CN110922547A - Double-anchoring type block copolymer and preparation method and application thereof - Google Patents
Double-anchoring type block copolymer and preparation method and application thereof Download PDFInfo
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- CN110922547A CN110922547A CN201911267734.5A CN201911267734A CN110922547A CN 110922547 A CN110922547 A CN 110922547A CN 201911267734 A CN201911267734 A CN 201911267734A CN 110922547 A CN110922547 A CN 110922547A
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 48
- 238000004873 anchoring Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 29
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 16
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 copper halide Chemical class 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000049 pigment Substances 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 9
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 8
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 8
- 229940045803 cuprous chloride Drugs 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 6
- XXSPGBOGLXKMDU-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid Chemical compound CC(C)(Br)C(O)=O XXSPGBOGLXKMDU-UHFFFAOYSA-N 0.000 claims description 5
- UEBARDWJXBGYEJ-UHFFFAOYSA-N 2-bromo-3-methylbutanoic acid Chemical compound CC(C)C(Br)C(O)=O UEBARDWJXBGYEJ-UHFFFAOYSA-N 0.000 claims description 5
- MYCXCBCDXVFXNE-UHFFFAOYSA-N 2-chloro-2-methylpropanoic acid Chemical compound CC(C)(Cl)C(O)=O MYCXCBCDXVFXNE-UHFFFAOYSA-N 0.000 claims description 5
- WNXNUPJZWYOKMW-UHFFFAOYSA-N 5-bromopentanoic acid Chemical compound OC(=O)CCCCBr WNXNUPJZWYOKMW-UHFFFAOYSA-N 0.000 claims description 5
- WTQLOILEMWBNTR-UHFFFAOYSA-N 7-bromo-2-oxoheptanoic acid Chemical compound OC(=O)C(=O)CCCCCBr WTQLOILEMWBNTR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- VHJFWJXYEWHCGD-UHFFFAOYSA-N 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine Chemical compound CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 VHJFWJXYEWHCGD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- QAYYEVPRIRMUJU-UHFFFAOYSA-N 12-[(2-bromo-2-methylpropanoyl)amino]dodecanoic acid Chemical compound BrC(C(=O)NCCCCCCCCCCCC(=O)O)(C)C QAYYEVPRIRMUJU-UHFFFAOYSA-N 0.000 claims description 2
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 30
- 239000007787 solid Substances 0.000 abstract description 14
- 239000006185 dispersion Substances 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 5
- VGUWFGWZSVLROP-UHFFFAOYSA-N 1-pyridin-2-yl-n,n-bis(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CC1=CC=CC=N1 VGUWFGWZSVLROP-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- HZTPKMIMXLTOSK-UHFFFAOYSA-N 2-bromohexanoic acid Chemical compound CCCCC(Br)C(O)=O HZTPKMIMXLTOSK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a preparation method of a double-anchoring type block copolymer, which comprises the steps of adding an initiator, styrene, acrylonitrile, copper halide and an organic ligand into an organic solvent, fully stirring, and preparing a polymer by adopting an atom transfer radical polymerization method to obtain poly (acrylonitrile-co-styrene); and dropwise adding a dimethylaminoethyl methacrylate monomer in protective gas into poly (acrylonitrile-co-styrene) for polymerization reaction, and after the reaction is finished, centrifuging, washing and drying a reaction product to obtain the block copolymer. Also discloses a double-anchoring type block copolymer prepared by the method and application thereof. The invention adopts a one-pot method for preparing the double-anchoring type block copolymer for the first time, is used for dispersing solid particles, can be prepared into an oily or aqueous solid particle dispersion, and can be applied to the fields of plastics, coatings, printing ink and the like. The method provided by the invention has the advantages of simple process, easy operation, mild reaction conditions and easy control, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of preparation of high polymer materials, and particularly relates to a double-anchoring type block copolymer, and a preparation method and application thereof.
Background
With the development of society, pigments are increasingly used in the industry of coating inks and the like, and in general, pigments are insoluble in a medium used and are often present in the form of aggregates. Therefore, the study of the opening and stabilization of the aggregates of the pigment is of great importance.
The hyper-dispersant is a novel and efficient polymer dispersant, has remarkable space shielding effect and electric repulsion when dispersing solid particles, can quickly and fully wet pigment particles, greatly improves the content of the solid particles in a dispersion system, and ensures that the dispersion system is more uniform and has good stability.
