CN101456937A - Polymethano-poly(methyl)acrylic ester two-block copolymer and preparation method thereof - Google Patents
Polymethano-poly(methyl)acrylic ester two-block copolymer and preparation method thereof Download PDFInfo
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- CN101456937A CN101456937A CNA2008102048739A CN200810204873A CN101456937A CN 101456937 A CN101456937 A CN 101456937A CN A2008102048739 A CNA2008102048739 A CN A2008102048739A CN 200810204873 A CN200810204873 A CN 200810204873A CN 101456937 A CN101456937 A CN 101456937A
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Abstract
The invention discloses a structurally controllable polymethylene/poly(methyl)acrylic esters block copolymer and a preparation method thereof. The preparation method comprises the following steps: using a structurally controllable polymethylene macromolecule initiator having the number average molecular weight capable of being regulated in a certain range(500-1*10<5>g/mol) and the narrow molecular weight distribution (PDI is equal to 1.01-1.49) to initiate the atom radical transfer active free radical polymerization (ATRP) of a (methyl)acrylic esters polymerization monomer; and further preparing the polymethylene/poly(methyl)acrylic esters block copolymer (Mn is equal to *10<3>-1*10<6>g/mol, PDI is equal to1.01-1.50) which enables the molecular weight regulation for both blocks and has the narrow molecular weight distribution. The two-block copolymer can be applied to the blending study of polyolefin and the preparation of a polymer porous membrane as a compatilizer.
Description
Technical field
The invention relates to polymethylene/poly-(methyl) acrylic ester two-block copolymer of a kind of controllable structure and preparation method thereof, belong to the technical field of polyolefin functional.
Background technology
Polyolefine has characteristics such as good mechanical property and chemical stability, low moisture absorption, easily processing, cheap and capable of circulation utilization again because of it, become one of consumption maximum, macromolecular material that range of application is the widest, development and national economy is played crucial effect.But because the molecular polyolefin chain is nonpolar, surface energy is very low, cause polyolefine cohesiveness, printing and dyeing property, gas permeability, static resistance and all poor, cause its range of application to be subjected to certain restriction with the consistency of other polar macromolecule material or mineral filler.Therefore, on the basis that keeps the original premium properties of polyolefine, in molecular polyolefin, introduce polar group, reactive group or other functional groups by appropriate means, polyolefine is carried out functionalization, be important channel [Chung, T.C.Functionalization of Polyolefins, the AcademicPress that realizes the polyolefine material high performance, London, 2002; Prog.Polym.Sci.2002,27,1347; CN 156617A; ZL03141200.9; Hu Youliang (Hu Y L), Qiao Jinliang (Qiao J L), Lv Lixin (Lu L X). polyolefin functional and modification-science and technology (Functionalization and Modification of Polyolefins-Scienceand Technology). Beijing: Chemical Industry Press (Beijing:Chemistry Industry Press), 2006.1-68].Polyolefine after the functionalization, its cohesiveness, coating, dyeability reach and the consistency of other material (as polar polymer, pigment, filler, glass fibre and metal etc.) all is greatly improved.
[the Lv Zhanxia (Lu Z X) of reactive group functional method in the polyolefin functional method, Hu Youliang (HuY L), Zhang Xin (Zhang X) etc. synthetic resins and plastics (Synthetic Resin and Plastic), 2002,19 (6): 51-56] be most widely used.Promptly in polyreaction, introduce reactive comonomer, so can be effectively, change reactive group into functional group selectively.This kind method is controlling polymers molecular structure and molecular weight distribution effectively, the diversified polyolefine of complex functionality group.The method [Chen Jianzhuan (Chen J Z), Cui's Kon (CK), Zhang Shuyuan (Zhang S Y), the Ma Zhi (Ma Z) that had wherein occurred the synthetic main chain end of the chain functional polyolefin of design of some novelties in the last few years
*Chemical progress 2,008 20 (11): 1740-1750 ISSN:1476-8186 CN:11-5350/TP], be about to polar group and optionally be incorporated into the polyolefinic main chain end of the chain, these main chain terminated radicals have good active, can be used as the reflecting point of a lot of reactions.Can utilize the groups converted reaction to generate based on polyolefinic macromole evocating agent, by polyreactions such as free radical, negatively charged ion, positively charged ions, and then synthetic (many) block polymers are with as effective compatilizer, in order to improve the surface interaction between polyolefine and other material.In recent years, K.J.Shea utilizes the non-olefinic polycoordination to prepare the polyolefine (J.Am.Chem.Soc.1997,119,9049) of terminal functionalityization by way of a ylide living polymerisation process, and it has molecular weight (M
n) the controlled and narrow characteristics of molecular weight distribution (PDI).Though they and other study group were the work [US5476915 of some groups converted in succession; Macromolecules 2000,33, and 4295], but carrying out groups converted, of no use its prepare macromole evocating agent, do not carry out research and the application of preparation based on the segmented copolymer of polymethylene yet.
