CN102503844A - Atom transfer free radical polymerization initiator with gemini surface activity and synthetic method thereof - Google Patents
Atom transfer free radical polymerization initiator with gemini surface activity and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses an atom transfer free radical polymerization initiator with gemini surface activity. A synthetic method of the initiator comprises the following steps of: undergoing an esterification reaction on halogenated carboxylic acid, a derivative thereof and N,N-dimethylethanolamine serving as raw materials; and undergoing a substitution reaction on dihalide to obtain a compound. The synthetic method is simple, is easy and convenient to operate, has a wide monomer application range, and has a wide application prospect in soap-free emulsion polymerization.
Description
Technical field
The present invention relates to chemical field, especially a kind of have Shuangzi (Gemini) surface-active ATRP (ATRP) initiator and a compound method thereof.
Background technology
Activity/controllable free-radical polymerisation (L/CRP) has that suitable monomers is wide, reaction conditions is easy to realize, can in different systems such as water, carry out, resulting polymers has plurality of advantages such as molecular weight size and distribution be controlled.Activity/controllable free-radical polymerisation (L/CRP) mainly contains ATRP (ATRP), reversible addition-fracture chain transfer polymerization (RAFT), NO free radical adjusting polymerization (Ouchi, M such as (NMP); Terashima, T; Sawamoto, M.
Acc. Chem. Res.
2008,
41, 1120-1132.).Realize activity/controllable free-radical polymerisation, reaction system also will be selected appropriate catalyst, initiator and reaction medium except suitable monomers.
ATRP (ATRP) has been a kind of novel active polymerization method of development since 1995, and its outstanding advantage shows as: 1) the suitable monomers kind is wider; 2) made molecular weight distribution is narrow; 3) monomer conversion and initiator efficiency of initiation are high; 4) can prepare the multipolymer (like block, random, grafting, alternately, gradient, star, comb shape, hyperbranched, crosslinked, water solubility copolymer etc.) and the homopolymer (like distant pawl, novel terminally functionalized polymers etc.) of multiple topological structure; 5) can in different systems such as water base grade, carry out; 6) initiator (Tsarevsky, N. V. simple in structure; Matyjaszewski, K.
Chem. Rev. 2007, 107,2270-2299.).Particularly " transfer transport produces the ATRP of spike " (the AGET ATRP) of developed recently overcome the deficiency of traditional ATRP; Can use the purified multipolymer with topological structure of high-valency metal Preparation of Catalyst, system is responsive no longer so to airborne oxygen.
Letex polymerization is the important method of preparation water-borne coatings, tackiness agent and other polymer materials, and its outstanding advantage has: the one, and be medium with water, to conduct heat easily, viscosity is low, and difficult generation gathers cruelly, is prone to realize continuous operation; The 2nd, cost is low, has avoided the trouble of using more expensive organic solvent and reclaiming solvent; The 3rd, because the blanketing effect of letex polymerization can effectively reduce double-basis and stop, polymerization rate and molecular weight are improved simultaneously; The 4th, environmental friendliness.But traditional letex polymerization generally need be used a certain amount of small-molecular emulsifier, with stabilized emulsion system.
At present, active free radical polymerization is successfully applied in letex polymerization, mini-emulsion polymerization, the micro-emulsion polymerization system.But these living radical letex polymerizations generally all need be used corresponding initiator and traditional small-molecular emulsifier simultaneously; Make troubles to operation, and small-molecular emulsifier finally can enter into polymeric articles, give the product deleterious impact; For example; Small-molecular emulsifier can make polymkeric substance water tolerance variation to surface transport, and influences optics, electricity and the surface property etc. of product.
The Gemini tensio-active agent is claimed Gemini surface active agent again, and its molecular structure is to connect basic one type of novel surfactant that the hydrophilic group of two common surfactant molecules is connected together and forms through one.Because the singularity of its structure, the Gemini tensio-active agent has shown the not available performance of conventional surfactants, as: (1) more is prone to assemble the generation micella; (2) has lower Krafft point; (3) Gemini surface active agent reduces the capillary tendency of the aqueous solution much larger than generation micellar tendency, thereby it is comparatively outstanding to reduce the capillary efficient of the aqueous solution; (4) be prone to be adsorbed on gas-liquid surface, thereby more effectively reduce the surface tension of the aqueous solution; (5) lower efficiency and the reduction ability as far as the aqueous solution is capillary, Gemini surface active agent and conventional surfactants especially can produce better synergistic effect with the composite of nonionogenic tenside; (6) has good calcium soap dispersiveness etc.
