CN104788865B - Composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst and its preparation method and application - Google Patents

Composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst and its preparation method and application Download PDF

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CN104788865B
CN104788865B CN201510129003.XA CN201510129003A CN104788865B CN 104788865 B CN104788865 B CN 104788865B CN 201510129003 A CN201510129003 A CN 201510129003A CN 104788865 B CN104788865 B CN 104788865B
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oxide
polymer
metallic catalyst
metal
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CN104788865A (en
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唐萍
李锐
司晶晶
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Fudan University
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Abstract

The invention belongs to technical field of polymer materials, specially a kind of nano-metal-oxide/macromolecule composite antistatic agent and its preparation method and application.The composite antistatic agent of the present invention is the compound for the Polymer-metallic Catalyst and nano-metal-oxide having been commercialized, applied to antistatic macromolecule material.The composite antistatic agent by the nano effect of nano-metal-oxide and with the intermolecular interaction of Polymer-metallic Catalyst, not only there is the excellent antistatic property of parent antistatic additive, permanent antistatic protection function and influenceed by ambient humidity smaller, and the filling usage amount and production cost of parent antistatic additive in high polymer material can be significantly reduced, so as to improve the thermodynamic property of high polymer material.The excellent antibacterial of nano-metal-oxide, anti-aging and stronger ultraviolet screening ability etc. impart the new potential premium properties of high polymer material, have widened its application field.The cost of the novel high polymer composite antistatic agent is relatively low, and preparation method is simple, suitable for industrialized production.

Description

The composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst and its preparation Methods and applications
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of nano-metal-oxide/polymeric antistatic Composite antistatic agent of agent and its preparation method and application.
Background technology
High polymer material is with its cheap price, outstanding electrical insulation capability, chemical-resistance and good processing characteristics Deng and obtain extensive use.But high polymer material is in use, because of external environment influences such as friction, external magnetic field sensings Easily build up of electrostatic charge, cause the disasters such as device surface dust suction, film closure, electronic device breakdown, electric shock and blast.To disappear Disaster is destaticed, industrially generally reduces the surface of high polymer material by adding the method for antistatic additive in polymer base material Resistivity（Surface resistivity,R s ）Or specific insulation（Volume resistivity,R v ）.Low molecule scale face Surfactant type antistatic agent is currently used antistatic additive, and its antistatic mechanism is to be inhaled using the antistatic additive in material surface Attached water point reducesR s , reach anlistatig effect.Many defects, such as durability in use be present in such antistatic additive Difference, not scrubbing resistance, it is big to the dependence of ambient humidity, reduce the heat resisting temperature of material and surface characteristic etc., and it is from high score Subbase material has a negative impact after departing to environment.
The durability for improving antistatic additive is one of important research direction of antistatic additive high performance.In order to make up small point The defects of sublist face surfactant type antistatic agent, people are by conductive filler（Metal and metal oxide or carbon-based material）Introduce high To improve the durability of antistatic additive in molecular material, its antistatic mechanism is to be formed using these fillers in macromolecule matrix Conductive network is percolated with dissipation of static charge, reaches anlistatig effect.But the formation of the electric charge transmission channel needs largely Conductive filler, this will cause high polymer material not easy coloring, filler it is easy to fall off or oxidation and high polymer material physical property decline etc. Shortcoming, it is limited its application in polymeric antistatic field.
Polymer-metallic Catalyst is a kind of containing hydrophilic or conductive unit polymer, be characterized in antistatic effect persistently and Substantially it is not protected from environmental.Polymer-metallic Catalyst can obtain quiet with permanently resisting after being blended with hydrophobic polymer matrix The polymer composite of electrical property.The composite not only preferably maintains the basic performance of macromolecule matrix, and it is anti-quiet Electric effect is lasting, no induction period, is not influenceed by the condition such as wiping and washing, and shows in wider humidity range good And stable antistatic effect.However, inevitably occur various problems during Polymer-metallic Catalyst use, it is such as permanent Type Polymer-metallic Catalyst itself is on the high side, and the filling usage amount formed needed for static charge inside leakage network is also higher, and And its physicochemical property difference between macromolecule matrix material will cause the decline of high polymer material hot property and mechanical performance. Therefore, it is a primary object of the present invention to the filling that permanent type Polymer-metallic Catalyst is controlled by simple effective method to use Amount, and improve the hot property and mechanical performance of high polymer material.
