CN1246352C - Nano macromolecule microball of carboxy function type cross-linked nucleocapsid structure and preparation process thereof - Google Patents
Nano macromolecule microball of carboxy function type cross-linked nucleocapsid structure and preparation process thereof Download PDFInfo
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- CN1246352C CN1246352C CN 200410008466 CN200410008466A CN1246352C CN 1246352 C CN1246352 C CN 1246352C CN 200410008466 CN200410008466 CN 200410008466 CN 200410008466 A CN200410008466 A CN 200410008466A CN 1246352 C CN1246352 C CN 1246352C
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- monoolefine
- stratum nucleare
- olefin monomer
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002521 macromolecule Polymers 0.000 title abstract description 10
- 239000011806 microball Substances 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 145
- 239000004005 microsphere Substances 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 125000000524 functional group Chemical group 0.000 claims abstract description 35
- 239000011258 core-shell material Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- -1 isobutyl diene Chemical class 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 25
- 239000000872 buffer Substances 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 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 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-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
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 238000012545 processing Methods 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 3
- 235000013336 milk Nutrition 0.000 claims description 3
- 239000008267 milk Substances 0.000 claims description 3
- 210000004080 milk Anatomy 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- CBSOFSBFHDQRLV-UHFFFAOYSA-N N-methylbenzylamine hydrochloride Chemical compound [Cl-].C[NH2+]CC1=CC=CC=C1 CBSOFSBFHDQRLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- RCTOVWPTGOZSPJ-UHFFFAOYSA-N benzyl(ethyl)azanium;chloride Chemical compound Cl.CCNCC1=CC=CC=C1 RCTOVWPTGOZSPJ-UHFFFAOYSA-N 0.000 claims description 2
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 125000006178 methyl benzyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether 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
- 150000003839 salts Chemical class 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims 2
- 239000000600 sorbitol Substances 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Polymers C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract 2
- 239000006172 buffering agent Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 125000005395 methacrylic acid group Chemical class 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 241000238367 Mya arenaria Species 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical class [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- YTRIOKYQEVFKGU-UHFFFAOYSA-M benzyl(tripropyl)azanium;chloride Chemical class [Cl-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 YTRIOKYQEVFKGU-UHFFFAOYSA-M 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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Abstract
The present invention relates to nanometer macromolecule microspheres with carboxyl function type cross-linked core-shell structures and a preparation process thereof, which belong to the technical field of macromolecule materials. The present invention uses a plurality of alkene monomers and alkene monomers with carboxyl functional groups as raw materials, under the condition of the existence of emulsifying agents, initiating agents and buffering agents, the nanometer macromolecule microspheres with carboxyl function type cross-linked core-shell structures are prepared by emulsion using water as media or suspension polymerization. Production is in a core-shell structure, inner parts of cores and shells are in a cross-linked state, the cores and the shells are connected by chemical bonds, the carboxyl functional groups are grafted on surfaces of the microspheres, and grain diameter is less than 100 nm. The present invention can change the composite and structures of the core and the shells so as to obtain a plurality of nanometer macromolecule microspheres with different physical and chemical characteristics, and the present invention has very high freedom on the selection of structural design. The present invention solves problems that in past, core-shell macromolecule microspheres have no nanometer sizes, and the cores and the shells are linear polymer; simultaneously, the present invention has wide application prospect in the technical field of nanotechnology by introducing the carboxyl functional groups capable of ionizing and reacting.
Description
Technical field
The present invention relates to nano polymer microspheres of a kind of carboxyl function type cross-linked core-shell structure and preparation method thereof, belong to technical field of polymer materials.
Background technology
Prepare the concern that the nano polymer microspheres with nucleocapsid structure has been subjected to more and more researchers in recent years.This nucleocapsid polymer microsphere not only has nanoscale, can change the composition of nuclear and shell simultaneously as required, obtains having the product of different physicochemical properties, has very high design freedom.
