present, aspect the selection and complete processing of material, main development trend is a fusion intercalation in the direct graft process of polymkeric substance.
2. have the deficiency of polynite treatment technology now
The common technical process that organ-mmt is handled is:------water alkyl quaternary ammonium salts intercalation---dehydrates---nano imvite to natural montmorillonite in the water purification, common methods is a wet method, be dispersion medium exactly with water, with polynite slurrying, after sorting purification, remodeling and the activation, carry out permutoid reaction with quaternary ammonium salt cationic, after filtration, drying, abrasive dust, sieving obtains the organo montmorillonite product.This treatment process complex process, long reaction time, energy consumption is many, and the products production cost is higher, and the interlamellar spacing of organo montmorillonite is generally between 1.5nm-4.0nm.
The applicant is 03137638.X at number of patent application, and name is called and proposes to utilize epoxy oligomer modified quaternary ammonium salt organo montmorillonite in the patent application of " masterbatch of a kind of high organo montmorillonite content and preparation method thereof ", preparation intercal type organo montmorillonite.Organo montmorillonite content is more than 50%, and the cheating engaging layer spacing is greater than 3.5nm.Its technical process is: the alkyl quaternary ammonium salts organic montmorillonoid---the epoxy oligomer modification is handled.Masterbatch is an intercal type, need prepare exfoliated matrix material by polymer molecular chain being used between crystal layer in plastic milling apparatus.
Use the quaternary ammonium salt organo montmorillonite and prepare nano composite material, utilize the intercalation method, polynite can be in resin by intercalation with peel off, reach nano level and disperse, as the nylon/montmorillonoid nano composite material etc.But the thermostability that shows organo montmorillonite in resins such as polyvinyl chloride and polycarbonate is very poor, and in general plastic milling apparatus, under the high temperature high shear, quaternary ammonium salt easily decomposes variable color, and the matrix material that is not easy to be peeled off fully.
Summary of the invention
It is that epoxy compounds replaces alkyl quaternary ammonium salts as intercalator that the present invention adopts a kind of low molecular activity oligopolymer, selects purification polynite (sodium base or calcium base) for use, uses solid phase intercalation technique proposed by the invention and prepares exfoliated nano montmorillonite masterbatch.This method complete processing is simple, cost is low; The nano imvite stable performance, applied range.
A kind of solid phase intercalation preparation method of nano imvite, after epoxy compounds and purification polynite mixed, under 150 ℃ of-200 ℃ of temperature condition, mixing through the powerful shearing of two rollers, twin screw or Banbury mixer, be solidified into the exfoliated nano montmorillonite masterbatch of closely knit powdery.
Its technical process: purification polynite (sodium base or calcium base)---epoxy compounds solid phase intercalation processing---nano montmorillonite masterbatch.
Described purification polynite is the polynite of cation exchange capacity 80-120mmol/100g, and polynite purity is more than 90%, interlamellar spacing 1.0nm-1.5nm.
Described epoxy compounds is: bisphenol A epoxide resin, linear novolac epoxy, brominated bisphenol A Resins, epoxy and end group contain the simple function or the polyfunctional group organic compound of epoxide group.
Epoxy compounds can form the reactive organic cation of unstable state under conditions such as high temperature, and the positively charged ion between the polynite crystal layer carries out cationic exchange, inserts between the polynite crystal layer; Autohemagglutination takes place in epoxy compounds between the polynite crystal layer, further enlarge the interlamellar spacing of polynite, forms exfoliated nano imvite, and the interlamellar spacing of nano imvite can be between 3.5nm-10.0nm.
A kind of nano montmorillonite masterbatch prepared according to the methods of the invention, it consists of: (by weight percentage)
Polynite: 65%-75%
Epoxy compounds: 25%-35%
The nano imvite of the inventive method preparation, it is exfoliated that interlayer is, polynite content 65%-75%, cheating engaging layer spacing 3.5nm-10.0nm.Can be applicable to material modified as general-purpose plastics such as polyvinyl chloride, Polyolefin and engineering plastics such as polycarbonate.In general plastic milling apparatus, add material of the present invention, can prepare the high-performance nano montmorillonite composite material.Add the material modified of nano imvite of the present invention, through XRD (X-ray diffraction) test, 001 diffractive features peak does not appear in 2 θ angles in 1-15 °, illustrates that this exfoliated nano imvite reaches nano level substantially and disperses in macromolecular material.
Description of drawings
Fig. 1 adopts the XRD figure of the proportioning of embodiment 1 for the present invention;
Fig. 2 adopts the XRD figure of the proportioning of embodiment 2 for the present invention;
Fig. 3 adopts the XRD figure of the proportioning of embodiment 3 for the present invention;
Fig. 4 is the material modified XRD figure of UPVC that is added with the masterbatch of 5 parts of embodiment of the invention 1;
Fig. 5 is the material modified XRD figure of UPVC that is added with the masterbatch of 8 parts of embodiment of the invention 1;
Fig. 6 is the material modified XRD figure of PP that is added with the 15 parts of embodiment of the invention 2 masterbatch;
Fig. 7 is the material modified XRD figure of PC that is added with 5 parts of masterbatch of the present invention.
