CN106928414A - A kind of preparation method of polymeric sorbent predecessor di-block copolymer - Google Patents

A kind of preparation method of polymeric sorbent predecessor di-block copolymer Download PDF

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CN106928414A
CN106928414A CN201710211121.4A CN201710211121A CN106928414A CN 106928414 A CN106928414 A CN 106928414A CN 201710211121 A CN201710211121 A CN 201710211121A CN 106928414 A CN106928414 A CN 106928414A
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pma
reaction
block copolymer
trithiocarbonate
azodiisobutyronitrile
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黄定海
柳盼盼
李纳川
宋丽
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Tianjin University
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Tianjin University
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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
    • C08F293/005—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 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The present invention relates to a kind of preparation method of polymeric sorbent predecessor di-block copolymer；Macromolecular chain transfer agent PMA is synthesized by the method that RAFT is polymerized：It is the first monomer with methyl acrylate, trithiocarbonate is chain-transferring agent, and azodiisobutyronitrile is initiator, Isosorbide-5-Nitrae dioxane or N, N dimethylformamide are solvent, obtain one end and contain carboxyl, the other end contains the yellow viscous liquid PMA of three thioether bonds；With N N-isopropylacrylamides as second comonomer, the PMA of synthesis is Macromolecular chain transfer agent, obtains di-block copolymer PMA b PNIPAM.The present invention is using RAFT polymerizations, the chain-transferring agent reacted as the next stage as the PMA of the chain-transferring agent synthesis hydrophilic of activity/controllable polymerization using chain transfer constant three thioesters higher.Designed by changing the different degree of polymerization, synthesize the di-block copolymer PMA b PNIPAM of different block ratios.

Description

A kind of preparation method of polymeric sorbent predecessor di-block copolymer
Technical field
The present invention relates to polymeric material field, and in particular to one kind is used as the block copolymerization of polymeric sorbent predecessor two The preparation method of thing.
Background technology
Heavy metal contaminants have the residence time long, easily accumulation, obtain in recent years the features such as difficult degradation and wide material sources The attention of many researchers.The method for processing heavy metal wastewater thereby can be divided into three major types：Method of chemical treatment, physical chemistry treatment Method, biological treatment.Heavy metal polymeric sorbent is the focus of research, heavy metal polymer adsorption in chemical treatment method Agent contains substantial amounts of adsorption group, and high adsorption capacity by MOLECULE DESIGN, can also introduce the adsorption group of specific function, counterweight Metal ion carries out selective absorption, is conducive to the recovery of the high-purity of heavy metal ion.Chemical group with adsorption property Many functional polymers of (carboxyl, hydroxyl, sulfonic group etc.), to many transition metal, rare earth metal etc. has certain absorption Performance.Chemical group with adsorption property and Thermo-sensitive segment are incorporated into polymer molecule simultaneously and synthesize Thermo-sensitive high score Sub- heavy metal absorbent, and will be applied onto water process, the research of this part causes special attention.
The polymeric sorbent with adsorption group and temperature sensitive group is prepared, is generally required with adsorption property Chemical group synthesizes predecessor in being incorporated into polymer molecule with Thermo-sensitive segment, and functional modification is then carried out again.Therefore exist Before carrying out functional modification, the predecessor of synthesized straight chain type adsorbent is very big to its performance impact.Due to the predecessor Generally all it is to be synthesized by polymerisation in solution, but heat is difficult discharge in its course of reaction, easily causes implode, causes molecule Quantitative change is big, and distribution broadens, and reacts uncontrollable.Reversible addition-fracture chain transfer polymerization (RAFT) is then in polymerization system The chain-transferring agent for adding a kind of chain transfer constant higher, makes Propagating Radical and chain-transferring agent to enter row degradation each other and turns Move, reduce the concentration of free radical.It is polymerized using RAFT, can be by regulating and controlling the ratio between monomer and chain-transferring agent, synthesis is different The di-block copolymer of segment ratio.Therefore the present invention is polymerized by RAFT.With NIPA (NIPAM) for second Monomer, PMA (PMA) is Macromolecular chain transfer agent, and by changing the addition ratio of NIPAM and PMA, synthesis one kind can As a kind of di-block copolymer of polymeric sorbent predecessor.