The inventor had once successfully prepared cross-linked core-shell structure nano polymer microsphere, and it has been carried out surperficial epoxide functionization, solved forefathers do not possess nanoscale about the nucleocapsid polymer microsphere problem, solve forefathers' synthetic nucleocapsid polymer microsphere general kernel or shell and be linear macromolecule, microballoon swelling ratio in solvent is very low, the problem that good solubility-resistence energy and oil absorptiveness are also relatively poor, and by being grafted on cross-linked core-shell nano polymer microspheres surface with the epoxy-functional of multiple polymer-based precursor reactant, make it can and then form chemical bond by surface functional group and matrix generation chemical reaction when the filled high polymer matrix, the interface interacts and the dispersiveness of microballoon in matrix between microballoon and matrix thereby strengthened.But epoxy-functional belongs to non-ionic type functional group, does not possess ionizing power, thereby has been subjected to bigger restriction in its application of the Ionized occasion of numerous needs; The group that can react with it simultaneously is comparatively limited, so the Application Areas of this nano polymer microspheres has been subjected to certain limitation, among the main modification that is applied to a part of macromolecule matrix.
The present invention intends on the basis that synthesizes the cross-linked core-shell nano polymer microspheres, it is stronger to introduce chemical reactivity at microsphere surface, but reaction range is broader and possess the carboxyl functional group of ionizing power, make that this carboxyl function type nano polymer microspheres not only can be by reacting the interface compatibility that improves nano polymer microspheres and matrix with the filling matrix, the more important thing is the chemical reaction scope of utilizing the carboxyl broadness and being easy to Ionized characteristic has given this nano polymer microspheres very high reactive behavior and ionization property, make it to be widely used in the polymer modification agent, water conditioner, catalyzer, sensing agent and protein carrier, field such as microcapsule embedded get a qualitative improvement its using value.
Summary of the invention
The purpose of this invention is to provide a kind of carboxyl function type cross-linked core-shell structure nano polymer microsphere and preparation method thereof, this method is incited somebody to action in the past on the one hand, and the yardstick of polymer core-shell particles is reduced in the nanoscale scope, make the nuclear and the shell inside of product all form crosslinking structure simultaneously, have the problem of nanoscale nucleocapsid latex particle thereby not only solved preparation, but also solved nucleocapsid latex particle good solubility-resistence and the relatively poor problem of oil absorbency in the past; Simultaneously, can and have the carboxyl functional group of ionization property with multiple polymer-based precursor reactant by introducing at microsphere surface, make that it can be widely used in that macromolecule matrix is filling-modified, water purification agent, catalyzer, protein carrier, field such as microcapsule embedded, and show various good properties.The present invention can design nuclear and the composition of shell and structure, yardstick as required, thereby obtain various the have soft nuclear duricrust of different physicochemical properties and application value or the nanoparticles of stone soft shell type, on form and structure Design, have very high degree of freedom, greatly widened its Application Areas and application prospect.
The objective of the invention is to be achieved through the following technical solutions:
A kind of carboxyl function type cross-linked core-shell structure nano polymer microsphere, it is characterized in that: this microballoon has nucleocapsid structure, and the connection structure is all presented in the inner and shell inside of nuclear, examine with shell between be connected by chemical bond, at microsphere surface, its particle diameter is less than 100nm by the chemical bond grafting for carboxyl functional group; It is a raw material with following material, by being that medium adopts the method for letex polymerization or suspension polymerization to be prepared from water:
1) monoolefine monomer: count 100 parts (other each components are carried out quantitatively as benchmark) with the total mass of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
2) multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
3) contain the olefinic monomer of carboxyl functional group: 0.01～40 part;
4) buffer reagent: be 50～150% of the olefinic monomer quality that contains carboxyl functional group;
5) emulsifying agent: 2～7 parts;
6) initiator: 0.5～2 part.
Monoolefine of the present invention is meant one or more in the alpha-olefin that contains a carbon-carbon double bond (C=C) in the molecule, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester, and should guarantee that stratum nucleare monoolefine monomer and shell monoolefine monomer are incomplete same; Described Polyene Hydrocarbons material is meant the material that contains two or more carbon-carbon double bonds in the molecule, is selected from suitable divinyl, isobutyl diene, isoprene, Vinylstyrene, the trihydroxy methyl propane trimethyl acrylate one or more.
