CN1583860A - Preparing method for high cross-linked olefinic polymer/calcium carbonate composite nanometer particle - Google Patents
Preparing method for high cross-linked olefinic polymer/calcium carbonate composite nanometer particle Download PDFInfo
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- CN1583860A CN1583860A CN 200410048033 CN200410048033A CN1583860A CN 1583860 A CN1583860 A CN 1583860A CN 200410048033 CN200410048033 CN 200410048033 CN 200410048033 A CN200410048033 A CN 200410048033A CN 1583860 A CN1583860 A CN 1583860A
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- divinyl
- calcium carbonate
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- olefinic monomer
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- 239000002131 composite material Substances 0.000 title claims abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract 18
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract 9
- 239000002245 particle Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 18
- 229920000642 polymer Polymers 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- 229920000098 polyolefin Polymers 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- -1 vinylformic acid allyl ester Chemical class 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 239000012875 nonionic emulsifier Substances 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 claims description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 2
- 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
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 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 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000002612 dispersion medium Substances 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 claims description 2
- HBRNMIYLJIXXEE-UHFFFAOYSA-N dodecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN HBRNMIYLJIXXEE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 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
- 150000003254 radicals Chemical class 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 10
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 235000010216 calcium carbonate Nutrition 0.000 abstract 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 3
- 239000011858 nanopowder Substances 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001400 nonyl 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])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
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Abstract
Preparation of highly cross-linked olefin polymer/calcium carbonate composite nano powders is carried out by: using lipophilic nano CaCO3 powders, olefin monomer and coupling agent as raw materials, and emulsion polymerizing them in water as dispersing medium with existence of emulsifier and initiator. Their weight percentage is as below: olefin monomer (54.5 - 97.8), CaCO3 powders (1 - 25), coupling agent (0.1 - 15), emulsifier (1 - 5), and initiator (0.1 - 0.5). The nano powders have CaCO3 as cores and organic olefin cross-linked net liked polymer as shells in spherical or elliptical ball with granular size distribution <100nm.
Description
Technical field
The present invention relates to a kind of highly cross-linked type olefin polymer/lime carbonate (CaCO
3) preparation method of composite nano particle, belong to polymeric material field.
Background technology
Nanometer CaCO
3Because it is cheap, have the performance of multiple excellence again, be widely used as filler in fields such as plastics, rubber, coating, printing ink.But because its surface energy height, particle is reunited easily; And the surface be alkalescence and have certain polarity, bad with the affinity of organic matrix, its use in organic phase is very limited.Usually all need its surface modification to improve its dispersiveness and consistency in organic matrix.Low molecule properties-correcting agent commonly used is stearic acid, also has vinylformic acid, condensed phosphoric acid etc. in addition, and mechanism of modification is to utilize acid and CaCO
3The Ca of particle surface
+Reaction generates salt sedimentation or is coated on CaCO
3Thereby the surface of particle changes its surface property.Except acid, coupling agent also is the properties-correcting agent of using always, such as handling CaCO with titanate coupling agent earlier
3The surface coats polystyrene on its surface again, strengthens polymkeric substance and CaCO by coupling agent
3The interface interaction on surface.At CaCO
3The surface coats one layer of polymeric, can make water-wetted surface become oleophylic on the one hand; In the application scenario of filled polymer, by the physical entanglement between the macromolecular chain, effectively therefore consistency between reinforcement filler and the matrix and boundary strength are a kind of important method of modifying on the other hand.
Preparation polymer/inorganic composite nano particle has two kinds of main methods at present, promptly coats method and grafting method.Wherein coating method is to select for use the polymkeric substance that has prepared by physical actions such as solvations, or select for use some monomer to make it on the inorganic nano-particle sub-surface, to form the method for polymer covering layer by chemical reactions such as polymerizations, but because of there not being chemical bond to connect, be easy under solvent action or shearing action, come off between this method polymer layer and the inorganic particulate surface in mechanical force; And the grafting method be select for use have can and the inorganic particulate surface or can and importing at the polymkeric substance or the monomer of the lip-deep functional group reactions of inorganic particulate, by functional group reactions or by polyreaction etc., make it to be grafted on the method that forms polymer covering layer on the inorganic nano-particle sub-surface, have stronger chemical bond to connect between polymer layer in this method and the inorganic particulate surface, thereby coating layer is difficult for coming off.Past prepare polymkeric substance/CaCO about emulsion method
3Mostly the documentation of composite particles is the CaCO at micron order or submicron order
3Particle, and cladding ratio is generally less than 100%, and finally be coated on CaCO
3Can not extractive part generally be no more than 20% in the polymkeric substance on surface.
