CN103254365B - Method for preparing ASA (Acrylonitrile-Styrene-Acrylate) copolymer latex by using water-solubility redox initiator at low temperature - Google Patents

Method for preparing ASA (Acrylonitrile-Styrene-Acrylate) copolymer latex by using water-solubility redox initiator at low temperature Download PDF

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CN103254365B
CN103254365B CN201310185593.9A CN201310185593A CN103254365B CN 103254365 B CN103254365 B CN 103254365B CN 201310185593 A CN201310185593 A CN 201310185593A CN 103254365 B CN103254365 B CN 103254365B
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emulsion
drip
asa
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nuclear layer
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CN103254365A (en
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史铁钧
张方
吴竞
王启东
周海鸥
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Hefei University of Technology
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Hefei University of Technology
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Abstract

The invention discloses a method for preparing ASA (Acrylonitrile-Styrene-Acrylate) copolymer latex by using a water-solubility redox initiator at low temperature. The method comprises unit processes of preparing polyacrylate seeds, preparing a polyacrylate core, preparing an ASA resin shell and post processing. The water-solubility initiator adopted by the method can initiate polymerization at a lowest temperature of 35 DEG C and reach a high conversion rate. The method has the characteristics of good repeatability, warm reaction condition, low energy consumption, easiness in operation and low price of raw materials, so that the industrial implementation is facilitated.

Description

A kind of method adopting water soluble, redox initiator low-temperature growth ASA copolymer emulsion
One, technical field
The present invention relates to the preparation method of a kind of Acrylate-styrene bipolymer-vinyl cyanide ternary graft copolymer, specifically a kind of method adopting water soluble, redox initiator low-temperature growth ASA copolymer emulsion.
Two, background technology
ASA resin also claims AAS resin, the graft copolymer be made up of acrylate, vinylbenzene and vinyl cyanide (Acrylate-Styrene-Acrylonitrile), it presents and is external phase with styrene-acrylonitrile (SAN) resin, take acrylic elastomer as the island structure of disperse phase.Vinylbenzene gives its gloss and processibility, and vinyl cyanide gives its rigidity and chemical proofing, and acrylic elastomer gives its shock resistance and ageing resistance, the copolymerization of three kinds of materials, makes ASA resin possess premium properties.
First ASA resin nineteen sixty-eight achieves industrialization by BASF Corp. of Germany, and commodity are called Luran ?s.Japan achieves the industrialization of ASA resin in early seventies by Hitachi Chemical Co., Ltd., and commodity are called VITAX.The Subsidiary Company GE plastics 2003 of GE are proposed the more excellent ASA rosin products of new generation of a kind of performance-poly-happy resin to market, it has more ageing-resistant function and tint permanence and glossiness, and commodity are called GELOY ?xTW.The producer producing ASA resin at present in the world mainly contains: BASF Corp. of Germany, FDAC change into Co., Ltd., Japanese UMG ABS Ltd., GE, Dow Chemical company etc.
It is fewer that the research work that China's ASA resin is correlated with is carried out, from the early 1990s till now, Beijing University of Chemical Technology, Zhejiang University, Lan Hua research institute, Dalian University of Technology carried out correlative study work.The ASA resin of China does not also realize suitability for industrialized production, and each side research work all needs deeply to be carried out further.
The initiator system of ASA resin is generally adopted in two ways, i.e. thermal initiation and redox initiation.The requirement of thermal booster reaction temperature higher operability is high, energy consumption is larger.Therefore industrial application generally adopt redox system (J. Herbig, I. 0. Salyer. Monsanto Co., US3118855 [P]. 1960; H. P. Siebel, H. W. Otto. BASFAG, DE1238207 [P]. 1963).Redox system is divided into again the water-soluble and large class of oil soluble two, oil-soluble initiator is one of study hotspot (Liu Zhenguo instantly, Han Ye, Zhang Huixuan, butyl acrylate/styrene-acrylonitrile letex polymerization kinetics, polymer material science and engineering, 2010, 8:12-15 [J]), in ASA letex polymerization, the research emphasis of most people is placed on the initiator system that oil-soluble initiator or oil soluble and water soluble starter combine always, but because oil-soluble initiator aftertreatment technology more or less has toxic substance to produce, be unfavorable for that the environmental protection of product is produced, and all adopt water soluble initiator not only perfectly to address these problems, and reaction conditions is gentle, energy consumption is low, easy handling, the feature of low in raw material price, be convenient to industrializing implementation.In addition because water soluble starter is with its wide material sources, the advantage such as to have no side effect also gradually paid attention to (Cheng Yanling, Xu Zushun by people; redox initiation emulsifier-free emulsion polymerization prepares single dispersing thermo-sensitivity microballoon; polymer material science and engineering, 2008,12: 38-42; Old snow duckweed, father-in-law sets the mind on study, the polymerization kinetics of Sodium Acrylate Initiated by Ammonium Persulfate/Aliphatic Amine, chemical reaction engineering and technique, 2004,9:245-249).
