CN1202139C - Preparation method of polymer/layered silicale nano in tercalation composite material - Google Patents
Preparation method of polymer/layered silicale nano in tercalation composite material Download PDFInfo
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- CN1202139C CN1202139C CNB031397859A CN03139785A CN1202139C CN 1202139 C CN1202139 C CN 1202139C CN B031397859 A CNB031397859 A CN B031397859A CN 03139785 A CN03139785 A CN 03139785A CN 1202139 C CN1202139 C CN 1202139C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229920000642 polymer Polymers 0.000 title abstract description 15
- 239000002131 composite material Substances 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 31
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 150000004760 silicates Chemical class 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims description 15
- 235000012222 talc Nutrition 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- -1 polynite Substances 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 238000005502 peroxidation Methods 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 description 17
- 230000002687 intercalation Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 239000002114 nanocomposite Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 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 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282326 Felis catus Species 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
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000013339 polymer-based nanocomposite Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention belongs to the technical field of nanometer intercalated composite materials, and discloses a fine new preparation method for polymer/layer silicate nanometer intercalated composite materials. The method is characterized in that monomers and layer silicates are adopted for synthesis under the action of an initiator, and synthetic processes are carried out among supercritical carbon dioxide at the reaction temperature of 31.2 to 200 DEG C under the reaction pressure of 7.5 to 150MPa. The method proposed by the present invention has the advantages of simplicity, easy realization, better heat radiation of the system, steady reaction, difficulty in the occurrence of implosion, safety, practicality, no necessity for solvent recovery devices, easy separation and purification of final products and no necessity for washing or drying devices or a great amount of thermal energy consumption, and the layer silicates in the prepared composite material can be dispersed at nanometer level.
Description
Technical field the present invention relates to nano intercalated field of compound material, especially the preparation method of the nano intercalated matrix material of polymer/laminated silicate.
The technical background nano composite material be meant the one or more components in the compound system have at least one dimension with nano-scale (≤100nm) be evenly dispersed in the matrix of another component, thereby obtain so-called nano composite material.Owing to have superfine nanophase farmland size in the composite structure, and the nanoparticle specific surface area is big, the surface energy height, so its performance has the raising of highly significant than corresponding macroscopic view or micron order matrix material, even qualitative leap appears, show brand-new performance or function, as high strength, high-modulus, high tenacity, high heat resistance, high transparent, high conductivity, high barrier to oils and gas, the contraction of minimizing material and warpage etc., some is also in magnetic, optical property, aspects such as chemically reactive present diversified excellent specific property, and all these advantages all are to obtain under the condition of not obvious raising mixture density.Disperse blend method to prepare polymer based nanocomposites owing to the reunion of inorganic nanometer-powder self, in the high-viscosity polymer matrix, be difficult to homodisperse and inorganic disperse phase combines technical barriers such as weak with organic polymer matrix boundary face with the fusion of routine, solution, be difficult to obtain the nano composite material of application prospect.Since Japan's report in 1987 prepares nylon 6/ clay nano hybrid materials with the intercalation polymeric method, realized inorganic nano phase homodisperse, inorganic/organic strong interface structure, self-assembly and had than conventional polymer/incomparable advantage of inorganic fillers matrix material, therefore, the polymer/laminated silicate matrix material receives much concern, and becomes a class matrix material very promising in the nano composite material.
Intercalation compounding is the method for preparing nano composite polymer/laminated silicate material.At first monomer or polymkeric substance are inserted between the layered silicate lamella after the intercalator processing, and then destroy the laminated structure of silicate, make it peel off into thick be 1nm, the length * wide 100 * 100nm of being
2Elementary cell, and be dispersed in the polymeric matrix, to realize compound on nanoscale of polymer and clay.According to the compound process, intercalation compounding can be divided into two big classes.(1) intercalation polymeric method promptly enters polymer monomer dispersion, intercalation in the layered silicate lamella earlier, then in-situ polymerization, a large amount of heats of emitting when utilizing polymerization, overcome the Coulomb's force of silicate plate interlayer, it is peeled off, thereby make the silicate lamella mutually compound with nanoscale with polymeric matrix; (2) polyalcohol intercalation is about to polymer melt or solution and mixes with layered silicate, utilizes power chemistry or thermodynamics effect to make layered silicate peel off into the lamella of nanoscale and be dispersed in the polymeric matrix.