The olefinic monomer that contains carboxyl functional group of the present invention is meant the olefinic monomer that contains simultaneously in the molecule with the carboxyl functional group shown in carbon-carbon double bond shown in the chemical skeleton symbol (a) and the chemical skeleton symbol (b), can select in vinylformic acid, methacrylic acid, butenoic acid, oleic acid, the 1-lauroleic acid one or more for use.
-COOH -(b)
Buffer reagent of the present invention is meant the salt or the alkali that can react with acid, selects in sodium bicarbonate, sodium hydroxide, the salt of wormwood one or more for use.
Emulsifying agent described in the present invention can adopt one or more in the following material:
A. cationic: as to comprise three C
1～18Alkyl methyl ammonium chloride, three C
1～18Alkyl methyl brometo de amonio, three C
1～18Alkyl benzyl ammonium chloride, three C
1～18Alkyl benzyl brometo de amonio or three C
1～18Alkyl methyl benzyl ammonium chloride, three C
1～18Alkyl ethylbenzylammonium chloride, three C
1～18Alkyl methyl benzyl brometo de amonio, three C
1～18Alkyl Ethylbenzyl brometo de amonio.
B. anionic: comprise C12～18 sodium alkyl sulfates, C12～18 alkylsurfuric acid potassium, C12～18 alkyl sodium sulfonates, C12～18 alkylsulphonic acid potassium, C12～18 sodium alkyl benzene sulfonates, C12～18 alkyl benzene sulphonate (ABS) potassium.
C. non-ionic type: comprise C3～10 alkyl phenol polyoxyethylenes (4～50) ether, C2～18 aliphatic alcohol polyethenoxies (4～50) ether, polyoxyethylene (4～50) sorbyl alcohol list C11～18 fatty acid esters or polyoxyethylene (4～50) sorbyl alcohol three C11～18 fatty acid esters.
Described initiator is meant can be under 40～95 ℃ of conditions, also can produce free radical causes olefinic monomer polymeric material to have 30～35kcal/mol ionic dissociation energy, comprises water miscible persulfuric acid salt, hydroperoxide kind material or oil-soluble azo class, peroxide material.Can be selected from Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile), or the redox system formed with ferrous salt, sulphite, thiosulphate respectively of hydrogen peroxide, dibenzoyl peroxide.
The preparation method of a kind of cross-linked core-shell structure nano polymer microsphere provided by the invention is characterized in that adopting emulsion polymerisation process, and this method is a raw material with following material:
Monoolefine monomer: count 100 parts (other each components are carried out quantitatively as benchmark) with the total mass of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
Multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
The olefinic monomer that contains carboxyl functional group: 0.01～40 part;
Buffer reagent: be 50～150% of the olefinic monomer quality that contains carboxyl functional group;
Emulsifying agent: 2～7 parts;
Water soluble starter: 0.5～2 part.
The processing step of this method is as follows:
(1) preparation of stratum nucleare:
(a) by the above-mentioned raw materials proportioning with the stratum nucleare multi-olefin monomer of the stratum nucleare monoolefine monomer of 30-70% and 30-70% mixed evenly put into to contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor form uniform emulsion, in this reactor, add and account for the water soluble starter of total amount 20～80%, and make it to be warming up to 70 ℃～95 ℃ temperature range internal reaction 0.5～2 hour;
(b) evenly add in the above-mentioned system remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer are mixed, said temperature scope internal reaction 1～3 hour;
(2) preparation of shell:
(c) in the reacted system of step (b), add remaining water soluble starter, then according to described proportion of raw materials select for use the monoolefine monomer different with the stratum nucleare monoolefine monomer as shell monoolefine monomer and shell multi-olefin monomer mixed evenly and the adding system, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(3) grafting of surperficial carboxyl functional group:
(d) buffer reagent of adding said ratio in the reacted system of step (2) adds the olefinic monomer that contains carboxyl functional group then, reacts then 0.5～3 hour;
(e) behind the cooling discharging, and after breakdown of emulsion, washing and drying step are handled, can obtain the carboxyl function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes.