The present invention using nano-metal-oxide particle nano effect and its with permanent type Polymer-metallic Catalyst molecule Between interaction (such as Van der Waals force and hydrogen bond), effectively reduce high polymer materialR v .The introducing of nano-metal-oxide can The filling usage amount of permanent type Polymer-metallic Catalyst is reduced, improves the hot property and mechanical performance of high polymer material, makes simultaneously The sub- material that secures satisfactory grades possesses other good characteristics of nano-metal-oxide particle, such as anti-microbial property, ageing resistance and stronger The new characteristic such as ultraviolet screening ability.
The content of the invention
Nano-metal-oxide/the high score lasting and cheap it is an object of the invention to provide a kind of antistatic property The composite antistatic agent of sub- antistatic additive, and the preparation method of the composite antistatic agent and its answering in high polymer material With.
The preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst provided by the present invention, Its specific preparation process is as follows：
（1）The drying process of nano-metal-oxide, permanent type Polymer-metallic Catalyst
Nano-metal-oxide and permanent type Polymer-metallic Catalyst are respectively placed in vacuum drying chamber, at 45~80 DEG C At a temperature of, freeze-day with constant temperature 12~48 hours；
（2）The preparation of permanent type Polymer-metallic Catalyst solution
Dried permanent type Polymer-metallic Catalyst is dissolved in organic solvent, ultrasonic 15 in ultrasonic disperse machine~ 120 minutes, 20~60kHz of working frequency, 50~200W of power, 20~70 DEG C of temperature；Then, the mixed solution is persistently stirred Heating 60~120 DEG C of heating-up temperature, obtains permanent type Polymer-metallic Catalyst solution in 1~6 hour to being completely dissolved；
（3）Nano-metal-oxide/Polymer-metallic Catalyst prepares composite antistatic agent
Dried nano-metal-oxide is added in Polymer-metallic Catalyst organic solution, surpassed in ultrasonic disperse machine Sound 15~120 minutes, 20~60kHz of working frequency, 50~200W of power, 20~70 DEG C of temperature；Then, the mixed solution is held Continuous stirring and dissolving 0.5~120 hour, 20~150 DEG C of whipping temp, 50~2000rpm of stir speed (S.S.), obtains nano metal oxide The mixed solution of thing and permanent type Polymer-metallic Catalyst；
Then the mixed solution is separated, washed, and is dried in vacuo 12~60 hours at 40~80 DEG C, is finally obtained Obtain the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst.
In the present invention, in step (1), the permanent type Polymer-metallic Catalyst is the oleophylic for including polymer molecule segment Property part and with the inorganic salts ionic hydrophilic group that can dissociate, including polyacrylate, maleic anhydride and it is other not The salt and polystyrene sulfonate salt of saturation monomer copolymer.
In the present invention, in step (1), the nano-metal-oxide is：Particle diameter is between 50~2000nm, electrical conductivity Semi-conducting material is characterized as, appearance luster is white powder, and active ingredient is simple substance or mixture.The nano-metal-oxide For ZnO, TiO2And Kaolin.
In the present invention, in step (2), the organic solvent is 1-METHYLPYRROLIDONE, or is resisted for permanent type macromolecule The good solvent of electrostatic agent；The stirring is electromagnetic agitation or mechanical agitation.
In the present invention, in step (3), the separation method is that normal pressure filters, vacuum decompression is dried and removes solvent；It is described to wash The method of washing is：By the good solvent of permanent type Polymer-metallic Catalyst with 1~10 times of permanent type Polymer-metallic Catalyst meltage It is quantitative, wash 1~10 time.