According to the difference of polyreaction type, intercalation polymeric also can be divided into two types of intercalation polycondensation and intercalation addition polymerizations, and polyalcohol intercalation then can be divided into two kinds of polymers soln intercalation and polymer melt intercalations.The polymers soln intercalation be the polymer macromolecule chain intercalation enters the silicate plate interlayer of polynite by means of solvent in solution, and then volatilization removes and to desolvate.This mode needs suitable solvent to come dissolve polymer and dispersed clay simultaneously, and the difficult recovery of a large amount of solvents, and is unfavorable to environment.To be polymkeric substance heat being higher than under its softening temperature the polymer melt intercalation, and directly intercalation enters the silicate plate interlayer of polynite under quiescent conditions or shear action.Advantages such as the polymer melt graft process is not owing to need organic solvent, and technology is simple, and is environmentally friendly have caused people's interest.
Summary of the invention the purpose of this invention is to provide the preparation method of the nano intercalated matrix material of a kind of polymer/laminated silicate, and different with in the past method, it is to utilize super critical CO 2 technology to prepare nano composite polymer/laminated silicate material.This method reacting balance is difficult for implode, and reaction medium is a carbonic acid gas, and cheapness is nontoxic, pollution-free, does not have incendiary danger, the easy purifying of polymerisate, and also most of product is pressed powder, storage, transportation and extremely easy to use.
Method provided by the invention is to soak layered silicate with monomer and initiator, the modes such as absorption, infiltration that make it enter between the synusia, initiated polymerization in supercritical CO 2 medium, expansion by the polymkeric substance that generates between the superpower dissolving of supercritical co and osmosis and the synusia struts synusia, make layered silicate reach nano level and disperse, form good nano composite material.
The method for preparing the nano intercalated matrix material of polymer/laminated silicate provided by the invention is to adopt monomer and layered silicate synthetic under initiator, building-up process is carried out in supercritical co, 31.2～200 ℃ of temperature of reaction, reaction pressure 7.5～150MPa.
Consider that from aspects such as conversion units wherein temperature of reaction is preferred 31.2～100 ℃, the preferred 7.5～40MPa of reaction pressure.
The monomer that synthetic polymer among the present invention/phyllosilicate nano intercalation composite material uses, layered silicate, initiator etc. all can be monomer used in the prior art, layered silicate, initiator etc.Monomer can be selected from water-soluble monomer and/or oil-soluble monomer, water-soluble monomer such as acrylamide, vinyl ether, propylene ether, vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, maleic anhydride; Oil-soluble monomer such as vinyl acetate, vinyl cyanide, vinylbenzene, ethene soya-bean oil ester, ester group carbon number are 2～40 acrylate and/or methacrylic ester, also can be that 1～50 siliceous and/or fluorine-containing ester group carbon number is 2～40 acrylate and/or methacrylic ester for the number of silicon and/or fluorine.Nano composite polymer/laminated silicate material among the present invention can be that above various monomer itself is composited with layered silicate, also can be to be composited with layered silicate after multiple monomer mixes again.
Layered silicate can be selected from kaolin, polynite, mica, talcum, marlstone and their modifier etc., especially kaolin, polynite and their modifier.The modifier of layered silicate generally is that layered silicate carries out modification by cats product.Consumption is generally 0.1%～50% of monomer weight, and preferred 1%～10%.
Initiator can be selected from azo-compound, superoxide, persulphate, oxidation-reduction system, as Diisopropyl azodicarboxylate (AIBN), and 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide (BPO), peroxidation two acyls, Potassium Persulphate, ammonium persulphate or the like.Consumption is generally 0.01%～15% of monomer weight, and preferred 0.1%～10%.
The method for preparing nano composite polymer/laminated silicate material in the supercritical CO 2 medium provided by the invention specifically may further comprise the steps:
(a) take by weighing a certain amount of water-soluble monomer and/or oil-soluble monomer, layered silicate, initiator, etc. join in the reactor.
(b) sealing is squeezed into CO with pump
2Gas is forced into certain value, fastens terminal valve then, heating.
(c) be warming up to temperature required, as less than required pressure the time, restock CO
2Gas.Start agitator, the reaction certain hour.