Summary of the invention
The object of the invention just provides a kind of ATRP (ATRP) initiator and compound method thereof with Gemini surface active.
Atom transfer radical polymerization initiator with Gemini surface active of the present invention, its general structure is as follows:
Wherein, X is chlorine or bromine or iodine;
T representes-(CH
2)
n-, or
, or
, n=0-18 is preferably n=0-4;
R does
Or
, X wherein
1=Cl or Br, R
1=H or C
1-C
6Alkyl; X
2=Cl or Br, R
2=H or methyl, m=0-5.
The compound method of the atom transfer radical polymerization initiator with Gemini surface active of the present invention is shown in reaction formula (A), at first with the carboxylic acid or derivatives thereof
With
N, N-dimethylethanolamine carries out esterification, obtain corresponding ester midbody (
II), and then and dihalide
The reaction, promptly get the target initiator (
I), wherein R, T, X such as aforementioned definitions, Y is Lu Su Huo – OR
3, R
3=H or C
1-C
6Alkyl.
In the compound method, if Y is a halogen, need add alkali as acid binding agent when then the first step is reacted, said alkali can be one or more in pyridine, the trialkyl tertiary amine, and wherein alkyl can be C
1-C
18Alkyl, naphthenic base, preferred pyridine or triethylamine; Solvent for use can be methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, 1, vinyl trichloride, sym.-tetrachloroethane, ether, MTBE, DIPE, THF, 1, the 4-dioxane,
N, N-N,
N, NIn-N,N-DIMETHYLACETAMIDE, the DMSO 99.8MIN. one or more.Reaction can be-10
oC carries out to the reflux temperature of solvent, preferred room temperature.
In the compound method, if Y Wei – is OH, then need add acid catalyst and band aqua during the first step reaction, said acid catalyst is arranged can be in the vitriol oil, Phenylsulfonic acid, tosic acid, the polyphosphoric acid one or more; Described band aqua can be benzene,toluene,xylene, hexanaphthene, sherwood oil, methylene dichloride, chloroform, tetracol phenixin, 1, one or more in the 2-ethylene dichloride etc.Reaction needed is carried out under the reflux temperature of solvent.
Second of compound method goes on foot in the reaction, only need ester midbody that obtain
and dihalide
be reacted to get final product in suitable solvent.Described reaction solvent can be methylene dichloride, chloroform, tetracol phenixin, ether, MTBE, DIPE, THF, 1, the 4-dioxane,
N, N-N,
N, NIn-N,N-DIMETHYLACETAMIDE, the DMSO 99.8MIN. one or more.Temperature of reaction can be-10
oC carries out to the reflux temperature of solvent, preferred room temperature.
Atom transfer radical polymerization initiator with Gemini surface active of the present invention; Owing to contain bi-quaternary ammonium salt and hydrophobic segment simultaneously in the molecular structure; Itself be Gemini surface active agent, have the ATRP initiating activity again, can directly be used for the atom transferred free radical emulsion polymerization systems; Other emulsifying agent need be do not used, stable emulsion system can be obtained.
Atom transfer radical polymerization initiator with Gemini surface active of the present invention can successfully be applied in " ATRP that transfer transport produces spike " (AGET ATRP) emulsion polymerization systems as emulsifying agent and initiator.AGET ATRP letex polymerization with TEB 3K (MMA) is an example: in reactor drum, add copper chloride catalyst successively, five methyl diethylentriamine (PMDETA) part, TEB 3K (MMA) monomer and stirrer.After stirring, add New-type emulsifier/initiator.Stir preparatory emulsification earlier fast,, charge into rare gas element such as nitrogen in the pre-emulsified while; After emulsification is accomplished in advance, stop inflation, cover the rubber plug (purpose is to prevent the monomer volatilization) of band pin hole, place oil bath to be heated to 60 reaction flask
oC slowly splashes into aqueous ascorbic acid, drips off back 60
oIsothermal reaction 5 h obtain the stable polymer emulsion under the C.Reaction is used the lower alcohol breakdown of emulsion after finishing, and mixture is through neutral Al
2O
3Pillar filters, and is solvent then with the THF, and lower alcohol is the precipitation agent purified polymer.
