CN104788865A - Composite antistatic agent of nano-metal oxide/polymer antistatic agent, as well as preparation method and application of composite antistatic agent - Google Patents
Composite antistatic agent of nano-metal oxide/polymer antistatic agent, as well as preparation method and application of composite antistatic agent Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer materials, particularly relates to a composite antistatic agent of a nano-metal oxide/polymer antistatic agent, as well as a preparation method and application of the composite antistatic agent. The composite antistatic agent is a compound of commercialized polymer antistatic agent and nano-metal oxide, and is applied to the antistatic polymer materials. The composite antistatic agent not only has excellent antistatic performance, permanent static protection function, less environmental humidity influence and other characteristics of a mother antistatic agent, but also can significantly reduce the filling usage amount and production cost of the mother antistatic agent in the polymer materials through the nanometer effect of nano-metal oxide and the interaction with polymer antistatic agent molecules, so as to improve the thermodynamic properties of polymer materials. The excellent antibacterial and anti-aging properties and strong ultraviolet shielding ability of nano-metal oxide give the polymer materials new potential excellent properties and broaden the application field of the polymer materials. The novel polymer composite antistatic agent is low in cost, simple in preparation method, and suitable for industrial production.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to composite antistatic agent of a kind of nano-metal-oxide/Polymer-metallic Catalyst and its preparation method and application.
Background technology
Macromolecular material obtains widespread use with its cheap price, outstanding electrical insulation capability, chemical resistance and good processing characteristics etc.But macromolecular material in use, because of external environment influence very easily build up of electrostatic charge such as friction, foreign field inductions, causes device surface dust suction, film is closed, electron device punctures, shocks by electricity and the disaster such as blast.For eliminating electrostatic hazard, industrial usually by the method for adding static inhibitor in polymer base material reduce macromolecular material surface resistivity (Surface resistivity,
r s ) or volume specific resistance (Volume resistivity,
r v ).Low molecular weight surfactants type static inhibitor is static inhibitor conventional at present, and its antistatic mechanism utilizes this static inhibitor to reduce at material surface adsorption moisture
r s , reach anlistatig effect.In use there is many defects in this type of static inhibitor, as poor durability, non-scrubbing resistance, the heat resisting temperature that reduce material large to the dependency of ambient moisture and surface property etc., and it has a negative impact to environment after polymer base material departs from.
The weather resistance improving static inhibitor is one of important research direction of static inhibitor high performance.In order to make up the defect of Small molecular surfactant type static inhibitor, conductive filler material (metal and metal oxide or carbon-based material) is introduced in macromolecular material to improve the weather resistance of static inhibitor by people, its antistatic mechanism utilizes these fillers in macromolecule matrix, to form diafiltration conductive network with dissipation of static charge, reaches anlistatig effect.But the formation of this transferring charge passage needs a large amount of conductive filler materials, this will cause macromolecular material not easy coloring, filler easily come off or be oxidized and degradation shortcoming under macromolecular material physical property, make it limited in the application in polymeric antistatic field.
Polymer-metallic Catalyst is a class containing polymkeric substance that is hydrophilic or conductive unit, is characterized in that antistatic effect is lastingly and substantially not by the impact of environment.Polymer-metallic Catalyst and hydrophobic polymer matrix blended after can obtain the polymer composite with permanence antistatic performance.This matrix material not only maintains the fundamental property of macromolecule matrix preferably, and its antistatic effect is lasting, without inductive phase, does not affect by the condition such as wiping and washing, and show good and stable antistatic effect in wider humidity range.But, various problem is inevitably there is in Polymer-metallic Catalyst use procedure, as on the high side in permanent type Polymer-metallic Catalyst self, form the filling usage quantity of static charge inside leakage needed for network also higher, and the physico-chemical property difference between itself and macromolecule matrix material will cause the decline of macromolecular material thermal characteristics and mechanical property.Therefore, main purpose of the present invention is the filling usage quantity being controlled permanent type Polymer-metallic Catalyst by simple effective method, and improves thermal characteristics and the mechanical property of macromolecular material.
The present invention utilize the nano effect of nano-metal-oxide particle and with the intermolecular interaction of permanent type Polymer-metallic Catalyst (as Van der Waals force and hydrogen bond), effectively to reduce macromolecular material
r v .The introducing of nano-metal-oxide can reduce the filling usage quantity of permanent type Polymer-metallic Catalyst, improve thermal characteristics and the mechanical property of macromolecular material, make macromolecular material possess other good characteristic of nano-metal-oxide particle, characteristic as new in anti-microbial property, resistance of aging and stronger ultraviolet screening ability etc. simultaneously.
