CN1258544C - 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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- CN1258544C CN1258544C CN 200410008467 CN200410008467A CN1258544C CN 1258544 C CN1258544 C CN 1258544C CN 200410008467 CN200410008467 CN 200410008467 CN 200410008467 A CN200410008467 A CN 200410008467A CN 1258544 C CN1258544 C CN 1258544C
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- monoolefine
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002521 macromolecule Polymers 0.000 title abstract description 7
- 239000011806 microball Substances 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 124
- 239000004005 microsphere Substances 0.000 claims abstract description 35
- 125000000524 functional group Chemical group 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011258 core-shell material Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 14
- 150000007942 carboxylates Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000007858 starting material Substances 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- 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 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- -1 isobutyl diene Chemical class 0.000 claims description 5
- 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 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 239000008267 milk Substances 0.000 claims description 4
- 235000013336 milk Nutrition 0.000 claims description 4
- 210000004080 milk Anatomy 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 239000004159 Potassium 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 239000000344 soap Substances 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010556 emulsion polymerization method Methods 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 3
- 150000001336 alkenes Chemical class 0.000 abstract 2
- 238000009826 distribution Methods 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 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 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 241000238367 Mya arenaria Species 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical group [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical class [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to nanometer macromolecule microspheres with carboxyl function type crosslinking 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, and the nanometer macromolecule microspheres with carboxyl function type crosslinking core-shell structures are prepared by soap-free emulsion using water as media or soap-free suspension polymerization. Production is in a core-shell structure, inner parts of cores and shells are in a crosslinking 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 enables the production to be easily purified by using a soap-free polymerization way. The present invention is suitable for various fields of very high purity requirements, and greatly reduces production cost. Simultaneously, the present invention has wide application prospect in the technical field of nanotechnology by introducing the carboxyl functional groups with high reactive activity and ionicity.
Description
Technical field
The present invention relates to a kind of preparation method of carboxyl function type cross-linked core-shell structure nano polymer microsphere, belong to macromolecular material
Technical field.
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.Conventional letex polymerization or suspension polymerization are the important means of synthetic this class Nano microsphere.
The inventor had once successfully prepared cross-linked core-shell structure nano polymer microsphere, and carried out it surface carboxyl functionalized, 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 high reaction activity and ionogenic carboxyl functional group will be grafted on cross-linked core-shell nano polymer microspheres surface by having very, make its using value in reactive blending and a lot of association area obtain the raising of matter.But, the synthetic employing of this carboxyl function type nano polymer microspheres be conventional letex polymerization or suspension polymerization, using to product separation purification and purification of emulsifying agent or dispersion agent brought big difficulty, makes it to be subjected to bigger restriction in the Application for Field that product purity is had relatively high expectations.Simultaneously, increased the difficulty of purifying and meaned and improved production cost, and the use of emulsifying agent or dispersion agent itself makes that promptly production cost increases greatly.
Summary of the invention
The objective of the invention is to adopt the synthetic a kind of carboxyl function type cross-linked core-shell nano polymer microspheres of method of soap-free polymerization, this method is intended selecting for use multiple olefinic monomer to react means by soap-free polymerization, make it at first to form nano polymer microspheres, can react and have the carboxyl functional group of ionization property then in the shell surface introducing of microballoon with multiple macromolecule matrix with nucleocapsid structure.Soap-free polymerization method of the present invention is not additionally used emulsifying agent, serve as emulsifying agent but choose the monomer that has carboxyl functional group that to participate in polyreaction, final this monomer has saved the step of washing emulsifying agent by being reacted into the part for composite particles.So both can solve in the production technique in the past because the cost that the use of emulsifying agent brings improves, product separation purifies problems such as purification difficult is bigger, and make product can be competent at the Application Areas very high purity requirement; Again can be by introducing very high, the ionogenic carboxyl functional group of reactive behavior at microsphere surface, make it to be widely used in polymer modification agent, water conditioner, catalyzer, sensing agent and protein carrier, field such as microcapsule embedded, improved its using value greatly.The soap-free polymerization method that the present invention adopts prepares carboxyl function type nano polymer microspheres, the size that can not only keep its particle nanometer scale, therefore and having very high design freedom at aspects such as particle structure, size of particles, particle surface physical and chemical characters, is a kind of preparation method of valuable composite nanoparticle.
