CN101481432B - Atom transfer radical polymerization method for ion liquid microemulsion - Google Patents

Atom transfer radical polymerization method for ion liquid microemulsion Download PDF

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CN101481432B
CN101481432B CN2009100290179A CN200910029017A CN101481432B CN 101481432 B CN101481432 B CN 101481432B CN 2009100290179 A CN2009100290179 A CN 2009100290179A CN 200910029017 A CN200910029017 A CN 200910029017A CN 101481432 B CN101481432 B CN 101481432B
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ionic liquid
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chloride
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CN101481432A (en
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严锋
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Suzhou University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a method for preparing a nano-polymer, gel and a porous polymer with micro-emulsion. The method comprises the following steps: using micro-emulsion consisting of ionic liquid and an emulsifier, allowing atom transfer radical polymerization in the micro-emulsion system, dispersing monomers in the ionic liquid in nano scale, and separating polymer nano-particles or the gel from the reaction system by virtue of poor solvents of the polymers after completion of the polymerization reaction, evaporating mixture of the emulsifier, a catalyst, the ionic liquid and the solvents to remove the solvents. The ionic liquid does not lose in the evaporation due to very low volatility and high boiling point of the ionic liquid. The ratio of the recovered emulsifier, the catalyst and the ionic liquid remains almost unchanged. New micro-emulsion polymerization can occur after adding the system with the monomers again, thus the method is economical and environmentally friendly.

Description

Atom transfer radical polymerization method in a kind of ion liquid microemulsion
Technical field
The present invention relates to the preparation method of a kind of polymer nano-particle, gel and porous material, be specifically related in ion liquid medium, carry out the method that micro-emulsion polymerization prepares polymkeric substance.
Background technology
Microemulsion one speech is proposed in nineteen forty-three by Hear and Schalmer the earliest, be transparent even, the thermodynamically stable profit dispersion system that under the emulsifying agent effect immiscible water/oil is formed by a certain percentage, the droplet diameter of disperse phase is in the 10-100nm scope.
Atom transfer radical polymerization in the microemulsion system can prepare and has the terminal band of surface molecular specific function group, further " activity " polymer nano-particle of initiated polymerization; With duct internal surface molecular end band specific function group, further " activity " polymer porous material (making) of initiated polymerization in the duct from polymer gel.But (general emulsifying agent weight accounts for more than 10% of whole reaction system weight except needs use a large amount of emulsifying agents in this reaction system, be generally about 15%), also need to add a large amount of transition-metal catalysts (general transition-metal catalyst weight account for whole reaction system weight about 2%).The use of a large amount of emulsifying agents and transition-metal catalyst has strengthened polyreaction and has finished post-processing difficulty, and causes environmental pollution.For example: after reaction was finished, the emulsifying agent of polymkeric substance meeting wrapping portion need come out emulsifying agent with organic solvents such as methyl alcohol from polymkeric substance.The mixing solutions of water, methyl alcohol, catalyzer, emulsifying agent can't be recycled (when methyl alcohol is removed in evaporation, because water also can be evaporated part, cause the ratio of water, catalyzer and emulsifying agent that variation has taken place like this, can't directly recycle, the ratio that need readjust water and emulsifying agent forms microemulsion system).
Therefore, need seek a kind of new reaction system, make things convenient for the recycling of transition-metal catalyst and emulsifying agent.
Summary of the invention
The object of the invention provides a kind of method for preparing nanoparticle, gel and porous material, makes things convenient for the recovery of transition-metal catalyst and emulsifying agent, and can recycle the transition-metal catalyst and the emulsifying agent of recovery.
For achieving the above object, the technical solution used in the present invention is:
Prepare the method for nanoparticle in a kind of microemulsion system, may further comprise the steps:
(1) monomer, ionic liquid, emulsifying agent, initiator, part, catalyzer are with weight ratio 1～20: mix at 80～200: 30～70: 1～5: 1～5: 1～5;
(2) in 0～120 ℃ of temperature range, carry out atom transition free radical polymerization reaction under the oxygen free condition and prepare polymer nano-particle;
(3) after reaction finishes, polymerization reaction system is poured in the polymkeric substance poor solvent, obtained polymer precipitation, filtering separation;
(4) polymkeric substance poor solvent distillation in the filtrate is removed, emulsifying agent, catalyzer and ionic liquid are recovered utilization.