Summary of the invention
The composite antistatic agent of the nano-metal-oxide/Polymer-metallic Catalyst that the object of the present invention is to provide a kind of antistatic property lasting and cheap, and the preparation method of this composite antistatic agent and the application in macromolecular material thereof.
The preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst provided by the present invention, its concrete preparation process is as follows:
(1) drying treatment of nano-metal-oxide, permanent type Polymer-metallic Catalyst
Nano-metal-oxide and permanent type Polymer-metallic Catalyst are placed in vacuum drying oven respectively, at 45 ~ 80 DEG C of temperature, freeze-day with constant temperature 12 ~ 48 hours;
(2) preparation of permanent type Polymer-metallic Catalyst solution
Dried permanent type Polymer-metallic Catalyst is dissolved in organic solvent, in ultrasonic disperse machine ultrasonic 15 ~ 120 minutes, operating frequency 20 ~ 60kHz, power 50 ~ 200W, temperature 20 ~ 70 DEG C; Then, by little of dissolving completely for the heating 1 ~ 6 of this mixing solutions Keep agitation, Heating temperature 60 ~ 120 DEG C, obtains permanent type 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 organic solution, in ultrasonic disperse machine ultrasonic 15 ~ 120 minutes, operating frequency 20 ~ 60kHz, power 50 ~ 200W, temperature 20 ~ 70 DEG C; Then, dissolved 0.5 ~ 120 hour by this mixing solutions Keep agitation, whipping temp 20 ~ 150 DEG C, stir speed (S.S.) 50 ~ 2000rpm, obtains the mixing solutions of nano-metal-oxide and permanent type Polymer-metallic Catalyst;
Subsequently this mixing solutions is carried out being separated, washing, and vacuum-drying 12 ~ 60 hours at 40 ~ 80 DEG C, finally obtain the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst.
In the present invention, in step (1), described permanent type Polymer-metallic Catalyst be comprise polymer molecule segment lipophilic fraction and there is the inorganic salts ionic hydrophilic group that can dissociate, comprise salt and the polystyrene sulfonate salt of polyacrylate, maleic anhydride and other unsaturated monomer multipolymer.
In the present invention, in step (1), described nano-metal-oxide is: particle diameter is between 50 ~ 2000nm, and specific conductivity is characterized as semiconductor material, and appearance luster is white powder, and effective constituent is simple substance or mixture.Described nano-metal-oxide is ZnO, TiO
2and Kaolin.
In the present invention, in step (2), described organic solvent is N-Methyl pyrrolidone, or is the good solvent of permanent type Polymer-metallic Catalyst; Described stirring is induction stirring or mechanical stirring.
In the present invention, in step (3), described separation method is normal pressure suction filtration, solvent is removed in vacuum decompression drying; Described washing methods is: by quantitative with permanent type Polymer-metallic Catalyst meltage 1 ~ 10 times of the good solvent of permanent type Polymer-metallic Catalyst, wash 1 ~ 10 time.
In the present invention, composite antistatic agent is preparing the application in antistatic macromolecule material, and after it adopts melting or solution blending, injection moulding, mold pressing or mixing solutions knifing, to water film shaping.Wherein:
The concrete preparation process of melt blending processing method is as follows:
Vacuum-drying 12 ~ 48h at 60 ~ 120 DEG C by prepared composite antistatic agent and macromolecular material, after physical mixed is even, carry out melt blending, blending temperature is 160 ~ 220 DEG C, and shearing rate is 5 ~ 120rpm, and the blended time is 5 ~ 15 minutes;
Then carry out mold pressing and prepare test sample, molding temperature is 180 ~ 210 DEG C, and pressure is 25 ~ 45kg/cm
2, test sample specification is diameter 8 ~ 12cm, the disk of thickness 0.5 ~ 3mm and other test needed for standard batten.