The content of the invention
The invention provides a kind of preparation method of the di-block copolymer as polymeric sorbent predecessor.Utilize The method of RAFT polymerizations, with NIPA (NIPAM) as second comonomer, PMA (PMA) is macromolecular Chain-transferring agent, by changing the addition ratio of NIPAM and PMA, synthesizes the di-block copolymer PMA-b- of different segment ratios PNIPAM。
Technical scheme is as follows in order to achieve the above object：
A kind of preparation method of polymeric sorbent predecessor di-block copolymer；Step is as follows：
1) Macromolecular chain transfer agent PMA is synthesized by the method that RAFT is polymerized：It is the first monomer, trithio with methyl acrylate It is chain-transferring agent for carbonic ester, azodiisobutyronitrile is initiator, Isosorbide-5-Nitrae-dioxane or DMF are solvent, It is added in reactor, adds rotor stirring it is all dissolved, is passed through nitrogen, the stirring reaction in 70-80 DEG C of oil bath pan, Reaction cools down terminating reaction in being put into ice bath after terminating rapidly, and the yellow liquid that will be obtained after reaction is precipitated in distilled water, with Solvent Isosorbide-5-Nitrae-dioxane and unreacted monomer are removed, finally vacuum drying obtains one end and contains carboxyl, and the other end contains three The yellow viscous liquid PMA of thioether bond；
2) using the method for RAFT polymerizations：With NIPA as second comonomer, step 1) synthesis polypropylene Sour methyl esters is Macromolecular chain transfer agent, and azodiisobutyronitrile is initiator, and Isosorbide-5-Nitrae-dioxane or DMF are Solvent, is added in reactor, adds rotor stirring it is all dissolved, and after leading to nitrogen, is stirred in 70-80 DEG C of oil bath pan Reaction, reaction cools down terminating reaction in being put into ice bath after terminating rapidly；It is with molecular cut off by the product obtained after reaction 3500 bag filter dialysis, then freeze-drying, the white fluffy solid poly- (propylene of as di-block copolymer obtained after freezing Sour methyl esters-b- N-isopropylacrylamides) PMA-b-PNIPAM.
The step 1) in the ratio between the amount of material of trithiocarbonate and azodiisobutyronitrile be 2-5:1.
The step 1) in 70-80 DEG C of oil bath pan stirring reaction 5-8h；The yellow liquid obtained after reaction is existed Precipitated 2-3 times in distilled water.
The step 2) in the amount of substance ratio of PMA and azodiisobutyronitrile be 2-5:1.
The step 2) in 70-80 DEG C of oil bath pan stirring reaction 10-24h；With molecular cut off be 3500 it is saturating Analysis bag is dialysed 2-3 days.
It is preferably pressed into nitrogen 10-30min；
Three described thioesters are S- dodecyls-S'- (α, α '-dimethyl-α "-acetic acid) trithiocarbonate, S, S'- (α, α '-dimethyl-α "-acetic acid) trithiocarbonate, S- dodecyls-S "-isopropyl acid-trithiocarbonates or S, S'- bis- One kind in (dodecyl) trithiocarbonate.
The step 1) in the mass ratio of methyl acrylate and trithiocarbonate as the degree of polymerization, determine that monomer and chain turn Move the proportioning of agent addition.
The step 2) in the mass ratio of NIPA and PMA as the degree of polymerization, determine that N- is different Propylacrylamide and the proportioning of PMA, select to devise different block ratios by changing the different degree of polymerization Di-block copolymer.
