CN103450372A - Synthesis of novel chain transfer agent with thermal initiation function - Google Patents
Synthesis of novel chain transfer agent with thermal initiation function Download PDFInfo
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- CN103450372A CN103450372A CN201310298956XA CN201310298956A CN103450372A CN 103450372 A CN103450372 A CN 103450372A CN 201310298956X A CN201310298956X A CN 201310298956XA CN 201310298956 A CN201310298956 A CN 201310298956A CN 103450372 A CN103450372 A CN 103450372A
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- trithiocarbonate
- dodecyl
- transfer agent
- acidic group
- chain transfer
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- 239000012986 chain transfer agent Substances 0.000 title claims abstract description 24
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title abstract 2
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims abstract description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012989 trithiocarbonate Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims description 11
- -1 trithio ester Chemical class 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 241000233803 Nypa Species 0.000 claims 1
- 235000005305 Nypa fruticans Nutrition 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 18
- 238000012662 bulk polymerization Methods 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 238000013467 fragmentation Methods 0.000 abstract 1
- 238000006062 fragmentation reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 23
- 239000000126 substance Substances 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 125000005022 dithioester group Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 102100022595 Broad substrate specificity ATP-binding cassette transporter ABCG2 Human genes 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000012988 Dithioester Substances 0.000 description 2
- 101000823298 Homo sapiens Broad substrate specificity ATP-binding cassette transporter ABCG2 Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical class CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SGZOTQPYJLDQRT-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)C1=CC=CC=C1C=C SGZOTQPYJLDQRT-UHFFFAOYSA-N 0.000 description 1
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical group CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 1
- 0 CC(CCCO)(C#N)N=N[C@](CC*)CCC* Chemical compound CC(CCCO)(C#N)N=N[C@](CC*)CCC* 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010019133 Hangover Diseases 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a synthesis of a novel chain transfer agent with a thermal initiation function, which comprises the steps of firstly, carrying out esterification reaction on trithiocarbonate S-n-dodecyl-S ' - (2-isobutyric acid group) trithiocarbonate with carboxyl and azo initiator 4, 4-azodicyanobentanol containing hydroxyl to synthesize bis- [ S-n-dodecyl-S ' - (2-isobutyric acid group-4, 4 ' -azodicyanobentyl) ] trithiocarbonate, then bis- [ S-n-dodecyl-S '- (2-isobutyric acid group-4, 4' -azo cyano amyl ester) ] trithiocarbonate is taken as an initiator and a chain transfer agent, the reversible addition-fragmentation chain transfer (RAFT) bulk polymerization behavior of monomers such as styrene, methyl acrylate, and N-isopropylacrylamide was examined. The invention introduces an initiator structure into an RAFT reagent structure to prepare the chain transfer reagent with initiating function, and can successfully carry out the living radical polymerization of monomers such as styrene and the like.
Description
Technical field
The present invention relates to the synthetic of a kind of multi-functional regulation and control reagent, what be specifically related to is the synthetic of a kind of novel chain transfer agent that contains the thermal initiation function.
Background technology
1998, the people such as Rizzardo find to use dithioesters can obtain molecular weight distribution and control good polymkeric substance, reversible addition-fracture chain transfer polymerization, i.e. RAFT method, introduced thus " activity "/controllable free-radical polymerisation, and become Recent study and obtain a kind of method often.The advantage of RAFT polymerization maximum is that applicable monomer scope is wide, except common monomer styrene, (methyl) esters of acrylic acid, also be applicable to hydroxyethyl methylacrylate, to functional monomers such as vinylbenzenesulfonic acid sodium, so the RAFT polymerization extremely is conducive to the polyreaction containing specific functional groups (as carboxyl, hydroxyl, di alkylamino group etc.) vinyl monomer.RAFT polymerizable molecular amount narrow distribution (generally all below 1.3), and the scope of polymerization temperature is also wider, and reaction process is conciliate protection without protection.The designed capacity of molecule is strong, by means of reactive terminal, introduces functional group, can be used for preparing block, grafting, the multiple polymer with fine structure such as star-like.Be used for the chain-transfer agent of RAFT polymerization mainly according to the difference of Z group, mainly contain four classes: (1) dithioesters class; (2) trithiocarbonate class; (3) xanthate class; (4) dithiocarbamate.