The concrete preparation process of solution blending processing method is as follows:
By prepared composite antistatic agent and macromolecular material vacuum-drying 12 ~ 48h at 80 ~ 120 DEG C of temperature respectively; Quantitative composite antistatic agent is joined in the N-Methyl pyrrolidone solvent of 2 ~ 15 times of mass ratioes, ultrasonic disperse 0.5 ~ 5 hour, operating frequency 20 ~ 60 kHz, power 50 ~ 1500W, temperature 20 ~ 70 DEG C, obtain the dispersed mixed solution of composite antistatic agent;
Then, joined by macromolecular material in this mixing solutions, Keep agitation dissolves 0.5 ~ 130 hour, whipping temp 20 ~ 150 DEG C, and stir speed (S.S.) 50 ~ 2000rpm, obtains the blend solution of composite antistatic agent/macromolecular material; Carry out in a mold watering film or knifing with by this mixing solutions, namely obtain test sample after then the mould of load mixed solution being carried out the vacuum-drying demoulding, vacuum-drying temperature is 60 ~ 120 DEG C, and time of drying is 2 ~ 48 hours.
In the present invention, composite antistatic agent is preparing the application in antistatic macromolecule material, and wherein the proportioning of composite antistatic agent and macromolecular material is the mass ratio of 1:1 ~ 1:50.
In the present invention, described macromolecular material is polystyrene (PS).
The present invention adopts novel business-like permanent type Polymer-metallic Catalyst to be parent, by physical blending process, it is blended with cheap nano-metal-oxide, is prepared into a kind of novel composite antistatic agent, is applied to antistatic macromolecule material.It is less by the humidity effect of environment that this NEW TYPE OF COMPOSITE static inhibitor not only has the excellent antistatic capability of parent static inhibitor, permanent antistatic protection function and electrostatic dissipation ability, the filling usage quantity of permanent type Polymer-metallic Catalyst in matrix material can be reduced simultaneously, thus improve thermal characteristics and the mechanical property of matrix material.This NEW TYPE OF COMPOSITE static inhibitor by the nano effect of nano-metal-oxide particle and with the intermolecular interaction of permanent type Polymer-metallic Catalyst (as Van der Waals force and hydrogen bond), be not only conducive to improving the various problems that the latter in use occurs: as the matrix material thermomechanical property formed in polymer base material caused by physico-chemical property (as than hot melt, the viscosity ratio) difference between loading level higher needed for static charge inside dissipative network and polymer base material reduces.Simultaneously, nano-metal-oxide is blended into the macroscopic features (as color, transmittance) not only not changing material after in body material, and other good characteristic of nano-metal-oxide particle (as anti-microbial property, resistance of aging and stronger ultraviolet screening ability impart the new potential premium properties of polymer composite, can widen its Application Areas.The cost of this NEW TYPE OF COMPOSITE static inhibitor is lower, and preparation method is simple, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 (a) ~ (e) is followed successively by PS and eSTAT/PS, ZnO/eSTAT/PS, TiO
2the outside drawing of/eSTAT/PS and Kaolin/eSTAT/PS matrix material.
Fig. 2 is PS material
r v with the graph of a relation of the loading level of composite antistatic agent.Wherein, in (a) ~ (d) relation line, composite antistatic agent is followed successively by eSTAT, ZnO/eSTAT, TiO
2/ eSTAT and Kaolin/eSTAT.
Fig. 3 (a) ~ (d) is followed successively by eSTAT/PS, ZnO/eSTAT/PS, TiO
2the SEM figure of/eSTAT/PS and Kaolin/eSTAT/PS matrix material.
Fig. 4 is the TGA graphic representation of matrix material.Wherein, (a) ~ (f) curve is followed successively by eSTAT, PS, eSTAT/PS, ZnO/eSTAT/PS, TiO
2the TGA curve of/eSTAT/PS, Kaolin/eSTAT/PS.
Fig. 5 is the thermal expansivity figure of matrix material.Wherein, (a) ~ (e) histogram is followed successively by PS, eSTAT/PS, ZnO/eSTAT/PS, TiO
2the thermal expansivity figure of/eSTAT/PS and Kaolin/eSTAT/PS.
Fig. 6 is the tensile stress-strain curve figure of matrix material.Wherein, (a) ~ (e) curve is followed successively by PS, eSTAT/PS, ZnO/eSTAT/PS, TiO
2the tensile stress-strain curve figure of/eSTAT/PS and Kaolin/eSTAT/PS.