In the present invention, application of the composite antistatic agent in antistatic macromolecule material is prepared, it uses melting or solution After blending, injection, molding or mixed solution knifing, film shaping is poured.Wherein：
The specific preparation process of melt blending processing method is as follows：
Prepared composite antistatic agent and high polymer material are dried in vacuo 12~48h at 60~120 DEG C, physics mixes After closing uniformly, carry out melt blending, blending temperature is 160~220 DEG C, and shear rate be 5~120rpm, the blending time for 5~ 15 minutes；
Then carry out molding and prepare test sample, molding temperature is 180~210 DEG C, and pressure is 25~45kg/cm2, test Exemplar specification is the standard batten needed for 8~12cm of diameter, 0.5~3mm of thickness disk and other tests.
The specific preparation process of solution blending processing method is as follows：
By prepared composite antistatic agent and high polymer material respectively at a temperature of 80~120 DEG C vacuum drying 12~ 48h；Quantitative composite antistatic agent is added in the 1-METHYLPYRROLIDONE solvent of 2~15 times of mass ratioes, ultrasonic disperse 0.5~ 5 hours, the kHz of working frequency 20~60,50~1500W of power, 20~70 DEG C of temperature, it is dispersed to obtain composite antistatic agent Mixed liquor；
Then, high polymer material is added in the mixed solution, continues stirring and dissolving 0.5~130 hour, whipping temp 20~150 DEG C, 50~2000rpm of stir speed (S.S.), obtain the blend solution of composite antistatic agent/high polymer material；With will should Mixed solution is carried out pouring film or knifing in a mold, and survey is produced after the mould for loading mixed liquor then is carried out into the vacuum drying demoulding Sample coupon, vacuum drying temperature are 60~120 DEG C, and drying time is 2~48 hours.
In the present invention, application of the composite antistatic agent in antistatic macromolecule material is prepared, wherein composite antistatic agent Proportioning with high polymer material is 1:1~1:50 mass ratio.
In the present invention, described high polymer material is polystyrene（PS）.
The present invention use the new permanent type Polymer-metallic Catalyst having been commercialized as parent, by physical blending process by its It is blended with cheap nano-metal-oxide, a kind of new composite antistatic agent is prepared into, applied to antistatic macromolecule material Material.The NEW TYPE OF COMPOSITE antistatic additive not only has excellent antistatic capability, the permanent electrostatic protection work(of parent antistatic additive Can and electrostatic dissipation ability influenceed by the humidity of environment it is smaller, while can reduce permanent type macromolecule in composite resist it is quiet The filling usage amount of electric agent, so as to improve the hot property of composite and mechanical property.This NEW TYPE OF COMPOSITE antistatic additive passes through The nano effect of nano-metal-oxide particle and its with the intermolecular interaction of permanent type Polymer-metallic Catalyst（Such as model moral Hua Li and hydrogen bond）, not only contribute to improve the various problems that the latter occurs in use：Such as formed in polymer base material Physicochemical property needed for static charge inside dissipative network between higher loading and polymer base material（Such as than hot melt, ratio of viscosities） Composite thermodynamic property caused by difference reduces.Meanwhile nano-metal-oxide be blended into matrix material after not only not Change the macroscopic features of material（Such as color, light transmittance）, and other good characteristics of nano-metal-oxide particle are (as resisted Bacterium performance, ageing resistance and stronger ultraviolet screening ability impart the new potential Optimality of polymer composite Can, its application field can be widened.The cost of the NEW TYPE OF COMPOSITE antistatic additive is relatively low, and preparation method is simple, suitable for industrial metaplasia Production.
Brief description of the drawings
Fig. 1 (a) ~ (e) is followed successively by PS and eSTAT/PS, ZnO/eSTAT/PS, TiO2/ eSTAT/PS and Kaolin/ The outside drawing of eSTAT/PS composites.
Fig. 2 is PS materialsR v With the graph of a relation of the loading of composite antistatic agent.Wherein, it is multiple in (a) ~ (d) relation lines Close antistatic additive and be followed successively by eSTAT, ZnO/eSTAT, TiO2/ eSTAT and Kaolin/eSTAT.
