CN104628948B - Acrylate-type poly-chain transfer agent as well as preparation method and application of poly-chain transfer agent in preparation of columnar polymer brush - Google Patents
Acrylate-type poly-chain transfer agent as well as preparation method and application of poly-chain transfer agent in preparation of columnar polymer brush Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 59
- 239000012986 chain transfer agent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 disulfide ester Chemical class 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 238000012546 transfer Methods 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical class CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 claims description 2
- JEAVBVKAYUCPAQ-UHFFFAOYSA-N ethyl 2-chloropropanoate Chemical compound CCOC(=O)C(C)Cl JEAVBVKAYUCPAQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000012634 fragment Substances 0.000 abstract description 8
- 239000004793 Polystyrene Substances 0.000 abstract description 3
- 229920001400 block copolymer Polymers 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 229920001519 homopolymer Polymers 0.000 abstract description 3
- 229920002223 polystyrene Polymers 0.000 abstract description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 125000001309 chloro group Chemical group Cl* 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229920000058 polyacrylate Polymers 0.000 abstract 1
- 229920000193 polymethacrylate Polymers 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 17
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 230000005311 nuclear magnetism Effects 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 230000000379 polymerizing effect Effects 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 150000007970 thio esters Chemical class 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- QXDYJUSFCUKOQD-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-bromo-2-methylpropanoate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)(C)Br QXDYJUSFCUKOQD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 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 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000012988 Dithioester Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000005022 dithioester group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000003808 methanol extraction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 101000727772 Homo sapiens Thiamine transporter 1 Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 102100030104 Thiamine transporter 1 Human genes 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 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
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035892 strand transfer Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 208000006446 thiamine-responsive megaloblastic anemia syndrome Diseases 0.000 description 1
- YFNCATAIYKQPOO-UHFFFAOYSA-N thiophanate Chemical compound CCOC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OCC YFNCATAIYKQPOO-UHFFFAOYSA-N 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses an acrylate-type poly-chain transfer agent as well as a preparation method and an application of the poly-chain transfer agent in the preparation of a columnar polymer brush. The acrylate-type poly-chain transfer agent is prepared by synthesizing a main chain containing bromine (or chlorine) functional groups by virtue of RAFT and then introducing disulfide ester functional fragments by virtue of a one-step method. The columnar polymer brush is synthesized from the obtained acrylate-type poly-chain transfer agent by adopting a synthesis strategy of 'grafting from main chain' through the RAFT method, homopolymer and block copolymer containing multifunctional branched monomers can be obtained, namely, a brush-shaped homopolymer and a copolymer are obtained. The main chain of the polymer molecular brush is a (meth) acrylate polymer and the side chain of the polymer molecular brush is polystyrene, poly(meth)acrylate and poly(meth)acrylamide or a copolymer thereof. By the preparation method, the tedious steps used in the synthesis of a complex chain transfer reagent are avoided, the pollution caused by the tedious steps is decreased, the synthesized columnar polymer brush has a controllable structure and the preparation method provides a more simple and efficient method to synthesize the functional columnar polymer brush.
Description
Technical field
The invention belongs to synthesis of polymer material and preparing technical field are and in particular to a kind of acrylic ester type poly chain shifts
Agent, its preparation method and the application in preparing process for preparing column type polymer brush.
Background technology
Process for preparing column type polymer molecular brush (Cylindrical Polymer Brush), refers to the polymer molecule as side chain
One end of chain is chemically bound in the graft copolymer of the macromole such as the linear, dendroid as main chain to high-density.Due to highly dense
Spend the presence of long side chain, molecular brush presents unique molecular form, bulk properties and the solution behavior differing from linear molecule, because
And make polymer brush in nanometer polymer material (Macromolecules 2012,45,2619 2631；
Macromolecules 2003,36,7894 7898), drug release (J.Am.Chem.Soc.2010,133,559 566), super
There is potential application prospect in the fields such as molecular chemistry (Macromolecules 1997,30,2002 2007).