Embodiment
Further illustrate the present invention below by embodiment, but protection scope of the present invention is not limited in embodiment.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 are also included within scope.
embodiment 1
(1) preparation of permanent type Polymer-metallic Catalyst solution
By as shown in table 1 for ZnO(physical features) and Ionomer type Polymer-metallic Catalyst eSTAT(physical features as shown in table 1) put into vacuum drying oven respectively, in 60 DEG C of freeze-day with constant temperature 48 hours; Dried eSTAT 12.5g is dissolved in 150ml organic solvent N-Methyl pyrrolidone, in ultrasonic disperse machine ultrasonic 120 minutes, operating frequency 60kHz, power 150W, temperature 25 DEG C; Then this solution Keep agitation is dissolved 2 hours, obtain the solution of static inhibitor eSTAT;
The physical features of table 1 polystyrene, nano-metal-oxide and Polymer-metallic Catalyst
(2)
composite antistatic agent prepared by ZnO/eSTAT static inhibitor
Dried ZnO 8.8g is joined in above-mentioned static inhibitor eSTAT solution, in ultrasonic disperse machine ultrasonic 120 minutes, operating frequency 60kHz, power 150W, temperature 25 DEG C; Then this mixing solutions Keep agitation is dissolved 48 hours, whipping temp 25 DEG C, stir speed (S.S.) 800rpm, obtains ZnO/eSTAT static inhibitor mixing solutions, it is separated, washs, dry.Vacuum-drying 24 hours, temperature 60 C, obtains ZnO/eSTAT composite antistatic agent;
(3) application of composite antistatic agent in macromolecular material
The applying step of ZnO/eSTAT composite antistatic agent of the present invention in PS is as follows: by PS and the 21.3g composite antistatic agent physical mixed of 50.0g, carry out melt blending, blending temperature is 160 ~ 220 DEG C, and shearing rate is 5 ~ 120rpm, and the blended time is 5 ~ 15 minutes;
Then carry out mold pressing and prepare test specimens, molding temperature is 180 ~ 210 DEG C, and pressure is 25 ~ 45kg/cm
2, test sample specification is diameter 8 ~ 12cm, the disk of thickness 0.5 ~ 3mm and other test needed for standard batten.
Fig. 1 (a), (b) and (c) are respectively the normal disc sample characteristics outside drawing of macromolecular material PS, matrix material eSTAT/PS, ZnO/eSTAT/PS.As can be seen from Figure, Polymer-metallic Catalyst eSTAT is blended into after in PS, and matrix material becomes white, and after being blended into the composite antistatic agent containing Nano-ZnO, matrix material is still white, does not change the outward appearance service performance of Polymer-metallic Catalyst eSTAT.
(a) and (b) relation line in Fig. 2 is respectively matrix material eSTAT/PS, ZnO/eSTAT/PS's
r v and permanent type Polymer-metallic Catalyst eSTAT, composite antistatic agent fill the relation curve between usage quantity.PS and composite sample thereof
r v test reference standard be GB/T1410-2006(matrix material
r v < 10
12ohm.cm is antistatic material), PS's
r v value is 1.02 × 10
18ohm.cm.In Fig. 2 (a) relation line display, the filling usage quantity of eSTAT at below 30wt%, matrix material
r v value is between 10
16~ 10
17between ohm/cm, there is no too large change.When the filling usage quantity of eSTAT is 35 wt%,
r v value is 3.33 × 10
14ohm.cm, shows that composite inner local starts to form electric charge Percolation Network structure.As the eSTAT of blended 40wt%,
r v value is 2.32 × 10
11ohm.cm, matrix material has antistatic effect, shows that now matrices of composite material has formed diafiltration conductive network structure.Then, along with the increase of eSTAT blending amount, matrix material
r v value change tends towards stability.Show that the critical diafiltration conductive network loading level of eSTAT in matrix material eSTAT/PS is at about 40wt%.In like manner, as shown in (b) relation line in Fig. 2, in matrix material ZnO/eSTAT/PS, during the filling usage quantity 20wt% of eSTAT, material internal local starts to form electric charge Percolation Network structure.When the filling usage quantity of eSTAT is increased to 30wt%, matrices of composite material forms overall diafiltration conductive network structure, and namely critical diafiltration conductive network loading level is at about 30wt%, and, along with the continuation of the filling usage quantity of eSTAT increases, matrix material
r v value continues to be down to 8.73 × 10
8ohm.cm, with eSTAT's
r v value 1.15 × 10
8ohm.cm is comparatively close.This shows, adding of nano zine oxide, significantly reduces the critical diafiltration conductive network usage quantity of eSTAT in PS matrix.