High polymer alloy is the multicomponent polymeric that is made with physics or chemical process by two or more polymkeric substance, and it can improve the performance of original macromolecular material or the macromolecular material that formation has brand-new performance.A large amount of segmented copolymers that studies show that have tangible compatibilization to co-mixing system, can improve the interface cohesive force between the incompatible polymer, give the performance of high polymer alloy excellence.Segmented copolymer can be used for preparing porous-film in addition, can design the porous-film of multiple material as template.As inorganics being sneaked into the polymers soln film forming, calcination at high temperature, under residual might be the porous-film of inorganics.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology polymethylene/poly-(methyl) acrylic ester two-block copolymer of controllable structure;
Purpose of the present invention also provides the preparation method of the controlled polymethylene of a kind of said structure/poly-(methyl) acrylic ester two-block copolymer.
The present invention is from the molecular chain structure design point of view, utilization by the main chain terminal hydroxy group polymethylene of controllable structure (with reference to J.Am.Chem.Soc.1997,119,9049 is synthetic) carry out preparation-obtained macromole evocating agent (Chinese invention patent ublic specification of application after the groups converted, CN 101215345 A, Ma Zhi etc.), carry out (methyl) esters of acrylic acid and can gather monomeric ATRP polymerization, prepare the di-block copolymer of polymethylene/poly-(methyl) esters of acrylic acid of controllable structure.
The polymethylene of controllable structure of the present invention/poly-(methyl) acrylic ester two-block copolymer has following molecular structure:
R
1=H or CH
3
R
2=C
1～C
20Alkyl (as: CH
3Or C
2H
5Or n-C
4H
9Or i-C
4H
9Or t-C
4H
9Or n-C
6H
13Or i-C
8H
17Or n-C
12H
23Or n-C
14H
29And n-C
18H
37Deng);
C
1～C
20Halo alkyl (as: CH
2CF
3Or CH (CF
3)
2Or CH
2CF
2C (H) F
2Or CH
2CF
2C (H) FCF
3Or CH
2CH
2C
8F
17Deng); Contain heteroatomic group (as: CH such as aerobic, nitrogen, silicon
2CH
2OH or CH
2CH
2OC
6H
6Or (CH
2CH
2O)
nCH
3Or (CH
2)
2N (CH
3)
2Or Si (CH
3)
3Or CH
2CH
2CH
2Si[OSi (CH
3)
3]
3Deng);
n＝20～7000；
m＝10～10000；
Its number-average molecular weight (M
n) 1 * 10
3～1 * 10
6Between the g/mol (n=20～7000, m=10～10000), and has the di-block copolymer based on polymethylene of narrow molecular weight distributions (PDI=1.01～1.50).
The present invention relates to a class with main chain terminal hydroxy group polymethylene (with reference to J.Am.Chem.Soc.1997,119,9049, by ylide living polymerization preparation) carry out preparation-obtained macromole evocating agent (Chinese invention patent ublic specification of application after the groups converted, CN 101215345 A, Ma Zhi etc.) be used for the ATRP polymerization of (methyl) esters of acrylic acid polymerisable monomer, and then the segmented copolymer of the polymethylene of preparation controllable structure/poly-(methyl) esters of acrylic acid.