Fig. 3 (a) ~ (d) is followed successively by eSTAT/PS, ZnO/eSTAT/PS, TiO2/ eSTAT/PS and Kaolin/eSTAT/PS The SEM figures of composite.
Fig. 4 is the TGA curve maps of composite.Wherein, (a) ~ (f) curves be followed successively by eSTAT, PS, eSTAT/PS, ZnO/eSTAT/PS、TiO2/ eSTAT/PS, Kaolin/eSTAT/PS TGA curves.
Fig. 5 is the thermal coefficient of expansion figure of composite.Wherein, (a) ~ (e) block diagrams are followed successively by PS, eSTAT/PS, ZnO/ eSTAT/PS、TiO2/ eSTAT/PS and Kaolin/eSTAT/PS thermal coefficient of expansion figure.
Fig. 6 is the tensile stress-strain curve figure of composite.Wherein, (a) ~ (e) curves are followed successively by PS, eSTAT/ PS、ZnO/eSTAT/PS、TiO2/ eSTAT/PS and Kaolin/eSTAT/PS tensile stress-strain curve figure.
Embodiment
The present invention is further illustrated below by embodiment, but protection scope of the present invention is not limited in embodiment.It is right The other changes and modifications that those skilled in the art makes in the case of without departing from the spirit and scope of protection of the present invention It is also included within the scope of the present invention.
Embodiment 1
（1）The preparation of permanent type Polymer-metallic Catalyst solution
By ZnO（Physical features are as shown in table 1）With Ionomer type Polymer-metallic Catalyst eSTAT（Physical features As shown in table 1）It is respectively put into vacuum drying chamber, in 60 DEG C of freeze-day with constant temperature 48 hours；Dried eSTAT 12.5g are dissolved In 150ml organic solvent 1-METHYLPYRROLIDONEs, ultrasound 120 minutes, working frequency 60kHz, power in ultrasonic disperse machine 150W, 25 DEG C of temperature；Then the solution is continued into stirring and dissolving 2 hours, obtains antistatic additive eSTAT solution；
The physical features of the polystyrene of table 1, nano-metal-oxide and Polymer-metallic Catalyst
（2）ZnO/eSTAT antistatic additive prepare composite antistatic agent
Dried ZnO 8.8g are added in above-mentioned antistatic additive eSTAT solution, the ultrasound 120 in ultrasonic disperse machine Minute, working frequency 60kHz, power 150W, 25 DEG C of temperature；Then the mixed solution is continued into stirring and dissolving 48 hours, stirring 25 DEG C, stir speed (S.S.) 800rpm of temperature, obtains ZnO/eSTAT antistatic additive mixed solutions, and it is separated, washed, is dried. Vacuum drying 24 hours, temperature 60 C, obtains ZnO/eSTAT composite antistatic agents；
（3）Application of the composite antistatic agent in high polymer material
Applying step of the ZnO/eSTAT composite antistatic agents of the present invention in PS is as follows：By 50.0g PS and 21.3g composite antistatic agent physical mixeds, carry out melt blending, blending temperature be 160~220 DEG C, shear rate be 5~ 120rpm, blending time are 5~15 minutes；
Then carry out molding and prepare test specimens, molding temperature is 180~210 DEG C, and pressure is 25~45kg/cm2, test specimens Part specification is the standard batten needed for 8~12cm of diameter, 0.5~3mm of thickness disk and other tests.
Fig. 1 (a), (b) and (c) are respectively high polymer material PS, composite eSTAT/PS, ZnO/eSTAT/PS standard Disk sample characteristics outside drawing.It is seen that after Polymer-metallic Catalyst eSTAT is blended into PS, composite is changed into White, and after being blended into the composite antistatic agent containing Nano-ZnO, composite is still white, does not change Polymer-metallic Catalyst ESTAT outward appearance uses characteristic.