The synthetic method of current process for preparing column type polymer brush mainly has：(1) " grafting through " (polymeric monomer polymerization),
It is polymerized as monomer by the macromonomer polymer with double bond, obtained process for preparing column type polymer；(2)“grafting onto”
(being grafted to main chain method), by being connected to the active end group of polymer on the active lateral group of another kind of polymer, to prepare phase
Emergencing copolymer molecular brush；(3) " grafting from " (from main chain Graft Method), the main polymer chain having initiating activity center draws
Bill body carries out polymerization and forms side chain, obtains polymer brush (Polymer 2003,44,1,449 1458).Controlled/" active " is certainly
After being made a breakthrough by base polymerization (Controlled/ " living " radical polymerization, CRP) technology, molecular brush
Synthetic method and species obtained large development.Using synthetic technology have atom transfer radical polymerization (ATRP), nitrogen oxygen
Stable free radical polymerization (NMRP) and reversible addition-fragmentation chain transfer free radical polymerization (RAFT) etc..In these methods, RAFT
The applicable species of polymerization monomer is many, and synthesis condition is gentle, and efficiency of initiation is high, and polymer architecture is easily controllable, gradually becomes in recent years
For study hotspot (Progress in Polymer Science 2012,37,38 105；Eur.Polym.J.2005,41,
2264–2277).
Prepare process for preparing column type polymer brush mostly using the main polymer chain first synthesizing active side base currently with RAFT, lead to afterwards
Cross the method that chemical reaction is bonded chain tra nsfer function fragment.Sulfur is introduced by methods such as esterification, click-reaction, substitution reactions
Ester fragment (Macromolecules 2004,37,2371 2382；Polym.Chem.,2013,4,2025–2032；Journal
of Polymer Science:Part A:Polymer Chemistry 2006,44,4,372 4383), but small molecule used by it
Thioester compound complex structure, building-up process is loaded down with trivial details, relatively costly, thus limits its answering in process for preparing column type polymer brush field
With.
Content of the invention
The invention provides a kind of acrylic ester type poly chain transfer agent, its preparation method and preparing process for preparing column type polymer brush
In application, the process that this preparation method introduces the function fragment of chain tra nsfer containing thioesters is easy reliable, and the acrylic ester type obtaining is poly-
Chain-transferring agent can be used for synthesis and contains multi-functional homopolymerization, block polymer brush.
A kind of preparation method of acrylic ester type poly chain transfer agent, comprises the steps：
(1) in the presence of micromolecule chain transfer agent, there is polyreaction in halogen acrylate-type monomer, obtain halogen third
Olefin(e) acid ester type polymer；
The structure of described halogen acrylate-type monomer is as shown in formula I：
In formula I, R1For H or methyl；X is Br or Cl；The integer of n=1～10；
(2) under conditions of the presence of halo initiator, cuprous halide, many nitrogen ligands and reducing agent, step (1) obtains halogen
Acrylate based polymer and small molecule thioesters reagent carry out substitution reaction, obtain described acrylic ester type poly chain transfer agent；
The structure of described small molecule thioesters reagent is as shown in formula II：
In formula II, R is alkyl or aryl；Described alkyl is preferably C1～C5Alkyl, described aryl is preferably benzene
Base.
This preparation method uses that radical reaction one step is easy to introduce the function fragment of chain tra nsfer containing thioesters, it is to avoid multistep behaviour
Required intermediate separating-purifying in work, decreases the pollution that solvent is brought, reduces production cost.The acrylic acid obtaining
Ester type poly chain transfer agent RAFT method synthesizes the polymer brush that side chain contains multi-functional homopolymerization, block copolymer, process letter
Just efficient, the function monomer that simultaneously successfully the methods such as ATRP can be unable to controllable polymerization is incorporated in polymer brush.
Preferably, described halogen acrylate-type monomer includes brominated (or chlorine) acrylate, brominated (or chlorine) first
Base acrylate.
Preferably, described micromolecule chain transfer agent is selected from one of compound shown in following formula：
Preferably, the polyreaction of step (1) is carried out in the presence of initiator；
The mol ratio of halogen acrylate-type monomer, initiator and micromolecule chain transfer agent is 50～800:0.3:1.Its
In, initiator is azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Preferably, the polyreaction of step (1) is carried out in reaction dissolvent, described halogen acrylate-type monomer
Molar concentration is 0.1～10mol/L.
Preferably, in step (1), the temperature of polyreaction is 60～90 DEG C, the time of polyreaction is 3～24h.
Through the reaction of step (1), the clear and definite line polymer of structure can be obtained, the degree of polymerization (is passed through for 50～1000
Nuclear magnetic resonance result calculates), molecular weight distribution is 1.01～1.45 (gel permeation chromatographies), preferably 1.1～1.3；It is worth
It is noted that when preparing main chain by different initiators, molecular weight and molecular weight distribution are different.
Preferably, in step (2), halogen acrylate based polymer (in terms of halogen unit), reducing agent, small molecule sulfur
Ester reagent, halo initiator, cuprous halide, the mol ratio of many nitrogen ligands are 1:1.8:1.3:0.4:1:6.