Atom transfer radical polymerization initiator with Gemini surface active of the present invention is used to prepare segmented copolymer.Segmented copolymer with AGET ATRP emulsion polymerization prepared TEB 3K (MMA) and Bing Xisuandingzhi (BA) is an example: in reactor drum, add copper chloride catalyst successively; N; N; N ', N '-Tetramethyl Ethylene Diamine (TMEDA) part, TEB 3K (MMA) monomer and stirrer.After stirring, adding New-type emulsifier/initiator (
I).Stir preparatory emulsification earlier fast,, charge into rare gas element such as nitrogen in the pre-emulsified while; After emulsification is accomplished in advance, stop inflation, cover the rubber plug of band pin hole, place oil bath to be heated to 60 reaction flask
oC slowly splashes into aqueous ascorbic acid, drips off back 60
oIsothermal reaction 5 h obtain the stable polymer emulsion under the C.In reaction system, inject Bing Xisuandingzhi (BA) monomer then, keep the reaction conditions of front, isothermal reaction 5 h obtain the stable polymer emulsion.
Atom transfer radical polymerization initiator with Gemini surface active of the present invention, compound method is simple, and is easy and simple to handle, and the suitable monomers scope is wide, is applied to have broad prospects in the emulsifier-free emulsion polymerization.
Embodiment
Further set forth the present invention below in conjunction with embodiment.All embodiment only are used to explain the present invention, and are not used in restriction scope of the present invention.The experimental technique of the unreceipted actual conditions of the following example, usually according to normal condition, the condition that perhaps provides or advise according to manufacturer.
Embodiment 1
N 1 , N 6 -Two (2-(2-bromine isobutyl acyloxy) ethyls)-
N 1 , N 1 , N 6 , N 6 -tetramethyl-hexane-1,6-dibrominated ammonium (compound
I-a) synthetic
In reaction flask, add 20 mL (0.3 mmol) methylene dichloride (DCM) successively, 4.45 g (50 mmol)
N, N-dimethylethanolamine, 9 mL (63 mmol) triethylamines (TEA).Magnetic agitation fully stirs and makes it dissolving, mixes.Under the room temperature, 7.5 mL (60mmol) 2-bromine isobutyl acylbromide slowly is added drop-wise in the reaction solution.React 2 h after dripping off again.Filter, remove solids.After filtrating concentrates, add acetic acid ethyl dissolution, respectively with washing, saturated Na
2CO
3Wash anhydrous Na
2SO
4Drying, underpressure distillation obtains product
II-a(9.05 g, 86.1%).
1H?NMR?(400?MHz,?CDCl
3):?δ?4.29?(2H,?d,?J=?4?Hz),?2.64?(2H,?d,?J?=?4?Hz),?2.32?(6H,?s),?1.94?(6H,?s);?
13C?NMR?(100?MHz,?CDCl
3):?δ?171.5,?64.1,?57.2,?55.7,?45.7,?30.7；
Under the nitrogen protection, with intermediate II-a (3.33 g, 14 mmol), 10 mL acetone add 1 again, 6-dibromo-hexane (1.5 g, 6 mmol), stirring at room 5 h.Filtration obtains the reddish slightly solid of white, and it is inferior to give a baby a bath on the third day after its birth with ether, 40 ℃ of dryings of baking oven, and weighing obtains the white solid powder
I-a(3.57 g, 82.1%); M.P. 130-133
oC;
IR:
ν（cm
-1）2950,?2864,?1738,?1164；
1H-NMR?(CDCl
3):?
δ4.60?(4H,?m),?3.74(4H,?m),?3.37?(4H,?m),?3.11?(12H,?s),?1.88?(12H,?m),?1.80?(4H,?m),?1.40?(4H,?m)；
13C-NMR?(CDCl
3):
δ171.56,?64.16,?57.28,?55.70,?45.78,?30.73；
Ultimate analysis (C
22H
44Br
4N
2O
4): C, 36.69; H, 6.16; N, 3.89. Found:C, 36.73; H, 6.15; N, 3.85.