The present invention also provides the preparation method of another kind of cross-linked core-shell structure nano polymer microsphere, it is characterized in that adopting suspension polymerization to be prepared, and this method is a raw material with following material:
Monoolefine monomer: count 100 parts (other each components are carried out quantitatively as benchmark) with the total mass of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
Multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
The olefinic monomer that contains carboxyl functional group: 0.01～40 part;
Buffer reagent: be 50～150% of the olefinic monomer quality that contains carboxyl functional group;
Emulsifying agent: 2～7 parts;
Oil-soluble initiator: 0.5～2 part;
The processing step of this method is as follows:
(1) preparation of stratum nucleare:
(a) by the proportioning in the described raw material with the oil-soluble initiator of the stratum nucleare multi-olefin monomer of the stratum nucleare monoolefine monomer of 30-70%, 30-70% and 20-80% mixed evenly put into to contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor form uniform milk sap, and make it to be warming up to 70 ℃～95 ℃ temperature range internal reaction 0.5～2 hour;
(b) with in the mixed reaction system that evenly adds above-mentioned steps (a) of remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(2) preparation of shell:
(c) select for use the monoolefine monomer different as shell monoolefine monomer and shell multi-olefin monomer with remaining oil-soluble initiator is mixed evenly joins in the reacted system of step (b) by the proportioning in the described raw material, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour with the stratum nucleare monoolefine monomer;
(3) grafting of surperficial carboxyl functional group:
(d) buffer reagent of adding said ratio in the reacted system of step (2) adds the olefinic monomer that contains carboxyl functional group then, reacts then 0.5～3 hour;
(e) behind the cooling discharging, and after breakdown of emulsion, washing and drying step are handled, can obtain the carboxyl function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes.
Carboxyl function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes and preparation method thereof, under the condition that emulsifying agent and initiator exist by the polymer microsphere that with water is that the emulsion or the suspension polymerization of medium has obtained having nucleocapsid structure, nanoscale and surface have carboxyl functional group.Be connected with chemical bond between the carboxyl function type cross-linked core-shell structure nano polymer microsphere of the present invention, stratum nucleare and shell, have very strong interface interaction; Nuclear all is crosslinked form with shell inside, has not only solved preparation and has had the problem of nanoscale nucleocapsid latex particle, and nucleocapsid emulsion particle daughter nucleus and shell mostly are simple linear polymer thereby good solubility-resistence energy and all lower problem of oil absorptiveness but also solved in the past.What is more important, by having the introducing of very high chemical reactivity and ionogenic carboxyl functional group, make this microballoon not only can with a lot of macromolecule matrix generation chemical reactions, strengthen the interface compatibility when filling, but also can be widely used in the field that shows ionization character such as numerous needs such as water conditioner, catalyzer, microcapsule embedded, protein carriers.In addition, can design the nuclear and the composition of shell and structure, yardstick as required, thereby obtain various the have soft nuclear duricrust of different physicochemical properties and application value or the nano polymer microspheres of stone soft shell type, and place nucleocapsid structure for a long time and can not reverse, on form and structure Design, have very high degree of freedom.Overall yield of reaction and gel fraction are generally all more than 90%.In addition, preparation technology is simple to operate, easily realizes suitability for industrialized production, and the nano polymer microspheres of making can be preserved for a long time, also can be dried to pulverulence, is easy to store and use.The particle diameter of this cross-linked core-shell structure nano polymer microsphere has the property that nanoscale and nanoparticle possess all less than 100nm.These characteristics will make carboxyl function type cross-linked core-shell structure nano polymer microsphere of the present invention have purposes widely in from now on nanometer material science and technical development.
Description of drawings
Fig. 1 is the electron micrograph of carboxyl function type cross-linked core-shell nano polymer microspheres PS/PBA/PMAA.
Fig. 2 is the grain size distribution curve figure of carboxyl function type cross-linked core-shell nano polymer microspheres PS/PBA/PMAA.
Embodiment
The invention will be further described below by embodiment, understands the present invention with further.