The preparation method of the segmented copolymer of the polymethylene of controllable structure of the present invention/poly-(methyl) esters of acrylic acid may further comprise the steps:
Under the anhydrous and oxygen-free condition, at a certain temperature with macromole evocating agent (MI), catalyzer (C)/part (L) and (methyl) esters of acrylic acid polymerisable monomer carry out ATRP polymerization 1h～80h in aromatic hydrocarbon solvent, reaction product is precipitated in excessive precipitation solvent, obtains after washing, filtration and the vacuum-drying molecular weight can be regulated and control, the di-block copolymer of narrow molecular weight distributions.
Macromole evocating agent of the present invention (MI).Typically have following molecular structure:
Or
This macromole evocating agent carries out chemical conversion by the polymethylene of terminal hydroxy group and obtains its number-average molecular weight (M
n) 500～1 * 10
5Between the g/mol (n=20～7000), and has narrow molecular weight distributions (PDI=1.01～1.49).
Catalyzer of the present invention (C) is: (C
1) cuprous bromide CuBr or cuprous chloride CuCl or (C
2) cuprous bromide/cupric bromide CuBr/CuBr
2Described part (L) is b-Py=2,2 '-dipyridyl or its alkyl derivative, PMDETA (N, N, N ', N ', N "-PMDETA), MA
5-DETA (N, N, N ', N ', N "-pentamethyl-methyl acrylate base divinyl triamine), BA
6-TREN (N, N, N ', N ', N ", N "-hexamethyl n-butyl acrylate base trivinyl tetramine) and MA
6-TREN (N, N, N ', N ', N ", N "-hexamethyl methyl acrylate base trivinyl tetramine) etc.
(methyl) of the present invention esters of acrylic acid polymerisable monomer (S) is: contain C
1～C
20The ester class (as: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid is (XOR uncle) butyl ester, positive Ethyl acrylate, Isooctyl acrylate monomer, lauryl methacrylate(LMA), vinylformic acid tetradecane ester, (methyl) vinylformic acid stearyl etc. just) of alkyl; Contain C
1～C
20The ester class (as: trifluoroethyl methacrylate, 2,2,3,3-tetrafluoro propyl methyl acid esters, methacrylic ester hexafluoro butyl ester, 1H, 1H, 2H, 2H-perfluor decyl acrylate etc.) of halo alkyl; The ester class (as: (methyl) Hydroxyethyl acrylate, vinylformic acid-2-phenoxy ethyl, (methoxyl group) polyoxyethylene glycol (methyl) acrylate, methacrylic acid-2 (dimethylamino) ethyl ester etc.) that contains heteroatomic groups such as aerobic, nitrogen, silicon;
Macromole evocating agent of the present invention (MI), catalyzer 1 (C
1), catalyzer 1 (C
2), the mol ratio of part (L) and (methyl) esters of acrylic acid polymerisable monomer (S) is recommended as 1:(1～4): (0～0.2): (1～8): (10～10000).
Aromatic hydrocarbon solvent of the present invention is recommended as benzene, methyl-phenoxide, toluene, dimethylbenzene, chlorobenzene, orthodichlorobenzene or 1,2,4-trichlorobenzene.
ATRP polymeric temperature of the present invention is recommended as 50 ℃～solvent refluxing temperature; It is 1h～80h that polymerization time is recommended.
It is methyl alcohol, ether, just (ring) hexane water or acetone that precipitation solvent of the present invention is recommended.
Adopt preparation method of the present invention, can obtain molecular weight and can regulate and control (1 * 10 in certain limit
3～1 * 10
6G/mol, n=20～7000, m=10～10000), and have polymethylene/(methyl) acrylic ester two-block copolymers of narrow molecular weight distributions (PDI=1.01～1.50); Wherein the chain structure of polymethylene and poly-two blocks of (methyl) esters of acrylic acid all can well be regulated and control respectively.Resulting segmented copolymer can be used as compatilizer and is used for blending study between polyolefine and other polymer materials.In addition, can prepare porous-film, be used for the template of other material porous-film preparation with the block polymer that obtains.