The objective of the invention is to be achieved through the following technical solutions:
A kind of emulsifier-free emulsion polymerization method of carboxyl function type cross-linked core-shell structure nano polymer microsphere is characterized in that 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 has carboxyl or carboxylate group functional group: 2～40 parts;
Water soluble starter: 0.2～3 part;
Its concrete processing step is as follows:
(a) be that the water-soluble alkali adding that contains the olefinic monomer 50～150% of carboxyl functional group contains in the olefinic monomer of carboxyl functional group with quality; If what adopt is the olefinic monomer that contains carboxylate group, then do not need to add alkali;
(b) press the above-mentioned raw materials proportioning stratum nucleare monoolefine monomer of 30-70% and the stratum nucleare multi-olefin monomer of 30-70% are mixed evenly, stand-by;
(c) add 20～80% of the total material that obtains by step (a) in 40 ℃～50 ℃ the reactor to containing deionized water and being warming up to, add the mixture that step (b) obtains then and form uniform milk sap;
(d) in same reactor, add 20～50% of whole water soluble starters, and be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～6 hour;
(e) add 20～30% of whole water soluble starters, then with in the above-mentioned system of the mixed evenly adding of remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer, said temperature scope internal reaction 0.5～6 hour;
(f) add the residue water soluble starter, select for use the monoolefine monomer different evenly to add in the reacted system of step (e) according to described proportion of raw materials again, then 60 ℃～95 ℃ temperature range internal reaction 0.5～4 hour as shell monoolefine monomer and shell multi-olefin monomer are mixed with the stratum nucleare monoolefine monomer;
(g) add the remaining material that obtains by step (a), said temperature scope internal reaction 0.5～4 hour;
(h) behind the cooling discharging, adding quality is the water soluble acid that contains the olefinic monomer quality 50～150% of carboxyl functional group, 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.
Monoolefine monomer of the present invention is meant one or more in the alpha-olefin that only contains a carbon-carbon double bond in the molecule, vinylbenzene, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester; Described multi-olefin monomer 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.
Carboxyl or the carboxylate group functional group olefinic monomer of containing of the present invention is meant and contains simultaneously in molecular structure with the represented carbon carbon unsaturated double-bond of chemical structure skeleton symbol (a) with the olefines material of the carboxyl functional group of formula (b) expression; Perhaps in molecular structure, contain simultaneously with the represented carbon carbon unsaturated double-bond of chemical structure skeleton symbol (a) with the olefines material of the carboxylate group functional group of formula (c) expression.
-COOH ——(b)
-COO
M
---(c) M
=Li
Or Na
Or K
Or NH
4
Water soluble starter of the present invention is meant that under 40～95 ℃ of conditions also can produce free radical causes olefinic monomer polymeric persulfuric acid salt and hydroperoxide kind water-soluble substances to have 30～35kcal/mol ionic dissociation energy.For example adopt 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 no soap suspension polymerization of another kind of carboxyl function type cross-linked core-shell structure nano polymer microsphere provided by the invention, tool is characterised in that 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 has carboxyl or carboxylate group functional group: 2～40 parts;
Oil-soluble initiator: 0.2～3 part;
Its processing step is as follows:
(a) be that the water-soluble alkali adding that contains the olefinic monomer 50～150% of carboxyl functional group contains in the olefinic monomer of carboxyl functional group with quality; If what adopt is the olefinic monomer that contains carboxylate group, then do not need to add alkali;
(b) press the above-mentioned raw materials proportioning stratum nucleare monoolefine monomer of 30-70%, stratum nucleare multi-olefin monomer and 20～50% of the whole oil-soluble initiators of 30-70% are mixed evenly, stand-by;
(c) add 20～80% of the total material that obtains by step (a) in 40 ℃～50 ℃ the reactor to containing deionized water and being warming up to, add the mixture that step (b) obtains then and form uniform milk sap;
(d) system that step (c) is obtained is warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～6 hour;
(e) with remaining stratum nucleare monoolefine monomer, remaining stratum nucleare multi-olefin monomer and whole 20～30% mixed evenly addings in the above-mentioned system of oil-soluble initiators, said temperature scope internal reaction 0.5～6 hour;
(f) select for use the monoolefine monomer different as shell monoolefine monomer and shell multi-olefin monomer and remaining oil-soluble initiator is mixed evenly adds in the reacted system of step (e) according to described proportion of raw materials again, then 60 ℃～95 ℃ temperature range internal reaction 0.5～4 hour with the stratum nucleare monoolefine monomer;
(g) add the remaining material that obtains by step (a), said temperature scope internal reaction 0.5～4 hour;
(h) behind the cooling discharging, adding quality is the water soluble acid that contains the olefinic monomer quality 50～150% of carboxyl functional group, 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.