Prepare the method for gel in a kind of microemulsion system, may further comprise the steps:
(1) monomer, ionic liquid, emulsifying agent, initiator, part, catalyzer are with weight ratio 50～80: mix at 80～200: 70～120: 1～5: 1～5: 1～5;
(2) in 0～120 ℃ of temperature range, carry out atom transition free radical polymerization reaction under the oxygen free condition and prepare the polymer nanocomposite gel;
(3) polymer gel is poured in the polymkeric substance poor solvent, polymer gel intermediate ion liquid is aggregated the thing poor solvent and extracts, and obtains polymer porous material;
(4) the polymkeric substance poor solvent is distilled out, emulsifying agent, catalyzer and ionic liquid are recovered utilization.
In the technique scheme, described initiator is selected from a kind of in thermal initiator, light trigger or the halogenated compound initiator, described thermal initiator is selected from a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Potassium Persulphate, ammonium persulphate, Sodium Persulfate, dibenzoyl peroxide, peroxidation two (2,4 dichloro benzene formyl), diacetyl peroxide, dioctanoyl peroxide and dilauroyl peroxide, peroxidation two (dodecanoyl) or the peroxy dicarbonate; Described light trigger is selected from benzophenone, benzoin ether, thioxanthone, 2,2-dimethyl Alpha-hydroxy methyl phenyl ketone, 2, a kind of in 2-dimethyl Alpha-hydroxy p-isopropyl methyl phenyl ketone or the 1-hydroxy-cyclohexyl benzophenone; Described halogenated compound initiator is selected from; Alpha-chloro phenylethane, alpha-brominated phenylethane, benzyl chloride, bromotoluene, α-Lv Bingsuan ethyl ester, ethyl, alpha-brominated ethyl isobutyrate, chloroform, methylene dichloride, monochloro methane, α-chloromethyl cyanide or α-chloroethyl nitrile, chlorine third benzyl chloride, 1,4-xylylene dichlorides, 2-methyl chloropropionate, tetracol phenixin or 1-chlorine, a kind of in the 1-diphenylphosphino ethane;
In the technique scheme, described monomer is selected from vinylbenzene, sulfonated phenylethylene, alpha-methyl styrene, α, β, β-trifluorostyrene, the Alpha-Methyl sulfonated phenylethylene, octafluorostyrene, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, vinylformic acid, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid, methacrylic acid, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinyl pyrrolidone, vinyl cyanide, methacrylonitrile, acrylamide, or in the vinyl alcohol one or more;
Described ionic liquid is for containing ammonium ion or the unitary ionic liquid of fragrant heterocycle structure, is selected from a kind of in the following structural:
Figure G2009100290179D00031
In the formula, R1, R2 are C nH 2n+1Or C mH 2m, n=0～8 wherein, m=0～6; R3, R4 are C nH 2nO, n=0～8; X is selected from Br, Cl, I, NO 3, BF 4, PF 6, HSO 4, H 2PO 4, CF 3SO 3Or N (SO 2CF 3) 2In a kind of.
Described emulsifying agent is for can be dissolved in ion liquid emulsifying agent, be selected from: commodity emulsifier op-10, TX-10, brij-30 contain ammonium ion or the ionic liquid emulsifier of fragrant heterocycle structure in a kind of, the described ionic liquid emulsifier that contains ammonium ion or fragrant heterocycle structure is expressed by following structural:
Figure G2009100290179D00032
Figure G2009100290179D00041
In the formula, R6=CH 3Or H, p=6～18, Y is selected from Br, BF 4, PF 6Or CF 3SO 3In a kind of.