Description of drawings
Fig. 1. the segmented copolymer P-08's that the ATRP polymerization of macromole evocating agent MI-02 and MMA (methyl methacrylate) obtains
1H NMR spectrum;
Fig. 2. the segmented copolymer P-1S's that macromole evocating agent MI-02 and n-BA (n-butyl acrylate) ATRP polymerization obtains
1H NMR spectrum;
Fig. 3. the segmented copolymer P-20's that macromole evocating agent MI-02 and Acryl-PEG (methoxy poly (ethylene glycol) acrylate) ATRP polymerization obtains
1H NMR spectrum;
Fig. 4. obtain among the embodiment 8,9 controllable structure based on polyolefinic segmented copolymer P-08, the folded figure of the high temperature GPC curve of P-09 and MI-02;
Fig. 5. obtain among the embodiment 15,16 controllable structure based on polyolefinic segmented copolymer P-15, the folded figure of the high temperature GPC curve of P-16 and MI-02;
Fig. 6. the segmented copolymer P-32 that obtains among the embodiment 32 is used for the scanning electron microscope picture of blending study, (a) PE/PMMA=75/25, (b) PE/PMMA/P-32=75/25/5, (c) PE/PMMA/P-32=75/25/15;
Fig. 7. the scanning electron microscope picture based on the porous-film of segmented copolymer of preparation among the embodiment 33, (a) porous-film of segmented copolymer P-02 preparation, (b) porous-film of segmented copolymer P-05 preparation.
Embodiment
Embodiment will help further to understand the present invention, but can not limit content of the present invention.
Among the embodiment, polymericular weight (M
w, M
n) and molecular weight distribution (PDI) utilize Waters AllianceGPC2000 1,2, in 4 trichlorobenzene (flow velocity 1.0 mL/min) under 135 ℃, be that standard specimen is measured with the polyethylene.
Polymkeric substance
1H-NMR composes on the Avance500MHz nuclear magnetic resonance analyser with D
4-o-dichlorobenzene is a solvent, measures down at 80 ℃ or 120 ℃.
The scanning electron microscope diagram sheet of polymkeric substance is to go up to observe in scanning electronic microscope (JSM-6390LV) to measure among the embodiment.
Batten among the embodiment 32 is to prepare with micro-injection moulding sampling machine (ISO527-2-A5a Elongation test mould).
The bromine content basis of polymkeric substance
1The H-NMR spectrum calculates.
Embodiment 1
The preparation of the polymethylene of controllable structure of the present invention/poly-(methyl) acrylate based block copolymer:
In having the 10mL exsiccant round-bottomed flask A of magnetic stir bar, under nitrogen protection, add macromole evocating agent MI-01 0.10g (0.054 mmol Br) (M
n=1856, PDI=1.23, n=120, bromine content=540 μ mol/g polymkeric substance,
1H NMR (500MHz, δ ppm): 3.92 (t, 2H), 1.69 (s, 6H), 1.42 (t, 2H), 1.10 (m, 240H), 0.67 (s, 12H)), vacuumize 30min after, charge into nitrogen.Have among the 10mL exsiccant round-bottomed flask B of magnetic stir bar in another one; under nitrogen protection, add CuBr 7.7mg (0.054mmol), PMDETA (N; N; N '; N '; N "-PMDETA) MMA (methyl methacrylate) 0.58mL (5.4mmol 22.5 L 0.108mmol); through underpressure distillation) and toluene 2.5mL (through the sodium Metal 99.5 reflow treatment); after stirring 30min; under nitrogen protection said mixture is transferred among the round-bottomed flask A with exsiccant double end needle tubing, polyreaction is carried out 6h at 90 ℃.After reaction finishes, cool off with ice-water bath, add an amount of toluene, heated condition descended the neutral alumina short column, remove mantoquita, mixture is poured in the 100mL methyl alcohol precipitates then, filter, use twice of 20mL methanol wash, at 60 ℃ of following vacuum-drying 20h, obtain 0.560g segmented copolymer P-01 (M
n=9884, PDI=1.48, n=120, m=80).
The preparation of the polymethylene of controllable structure of the present invention/poly-(methyl) acrylic ester two-block copolymer:
Operation is substantially with embodiment 1.Difference is that the kind of catalyzer, part in the ATRP polyreaction and consumption, reaction solvent and consumption thereof, temperature of reaction, reaction times all not exclusively are same as embodiment 1.Obtain polymethylene/poly-(methyl) acrylic ester two-block copolymer P-02 (n=120 of controllable structure respectively, m=20), P-03 (n=120, m=24), P-04 (n=120, m=50), P-05 (n=120, m=92), P-06 (n=120, m=66) and P-07 (n=120, m=96).