Embodiment 1: 70 parts of vinylbenzene (St) are evenly mixed as the stratum nucleare multi-olefin monomer, stand-by as stratum nucleare monoolefine monomer and 7 parts of Vinylstyrenes (DVB).In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 360 parts of deionized waters, 6.5 parts of sodium laurylsulfonates (SDS) and 0.5 part of nonylphenol Soxylat A 25-7, be warming up to 50 ℃, add the uniform emulsion of 30% formation of the miscellany for preparing previously.Add 80% of the initiator solution that is made into by 0.5 part of water soluble starter ammonium persulphate and 72 parts of deionized waters then, temperature is risen to 82 ℃ of reactions 30 minutes.In system, add the remaining mixture for preparing previously then, continue reaction 1 hour.Add whole remaining initiator solutions again, in system, add mixture, reacted then 1.5 hours by 30 parts of butyl acrylates (BA) (as the shell monoolefine monomer) and 3 parts of Vinylstyrenes (DVB) (as the shell multi-olefin monomer).Add 10 parts of buffer reagent sodium bicarbonates in system, the speed with 30ml/h at the uniform velocity drips 10 parts of methacrylic acids (MAA) then, drips the back and continues reaction 1 hour, cooling discharging.Part emulsion after the discharging gets the white powder product after breakdown of emulsion, washing, drying, another part emulsion places test tube, also find to store after 6 months deposited phenomenon not occur, and electron microscopic observation finds that down the nucleocapsid structure of microsphere particles still keeps better, and reversal development does not take place.Overall yield of reaction 92.6% as calculated, uses the chloroform extracting after 12 hours exsiccant cross-linked core-shell structure nano polymer microsphere, and recording gel fraction is 95.1%, also illustrates that nucleocapsid all exists with crosslinked form.Can be clear that the nucleocapsid structure of expection from Fig. 1 (electromicroscopic photograph of PS/PBA/PMAA), as can be seen, its median size is 40～50nm to Fig. 2 (the size distribution test of PS/PBA/PMAA) simultaneously, and size distribution is very narrow.
Embodiment 2: 30 parts of butyl acrylates (BA) are evenly mixed as the stratum nucleare multi-olefin monomer, stand-by as stratum nucleare monoolefine monomer and 3 parts of trihydroxy methyl propane trimethyl acrylates (TM).In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 360 parts of deionized waters, 4 parts of sodium laurylsulfonates (SDS) and 0.5 part of nonylphenol Soxylat A 25-7, be warming up to 50 ℃, add the uniform emulsion of 70% formation of the miscellany for preparing previously.Add 20% of the initiator solution that is made into by 0.5 part of water soluble starter ammonium persulphate and 72 parts of deionized waters then, temperature is risen to 70 ℃ of reactions 2 hours.Be warming up to 82 ℃ then, in system, add the remaining mixture for preparing previously, continue reaction 1 hour.Add whole remaining initiator solutions again, in system, add mixture, reacted then 1 hour by 70 parts of methyl methacrylates (MMA) (as the shell monoolefine monomer) and 7 parts of trihydroxy methyl propane trimethyl acrylates (TM) (as the shell multi-olefin monomer).In system, add 15 parts in buffer reagent salt of wormwood again, add 10 parts of 1-butylene acid then, continue reaction 1 hour, cooling discharging.The products therefrom performance index see Table 1.
Embodiment 3: change methacrylic acid among the embodiment 1 into 40 parts oleic acid, the sodium bicarbonate consumption changes 20 parts into, initiator amount increases to 2 parts simultaneously, system temperature is 70 ℃, each following reaction times of step was respectively 2 hours, 3 hours, 3 hours, 3 hours, and all the other prescriptions are identical with embodiment 1 with step.The products therefrom performance index see Table 1.
Embodiment 4: the mixture that the stratum nucleare monoolefine monomer among the embodiment 1 is become St and MMA, wherein St and MMA mass ratio are 4: 1, with the butyl acrylate of quality such as the shell monoolefine monomer becomes and the mixture of methyl acrylate, emulsifying agent adopts 2 parts of Sodium dodecylbenzene sulfonatees, and all the other prescriptions are identical with example 1.The products therefrom performance index see Table 1.
Embodiment 5: stratum nucleare multi-olefin monomer among the embodiment 2 and shell multi-olefin monomer are all become 1 part of N, the N-methylene diacrylamine, and methacrylic acid changed into 0.01 part 1-lauroleic acid, buffer reagent adopts 0.015 part of sodium hydroxide, system temperature is 95 ℃, and each following reaction times of step was respectively 0.5 hour, 1 hour, 1 hour, 0.5 hour.All the other prescriptions are identical with embodiment 2 with step.The products therefrom performance index see Table 1.