Except above-mentioned coating method and grafting method, the polymkeric substance/CaCO of cross-linking type
3Composite particles is very rare.In fact, using linking agent to obtain firmly to coat is another kind of important method except that the grafting method, and it is different from the grafting method is to solve the problem of caving in of utilizing simple graft type or occurring when the cladded type microballoon prepares hollow ball merely.Chinese patent CN1351896 utilizes CaCO
3As the solid pore former, cooperate the liquid pore former, they are mixed the back make microballoon with monomer, linking agent, initiator by suspension polymerization, prepare the porous separating medium by ethanol extracting, acid soak, drying and other steps again.
Summary of the invention
The purpose of this invention is to provide a kind of highly cross-linked type olefin polymer/CaCO
3The preparation method of composite nano particle, the nanoparticle that adopts this method to prepare has with nanometer CaCO
3Particle is the constitutional features of shell for nuclear with organic alkene crosslinking net polymkeric substance, has spherical in shape or elliposoidal, narrow diameter distribution and less than the morphological specificity of 100 nanometers, and has highly cross-linked feature.
The highly cross-linked type olefin polymer/CaCO of the present invention
3The preparation method of composite nano particle is with CaCO
3Particle, olefinic monomer, linking agent are raw material, under emulsifying agent, the initiator existence condition, realize by letex polymerization, it is characterized in that described CaCO
3Particle dia is less than 100nm, has oil-wetted surface, described olefinic monomer is the monoene hydrocarbons that contains a carbon carbon unsaturated double-bond in the molecule, can be vinylbenzene, vinylchlorid, vinyl cyanide, acrylate, in the methacrylic ester any or several, described linking agent, can be in the coupling agent that contains a carbon carbon unsaturated double-bond in the material that contains polymerisable vinyl unsaturated link(age) more than in the molecule and the molecule at least any, the material that contains polymerisable vinyl unsaturated link(age) more than in the molecule can be 1, the 3-divinyl, the 2-methyl isophthalic acid, the 3-divinyl, 2,3-dimethyl-1, the 3-divinyl, isoprene, 2-chloro-1, the 3-divinyl, Vinylstyrene, the divinyl naphthalene, glycol diacrylate, ethylene glycol dimethacrylate, the vinylformic acid allyl ester, Viscoat 295, trimethylolpropane trimethacrylate, iso-cyanuric acid triallyl ester, polyhutadiene, the divinyl silane compound, at least contain in diallylsilane compound and the molecule in the lower molecular weight organopolysiloxane of two vinyl any or several, at least the coupling agent that contains a carbon carbon unsaturated double-bond in the molecule can be silane type, aluminic acid ester type, borate-type, in the titanic acid ester type coupling agent any or several, described emulsifying agent is cationic and compound system nonionic emulsifier, cationic emulsifier can be dodecyl chlorination ammonium, the dodecyl ammonium acetate, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, in the hexadecyl pyridinium bromide any or several, nonionic emulsifier can be C
3-10Alkylphenol-polyethenoxy (4～50) ether, C
2～18Aliphatic alcohol polyethenoxy (4～50) ether, polyoxyethylene (4～50) sorbyl alcohol list C
11～18Fatty acid ester, polyoxyethylene (4～50) sorbyl alcohol three C
11～18In the fatty acid ester any or several, described initiator is can be under 40～95 ℃ of conditions, have 105～150kJ/mol ionic dissociation energy and can produce free radical and cause olefinic monomer polymeric material, this material can be in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the dibenzoyl peroxide any, its polymerization process is to be the letex polymerization of dispersion medium with water, during polymerization, olefinic monomer, CaCO
3The weight percent of particle, linking agent, emulsifying agent, each component of initiator is:
Olefinic monomer: 54.5～97.8%
CaCO
3Particle: 1～25%
Linking agent: 0.1～15%
Emulsifying agent: 1～5%
Initiator: 0.1～0.5%
Concrete preparation process of the present invention is as follows:
(1) with CaCO
3Particle joins and makes it in the olefinic monomer to mix and be uniformly dispersed;
(2) said mixture is joined contain deionized water, emulsifying agent and initiator and be warmed up in advance in 40 ℃ the reactor, and make it to be warming up to 70～95 ℃ temperature range internal reaction 0.5～10 hour;
(3) linking agent can add reactor with olefinic monomer in step (1), also can adopt continuous processing or semi-continuous process to add in reaction beginning back, and the present invention preferentially selects single stage method for use;
(4) behind the cooling discharging, can obtain the highly cross-linked type olefin polymer/CaCO of emulsion state
3The composite nano particle also can carry out breakdown of emulsion, washing, drying treatment to emulsion, thereby obtains the highly cross-linked type olefin polymer/CaCO of pulverulence
3The composite nano particle.