The microscopic appearance figure that Fig. 3 (a) and (b) are matrix material eSTAT/PS, ZnO/eSTAT/PS, in figure, the filling usage quantity of eSTAT is 30wt%.Fig. 3 (a) shows, in PS matrix, eSTAT dispersiveness is poor, and the consistency between itself and PS matrix is poor, easily gathers form large microballoon between eSTAT due to stronger avidity effect.On the contrary, Fig. 3 (b) shows, and eSTAT is better dispersed in PS matrix, is easy to form homogeneous texture.This is owing to the molecular interaction of ZnO and eSTAT, thus reduces eSTAT molecular interaction, causes eSTAT reunion probability to decline, thus is conducive to it and forms conductive network structure better.
(a), (b), (c) in Fig. 4 and (d) curve are respectively thermogravimetric analysis (TGA) curve of eSTAT, PS, eSTAT/PS, ZnO/eSTAT/PS.According to curve, after being mixed into eSTAT in PS matrix, its heat decomposition temperature is down to 376.7 DEG C by 387.8 DEG C, and contrary composite antistatic agent is mixed into after in PS matrix, and its heat decomposition temperature increases to 409.2 DEG C by 376.7 DEG C.In addition, shown by the thermal expansivity of PS, eSTAT/PS and the ZnO/eSTAT/PS shown in (a), (b) and (c) histogram in Fig. 5, compare eSTAT, composite antistatic agent blended with PS matrix after, significantly can reduce the thermal expansivity of matrix material.Therefore, the thermal characteristics can improving the macromolecule matrix material caused by eSTAT that adds of ZnO declines, and improves the thermostability of matrix material.
(a), (b) and (c) curve in Fig. 6 is respectively the tensile stress-strain curve of PS, eSTAT/PS, ZnO/eSTAT/PS.ESTAT is introduced in PS matrix, tensile strength, modulus in tension, elongation at break and maximum stretching force all have and reduce in various degree, and ZnO/eSTAT composite antistatic agent is blended in PS matrix, related data is all significantly increased (table 2), shows that the introducing of ZnO can the tensile property of reinforced composite.
The mechanical property of table 2 polystyrene and matrix material thereof
。
embodiment 2
(1) preparation of permanent type Polymer-metallic Catalyst solution
By TiO
2(physical features is as shown in table 1) and Polymer-metallic Catalyst eSTAT put into vacuum-drying mutually respectively, in 60 DEG C of freeze-day with constant temperature 48 hours; Dried for 12.5g static inhibitor eSTAT is dissolved in 150ml organic solvent N-Methyl pyrrolidone, in ultrasonic disperse machine ultrasonic 120 minutes, operating frequency 60kHz, power 150W, temperature 25 DEG C, then this mixing solutions Keep agitation is dissolved 2 hours, obtain the solution of static inhibitor eSTAT;
(2) TiO
2composite antistatic agent prepared by/eSTAT static inhibitor
By dried TiO
28.8g adds in above-mentioned static inhibitor eSTAT solution, in ultrasonic disperse machine ultrasonic 120 minutes, operating frequency 60kHz, power 150W, temperature 25 DEG C; Then this mixing solutions Keep agitation is dissolved 48 hours, whipping temp 25 DEG C, stir speed (S.S.) 800rpm, obtains TiO
2/ eSTAT static inhibitor mixing solutions, is separated it, washs, dry; In 60 DEG C of vacuum-dryings 24 hours, obtain TiO
2/ eSTAT composite antistatic agent;
(3) application of composite antistatic agent in macromolecular material
By 50.0gPS and 21.3g composite antistatic agent physical mixed, carry out melt blending, blending temperature is 160 ~ 220 DEG C, and shearing rate is 5 ~ 120rpm, and the blended time is 5 ~ 15 minutes;
Then carry out mold pressing and prepare test specimens, molding temperature is 180 ~ 210 DEG C, and pressure is 25 ~ 45kg/cm
2, test sample specification is diameter 8 ~ 12cm, the disk of thickness 0.5 ~ 3mm and other test needed for standard batten.
Fig. 1 (d) is matrix material TiO
2the normal disc sample outside drawing of/eSTAT/PS.According to Fig. 1 (a), (b) and (d) known, compare eSTAT, add TiO
2the body material of/eSTAT composite antistatic agent is still white, does not change the outward appearance service performance of Polymer-metallic Catalyst eSTAT.