Conventional water soluble, redox system is as persulfate-mercaptan, due in styrene emulsion polymerization reaction process, mercaptan only plays the effect of molecular weight regulator, does not have very large promoter action to polyreaction, make to be polymerized rear molecular weight lower, mechanical strength can not meet service requirements; For another example hydrogen peroxide-ferrous salt, organic hydroperoxide-ferrous salt, containing iron ion after polymerization, comparatively large on the color and luster impact of product, and production cost is higher.
Three, summary of the invention
The present invention aims to provide a kind of method adopting water soluble, redox initiator low-temperature growth ASA copolymer emulsion, select comparatively common and cheap water soluble, redox system, and control its reaction process, successfully prepare the ASA resin compared with high impact by letex polymerization at a lower temperature.
The present invention adopts emulsion polymerization, carries out initiated polymerization by water-soluble oxidizers and reductive agent, and solves that two kinds of water-soluble mono precursor reactants are not easy to control, the repeatability technical barrier such as bad.
Technical solution problem of the present invention adopts following technical scheme:
The present invention adopts the method for water soluble, redox initiator low-temperature growth ASA copolymer emulsion, it is characterized in that operating according to the following steps:
1) preparation of polyacrylic ester seed:
Under nitrogen protection the emulsifying agent of 15-25% is added in deionized water, after being uniformly dispersed, add the nuclear layer monomer of 25-75%, after stirring, drip the oxygenant of 10-20% and the reductive agent of 10-20% respectively simultaneously, in 35-60 DEG C of reaction 2-4h, obtain seed emulsion;
2) preparation of polyacrylic ester core
The oxygenant of 20-40% is dripped in the seed emulsion of step 1), in reaction solution, nuclear layer monomer pre-emulsion is dripped again after dripping off, in 35-60 DEG C of reaction 2-4 hour after nuclear layer monomer pre-emulsion drips off, obtain polyacrylic ester core emulsion, the dropping of nuclear layer monomer pre-emulsion controls at 1-2 hour.The size of elastomer particle can be controlled by changing the consumption adding nuclear layer monomer.
Described nuclear layer monomer pre-emulsion is obtained by the reductive agent of the emulsifying agent of the shell monomers of the nuclear layer monomer of surplus, 5-20%, 25-35%, linking agent, 20-40% and deionized water and stirring emulsification;
3) preparation of ASA resin shell
To step 2) polyacrylic ester core emulsion in drip the oxygenant of surplus, in reaction solution, drip shell monomers pre-emulsion again after dripping off, after shell monomers pre-emulsion drips off, within 2-4 hour, obtain the ASA emulsion of solid content 45-55% in 35-60 DEG C of reaction; The dropping of shell monomers pre-emulsion controls at 1-2 hour;
Described shell monomers pre-emulsion is obtained by the emulsifying agent of the shell monomers of surplus, surplus, the reductive agent of surplus and deionized water and stirring emulsification;
4) aftertreatment
In ASA emulsion, add the NaCl aqueous solution breakdown of emulsion of mass concentration 5%, ASA emulsion and NaCl solution volume ratio are 1:1, suction filtration, washing and drying after obtain ASA resin.
By resin batten obtained after the injection moulding of modified ASA resin powder, test tensile property according to GB/T1040.2-2006.
