CN106629671A - Preparation method of multifunctional nanocluster - Google Patents

Preparation method of multifunctional nanocluster Download PDF

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Publication number
CN106629671A
CN106629671A CN201710004380.XA CN201710004380A CN106629671A CN 106629671 A CN106629671 A CN 106629671A CN 201710004380 A CN201710004380 A CN 201710004380A CN 106629671 A CN106629671 A CN 106629671A
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zrp
preparation
nano cluster
multifunctional nano
reaction
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CN106629671B (en
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樊海彬
朱美芳
周哲
杨新华
张林扬
周家良
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SUZHOU GOLD SPRING NEW MATERIAL Co Ltd
Donghua University
National Dong Hwa University
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SUZHOU GOLD SPRING NEW MATERIAL Co Ltd
Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to a preparation method of a multifunctional nanocluster and belongs to the technical field of material modification. The preparation method comprises the following steps: dispersing alpha-ZrP into a solvent; adding metal salt to carry out ion substitution reaction; dropwise adding a silane coupling agent to continuously react, so as to obtain KH550-modified functional alpha-ZrP; acidifying a carbon material, so as to obtain the acidified carbon material; carrying out epoxy modification on the acidified carbon material by virtue of an epoxy modifying agent E51, so as to obtain epoxy-C; adding the KH550-modified functional alpha-ZrP into epoxy-C to react; and separating, washing and drying solid-phase products, so as to obtain the multifunctional nanocluster. The multifunctional nanocluster has good antimicrobial effect, anion effect, heat conduction effect and anti-static effect, and can present good consistency with a polymer matrix, thereby meeting functional modification requirements to polymers.

Description

A kind of preparation method of multifunctional nano cluster
Technical field
The invention belongs to technical field of material modification, and in particular to a kind of preparation method of multifunctional nano cluster.
Background technology
Alpha zirconium phosphate（α-ZrP）It is a kind of layered phosphates, with outstanding feature, such as macroion switching performance（7 Meq/g, MMT are 1meq/g）, controllable area ratio, thermally and chemically stability it is high, compared with other laminar nano fillers, more hold By intercalation or stripping easily in polymeric matrix, it be widely used in catalyst, fuel cell, photochemistry, environmental protection, The fields such as fire retardant.
However, the same with most of inorganic nanometer powders, α-ZrP contain substantial amounts of oh group, hydrophily due to surface It is relatively strong, it is incompatible with most hydrophobic thermoplastic polymer, it is difficult to be evenly dispersed in polymeric matrix, so as to affect α- ZrP is to the fire-retardant of high molecular polymer and improves mechanical performance effect.Therefore to α-ZrP it is organically-modified be prepare macromolecule without The step of key one before machine composite.Covalence graft is modified then require modifying agent have reactive functional such as isocyanates, Acyl chlorides key etc., these groups can occur chemical reaction and set up the higher covalent bond of heat endurance with α-ZrP surface P-OH, so as to Go for further processing, wherein silane coupler class formation is more special, on each molecule containing two or more not Same reactive group, one of reactive group is methoxy or ethoxy, and it can be combined with inorganic material, such as glass Glass, metal, silica sand etc.；Another reactive group is vinyl, epoxy radicals, amino, methacryloxypropyl or sulfydryl etc., Can be formed with organic material and be chemically bonded, silane coupler class modifying agent can be played in organic/inorganic composite material is prepared Good function served as bridge.
Material with carbon element mainly includes CNT, nanometer carbon black, graphite etc., and material with carbon element has good conduction, heat conductivility, But it is difficult to be modified it because its surface group content is less, by carrying out acidification to it its surface can be made rich Containing group, the A of CN 103451931 carry out surface using a kind of carbon fiber surface activity agent rich in functional group to carbon fiber Process, carbon fiber after treatment has good lipophile, can be very good to be dispersed in high molecular polymer matrix.CN 104445134 A utilize a kind of structure directing agent of environment-friendly type, are simply and efficiently completed to CNT using one pot of hydro-thermal method It is modified with the surface of Graphene, can obtains in high molecular polymer matrix through modified CNT and Graphene Fine dispersion.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of preparation method of multifunctional nano cluster, The multifunctional nano cluster prepared by the method has good antibacterial, anion, heat conduction, antistatic property and can show The compatibility good with polymeric matrix and use the functional modification requirement met to polymer.