The application of the amphiphilic acrylate block copolymer synthesized by a DPE method and used as a pigment dispersant [ J ].2014, 65(6):2378) in Rexian et al (chemical Proc., DPE method) is characterized in that 1, 1-Diphenylethylene (DPE) is used as a molecular weight regulator, and Azobisisobutyronitrile (AIBN) is used as an initiator to carry out controllable free radical polymerization on Butyl Methacrylate (BMA), so that Polybutylmethacrylate (PBMA) containing a DPE semiquinone type dormant seed structure is obtained. And initiating polymerization of dimethylaminoethyl methacrylate (DMAEMA) by taking PBMA as an initiator to obtain the amphiphilic block copolymer (PBMA-b-PDMAEMA) dispersing agent. However, the PBMA dormant chain with DPE end group needs a certain time for reactivation to initiate the polymerization of the second monomer, and the industrial production is not easy. The amphiphilic acrylic ester block copolymer has no double anchoring property, can only be suitable for a certain type of solid pigment, and has a limited application range.
Zhang et al (Zhang X, HuH-R. Synthesis and application of a Polyacetylatedispersant on the preparation of the fine ground calcium carbonate in organic media mill, 2014,266:218-227) free radical polymerization was used to prepare a series of P (AA/AMPS) polymers using Acrylic Acid (AA) and 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) as monomers, ammonium persulfate as initiator and isopropanol as chain transfer agent. The influence of the weight ratio of AA/AMPS to isopropanol to water, the amount of initiator, the reaction time and the reaction temperature on the P (AA/AMPS) performance and the grinding effect was investigated. The reaction is carried out by heating to a predetermined temperature and then adding the monomer, and when the reaction is completed, removing the chain transfer agent isopropanol and the solvent distilled water from the system by using a rotary evaporator. The operation steps are complicated, the requirement on the device is high, and the industrial production is not easy to realize. The P (AA/AMPS) polymer has no double anchoring property, can only be applied to solid particles such as calcium carbonate, and has limited application range.
CN108641051A discloses a method for preparing an oil-soluble hyperdispersant based on a block copolymer, which comprises synthesizing a poly (methacrylate-b- (styrene-co-p-chloromethyl styrene)) oil-soluble copolymer by a reversible addition-fragmentation chain transfer polymerization method, and then preparing the block copolymer hyperdispersant grafted with a polyamine compound by a nucleophilic substitution reaction with methylene chloride in the polymer. However, the obtained macromolecular chain transfer agent PMA needs to be precipitated, centrifugally washed and then subjected to the next polymerization reaction. The process is complicated and not easy for industrial production. The poly (methacrylate-b- (styrene-co-p-chloromethyl styrene)) has no double anchorage, can only be applied to oil-soluble solid particle dispersions, and has a limited application range.
Disclosure of Invention
In view of the above, the present invention is directed to a double-anchored block copolymer, a method for preparing the same, and a use thereof as a hyperdispersant, wherein the polymerization reaction is directly performed in the next step without purification, drying, etc. after the synthesis of the polymer in the first step. The prepared double-anchoring type block copolymer can be used as a hyper-dispersant to anchor different types of solid particles and realize uniform and ordered dispersion of pigment particles. The method has the advantages of simple process, easy operation, mild reaction conditions, easy control, low cost and easy industrialization.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a bi-anchored block copolymer, comprising the steps of:
s1, adding an initiator, styrene, acrylonitrile, copper halide and an organic ligand into an organic solvent, fully stirring, and preparing a polymer by adopting an atom transfer radical polymerization method to obtain poly (acrylonitrile-co-styrene);
s2, dropwise adding the dimethylaminoethyl methacrylate monomer in the protective gas into poly (acrylonitrile-co-styrene) for polymerization reaction, and after the reaction is finished, centrifuging, washing and drying the reaction product to obtain poly ((acrylonitrile-co-styrene) -b-dimethylaminoethyl methacrylate), namely the block copolymer.
In step S1, the atom transfer radical polymerization process includes: adding an initiator, styrene, acrylonitrile, copper halide and an organic ligand into a Schlenk bottle filled with an organic solvent, and fully stirring; and introducing protective gas, freezing by liquid nitrogen, carrying out vacuum deoxygenation treatment, adding cuprous halide, heating, and carrying out graft reaction on styrene and acrylonitrile monomers to obtain the poly (acrylonitrile-co-styrene).