Each raw material is configured to by mass fraction:
Nuclear layer monomer 10-90 part,
Shell monomers 90-10 part,
Emulsifying agent 0.6-3 part,
Oxygenant 0.2-1 part,
Reductive agent 0.2-0.6 part,
Linking agent 0.5-2 part;
Described nuclear layer monomer is selected from one or more in n-butyl acrylate (BA), n-BMA, ethyl propenoate, propyl acrylate, Hydroxyethyl acrylate;
Described nuclear layer monomer also comprises vinylbenzene and/or vinyl cyanide.
Described shell monomers is selected from one or more in vinylbenzene, alpha-methyl styrene, vinyl cyanide, methyl methacrylate;
Described emulsifying agent is anionic emulsifier or ion-non-ionic composite emulsifying agent, preferably sodium dodecyl sulfate (SDS).
Described oxygenant is selected from Potassium Persulphate (KPS), Sodium Persulfate, ammonium persulphate, azo diisobutyl amidine hydrochloride (AIBA, V-50), azo two isobutyl imidazoline hydrochloride (AIBA, VA-044), azo dicyano valeric acid (ACVA, or azo di-isopropyl tetrahydroglyoxaline (AIP, VA-061) V-501); The preferred KPS of described oxygenant.
Described reductive agent is selected from sodium bisulfite, S-WAT, Sulfothiorine or diamine;
Described linking agent is selected from one or more in butyleneglycol double methacrylate, 1,6 hexanediol diacrylate (HDDA), methacrylic acid, allyl methacrylate(AMA), dialkylene benzene.
Each raw material is preferably by mass fraction:
Nuclear layer monomer 15-25 part,
Shell monomers 60-80 part,
Emulsifying agent 0.7-1.5,
Oxygenant 0.4-0.6 part,
Reductive agent 0.2-0.4 part,
Linking agent 1-1.5 part.
The mol ratio of described oxygenant and described reductive agent is 1:0.6.
The reaction mechanism of redox system of the present invention is: X+A-B → X ++ B -+ A
Wherein X is reductive agent, and A-B is oxygenant.React the free radical produced whether to be of practical significance to polyreaction, depend on the size of the power of A-B key and the reducing power of reductive agent X.Owing to adopting redox system to greatly reduce the activation energy generating free radical, so when reaction conditions is constant, adopts redox system to improve polymerization rate, namely can improve throughput; And when maintaining certain throughput, then can reduce temperature of reaction, polymer performance is improved.
The present invention, by following performance index, characterizes the change of molecular chain and the formation of nucleocapsid three-dimensional arrangement.
1, transformation efficiency (C)
C = m 3 - m 1 - ( m 2 - m 1 ) × W 1 - ( m 2 - m 1 ) × W 5 - m 4 × W 3 ( m 2 - m 1 ) × W 2
Wherein m 1for weighing bottle quality; m 2for emulsion and weighing bottle total mass; m 3for gained solid after drying and weighing bottle total mass; m 4for the quality of stopper; W 1for the mass percentage concentration of initiator; W 2for the mass percentage concentration of monomer, W 4for the mass percentage concentration of stopper; W 5for the mass percentage concentration of emulsifying agent.
Sample is placed in 120 DEG C of dry 48h of vacuum drying oven to constant weight, weighs, calculate transformation efficiency.
2, percentage of grafting
Solvent made by toluene, extracting in Soxhlet extractor.Finally calculate percentage of grafting according to above formula.
3, particle diameter
Adopt Malvern company of Britain to produce Nano-ZS90 model zeta potential instrument, utilize dynamic light scattering technique (DLS) to measure particles size and distribution by non-intruding back scattering (NIBS).
4, tensile strength
By resin batten obtained after the injection moulding of modified ASA resin powder, test tensile property according to GB/T1040.2-2006.
The present invention take water as dispersion medium, emulsion stabilizer is done with anionic emulsifier or ion-non-ionic composite emulsifying agent, water soluble, redox system is made initiator and is carried out initiated polymerization, the inventive method reproducible, there is reaction conditions gentleness, energy consumption is low, and the feature of easy handling, is convenient to industrializing implementation.