The invention is characterised in that be polymerized using RAFT, using chain transfer constant three thioesters higher as active/controllable poly- The chain-transferring agent that the PMA of the chain-transferring agent synthesis hydrophilic of conjunction reacts as the next stage.Because polymeric sorbent predecessor is The macromolecule sample of different molecular weight is needed to test its performance quality, and polymer molecular weight is determined by its degree of polymerization, The degree of polymerization is bigger, and molecular weight is higher.Therefore the present invention is designed by changing the different degree of polymerization, synthesizes the two of different block ratios Block copolymer PMA-b-PNIPAM.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the PMA-b-PNIPAM described in embodiment.
Fig. 2 is the GPC spectrograms of the obtained PMA-b-PNIPAM described in embodiment 4.
Specific embodiment
The present invention is illustrated below by specific embodiment：
1) it is polymerized by RAFT, synthetic macromolecule chain-transferring agent PMA first, with methyl acrylate (MA) for the first monomer n1, trithiocarbonate n2(BDMAT) it is chain-transferring agent, azodiisobutyronitrile n3(AIBN) it is initiator, Isosorbide-5-Nitrae-dioxane is Solvent, is added in reactor, with n1(MA)：n2(BDMAT)=degree of polymerization the amount of material (n for) determines monomer and chain tra nsfer The proportioning of agent addition, wherein n2And n (BDMAT)3(AIBN) the ratio between amount of material 2-5:1, it is ensured that whole stable reaction Under reaction rate higher, rotor stirring is added it is all dissolved, after being passed through nitrogen 10-30min, in 70-80 DEG C of oil Stirring reaction 8h in bath, reaction cools down terminating reaction in being put into ice bath after terminating rapidly, the yellow liquid that will be obtained after reaction Precipitated 2-3 times in distilled water, to remove solvent Isosorbide-5-Nitrae-dioxane and unreacted monomer, finally vacuum drying obtains one end Containing carboxyl, the other end contains the yellow viscous liquid PMA of three thioether bonds.
2) using the method for RAFT polymerizations, with NIPA (NIPAM) as second comonomer, it is poly- that upper step synthesizes Methyl acrylate (PMA) is Macromolecular chain transfer agent, according to the degree of polymerization of design, with n (NIPAM)：N (the PMA)=degree of polymerization (n It is the amount of material) determine the proportioning of NIPAM and PMA additions, by changing the different degree of polymerization select to devise six kinds not With the di-block copolymer of block ratio.With azodiisobutyronitrile (AIBN) as initiator, Isosorbide-5-Nitrae-dioxane is solvent, is added To in reactor, the amount of substance ratio of wherein PMA and AIBN is 2-5:1, add rotor stirring it is all dissolved, lead to nitrogen 10- After 30min, the stirring reaction 10-24h in 70-80 DEG C of oil bath pan, reaction cools down termination instead in being put into ice bath after terminating rapidly Should.The product molecular cut off that will be obtained after reaction be 3500 bag filter dialyse three days, then freeze-drying, freeze after Poly- (methyl acrylate-b- N-isopropylacrylamides) PMA-b-PNIPAM of the white fluffy solid for arriving as target.