What the task of the present invention was performed by, a kind of preparation method of multifunctional nano cluster is comprised the following steps：
1）α-ZrP are scattered in solvent；
2）Slaine is added to carry out ion exchange reaction；
3）Silane coupler continuation reaction is added dropwise and obtains the modified functional alpha-ZrP of KH550；
4）Acidification material with carbon element, to material with carbon element acidification is carried out, and obtains the material with carbon element of acidification；
5）The material with carbon element of acidification is carried out by epoxy modifying agent E51 epoxide modified, obtain epoxy-C；
6）Functional alpha-the ZrP that KH550 is modified is added in epoxy-C and is reacted;
7）Solid product separating, washing and drying, obtain multifunctional nano cluster.
In a specific embodiment of the present invention, step 1）Described in solvent be tetrahydrofuran, chloroform or DMF, the concentration of α-ZrP is 0.05 ~ 0.2g/ml after dispersion.
In another specific embodiment of the present invention, step 1）Described in disperse to refer at ambient temperature, ultrasound And mechanical agitation, churned mechanically rotating speed is 200 ~ 800r/min, and the time is 20 ~ 50min；The ultrasound is referred in room temperature condition Under, ultrasonic power is 50 ~ 90W, and the time is 20 ~ 50min.
In another specific embodiment of the present invention, step 2）Described in slaine and step 1）Described in α- The mol ratio of ZrP is 1:10~1:40, the time of the displacement reaction is 6 ~ 18h.
In another specific embodiment of the present invention, step 3）Described in slaine be silver nitrate, copper nitrate, sulfuric acid Copper, copper chloride or germanium chloride.
In an also specific embodiment of the present invention, step 3）Described in silane coupler general formula of molecular structure For KH550, the dripping quantity of silane coupler is 0.5 with the mass ratio of the α-ZrP:1~2.0:1；Drop rate be 0.1 ~ 1.5ml/min；The time for continuing to react is 3 ~ 8h.
In the present invention more and in a specific embodiment, step 4）Described in material with carbon element be CNT, carbon black or Graphite.
The present invention's and then in a specific embodiment, step 4）Described in acidification be concentration of nitric acid be 50 Wt% ~ 80 wt%, reaction temperature is 60 ~ 100 DEG C, and the time of reaction is 12 ~ 48 h.
The present invention's and more and in a specific embodiment, step 5）Described in the material with carbon element of acidification carry out The epoxide modified material with carbon element for acidification is 1 with the mol ratio of epoxy modifying agent E51:1~1:10, reaction temperature is 60 ~ 80 DEG C, the reaction time is 12 ~ 36 h.
Of the invention again and then in a specific embodiment, step 7）Described in solid product it is separated be will be solid Phase product is separated with solvent using Rotary Evaporators；The washing is first the acetone and water in quality % specific concentration for 90 ~ 98% Mixed solution soaks 24 ~ 36h, and 3 ~ 5 reaction raw materials up to noresidue in product are then cleaned with acetone soln；The drying In to be placed in vacuum drying oven, 60 ~ 80°C, dries 24 ~ 36h under the conditions of 0.05 ~ 0.1MPa of vacuum.
The technical scheme that the present invention is provided has compared with prior art following advantages：
1st, it is multi-functional：With α-ZrP as carrier, there is ion exchange in functional metal salt, and silane coupler is modifying agent and Jing The material with carbon element of the modified acidification of epoxy-functional is reacted, and is prepared for multifunctional integrated functional nano cluster, The nanocluster has programmable function, with antibacterial, anion, heat conduction, anlistatig effect.