(c) relation line in Fig. 2 is matrix material TiO
2/ eSTAT/PS's
r v with TiO
2/ eSTAT composite antistatic agent fills the relation curve between usage quantity.Known according to curve, matrix material TiO
2the critical diafiltration conductive network loading level of/eSTAT/PS at about 30 wt%, and, along with the continuation of the filling usage quantity of eSTAT increases, matrix material
r v value continues to be down to eSTAT's
r v value quite.This shows nano-TiO
2add the critical diafiltration conductive network usage quantity significantly reducing eSTAT in PS matrix.
Fig. 3 (c) is matrix material TiO
2the microscopic appearance figure of/eSTAT/PS, compared with Fig. 3 (a), TiO
2/ eSTAT composite antistatic agent is better dispersed in PS matrix, is tending towards forming homogeneous texture.This is due to TiO
2be easy to interact with eSTAT, thus reduce the intermolecular interaction of eSTAT, cause eSTAT reunion probability to decline, be conducive to it and form conductive network structure better.
(e) curve in Fig. 4 is TiO
2the TGA curve of/eSTAT/PS.As shown in Figure 4, TiO
2/ eSTAT composite antistatic agent improves the heat decomposition temperature of PS.In addition, (d) histogram display TiO in Fig. 5
2the thermal expansivity of/eSTAT/PS is significantly lower than eSTAT/PS.Therefore, TiO
2the thermal characteristics can improving the macromolecule matrix material caused by eSTAT declines, thus improves the thermostability of matrix material.
(d) curve in Fig. 6 is TiO
2the tensile stress-strain curve of/eSTAT/PS.From (b) curve in Fig. 6 and table 2, eSTAT is blended in PS matrix, and tensile strength, modulus in tension, elongation at break and maximum stretching force all have reduction in various degree.By TiO
2/ eSTAT composite antistatic agent is blended in PS matrix, and related data is all significantly increased, and this shows TiO
2can the tensile property of reinforced composite.
embodiment 3
(1) preparation of permanent type Polymer-metallic Catalyst solution
By as shown in table 1 for Kaolin(physical features) and Polymer-metallic Catalyst eSTAT put into vacuum-drying respectively mutually, in 60 DEG C of freeze-day with constant temperature 48 hours; Dried static inhibitor eSTAT 12.5g is dissolved in 150ml organic solvent N-Methyl pyrrolidone, in ultrasonic disperse machine ultrasonic 120 minutes, operating frequency 60kHz, power 150W, temperature 25 DEG C, then this mixing solutions Keep agitation is dissolved 2 hours, obtain the solution of static inhibitor eSTAT;
(2) composite antistatic agent prepared by Kaolin/eSTAT static inhibitor
Dried Kaolin 8.8g is added in above-mentioned static inhibitor eSTAT solution, in ultrasonic disperse machine ultrasonic 120 minutes, operating frequency 60 kHz, power 150W, temperature 25 DEG C, then by little for this mixing solutions Keep agitation 48 up to dissolving completely, whipping temp 25 DEG C, stir speed (S.S.) 800rpm, obtains Kaolin/eSTAT static inhibitor mixing solutions, is separated, washs it, dry; At 60 DEG C, vacuum-drying 24 hours, obtains Kaolin/eSTAT composite antistatic agent;
(3) application of composite antistatic agent in macromolecular material
By 50.0gPS and 21.3g composite antistatic agent physical mixed, carry out melt blending, blending temperature is 160 ~ 220 DEG C, and shearing rate is 5 ~ 120rpm, and the blended time is 5 ~ 15 minutes;
Then carry out mold pressing and prepare test specimens, molding temperature is 180 ~ 210 DEG C, and pressure is 25 ~ 45kg/cm
2, test sample specification is diameter 8 ~ 12cm, the disk of thickness 0.5 ~ 3mm and other test needed for standard batten.
The normal disc sample outside drawing that Fig. 1 (e) is matrix material Kaolin/eSTAT/PS.From Fig. 1 (a), (b) and (e), compare eSTAT, the body material of blended Kaolin/eSTAT composite antistatic agent is still white, does not change the service performance of eSTAT.
(d) relation line in Fig. 2 is matrix material Kaolin/eSTAT/PS's
r v and the relation curve between Kaolin/eSTAT composite antistatic agent loading level.As seen from the figure, the critical diafiltration conductive network loading level of matrix material Kaolin/eSTAT/PS at about 30 wt%, and, along with the continuation of the filling usage quantity of eSTAT increases, matrix material
r v value continues to be down to eSTAT's
r v value quite.This shows that Kaolin's adds the critical diafiltration conductive network usage quantity significantly reducing eSTAT in PS matrix.