Preferably, the protective gas is nitrogen or an inert gas.
In a further scheme, in step S1, the initiator is a compound containing both halogen and carboxyl in an organic molecular structure;
the organic solvent comprises one of dimethylformamide, anisole, dimethyl sulfoxide, sulfolane and ethylene nitrate;
the copper halide is copper chloride or copper bromide;
the organic ligand comprises one of 4,4 '-dinonyl-2, 2' -bipyridine, tri (2-pyridylmethyl) amine, tri (2-dimethylaminoethyl) amine and pentamethyldiethylenetriamine.
In a further embodiment, the compound containing both halogen and carboxyl is selected from the group consisting of α -chloroisobutyric acid, 12- (2-bromoisobutyramido) dodecanoic acid, 2-bromoisobutyric acid, α -bromoisovaleric acid, 5-bromovaleric acid, a-bromohexanoic acid, and 7-bromo-2-oxoheptanoic acid.
Further, in step S2, the dimethylaminoethyl methacrylate monomer is added dropwise by using a syringe; the end point of the polymerization reaction is based on the molecular weight of the reaction product, as determined by GPC after sampling with a syringe.
In a further scheme, the cuprous halide is cuprous chloride or cuprous bromide.
In a further scheme, the molar ratio of the initiator, the styrene, the acrylonitrile, the copper halide, the cuprous halide and the organic ligand is 1: (200-600): (200-600): (0.1-1.0): (0.9-10): (2-20). The preferred range of the molar ratio in the present invention allows for a more efficient and rapid reaction and maximum utilization of the drug.
It is a second object of the present invention to provide a block copolymer having double anchorability prepared by the above-mentioned preparation method.
A third object of the present invention is to provide the use of the above block copolymer as a hyperdispersant for pigments. Can be applied to various inorganic or polymer solid particles and used for aqueous and oily systems.
It is understood that the reaction time of the atom transfer radical polymerization method for preparing the polymer in the present invention is not specifically limited, and can be adjusted according to the molecular weight of the desired polymer, and in some embodiments of the present invention, the preferred reaction time is 5-48h, and the processing parameters thereof are also routine adjustment of atom transfer radical polymerization, and can be adjusted by those skilled in the art according to the needs, and is not specifically limited herein.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts a one-pot method, namely, after the first step of polymer synthesis, the next step of polymerization reaction is directly carried out without the steps of settling, drying and the like, the operation is simple, and the method is suitable for industrial production.
2. The block copolymer synthesized by the invention is a double-anchoring block copolymer, can be respectively and tightly combined with the surfaces of organic or inorganic particles, plays a good anchoring role, avoids agglomeration among the particles, and obtains a uniformly dispersed dispersoid.
3. The block copolymer prepared by the invention can be used as a hyper-dispersant, and utilizes the affinity of functional poly (acrylonitrile-co-styrene) to organic particles, and the poly (acrylonitrile-co-styrene) is connected to the surface of a pigment through adsorption and is used for the surface of dispersion particles, so that the dropping of dispersant molecules can be effectively prevented; and the hydrophilic dimethylaminoethyl methacrylate chain segment generates a stereo adsorption layer to form an effective space barrier layer, and the stable solid particle aqueous dispersion can be configured and applied to an aqueous system.
In addition, the affinity of functional polydimethylaminoethyl methacrylate to inorganic particles can be utilized, the polydimethylaminoethyl methacrylate is connected to the surface of solid particles through adsorption, an oleophilic poly (acrylonitrile-co-styrene) chain segment generates a stereo adsorption layer to form an effective steric barrier layer, and a stable oily solid particle dispersion can be prepared.