Oil-soluble initiator of the present invention is meant that under 40～95 ℃ of conditions also can produce free radical causes olefinic monomer polymeric azo class and peroxide oil-soluble substance to have 30～35kcal/mol ionic dissociation energy.The redox system that can adopt Diisopropyl azodicarboxylate, dibenzoyl peroxide or dibenzoyl peroxide to form with ferrous salt, sulphite, thiosulphate respectively.
The preparation method of the carboxyl function type cross-linked core-shell structure nano polymer microsphere that the present invention proposes, additionally do not use emulsifying agent, significantly reduced production cost, play a part that becomes particle after the olefinic monomer reaction that has carboxyl functional group of emulsifying effect simultaneously, saved the step of washing emulsifying agent, be easy to product separation and purify purification, improved production efficiency, and made product can be widely used in the field very high purity requirement.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, its overall yield of reaction and gel fraction are generally all more than 90%.Nuclear all is crosslinked form with shell inside, not only solve preparation and had the problem of nanoscale nucleocapsid latex particle, but also solved in the past nucleocapsid emulsion particle daughter nucleus and shell mostly be simple linear polymer thereby good solubility-resistence can and all lower problem of oil absorptiveness, finally show various good properties in actual applications.Simultaneously, the present invention makes it to have broad application prospects in fields such as reactive blending, water purification agent, catalyzer, protein carrier by introducing reactive behavior height, ionogenic carboxyl functional group on cross-linked core-shell nano polymer microspheres surface.In addition, 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 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.The preparation manipulation of this carboxyl function type connection nuclear shell structure nano polymer microsphere is simple, easily realizes suitability for industrialized production, and the product of making can steady in a long-termly be preserved, and also can be dried to pulverulence, is easy to store and use.These characteristics will make carboxyl function type cross-linked core-shell nano polymer microspheres 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 nanometer PBA/PMMA/POA polymer microsphere.
Fig. 2 is the grain size distribution curve figure of carboxyl function type cross-linked core-shell nanometer PBA/PMMA/POA polymer microsphere.
Embodiment
The following examples will further specify the present invention.
Embodiment 1: add 20% of the mixing solutions that is made into by 40 parts of oleic acid (OA), 20 parts of sodium hydroxide and 100 parts of deionized waters in 40～50 ℃ the reactor to containing 370 parts of deionized waters and being warming up to, add then by 70 parts of butyl acrylates (BA) as stratum nucleare monoolefine monomer and 7 parts of trihydroxy methyl propane trimethyl acrylates (TM) as 30% of the uniform mixture of stratum nucleare multi-olefin monomer.Be warming up to 60 ℃, add 50% of the solution that is made into by 0.2 part of ammonium persulphate and 50ml deionized water, then 80 ℃ of reactions 1.5 hours down.Add 30% of whole initiator solutions, the mixture of remaining BA and TM is added in the above-mentioned system, continue reaction 1.5 hours.Add remaining initiator solution, in system, add mixture, dripped afterreaction 1 hour by 30 parts of methyl methacrylates (MMA) (as the shell monoolefine monomer) and 3 parts of trihydroxy methyl propane trimethyl acrylates (TM) (as the shell multi-olefin monomer).The mixing solutions of remaining oleic acid, sodium hydroxide slowly is added drop-wise in the above-mentioned system, and in said temperature scope internal reaction 1 hour.To add the hydrochloric acid of 20 parts of 1mol/l behind a part of emulsion cooling discharging, and after breakdown of emulsion, drying treatment, obtain the white powder product, another part emulsion places test tube, finds to store after 6 months deposited phenomenon not occur.Fig. 1 is the electron micrograph of synthetic PBA/PMMA/POA carboxyl function type cross-linked core-shell polymer microsphere, can see desired nucleocapsid structure clearly, overall yield of reaction 97.1%, gel fraction 93.6% from photo; Fig. 2 is the grain size distribution curve of this microballoon, can see that its size distribution is in 40～50nm scope.