(a) and (b) relation line in Fig. 2 is respectively composite eSTAT/PS, ZnO/eSTAT/PSR v With permanent type Relation curve between Polymer-metallic Catalyst eSTAT, composite antistatic agent filling usage amount.PS and its composite sample 'sR v Test reference standard be GB/T1410-2006（CompositeR v ＜ 1012 Ohm.cm is anti-static material）, PS'sR v It is worth for 1.02 × 1018 ohm.cm.(a) relation line in Fig. 2 shows that eSTAT filling usage amount is in below 30wt%, composite wood MaterialR v Value is between 1016 ~1017Between ohm/cm, too big change is had no.When eSTAT filling usage amount is 35 wt%,R v Value For 3.33 × 1014 Ohm.cm, show that composite inner locally initially forms electric charge Percolation Network structure.When blending 40wt%'s During eSTAT,R v It is worth for 2.32 × 1011Ohm.cm, composite have antistatic effect, show that now matrices of composite material is Form diafiltration conductive network structure.Then, with the increase of eSTAT blending amounts, compositeR v Value changes tend towards stability. Show the critical diafiltration conductive network loading of eSTAT in composite eSTAT/PS in 40wt% or so.Similarly, as in Fig. 2 (b) shown in relation line, in composite ZnO/eSTAT/PS, during eSTAT filling usage amount 20wt%, material internal is locally opened Beginning forms electric charge Percolation Network structure.When eSTAT filling usage amount increases to 30wt%, matrices of composite material forms the overall situation Conductive network structure is percolated, i.e., critical diafiltration conductive network loading uses in 30wt% or so, also, with eSTAT filling Amount continues to increase, compositeR v Value continues to be down to 8.73 × 108 Ohm.cm, with eSTAT'sR v Value 1.15 × 108 Ohm.cm is closer to.This shows that the addition of nano zine oxide, the critical diafiltration for significantly reducing eSTAT in PS matrixes is led Electric network usage amount.
Fig. 3 (a) and (b) are composite eSTAT/PS, ZnO/eSTAT/PS microscopic appearance figure, and eSTAT's fills out in figure It is 30wt% to fill usage amount.Fig. 3 (a) shows that eSTAT dispersivenesses are poor in PS matrixes, its compatibility between PS matrixes compared with Difference, because stronger affinity effect easily accumulation forms big microballoon between eSTAT.On the contrary, Fig. 3 (b) shows that eSTAT is in PS Dispersiveness preferably, is easily formed homogeneous texture in matrix.This is attributed to ZnO and eSTAT intermolecular interaction, so as to weaken ESTAT intermolecular interactions, cause eSTAT reunions probability to decline, so as to be advantageous to it preferably form conductive network knot Structure.
(a), (b), (c) and (d) curve in Fig. 4 are respectively eSTAT, PS, eSTAT/PS, ZnO/eSTAT/PS thermogravimetric Analysis（TGA）Curve.It can be seen from curve, after eSTAT is mixed into PS matrixes, its heat decomposition temperature is down to by 387.8 DEG C 376.7 DEG C, after opposite composite antistatic agent is mixed into PS matrixes, its heat decomposition temperature increases to 409.2 DEG C by 376.7 DEG C.In addition, Shown as the thermal coefficient of expansion of PS, eSTAT/PS and ZnO/eSTAT/PS shown in (a) in Fig. 5, (b) and (c) block diagram, Compared to eSTAT, after being blended with PS matrixes of composite antistatic agent, the thermal coefficient of expansion of composite can be significantly reduced.Therefore, The hot property that ZnO addition can improve the macromolecule matrix material as caused by eSTAT declines, and improves the thermostabilization of composite Property.
(a), (b) and (c) curve in Fig. 6 are respectively PS, eSTAT/PS, ZnO/eSTAT/PS tensile stress-strain Curve.ESTAT is introduced in PS matrixes, tensile strength, tensile modulus of elasticity, elongation at break and maximum stretching force have not Reduced with degree, and ZnO/eSTAT composite antistatic agents are blended into PS matrixes, related data is significantly increased（Table 2）, table Bright ZnO introducing can strengthen the tensile property of composite.