The trithiocarbonate class, compare with other RAFT reagent, and maximum advantage is to stablize very much, under high temperature, does not decompose, and can produce in a large number.Trithiocarbonate is mostly easily synthetic, there is no very dark color and niff.The very important point, used dithioesters, and especially dithiobenzoic acid ester class has very serious retardation effect, and this can reduce the speed of polymerization greatly.And the trithiocarbonate class does not almost have retardation effect.
In this system, selected the trithio ester that contains carboxyl, and the azo-initiator that contains two hydroxyls is raw material, by esterification, synthesized a kind of novel compound that causes function and chain forwarding function that integrates.Take that it carries out polymerization as initiator and chain-transfer agent regulation and control various of monomer, demonstrated control preferably.
Summary of the invention
The object of the invention is to overcome the above problem that prior art exists, the synthetic of a kind of novel chain transfer agent that contains the thermal initiation function is provided, synthesized the novel adjusting control agent that not only contains initiator but also contain chain-transfer agent, for the RAFT polymerization, greatly reduce the usage quantity of chain-transfer agent, simplified the implementation process of polyreaction, original three component polymerization systems successfully have been reduced to two component polymerization systems.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
Synthesizing of a kind of novel chain transfer agent that contains the thermal initiation function, comprise the following steps:
The synthetic trithio ester S-dodecyl-S ' with carboxyl of step 1)-(2-isobutyl acidic group) trithiocarbonate: by positive Dodecyl Mercaptan, acetone and aliquat 10
omixing and stirring during C, drip the mixing solutions of dithiocarbonic anhydride and acetone in mixture, and add chloroform after stirring 10 min, dropwise add again sodium hydroxide solution, after mixture stirs and spends the night, add a large amount of deionized waters, and drip hydrochloric acid soln to pH ≈ 2, suction filtration obtains solid, stir energetically dissolution of solid in Virahol, remove insoluble part, filtrate is revolved steaming, recrystallization in normal hexane, obtain glassy yellow crystal S-dodecyl-S '-(2-isobutyl acidic group) trithiocarbonate
Step 2) synthetic pair-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate: S-dodecyl-S '-(2-isobutyl acidic group) trithiocarbonate, 4,4-azo dicyanogen methyl isophorone amylalcohol, the catalyzer DMAP, 0
ostir under the C condition, dewatering agent 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate is dissolved in to CH
2cl
2in, dropwise drip, at room temperature, reaction is spent the night, mixed solution is revolved to steaming, mixture cross silicagel column (developping agent: ethyl acetate: sherwood oil), obtain contain simultaneously cause function and chain forwarding function two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate
Step 3) RAFT polymerization: with two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate is initiator and chain-transfer agent, take vinylbenzene, methyl acrylate, NIPA is monomer, carry out the RAFT polymerization, temperature is 40 ~ 120 ℃.
Further, in molar ratio, monomer: two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate=10 ~ 10000: 1, preferred, in cinnamic RAFT mass polymerization, vinylbenzene and two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] molar ratio of trithiocarbonate is 400: 1, in cinnamic RAFT mass polymerization, preferably temperature is 60 ℃.
The invention has the beneficial effects as follows:
1, the RAFT polymerization process is to realize controlled to polymerization process by the reversible addition cleavage reaction between growing chain free radical and RAFT reagent.In order to guarantee growing chain free radical passivation fully in polymerization process, need to use a large amount of RAFT reagent.The molar ratio of general RAFT reagent and initiator need to reach even 10:1 of 5:1.Because the present invention introduces structure of initiator in the RAFT agent structure, preparation has and causes the functional chain transfering reagent, can successfully carry out the active free radical polymerization of the monomer such as vinylbenzene;
2, by using the mode of chain-transfer agent and initiator combination, can greatly reduce the usage quantity of chain-transfer agent;
3, integrated due to chain-transfer agent and initiator, simplified the implementation process of polyreaction, and the original three component polymerization systems of RAFT mass polymerization successfully are reduced to two component polymerization systems.