Four, embodiment
Embodiment 1:
Each raw material is configured to by mass fraction:
Preparation method is as follows:
1) under nitrogen protection 0.088 part of SDS is added in deionized water, after being uniformly dispersed, add 3.7 parts of BA, after stirring, drip the aqueous solution and 0.04 part of NaHSO of 0.054 part of KPS respectively simultaneously 3the aqueous solution, drip off in ten minutes, in 60 DEG C reaction 2h;
2) in the reaction solution of step 1), drip 0.054 part of KPS aqueous solution, after dripping off, in reaction solution, drip nuclear layer monomer pre-emulsion again, in 60 DEG C of reactions 3 hours;
Described nuclear layer monomer pre-emulsion is by 7.4 parts of BA, 4.4 parts of St, 2.2 parts of AN, 0.74 part of HDDA, 0.132 part of SDS, 0.04 part of NaHSO 3obtain with deionized water and stirring emulsification;
3) to step 2) reaction solution in drip 0.162 part of KPS aqueous solution, in reaction solution, drip shell monomers pre-emulsion again after dripping off, within 3 hours, obtain the ASA emulsion of solid content 50% in 60 DEG C of reactions;
Described shell monomers pre-emulsion is by 17.8 parts of St, 8.9 parts of AN, 0.22 part of SDS, 0.12 part of NaHSO 3obtain with deionized water and stirring emulsification.
4) sodium chloride aqueous solution of the ASA emulsion mass concentration 5% obtained above is carried out breakdown of emulsion by the volume ratio mixing of 1:1, ASA resin can be obtained through heated and stirred, washing, suction filtration, oven dry.
Embodiment 2: comparative example-thermolysis causes
Each raw material is configured to by mass fraction:
Preparation method is as follows:
1) under nitrogen protection 0.088 part of SDS is added in deionized water, after being uniformly dispersed, add 3.7 parts of BA, drip the aqueous solution of 0.054 part of KPS after stirring, drip off in ten minutes, in 75 DEG C of reaction 2h;
2) in the reaction solution of step 1), drip 0.054 part of KPS aqueous solution, after dripping off, in reaction solution, drip nuclear layer monomer pre-emulsion again, in 75 DEG C of reactions 3 hours;
Described nuclear layer monomer pre-emulsion is obtained by 7.4 parts of BA, 4.4 parts of St, 2.2 parts of AN, 0.74 part of HDDA, 0.132 part of SDS and deionized water and stirring emulsifications;
3) to step 2) reaction solution in drip 0.162 part of KPS aqueous solution, in reaction solution, drip shell monomers pre-emulsion again after dripping off, within 3 hours, obtain the ASA emulsion of solid content 48% in 75 DEG C of reactions;
Described shell monomers pre-emulsion is obtained by 17.8 parts of St, 8.9 parts of AN, 0.22 part of SDS and deionized water and stirring emulsification.
4) sodium chloride aqueous solution of the ASA emulsion mass concentration 5% obtained above is carried out breakdown of emulsion by the volume ratio mixing of 1:1, ASA resin can be obtained through heated and stirred, washing, suction filtration, oven dry.
Embodiment 3:
Each raw material is configured to by mass fraction:
Preparation method is as follows:
1) under nitrogen protection 0.088 part of SDS is added in deionized water, after being uniformly dispersed, add 3.7 parts of BA, after stirring, drip the aqueous solution and 0.04 part of NaHSO of 0.054 part of KPS respectively simultaneously 3the aqueous solution, drip off in ten minutes, in 60 DEG C reaction 2h;
2) in the reaction solution of step 1), drip 0.054 part of KPS aqueous solution, after dripping off, in reaction solution, drip nuclear layer monomer pre-emulsion again, in 60 DEG C of reactions 3 hours;
Described nuclear layer monomer pre-emulsion is by 7.4 parts of BA, 4.4 parts of St, 2.2 parts of AN, 0.132 part of SDS, 0.04 part of NaHSO 3obtain with deionized water and stirring emulsification;
3) to step 2) reaction solution in drip 0.162 part of KPS aqueous solution, in reaction solution, drip shell monomers pre-emulsion again after dripping off, within 3 hours, obtain the ASA emulsion of solid content 53% in 60 DEG C of reactions;
Described shell monomers pre-emulsion is by 17.8 parts of St, 8.9 parts of AN, 0.22 part of SDS, 0.12 part of NaHSO 3obtain with deionized water and stirring emulsification.