The mechanical property of the polystyrene of table 2 and its composite
。
Embodiment 2
（1）The preparation of permanent type Polymer-metallic Catalyst solution
By TiO2（Physical features are as shown in table 1）It is respectively put into Polymer-metallic Catalyst eSTAT in vacuum drying phase, in 60 DEG C of freeze-day with constant temperature 48 hours；The dried antistatic additive eSTAT of 12.5g are dissolved in 150ml organic solvent N- methylpyrroles In alkanone, ultrasound 120 minutes, working frequency 60kHz, power 150W, 25 DEG C of temperature, then mix this in ultrasonic disperse machine Solution continues stirring and dissolving 2 hours, obtains antistatic additive eSTAT solution；
（2）TiO2/ eSTAT antistatic additive prepare composite antistatic agent
By dried TiO2 8.8g is added in above-mentioned antistatic additive eSTAT solution, 120 points of the ultrasound in ultrasonic disperse machine Clock, working frequency 60kHz, power 150W, 25 DEG C of temperature；Then the mixed solution is continued into stirring and dissolving 48 hours, stirring temperature 25 DEG C of degree, stir speed (S.S.) 800rpm, obtains TiO2/ eSTAT antistatic additive mixed solutions, it is separated, washed, is dried； It is dried in vacuo 24 hours in 60 DEG C, obtains TiO2/ eSTAT composite antistatic agents；
（3）Application of the composite antistatic agent in high polymer material
By 50.0gPS and 21.3g composite antistatic agent physical mixeds, melt blending is carried out, blending temperature is 160~220 DEG C, shear rate is 5~120rpm, and the blending time is 5~15 minutes；
Then carry out molding and prepare test specimens, molding temperature is 180~210 DEG C, and pressure is 25~45kg/cm2, test specimens Part specification is the standard batten needed for 8~12cm of diameter, 0.5~3mm of thickness disk and other tests.
Fig. 1 (d) is composite TiO2/ eSTAT/PS normal disc sample outside drawing.According to Fig. 1 (a), (b) and (d) Understand, compared to eSTAT, add TiO2The matrix material of/eSTAT composite antistatic agents is still white, does not change macromolecule and resists Electrostatic agent eSTAT outward appearance uses characteristic.
(c) relation line in Fig. 2 is composite TiO2/ eSTAT/PS'sR v With TiO2/ eSTAT composite antistatic agents are filled out The relation curve filled between usage amount.Understood according to curve, composite TiO2/ eSTAT/PS critical diafiltration conductive network filling Amount continues to increase in 30 wt% or so, also, with eSTAT filling usage amount, compositeR v Value continue to be down to ESTAT'sR v Value is suitable.This shows nano-TiO2Addition significantly reduce the critical diafiltration conductive mesh of eSTAT in PS matrixes Network usage amount.
Fig. 3 (c) is composite TiO2/ eSTAT/PS microscopic appearance figure, compared with Fig. 3 (a), TiO2/ eSTAT is compound Antistatic additive dispersiveness in PS matrixes preferably, tends to form homogeneous texture.This is due to TiO2It is easy to occur mutually with eSTAT Effect, so as to reduce the intermolecular interactions of eSTAT, cause eSTAT reunions probability to decline, be advantageous to it and preferably formed Conductive network structure.
(e) curve in Fig. 4 is TiO2/ eSTAT/PS TGA curves.As shown in Figure 4, TiO2/ eSTAT composite anti-statics Agent improves PS heat decomposition temperature.In addition, (d) block diagram in Fig. 5 shows TiO2/ eSTAT/PS thermal coefficient of expansion shows Work is less than eSTAT/PS.Therefore, TiO2The hot property that the macromolecule matrix material as caused by eSTAT can be improved declines, so as to Improve the heat endurance of composite.
(d) curve in Fig. 6 is TiO2/ eSTAT/PS tensile stress-strain curve.By (b) curve in Fig. 6 and Table 2 understands that eSTAT is blended into PS matrixes, and tensile strength, tensile modulus of elasticity, elongation at break and maximum stretching force are equal There is different degrees of reduction.By TiO2/ eSTAT composite antistatic agents are blended into PS matrixes, and related data is significantly increased, This shows TiO2The tensile property of composite can be strengthened.