Embodiment 6: 30 parts of vinylbenzene are evenly mixed as the stratum nucleare multi-olefin monomer, stand-by as stratum nucleare monoolefine monomer and 20 parts of isoprene.In the four-hole bottle that mechanical stirring, reflux condensing tube and thermometer are housed, add 360 parts of deionized waters, 2 parts of tripropyl ammonio methacrylates, be warming up to 50 ℃, the 70% and 0.1 part of oil-soluble initiator Diisopropyl azodicarboxylate that adds the miscellany for preparing previously forms uniform milk sap.Temperature is risen to 70 ℃ of reactions 2 hours.In system, add the mixture of remaining vinylbenzene and DVB then, continue reaction 3 hours.In system, add mixture again, reacted then 3 hours by 0.4 part of Diisopropyl azodicarboxylate, 70 parts of butyl acrylates (as the shell monoolefine monomer) and 30 parts of low polyhutadiene (as the shell multi-olefin monomer).In system, add 20 parts of buffer reagent sodium bicarbonates again, drip 40 parts of methacrylic acids, dripped off afterreaction 3 hours, cooling discharging.The products therefrom performance index see Table 1.
Embodiment 7: the mixture that the emulsifying agent among the embodiment 6 is adopted 6 parts of tripropyl benzyl ammonium chlorides and 1 part of 12 fatty alcohol-polyoxyethylene ether, Diisopropyl azodicarboxylate is changed into the oil-soluble initiator dibenzoyl peroxide of measuring, system temperature is 95 ℃, each step time was respectively 0.5 hour, 1 hour, 1 hour, 0.5 hour, and all the other prescriptions are identical with embodiment 6 with step.The products therefrom performance index see Table 1.
Embodiment 8: change the tripropyl ammonio methacrylate among the embodiment 6 into Sodium dodecylbenzene sulfonate, the stratum nucleare monoolefine monomer changes 70 parts of BA into, the shell monoolefine monomer changes 30 parts of MMA into, and initiator is that all the other prescriptions are identical with embodiment 6 with step with the oil-soluble initiator Diisopropyl azodicarboxylate of amount.The products therefrom performance index see Table 1.
Embodiment 9: the emulsifying agent among the embodiment 6 is changed into the tripropyl methyl brometo de amonio of measuring, initiator is 2 parts of oil-soluble initiator BPO, buffer reagent is 0.015 part of sodium hydroxide, and changes methacrylic acid into 0.01 part oleic acid, and all the other prescriptions are identical with embodiment 6 with step.The products therefrom performance index see Table 1.
Comparative example 1: the preparation method is with example 1, but all do not add multi-olefin monomer among BA and the MMA, and the products therefrom performance index see Table 1.
Comparative example 2: the preparation method is with example 2, but do not add buffer reagent, adds system generation breakdown of emulsion after the 1-butylene acid, has a large amount of block precipitations to generate.
More than the results are shown in Table shown in 1 of each example.
The product property index of each embodiment of table 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Comparative example 1 | Comparative example 2 | |
| Fundamemtal phenomena | Well | Well | Well | Well | Well | Well | Well | Well | Well | A | Breakdown of emulsion |
| Productive rate (%) | 92.6 | 90.7 | 88.1 | 94.4 | 96.5 | 89.4 | 91.6 | 95.3 | 93.0 | 86.7 | - |
| Gel fraction (%) | 95.1 | 91.2 | 94.8 | 93.7 | 89.7 | 92.7 | 90.9 | 97.8 | 96.1 | 0 | - |
| Particle diameter (nm) | 40～50 | 40～ 50 | 40～ 50 | 40～ 50 | 40～ 50 | 40～ 50 | 40～ 50 | 40～ 50 | 40～ 50 | 30～ 60 | - |
Annotate: the A. phenomenon is that gel fraction is 0, and the product microballoon is shaped as irregular sphere simultaneously, and size distribution is wide.