In the technique scheme, described catalyzer is selected from cupric chloride, cuprous chloride, iron(ic) chloride, iron protochloride, cupric bromide, cuprous bromide, iron bromide, ferrous bromide, chlorination nail, protochloride nail, chlorination grand-mother, protochloride grand-mother, nickelous chloride, protochloride nickel; Described part is selected from dipyridyl, N, N, N ', N "; N "-five methyl diethylentriamine, imines (as 2-pyridylaldehyde contract Tri N-Propyl Amine, alpha-diimine, N-propyl group-2-pyridine azomethine, beta-diketon diimine), amino ethers compounds are as two (dimethyl aminoethyl) ether;
The selection of described polymkeric substance poor solvent belongs to prior art, because polymkeric substance is nonpolar, and ion liquid boiling point is usually above 300 ℃, so generally need to select the polar boiling point be lower than 150 ℃ solvent, can be selected from but be not limited to: a kind of in saturated alcohol, dimethyl formamide (DMF) or the dimethyl sulfoxide (DMSO) (DMSO) that water, C atomicity are 1～6.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
The present invention uses ionic liquid, monomer and emulsifying agent to form microemulsion, and in this microemulsion system, carry out atom transfer radical polymerization, monomer is dispersed in the ionic liquid with nanoscale, after polyreaction finishes, utilize the poor solvent of polymkeric substance polymkeric substance is separated out from reaction system and to separate.Mixture evaporation with emulsifying agent, catalyzer, ionic liquid and solvent can remove and desolvate.Because the ionic liquid volatility is extremely low, the boiling point height, so in evaporative process, the ionic liquid free of losses.The emulsifying agent, catalyzer and the ion liquid ratio that reclaim are almost constant, and in this system, add monomer again and can carry out new micro-emulsion polymerization, so this method not only economy but also environmental protection.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
(1) match well preparation microemulsion reaction system by following quality:
Monomer: 1～2g vinylbenzene;
Emulsifying agent: 3～7g
Figure G2009100290179D00051
Ionic liquid: 8～20g
Figure G2009100290179D00052
Initiator: 0.1～0.2g alpha-chloro phenylethane,
Catalyzer: 0.1～0.2g cuprous chloride;
Part: 0.1～0.2g 2-pyridylaldehyde Tri N-Propyl Amine that contracts
(2) under oxygen free condition, 40 ℃ were reacted 8 hours;
(3) after reaction finishes, polymerization reaction system is poured in the methyl alcohol, obtained polymer precipitation, filter and obtain polystyrene particle particle diameter 20～50nm; Methyl alcohol in the filtrate is distilled out, and emulsifying agent, catalyzer and ionic liquid are recovered utilization.
Embodiment two:
(1) match well preparation microemulsion reaction system by following quality:
Monomer: 5～8g vinylbenzene,
Emulsifying agent: 7～12g
Figure G2009100290179D00053
Ionic liquid: 8～20g
Figure G2009100290179D00054
Initiator: 0.1～0.2g Diisopropyl azodicarboxylate,
Catalyzer: 0.4～0.5g cupric chloride;
Part: 0.4～0.5g N, N, N ', N ", N "-five methyl diethylentriamine
(2) under oxygen free condition, 120 ℃ were reacted 3 hours.
(3) polymerization reaction system is poured into and is obtained polymer gel in the propyl alcohol, extracts gel with propyl alcohol, obtains the polystyrene porous material, aperture 20～50nm; Propyl alcohol is distilled out, and emulsifying agent, catalyzer and ionic liquid are recovered utilization.
Embodiment three:
(1) match well preparation microemulsion reaction system by following quality:
Monomer 1:0.5～1g methyl methacrylate;
Monomer 2:0.5～1g vinyl cyanide;
Emulsifying agent: 3～7g
Figure G2009100290179D00061
Ionic liquid: 8～20g
Figure G2009100290179D00062
Initiator: 0.1～0.2g α-chloromethyl cyanide,
Catalyzer: 0.1～0.2g iron protochloride;
Two (dimethyl aminoethyl) ethers of part: 0.1～0.2g
(2) under oxygen free condition, 0 ℃ was reacted 18 hours;
(3) after reaction finishes, polymerization reaction system is poured among the DMF, obtained copolymer particle, particle diameter 20～50nm distills out DMF in the filtrate, and emulsifying agent, catalyzer and ionic liquid are recovered utilization.