Concrete experiment condition and polymer characterization data see Table 1:
R in the product of embodiment 2～7
1And R
2Be CH
3
Table 1
Annotate: b-Py=2,2 '-dipyridyl or its alkyl derivative, PMDETA (N, N, N ', N ', N "-PMDETA)
Embodiment 8
The preparation based on polyolefinic polymethylene/poly-(methyl) acrylic ester two-block copolymer of controllable structure of the present invention:
In having the 10mL exsiccant Schlenk reaction flask of magnetic stir bar, under nitrogen protection, add macromole evocating agent MI-02 0.10g (0.016mmol Br) (M
n=6105, PDI=1.10, n=440, bromine content=165 μ mol/g polymkeric substance,
1H NMR (500MHz, δ ppm): 3.93 (t, 2H), 1.68 (s, 6H), 1.41 (t, 2H), 1.10 (m, 300H), 0.67 (s, 12H), vacuumize 30min after, charge into nitrogen.Under nitrogen protection, add CuBr 2.3mg (0.016mmol), CuBr
20.2mg (0.80umol), vacuumize 30min after, charge into nitrogen once more.Add PMDETA (N, N, N ', N ', N "-PMDETA) 6.8L (0.032mmol), methacrylic ester 0.52mL (4.80mmol is through underpressure distillation) polyreaction by syringe and carry out 1h at 90 ℃.After reaction finishes, use the liquid nitrogen freezing cancellation, add an amount of toluene, mixture solution is poured in the 100mL methyl alcohol precipitates then, filter, use 50mL methanol wash twice,, obtain 0.188g segmented copolymer P-08 (M at 80 ℃ of following vacuum-drying 12h
n=8454, PDI=1.14, n=440, m=24).
Embodiment 9～embodiment 13
The preparation based on polyolefinic polymethylene/poly-(methyl) acrylic ester two-block copolymer of controllable structure of the present invention:
Operation is substantially with embodiment 8.Difference is the catalyzer in the ATRP polyreaction, the kind of part, temperature of reaction, poly-(methyl) esters of acrylic acid polymerisable monomer of reaction times and use not exclusively is same as embodiment 8, obtain segmented copolymer P-09 (n=440 respectively, m=63), P-10 (n=440, m=228), P-11 (n=440, m=104), P-12 (n=440, m=126), P-13 (n=440, m=160), P-14 (n=440, m=10), P-15 (n=440, m=19), P-16 (n=440, m=24), P-17 (n=440, m=6), P-18 (n=440, m=10), P-19 (n=440, m=18), P-20 (n=440, m=7), P-21 (n=440, m=2), P-22 (n=440, m=8), P-23 (n=440, m=40) and P-24 (n=440, m=13).
Concrete experiment condition and polymer characterization data see Table 2.
R in the product of embodiment 9～12
1And R
2Be CH
3
R in the product of embodiment 13～20
1Be H, R
2Be n-C
4H
9
R in the product of embodiment 20～24
1Be H, R
2Be (CH
2CH
2O)
nCH
3(methoxy poly (ethylene glycol) base).
Table 2
Annotate: MA
5-DETA=N, N, N ', N ', N "-pentamethyl-methyl acrylate base divinyl triamine, BA
6-TREN=N, N, N ', N ', N ", N "-hexamethyl n-butyl acrylate base trivinyl tetramine, MA
6-TREN=N, N, N ', N ', N ", N "-hexamethyl methyl acrylate base trivinyl tetramine; MMA=methyl methacrylate, n-BA=n-BMA, Acryl-PEG=methoxy poly (ethylene glycol) acrylate;
Obtain among the embodiment 8,9 controllable structure based on polyolefinic segmented copolymer P-08, the folded figure of the GPC curve of P-09 and MI-02 (seeing accompanying drawing 4).
Obtain among the embodiment 15,16 controllable structure based on polyolefinic segmented copolymer P-15, the folded figure of the GPC curve of P-16 and MI-02 (seeing accompanying drawing 5).