4, with same principle, the xanthate that utilizes some to contain carboxyl, be connected with azo-initiator, applicable monomer scope can be expanded to the non-conjugated vinyl monomers such as vinyl acetate, N-vinylcarbazole.
The accompanying drawing explanation
Fig. 1 is that two in embodiment mono--[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate (X6) is at CDCl
3in the hydrogen spectrogram that characterizes of nuclear-magnetism;
Fig. 2 is in embodiment tri-90
oduring C, the GPC elution curve of the RAFT solution polymerization of vinylbenzene (St);
Fig. 3 be the polystyrene PS that in embodiment tri-, the RAFT polymerization obtains (
m n, GPC=5000 g/mol,
m w/
m n=1.08) at CDCl
3in the hydrogen spectrogram that characterizes of nuclear-magnetism;
Fig. 4 is that in embodiment tri-, vinylbenzene is the polymerization kinetics graphic representation under the 400:1 condition with the initial molar ratio of regulation and control reagent X6;
Fig. 5 is that in embodiment tri-, vinylbenzene is the polymericular weight under the 400:1 condition and distributes with the graph of relation of monomer conversion with the initial molar ratio of regulation and control reagent X6;
Fig. 6 is the GPC elution curve before and after the polystyrene chain extension in embodiment tetra-;
Fig. 7 be polystyrene (PSt,
m n, GPC=3500 g/mol,
m w/
m n=1.05) substance assistant laser desorpted/ionization time of flight mass spectrometry figure;
Fig. 8 is for inferring the possible structure of polymkeric substance that according to Fig. 7;
Fig. 9 is the GPC elution curve before and after polystyrene ammonia solution in embodiment six;
Figure 10 is the hydrolytic process schematic diagram of polystyrene in embodiment seven;
Figure 11 is the GPC elution curve before and after the polystyrene hydrolysis in embodiment seven.
Embodiment
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
Embodiment mono-
The synthetic trithio ester S-dodecyl-S ' with carboxyl of step 1)-(2-isobutyl acidic group) trithiocarbonate (X5): add successively positive Dodecyl Mercaptan (37.3 g in the round-bottomed flask of 250 mL, 0.184 mol), acetone (107 g, 1.84 mol), Aliquat 336(2.99 g, 7.37 mol), 10
omixing and stirring during C, dropwise add sodium hydroxide solution (50 wt %) (15.5 g, 0.193 mol), 10
ostir 30 min during C, CS
2the mixing solutions of (14.0 g, 0.18 mol) and acetone (18.6 g, 0.32 mol) drips 20 min, and stirs 10 min.Disposablely add chloroform (32.8 g, 0.28 mol), more dropwise add sodium hydroxide solution (50 wt %) (73.7 g, 0.922 mol).Mixture stirs and spends the night.Stop reaction, in three-necked bottle, add 300 mL deionized waters, continue to drip HCl solution to pH ≈ 2.Suction filtration obtains solid part, under stirring energetically, is dissolved in Virahol (300 mL), removes insoluble part, and filtrate is revolved steaming, recrystallization in normal hexane.Obtain glassy yellow crystal S-dodecyl-S '-(2-isobutyl acidic group) trithiocarbonate X5(16.5 g, productive rate 48 %)
Step 2) two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] preparation of trithiocarbonate (X6): then in the three-necked bottle of 100 mL, add the synthetic X5(3 g of back, 8.2 mmol), 4,4-azo dicyanogen methyl isophorone amylalcohol (ABCP) (1.03 g, 4.1 mmol), catalyzer DMAP(0.092 g, 0.82 mmol), 0
ounder the C condition, stir, by dewatering agent EDC(1.28 g, 8.2 mmol) be dissolved in the CH of 3 mL
2cl
2in, dropwise drip.At room temperature, reaction is spent the night.Mixed solution is revolved to steaming, and mixture is crossed silicagel column (developping agent: ethyl acetate: sherwood oil=1:2).Contain simultaneously cause function and chain forwarding function two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate (2.1 g, productive rate 51 %)
.