Embodiment four:
(1) match well preparation microemulsion reaction system by following quality:
Monomer: 5～8g methyl methacrylate,
Emulsifying agent: 7～12g
Figure G2009100290179D00063
Ionic liquid: 8～20g
Initiator: 0.1～0.2g Potassium Persulphate,
Catalyzer: 0.4～0.5g cupric bromide;
Part: 0.4～0.5g 2-pyridylaldehyde Tri N-Propyl Amine that contracts
(2) under oxygen free condition, 70 ℃ were reacted 8 hours.
(3) polymerization reaction system is poured methanol solution into and is obtained polymer gel, extracts gel with butanols, obtains the polymethylmethacrylate porous material, aperture 20～50nm; Butanol solution is distilled out, and emulsifying agent, catalyzer and ionic liquid are recovered utilization.
Embodiment five:
(1) match well preparation microemulsion reaction system by following quality:
Monomer: 1～2g Hydroxyethyl acrylate;
Emulsifying agent: 3～7g emulsifier op-10,
Ionic liquid: 8～20g
Figure G2009100290179D00071
Initiator: 0.1～0.2g Potassium Persulphate,
Catalyzer: 0.1～0.2g iron(ic) chloride;
Part: 0.1～0.2g 2-pyridylaldehyde Tri N-Propyl Amine that contracts
(2) under oxygen free condition, 70 ℃ were reacted 8 hours.
(3) after reaction finishes, polymerization reaction system is poured in the methanol solution, obtained polymer poly Hydroxyethyl acrylate particle, particle diameter 20～50nm; Methanol solution in the filtrate is distilled out, and emulsifying agent, catalyzer and ionic liquid are recovered utilization.
Embodiment six:
(1) match well preparation microemulsion reaction system by following quality:
Monomer 1:0.3～0.6g vinyl pyrrolidone;
Monomer 2:0.3～0.6g vinylformic acid hydroxyl methyl esters;
Monomer 3:0.4～0.7g methyl methacrylate;
Emulsifying agent: 3～7g TX-10,
Ionic liquid: 8～20g
Figure G2009100290179D00072
Initiator: 0.1～0.2g peroxidation two (2,4 dichloro benzene formyl),
Catalyzer: 0.1～0.2g chlorination nail;
Part: 0.1～0.2g beta-diketon diimine
(2) under oxygen free condition, 70 ℃ were reacted 8 hours.
(3) after reaction finishes, polymerization reaction system is poured in the methanol solution, obtained the polymers copolymers particle, particle diameter 20～50nm; Methanol solution in the filtrate is distilled out, and emulsifying agent, catalyzer and ionic liquid are recovered utilization.
Embodiment seven:
(1) match well preparation microemulsion reaction system by following quality:
Monomer: 5～8g vinylbenzene;
Emulsifying agent: 7～12g brij-30,
Ionic liquid: 8～20g
Figure G2009100290179D00081
Initiator: 0.4～0.5g benzophenone
Catalyzer: 0.4～0.5g cupric chloride;
Part: 0.1～0.2g alpha-diimine
(2) wavelength 250nm ultraviolet lighting is 8 hours;
(3) after reaction finishes, polymerization reaction system is poured in the aqueous solution, obtained the polystyrene porous material, aperture 20～50nm; The aqueous solution in the filtrate is distilled out, and emulsifying agent, catalyzer and ionic liquid are recovered utilization.