4. The special dual anchorage property of the poly (acrylonitrile-co-styrene) and the poly (dimethylaminoethyl methacrylate) dispersed solid particles in the block copolymer prepared by the invention overcomes the defects of the traditional dispersing agent on the molecular structure and single adaptability, so that the block copolymer can quickly and fully wet the particles, can be prepared with an oil-soluble or water-soluble solid particle dispersion body, improves the dispersibility, the color development, the stability and the like of a dispersion system, and can be applied to the fields of plastics, coatings, printing ink and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the pigment of example 1;
FIG. 2 is a graph showing the particle size distribution of the pigment of example 1 after addition of the block copolymer;
FIG. 3 is a chart of the infrared spectra of the block copolymer, the pigment and the block copolymer obtained in example 1 after the addition of the pigment;
FIG. 4 is a thermogravimetric analysis of the pigment and the block copolymer obtained in example 1 after addition to the pigment.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Anisole (30mL), 2-bromoisobutyric acid, styrene, acrylonitrile, copper bromide and tris (2-pyridylmethyl) amine were added to a Schlenk flask and stirred well; and then introducing nitrogen, discharging air, freezing by liquid nitrogen, carrying out vacuum deoxygenation treatment, adding cuprous bromide, and reacting at 60 ℃, wherein the molar ratio of 2-bromoisobutyric acid to styrene to acrylonitrile to copper bromide to cuprous bromide to tris (2-pyridylmethyl) amine is 1: 500: 300: 0.5: 2.5: 9, styrene and acrylonitrile are grafted by using 2-bromoisobutyric acid as an initiator until the desired polymer molecular weight (1.02X 10)4) When the air had been excluded, dimethylaminoethyl methacrylate monomer (6mL) was added to the Schlenk bottle by syringe. When the desired polymer molecular weight (2.0X 10) is reached5) When the reaction is terminated, the reaction product is centrifugally purified, and the product is dried in an oven at 40 ℃ for 10 hours to obtain a block copolymer which is marked as PSAN-b-PDMAEMA.
Test example
FIG. 1 is a scanning electron micrograph of the pigment of example 1, from which it can be seen that the pigment particles have a platelet structure with a size of about 70-300 nm.
In FIG. 2, a is a distribution diagram of the particle size of the pigment of example 1, and in FIG. 2, b is a distribution diagram of the particle size of the block copolymer obtained in example 1 after the addition of the pigment, as can be seen from the following figures: the pigment had a particle size of about 774nm and the pigment had a particle size of about 295nm after addition of the block copolymer. It can be seen that: the addition of the block copolymer makes the particle size of the pigment significantly smaller. This is because the block copolymer can effectively reduce the agglomeration of pigment particles.
FIG. 3 is an infrared spectrum of the block copolymer (c) obtained in example 1, the pigment (a) and the mixture (b) of the block copolymer with the pigment added, in which: the block copolymer-added pigments were found to have infrared spectra at 2233, 1727 and 1467cm-1A new peak appeared. It can thus be derived: the block copolymer adsorbs on the surface of the pigment particles.
FIG. 4 is a thermogravimetric analysis of the pigment after the block copolymer obtained in example 1 was added to the pigment, and it can be seen that 20% of the original pigment remained (a) and 1% of the original pigment remained after the dispersant was added (b), giving a polymer mass fraction adsorbed on the surface of the pigment particles of about 19%, further demonstrating that the product was adsorbed on the surface of the pigment particles.
Adding 0.5g of pigment (PR146) into 20mL of toluene, and carrying out ultrasonic treatment for 10min to obtain a solution A; meanwhile, 0.5g of pigment (PR146) and 50mg, 100mg and 150mg of the block copolymer prepared in example 1 were added together to 20mL of toluene, and sonicated for 10min to obtain solutions B (10 wt%), C (20 wt%) and D (30 wt%), respectively. The solution A, B, C, D was allowed to stand for 24h and its change was observed (as shown in Table 1 below).
Then, 4mL of the solution A, B, C, D was centrifuged at 5000r/min for 10min, and the centrifugation stability was measured by observing the state after centrifugation (see Table 2 below).
TABLE 1
TABLE 2
As can be seen from tables 1 and 2 above, the pigment solution without the hyperdispersant block copolymer prepared according to the present invention was left standing for a while, the pigment was deposited on the bottom of the sample bottle in a clearly layered state and could not be dispersed in the toluene solution. It was centrifuged and the pigment was found to have all settled to the bottom of the centrifuge tube. And with the increase of the mass of the hyper-dispersant, the pigment can be gradually dispersed in the toluene, when the mass fraction of the hyper-dispersant reaches 20 wt% of the mass of the pigment, no layering phenomenon occurs, and only a very small amount of pigment is deposited at the bottom of the centrifuge tube. When the mass fraction of the hyperdispersant reached 30 wt% of the mass of the pigment, it was subjected to a centrifugal stability test and found that the pigment was completely dispersed in the toluene solvent. Therefore, it was further demonstrated that the block copolymer poly (dimethylaminoethyl methacrylate-b- (acrylonitrile-co-styrene)) can effectively reduce the agglomeration of pigment particles, thereby achieving the pigment dispersing effect.