The present invention compared with prior art has some advantages and high-lighting effect: a kind of highly cross-linked type olefin polymer/CaCO that the present invention proposes
3Composite nano particle, overall yield of reaction about 80%, can not extractive amount of polymers about 90%, all be higher than the present report that can see pertinent literature or patent.After finishing, preparation both can remain on emulsion state, also can be dry and remain on pulverulence, but no matter remain on which kind of state, its composite nano particle all will have with nanometer CaCO
3Particle is nuclear, with organic alkene crosslinking net polymkeric substance is the constitutional features of shell, has spherical in shape or elliposoidal, narrow diameter distribution and less than the morphological specificity of 100 nanometers, and has highly cross-linked feature, can directly use, also can further be prepared into the hollow ball shaped nanometer particle and use.This method can not only solve the low and low problem of grafting efficiency of percentage of grafting that simple graft type nanoparticle exists in preparation, and overcome fundamentally that the coating layer that simple in the past cladding nanometer particle in use exists is easy to come off, the problem of coalescence easily between thermotolerance, poor solvent resistance and the particle, the more important thing is, can solve the problem or the like of caving in that occurs when utilizing simple graft type or simple cladding nanometer particle preparation hollow ball shaped nanometer particle.Simple to operate in the preparation, easily realize suitability for industrialized production, the crosslinked composite nano particle of making can stably remain on emulsion state, also can be dried to pulverulence, be easy to store and use, in from now on nanometer material science and technical development, have purposes widely.
Description of drawings
Fig. 1 is polystyrene/CaCO
3Cross-linking type composite nanoparticle Electronic Speculum figure
Embodiment:
Embodiment 1: add the 60ml deionized water in the four-hole bottle that mechanical stirring, reflux condensing tube, nitrogen protection and thermometer are housed; 0.5g cetyl trimethylammonium bromide and 0.1g Nonyl pheno (10) ether; be warming up to 40 ℃; after the stirring and dissolving, adding the 2g median size is the CaCO with oil-wetted surface of 40nm
3The mixture of particle and 15ml styrene monomer, 0.68g trimethylolpropane trimethacrylate (TMPTMA), 0.1g Diisopropyl azodicarboxylate is warming up to 80 ℃, reacts after 1～2 hour, is warming up to 90 ℃ again, continues reaction 0.5～1 hour, cooling discharging.Part emulsion after the discharging gets the white powder product after breakdown of emulsion, washing, drying, overall yield of reaction is 76% as calculated, uses the dimethylbenzene extracting after 12 hours on exsiccant composite nano particle, and recording it can not extractive amount of polymers be 99%.From the electron micrograph of Fig. 1 composite nano particle as can be seen, its particle diameter mainly is distributed in 50～70nm scope.In addition, the cross-linking type composite nanoparticle soaked 24 hours with excessive dilute hydrochloric acid after, CaCO
3Nuclear is removed and the mode of appearance of particle does not change, and obtains hollow nanoparticle, and this hollow Nano particle can keep original dispersing morphology and particle diameter.
Embodiment 2: add the 60ml deionized water in the four-hole bottle that mechanical stirring, reflux condensing tube, nitrogen protection and thermometer are housed; 0.07g ammonium persulphate; 0.5g cetyl trimethylammonium bromide and 0.1g Nonyl pheno (10) ether; be warming up to 40 ℃; after the stirring and dissolving, adding the 2g median size is the CaCO with oil-wetted surface of 40nm
3The mixture of particle and 15ml styrene monomer is warming up to 80 ℃, reacts after 1～2 hour, is warming up to 90 ℃ again, continues reaction 0.5～1 hour, cooling discharging.Part emulsion after the discharging gets the white powder product after breakdown of emulsion, washing, drying, overall yield of reaction 74% as calculated, uses the dimethylbenzene extracting after 12 hours on exsiccant composite nano particle, and recording it can not extractive amount of polymers be 96%.In addition, the cross-linking type composite nanoparticle soaked 24 hours with excessive dilute hydrochloric acid after, CaCO
3Nuclear is removed and the mode of appearance of particle does not change, and obtains hollow nanoparticle, and this hollow Nano particle can keep original dispersing morphology and particle diameter.
Embodiment 3: the preparation method changes vinylbenzene into methyl methacrylate with embodiment 1.Gained the results are shown in Table 1.
Embodiment 4: the preparation method replaces with Vinylstyrene with embodiment 1 with TMPTMA.Gained the results are shown in Table 1.
Embodiment 5: the preparation method replaces with γ-methacryloxypropyl trimethoxy silane with embodiment 1 with TMPTMA.Gained the results are shown in Table 1.
Embodiment 6: the preparation method replaces with vinyltriethoxysilane with embodiment 1 with TMPTMA.Gained the results are shown in Table 1.