The microscopic appearance figure that Fig. 3 (d) is matrix material Kaolin/eSTAT/PS.Compared with Fig. 3 (a), Kaolin/eSTAT composite antistatic agent is better dispersed in PS matrix, is tending towards forming uniform texture.This is because Kaolin is easy to interact with eSTAT, reduces eSTAT molecular interaction, causes eSTAT reunion probability to decline, is conducive to it and forms conductive network structure better.
(f) curve in Fig. 4 is the TGA curve of Kaolin/eSTAT/PS.As seen from Figure 4, Kaolin/eSTAT composite antistatic agent can improve the heat decomposition temperature of PS matrix material.In addition, lower than eSTAT/PS as can be seen from the thermal expansivity of (e) histogram in Fig. 5: Kaolin/eSTAT/PS.Therefore, the thermal characteristics can improving the macromolecule matrix material caused by eSTAT that adds of Kaolin declines, and improves the thermostability of matrix material.
(e) curve in Fig. 6 is the tensile stress-strain curve of Kaolin/eSTAT/PS.From (b) curve in Fig. 6 and table 2, eSTAT is blended in PS matrix, and the tensile strength of system, modulus in tension, elongation at break and maximum stretching force all have and reduce in various degree.Be blended in PS matrix by Kaolin/eSTAT composite antistatic agent, related data is significantly increased, and this shows that Kaolin can the tensile property of reinforced composite.
Claims (10)
1. a preparation method for the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst, is characterized in that concrete steps are:
(1) drying treatment of nano-metal-oxide and Polymer-metallic Catalyst
Nano-metal-oxide and Polymer-metallic Catalyst are put into vacuum drying oven respectively, at 45 ~ 80 DEG C of temperature, freeze-day with constant temperature 12 ~ 48 hours;
(2) preparation of Polymer-metallic Catalyst solution
Dried Polymer-metallic Catalyst is dissolved in organic solvent, in ultrasonic disperse machine ultrasonic 15 ~ 120 minutes, operating frequency 20 ~ 60kHz, power 50 ~ 200W, temperature is 20 ~ 70 DEG C; Then, heated and make it dissolve completely in 1 ~ 6 hour by this mixing solutions Keep agitation, Heating temperature is 60 ~ 120 DEG C, obtains Polymer-metallic Catalyst solution;
(3) nano-metal-oxide/Polymer-metallic Catalyst prepares composite antistatic agent
Added by dried nano-metal-oxide in Polymer-metallic Catalyst solution, in ultrasonic disperse machine ultrasonic 15 ~ 120 minutes, operating frequency 20 ~ 60kHz, power 50 ~ 200W, temperature is 20 ~ 70 DEG C; Then, within 0.5 ~ 120 hour, make it dissolve completely this mixing solutions Keep agitation, whipping temp is 20 ~ 150 DEG C, and stir speed (S.S.) 50 ~ 2000rpm obtains the mixing solutions of nano-metal-oxide static inhibitor and Polymer-metallic Catalyst;
Nano-metal-oxide and the mixing solutions of Polymer-metallic Catalyst are carried out being separated, washing, and vacuum-drying 12 ~ 60 hours at 40 ~ 80 DEG C of temperature, obtain nano-metal-oxide/high molecular composite antistatic agent.
2. the preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst as claimed in claim 1, it is characterized in that in step (1), described Polymer-metallic Catalyst be comprise polymer molecule segment lipophilic fraction and there is the inorganic salts ionic hydrophilic group that can dissociate.
3. the preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst as claimed in claim 1 or 2, it is characterized in that in step (1), described nano-metal-oxide static inhibitor is nano-metal-oxide is nano zine oxide, nano titanium oxide or nano kaoline, particle diameter is between 50 ~ 2000nm, and specific conductivity is semi-conductor.
4. the preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst as claimed in claim 3, is characterized in that, in step (2), described organic solvent is N-Methyl pyrrolidone, or is the good solvent of Polymer-metallic Catalyst; Described stirring is induction stirring or mechanical stirring.
5. the preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst as claimed in claim 4, is characterized in that in step (3), and described separation method is normal pressure suction filtration, solvent is removed in vacuum decompression drying; Described washing methods is: by quantitative with its meltage 1 ~ 10 times of the good solvent of composite antistatic agent, wash 1 ~ 10 time.