2nd, hydrophobicity：Multifunctional nano cluster prepared by the method has a good hydrophobicity, the equal Jing of two kinds of nano materials The modified of hydrophobization is crossed, therefore is showed for the good compatibility of polymeric matrix, functionalized modified need can be met Ask.
Description of the drawings
Fig. 1 is the flow chart of the preparation method of multifunctional nano cluster of the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this Bright rather than restriction the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.
The metal ion displacement α-ZrP of the present invention, outward appearance is white powder, and KH550 modified alphas-ZrP is lamellar compound, Ability with preferable antibiotic property and transmitting anion；Surface is rich in functional group, Jing E51 after the acidified process of the material with carbon element Carbon material surface is rich in epoxy-functional after process；Using the chemical reaction between amino and epoxy radicals, will with antibacterial, bear from The basic zirconium phosphate of son is connected to form with conduction, heat conduction, antibacterial, the nanocluster of anion with the conductive, material with carbon element of heat conduction, and by In surface, modified bonnet nanocluster has good hydrophobicity, can preferably be dispersed in polymeric matrix.
The step of preparation method of the multifunctional nano cluster of the present invention, is as follows：
1）α-ZrP are scattered in solvent, α-ZrP contain on surface great amount of hydroxy group group, hydrophily is strong, can preferably be scattered in In solvent, the dispersion of α-ZrP can be promoted by the effect such as ultrasound；
2）Metal salt solution is added to carry out ion exchange reaction, α-ZrP have very high ion-exchange capacity, with functional Metal ion easily enters α-ZrP, is formed and has functional α-ZrP；
3）Silane coupler is added dropwise again to continue to react, the silica group in silane coupler is met water and hydrolyzed, and reaction of formation is lived Property higher silanol key Si-OH, Si-OH can occur dehydration condensation with P-OH on α-ZrP lamellas, in α-ZrP lamella tables Face generates the higher P-O-Si covalent bonds of heat endurance, simultaneously because contain hydrophobic chain segment in silane coupled agent molecule, when connecing α-ZrP can be changed into hydrophobic material when reaching certain value by branch rate from hydrophilic material, increase itself and hydrophobic polymer it Between compatibility；
4）Acidification is carried out to material with carbon element using the strong oxidizing property of strong acid, after making carbon material surface be rich in hydroxyl, carboxyl conveniently It is continuous to carry out functionalization；
5）The material with carbon element being acidified is modified using epoxy-modified dose of E51, prepares the carbon materials that surface has epoxy-functional Material；
6）By KH550 be modified functionalization α-ZrP with it is epoxide modified after material with carbon element reacted, prepare have it is multi-functional Nanocluster；
7）Described nanocluster goes the removal of impurity through repeatedly washing, is placed in very red oven drying, that is, multi-functional receiving is obtained Rice cluster, nano material through modified with good hydrophobicity, this be conducive to being applied to great majority by melting plus In the macromolecular material of work.
Fig. 1 is referred to, the Fig. 1 is the flow chart of the preparation method of multifunctional nano cluster, wherein α-ZrP elder generation Jing ions are handed over Change, then graft reaction occurs with KH550.Chemical bond is formed using epoxide group and amino, washing, drying is eventually passed i.e. Obtain CNT/α-ZrP multifunctional nano clusters.