Embodiment 2: add 80% of 10 parts of sodium acrylates in 40～50 ℃ the reactor to containing 370 parts of deionized waters and being warming up to, add then by 30 parts of vinylbenzene (St) as stratum nucleare monoolefine monomer and 3 parts of Vinylstyrenes (DVB) as 70% of the uniform mixture of stratum nucleare multi-olefin monomer.Be warming up to 60 ℃, add 20% of the solution that is made into by 3 parts of ammonium persulphates and 50ml deionized water, then 60 ℃ of reactions 6 hours down.Add 20% of whole initiator solutions, the mixture of remaining St and DVB is added in the above-mentioned system, continue reaction 6 hours.Add remaining initiator solution, in system, add mixture, reacted then 4 hours by 7 parts of methyl acrylates (BMA) (as the shell monoolefine monomer) and 3 parts of Vinylstyrenes (DVB) (as the shell multi-olefin monomer).Remaining sodium acrylate is added in the above-mentioned system, and in said temperature scope internal reaction 4 hours.The sulfuric acid that adds 15 parts of 1mol/l behind the cooling discharging, and breakdown of emulsion, drying.Overall yield of reaction 97.1%, gel fraction 93.6%, size distribution is in 40～50nm scope.
Embodiment 3: the ethyl propenoate that the methyl methacrylate among the embodiment 1 is changed into equivalent, and initiator is changed into the redox initiation system of 2 parts of hydrogen peroxide and 1 part of S-WAT, the amount that adds for the second time initiator is 30% of whole initiator solutions, and all the other prescriptions are identical with embodiment 1 with step.The productive rate of products therefrom, gel fraction are respectively 89.2%, 3478% and 88.1%, and size distribution is 40～50nm.
Embodiment 4: change 30 parts of vinylbenzene among the embodiment 2 methyl methacrylate of identical weight into, and change all Vinylstyrenes the isoprene of equivalent weight into, initiator is the Potassium Persulphate of equivalent, and all the other prescriptions are identical with embodiment 1 with step.The productive rate of products therefrom, percentage of grafting and grafting efficiency are respectively 86.4%, 3639% and 92.2%, and size distribution is 50～60nm.
Embodiment 5: change the sodium acrylate among the embodiment 2 into 2 parts of 1-lauroleic acid sodium, be reflected under 95 ℃ and carry out, each goes on foot the reaction times and is 0.5 hour, and all the other prescriptions are identical with embodiment 2 with step.The productive rate of products therefrom and gel fraction are respectively 91.3%, 89.5%, and size distribution is 40～50nm.
Embodiment 6: add 20% of the mixing solutions that is made into by 40 parts of vinylformic acid (MAA), 20 parts of potassium hydroxide and 100 parts of deionized waters in 40～50 ℃ the reactor to containing 370 parts of deionized waters and being warming up to, add 30% of the uniform mixture that is made into as stratum nucleare multi-olefin monomer and 0.1 part of Diisopropyl azodicarboxylate as stratum nucleare monoolefine monomer and 7 parts of trihydroxy methyl propane trimethyl acrylates (TM) by 70 parts of low polyhutadiene (LPB) then.Reacted 1.5 hours down at 80 ℃ then.Adding continues reaction 1.5 hours by the mixture of 0.06 part of Diisopropyl azodicarboxylate and remaining LPB and TM.Adding was reacted 1 hour then by the mixture of 0.04 part of nitrogen bis-isobutyronitrile and 30 parts of methyl methacrylates (MMA) (as the shell monoolefine monomer) and 3 parts of trihydroxy methyl propane trimethyl acrylates (TM) (as the shell multi-olefin monomer).The mixing solutions of remaining oleic acid, potassium hydroxide slowly is added drop-wise in the above-mentioned system, drips the back in said temperature scope internal reaction 1 hour.Add the hydrochloric acid of 60 parts of 1mol/l behind the cooling discharging, and after breakdown of emulsion, drying treatment, obtain the white powder product.Overall yield of reaction 97.1%, gel fraction 93.6%, its size distribution is in 40～50nm scope.
Embodiment 7: add 1.6 parts of 1-lauroleic acid sodium in 40～50 ℃ the reactor to containing 370 parts of deionized waters and being warming up to, add 30% of the uniform mixture that is made into as stratum nucleare multi-olefin monomer and 0.04 part of dibenzoyl peroxide as stratum nucleare monoolefine monomer and 7 parts of trihydroxy methyl propane trimethyl acrylates (TM) by 70 parts of vinylbenzene (St) then.Reacted 6 hours down at 60 ℃ then.Adding continues reaction 6 hours by the mixture of 0.06 part of dibenzoyl peroxide and remaining St and TM.Adding was reacted 4 hours then by the mixture of 0.1 part of dibenzoyl peroxide and 30 parts of ethyl propenoates (MBA) (as the shell monoolefine monomer) and 3 parts of Vinylstyrenes (DVB) (as the shell multi-olefin monomer).0.4 part of 1-lauroleic acid sodium is added in the above-mentioned system, then in said temperature scope internal reaction 4 hours.Add the sulfuric acid of 1 part of 1mol/l behind the cooling discharging, and after breakdown of emulsion, drying treatment, obtain the white powder product.Overall yield of reaction 97.1%, gel fraction 93.6%, its size distribution is in 60～70nm scope.