Claims (6)

1. the method for preparing nanoparticle in the microemulsion system, with monomer, initiator, part and catalyzer with weight ratio 1～20: add in microemulsion at 1～5: 1～5: 1～5, carry out atom transition free radical polymerization reaction under the oxygen free condition and prepare polymer nano-particle, it is characterized in that:
(1) described microemulsion by ionic liquid and emulsifying agent by weight 80～200: 30～70 form;
(2) monomer and ion liquid weight ratio are 1～20: 80～200;
(3) after reaction finishes, polymerization reaction system is poured in the solvent, obtained polymer precipitation, filtering separation;
(4) solvent distillation in the filtrate is removed, emulsifying agent, catalyzer and ionic liquid are recycled;
Described solvent is selected from: a kind of in saturated alcohol, dimethyl formamide or the dimethyl sulfoxide (DMSO) that water, C atomicity are 1～6;
Described ionic liquid is selected from a kind of in the following structural:
Figure FSB00000463131300011
In the formula, R1, R2 are C nH 2n+1, n=0～8 wherein; X is selected from Br, Cl, I, NO 3, BF 4, PF 6, HSO 4, H 2PO 4, CF 3SO 3Or N (SO 2CF 3) 2In a kind of;
Described emulsifying agent is selected from: commodity emulsifier op-10, TX-10, brij-30, contain the liquid emulsifier of ammonium ion or contain a kind of in the fragrant heterocycle structure ionic liquid emulsifier, the liquid emulsifier of described ammonium ion is selected from:
Figure FSB00000463131300012
R5 is selected from methyl or hydrogen in the formula, h=6～18, and Z is selected from Br, BF 4, PF 6Or CF 3SO 3
Or
R=6 in the formula～18, Z is selected from Br, BF 4, PF 6Or CF 3SO 3In a kind of;
Describedly contain fragrant heterocycle structure ionic liquid emulsifier and be selected from:
D=6 in the formula～18, Y is selected from Br, BF 4, PF 6Or CF 3SO 3, in a kind of;
Or
In the formula, R6 is selected from methyl or hydrogen, p=6～18, and Y is selected from Br, BF 4, PF 6Or CF 3SO 3In a kind of.
2. the method for preparing nanoparticle according to claim 1, it is characterized in that described monomer is selected from: vinylbenzene, sulfonated phenylethylene, alpha-methyl styrene, α, β, β-trifluorostyrene, the Alpha-Methyl sulfonated phenylethylene, octafluorostyrene, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, vinylformic acid, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinyl pyrrolidone, vinyl cyanide, methacrylonitrile, acrylamide, or in the vinyl alcohol one or more.
3. the method for preparing nanoparticle according to claim 1, it is characterized in that described initiator is selected from a kind of in thermal initiator, light trigger or the halogenated compound initiator, described thermal initiator is selected from a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Potassium Persulphate, ammonium persulphate, Sodium Persulfate, dibenzoyl peroxide, peroxidation two (2,4 dichloro benzene formyl), diacetyl peroxide, dioctanoyl peroxide and dilauroyl peroxide or the peroxy dicarbonate; Described light trigger is selected from benzophenone, benzoin ether, thioxanthone, 2,2-dimethyl Alpha-hydroxy methyl phenyl ketone, 2, a kind of in 2-dimethyl Alpha-hydroxy p-isopropyl methyl phenyl ketone or the 1-hydroxy-cyclohexyl benzophenone; Described halogenated compound initiator is selected from: alpha-chloro phenylethane, alpha-brominated phenylethane, benzyl chloride, bromotoluene, α-Lv Bingsuan ethyl ester, ethyl, alpha-brominated ethyl isobutyrate, tetracol phenixin, chloroform, methylene dichloride, monochloro methane, α-chloromethyl cyanide or α-chloroethyl nitrile, 1,4-xylylene dichlorides, 2-methyl chloropropionate or 1-chlorine, a kind of in the 1-diphenylphosphino ethane;
Described part is selected from: dipyridyl, N, N, N ', N ", N "-contract a kind of in Tri N-Propyl Amine, two (dimethyl aminoethyl) ether, alpha-diimine, N-propyl group-2-pyridine azomethine, the beta-diketon diimine of five methyl diethylentriamine, 2-pyridylaldehyde;
Described catalyzer is selected from: a kind of in cupric chloride, cuprous chloride, iron(ic) chloride, iron protochloride, cupric bromide, cuprous bromide, iron bromide, ferrous bromide, rhodium chloride, protochloride rhodium, nickelous chloride, the protochloride nickel.