(d) carry out situation by the pressure change monitoring reaction, after final system pressure no longer changed, reaction finished.
(e) naturally cool to room temperature, open air outlet valve, slowly reduce to normal pressure.
(f) utilize the supercritical co extracting 2～3 times, remove unreacted monomer, initiator etc.
(g) collect product.
Among the present invention in the supercritical carbon dioxide systems spendable polymerization process have: mass polymerization and solution polymerization (can add cosolvent).
Method provided by the invention is compared with ordinary method, has following characteristics:
(1) the system heat radiation better.Because the spread coefficient of supercritical co is bigger hundreds of times than liquid, thus it can be preferably with the transfer of heat that produces in the system in external environment, be difficult for taking place implode.
(2) medium of present method use is a carbonic acid gas, and cheapness is easy to get, and is nontoxic, pollution-free, do not have incendiary danger, also do not need solvent reclaimer.And the supercritical temperature of carbonic acid gas is 31.1 ℃, and pressure is 7.4MPa, reaches than being easier to, and is not high to equipment requirements.
(3) the easy purifying of polymerisate.Supercritical co becomes gas by decompression, be easy to separate with product, has save the last handling process that uses the complexity that conventional solvent brings fully.The monomer, initiator etc. of reaction final residue can by supercritical co repeatedly extracting remove, can directly obtain purified polymerisate.
(4) most of polymerisate is a pressed powder, easily separated purifying, thereby do not need to wash drying plant and a large amount of heat energy consumptions, and storage, transportation and extremely easy to use.
Present method prepares in the nano composite polymer/laminated silicate material system, and polymer molecule enters between the silicate synusia in a large number, causes the silicate synusia to be strutted, and the interaction force between the synusia weakens or disappears.The silicate synusia exists with more unordered tangleweed, and the distance between the silicate synusia can form good nano composite material by expanding 2～15nm to about original 1nm.
Preferred forms
Umber in following examples by weight.
Embodiment 1
With 100 parts of acrylamides, 2 parts of sodium-based montmorillonites, 1 part of Diisopropyl azodicarboxylate is put into reactor, and sealing is squeezed into CO with pump
2Gas is forced into 8MPa, fastens terminal valve then, heating.Be warming up to 63 ℃, start agitator, reacted 10 hours.Reaction naturally cools to room temperature after finishing.Open air outlet valve, slowly reduce to normal pressure, product is a white powder.The result of X-ray diffraction and transmission electron microscope shows that the distance between montmorillonite layer is 10.2nm.
Embodiment 2
Act on 8 hours with vinyl etamon chloride and talcum down at 80 ℃ earlier, be inserted in the talcum, make the modification talcum by cationic exchange.Then, with 100 parts of vinylbenzene, 10 parts of modification talcums, 8 parts of dibenzoyl peroxide are put into reactor, and sealing is squeezed into CO with pump
2Gas is forced into 10MPa, fastens terminal valve then, heating.Be warming up to 80 ℃, start agitator, reacted 7 hours.Reaction naturally cools to room temperature after finishing.Open air outlet valve, slowly reduce to normal pressure, take out product, handle obtaining solid matter with vinylbenzene-methyl alcohol method.The result of X-ray diffraction and transmission electron microscope shows that the distance of talcum sheet interlayer is 3.6nm.
Embodiment 3
Act on 8 hours with ethenylphenyl trioctylphosphine ammonium chloride and polynite down at 80 ℃ earlier, be inserted in the polynite, make modified montmorillonoid by cationic exchange.Then, with 100 parts of Isooctyl acrylate monomers, 15 parts of methylene-succinic acids, 30 parts of modified montmorillonoids, 5 parts of Diisopropyl azodicarboxylates are put into reactor, and sealing is squeezed into CO with pump
2Gas is forced into 10MPa, fastens terminal valve then, heating.Be warming up to 80 ℃, start agitator, reacted 10 hours.Reaction naturally cools to room temperature after finishing.Open air outlet valve, slowly reduce to normal pressure, product is a white powder.The result of X-ray diffraction and transmission electron microscope shows that the distance between montmorillonite layer is 5.2nm.