Embodiment 2
N 1 , N 4 -Two [(4-chloromethylbenzene methanoyl) ethyls]-
N 1 , N 1 , N 4 , N 4 -tetramethyl-hexane-1,4-dibrominated ammonium (compound
I-b) synthetic
4-chloromethyl benzoic acid (10.53 g, 60 mmol) is dissolved in the sulfur oxychloride (40 mL), the adding catalytic amount
N, N-N (DMF), 5 h that reflux concentrate.Resistates is dissolved in anhydrous tetrahydro furan (20 mL), is added drop-wise under the ice bath cooling
N, NIn the tetrahydrofuran solution of-dimethylethanolamine (4.45 g, 50 mmol) and pyridine (4.98 g, 63 mmol).After dripping off, room temperature reaction 3 h.Handle with embodiment 1 similar method then, get midbody
II-b(9.21 g, 76.2%).
1H?NMR?(400?MHz,?CDCl
3):?
δ8.04?(d,?2H),?7.46?(d,?2H),?4.62?(s,?2H),?4.28?(d,?2H),?2.64?(d,?2H),?2.32?(s,?6H);?
13C?NMR?(100?MHz,?CDCl
3):?
δ?166.1,?142.3,?130.3,?130.0,?128.4,?64.2,?57.2,?55.7,?46.3,?45.7；
Under the nitrogen protection, with midbody
II-b(3.38 g, 14 mmol), 10 mL acetone add 1 again, 4-dibromo-hexane (1.3 g, 6 mmol), stirring at room 5 h.Filtration obtains the reddish slightly solid of white, and it is inferior to give a baby a bath on the third day after its birth with ether, 40 ℃ of dryings of baking oven, and weighing obtains the white solid powder
I-b(2.67 g, 63.7%); M.P. 151-153
oC;
IR:
ν（cm
-1）3343,?1753,?1599,?1161；
1H-NMR?(CDCl
3):?
δ8.03?(d,?4H),?7.46?(d,?4H),?4.68?(m,?4H),?4.63?(s,?4H),?3.69?(m,?4H),?3.25?(m,?4H),?3.12?(s,?12H),?1.76?(m,?4H)；
13C-NMR?(CDCl
3):
δ166.2,?142.3,?130.3,?130.1,?128.4,?64.7,?64.2,?61.3,?53.4,?20.1；
Ultimate analysis (C
28H
40Br
2Cl
2N
2O
4): C, 48.09; H, 5.77; N, 4.01. Found:C, 48.13; H, 5.75; N, 4.05.
Embodiment 3
N-{ 4-[((2-bromine isobutyl acyloxy) ethyl) dimethylaminomethyl] benzoyl-benzyl }-2-(2-bromine isobutyl acyloxy)-
N, N-dimethyl-ethane brometo de amonio (compound
I-c) synthetic
At first according to preparing midbody with embodiment 1 identical method
II-a,
Prepare 4,4 '-two (brooethyl) UVNUL MS-40 then.With 4,4 '-dimethyl benzophenone (1.5 g, 7.1 mmol) and urea peroxide (1.47 g; 15.7 mmol) be dissolved in methylene dichloride (20 mL), reflux, carry out illumination with 100 W incandescent light; Drip Hydrogen bromide (2.9 mL, 14.3 mmol) then, drip off continued and react 30 min.Cooling adds deionized water in the reaction solution, separatory, and organic phase is used anhydrous sodium sulfate drying, filters, and revolves solvent evaporated and obtains white solid, uses the absolute ethyl alcohol recrystallization again, obtains product 4,4 '-two (brooethyl) UVNUL MS-40 (1.20 g, 46%).M.p. 120-122
oC. IR:
ν(cm
-1) 3051,1670,1602,1587,1410,850,609.
1H NMR (CDCl
3):
δ7.78 (d, 4H,
J=7.20 Hz), 7.51 (d, 4H,
J=7.24 Hz), 4.54 (s, 4H).