Wherein, raw material: 4,4-azo dicyanogen methyl isophorone amylalcohol (ABCP): analytical pure, Langfang development in science and technology company limited of person of outstanding talent section, twice recrystallization of methyl alcohol ,-5
oc refrigeration; Acetone: analytical pure, Shanghai reagent four factories, directly used; Positive Dodecyl Mercaptan: analytical pure, China Medicine (Group) Shanghai Chemical Reagent Co.,, directly used; Aliquat 336: analytical pure, and China Medicine (Group) Shanghai Chemical Reagent Co.,, directly used; Methylene dichloride: analytical pure, Solution on Chemical Reagents in Shanghai company, 5% Na
2cO
3solution washing one time, deionized water wash three times, the Calcium Chloride Powder Anhydrous drying, take hydrolith as the water-removal agent air distillation; 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC): analytical pure, China Medicine (Group) Shanghai Chemical Reagent Co.,, directly used; DMAP (DMAP): analytical pure, China Medicine (Group) Shanghai Chemical Reagent Co.,, directly use trichloromethane: analytical pure, Solution on Chemical Reagents in Shanghai company, directly used.
Embodiment bis-: they with two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate (X6), are initiator and chain-transfer agent, and the polymerization of regulation and control various of monomer
The X6 of usining, simultaneously as initiator and chain-transfer agent, investigates the RAFT mass polymerization behavior of vinylbenzene (St), methyl acrylate (MA), NIPA (NIPAM).Polymerization result is as shown in table 1.Result shows that X6 has extraordinary control to St, MA and NIPAM, and the theoretical molecular of polymkeric substance and GPC molecular weight are more identical, the molecular weight distribution of polymkeric substance narrower (
m w/
m n<1.16).
The GPC measurement result of the lower various of monomer polymerization of table 1 X6 effect
| Numbering | Monomer and the initial molar ratio that regulates and controls reagent X6 | Reaction times (h) | Transformation efficiency (%) | The equal molecule of theoretical value (g/mol) | Equal molecule (the g/mol of actual measurement number ) | Molecular weight distributing index |
| 1 | [St]0:[X6]0=200:1 | 24 | 64.1 | 13400 | 12700 | 1.11 |
| 2 | [St] 0:[X6] 0=500:1 | 24 | 45.3 | 23500 | 22500 | 1.15 |
| 3 | [MA] 0:[X6] 0=200:1 | 3 | 62.0 | 10700 | 17000 | 1.09 |
| 4 | [MA] 0:[X6] 0=500:1 | 3 | 50.1 | 21600 | 24300 | 1.16 |
| 5 | [NIPAM] 0:[X6] 0=500:1 | 12 | 72.0 | 41100 | 51000 | 1.43 |
Wherein, being calculated as follows of theoretical value average molecular weight:
a M n,th = ([St]
0/[X6]
0)×
M St×conversion %。
Embodiment tri-: take X6 as initiator and chain-transfer agent, the research of the polymerization behavior of the St under the differing temps different ratios
According to the polymerization result of embodiment bis-, take the St monomer as research object, its polymerization behavior has been carried out to detailed investigation.
At first investigated and usingd X6 simultaneously as initiator and chain-transfer agent, under differing temps, with the polymerization behavior of the polymerization system of St.60
oc, 70
oc, 90
odone RAFT mass polymerization and the solution polymerization of St during C, polymerization result is as shown in table 2, table 3, table 4.As can be seen from the table, at three kinds of temperature, X6 has good control to St, and still, along with the rising of temperature of reaction, polymerization velocity is accelerated, especially 90
oduring C, in 3 h, the transformation efficiency of polymkeric substance just can reach 85 %.M
w/ M
nthe trend that is rise is also arranged, and the block polymer molecular weight distribution is less than 1.3.In addition, investigated vinylbenzene 60
oc and 90
osolution polymerization behavior during C.Result is as shown in table 5 and table 6, and rate of polymerization is compared with solution polymerization slightly and descended, and molecular weight distributing index maintains below 1.3.
Annotate: in this example, the actual measurement number-average molecular weight all adopts the gel permeation chromatograph side to obtain.