Embodiment 4
With 100 parts of vinylformic acid, 4 parts of kaolin, 2.5 parts of Diisopropyl azodicarboxylates are put into reactor, and sealing is squeezed into CO with pump
2Gas is forced into 7.5MPa, fastens terminal valve then, heating.Be warming up to 60 ℃, start agitator, reacted 8 hours.Reaction naturally cools to room temperature after finishing.Open air outlet valve, slowly reduce to normal pressure, product is a white powder.The result of X-ray diffraction and transmission electron microscope shows that the distance of kaolin sheet interlayer is 5.7nm.
Embodiment 5
Act on 8 hours with ethenylphenyl trimethyl ammonium chloride and mica down at 80 ℃ earlier, be inserted in the mica, make modified micaceous by cationic exchange.Then, with 100 parts of vinyl cyanide, 20 parts of methacrylic acids, 0.2 part of dibenzoyl peroxide, 6 parts of modified micaceous reactors of putting into, sealing is squeezed into CO with pump
2Gas is forced into 10MPa, fastens terminal valve then, heating.Be warming up to 80 ℃, start agitator, reacted 7 hours.Reaction naturally cools to room temperature after finishing.Open air outlet valve, slowly reduce to normal pressure, take out product, handle obtaining solid matter with vinylbenzene-methyl alcohol method.The result of X-ray diffraction and transmission electron microscope shows that the distance between mica splittings is 3.1nm.
Claims (9)
1, the preparation method of the nano intercalated matrix material of a kind of polymer/laminated silicate, adopt monomer and layered silicate synthetic under initiator, it is characterized in that building-up process carries out 31.2～100 ℃ of temperature of reaction, reaction pressure 7.5～40MPa in supercritical co.
2, the process of claim 1 wherein that monomer is selected from water-soluble monomer and oil-soluble monomer.
3, the method for claim 2, wherein water-soluble monomer is selected from acrylamide, vinyl ether, propylene ether, vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, maleic anhydride; It is that the number of 2～40 acrylate and methacrylic ester, silicon and/or fluorine is that 1～50 siliceous and/or fluorine-containing ester group carbon number is 2～40 acrylate and methacrylic ester that oil-soluble monomer is selected from vinyl acetate, vinyl cyanide, vinylbenzene, ethene soya-bean oil ester, ester group carbon number.
4, claim 1 or 2 method, wherein layered silicate is selected from kaolin, polynite, mica, talcum, marlstone and their modifier, consumption is 0.1%～50% of a monomer weight.
5, the method for claim 4, wherein layered silicate is selected from kaolin, polynite and their modifier.
6, the method for claim 4, wherein the consumption of layered silicate is 1%～10% of a monomer weight.
7, claim 1 or 2 method, wherein initiator is selected from azo-compound, superoxide, persulphate, oxidation-reduction system, and consumption is 0.01%～15% of a monomer weight.
8, the method for claim 7, wherein initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxidation two acyls, Potassium Persulphate, ammonium persulphate.
9, the method for claim 7, wherein the consumption of initiator is 0.1%～10% of a monomer weight.
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| CN100386365C (en) * | 2006-05-30 | 2008-05-07 | 武汉理工大学 | Inorganic mineral-proton conduction resin intercalation composite proton exchange membrane, and its preparing method |
| CN102604388B (en) * | 2012-03-22 | 2013-11-13 | 北京化工大学 | Low-compressive-deformation and high-conductivity rubber composite material and preparation method thereof |
| CN103539141B (en) * | 2013-10-23 | 2015-08-26 | 江苏麒祥高新材料有限公司 | Kaolin of a kind of methacrylic acid metal salt intercalation modifying and preparation method thereof |
| CN105294911A (en) * | 2015-11-30 | 2016-02-03 | 桂林市和鑫防水装饰材料有限公司 | Preparation method of styrene-butyl acrylate/montmorillonoid composite emulsion |
| CN106832568B (en) * | 2016-12-21 | 2019-02-12 | 湖南登科材料科技有限公司 | A kind of enhancement filling plastic lubrication masterbatch and preparation method thereof |
| CN107892408A (en) * | 2017-10-10 | 2018-04-10 | 华北理工大学 | A kind of farmland agricultural chemicals waste water purification method |
| CN108164752A (en) * | 2018-01-26 | 2018-06-15 | 刘成旭 | The PVC cable material fire retardant prepared based on nano combined intercalation technique |
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