13C-NMR (CDCl
3):
δ195.5,142.7,137.6,130.9,129.4,32.6. ultimate analysis (C
15H
12Br
2O): C, 48.95; H, 3.29. Found:C, 48.91; H, 3.32;
Under the argon shield, with 4,4 '-two (brooethyl) UVNUL MS-40 (2.20 g, 6 mmol) is dissolved in acetone, adds midbody then
II-a(3.33 g, 14 mmol), stirred overnight at room temperature.Filter, filter cake is washed five times with ether, at last the white solid that obtains is product 40 ℃ of vacuum-drying to constant weights
I-c(4.37g, 86.4%).
Embodiment 4 utilizes embodiment 1 preparation
N 1 , N 6 -Two (2-(2-bromine isobutyl acyloxy) ethyls)-
N 1 , N 1 , N 6 , N 6 -tetramethyl-hexane-1,6-dibrominated ammonium (compound
I-a) carry out the ATRP letex polymerization as emulsifying agent/initiator, preparation polymethylmethacrylate (PMMA)
The removal of stopper among the monomer M MA: with 5% sodium hydroxide solution that the MMA washing is extremely colourless earlier; Be washed till neutrality with deionized water again; Remove residual moisture with anhydrous sodium sulfate drying, last underpressure distillation accesses cut, and the lucifuge sealing is preserved subsequent use at low temperatures.Like no specified otherwise, also all use this method to remove monomeric stopper in other polymerization;
In order with a certain amount of catalyzer (CuBr), part (2,2 '-dipyridyl), monomer (MMA), compound
I-a,Deionized water adds in the there-necked flask of 100ml, mixes with the magnetic stirrer high-speed stirring, in advance emulsification 15 min.Catalyzer wherein: part: compound
I-a: monomer=1: 1: 0.5: 100 (mol ratios).The preparatory good reaction system of emulsification through cooled with liquid nitrogen-vacuumize-fill nitrogen-thaw, repeats 3 times.Reaction flask is placed water-bath, 60
oMiddling speed stirs under the C, and isothermal reaction 5 h obtain the stable polymer emulsion.In the reaction process, take a sample at regular intervals, to follow the tracks of reaction process.Reaction is used the lower alcohol breakdown of emulsion after finishing, and mixture is through neutral Al
2O
3Pillar filters, and is solvent with the THF then, and lower alcohol is the precipitation agent purified polymer, places 60
oVacuum-drying in the loft drier of C.Monomer conversion is through gravimetric determination; Molecular weight and MWD are measured with gel permeation chromatography (GPC).As do not have specified otherwise, other polymeric aftertreatment is all carried out as stated above.Monomer conversion 91%; Theoretical molecular M
N, th=18920; Gel permeation chromatography (GPC) determining molecular weight M
N, GPC=21630; MWD PDI=1.27.
Embodiment 5 utilizes embodiment 1 preparation
N 1 , N 6 -Two (2-(2-bromine isobutyl acyloxy) ethyls)-
N 1 , N 1 , N 6 , N 6 -tetramethyl-hexane-1,6-dibrominated ammonium (compound
I-a) carry out the ATRP letex polymerization that transfer transport produces spike as emulsifying agent/initiator, preparation polymethylmethacrylate (PMMA)
In order with a certain amount of catalyzer (CuBr
2), part (N, N-dimethyl n lauryl amine), monomer (MMA), compound
I-a,Deionized water adds in the there-necked flask of 100ml, mixes with the magnetic stirrer high-speed stirring, in advance emulsification 15 min.Catalyzer wherein: part: compound
I-a: monomer=1: 4: 1: 100 (mol ratios).The good reaction system of emulsification feeds nitrogen protection in advance.Add the reductive agent xitix, wherein catalyzer: xitix=1:2 (mol ratio).Reaction flask is placed 60
oIn the C water-bath, middling speed stirs 4 h, obtains the stable polymer emulsion.Monomer conversion 93%; Theoretical molecular M
N, th=10020; Gel permeation chromatography (GPC) determining molecular weight M
N, GPC=9620; MWD PDI=1.12.
Embodiment 6 utilizes the PMMA emulsion of embodiment 5 preparations to carry out the ATRP letex polymerization that transfer transport produces spike, the segmented copolymer of preparation polymethylmethacrylate (PMMA) and PS (PS)
At first, in the above-mentioned emulsion system, add vinylbenzene, wherein catalyzer: vinylbenzene=1: 100 (mol ratio) according to embodiment 5 preparation PMMA emulsions.Be warming up to 80 to system temperature
oC continues reaction 5 h, gets the stable polymer emulsion.Record styrene conversion rate 52%.Theoretical molecular M
N, th=15440; Gel permeation chromatography (GPC) determining molecular weight M
N, GPC=17830; MWD PDI=1.31.