Embodiment 3
（1）The preparation of permanent type Polymer-metallic Catalyst solution
By Kaolin（Physical features are as shown in table 1）It is respectively put into Polymer-metallic Catalyst eSTAT in vacuum drying phase, In 60 DEG C of freeze-day with constant temperature 48 hours；Dried antistatic additive eSTAT 12.5g are dissolved in 150ml organic solvent N- methyl pyrroles In pyrrolidone, ultrasound 120 minutes, working frequency 60kHz, power 150W, 25 DEG C of temperature, then mix this in ultrasonic disperse machine Close solution and continue stirring and dissolving 2 hours, obtain antistatic additive eSTAT solution；
（2）Kaolin/eSTAT antistatic additive prepare composite antistatic agent
Dried Kaolin 8.8g are added in above-mentioned antistatic additive eSTAT solution, it is ultrasonic in ultrasonic disperse machine 120 minutes, the kHz of working frequency 60, power 150W, 25 DEG C of temperature, the mixed solution is persistently then stirred 48 hours to complete Dissolving, 25 DEG C, stir speed (S.S.) 800rpm of whipping temp, obtains Kaolin/eSTAT antistatic additive mixed solutions, it is divided From, washing, dry；It is dried in vacuo 24 hours at 60 DEG C, obtains Kaolin/eSTAT composite antistatic agents；
（3）Application of the composite antistatic agent in high polymer material
By 50.0gPS and 21.3g composite antistatic agent physical mixeds, melt blending is carried out, blending temperature is 160~220 DEG C, shear rate is 5~120rpm, and the blending time is 5~15 minutes；
Then carry out molding and prepare test specimens, molding temperature is 180~210 DEG C, and pressure is 25~45kg/cm2, test specimens Part specification is the standard batten needed for 8~12cm of diameter, 0.5~3mm of thickness disk and other tests.
Fig. 1 (e) is composite Kaolin/eSTAT/PS normal disc sample outside drawing.By Fig. 1 (a), (b) and (e) Understand, compared to eSTAT, the matrix material that Kaolin/eSTAT composite antistatic agents are blended is still white, does not change making for eSTAT Use characteristic.
(d) relation line in Fig. 2 is composite Kaolin/eSTAT/PS'sR v With Kaolin/eSTAT composite anti-statics Relation curve between agent loading.As seen from the figure, composite Kaolin/eSTAT/PS critical diafiltration conductive network filling Amount continues to increase in 30 wt% or so, also, with eSTAT filling usage amount, compositeR v Value continue to be down to ESTAT'sR v Value is suitable.This shows that Kaolin addition significantly reduces the critical diafiltration conductive network of eSTAT in PS matrixes Usage amount.
Fig. 3 (d) is composite Kaolin/eSTAT/PS microscopic appearance figure.Compared with Fig. 3 (a), Kaolin/eSTAT Composite antistatic agent dispersiveness in PS matrixes preferably, tends to form homogeneous texture.This is due to that Kaolin is easy to send out with eSTAT Raw interaction, reduces eSTAT intermolecular interactions, causes eSTAT reunions probability to decline, is advantageous to it and is preferably formed Conductive network structure.
The TGA curves that (f) curve in Fig. 4 is Kaolin/eSTAT/PS.From fig. 4, it can be seen that Kaolin/eSTAT is compound anti- Electrostatic agent can improve the heat decomposition temperature of PS composites.In addition, it can be seen that from (e) block diagram in Fig. 5：Kaolin/ ESTAT/PS thermal coefficient of expansion is lower than eSTAT/PS.Therefore, Kaolin addition can improve the high score as caused by eSTAT The hot property of sub- matrix material declines, and improves the heat endurance of composite.
The tensile stress-strain curve that (e) curve in Fig. 6 is Kaolin/eSTAT/PS.By (b) curve in Fig. 6 Visible with table 2, eSTAT is blended into PS matrixes, tensile strength, tensile modulus of elasticity, elongation at break and the maximum of system Tensile force has different degrees of reduction.Kaolin/eSTAT composite antistatic agents are blended into PS matrixes, related data is aobvious Write and improve, this shows that Kaolin can strengthen the tensile property of composite.