Preferably, in step (2), the temperature of substitution reaction is 60～120 DEG C, the time of substitution reaction is 1～48h.
Reaction concrete operations in step (2) are as follows：
Halogen acrylate based polymer, reducing agent, small molecule thioesters reagent, halo initiator and solvent are added reaction
In bottle；Subsequently by the cuprous halide of deoxygenation/(mol ratio is 1 to many nitrogen ligands:6) catalyst forming adds reaction by injector
In bottle, 60～120 DEG C of reaction 1～48h；Obtain the Macromolecular chain transfer agent containing dithioesters fragment.Functional group conversions lead as 50
～100% (being calculated by nuclear magnetic resonance result), connecting the molecular weight distribution after thioesters is that 1.1～1.45 (gel oozes
Chromatography thoroughly), preferably 1.1～1.3.It should be noted that when preparing main chain by different reducing agents, thioesters conversion ratio and molecule
Amount changes in distribution amplitude is different.
Wherein, halogen acrylate based polymer (in terms of halogen unit), reducing agent, small molecule thioesters reagent, halo draw
Send out agent, cuprous halide, many nitrogen ligands mol ratio be 1:1.8:1.3:0.4:1:6.
In step (2), described many nitrogen ligands are PMDETA, TERPY, BPOA, Bipy, Me6In TREN, TRMA and DMCBCy
One kind, the structural formula of each many nitrogen ligands is as follows：
In step (2), halo initiator is in α-chloro-propionicacid ethyl ester, ethyl α bromopropionate and alpha-brominated ethyl isobutyrate
A kind of.
In step (2), reducing agent is one of stannous octoate, copper simple substance.
In step (2), described small molecule thioesters reagent is arylthio dithio peroxide anhydride or thio two sulfur of fat-based
For peroxide anhydride.
Present invention also offers a kind of acrylic ester type poly chain transfer agent, obtained by described preparation method.
Present invention also offers a kind of preparation method of process for preparing column type polymer brush, comprise the steps：
In the presence of initiator, described acrylic ester type poly chain transfer agent carries out RAFT with side chain monomer to be polymerized instead
Should, obtain described process for preparing column type polymer brush.
Preferably, described side chain monomer includes at least one in the compound shown in following formula：
Wherein, R2And R4Independently selected from H or methyl；
R3、R5、R6And R7Independently selected from H, aryl or alkyl；Described alkyl is preferably C1～C5Alkyl, described virtue
Base is preferably phenyl.
As further preferred, when described side chain monomer is multiple, each side chain monomer successively with acrylate
Type poly chain transfer agent carries out RAFT polyreaction.For example, when described side chain monomer is two kinds, first make one of which side chain list
Body and acrylic ester type poly chain transfer agent carry out first time RAFT polyreaction, form the transfer agent of poly chain containing side chain；Obtain contains
Side chain poly chain transfer agent proceeds second RAFT polyreaction again with another kind of side chain monomer, obtains described column polymerization
Thing brush, the side chain of process for preparing column type polymer brush now is block copolymer.
Described RAFT polyreaction is carried out in the presence of initiator, each time in polyreaction, side chain monomer, initiation
Agent and acrylic ester type poly chain transfer agent (being calculated with thioesters unit) mol ratio are for 50～400:0.3:1, side chain monomer is in reaction
Molar concentration in solvent is between 0.1～10mol/L.Wherein, initiator is azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Preferably, the temperature of described RAFT polyreaction is 60～90 DEG C, the response time is 1～48 hour.
Reaction dissolvent in the present invention be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, toluene, methyl phenyl ethers anisole, two
One of oxygen six ring, dimethyl sulfoxide, acetonitrile, chloroform, N-Methyl pyrrolidone and oxolane.
Polymer in the present invention carries out purification by the method for dissolution precipitation, precipitant be methanol, water, ether and just oneself
One of alkane.
Present invention also offers a kind of process for preparing column type polymer brush, prepared by described preparation method.
Compared with the process for preparing column type polymer brush technology constructed with existing CRP technology, the present invention has significantly beneficial technique effect：
(1) in structure, the polymer molecule brush of the new construction that the present invention provides, containing various selectable function side chain,
In biological medicine, the field such as nano material is brushed with more potential applications than the molecule of common side chain.
