CN103497293A - Method for preparing DMAEMA based amphiphilic block copolymer through single electron transfer living free radical polymerization - Google Patents
Method for preparing DMAEMA based amphiphilic block copolymer through single electron transfer living free radical polymerization Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 28
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229920000469 amphiphilic block copolymer Polymers 0.000 title claims abstract description 17
- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 9
- 230000027756 respiratory electron transport chain Effects 0.000 title claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 10
- -1 dimethyl amino ethyl Chemical group 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 claims description 11
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical class CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 1
- 229920001400 block copolymer Polymers 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 13
- 230000004087 circulation Effects 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 239000003643 water by type Substances 0.000 description 11
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing a DMAEMA based amphiphilic block copolymer through single electron transfer living free radical polymerization. The method comprises the following steps: adding an initiator, a monomer, deionized water and a catalyst into a reactor, filling nitrogen, stirring for 20 min, adding a ligand under the protection of nitrogen, maintaining the nitrogen atmosphere, reacting at 0-90 DEG C for 10-150 min, taking out the catalyst, dewatering and vacuum drying to obtain a target product. The catalyst is a copper wire, and the initiator is active polymethylacrylic acid dimethyl amino ethyl ester; and the monomer is oil soluble acrylate. The preparation method provided by the invention is high in polymerization speed, high in monomer conversion rate (67% can be achieved within 60 min) and narrow in molecular weight distribution (the minimum can be 1.40), and the molecular weight of each segment of the block copolymer is controllable. The preparation method is simple, convenient and easy to realize and is clean and environment-friendly, thereby providing convenience for industrial production.
Description
Technical field
The present invention relates to a kind of method of the DMAEMA of preparation base amphiphilic block copolymer, be specially a kind of method that single electron transfer active free radical polymerization prepares DMAEMA base amphiphilic block copolymer.
Background technology
Amphiphilic block copolymer can be used as dispersion agent, stablizer, and compatilizer, tensio-active agent, obtained a lot of research in recent years.Dimethylaminoethyl methacrylate (DMAEMA) is a kind of water-soluble acrylic ester, there is temperature and pH susceptibility, the amphiphilic block copolymer that contains the PDMAEMA section also has environmental sensitivity as a kind of functional polymer, thereby has a lot of special purposes.PDMAEMA is affinity DNA well, plays the medium transfer function in different cells, has biocompatibility, anticoagulant functions, and therefore, DMAEMA base amphiphilic block copolymer has potential using value at biological field and medical system.
Usually prepared by anionoid polymerization by amphiphilic block copolymer, but anionoid polymerization condition harshness has limited its development.The synthetic amphiphilic block copolymer reaction conditions of atom transfer radical polymerization (ATRP) is gentleer, but the required catalyzer of ATRP is more, and the transition metal-type that its catalyzer is low-oxidation-state, Typical Representative is copper halide, often color is very dark the adding of mantoquita to make polymerisate, need to carry out aftertreatment, not only technical process is comparatively complicated, has also increased its production cost.
The single electron transfer active free radical polymerization (SET-LRP) proposed by Percec seminar, the advantage such as the method has the reaction conditions gentleness, rate of polymerization is high, and suitable monomers is wide, controllability is strong, obtained paying close attention to widely in recent years.SET-LRP grows up on the ATRP basis, it is compared maximum advantage and has been to use the copper of zeroth order as catalyzer with ATRP, no matter use copper powder or copper wire, can filter easily, the polymerisate color can not be affected, all right recycling of catalyzer, thereby greatly reduce production cost, simplified technical process, met environmental protection at present, the thought of cleaner production.At present, research for SET-LRP mainly concentrates on the polymerization of the oil-soluble monomers such as acrylate, and it is also comparatively rare for the polymerization studies of water-soluble monomer, therefore, utilize its advantage of polymerization in water medium to realize the homopolymerization of water-soluble monomer, and using it as macromole evocating agent, then cause other oil-soluble monomer and carry out copolymerization, the amphiphilic block copolymer of synthetic polyfunctionality will be opened up the frontier of SET-LRP research.
Summary of the invention
The present invention seeks to provides a kind of simple and easy to do and polymerization process that controllability is strong for DMAEMA base amphiphilic block copolymer.The method is used the synthetic DMAEMA base amphiphilic block copolymer of SET-LRP method, and this method has been simplified this polymkeric substance polymerization technique flow process in the past greatly: take water as reaction medium, clean environment firendly; Can be in the polymerization of room temperature left and right, save energy; Use copper wire catalysis, after polymerization, system is colourless, exempts aftertreatment; Polymerization efficiency is high, and short dozens of minutes obtains product.