Embodiment 25～embodiment 31
The preparation based on polyolefinic polymethylene/poly-(methyl) acrylic ester two-block copolymer of controllable structure of the present invention:
Operation is substantially with embodiment 1.Difference be macromole evocating agent MI in the ATRP polyreaction kind and consumption thereof, (methyl) esters of acrylic acid can gather the monomer consumption and the reaction times not exclusively is same as embodiment 1.Obtain polymethylene/poly-(methyl) acrylic ester two-block copolymer P-25 (n=140 of controllable structure respectively, m=45), P-26 (n=250, m=100), P-27 (n=320, m=90), P-28 (n=410, m=280), P-29 (n=650, m=200), P-30 (n=800, m=160) and P-31 (n=1070, m=270).
Concrete experiment condition and polymer characterization data see Table 3.
R in the product of embodiment 25～31
1And R
2Be-CH
3
Table 3
Embodiment 32
Synthetic can be used as compatilizer based on polyolefinic polymethylene/poly-(methyl) acrylic ester two-block copolymer, is applied in the polyolefin blend research.(n=440 m=63) is example, gets the there-necked flask a of three 100ml with the P-09 that obtains among the embodiment 9, b, c respectively claim the new LDPE (film grade) (Mn=4 ten thousand) of 2.5g, 0.83g polymethylmethacrylate (Mn=1.5 ten thousand), add P-090.17g among the bottle b, add P-090.51g among the bottle c.The chlorobenzene that respectively adds 60ml in three bottles, under 100 ℃, carry out the about 15min of solution blending (being homogeneous phase transparent solution) to system, splash into then in the excessive methanol solution and precipitate, filter dried solid and on miniature injection machine, prepare the dumbbell shape batten, nip off behind the liquid nitrogen freezing, under scanning electron microscope, observe the fracture morphology (see figure 6).Illustrate that segmented copolymer P-09 has promoted the comixing compatibility of polyethylene and polystyrene as compatilizer.
Embodiment 33
Synthetic is used to prepare porous-film based on polyolefinic polymethylene/poly-(methyl) acrylic ester two-block copolymer, is used as the template of the porous-film preparation of other material.The P-02 for preparing with embodiment 2 and embodiment 5, P-05 is an example, be configured to massfraction respectively and be 3% dithiocarbonic anhydride solution, drip on the sheet glass of the cleaning of in water surrounding, placing then and be coated with above-mentioned solution, after leaving standstill 30min, scanning electron microscopic observation can be seen the porous membrane structure (see figure 7) that the porous-film block polymer forms.
Claims (8)
1, a kind of polymethylene of controllable structure-poly-(methyl) acrylic ester two-block copolymer is characterized in that described di-block copolymer has following molecular structure:
Wherein, R
1=H or CH
3
R
2=C
1～C
20Alkyl (as: CH
3Or C
2H
5Or n-C
4H
9Or i-C
4H
9Or t-C
4H
9Or n-C
6H
13Or i-C
8H
17Or n-C
12H
23Or n-C
14H
29And n-C
18H
37);
C
1～C
20Halo alkyl (as: CH
2CF
3Or CH (CF
3)
2Or CH
2CF
2C (H) F
2Or CH
2CF
2C (H) FCF
3Or CH
2CH
2C
8F
17); Group (as: the CH that contains aerobic, nitrogen or sila atom
2CH
2OH or CH
2CH
2OC
6H
6Or (CH
2CH
2O)
nCH
3Or (CH
2)
2N (CH
3)
2Or Si (CH
3)
3Or CH
2CH
2CH
2Si[OSi (CH
3)
3]
3);
n＝20～7000；
m＝10～10000；
Its number-average molecular weight M
n1 * 10
3～1 * 10
6Between the g/mol, and has the di-block copolymer based on polymethylene alkene of molecular weight distribution PDI=1.01～1.50.