In above each embodiment, embodiment 1,2,3,4,5 belongs to method of emulsion polymerization, and embodiment 6,7,8,9 belongs to the method for suspension polymerization.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only be thought can not limit the present invention to explanation of the present invention, claims have been pointed out scope of the present invention, therefore, any change in claims scope of the present invention all should be thought to be included in the scope of claims.
Claims (9)
1. carboxyl function type cross-linked core-shell structure nano polymer microsphere, it is characterized in that: this microballoon has nucleocapsid structure, and the connection structure is all presented in the inner and shell inside of nuclear, examine with shell between be connected by chemical bond, at microsphere surface, its particle diameter is less than 100nm by the chemical bond grafting for carboxyl functional group; It is a raw material with following material, by being that medium adopts the method for letex polymerization or suspension polymerization to be prepared from water:
1) monoolefine monomer: 100 parts of the total mass meters of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
2) multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
3) contain the olefinic monomer of carboxyl functional group: 0.01～40 part;
4) buffer reagent: be 50～150% of the olefinic monomer quality that contains carboxyl functional group;
5) emulsifying agent: 2～7 parts;
6) initiator: 0.5～2 part;
Described monoolefine monomer is meant one or more in the alpha-olefin that only contains a carbon-carbon double bond in the molecule, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester, and should guarantee that stratum nucleare monoolefine monomer and shell monoolefine monomer are incomplete same; Described multi-olefin monomer is meant the material that contains two or more carbon-carbon double bonds in the molecule.
2. according to the described carboxyl function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: the described material that contains two or more carbon-carbon double bonds is selected from along in the divinyl, isobutyl diene, isoprene, Vinylstyrene, trihydroxy methyl propane trimethyl acrylate one or more.
3. according to the described carboxyl function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: the described olefinic monomer that contains carboxyl functional group is meant the olefinic monomer that contains simultaneously in the molecule with the carboxyl functional group shown in carbon-carbon double bond shown in the chemical skeleton symbol (a) and the chemical skeleton symbol (b), selects in vinylformic acid, methacrylic acid, butenoic acid, oleic acid, the 1-lauroleic acid one or more for use.
-COOH -(b)
4. according to the described carboxyl function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: described buffer reagent is meant the salt or the alkali that can react with acid, selects in sodium bicarbonate, sodium hydroxide, the salt of wormwood one or more for use.
5. according to the described carboxyl function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: described emulsifying agent adopts one or more in the following material:
A. cationic: as to comprise three C
1～18Alkyl methyl ammonium chloride, three C
1～18Alkyl methyl brometo de amonio, three C
1～18Alkyl benzyl ammonium chloride, three C
1～18Alkyl benzyl brometo de amonio or three C
1～18Alkyl methyl benzyl ammonium chloride, three C
1～18Alkyl ethylbenzylammonium chloride, three C
1～18Alkyl methyl benzyl brometo de amonio, three C
1～18Alkyl Ethylbenzyl brometo de amonio;
B. anionic: comprise C12～18 sodium alkyl sulfates, C12～18 alkylsurfuric acid potassium, C12～18 alkyl sodium sulfonates, C12～18 alkylsulphonic acid potassium, C12～18 sodium alkyl benzene sulfonates, C12～18 alkyl benzene sulphonate (ABS) potassium;
C. non-ionic type: comprise C3～10 polyoxyethylene alkylphenol ethers, C2～18 fatty alcohol-polyoxyethylene ether, the single C11 of polyoxyethylene sorbitol～18 fatty acid esters or polyoxyethylene sorbitol three C11～18 fatty acid esters; Described polyoxyethylated ethylene oxide number of repeat unit is 4～50.
6. according to the described carboxyl function type of claim 1 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: described initiator is meant can be under 40～95 ℃ of conditions, have 30～35kcal/mol ionic dissociation energy and can produce free radical to cause olefinic monomer polymeric water-soluble persulfuric acid salt material or oil-soluble azo class, peroxide material.
7. according to the described carboxyl function type of claim 6 cross-linked core-shell structure nano polymer microsphere, it is characterized in that: described initiator is a kind of in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or the 2,2'-Azobis(2,4-dimethylvaleronitrile); The perhaps redox system of forming with ferrous salt, sulphite, thiosulphate respectively for hydrogen peroxide, dibenzoyl peroxide.