Technical scheme of the present invention is:
A kind of single electron transfer active free radical polymerization prepares the method for DMAEMA base amphiphilic block copolymer, comprises the following steps:
Initiator, monomer, deionized water and catalyzer are joined in reactor; after logical nitrogen gas stirring 20min, under nitrogen protection, add part, keep nitrogen atmosphere; react 10～150min under 0～90 ℃, take out catalyzer and obtain target product by dehydration, vacuum-drying.
Wherein, the add-on of initiator is that every 10mL monomer adds initiator 0.10g, material proportion is volume ratio monomer: water=1:0.25～10, mol ratio monomer: part=2.5～800:1, described catalyzer is copper wire, and the add-on of catalyzer is that every 10mL monomer adds copper wire 1～200cm that diameter is 0.02～2.00mm;
Described initiator is active polymethyl acrylic acid dimethylaminoethyl (PDMAEMA～Br);
Described monomer is oil-soluble acrylate.
Described monomer is methyl acrylate, ethyl propenoate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate or n-BMA.
Described part is 1,4,8, the 11-tetra-azo-cycle tetradecanes (Cyclam), dipyridyl (Bpy), Tetramethyl Ethylene Diamine (TMEDA), pentamethyl-diethylenetriamine (PMDETA), three amido ethylamines (TREN) or three (N, N-dimethyl aminoethyl) amine (Me
6-TREN).
Beneficial effect of the present invention is:
Preparation method's rate of polymerization provided by the invention is fast, and monomer conversion high (in 60min, can reach 67%), can make the molecular weight of each section of segmented copolymer controlled, and molecular weight distribution narrower (minimum reach 1.40).The preparation method is simple and easy to do, and clean environment firendly, for suitability for industrialized production is provided convenience.
The accompanying drawing explanation
Fig. 1. the nuclear magnetic spectrogram of PDMAEMA-b-PBA in embodiment mono-
Fig. 2. the GPC curve of PDMAEMA～Br and PDMAEMA-b-PBA in embodiment mono-
Fig. 3. the DMA of PDMAEMA-b-PBA figure in embodiment mono-
Fig. 4. the nuclear magnetic spectrogram of PDMAEMA-b-PBMA in embodiment ten
Fig. 5. the GPC curve of PDMAEMA～Br and PDMAEMA-b-PBMA in embodiment ten
Fig. 6. the DMA of PDMAEMA-b-PBMA figure in embodiment ten
Embodiment
Below describe the present invention in detail and provide several embodiment:
The preparation of active macromole PDMAEMA～Br that the present invention uses:
By 10mL DMAEMA(0.0602mol), 0.0503gMBP(0.0003mol), the 50mL deionized water joins in the 100mL round-bottomed flask, add copper wire Φ 0.6mm, L80cm, after logical nitrogen gas stirring 20min, add 0.0522gPMDETA(0.0003mol under nitrogen protection), after vacuumizing-fill five circulations of nitrogen, flask is placed in to 35 ℃ of waters bath with thermostatic control, after reaction 60min, detaching device, pour reaction mixture into beaker, take out copper wire, beaker is placed in to 70 ℃ of water-baths, treat the product precipitation fully, by deionized water water washing and precipitating repeatedly, vacuum-drying is to constant weight, obtain the water white transparency product.
Embodiment mono-:
By 0.1gPDMAEMA～Br(M
n gPC=7.04 * 10
4, PDI=1.30), the 10mLBA(n-butyl acrylate) (0.0701mol); the 65mL deionized water joins in the 200mL round-bottomed flask; add copper wire Φ 0.26mm, L60cm, after logical nitrogen gas stirring 20min; add 0.6823gTREN(0.0047mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 60 ℃ of waters bath with thermostatic control, after reaction 120min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 64%, GPC records polymkeric substance M that weighting method records monomer conversion
n=13.25 * 10
4, PDI=1.85.
Polymkeric substance is carried out
1h-NMR analyzes, and as shown in Figure 1, the fignal center in spectrogram is fully corresponding with the hydrogen proton on two kinds of structural units in segmented copolymer.As shown in Figure 2, the elution time of segmented copolymer obviously shifts to an earlier date, and is unimodal for macromole evocating agent PDMAEMA～Br and the segmented copolymer GPC curve that obtains, illustrates that molecule grows with the straight chain direction.Block polymer is carried out to the DMA test, from Fig. 3, we can find out that the second-order transition temperature of pure PBA is-60 ℃, the second-order transition temperature of pure PDMAEMA is 18 ℃, two peaks appear in the tan δ of PDMAEMA-b-PBA-T curve, and two peaks are drawn close to centre, this is the characteristic feature of segmented copolymer, illustrates and successfully synthesizes segmented copolymer.