Embodiment 8: change the initiator amount that each step adds among the embodiment 6 into 1.5 parts, 0.9 part, 0.6 part respectively, be reflected under 95 ℃ and carry out, each goes on foot the reaction times and is 0.5 hour, and all the other prescriptions are identical with embodiment 6 with step.Reaction yield is 88.7%, and gel fraction is 93.5%, size distribution 60～70nm.
Embodiment 9: change the initiator in each step among the embodiment 7 into the dibenzoyl peroxide of equal consumption and the redox initiation system that S-WAT (the two mass ratio is 2: 1) is formed, and adopting low polyhutadiene as the stratum nucleare multi-olefin monomer, each goes on foot the reaction times and is 1 hour.All the other prescriptions are identical with embodiment 7 with step.Reaction yield is 95.2%, and gel fraction is 92.8%, size distribution 50～60nm.
Comparative example 1: the preparation method is with embodiment 1, but with the disposable whole adding systems of the mixing solutions of oleic acid and sodium hydroxide, the slight breakdown of emulsion of system has precipitation.The productive rate of products therefrom and gel fraction are respectively 72.3% and 46.8%, and size distribution is 30～110nm (it is very wide to distribute).
Comparative example 2: the preparation method is with embodiment 6, but do not add potassium hydroxide in the acryllic acid, system layering and serious breakdown of emulsion and precipitation take place in reaction process.
In above each embodiment, embodiment 1,2,3,4,5 belongs to the method for emulsifier-free emulsion polymerization, and embodiment 6,7,8,9 belongs to the method for no soap 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 (8)
1. the emulsifier-free emulsion polymerization method of a carboxyl function type cross-linked core-shell structure nano polymer microsphere is characterized in that this method is a raw material with following material:
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; Described monoolefine monomer is meant one or more in the alpha-olefin that only contains a carbon-carbon double bond in the molecule, vinylbenzene, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester;
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; Described multi-olefin monomer is meant the material that contains two or more carbon-carbon double bonds in the molecule;
3) have the olefinic monomer of carboxyl or carboxylate group functional group: 2～40 parts;
4) water soluble starter: 0.2～3 part;
Its concrete processing step is as follows:
(a) be that the water-soluble alkali adding that contains the olefinic monomer 50～150% of carboxyl functional group contains in the olefinic monomer of carboxyl functional group with quality; If what adopt is the olefinic monomer that contains carboxylate group, then do not need to add alkali;
(b) press the above-mentioned raw materials proportioning stratum nucleare monoolefine monomer of 30-70% and the stratum nucleare multi-olefin monomer of 30-70% are mixed evenly, stand-by;
(c) add 20～80% of the total material that obtains by step (a) in 40 ℃～50 ℃ the reactor to containing deionized water and being warming up to, add the mixture that step (b) obtains then and form uniform milk sap;
(d) in same reactor, add 20～50% of whole water soluble starters, and be warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～6 hour;
(e) add 20～30% of whole water soluble starters, then with in the above-mentioned system of the mixed evenly adding of remaining stratum nucleare monoolefine monomer and remaining stratum nucleare multi-olefin monomer, said temperature scope internal reaction 0.5～6 hour;
(f) add the residue water soluble starter, select for use the monoolefine monomer different evenly to add in the reacted system of step (e) according to described proportion of raw materials again, then 60 ℃～95 ℃ temperature range internal reaction 0.5～4 hour as shell monoolefine monomer and shell multi-olefin monomer are mixed with the stratum nucleare monoolefine monomer;
(g) add the remaining material that obtains by step (a), said temperature scope internal reaction 0.5～4 hour;
(h) behind the cooling discharging, adding quality is the water soluble acid that contains the olefinic monomer quality 50～150% of carboxyl functional group, 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.
2. according to the described preparation method of claim 1, it is characterized in that: the described material that contains two or more carbon-carbon double bonds is selected from one or more in suitable divinyl, isobutyl diene, isoprene, Vinylstyrene, the trihydroxy methyl propane trimethyl acrylate.