Claims (6)

  1. A kind of 1. preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst, it is characterised in that tool Body step is：
    （1）The drying process of nano-metal-oxide and Polymer-metallic Catalyst
    Nano-metal-oxide and Polymer-metallic Catalyst are respectively put into vacuum drying chamber, it is permanent at a temperature of 45~80 DEG C Temperature is dried 12~48 hours；
    （2）The preparation of Polymer-metallic Catalyst solution
    Dried Polymer-metallic Catalyst is dissolved in organic solvent, ultrasound 15~120 minutes, work in ultrasonic disperse machine 20~60kHz of working frequency, 50~200W of power, temperature are 20~70 DEG C；Then, the mixed solution is persistently stirred and heats 1 It is completely dissolved it within~6 hours, heating-up temperature is 60~120 DEG C, obtains Polymer-metallic Catalyst solution；
    （3）Nano-metal-oxide/Polymer-metallic Catalyst prepares composite antistatic agent
    Dried nano-metal-oxide is added in Polymer-metallic Catalyst solution, ultrasonic 15 in ultrasonic disperse machine~ 120 minutes, 20~60kHz of working frequency, 50~200W of power, temperature was 20~70 DEG C；Then, the mixed solution is persistently stirred Mixing 0.5~120 hour is completely dissolved it, and whipping temp is 20~150 DEG C, 50~2000rpm of stir speed (S.S.), obtains nanogold Belong to the mixed solution of oxide and Polymer-metallic Catalyst；
    The mixed solution of nano-metal-oxide and Polymer-metallic Catalyst is separated, washed, and in 40~80 DEG C of temperature Lower vacuum drying 12~60 hours, obtains nano-metal-oxide/high molecular composite antistatic agent；
    Wherein, the Polymer-metallic Catalyst is eSTAT；The quality of the nano-metal-oxide and Polymer-metallic Catalyst is matched somebody with somebody Than for 1:1~1:100.
  2. 2. the preparation side of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst as claimed in claim 1 Method, it is characterised in that step（1）In, the nano-metal-oxide is nano zine oxide or nano titanium oxide, and particle diameter is 50 Between~2000nm.
  3. 3. the preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst as claimed in claim 2, It is characterized in that step（2）In, the organic solvent is 1-METHYLPYRROLIDONE；The stirring is stirred for electromagnetic agitation or machinery Mix.
  4. 4. the preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst as claimed in claim 3, It is characterized in that step（3）In, the separation method is that normal pressure filters, vacuum decompression is dried and removes solvent.
  5. 5. nano-metal-oxide/Polymer-metallic Catalyst that the preparation method according to one of claim 1-4 obtains Composite antistatic agent.
  6. 6. application of the composite antistatic agent as claimed in claim 5 in antistatic macromolecule material is prepared.
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CN104945730B (en) * 2015-05-28 2017-10-10 复旦大学 Nucleator and high molecular composite antistatic agent and its preparation method and application
CN105218970B (en) * 2015-09-30 2017-07-25 东莞市华立实业股份有限公司 A kind of antistatic PVC base wood-plastic composite materials and preparation method thereof
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CN107418108A (en) * 2017-07-17 2017-12-01 广州市兴胜杰科技有限公司 A kind of antistatic teflon film and preparation method and application
CN109320968B (en) * 2018-09-04 2021-11-02 广州市瑞合新材料科技有限公司 Composite permanent antistatic agent and application thereof
CN111662528B (en) * 2020-07-13 2022-07-15 西南科技大学 PMMA/PC-based ultrathin composite optical film and preparation method and application thereof
CN112321415B (en) * 2020-09-30 2023-04-28 南通新邦化工科技有限公司 Method and device for eliminating static electricity of calcium stearate

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CN1670118A (en) * 2005-03-11 2005-09-21 华南理工大学 Polymer base antistatic agent and method for preparing same

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