Table 2 60
oduring C, the impact of the consumption of X6 on Bulk Polymerization of Styrene
| Numbering | Vinylbenzene and the initial molar ratio that regulates and controls reagent X6 | Reaction times (h) | Transformation efficiency (%) | Theoretical value divided dose (g/mol) | Actual measurement number-average molecular weight (g/mol) | Molecular |
| 1 | 100:1 | 7 | 39.6 | 4100 | 4200 | 1.07 |
| 2 | 100:1 | 24 | 81.1 | 8400 | 8300 | 1.10 |
| 3 | 200:1 | 24 | 64.1 | 13400 | 12700 | 1.11 |
| 4 | 400:1 | 24 | 50.0 | 20800 | 19900 | 1.14 |
| 5 | 500:1 | 24 | 45.3 | 23500 | 22500 | 1.15 |
| 6 | 1000:1 | 24 | 32.4 | 33700 | 33100 | 1.17 |
| 7 | 2000:1 | 24 | 28.0 | 58300 | 56700 | 1.21 |
Wherein, cinnamic initial content is 0.5 mL (4.35 mmol), being calculated as follows of theoretical value average molecular weight:
a M n,th = ([St]
0/[X6]
0)×
M St×conversion %。
Table 3 70
oduring C, the impact of the consumption of X6 on Bulk Polymerization of Styrene
| Numbering | Vinylbenzene and the initial molar ratio that regulates and controls reagent X6 | Transformation efficiency (%) | M n,th a(g/mol) | Actual measurement number divided dose (g/mol) | Molecular |
| 1 | 100:1 | 87.0 | 9100 | 9200 | 1.14 |
| 2 | 200:1 | 74.7 | 15600 | 14900 | 1.16 |
| 3 | 400:1 | 58.5 | 24400 | 21900 | 1.19 |
| 4 | 500:1 | 56.4 | 29400 | 28500 | 1.20 |
| 5 | 1000:1 | 42.6 | 44400 | 42200 | 1.23 |
| 6 | 2000:1 | 33.2 | 69200 | 66500 | 1.24 |
Wherein, the reaction times is 24 hours, and cinnamic initial content is 0.5 mL (4.35 mmol), being calculated as follows of theoretical value average molecular weight:
a M n,th = ([St]
0/[X6]
0)×
M St×conversion %。
Table 4 90
oduring C, the impact of the consumption of X6 on Bulk Polymerization of Styrene
| Numbering | Vinylbenzene and the initial molar ratio that regulates and controls reagent X6 | Transformation efficiency (%) | The equal molecule of theoretical value (g/mol) | Actual measurement number divided dose (g/mol) | Molecular |
| 1 | 100:1 | 85.4 | 8900 | 8600 | 1.19 |
| 2 | 200:1 | 69.6 | 14500 | 13400 | 1.23 |
| 3 | 400:1 | 54.6 | 22700 | 20700 | 1.25 |
| 4 | 500:1 | 48.1 | 25000 | 23500 | 1.25 |
| 5 | 1000:1 | 37.0 | 38500 | 38000 | 1.28 |
| 6 | 2000:1 | 28.8 | 60000 | 55300 | 1.30 |
Wherein, the reaction times is 3 hours, and cinnamic initial content is 0.5 mL (4.35 mmol), being calculated as follows of theoretical value average molecular weight:
a M n,th = ([St]
0/[X6]
0) ×
M St ×conversion %。
Table 5 60
oduring C, the impact of the consumption of X6 on the styrene solution polymerization
| Numbering | Vinylbenzene and the initial molar ratio that regulates and controls reagent X6 | Transformation efficiency (%) | Theoretical value average molecular weight (g/mol) | M n,GPC(g/mol) | Molecular |
| 1 | 100:1 | 56.0 | 5800 | 5600 | 1.13 |
| 2 | 200:1 | 41.9 | 8700 | 8500 | 1.16 |
| 3 | 400:1 | 30.9 | 12900 | 11700 | 1.17 |
| 4 | 500:1 | 24.8 | 12900 | 13100 | 1.16 |
| 5 | 1000:1 | 18.6 | 19400 | 19000 | 1.21 |
Wherein, the reaction times is 18 hours, and the original volume of vinylbenzene and toluene is than being 1:1, and cinnamic initial content is 0.5 mL (4.35 mmol), being calculated as follows of theoretical value average molecular weight:
a M n,th = ([St]
0/[X6]
0)×
M St×conversion %。
Table 6 90
oduring C, the impact of the consumption of X6 on the styrene solution polymerization
Wherein, the reaction times is 3 hours, and the original volume of vinylbenzene and toluene is than being 1:1, and cinnamic initial content is 0.5 mL (4.35 mmol), being calculated as follows of theoretical value average molecular weight:
a M n,th = ([St]
0/[X6]
0)×
M St×conversion %。
Embodiment tetra-: the polystyrene of take carries out chain extending reaction as the macromolecular chain transfer agent
Chain extending reaction is one of Main Means of investigating RAFT polymerization system living features.For the further polymerization process of proof body series is " activity ", the polystyrene obtained of take is chain-transfer agent, and the St of still take has carried out chain extending reaction as monomer.Result as shown in Figure 6.From result, can find out, 110
ounder C, reacted 72 h, 5200 g/mols of the molecular weight of polymkeric substance from chain extension rise to 20000 g/mol, and molecular weight distribution (
m w/
m nbecome 1.25 from 1.09) still remain narrower.The GPC elution curve is level and smooth without hangover, and the growth of molecular weight has further confirmed that the polymerization process of body series is " activity "/controlled.
Embodiment five: the MALDI-TOF test
For the structure of further clear and definite polymkeric substance, carried out the macromole mass spectroscopy.The trithio ester is unstable in the macromole mass spectrum, easily is decomposed into sulfydryl.As shown in Figure 7, by calculating, finding that connected two peak-to-peak differences are 104.08, just in time meet the molar mass (104.06) of vinylbenzene (St), is the repeating unit of St monomer in polymkeric substance.The experimental value that its isotopic mass distributes is followed following formula:
M theo = 247.07 + n104.06 + 38.96 (1)
In formula, the 247.07th, the molecular weight of the molecular structure in macromolecular structure except the St monomeric unit, n and 104.06 is respectively the number-average molecular weight of the quantity of monomeric repeating unit in polymer chain, 38.96 molecular masses that are the matrix potassium ion.Above result shows, only has the polymkeric substance of single molecular structure in polymkeric substance.The structure of inferring polymkeric substance by calculation result as shown in Figure 8.
Embodiment six: ammonolysis reaction
Verify that for further the end group of polymkeric substance is dodecyl trithio ester, polymkeric substance is carried out to ammonolysis reaction, ammonia solution prepolymer is the yellow solid powder, and after the ammonia solution, polymkeric substance is the white solid powder, and the GPC elution curve as shown in Figure 9.As can be seen from the figure, 7400 g/mols of the molecular weight of polymkeric substance before by the ammonia solution are reduced to 6700 g/mol, obvious reduction (~ 700 g/mol) has been arranged, and lost dodecyl trithio ester group result close (~ 500 g/mol), illustrated that end group is dodecyl trithio ester.
Embodiment seven: hydrolysis reaction
Whether have ester bond in order to verify in main polymer chain, in the highly basic condition, to the polymkeric substance reaction that is hydrolyzed, hydrolytic process as shown in figure 10.Polymkeric substance, in strong alkali aqueous solution, is decomposed into alcohol and acid.As shown in figure 11, as can be seen from the figure, after hydrolysis, by hydrolysis, 40100 front g/mol are reduced to 18100 g/mol to the molecular weight of polymkeric substance to the GPC elution curve, have approximately reduced half, more identical with the imagination value, have further verified the accuracy of inferring structure.