Concrete example is as follows：
Embodiment 1
With methyl acrylate (MA) for the first monomer, 0.05 part of MA is added, according to polymerization degree n (MA)：N (BDMAT)=30, 0.0017 part of the addition of BDMAT is obtained, azodiisobutyronitrile (AIBN) is initiator, and Isosorbide-5-Nitrae-dioxane is solvent, is added To in round-bottomed flask, the control of the ratio between amount of material of wherein BDMAT and AIBN is 2:1, the AIBN for calculating addition is 0.00085 Part, add rotor stirring it is all dissolved, after being passed through nitrogen 30min, the stirring reaction 5h in 70 DEG C of oil bath pan, reaction knot Rapid being put into ice bath cools down terminating reaction after beam, and the yellow liquid that will be obtained after reaction precipitate 2 times in distilled water, with removing Solvent Isosorbide-5-Nitrae-dioxane and unreacted monomer, finally vacuum drying obtain one end and contain carboxyl, and the other end contains three thioesters The yellow viscous liquid PMA PMA of key30-SC(S))S。
The method being polymerized using RAFT, with NIPA (NIPAM) as second comonomer, adds 0.005 part NIPAM monomers, the PMA (PMA) of upper step synthesis is Macromolecular chain transfer agent, and PNIPAM polymerization degree ns are designed first (NIPAM)：N (PMA)=100, it is determined that the PMA's for adding is 0.00005 part, with azodiisobutyronitrile (AIBN) as initiator, Isosorbide-5-Nitrae-dioxane is solvent, is added in round-bottomed flask, and the amount of substance ratio of wherein PMA and AIBN is 2:1, the AIBN of addition are 0.09 part, rotor stirring is added it is all dissolved, after leading to nitrogen 10min, the stirring reaction 10h in 70 DEG C of oil bath pan, instead Rapid being put into ice bath cools down terminating reaction after should terminating.The product molecular cut off that will be obtained after reaction is 3500 dialysis Bag dialysis three days, then freeze-drying, the poly- (methyl acrylate-b- isopropyls of white fluffy solid as target obtained after freezing Base acrylamide) PMA30-b-PNIPAM100。
Embodiment 2
With methyl acrylate (MA) for the first monomer, 0.05 part of MA is added, according to polymerization degree n (MA)：N (BDMAT)=30, 0.0017 part of the addition of BDMAT is obtained, azodiisobutyronitrile (AIBN) is initiator, and Isosorbide-5-Nitrae-dioxane is solvent, is added To in round-bottomed flask, the control of the ratio between amount of material of wherein BDMAT and AIBN is 3:1, add rotor stirring it is all dissolved, After being passed through nitrogen 30min, the stirring reaction 5h in 70 DEG C of oil bath pan, reaction cools down termination instead in being put into ice bath after terminating rapidly Should, the yellow liquid that will be obtained after reaction is precipitated 2 times in distilled water, to remove solvent Isosorbide-5-Nitrae-dioxane and unreacted list Body, finally vacuum drying obtains one end and contains carboxyl, and the other end contains the yellow viscous liquid PMA of three thioether bonds PMA30-SC(S))S。
The method being polymerized using RAFT, with NIPA (NIPAM) as second comonomer, adds 0.005 part NIPAM monomers, the PMA (PMA) of upper step synthesis is Macromolecular chain transfer agent, designs PNIPAM polymerization degree ns (NIPAM)：N (PMA)=200, it is determined that 0.000025 part of the PMA for adding, with azodiisobutyronitrile (AIBN) as initiator, 1, 4- dioxane is solvent, is added in round-bottomed flask, and the amount of substance ratio of wherein PMA and AIBN is 3:1, add rotor stirring to make It is all dissolved, and after leading to nitrogen 10min, the stirring reaction 10h in 70 DEG C of oil bath pan, reaction is put into ice bath rapidly after terminating Cooling terminating reaction.The product molecular cut off that will be obtained after reaction is that 3500 bag filter is dialysed three days, is then freezed dry Poly- (methyl acrylate-b- N-isopropylacrylamides) PMA of white fluffy solid as target that is dry, being obtained after freezing30-b- PNIPAM200。
Embodiment 3
With methyl acrylate (MA) for the first monomer, 0.05 part of MA is added, according to polymerization degree n (MA)：N (BDMAT)=30, 0.0017 part of the addition of BDMAT is obtained, azodiisobutyronitrile (AIBN) is initiator, and Isosorbide-5-Nitrae-dioxane is solvent, is added To in round-bottomed flask, the control of the ratio between amount of material of wherein BDMAT and AIBN is 4:1, add rotor stirring it is all dissolved, After being passed through nitrogen 30min, the stirring reaction 5h in 70 DEG C of oil bath pan, reaction cools down termination instead in being put into ice bath after terminating rapidly Should, the yellow liquid that will be obtained after reaction is precipitated 2 times in distilled water, to remove solvent Isosorbide-5-Nitrae-dioxane and unreacted list Body, finally vacuum drying obtains one end and contains carboxyl, and the other end contains the yellow viscous liquid PMA of three thioether bonds PMA30-SC(S))S。