Example 2
Adding N, N-dimethylformamide (30mL), α -chloroisobutyric acid, styrene, acrylonitrile, copper chloride and 4,4 '-dinonyl-2, 2' -bipyridine into a Schlenk bottle, fully stirring, introducing nitrogen, exhausting air, freezing by liquid nitrogen, removing oxygen by vacuum, adding cuprous chloride, and reacting at 60 ℃, wherein the molar ratio of α -chloroisobutyric acid, styrene, acrylonitrile, copper chloride, cuprous chloride and 4,4 '-dinonyl-2, 2' -bipyridine is 1: 500: 300: 1.0: 10: 20, the styrene and acrylonitrile are grafted under the action of α -chloroisobutyric acid as an initiator, and when the required polymer molecular weight (1.1X 10) is reached3) When the air had been excluded, dimethylaminoethyl methacrylate monomer (6mL) was added to the Schlenk bottle by syringe. When the desired polymer molecular weight (2.1X 10) is reached5) When the reaction is ended, the reaction is centrifuged and purified, and the product is dried in an oven at 40 ℃ for 10 hours to obtain the block copolymer.
Example 3
Adding dimethyl sulfoxide (30mL), α -bromoisovaleric acid, styrene, acrylonitrile, copper bromide and 2,2 '-bipyridine into a Schlenk bottle, fully stirring, introducing nitrogen, exhausting air, freezing by liquid nitrogen, vacuum deoxygenation treatment, adding cuprous bromide, and reacting at 60 ℃, wherein the molar ratio of α -bromoisovaleric acid, styrene, acrylonitrile, copper bromide, cuprous bromide and 2,2' -bipyridine is 1: 500: 300: 0.1: 0.9: 2, the styrene and acrylonitrile are subjected to grafting reaction under the action of α -bromoisovaleric acid as an initiator, and when the required polymer molecular weight (7.65X 10) is reached3) When the air had been excluded, dimethylaminoethyl methacrylate monomer (6mL) was added to the Schlenk bottle by syringe. When the desired polymer molecular weight (1.57X 10) is reached4) When the reaction is ended, the reaction is centrifuged and purified, and the product is dried in an oven at 40 ℃ for 10 hours to obtain the block copolymer.
Example 4
Adding sulfolane (30mL), 5-bromo-valeric acid, styrene, acrylonitrile, copper chloride and pentamethyldiethylenetriamine into a Schlenk bottle, and fully stirring; and then introducing nitrogen, discharging air, freezing by liquid nitrogen, carrying out vacuum deoxygenation treatment, adding cuprous chloride, and carrying out reaction at 60 ℃, wherein the molar ratio of 5-bromovaleric acid, styrene, acrylonitrile, copper chloride, cuprous chloride and pentamethyldiethylenetriamine is 1: 500: 300: 0.3: 1.5: 3.6 grafting of styrene and acrylonitrile with 5-bromovaleric acid as initiator until the desired polymer molecular weight (1.27X 10)4) When the air had been excluded, dimethylaminoethyl methacrylate monomer (6mL) was added to the Schlenk bottle by syringe. When the desired polymer molecular weight (2.5X 10) is reached5) When the reaction is ended, the reaction is centrifuged and purified, and the product is dried in an oven at 40 ℃ for 10 hours to obtain the block copolymer.
Example 5
Ethylene nitrate (30mL), 7-bromo-2-oxoheptanoic acid, styrene, acrylonitrile, cupric bromide, and tris (2-pyridylmethyl) amine were added to a Schlenk flask and stirred well; then introducing nitrogen, discharging air, freezing by liquid nitrogen, carrying out vacuum deoxygenation treatment, adding cuprous bromide, and carrying out reaction at 60 ℃, wherein the molar ratio of 7-bromo-2-oxoheptanoic acid, styrene, acrylonitrile, cupric bromide, cuprous bromide and tris (2-pyridylmethyl) amine is 1: 500: 300: 0.6: 4.5: 7, styrene and acrylonitrile are grafted under the action of 7-bromo-2-oxoheptanoic acid as an initiator until the desired polymer molecular weight (8.5X 10)3) When the air had been excluded, dimethylaminoethyl methacrylate monomer (6mL) was added to the Schlenk bottle by syringe. When the desired polymer molecular weight (1.88X 10) is reached4) Stopping reaction, centrifugal purifying, baking at 40 deg.CDrying in a box for 10h to obtain the block copolymer.