4) sodium chloride aqueous solution of the ASA emulsion mass concentration 5% obtained above is carried out breakdown of emulsion by the volume ratio mixing of 1:1, ASA resin can be obtained through heated and stirred, washing, suction filtration, oven dry.
Embodiment 4:
Each raw material is configured to by mass fraction:
Preparation method is as follows:
1) under nitrogen protection 0.088 part of SDS is added in deionized water, after being uniformly dispersed, add 2.1 parts of BA, after stirring, drip the aqueous solution and 0.04 part of NaHSO of 0.054 part of KPS respectively simultaneously 3the aqueous solution, drip off in ten minutes, in 60 DEG C reaction 2h;
2) in the reaction solution of step 1), drip 0.054 part of KPS aqueous solution, after dripping off, in reaction solution, drip nuclear layer monomer pre-emulsion again, in 60 DEG C of reactions 3 hours;
Described nuclear layer monomer pre-emulsion is by 4.3 parts of BA, 4.4 parts of St, 2.2 parts of AN, 0.74 part of HDDA, 0.132 part of SDS, 0.04 part of NaHSO 3obtain with deionized water and stirring emulsification;
3) to step 2) reaction solution in drip 0.162 part of KPS aqueous solution, in reaction solution, drip shell monomers pre-emulsion again after dripping off, within 3 hours, obtain the ASA emulsion of solid content 45-55% in 60 DEG C of reactions;
Described shell monomers pre-emulsion is by 21 parts of St, 10.5 parts of AN, 0.22 part of SDS, 0.12 part of NaHSO 3obtain with deionized water and stirring emulsification.
4) sodium chloride aqueous solution of the ASA emulsion mass concentration 5% obtained above is carried out breakdown of emulsion by the volume ratio mixing of 1:1, ASA resin can be obtained through heated and stirred, washing, suction filtration, oven dry.
Embodiment 5:
Each step of the present embodiment with embodiment 1, unlike step 1), step 2) and step 3) in temperature of reaction be 45 DEG C.
Embodiment 6:
Each step of the present embodiment is with embodiment 1, and the mass fraction unlike HDDA is 1 part.
Embodiment 7:
Each raw material is configured to by mass fraction:
Preparation method is as follows:
1) under nitrogen protection 0.088 part of SDS is added in deionized water, after being uniformly dispersed, add 3.7 parts of BMA, after stirring, drip the aqueous solution and 0.04 part of NaHSO of 0.054 part of KPS respectively simultaneously 3the aqueous solution, drip off in ten minutes, in 60 DEG C reaction 2h;
2) in the reaction solution of step 1), drip 0.054 part of KPS aqueous solution, after dripping off, in reaction solution, drip nuclear layer monomer pre-emulsion again, in 60 DEG C of reactions 3 hours;
Described nuclear layer monomer pre-emulsion is by 7.4 parts of BMA, 4.4 parts of MMA, 2.2 parts of AN, 0.74 part of HDDA, 0.132 part of SDS, 0.04 part of NaHSO 3obtain with deionized water and stirring emulsification;
3) to step 2) reaction solution in drip 0.162 part of KPS aqueous solution, in reaction solution, drip shell monomers pre-emulsion again after dripping off, within 3 hours, obtain the ASA emulsion of solid content 50% in 60 DEG C of reactions;
Described shell monomers pre-emulsion is by 17.8 parts of MMA, 8.9 parts of AN, 0.22 part of SDS, 0.12 part of NaHSO 3obtain with deionized water and stirring emulsification.
4) sodium chloride aqueous solution of the ASA emulsion mass concentration 5% obtained above is carried out breakdown of emulsion by the volume ratio mixing of 1:1, ASA resin can be obtained through heated and stirred, washing, suction filtration, oven dry.