The method being polymerized using RAFT, with NIPA (NIPAM) as second comonomer, adds 0.005 part NIPAM monomers, the PMA (PMA) of upper step synthesis is Macromolecular chain transfer agent, designs PNIPAM polymerization degree ns (NIPAM)：N (PMA)=300, it is determined that the PMA for adding is 0.000017 part, with azodiisobutyronitrile (AIBN) as initiator, 1, 4- dioxane is solvent, is added in round-bottomed flask, and the amount of substance ratio of wherein PMA and AIBN is 4:1, add rotor stirring to make It is all dissolved, and after leading to nitrogen 10min, the stirring reaction 10h in 70 DEG C of oil bath pan, reaction is put into ice bath rapidly after terminating Cooling terminating reaction.The product molecular cut off that will be obtained after reaction is that 3500 bag filter is dialysed three days, is then freezed dry Poly- (methyl acrylate-b- N-isopropylacrylamides) PMA of white fluffy solid as target that is dry, being obtained after freezing30-b- PNIPAM300。
Embodiment 4
With methyl acrylate (MA) for the first monomer, 0.05 part of MA is added, according to polymerization degree n (MA)：N (BDMAT)=50, 0.001 part of the addition of BDMAT is obtained, azodiisobutyronitrile (AIBN) is initiator, and Isosorbide-5-Nitrae-dioxane is solvent, is added to In round-bottomed flask, the control of the ratio between amount of material of wherein BDMAT and AIBN is 5:1, add rotor stirring it is all dissolved, lead to After entering nitrogen 30min, the stirring reaction 5h in 70 DEG C of oil bath pan, reaction cools down termination instead in being put into ice bath after terminating rapidly Should, the yellow liquid that will be obtained after reaction is precipitated 2 times in distilled water, to remove solvent Isosorbide-5-Nitrae-dioxane and unreacted list Body, finally vacuum drying obtains one end and contains carboxyl, and the other end contains the yellow viscous liquid PMA of three thioether bonds PMA50-SC(S))S。
The method being polymerized using RAFT, with NIPA (NIPAM) as second comonomer, adds 0.005 part NIPAM monomers, the PMA (PMA) of upper step synthesis is Macromolecular chain transfer agent, designs PNIPAM polymerization degree ns (NIPAM)：N (PMA)=100, it is determined that 0.00005 part of the PMA for adding, with azodiisobutyronitrile (AIBN) as initiator, 1, 4- dioxane is solvent, is added in round-bottomed flask, and the amount of substance ratio of wherein PMA and AIBN is 5:1, add rotor stirring to make It is all dissolved, and after leading to nitrogen 10min, the stirring reaction 10h in 70 DEG C of oil bath pan, reaction is put into ice bath rapidly after terminating Cooling terminating reaction.The product molecular cut off that will be obtained after reaction is that 3500 bag filter is dialysed three days, is then freezed dry Poly- (methyl acrylate-b- N-isopropylacrylamides) PMA of white fluffy solid as target that is dry, being obtained after freezing50-b- PNIPAM100。
Embodiment 5
With methyl acrylate (MA) for the first monomer, 0.05 part of MA is added, according to polymerization degree n (MA)：N (BDMAT)=50, 0.001 part of the addition of BDMAT is obtained, azodiisobutyronitrile (AIBN) is initiator, and Isosorbide-5-Nitrae-dioxane is solvent, is added to In round-bottomed flask, the control of the ratio between amount of material of wherein BDMAT and AIBN is 3:1, add rotor stirring it is all dissolved, lead to After entering nitrogen 30min, the stirring reaction 5h in 70 DEG C of oil bath pan, reaction cools down termination instead in being put into ice bath after terminating rapidly Should, the yellow liquid that will be obtained after reaction is precipitated 2 times in distilled water, to remove solvent Isosorbide-5-Nitrae-dioxane and unreacted list Body, finally vacuum drying obtains one end and contains carboxyl, and the other end contains the yellow viscous liquid PMA of three thioether bonds PMA50-SC(S))S。