4. the method for preparing polymer porous material in the microemulsion system, with monomer, initiator, part and catalyzer with weight ratio 50～80: add in microemulsion at 1～5: 1～5: 1～5, carry out atom transition free radical polymerization reaction under the oxygen free condition, it is characterized in that:
(1) described microemulsion by ionic liquid and emulsifying agent by weight 80～200: 70～120 form;
(2) monomer and ion liquid weight ratio are 50～80: 80～200;
(3) after reaction finishes, obtain polymer gel, polymer gel is poured in the solvent, polymer gel intermediate ion liquid is gone out by solvent extraction, obtains polymer porous material;
(4) solvent distillation in the ionic liquid is removed, emulsifying agent, catalyzer and ionic liquid are recycled;
Described solvent is selected from: a kind of in saturated alcohol, dimethyl formamide or the dimethyl sulfoxide (DMSO) that water, C atomicity are 1～6;
Described ionic liquid is selected from a kind of in the following structural:
Figure FSB00000463131300031
In the formula, R1, R2 are C nH 2n+1, n=0～8 wherein; X is selected from Br, Cl, I, NO 3, BF 4, PF 6, HSO 4, H 2PO 4, CF 3SO 3Or N (SO 2CF 3) 2In a kind of;
Described emulsifying agent is selected from: commodity emulsifier op-10, TX-10, brij-30, contain the liquid emulsifier of ammonium ion or contain a kind of in the fragrant heterocycle structure ionic liquid emulsifier, the described liquid emulsifier that contains ammonium ion is selected from:
R5 is selected from methyl or hydrogen in the formula, h=6～18, and Z is selected from Br, BF 4, PF 6Or CF 3SO 3
Or
Figure FSB00000463131300033
R=6 in the formula～18, Z is selected from Br, BF 4, PF 6Or CF 3SO 3In a kind of;
Describedly contain fragrant heterocycle structure ionic liquid emulsifier and be selected from:
Figure FSB00000463131300041
D=6 in the formula～18, Y is selected from Br, BF 4, PF 6Or CF 3SO 3, in a kind of
Or
Figure FSB00000463131300042
In the formula, R6=CH 3Or H, p=6～18, Y is selected from Br, BF 4, PF 6Or CF 3SO 3In a kind of.
5. the method for preparing polymer porous material in the microemulsion system according to claim 4, it is characterized in that described monomer is selected from: vinylbenzene, sulfonated phenylethylene, alpha-methyl styrene, α, β, β-trifluorostyrene, the Alpha-Methyl sulfonated phenylethylene, octafluorostyrene, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, vinylformic acid, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinyl pyrrolidone, vinyl cyanide, methacrylonitrile, acrylamide, or in the vinyl alcohol one or more.
6. the method for preparing polymer porous material in the microemulsion system according to claim 5, it is characterized in that described initiator is selected from a kind of in thermal initiator, light trigger or the halogenated compound initiator, described thermal initiator is selected from a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Potassium Persulphate, ammonium persulphate, Sodium Persulfate, dibenzoyl peroxide, peroxidation two (2,4 dichloro benzene formyl), diacetyl peroxide, dioctanoyl peroxide and dilauroyl peroxide or the peroxy dicarbonate; Described light trigger is selected from benzophenone, benzoin ether, thioxanthone, 2,2-dimethyl Alpha-hydroxy methyl phenyl ketone, 2, a kind of in 2-dimethyl Alpha-hydroxy p-isopropyl methyl phenyl ketone or the 1-hydroxy-cyclohexyl benzophenone; Described halogenated compound initiator is selected from: alpha-chloro phenylethane, alpha-brominated phenylethane, benzyl chloride, bromotoluene, α-Lv Bingsuan ethyl ester, ethyl, alpha-brominated ethyl isobutyrate, tetracol phenixin, chloroform, methylene dichloride, monochloro methane, α-chloromethyl cyanide or α-chloroethyl nitrile, 1,4-xylylene dichlorides, 2-methyl chloropropionate or 1-chlorine, a kind of in the 1-diphenylphosphino ethane;
Described part is selected from: dipyridyl, N, N, N ', N ", N "-contract a kind of in Tri N-Propyl Amine, two (dimethyl aminoethyl) ether, alpha-diimine, N-propyl group-2-pyridine azomethine, the beta-diketon diimine of five methyl diethylentriamine, 2-pyridylaldehyde;
Described catalyzer is selected from: a kind of in cupric chloride, cuprous chloride, iron(ic) chloride, iron protochloride, cupric bromide, cuprous bromide, iron bromide, ferrous bromide, rhodium chloride, protochloride rhodium, nickelous chloride, the protochloride nickel.
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