Example 6
Adding sulfolane (30mL), alpha-bromohexanoic acid, styrene, acrylonitrile, copper chloride and pentamethyldiethylenetriamine into a Schlenk bottle, and fully stirring; and then introducing nitrogen, discharging air, freezing by liquid nitrogen, carrying out vacuum deoxygenation treatment, adding cuprous chloride, and carrying out reaction at 60 ℃, wherein the molar ratio of the a-bromohexanoic acid to the styrene to the acrylonitrile to the cupric chloride to the cuprous chloride to the pentamethyldiethylenetriamine is 1: 500: 300: 0.8: 7.5: 8, styrene and acrylonitrile are grafted under the action of a-bromohexanoic acid as an initiator until the required polymer molecular weight (1.2X 10)4) When the air had been excluded, dimethylaminoethyl methacrylate monomer (6mL) was added to the Schlenk bottle by syringe. When the desired polymer molecular weight (2.3X 10) is reached5) When the reaction is ended, the reaction is centrifuged and purified, and the product is dried in an oven at 40 ℃ for 10 hours to obtain the block copolymer.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a double-anchoring type block copolymer is characterized by comprising the following steps:
s1, adding an initiator, styrene, acrylonitrile, copper halide and an organic ligand into an organic solvent, fully stirring, and preparing a polymer by adopting an atom transfer radical polymerization method to obtain poly (acrylonitrile-co-styrene);
s2, dropwise adding the dimethylaminoethyl methacrylate monomer in the protective gas into poly (acrylonitrile-co-styrene) for polymerization reaction, and after the reaction is finished, centrifuging, washing and drying the reaction product to obtain poly ((acrylonitrile-co-styrene) -b-dimethylaminoethyl methacrylate), namely the block copolymer.
2. The method according to claim 1, wherein in step S1, the atom transfer radical polymerization process comprises: adding an initiator, styrene, acrylonitrile, copper halide and an organic ligand into a Schlenk bottle filled with an organic solvent, and fully stirring; and introducing protective gas, freezing by liquid nitrogen, carrying out vacuum deoxygenation treatment, adding cuprous halide, heating, and carrying out graft reaction on styrene and acrylonitrile monomers to obtain the poly (acrylonitrile-co-styrene).
3. The method according to claim 1 or 2, wherein the protective gas is nitrogen or an inert gas.
4. The method according to claim 1, wherein in step S1, the initiator is a compound having both halogen and carboxyl in an organic molecular structure;
the organic solvent comprises one of dimethylformamide, anisole, dimethyl sulfoxide, sulfolane and ethylene nitrate;
the copper halide is copper chloride or copper bromide;
the organic ligand comprises one of 4,4 '-dinonyl-2, 2' -bipyridine, tri (2-pyridylmethyl) amine, tri (2-dimethylaminoethyl) amine and pentamethyldiethylenetriamine.
5. The method according to claim 4, wherein the compound containing both halogen and carboxyl is selected from the group consisting of α -chloroisobutyric acid, 12- (2-bromoisobutyramido) dodecanoic acid, 2-bromoisobutyric acid, α -bromoisovaleric acid, 5-bromovaleric acid, a-bromohexanoic acid, and 7-bromo-2-oxoheptanoic acid.
6. The method according to claim 1, wherein in step S2, the dimethylaminoethyl methacrylate monomer is added dropwise by using a syringe; the end point of the polymerization reaction is based on the molecular weight of the reaction product, as determined by GPC after sampling with a syringe.
7. The method according to claim 2, wherein the cuprous halide is cuprous chloride or cuprous bromide.
8. The method according to claim 2, wherein the molar ratio of the initiator, styrene, acrylonitrile, copper halide, cuprous halide and organic ligand is 1: (200-600): (200-600): (0.1-1.0): (0.9-10): (2-20).
9. A block copolymer prepared by the method of claim 1, wherein the block copolymer has double anchoring properties.
10. Use of a block copolymer according to claim 9 as a hyper-dispersant for pigments.
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