Embodiment 1：
The step of flow process as shown in Figure 1, preparation method of multifunctional nano cluster is：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 50W, and the time is 20min；It is churned mechanically Rotating speed is 200r/min, and the time is scattered in tetrahydrofuran solution for 20min, and the concentration of α-ZrP is 0.05g/ml after dispersion；
2) copper sulphate is added to carry out ion-exchange reactions, copper sulphate is 1 with the mol ratio of α-ZrP:10, add copper sulphate reaction Time is 6h；
3) Silane coupling agent KH550 is added dropwise to continue to react；The dripping quantity of KH550 is 0.5 with the mass ratio of α-ZrP:1；Speed is added dropwise Rate is 0.1ml/min；The time for continuing to react is 3h；
4) the nitric acid treatment multi-walled carbon nano-tubes that mass fraction is 80% is added；Reaction temperature is 80 DEG C, and the time of reaction is 12 h。
5) add E51 to be modified the multi-walled carbon nano-tubes of acidifying；Acidifying material with carbon element is 1 with epoxy modifying agent E51 mol ratios:5, Reaction temperature is 80 DEG C, and the reaction time is 12 h；
6) epoxide modified multi-walled carbon nano-tubes and the mol ratio of KH550- α-ZrP are 1:1；High-temperature is risen to 80 DEG C, continues anti- Answer 16h；
7) solid product separating, washing and drying is obtained multifunctional nano cluster, and solid product separates employing with solvent Rotary Evaporators；Washing is first to soak 24h with the mixed solution of water in the acetone that concentration is 90%, clear with a large amount of acetone solns afterwards Wash 3 reaction raw materials up to noresidue in product；In drying to be placed in vacuum drying oven, 60 °C, under the conditions of vacuum 0.05MPa Drying 24h；
Embodiment 2：
The step of flow process as shown in Figure 1, preparation method of multifunctional nano cluster is：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 90W, and the time is 50min；It is churned mechanically Rotating speed is 800r/min, and the time is scattered in chloroform for 50min, and the concentration of α-ZrP is 0. 2g/ml after dispersion；
2) silver nitrate is added to carry out ion-exchange reactions, silver nitrate is 1 with the mol ratio of α-ZrP:15, add silver nitrate reaction Time is 10h；
3) Silane coupling agent KH550 is added dropwise to continue to react；The dripping quantity of KH550 is 1 with the mass ratio of α-ZrP:1；Drop rate For 0.1ml/min；The time for continuing to react is 5h；
4) the nitric acid treatment nanometer carbon black that mass fraction is 70% is added；Reaction temperature is 75 DEG C, and the time of reaction is 12 h.
5) add E51 to be modified the nanometer carbon black of acidifying；Acidifying material with carbon element is 1 with epoxy modifying agent E51 mol ratios:10, instead Temperature is answered for 75 DEG C, the reaction time is 15 h；
6) epoxide modified nanometer carbon black and the mol ratio of KH550- α-ZrP are 1:1；High-temperature is risen to 75 DEG C, continues to react 18h；
7) solid product separating, washing and drying is obtained multifunctional nano cluster, and solid product separates employing with solvent Rotary Evaporators；Washing is first to soak 24h with the mixed solution of water in the acetone that concentration is 90%, clear with a large amount of acetone solns afterwards Wash 3 reaction raw materials up to noresidue in product；In drying to be placed in vacuum drying oven, 60 °C, under the conditions of vacuum 0.05MPa Drying 24h；
Embodiment 3：
The step of flow process as shown in Figure 1, preparation method of multifunctional nano cluster is：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 60W, and the time is 30min；It is churned mechanically Rotating speed is 500r/min, and the time is scattered in DMF solution for 30min, and the concentration of α-ZrP is 0.08g/ml after dispersion；
2) germanium chloride is added to carry out ion-exchange reactions, germanium chloride is 1 with the mol ratio of α-ZrP:40, add germanium chloride reaction Time is 18 h；
3) Silane coupling agent KH550 is added dropwise to continue to react；The dripping quantity of KH550 is 2 with the mass ratio of α-ZrP:1；Drop rate For 0.1ml/min；The time for continuing to react is 8 h；
4) the nitric acid treatment nano-graphite that mass fraction is 60% is added；Reaction temperature is 80 DEG C, and the time of reaction is 12 h.