(2) in method, because the introducing of thioesters function fragment is simple and effective, it is to avoid step-by-step polymerization and required centre
The separating-purifying of body compound, reduces the pollution that solvent is brought, and reduces production cost, and reaction condition is gentle, easy to control, easily
The process for preparing column type polymer brush of synthesis regular block type side chain.
The synthetic method of the present invention efficiently solves constructing based on ATRP technology and asks limited by molecular brush side chain functionalities
Topic.One-step method is simple and effective to introduce strand transfer fragment, has obtained the polymer brush of structure-controllable, in novel high polymer material
In have huge potential application foreground.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further detailed.
The molecular weight of gained process for preparing column type polymer brush adopts nuclear-magnetism following calculation and SEC to measure.Nuclear-magnetism is in Bruker ARX
400(1H:400MHz) measure on instrument, with deuterated dimethyl sulfoxide (DMSO-d6) or deuterochloroform (CDCl3) as solvent, four
Methyl-monosilane (TMS) is as internal standard.Number-average molecular weight is followed the tracks of conversion ratio by nuclear-magnetism and is obtained.The relative molecular weight of polymer and point
Son amount distribution is using Waters gel permeation chrommatograph (Waters 1525 HPLC configures Waters 2414 RI detector), chromatographic column
For Waters Styragel Columns HR4, HR3 and HR1, THF is mobile phase, and test temperature is 40 DEG C, and flow velocity is
1.0mL/min, the relative molecular mass of polymer is with polystyrene as standard calibration；And Waters 1515 Isocratic
Efficient liquid-phase chromatographic pump, 5 μm of MIEXD-C chromatographic columns of PLgel, the DMF containing 0.05mol/L LiBr as mobile phase, 60 DEG C,
Flow velocity is 1.0mL/min, and the relative molecular mass of polymer is with polymethyl methacrylate as standard calibration.Chemistry examination used
It is pure that agent is chemistry.
Embodiment 1
By 3.0g methacrylic acid -2- (2- bromo- 2- methylpropionyl) epoxide ethyl ester (BIEM), 11.7mg chain-transferring agent two
Thiobenzoate -2- phenyl propyl- 2- ester (CDB), 2.35mg AIBN, 10mL methyl phenyl ethers anisole add reaction bulb in, BIEM, AIBN and
The mol ratio of CDB is 250:0.33:24h is reacted, 3 removing small molecule lists of dissolution precipitation in 200mL normal hexane at 1,70 DEG C
Body, is vacuum dried to obtain lightpink homopolymer main chain polymethylacrylic acid -2- (2- bromo- 2- methylpropionyl) epoxide ethyl ester
(PBIEM), yield is 40%, and it is 19.4kDa that polymer main chain nuclear-magnetism calculates the degree of polymerization for 185, SEC number-average molecular weight, molecular weight
It is distributed as 1.27.
By 0.25g PBIEM, 0.515mL stannous octoate, 354.5mg benzimidazole thiophanate for dithio peroxide anhydride, 40 μ L 2- bromines
Add in reaction bulb for ethyl isobutyrate and 20mL toluene, logical argon 0.5h.By (127mg) cuprous bromide of deoxygenation/
(1.11mL) PMEDTA adds in reaction bulb, 85 DEG C of reaction 48h.With 200mL THF dissolving, remove copper with neutral alumina column,
Filtrate is precipitated in 100mL normal hexane after concentrating and is removed small molecular weight impurity.Vacuum drying obtains big point containing dithioesters fragment
Sub- initiator polymethylacrylic acid -2- (dithio benzoyloxy) propiono) epoxide ethyl ester (PTEM).By turning that nuclear-magnetism calculates
Rate is 74%, SEC number-average molecular weight is 19.6kDa, and molecular weight distribution is 1.44.
1.893g Tert-butyl Methacrylate, 20mg PTEM, 12.055mg AIBN and 10mL methyl phenyl ethers anisole are added reaction
In bottle, at 60 DEG C of sealing after deoxygenation, react 22h, after reaction terminates, with 3 removing monomers of 200mL methanol extraction, be vacuum dried
To polymethylacrylic acid -2- (2- bromo- 2- methylpropionyl) epoxide ethyl ester-g- polymethyl tert-butyl acrylate (PBIEM-g-
PtBMA), yield is 34.6%, and the degree of polymerization being calculated by nuclear-magnetism is 234.8kDa for 76, SEC number-average molecular weight, and molecular weight divides
Cloth is 1.20.