Claims (2)
1. a novel chain transfer agent that contains the thermal initiation function is synthetic, it is characterized in that, comprises the following steps:
The synthetic trithio ester S-dodecyl-S ' with carboxyl of step 1)-(2-isobutyl acidic group) trithiocarbonate: by positive Dodecyl Mercaptan, acetone and aliquat 10
omixing and stirring during C, drip the mixing solutions of dithiocarbonic anhydride and acetone in mixture, and add chloroform after stirring 10 min, dropwise add again sodium hydroxide solution, after mixture stirs and spends the night, add a large amount of deionized waters, and drip hydrochloric acid soln to pH ≈ 2, suction filtration obtains solid, stir energetically dissolution of solid in Virahol, remove insoluble part, filtrate is revolved steaming, recrystallization in normal hexane, obtain glassy yellow crystal S-dodecyl-S '-(2-isobutyl acidic group) trithiocarbonate
；
Step 2) synthetic pair-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate: S-dodecyl-S '-(2-isobutyl acidic group) trithiocarbonate, 4,4-azo dicyanogen methyl isophorone amylalcohol, the catalyzer DMAP, 0
ostir under the C condition, dewatering agent 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate is dissolved in to CH
2cl
2in, dropwise drip, at room temperature, reaction is spent the night, and mixed solution is revolved to steaming, and mixture is crossed silicagel column, contain simultaneously cause function and chain forwarding function two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate
Step 3) RAFT polymerization: with two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate is initiator and chain-transfer agent, take vinylbenzene, methyl acrylate, NIPA is monomer, carry out the RAFT polymerization, temperature is 40 ~ 120 ℃.
2. the novel chain transfer agent that contains the thermal initiation function according to claim 1 is synthetic, it is characterized in that: in molar ratio, monomer: two-[S-dodecyl-S '-(2-isobutyl acidic group-4,4 '-azo cyano group pentyl ester)] trithiocarbonate=10 ~ 10000: 1.
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Cited By (6)
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| EP3018151A1 (en) | 2014-11-06 | 2016-05-11 | Universiteit Gent | Process for preparing inert raft polymers |
| WO2017035570A1 (en) * | 2015-08-28 | 2017-03-09 | Commonwealth Scientific And Industrial Research Organisation | Amphiphilic raft agent |
| CN110760029A (en) * | 2019-09-29 | 2020-02-07 | 江苏学泰印务有限公司 | Preparation method of polymer for bridging layer |
| CN113929606A (en) * | 2021-09-23 | 2022-01-14 | 武汉海翎化学工业有限公司 | Trithioester chain transfer agent, low-molecular-weight sodium polyacrylate obtained by using same, application and preparation |
| CN115651188A (en) * | 2022-10-27 | 2023-01-31 | 南方科技大学 | RAFT chain transfer agent, preparation method and application thereof |
| CN116239766A (en) * | 2022-12-27 | 2023-06-09 | 科顺防水科技股份有限公司 | Water-soluble RAFT reagent and preparation method thereof, and polycarboxylate water reducer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3018151A1 (en) | 2014-11-06 | 2016-05-11 | Universiteit Gent | Process for preparing inert raft polymers |
| WO2017035570A1 (en) * | 2015-08-28 | 2017-03-09 | Commonwealth Scientific And Industrial Research Organisation | Amphiphilic raft agent |
| CN110760029A (en) * | 2019-09-29 | 2020-02-07 | 江苏学泰印务有限公司 | Preparation method of polymer for bridging layer |
| CN113929606A (en) * | 2021-09-23 | 2022-01-14 | 武汉海翎化学工业有限公司 | Trithioester chain transfer agent, low-molecular-weight sodium polyacrylate obtained by using same, application and preparation |
| CN115651188A (en) * | 2022-10-27 | 2023-01-31 | 南方科技大学 | RAFT chain transfer agent, preparation method and application thereof |
| CN115651188B (en) * | 2022-10-27 | 2023-09-05 | 南方科技大学 | RAFT chain transfer agent and preparation method and application thereof |
| CN116239766A (en) * | 2022-12-27 | 2023-06-09 | 科顺防水科技股份有限公司 | Water-soluble RAFT reagent and preparation method thereof, and polycarboxylate water reducer and preparation method thereof |
| CN116239766B (en) * | 2022-12-27 | 2024-08-02 | 科顺防水科技股份有限公司 | Water-soluble RAFT reagent and preparation method thereof, and polycarboxylate water reducer and preparation method thereof |
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