3. according to the described preparation method of claim 1, it is characterized in that: described carboxyl or the carboxylate group functional group olefinic monomer of containing, be meant and in molecular structure, contain simultaneously, perhaps in molecular structure, contain simultaneously with the represented carbon carbon unsaturated double-bond of chemical structure skeleton symbol (a) with the olefines material of the carboxylate group functional group of formula (c) expression with the represented carbon carbon unsaturated double-bond of chemical structure skeleton symbol (a) with the olefines material of the carboxyl functional group of formula (b) expression.
4. according to the described preparation method of claim 1, it is characterized in that: described water soluble starter is meant that under 40～95 ℃ of conditions also can produce free radical causes olefinic monomer polymeric persulfuric acid salt and hydroperoxide kind water-soluble substances to have 30～35kcal/mol ionic dissociation energy.
5. according to the described preparation method of claim 4, it is characterized in that: described water soluble starter is the redox system that Potassium Persulphate, ammonium persulphate or hydrogen peroxide are formed with ferrous salt, sulphite, thiosulphate respectively.
6. the no soap suspension polymerization of a carboxyl function type cross-linked core-shell structure nano polymer microsphere, it is characterized in that: this method is a raw material with following material,
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) have the olefinic monomer of carboxyl or carboxylate group functional group: 2～40 parts;
4) oil-soluble initiator: 0.2～3 part;
Its processing step is as follows:
(a) be that the water-soluble alkali adding that contains the olefinic monomer 50～150% of carboxyl functional group contains in the olefinic monomer of carboxyl functional group with quality; If what adopt is the olefinic monomer that contains carboxylate group, then do not need to add alkali;
(b) press the above-mentioned raw materials proportioning stratum nucleare monoolefine monomer of 30-70%, stratum nucleare polyene hydrocarbon act body and 20～50% of the whole oil-soluble initiators of 30-70% are mixed evenly, stand-by;
(c) add 20～80% of the total material that obtains by step (a) in 40 ℃～50 ℃ the reactor to containing deionized water and being warming up to, add the mixture that step (b) obtains then and form uniform milk sap;
(d) system that step (c) is obtained is warming up to 60 ℃～95 ℃ temperature range internal reaction 0.5～6 hour;
(e) with remaining stratum nucleare monoolefine monomer, remaining stratum nucleare multi-olefin monomer and whole 20～30% mixed evenly addings in the above-mentioned system of oil-soluble initiators, said temperature scope internal reaction 0.5～6 hour;
(f) select for use the monoolefine monomer different as shell monoolefine monomer and shell multi-olefin monomer and remaining oil-soluble initiator is mixed evenly adds in the reacted system of step (e) according to described proportion of raw materials again, then 60 ℃～95 ℃ temperature range internal reaction 0.5～4 hour with the stratum nucleare monoolefine monomer;
(g) add the remaining material that obtains by step (a), said temperature scope internal reaction 0.5～4 hour;
(h) behind the cooling discharging, adding quality is the water soluble acid that contains the olefinic monomer quality 50～150% of carboxyl functional group, 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.
7. according to the described preparation method of claim 6, it is characterized in that: described oil-soluble initiator is meant that under 40～95 ℃ of conditions also can produce free radical causes olefinic monomer polymeric azo class and peroxide oil-soluble substance to have 30～35kcal/mol ionic dissociation energy.
8. according to the described preparation method of claim 7, it is characterized in that: described oil-soluble initiator is the redox system that Diisopropyl azodicarboxylate, dibenzoyl peroxide or dibenzoyl peroxide are formed with ferrous salt, sulphite, thiosulphate respectively.
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| CN102234343B (en) * | 2010-04-20 | 2015-08-19 | 南开大学 | Monodispersed surface functionalized polymer microballoon resin and preparation method thereof |
| CN104624132B (en) * | 2013-11-07 | 2017-02-08 | 中国科学院化学研究所 | Epoxy resin self-repairing microcapsule and preparation method thereof |
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| CN105646789B (en) * | 2016-03-15 | 2018-02-16 | 大连理工大学 | A kind of preparation method of nanoscale fluorescent polymer rare earth coordination thing microballoon |
| CN110180475A (en) * | 2019-04-03 | 2019-08-30 | 沈阳化工大学 | A kind of preparation method of core-shell particles |
| CN110237785A (en) * | 2019-06-11 | 2019-09-17 | 扬州工业职业技术学院 | A kind of catalyst micro capsule and preparation method thereof |
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