The method being polymerized using RAFT, with NIPA (NIPAM) as second comonomer, adds 0.005 part NIPAM monomers, the PMA (PMA) of upper step synthesis is Macromolecular chain transfer agent, designs PNIPAM polymerization degree ns (NIPAM)：N (PMA)=200, it is determined that the PMA for adding is 0.000025 part, with azodiisobutyronitrile (AIBN) as initiator, 1, 4- dioxane is solvent, is added in round-bottomed flask, and the amount of substance ratio of wherein PMA and AIBN is 3:1, add rotor stirring to make It is all dissolved, and after leading to nitrogen 10min, the stirring reaction 10h in 70 DEG C of oil bath pan, reaction is put into ice bath rapidly after terminating Cooling terminating reaction.The product molecular cut off that will be obtained after reaction is that 3500 bag filter is dialysed three days, is then freezed dry Poly- (methyl acrylate-b- N-isopropylacrylamides) PMA of white fluffy solid as target that is dry, being obtained after freezing50-b- PNIPAM200。
Embodiment 6
With methyl acrylate (MA) for the first monomer, 0.05 part of MA is added, according to polymerization degree n (MA)：N (BDMAT)=50, 0.001 part of the addition of BDMAT is obtained, azodiisobutyronitrile (AIBN) is initiator, and Isosorbide-5-Nitrae-dioxane is solvent, is added to In round-bottomed flask, the control of the ratio between amount of material of wherein BDMAT and AIBN is 3:1, add rotor stirring it is all dissolved, lead to After entering nitrogen 30min, the stirring reaction 5h in 70 DEG C of oil bath pan, reaction cools down termination instead in being put into ice bath after terminating rapidly Should, the yellow liquid that will be obtained after reaction is precipitated 2 times in distilled water, to remove solvent Isosorbide-5-Nitrae-dioxane and unreacted list Body, finally vacuum drying obtains one end and contains carboxyl, and the other end contains the yellow viscous liquid PMA of three thioether bonds PMA50-SC(S))S。
The method being polymerized using RAFT, with NIPA (NIPAM) as second comonomer, adds 0.005 part NIPAM monomers, the PMA (PMA) of upper step synthesis is Macromolecular chain transfer agent, designs PNIPAM polymerization degree ns (NIPAM)：N (PMA)=300, it is determined that the PMA for adding is 0.000017 part, with azodiisobutyronitrile (AIBN) as initiator, 1, 4- dioxane is solvent, is added in round-bottomed flask, and the amount of substance ratio of wherein PMA and AIBN is 3:1, add rotor stirring to make It is all dissolved, and after leading to nitrogen 10min, the stirring reaction 10h in 70 DEG C of oil bath pan, reaction is put into ice bath rapidly after terminating Cooling terminating reaction.The product molecular cut off that will be obtained after reaction is that 3500 bag filter is dialysed three days, is then freezed dry Poly- (methyl acrylate-b- N-isopropylacrylamides) PMA of white fluffy solid as target that is dry, being obtained after freezing50-b- PNIPAM300。

Claims (9)

1. a kind of preparation method of polymeric sorbent predecessor di-block copolymer；It is characterized in that step is as follows：
1) Macromolecular chain transfer agent PMA is synthesized by the method that RAFT is polymerized：It is the first monomer, three thio carbon with methyl acrylate Acid esters is chain-transferring agent, and azodiisobutyronitrile is initiator, and Isosorbide-5-Nitrae-dioxane or DMF are solvent, are added To in reactor, add rotor stirring it is all dissolved, be passed through nitrogen, the stirring reaction in 70-80 DEG C of oil bath pan, reaction Rapid being put into ice bath cools down terminating reaction after end, and the yellow liquid that will be obtained after reaction precipitate in distilled water, with removing Solvent Isosorbide-5-Nitrae-dioxane and unreacted monomer, finally vacuum drying obtain one end and contain carboxyl, and the other end contains three thioesters The yellow viscous liquid PMA of key；
2) using the method for RAFT polymerizations：With NIPA as second comonomer, step 1) synthesis polyacrylic acid first Ester is Macromolecular chain transfer agent, and azodiisobutyronitrile is initiator, and Isosorbide-5-Nitrae-dioxane or DMF are solvent, It is added in reactor, adds rotor stirring it is all dissolved, after leading to nitrogen, the stirring reaction in 70-80 DEG C of oil bath pan, Reaction cools down terminating reaction in being put into ice bath after terminating rapidly；The product molecular cut off that will be obtained after reaction be 3500 it is saturating Analysis bag dialysis, then freeze-drying, it is lyophilized after the white fluffy solid as di-block copolymer that obtains it is poly- (methyl acrylate- B- N-isopropylacrylamides) PMA-b-PNIPAM.