5) add E51 to be modified the nano-graphite of acidifying；Acidifying material with carbon element is 1 with epoxy modifying agent E51 mol ratios:8, reaction Temperature is 75 DEG C, and the reaction time is 24 h；
6) epoxide modified nano-graphite and the mol ratio of KH550- α-ZrP are 1:1；High-temperature is risen to 75 DEG C, continues to react 36h；
7) solid product separating, washing and drying is obtained multifunctional nano cluster, and solid product separates employing with solvent Rotary Evaporators；Washing is first to soak 24h with the mixed solution of water in the acetone that concentration is 90%, clear with a large amount of acetone solns afterwards Wash 3 reaction raw materials up to noresidue in product；In drying to be placed in vacuum drying oven, 60 °C, under the conditions of vacuum 0.05MPa Drying 24h；
Embodiment 4：
The step of flow process as shown in Figure 1, preparation method of multifunctional nano cluster is：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 60W, and the time is 25min；It is churned mechanically Rotating speed is 500r/min, and the time is scattered in tetrahydrofuran for 30min, and the concentration of α-ZrP is 0. 1g/ml after dispersion；
2) copper nitrate is added to carry out ion-exchange reactions, copper nitrate is 1 with the mol ratio of α-ZrP:30, add copper nitrate reaction Time is 16h；
3) Silane coupling agent KH550 is added dropwise to continue to react；The dripping quantity of KH550 is 2 with the mass ratio of α-ZrP:1；Drop rate For 0.1ml/min；The time for continuing to react is 6h；
4) the nitric acid treatment multi-walled carbon nano-tubes that mass fraction is 70% is added；Reaction temperature is 80 DEG C, and the time of reaction is 36 h。
5) add E51 to be modified the multi-walled carbon nano-tubes of acidifying；Acidifying material with carbon element is 1 with epoxy modifying agent E51 mol ratios:1, Reaction temperature is 80 DEG C, and the reaction time is 36 h；
6) epoxide modified multi-walled carbon nano-tubes and the mol ratio of KH550- α-ZrP are 1:1；High-temperature is risen to 70 DEG C, continues anti- Answer 12h；
7) solid product separating, washing and drying is obtained multifunctional nano cluster, and solid product separates employing with solvent Rotary Evaporators；Washing is first to soak 24h with the mixed solution of water in the acetone that concentration is 90%, clear with a large amount of acetone solns afterwards Wash 3 reaction raw materials up to noresidue in product；In drying to be placed in vacuum drying oven, 60°C, under the conditions of vacuum 0.05MPa Drying 24h；
Embodiment 5：
The step of flow process as shown in Figure 1, preparation method of multifunctional nano cluster is：
1) by α-ZrP at ambient temperature, ultrasound and mechanical agitation, ultrasonic power is 60W, and the time is 35min；It is churned mechanically Rotating speed is 650r/min, and the time is scattered in chloroform for 25min, and the concentration of α-ZrP is 0.15 g/ml after dispersion；
2) copper sulphate and germanium chloride is added to carry out ion-exchange reactions, copper is 9 with the mol ratio of germanium:1, copper sulphate and germanium chloride with The mol ratio of α-ZrP is 1:10, the time for adding copper sulphate reaction is 18 h；
3) Silane coupling agent KH550 is added dropwise to continue to react；The dripping quantity of KH550 is 2 with the mass ratio of α-ZrP:1；Drop rate For 0.1ml/min；The time for continuing to react is 8h；
4) the nitric acid treatment multi-walled carbon nano-tubes that mass fraction is 80% is added；Reaction temperature is 80 DEG C, and the time of reaction is 24 h；
5) add E51 to be modified the multi-walled carbon nano-tubes of acidifying；Acidifying material with carbon element is 1 with epoxy modifying agent E51 mol ratios:10, instead Temperature is answered for 80 DEG C, the reaction time is 24 h；
6) epoxide modified multi-walled carbon nano-tubes and the mol ratio of KH550- α-ZrP are 1:1；High-temperature is risen to 80 DEG C, continues anti- Answer 6h；
Solid product separating, washing and drying are obtained multifunctional nano cluster, and solid product is separated using rotation with solvent Turn evaporimeter；Washing is first, in the acetone that concentration is 90% and the mixed solution immersion 24h of water, to clean 3 with a large amount of acetone solns afterwards The secondary reaction raw materials up to noresidue in product；In drying to be placed in vacuum drying oven, 60°C, dries under the conditions of vacuum 0.05MPa Dry 24h.