Embodiment 2
Other polymerizing conditions are same as Example 1, except that continuing synthesis with the PBIEM-g-PtBMA obtaining in 1
Block side chain.Monomer used is methacrylic acid oligomeric ethylene glycol ester (OEGMA), comprises the following steps that：By 1.111g OEGMA,
20mg PBIEM-g-PtBMA, 0.2436mg AIBN and 10mL methyl phenyl ethers anisole add in reaction bulb, react 27h, reaction knot at 60 DEG C
Shu Hou, removes monomer for 3 times with 200mL methanol extraction and obtains polymethylacrylic acid -2- (2- bromo- 2- methylpropionyl) epoxide second
Ester-g- (polymethyl tert-butyl acrylate-b- polymethylacrylic acid oligomeric ethylene glycol ester) PBIEM-g- (PtBMA-b-POEGMA),
Yield is 25%, and the side chain degree of polymerization being calculated by nuclear-magnetism is 62.5, SEC number-average molecular weight is 896.5kDa, molecular weight distribution
For 1.10.
Embodiment 3
Other polymerizing conditions are same as Example 1, except that the polymerized monomer of side chain is OEGMA, synthesize homopolymerization
Polymethylacrylic acid -2- (the 2- bromo- 2- methylpropionyl) epoxide ethyl ester-g- polymethylacrylic acid oligomeric ethylene glycol ester of side chain
(PBIEM-g-POEGMA), react 24h at 60 DEG C, after reaction terminates, precipitate 3 removing monomers with 150mL ether, yield is
37%, the side chain degree of polymerization being calculated by nuclear-magnetism is 50, SEC number-average molecular weight is 434.2kDa, and molecular weight distribution is 1.27.
Embodiment 4
Other polymerizing conditions are same as Example 1, except that the polymerized monomer of side chain is styrene, synthesize homopolymerization
Polymethylacrylic acid -2- (2- bromo- 2- methylpropionyl) epoxide ethyl ester-g- polystyrene (PBIEM-g-PSt) of side chain, 70 DEG C
Lower reaction 12h, after reaction terminates, precipitates 3 removing monomers with 150mL ether, yield is 36%, the side chain being calculated by nuclear-magnetism
The degree of polymerization is 73, SEC number-average molecular weight is 334.2kDa, and molecular weight distribution is 1.21.
Embodiment 5
Other polymerizing conditions are same as Example 1, except that the polymerized monomer of side chain is N- isopropyl acrylamide
Amine (NIPAM), polymethylacrylic acid -2- (the 2- bromo- 2- methylpropionyl) epoxide ethyl ester-g- poly- N- isopropyl of synthesis homopolymerization side chain
Base acrylamide (PBIEM-g-PNIPAM), reacts 12h at 60 DEG C, after reaction terminates, precipitate 3 times with 150mL ether and remove list
Body, yield is 31%, and the side chain degree of polymerization being calculated by nuclear-magnetism is 33, SEC number-average molecular weight is 218.2kDa, molecular weight distribution
For 1.38.
Embodiment 6
Other polymerizing conditions are same as Example 1, except that the polymerized monomer of side chain is acrylic acid, synthesize homopolymerization
Side chain polymethylacrylic acid -2- (2- bromo- 2- methylpropionyl) epoxide ethyl ester-g- polyacrylic acid (PBIEM-g-PAA), at 70 DEG C
Reaction 14h, after reaction terminates, with 3 removing monomers of 200mL water precipitation, yield is 29%, is polymerized by the side chain that nuclear-magnetism calculates
Spend for 25.
Embodiment 7
Other polymerizing conditions are same as Example 1, except that the polymerized monomer of side chain is methacrylic acid -4-
(3- oxo -3- PHENYLPROPIONYL) phenyl ester (DKMA), synthesizes homopolymerization side chain polymethylacrylic acid -2- (2- bromo- 2- methyl propionyl
Base) epoxide ethyl ester-g- polymethylacrylic acid -4- (3- oxo -3- PHENYLPROPIONYL) phenyl ester (PBIEM-g-PDKMA), at 70 DEG C
Reaction 18h, after reaction terminates, precipitates 3 removing monomers with 200mL ether, yield is 10.2%, the side chain being calculated by nuclear-magnetism
The degree of polymerization is 17, SEC number-average molecular weight is 138.5kDa, and molecular weight distribution is 1.47.