Embodiment 7 utilizes embodiment 3 preparations
N-{ 4-[((2-bromine isobutyl acyloxy) ethyl) dimethylaminomethyl] benzoyl-benzyl }-2-(2-bromine isobutyl acyloxy)-
N, N-dimethyl-ethane brometo de amonio (compound
I-c) carry out the ATRP letex polymerization that transfer transport produces spike as emulsifying agent/initiator, the segmented copolymer of preparation TEB 3K (MMA) and allyl methacrylate(AMA) (AMA)
In order with a certain amount of catalyzer (FeBr
3), part (N, N, N ', N '-Tetramethyl Ethylene Diamine), monomer (MMA), compound
I-c,Deionized water adds in the there-necked flask of 100ml, mixes with the magnetic stirrer high-speed stirring, in advance emulsification 15 min.Catalyzer wherein: part:
I-c:MMA=1: 4: 1: 70 (mol ratio).The good reaction system of emulsification feeds nitrogen protection in advance.Add the reductive agent xitix, wherein catalyzer: xitix=1:2 (mol ratio).Reaction flask is placed 60
oIn the C water-bath, middling speed stirs 5 h, obtains the stable polymer emulsion.Record the transformation efficiency 90% of MMA.And then add second kind of monomer A MA, and wherein, MMA:AMA=7:3 (mol ratio).Continue reaction 4 h.The transformation efficiency that records AMA is 85%.Theoretical molecular M
N, th=10360; Gel permeation chromatography (GPC) determining molecular weight M
N, GPC=13620; MWD PDI=1.28.
Claims (4)
1. atom transfer radical polymerization initiator with Gemini surface active, it is characterized in that: its general formula of molecular structure is following:
Wherein, X representes chlorine or bromine or iodine;
T representes-(CH
2)
n-, or
, or
, n=0-18 is preferably n=0-4;
R does
Or
, X wherein
1=Cl or Br,, R
1=H or C
1-C
6Alkyl, X
2=Cl or Br, R
2=H or methyl, m=0-5.
2. compound method with atom transfer radical polymerization initiator of Gemini surface active as claimed in claim 1 may further comprise the steps:
(1) with structural formula does
The carboxylic acid or derivatives thereof, wherein Y is halogen ， Huo – OR
3, R
3=H or C
1-C
6Alkyl, with
N, N-dimethylethanolamine carries out esterification, obtains structural formula
Compound;
(2) compound and the dihalide reaction of structural formula for
that step 1 are obtained obtain tying target compound.
3. the compound method with atom transfer radical polymerization initiator of Gemini surface active according to claim 2 is characterized in that: step (1) reaction solvent for use is selected from methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, 1; 1,1-trichloroethane, 1,1; 2-trichloroethane, 1,1,2; 2-tetrachloroethane, ether, MTBE, DIPE, THF, 1, the 4-dioxane,
N, N-N,
N, NIn-N,N-DIMETHYLACETAMIDE, the DMSO 99.8MIN. one or more; Step (2) reaction solvent for use is selected from methylene dichloride, chloroform, tetracol phenixin, ether, MTBE, DIPE, THF, 1, the 4-dioxane,
N, N-N,
N, NIn-N,N-DIMETHYLACETAMIDE, the DMSO 99.8MIN. one or more.
4. atom transfer radical polymerization initiator with Gemini surface active, the application in the atom transferred free radical emulsion polymerization.
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| CN105820274A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Cationic surface active initiator and preparation method thereof |
| CN105820275A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini type cationic surface active initiator and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015166335A (en) * | 2013-10-02 | 2015-09-24 | 三菱化学株式会社 | Method for producing epoxy compound and catalyst composition for epoxidation reaction |
| CN105820274A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Cationic surface active initiator and preparation method thereof |
| CN105820275A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini type cationic surface active initiator and preparation method thereof |
| CN105820275B (en) * | 2015-07-08 | 2018-03-30 | 宁波大学 | A kind of double type cation surface activating initiator and preparation method thereof |
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