6. the preparation method of the composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst as claimed in claim 5, it is characterized in that in step (3), the quality proportioning of described nano-metal-oxide and Polymer-metallic Catalyst is 1:1 ~ 1:100.
7. according to the composite antistatic agent of the nano-metal-oxide/Polymer-metallic Catalyst of the preparation method's acquisition one of claim 1-6 Suo Shu.
8. composite antistatic agent as claimed in claim 7 is preparing the application in antistatic macromolecule material.
9. composite antistatic agent according to claim 8 is preparing the application in antistatic macromolecule material, it is characterized in that by composite antistatic agent and macromolecular material by after melt blending, and injection moulding, mold pressing or mixing solutions knifing, to water film shaping; The concrete steps of melt blending processing method are as follows:
By the vacuum-drying 12 ~ 48 hours at 60 ~ 120 DEG C of composite antistatic agent and macromolecular material, physical mixed evenly after, carry out melt blending, blending temperature is 160 ~ 210 DEG C, and shearing rate is 5 ~ 120rpm, and the blended time is 5 ~ 15 minutes;
Then, carry out mold pressing and prepare test sample, molding temperature is 180 ~ 210 DEG C, and pressure is 25 ~ 45kg/cm
2, test sample specification is diameter 8 ~ 12cm, the disk of thickness 0.5 ~ 3mm and other test needed for standard batten;
Or after composite antistatic agent and macromolecular material are adopted solution blending, injection moulding, mold pressing or mixing solutions knifing, to water film shaping; Solution blending processing method concrete steps are as follows:
By the vacuum-drying 12 ~ 48 hours at 80 ~ 120 DEG C of temperature respectively of composite antistatic agent and macromolecular material; Quantitative composite antistatic agent is joined in the N-Methyl pyrrolidone of 2 ~ 15 times of mass ratioes, ultrasonic disperse 0.5 ~ 5 hour, operating frequency 20 ~ 60kHz, power 50 ~ 1500W, temperature 20 ~ 70 DEG C, obtain the dispersed mixing solutions of composite antistatic agent;
Joined by macromolecular material in above-mentioned mixing solutions, Keep agitation dissolves 0.5 ~ 130 hour, whipping temp 20 ~ 150 DEG C, and stir speed (S.S.) 50 ~ 2000rpm, obtains the blend solution of composite antistatic agent/macromolecular material;
Carry out in a mold watering film or knifing with by this mixing solutions, namely obtain test sample after the mould of load mixed solution is carried out the vacuum-drying demoulding, vacuum-drying temperature is 60 ~ 120 DEG C, and time of drying is 2 ~ 48 hours.
10. composite antistatic agent according to claim 9 is preparing the application in antistatic macromolecule material, it is characterized in that the mass ratio that the use proportioning of composite antistatic agent and macromolecular material is 1:1 ~ 1:50; Described macromolecular material is polystyrene.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104945730A (en) * | 2015-05-28 | 2015-09-30 | 复旦大学 | Nucleating agent and polymer composite antistatic agent, preparation method and applications thereof |
| CN105504758A (en) * | 2016-01-26 | 2016-04-20 | 湖北工程学院 | High-strength antistatic transparent polycarbonate film and preparing method thereof |
| 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 |
| 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 |
| CN109320968A (en) * | 2018-09-04 | 2019-02-12 | 广州市瑞合新材料科技有限公司 | A kind of footing permanent antistatic agent and its application |
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| CN104945730A (en) * | 2015-05-28 | 2015-09-30 | 复旦大学 | Nucleating agent and polymer composite antistatic agent, preparation method and applications thereof |
| 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 |
| CN105504758A (en) * | 2016-01-26 | 2016-04-20 | 湖北工程学院 | High-strength antistatic transparent polycarbonate film and preparing method thereof |
| CN105504758B (en) * | 2016-01-26 | 2017-05-10 | 湖北工程学院 | High-strength antistatic transparent polycarbonate film and preparing method thereof |
| 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 |
| CN109320968A (en) * | 2018-09-04 | 2019-02-12 | 广州市瑞合新材料科技有限公司 | A kind of footing permanent antistatic agent and its application |
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| CN112321415A (en) * | 2020-09-30 | 2021-02-05 | 南通新邦化工科技有限公司 | Calcium stearate static eliminating method and device |
| 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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