8. emulsion polymerisation process for preparing carboxyl function type cross-linked core-shell structure nano polymer microsphere as claimed in claim 1, it is characterized in that: this method is a raw material with monoolefine monomer, multi-olefin monomer, emulsifying agent and initiator, and wherein the content of each composition is:
Monoolefine monomer: 100 parts of the total mass meters of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
Multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
The olefinic monomer that contains carboxyl functional group: 0.01～40 part;
Buffer reagent: be 50～150% of the olefinic monomer quality that contains carboxyl functional group;
Emulsifying agent: 2～7 parts;
Water soluble starter: 0.5～2 part.
The processing step of this method is as follows:
(1) preparation of stratum nucleare:
(a) by the above-mentioned raw materials proportioning with the stratum nucleare multi-olefin monomer of the stratum nucleare monoolefine monomer of 30-70% and 30-70% mixed evenly put into to contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor form uniform emulsion, in this reactor, add and account for the water soluble starter of total amount 20～80%, and make it to be warming up to 70 ℃～95 ℃ temperature range internal reaction 0.5～2 hour;
(b) evenly add in the above-mentioned system remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer are mixed, said temperature scope internal reaction 1～3 hour;
(2) preparation of shell:
(c) in the reacted system of step (b), add remaining water soluble starter, then according to described proportion of raw materials select for use the monoolefine monomer different with the stratum nucleare monoolefine monomer as shell monoolefine monomer and shell multi-olefin monomer mixed evenly and the adding system, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(3) grafting of surperficial carboxyl functional group:
(d) buffer reagent of adding said ratio in the reacted system of step (2) adds the olefinic monomer that contains carboxyl functional group then, reacts then 0.5～3 hour;
(e) behind the cooling discharging, and after breakdown of emulsion, washing and drying step are handled, can obtain the carboxyl function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes.
9. one kind prepares the suspension polymerization of carboxyl function type cross-linked core-shell structure nano polymer microsphere according to claim 1, it is characterized in that: this method is a raw material with monoolefine monomer, multi-olefin monomer, emulsifying agent and initiator, and wherein the content of each composition is:
Monoolefine monomer: 100 parts of the total mass meters of stratum nucleare monoolefine monomer and shell monoolefine monomer; Wherein stratum nucleare monoolefine monomer quality is between 30-70 part, and the shell monoolefine monomer is corresponding between 70-30 part;
Multi-olefin monomer: stratum nucleare multi-olefin monomer and shell multi-olefin monomer total mass between 2-50 part, described stratum nucleare multi-olefin monomer and shell multi-olefin monomer the two all more than or equal to 1 part;
The olefinic monomer that contains carboxyl functional group: 0.01～40 part;
Buffer reagent: be 50～150% of the olefinic monomer quality that contains carboxyl functional group;
Emulsifying agent: 2～7 parts;
Oil-soluble initiator: 0.5～2 part;
The processing step of this method is as follows:
(1) preparation of stratum nucleare:
(a) by the proportioning in the described raw material with the oil-soluble initiator of the stratum nucleare multi-olefin monomer of the stratum nucleare monoolefine monomer of 30-70%, 30-70% and 20-80% mixed evenly put into to contain deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor form uniform milk sap, and make it to be warming up to 70 ℃～95 ℃ temperature range internal reaction 0.5～2 hour;
(b) with in the mixed reaction system that evenly adds above-mentioned steps (a) of remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour;
(2) preparation of shell:
(c) select for use the monoolefine monomer different as shell monoolefine monomer and shell multi-olefin monomer with remaining oil-soluble initiator is mixed evenly joins in the reacted system of step (b) by the proportioning in the described raw material, 70 ℃～95 ℃ temperature range internal reactions 1～3 hour with the stratum nucleare monoolefine monomer;
(3) grafting of surperficial carboxyl functional group:
(d) buffer reagent of adding said ratio in the reacted system of step (2) adds the olefinic monomer that contains carboxyl functional group then, reacts then 0.5～3 hour;
(e) behind the cooling discharging, and after breakdown of emulsion, washing and drying step are handled, can obtain the carboxyl function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes.
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