Claims (10)

1. a kind of preparation method of multifunctional nano cluster, it is characterised in that comprise the following steps：
1）α-ZrP are scattered in solvent；
2）Slaine is added to carry out ion exchange reaction；
3）Silane coupler continuation reaction is added dropwise and obtains the modified functional alpha-ZrP of KH550；
4）Acidification material with carbon element, to material with carbon element acidification is carried out, and obtains the material with carbon element of acidification；
5）The material with carbon element of acidification is carried out by epoxy modifying agent E51 epoxide modified, obtain epoxy-C；
6）Functional alpha-the ZrP that KH550 is modified is added in epoxy-C and is reacted;
7）Solid product separating, washing and drying, obtain multifunctional nano cluster.
2. a kind of preparation method of multifunctional nano cluster according to claim 1, it is characterised in that step 1）Described in Solvent be tetrahydrofuran, chloroform or DMF, after dispersion the concentration of α-ZrP be 0.05 ~ 0.2g/ml.
3. a kind of preparation method of multifunctional nano cluster according to claim 1, it is characterised in that step 1）Described in Dispersion refer at ambient temperature, ultrasound and mechanical agitation, churned mechanically rotating speed be 200 ~ 800r/min, the time be 20 ~ 50min；The ultrasound refers to that at ambient temperature ultrasonic power is 50 ~ 90W, and the time is 20 ~ 50min.
4. a kind of preparation method of multifunctional nano cluster according to claim 1, it is characterised in that step 2）Described in Slaine and step 1）Described in α-ZrP mol ratio be 1:10~1:40, the time of the displacement reaction is 6 ~ 18h.
5. a kind of preparation method of the multifunctional nano cluster according to claim 1 or 4, it is characterised in that step 3）Middle institute Slaine is stated for silver nitrate, copper nitrate, copper sulphate, copper chloride or germanium chloride.
6. a kind of preparation method of multifunctional nano cluster according to claim 1, it is characterised in that step 3）Described in The general formula of molecular structure of silane coupler is KH550, and the dripping quantity of silane coupler is 0.5 with the mass ratio of the α-ZrP:1~ 2.0:1；Drop rate is 0.1 ~ 1.5ml/min；The time for continuing to react is 3 ~ 8h.
7. a kind of preparation method of multifunctional nano cluster according to claim 1, it is characterised in that step 4）Described in Material with carbon element is CNT, carbon black or graphite.
8. a kind of preparation method of multifunctional nano cluster according to claim 1, it is characterised in that step 4）Described in Acidification be concentration of nitric acid be 50 wt% ~ 80 wt%, reaction temperature is 60 ~ 100 DEG C, and time of reaction is 12 ~ 48 h.
9. a kind of preparation method of multifunctional nano cluster according to claim 1, it is characterised in that step 5）Described in The material with carbon element of acidification to carry out the mol ratio of the epoxide modified material with carbon element for acidification and epoxy modifying agent E51 be 1:1~ 1:10, reaction temperature is 60 ~ 80 DEG C, and the reaction time is 12 ~ 36 h.
10. a kind of preparation method of multifunctional nano cluster according to claim 1, it is characterised in that step 7）Described in Solid product it is separated be to separate solid product using Rotary Evaporators with solvent；The washing is first than dense in quality % Spend and soak 24 ~ 36h with the mixed solution of water for 90 ~ 98% acetone, then clean 3 ~ 5 times up to nothing in product with acetone soln The reaction raw materials of residual；The drying is to be placed in vacuum drying oven, 60 ~ 80°C, under the conditions of 0.05 ~ 0.1MPa of vacuum 24 are dried ~36h。
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