Embodiment 8
Other polymerizing conditions are same as Example 7, except that continuing synthesis with the PBIEM-g-PDKMA obtaining in 7
Block side chain.Monomer used is OEGMA, comprises the following steps that：By 0.695g OEGMA, 10mg PBIEM-g-PtBMA,
0.4810mg AIBN and 10mL methyl phenyl ethers anisole add in reaction bulb, react 5h at 60 DEG C, after reaction terminates, with 200mL ether precipitation
Remove monomer 3 times and obtain polymethylacrylic acid -2- (2- bromo- 2- methylpropionyl) epoxide ethyl ester-g- (polymethylacrylic acid -4-
(3- oxo -3- PHENYLPROPIONYL) phenyl ester-b- polymethylacrylic acid oligomeric ethylene glycol ester) PBIEM-g- (PDKMA-b-
POEGMA), yield is 40%, and the side chain POEGMA section degree of polymerization being calculated by nuclear-magnetism for 65, SEC number-average molecular weight is
457.5kDa, molecular weight distribution is 1.23.
Embodiment 9
Other polymerizing conditions are same as Example 8, except that the degree of polymerization of PBIEM main chain used is 335, other behaviour
Make consistent, after second segment side chain polyreaction terminates, precipitated 3 times with 200mL ether remove monomers obtain polymethylacrylic acid-
2- (2- bromo- 2- methylpropionyl) epoxide ethyl ester-g- (polymethylacrylic acid -4- (3- oxo -3- PHENYLPROPIONYL) phenyl ester-b-
Polymethylacrylic acid oligomeric ethylene glycol ester) PBIEM-g- (PDKMA-b-POEGMA), yield for 53%, SEC number-average molecular weight is
799.8kDa, molecular weight distribution is 1.03.
Claims (10)
1. a kind of preparation method of acrylic ester type poly chain transfer agent is it is characterised in that comprise the steps：
(1) in the presence of micromolecule chain transfer agent, there is polyreaction in halogen acrylate-type monomer, obtain halogen acrylic acid
Ester type polymer；
The structure of described halogen acrylate-type monomer is as shown in formula I：
In formula I, R1For H or methyl；X is Br or Cl；The integer of n=1～10；
(2) under conditions of the presence of halo initiator, cuprous halide, many nitrogen ligands and reducing agent, step (1) obtains halogen propylene
Acid esters type polymer and small molecule thioesters reagent carry out substitution reaction, obtain described acrylic ester type poly chain transfer agent；
The structure of described small molecule thioesters reagent is as shown in formula II：
In formula II, R is alkyl or aryl；
Described halo initiator is one of α-chloro-propionicacid ethyl ester, ethyl α bromopropionate and alpha-brominated ethyl isobutyrate.
2. the preparation method of acrylic ester type poly chain transfer agent according to claim 1 is it is characterised in that described little point
Subchain transfer agent is selected from one of compound shown in following formula：
3. the preparation method of acrylic ester type poly chain transfer agent according to claim 1 is it is characterised in that step (1)
Polyreaction is carried out in the presence of initiator；
The mol ratio of halogen acrylate-type monomer, initiator and micromolecule chain transfer agent is 50～800:0.3:1.
4. the preparation method of acrylic ester type poly chain transfer agent according to claim 1 is it is characterised in that step (1)
Polyreaction is carried out in reaction dissolvent, and the molar concentration of described halogen acrylate-type monomer is 0.1～10mol/L.
5. the preparation method of acrylic ester type poly chain transfer agent according to claim 1 is it is characterised in that in step (1),
The temperature of polyreaction is 60～90 DEG C, and the time of polyreaction is 3～24h.
6. the preparation method of acrylic ester type poly chain transfer agent according to claim 1 is it is characterised in that in step (2),
Halogen acrylate based polymer, reducing agent, small molecule thioesters reagent, halo initiator, cuprous halide, many nitrogen ligands mole
Than for 1:1.8:1.3:0.4:1:6.
7. a kind of acrylic ester type poly chain transfer agent is it is characterised in that preparation method described in any one of claim 1～6
Obtain.
8. a kind of preparation method of process for preparing column type polymer brush is it is characterised in that comprise the steps：
In the presence of initiator, the acrylic ester type poly chain transfer agent described in claim 7 carries out RAFT with side chain monomer and gathers
Close reaction, obtain described process for preparing column type polymer brush.
9. the preparation method of process for preparing column type polymer brush according to claim 8 is it is characterised in that described side chain monomer includes
At least one in compound shown in following formula：
Wherein, R2And R4Independently selected from H or methyl；
R3、R5、R6And R7Independently selected from H, aryl or alkyl.
10. a kind of process for preparing column type polymer brush is it is characterised in that the preparation method described in claim 8 or 9 prepares.
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