Embodiment 8:
Each raw material is configured to by mass fraction:
Preparation method is as follows:
1) under nitrogen protection 0.088 part of SDS is added in deionized water, after being uniformly dispersed, add 3.7 parts of BA, after stirring, drip the aqueous solution and 0.04 part of NaHSO of 0.054 part of AIBA respectively simultaneously 3the aqueous solution, drip off in ten minutes, in 60 DEG C reaction 2h;
2) in the reaction solution of step 1), drip 0.054 part of AIBA aqueous solution, after dripping off, in reaction solution, drip nuclear layer monomer pre-emulsion again, in 60 DEG C of reactions 3 hours;
Described nuclear layer monomer pre-emulsion is by 7.4 parts of BA, 4.4 parts of St, 2.2 parts of AN, 0.74 part of DVB, 0.132 part of SDS, 0.04 part of NaHSO 3obtain with deionized water and stirring emulsification;
3) to step 2) reaction solution in drip 0.162 part of AIBA aqueous solution, in reaction solution, drip shell monomers pre-emulsion again after dripping off, within 3 hours, obtain the ASA emulsion of solid content 50% in 60 DEG C of reactions;
Described shell monomers pre-emulsion is by 17.8 parts of St, 8.9 parts of AN, 0.22 part of SDS, 0.12 part of NaHSO 3obtain with deionized water and stirring emulsification.
4) sodium chloride aqueous solution of the ASA emulsion mass concentration 5% obtained above is carried out breakdown of emulsion by the volume ratio mixing of 1:1, ASA resin can be obtained through heated and stirred, washing, suction filtration, oven dry.
Properties measurement result.
Table 1 ASA emulsion property is tested
Table 1 is the correlated performance test of ASA emulsion.As shown in Table 1,45 DEG C time, reaction conversion ratio slightly declines than 60 DEG C, but still higher; Improve the 3rd section of monomer add-on, Large stone particle can be obtained.
The resin stretched mechanical property contrast of table 2 ASA
The resin stretched mechanical experimental results of ASA that table 2 is prepared for embodiment.Result shows, adopts the resin stretched ASA resin being slightly obviously better than adopting thermal decomposition initiating (embodiment 2) obtained of the obtained ASA of water soluble, redox system.

Claims (3)

1. adopt a method for water soluble, redox initiator low-temperature growth ASA copolymer emulsion, it is characterized in that operating according to the following steps:
1) under nitrogen protection the emulsifying agent of 15-25% is added in deionized water, after being uniformly dispersed, add the nuclear layer monomer of 25-75%, after stirring, drip the oxygenant of 10-20% and the reductive agent of 10-20% respectively simultaneously, in 35-60 DEG C of reaction 2-4h;
2) to step 1) reaction solution in drip the oxygenant of 20-40%, in reaction solution, drip nuclear layer monomer pre-emulsion again after dripping off, in 35-60 DEG C of reaction 2-4 hour;
Described nuclear layer monomer pre-emulsion is obtained by the reductive agent of the emulsifying agent of the shell monomers of the nuclear layer monomer of surplus, 5-20%, 25-35%, linking agent, 20-40% and deionized water and stirring emulsification;
3) to step 2) reaction solution in drip the oxygenant of surplus, in reaction solution, drip shell monomers pre-emulsion again after dripping off, within 2-4 hour, obtain the ASA emulsion of solid content 45-55% in 35-60 DEG C of reaction;
Described shell monomers pre-emulsion is obtained by the emulsifying agent of the shell monomers of surplus, surplus, the reductive agent of surplus and deionized water and stirring emulsification;
Each raw material is configured to by mass fraction:
Described nuclear layer monomer is selected from one or more in n-butyl acrylate, n-BMA, ethyl propenoate, propyl acrylate, Hydroxyethyl acrylate;
Described shell monomers is selected from one or more in vinylbenzene, alpha-methyl styrene, vinyl cyanide, methyl methacrylate;
Described emulsifying agent is anionic emulsifier or ion-non-ionic composite emulsifying agent;
Described oxygenant is selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate;
Described reductive agent is selected from sodium bisulfite, S-WAT, Sulfothiorine or diamine;
Described linking agent is selected from one or more in butyleneglycol double methacrylate, 1,6 hexanediol diacrylate, allyl methacrylate(AMA), dialkylene benzene.
2. preparation method according to claim 1, is characterized in that each raw material is configured to by mass fraction:
3. preparation method according to claim 1, is characterized in that:
The mol ratio of described oxygenant and described reductive agent is 1:0.6.
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