2. the method for claim 1, it is characterized in that the step 1) in trithiocarbonate and azodiisobutyronitrile The ratio between amount of material is 2-5:1.
3. the method for claim 1, it is characterized in that the step 1) in 70-80 DEG C of oil bath pan stirring reaction 5- 8h；The yellow liquid that will be obtained after reaction is precipitated 2-3 times in distilled water.
4. the method for claim 1, it is characterized in that the step 2) in PMA and azodiisobutyronitrile Amount of substance ratio is 2-5:1.
5. the method for claim 1, it is characterized in that the step 2) in 70-80 DEG C of oil bath pan stirring reaction 10-24h；Dialysed 2-3 days with the bag filter that molecular cut off is 3500.
6. the method for claim 1, it is characterized in that being passed through nitrogen 10-30min；
7. the method for claim 1, it is characterized in that three described thioesters be S- dodecyls-S'- (α, α '-diformazan Base-α "-acetic acid) trithiocarbonate, S, S'- (α, α '-dimethyl-α "-acetic acid) trithiocarbonate, S- dodecyls-S "- One kind in isopropyl acid-trithiocarbonate or S, S'- bis- (dodecyl) trithiocarbonate.
8. the method for claim 1, it is characterized in that the step 1) in methyl acrylate and trithiocarbonate Mass ratio is the degree of polymerization, determines the proportioning of monomer and chain-transferring agent addition.
9. the method for claim 1, it is characterized in that the step 2) in NIPA and polyacrylic acid The mass ratio of methyl esters is the degree of polymerization, determines the proportioning of NIPA and PMA, different by changing Degree of polymerization selection devises the di-block copolymer of different block ratios.
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CN110964159A (en) * 2019-12-19 2020-04-07 中南大学 Star-shaped amphiphilic block copolymer and preparation method and application thereof
CN111100263A (en) * 2019-11-29 2020-05-05 广东省石油与精细化工研究院 Soluble linear conductive polymer and preparation method thereof
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CN114634639A (en) * 2022-02-28 2022-06-17 南开大学 Polycarboxylate dispersant, synthetic method thereof and application thereof in pesticide auxiliary

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CN109970933A (en) * 2019-03-28 2019-07-05 南京林业大学 It is a kind of that there is temperature and the amphipathic nature block polymer of photoresponse and preparation method thereof in ionic liquid
CN109970933B (en) * 2019-03-28 2021-09-28 南京林业大学 Amphiphilic block copolymer with temperature and light response in ionic liquid and preparation method thereof
CN111100263A (en) * 2019-11-29 2020-05-05 广东省石油与精细化工研究院 Soluble linear conductive polymer and preparation method thereof
CN111100263B (en) * 2019-11-29 2022-04-19 广东省石油与精细化工研究院 Soluble linear conductive polymer and preparation method thereof
CN110964159A (en) * 2019-12-19 2020-04-07 中南大学 Star-shaped amphiphilic block copolymer and preparation method and application thereof
CN112592444A (en) * 2020-12-15 2021-04-02 济南哈维化学科技发展有限公司 Temperature-sensitive water-soluble block polymer heavy oil viscosity reducer and preparation method and application thereof
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CN114634639A (en) * 2022-02-28 2022-06-17 南开大学 Polycarboxylate dispersant, synthetic method thereof and application thereof in pesticide auxiliary
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