Embodiment
Embodiment 1:
75 parts of sodium-based montmorillonites; 25 parts of the bisphenol A type epoxy resins of oxirane value 0.4-0.5 join surface temperature and are in 150 ℃-170 ℃ the double roll mill, after powerful mixing 15-20 minute, obtain a kind of closely knit powder-like product, through XRD analysis, the cheating engaging layer spacing is greater than 7.0nm, as shown in Figure 1.
Embodiment 2:
75 parts of sodium-based montmorillonites; 25 parts of the bisphenol A type epoxy resins of oxirane value 0.2-0.3 join in the double roll mill of 150 ℃-170 ℃ of surface temperatures, after powerful mixing 15-20 minute, obtain a kind of closely knit powder-like product, and through XRD analysis, the cheating engaging layer spacing is greater than 8.0nm, as shown in Figure 2.
Embodiment 3:
67 parts of sodium-based montmorillonites; 33 parts of the bisphenol A type epoxy resins of oxirane value 0.4-0.5 joined in the double roll mill of 150 ℃-170 ℃ of surface temperatures, after powerful mixing 10-15 minute, obtain a kind of closely knit powder-like product, through XRD analysis, the cheating engaging layer spacing reaches 10.0nm, as shown in Figure 3.
Embodiment 4:
75 parts of calcium-base montmorillonites; 25 parts of brominated bisphenol a type epoxy resin, joining barrel temperature profile is in 150 ℃ of-200 ℃ of twin-screw mixer machines, extrudes through mixing, obtains a kind of closely knit powder-like product, through XRD analysis, the cheating engaging layer spacing reaches 8.0nm.
Embodiment 5:
67 parts of calcium-base montmorillonites; 33 parts of the bisphenol A epoxide resins of oxirane value 0.4-0.5, joining temperature is in 150 ℃ of-170 ℃ of Banbury mixeies, mixing 5-8 minute, obtain a kind of closely knit powder-like product, through XRD analysis, the cheating engaging layer spacing reaches 8.0nm.
Application examples 1:
The exfoliated nano imvite of example 1 is joined respectively in 100 parts of UPVC Preblendes for 5 parts and 8 parts, on 170 ℃ of double roll mills mixing 10 minutes, colour-change does not appear in the PVC sheet material, mixing 10 minutes pulling-on pieces, through the XRD test, as Fig. 4,5,2 θ angles 001 diffractive features peak does not appear in 1-15 °, illustrate that polynite peels off fully in UPVC, be nano level substantially and disperse.And directly add untreated quaternary ammonium salt organo montmorillonite under similarity condition, carry out mixing, PVC sheet material flavescence blackout.
Application examples 2:
15 parts of the exfoliated nano imvites of example 2 are joined in 100 parts of transparent PP material that contain 5 parts of PP-g-MAH,, do not change the transparency of PP substantially through single screw mixing.Through compressing tablet sampling, the XRD test, as shown in Figure 6,001 diffractive features peak does not appear in 2 θ angles in 1-15 °, illustrate that polynite peels off in PP fully, is the nano level dispersion substantially.
Application examples 3:
5 parts of the exfoliated nano imvites of example 3 are joined in 100 parts of PC material that contain 5 parts of PP-g-MAH, through the twin-screw mixer extruding pelletization, material is tested through XRD, as shown in Figure 7,001 diffractive features peak does not appear in 2 θ angles in 1-15 °, illustrate that polynite peels off fully in PC, be nano level substantially and disperse.
Claims (4)
1. the solid phase intercalation preparation method of a nano imvite, it is characterized in that: after epoxy compounds and purification polynite are mixed, under 150 ℃ of-200 ℃ of temperature condition, mixing through the powerful shearing of two rollers, twin screw or Banbury mixer, be solidified into the exfoliated nano montmorillonite masterbatch of closely knit powdery.
2. the solid phase intercalation preparation method of a kind of nano imvite according to claim 1 is characterized in that: described epoxy compounds is that bisphenol A epoxide resin, linear novolac epoxy, brominated bisphenol A Resins, epoxy and end group contain a kind of in the simple function of epoxide group or the polyfunctional group organic compound.
3. a kind of nano montmorillonite masterbatch of preparation method's preparation according to claim 1, its weight percent consists of:
Polynite: 65%-75%
Epoxy compounds: 25%-35%.
4. a kind of nano montmorillonite masterbatch according to claim 3, its weight percent consists of:
Polynite: 65%-75%
Bisphenol A type epoxy resin: 25%-35%.
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| CN100451068C (en) * | 2005-12-02 | 2009-01-14 | 中国科学院金属研究所 | Epoxy/layersilicate hano composite material, and its preparing method |
| FR2908776B1 (en) * | 2006-11-21 | 2009-04-24 | Centre Nat Rech Scient | PROCESS FOR PREPARING NANOCOMPOSITE RIGID MATERIAL |
| CN103897144A (en) * | 2012-12-26 | 2014-07-02 | 江南大学 | Method used for preparing nano composite epoxy curing agent via depolymerization of PET with glycerine |
| CN115449216B (en) * | 2022-08-30 | 2023-09-05 | 浙江工业大学 | Preparation method of high-strength high-toughness PA66/GF |
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