Embodiment 7: the preparation method is with embodiment 1, and the addition of TMPTMA is reduced to 0.14g by 0.68g.Gained the results are shown in Table 1.
Embodiment 8: the preparation method is with embodiment 1, and the addition of TMPTMA is increased to 0.95g by 0.68g.Gained the results are shown in Table 1.
Embodiment 9: the preparation method is with embodiment 1, with CaCO
3Addition be increased to 4.0g by 2.0g.Gained the results are shown in Table 1.
Embodiment 10: the preparation method is with embodiment 1, with CaCO
3Amount reduce to 1.0g by 2.0g.Gained the results are shown in Table 1.
Embodiment 11: the preparation method is with embodiment 1, and the addition of cetyl trimethylammonium bromide is increased to 0.75g by 0.5g.Gained the results are shown in Table 1.
Embodiment 12: the preparation method changes cetyl trimethylammonium bromide into palmityl trimethyl ammonium chloride with embodiment 1.Gained the results are shown in Table 1.
Embodiment 13: the preparation method replaces with octyl phenol polyoxy ethene (20) ether with embodiment 1 with Nonyl pheno (10) ether.Gained the results are shown in Table 1.
Table 1 olefin polymer/CaCO
3The preparation data of crosslinked composite nano particle
| Embodiment | Polymerization yield % | Can not extractive amount of polymers % |
| Embodiment 1 | ????76 | ????99 |
| Embodiment 2 | ????74 | ????96 |
| Embodiment 3 | ????88 | ????87 |
| Embodiment 4 | ????89 | ????86 |
| Embodiment 5 | ????82 | ????94 |
| Embodiment 6 | ????80 | ????90 |
| Embodiment 7 | ????79 | ????94 |
| Embodiment 8 | ????74 | ????95 |
| Embodiment 9 | ????75 | ????83 |
| Embodiment 10 | ????80 | ????97 |
| Embodiment 11 | ????78 | ????96 |
| Embodiment 12 | ????77 | ????94 |
| Embodiment 13 | ????76 | ????95 |
Claims (1)
1, the preparation method of a kind of highly cross-linked type olefin polymer/lime carbonate composite nano particle, this method is to be raw material with calcium carbonate particles, olefinic monomer, linking agent, under emulsifying agent, initiator existence condition, realize by letex polymerization, it is characterized in that described calcium carbonate particles diameter is less than 100nm and have oil-wetted surface; Described olefinic monomer is the monoene hydrocarbons that contains a carbon carbon unsaturated double-bond in the molecule, can be in vinylbenzene, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester any or several; Described linking agent, can be in the coupling agent that contains a carbon carbon unsaturated double-bond in the material that contains polymerisable vinyl unsaturated link(age) more than in the molecule and the molecule at least any, the material that contains polymerisable vinyl unsaturated link(age) more than in the molecule can be 1, the 3-divinyl, the 2-methyl isophthalic acid, the 3-divinyl, 2,3-dimethyl-1, the 3-divinyl, isoprene, 2-chloro-1, the 3-divinyl, Vinylstyrene, the divinyl naphthalene, glycol diacrylate, ethylene glycol dimethacrylate, the vinylformic acid allyl ester, Viscoat 295, trimethylolpropane trimethacrylate, iso-cyanuric acid triallyl ester, polyhutadiene, the divinyl silane compound, at least contain in diallylsilane compound and the molecule in the lower molecular weight organopolysiloxane of two vinyl any or several, the coupling agent that contains a carbon carbon unsaturated double-bond in the molecule at least can be silane type, aluminic acid ester type, borate-type, in the titanic acid ester type coupling agent any or several; Described emulsifying agent is cationic and compound system nonionic emulsifier, cationic emulsifier can be in dodecyl chlorination ammonium, dodecyl ammonium acetate, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, the hexadecyl pyridinium bromide any or several, nonionic emulsifier can be C
3～10Alkylphenol-polyethenoxy (4～50) ether, C
2～18Aliphatic alcohol polyethenoxy (4～50) ether, polyoxyethylene (4～50) sorbyl alcohol list C
11～18Fatty acid ester, polyoxyethylene (4～50) sorbyl alcohol three C
11～18In the fatty acid ester any or several; Described initiator is can be under 40～95 ℃ of conditions, have 105～150kJ/mol ionic dissociation energy and can produce free radical and cause olefinic monomer polymeric material, this material can be in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the dibenzoyl peroxide any, its polymerization process is to be the letex polymerization of dispersion medium with water, during polymerization, the weight percent of olefinic monomer, calcium carbonate particles, linking agent, emulsifying agent, each component of initiator is:
Olefinic monomer: 54.5～97.8%
Calcium carbonate particles: 1～25%
Linking agent: 0.1～15%
Emulsifying agent: 1～5%
Initiator: 0.1～0.5%.
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