Embodiment bis-:
By 0.1gPDMAEMA～Br(M
n gPC=7.04 * 10
4, PDI=1.30), 10mLBA(0.0701mol); the 15mL deionized water joins in the 50mL round-bottomed flask; add copper wire Φ 0.50mm, L10cm, after logical nitrogen gas stirring 20min; add 0.0351gCyclam(0.00018mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 30 ℃ of waters bath with thermostatic control, after reaction 120min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 84%, GPC records polymkeric substance M that weighting method records monomer conversion
n=24.62 * 10
4, PDI=1.50.
Embodiment tri-:
By 0.1gPDMAEMA～Br(M
n gPC=7.04 * 10
4, PDI=1.30), 10mLBA(0.0701mol); the 40mL deionized water joins in the 100mL round-bottomed flask; add copper wire Φ 0.08mm, L80cm, after logical nitrogen gas stirring 20min; add 1.0183gTMEDA(0.0088mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 60 ℃ of waters bath with thermostatic control, after reaction 90min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 88%, GPC records polymkeric substance M that weighting method records monomer conversion
n=25.37 * 10
5, PDI=1.47.
Embodiment tetra-:
By 0.1gPDMAEMA～Br(M
n gPC=7.04 * 10
4, PDI=1.30), 10mLBA(0.0701mol); the 70mL deionized water joins in the 200mL round-bottomed flask; add copper wire Φ 1.00mm, L100cm, after logical nitrogen gas stirring 20min; add 0.2025gPMDETA(0.0012mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 30 ℃ of waters bath with thermostatic control, after reaction 90min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 78%, GPC records polymkeric substance M that weighting method records monomer conversion
n=21.66 * 10
4, PDI=1.64.
Embodiment five:
By 0.1gPDMAEMA～Br(M
n gPC=7.04 * 10
4, PDI=1.30), 10mLBA(0.0701mol); the 10mL deionized water joins in the 50mL round-bottomed flask; add copper wire Φ 2.00mm, L10cm, after logical nitrogen gas stirring 20min; add 0.0512gTREN(0.00035mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 10 ℃ of waters bath with thermostatic control, after reaction 60min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 67%, GPC records polymkeric substance M that weighting method records monomer conversion
n=16.43 * 10
4, PDI=1.70.
Embodiment six:
By 0.1gPDMAEMA～Br(M
n gPC=7.00 * 10
4, PDI=1.35), the 10mLBMA(n-BMA) (0.0629mol), the 5mL deionized water joins in the 50mL round-bottomed flask, adds copper wire Φ 0.06mm, and L60cm after logical nitrogen gas stirring 20min, adds 0.0482gMe under nitrogen protection
6-TREN(0.0002mol), after vacuumizing-fill five circulations of nitrogen, flask is placed in to 5 ℃ of waters bath with thermostatic control, after reaction 120min, copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 38%, GPC records polymkeric substance M that weighting method records monomer conversion
n=13.55 * 10
4, PDI=1.60.
Embodiment seven:
By 0.1gPDMAEMA～Br(M
n gPC=7.00 * 10
4, PDI=1.35), 10mLBMA(0.0629mol); the 30mL deionized water joins in the 100mL round-bottomed flask; add copper wire Φ 0.10mm, L40cm, after logical nitrogen gas stirring 20min; add 0.0218gPMDETA(0.0001mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 75 ℃ of waters bath with thermostatic control, after reaction 120min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 84%, GPC records polymkeric substance M that weighting method records monomer conversion
n=35.37 * 10
4, PDI=2.05.
Embodiment eight:
By 0.1gPDMAEMA～Br(M
n gPC=7.00 * 10
4, PDI=1.35), 10mLBMA(0.0629mol); the 85mL deionized water joins in the 200mL round-bottomed flask; add copper wire Φ 1.40mm, L30cm, after logical nitrogen gas stirring 20min; add 0.0982gBpy(0.0006mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 80 ℃ of waters bath with thermostatic control, after reaction 120min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 52%, GPC records polymkeric substance M that weighting method records monomer conversion
n=27.01 * 10
4, PDI=2.17.