2, according to the described di-block copolymer of claim 1, it is characterized in that described C
1～C
20Alkyl be CH
3, C
2H
5, n-C
4H
9, i-C
4H
9, t-C
4H
9, n-C
6H
13, i-C
8H
17, n-C
12H
23, n-C
14H
29With or n-C
18H
37Described C
1～C
20The halo alkyl be CH
2CF
3, CH (CF
3)
2, CH
2CF
2C (H) F
2, CH
2CF
2C (H) FCF
3Or CH
2CH
2C
8F
17); The described group that contains aerobic, nitrogen or sila atom is CH
2CH
2OH, CH
2CH
2OC
6H
6, (CH
2CH
2O)
nCH
3, (CH
2)
2N (CH
3)
2, Si (CH
3)
3Or CH
2CH
2CH
2Si[OSi (CH
3)
3]
3
3, a kind of preparation method according to the described di-block copolymer of claim 1, it is characterized in that macromole evocating agent, catalyzer, part and (methyl) esters of acrylic acid polymerisable monomer being carried out ATRP polymerization 1h～80h in aromatic hydrocarbon solvent or in its bulk system under the anhydrous and oxygen-free condition and under the 50 ℃～solvent refluxing temperature; The mol ratio of described macromole evocating agent, catalyzer 1, catalyzer 2, part and (methyl) esters of acrylic acid polymerisable monomer is 1:(1～4): (0～0.2): (1～8): (10～10000);
Described macromole evocating agent has following molecular structure:
Between n=20～7000;
Described catalyzer 1 is that cuprous bromide or cuprous chloride, catalyzer 2 are cuprous bromide/cupric bromide;
Described part is 2,2 '-dipyridyl or its alkyl derivative, N, N, N ', N ', N "-PMDETA, N, N, N '; N ', N "-pentamethyl-methyl acrylate base divinyl triamine, N, N, N ', N ', N "; N "-hexamethyl n-butyl acrylate base trivinyl tetramine and N, N, N ', N ', N ", N "-hexamethyl methyl acrylate base trivinyl tetramine;
Described (methyl) esters of acrylic acid polymerisable monomer is: contain C
1～C
20Alkyl ester compound, contain C
1～C
20The halo alkyl ester compound or contain the ester compound of the group of aerobic, nitrogen or sila atom.
4,, it is characterized in that in precipitation solvent, precipitating after the polymerization, after filtration, washing and dry according to the preparation method of the described di-block copolymer of claim 3.
5,, it is characterized in that described macromole evocating agent carries out chemical conversion by the polymethylene of terminal hydroxy group and obtains its number-average molecular weight M according to the preparation method of the described di-block copolymer of claim 3
n500～1 * 10
5G/mol, and have molecular weight distribution PDI=1.01～1.49.
6,, it is characterized in that the described C of containing according to the preparation method of the described di-block copolymer of claim 3
1～C
20The ester compound of alkyl be (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid just (XOR uncle) butyl ester, positive Ethyl acrylate, Isooctyl acrylate monomer, lauryl methacrylate(LMA), vinylformic acid tetradecane ester and (methyl) vinylformic acid stearyl; The described C that contains
1～C
20The ester compound of halo alkyl be trifluoroethyl methacrylate, 2,2,3,3-tetrafluoro propyl methyl acid esters, methacrylic ester hexafluoro butyl ester or 1H, 1H, 2H, 2H-perfluor decyl acrylate; The described ester compound that contains the group of aerobic, nitrogen or sila atom is (methyl) Hydroxyethyl acrylate, vinylformic acid-2-phenoxy ethyl, (methoxyl group) polyoxyethylene glycol (methyl) acrylate or methacrylic acid-2 (dimethylamino) ethyl ester etc.
7,, it is characterized in that described aromatic hydrocarbon solvent is benzene, methyl-phenoxide, toluene, dimethylbenzene, chlorobenzene, orthodichlorobenzene or 1,2, the 4-trichlorobenzene according to the preparation method of the described di-block copolymer of claim 3.
8, according to the preparation method of the described di-block copolymer of claim 3, its feature is methyl alcohol, ether, just (ring) hexane, water or acetone in described precipitation solvent.
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| CN101935382A (en) * | 2010-09-10 | 2011-01-05 | 广东工业大学 | Methyl methacrylate block copolymer and preparation method thereof |
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| CN101935382A (en) * | 2010-09-10 | 2011-01-05 | 广东工业大学 | Methyl methacrylate block copolymer and preparation method thereof |
| CN101935382B (en) * | 2010-09-10 | 2013-02-13 | 广东工业大学 | Methyl methacrylate block copolymer and preparation method thereof |
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