Embodiment nine:
By 0.1gPDMAEMA～Br(M
n gPC=7.00 * 10
4, PDI=1.35), 10mLBMA(0.0629mol); the 15mL deionized water joins in the 50mL round-bottomed flask; add copper wire Φ 0.80mm, L120cm, after logical nitrogen gas stirring 20min; add 1.4619gTMEDA(0.0126mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 60 ℃ of waters bath with thermostatic control, after reaction 100min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 78%, GPC records polymkeric substance M that weighting method records monomer conversion
n=31.34 * 10
4, PDI=2.13.
Embodiment ten:
By 0.1gPDMAEMA～Br(M
n gPC=7.00 * 10
4, PDI=1.35), 10mLBMA(0.0629mol); the 50mL deionized water joins in the 200mL round-bottomed flask; add copper wire Φ 1.20mm, L100cm, after logical nitrogen gas stirring 20min; add 0.9183gTREN(0.0063mol under nitrogen protection); after vacuumizing-fill five circulations of nitrogen, flask is placed in to 25 ℃ of waters bath with thermostatic control, after reaction 100min; copper wire is taken out, through dehydration, vacuum-drying, obtain target product.
It is that 92%, GPC records polymkeric substance M that weighting method records monomer conversion
n=70.06 * 10
4, PDI=1.40.
Polymkeric substance is carried out to the 1H-NMR analysis, and as shown in Figure 4, the fignal center in spectrogram is fully corresponding with the hydrogen proton on two kinds of structural units in segmented copolymer.As shown in Figure 5, the elution time of segmented copolymer obviously shifts to an earlier date, and is unimodal for macromole evocating agent PDMAEMA～Br and the segmented copolymer GPC curve that obtains, illustrates that molecular weight grows with the straight chain direction.Block polymer is carried out to the DMA test, from Fig. 6, we can find out that the second-order transition temperature of pure PBMA is 55 ℃, the second-order transition temperature of pure PDMAEMA is 18 ℃, two peaks appear in the tan δ of PDMAEMA-b-PBMA-T curve, and two peaks are drawn close to centre, this is the characteristic feature of segmented copolymer, illustrates and successfully synthesizes segmented copolymer.
Claims (3)
1. a single electron transfer active free radical polymerization prepares the method for DMAEMA base amphiphilic block copolymer, it is characterized by and comprises the following steps:
Initiator, monomer, deionized water and catalyzer are joined in reactor, after logical nitrogen gas stirring 20min, under nitrogen protection, add part, keep nitrogen atmosphere, react 10～150min under 0～90 ℃, take out catalyzer and obtain target product by dehydration, vacuum-drying;
Wherein, the add-on of initiator is that every 10mL monomer adds initiator 0.10g, material proportion is volume ratio monomer: water=1:0.25～10, mol ratio monomer: part=2.5～800: 1, described catalyzer is copper wire, and the add-on of catalyzer is that every 10mL monomer adds copper wire 1～200cm that diameter is 0.02～2.00mm;
Described initiator is active polymethyl acrylic acid dimethylaminoethyl (PDMAEMA～Br);
Described monomer is oil-soluble acrylate.
2. single electron transfer active free radical polymerization as claimed in claim 1 prepares the method for DMAEMA base amphiphilic block copolymer, it is characterized by described monomer is methyl acrylate, ethyl propenoate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate or n-BMA.
3. single electron transfer active free radical polymerization as claimed in claim 1 prepares the method for DMAEMA base amphiphilic block copolymer, it is characterized by described part is 1,4,8, the 11-tetra-azo-cycle tetradecanes (Cyclam), dipyridyl (Bpy), Tetramethyl Ethylene Diamine (TMEDA), pentamethyl-diethylenetriamine (PMDETA), three amido ethylamines (TREN) or three (N, N-dimethyl aminoethyl) amine (Me
6-TREN).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163178A (en) * | 2017-05-23 | 2017-09-15 | 常州大学 | A kind of quick method for preparing hyperbranched poly acrylic resin under normal temperature |
| CN113150190A (en) * | 2021-04-12 | 2021-07-23 | 常州大学 | Copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in aqueous solution and application |
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2013
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163178A (en) * | 2017-05-23 | 2017-09-15 | 常州大学 | A kind of quick method for preparing hyperbranched poly acrylic resin under normal temperature |
| CN113150190A (en) * | 2021-04-12 | 2021-07-23 | 常州大学 | Copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in aqueous solution and application |
| CN113150190B (en) * | 2021-04-12 | 2023-01-17 | 常州大学 | Copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in aqueous solution and application |
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