CN104945730B - Nucleator and high molecular composite antistatic agent and its preparation method and application - Google Patents
Nucleator and high molecular composite antistatic agent and its preparation method and application Download PDFInfo
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- CN104945730B CN104945730B CN201510282139.4A CN201510282139A CN104945730B CN 104945730 B CN104945730 B CN 104945730B CN 201510282139 A CN201510282139 A CN 201510282139A CN 104945730 B CN104945730 B CN 104945730B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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Abstract
The invention belongs to technical field of polymer materials, specially a kind of nucleator/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 nucleator having been commercialized, applied to antistatic macromolecule material.The composite antistatic agent changes the crystallization behavior of high polymer material by the addition of nucleator in component：Crystalline rate and crystal density are significantly improved, and crystallite dimension diminishes so that non-crystalline areas diminishes.Therefore, it is possible to significantly reduce loading of the antistatic additive in high polymer material, so as to reduce production cost.The composite antistatic agent not give only high polymer material permanent antistatic performance, while enhancing the mechanical property and processing characteristics of high polymer material.The cost of the novel high polymer composite antistatic agent is relatively low, and preparation method is simple, it is adaptable to industrialized production.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of nucleator and Polymer-metallic Catalyst it is compound
Antistatic additive 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
Etc. being widely used to the fields such as national defence and national economy.Generally, high polymer material is difficult to because of the covalent bond in its molecular structure
Ionization or transmission load, thus with higher surface resistivity（R S ）Or specific insulation（R V ）.Therefore, it is using process
In, it is easy to the build up of electrostatic charge because of external environment influences such as friction, external magnetic field sensings, cause device surface dust suction, film to be closed
Close, electronic device such as punctures, shocks by electricity and exploded the disaster.It is industrial generally by polymer base material to eliminate electrostatic hazard
The method of addition antistatic additive improves its electrostatic dissipation ability.The action effect of antistatic additive with itself, high polymer material knot
Compatibility and processing and forming condition between structure, antistatic additive and high polymer material is closely related.
Conventional antistatic additive can be divided at present：Low molecular weight surfactants type, conductive filler（Metal and metal oxidation
Thing or carbon-based material）And Polymer-metallic Catalyst.Low molecular weight surfactants type antistatic additive is can using itself small molecule
Migration characteristic, can be reduced in polymer surface adsorption moistureR S , reach anlistatig effect, antistatic effect and its point
Son amount, with matrix limited compatibility and add usage amount it is closely related.Thus, its poor durability, non-scrubbing resistance, to environmental wet
Heat resisting temperature and surface characteristic that the dependence of degree is big, reduce material etc., and be easy to from polymer base material depart from and produce environment
Raw negative effect.Conductive filler compensate for Small molecular surfactant type antistatic additive as the antistatic additive of high polymer material
Use defect, its antistatic mechanism be utilize from macromolecule matrix formed diafiltration conductive network with dissipation of static charge,
Reach anlistatig effect.But, the formation of the electric charge transmission channel needs substantial amounts of conductive filler, and this will cause macromolecule material
Material makes it in height the shortcomings of easy coloring, filler be not easy to fall off or oxidation, high polymer material physical property decline and machine-shaping is difficult
The application in the antistatic field of molecule is limited.
Polymer-metallic Catalyst is polymer of the class containing hydrophilic radical or conductive structure unit, is characterized in antistatic effect
Fruit is not persistently and substantially protected from environmental.After Polymer-metallic Catalyst is blended with insulating polymer matrix, using from height
Diafiltration conductive network is formed in molecular matrix with dissipation of static charge；The composite of itself and insulating body is not only preferably maintained
The basic performance of matrix, and antistatic effect persistently, without induction period, not by the condition such as wiping and washing influenceed and wider
Good, stable antistatic effect is shown in humidity range.The action effect of this kind of antistatic additive with its in the base point
The degree of dissipating and state are closely related, and it is mainly distributed in the surface of material and nearly table with fine stratiform or tendons of beef, mutton or pork shape in the base
Layer, and be distributed less in the core of material and mainly exist with graininess.Research shows, the distribution and macromolecule material
Crystallinity, crystal habit and the ordering degree of material are closely related.Therefore, the anti-static composite material in process because into
, inevitably there are various problems, such as because Topical Dispersion is uneven in type method, condition of molding, the shapes and sizes influence of product
Or tiny network goes to pot and causes excessive filling usage amount, adds production cost；Also, itself and macromolecule matrix material
Between physicochemical property difference high polymer material hot property and mechanical performance will be caused to decline.Therefore, the main object of the present invention
It is the filling usage amount that permanent type Polymer-metallic Catalyst is controlled by simple effective method, and improves high polymer material
Hot property and mechanical performance.
The present invention changes the crystallization row of high polymer material using the nucleation of nucleator in composite antistatic agent component
To accelerate crystalline rate, increasing crystal density and promote fine grain size, ordering degree improved, so that amorphous
Region diminishes, and further reduces the filling usage amount of Polymer-metallic Catalyst in composite, is effectively reduced production cost；Together
When can effectively improve the hot property and mechanical performance of high polymer material, enhance the mechanics and processing characteristics of composite.
The content of the invention
It is an object of the invention to provide a kind of antistatic property is lasting, cheap and nucleator of simple production process
With the composite antistatic agent of Polymer-metallic Catalyst, and the composite antistatic agent preparation method and its in high polymer material
Application.
The preparation method of the composite antistatic agent of nucleator and Polymer-metallic Catalyst provided by the present invention, its specific system
Standby step is as follows：
（1）The drying process of nucleator, permanent type Polymer-metallic Catalyst
Nucleator and Polymer-metallic Catalyst are respectively put into vacuum drying chamber, at a temperature of 60~120 DEG C, constant temperature is done
Dry 12~48 hours；
（2）The preparation of Polymer-metallic Catalyst solution
Dried Polymer-metallic Catalyst is dissolved in organic solvent, ultrasound 5~60 minutes in ultrasonic disperse machine,
50~60kHz of working frequency, 100~200W of power, temperature are 25~60 DEG C；Then, the mixed solution is persistently stirred and added
Heat is completely dissolved it in 0.5~2 hour, and heating-up temperature is 80~120 DEG C, obtains Polymer-metallic Catalyst solution；
（3）The preparation of composite antistatic agent
Dried nucleator is added in Polymer-metallic Catalyst solution, 5~60 points of the ultrasound in ultrasonic disperse machine
Clock, 50~60kHz of working frequency, 100~200W of power, temperature are 25~60 DEG C；Then, the mixed solution is persistently stirred
Be completely dissolved it within 0.5~2 hour, whipping temp be 25~120 DEG C, 500~2000rpm of stir speed (S.S.), obtain nucleator and
The mixed solution of Polymer-metallic Catalyst；
The mixed solution of nucleator and Polymer-metallic Catalyst is separated, washed, and it is true at a temperature of 40~80 DEG C
Sky is dried 12~72 hours, obtains nucleator and high molecular composite antistatic agent.
In the present invention, in step (1), the permanent type Polymer-metallic Catalyst is the polymer comprising lipophilic fraction point
Subchain section and the polymer containing hydrophilic radical or conductive structure unit, including：Polyacrylate, maleic anhydride and other insatiable hungers
With the salt and polystyrene sulfonate salt of monomer copolymer.
In the present invention, in step (1), the nucleator is inorganic nucleator, organic nucleating agent or high molecular nucleating agent.Allusion quotation
Type such as alpha-crystal form organic nucleating agent, specifically such as：Dibenzyl sorbitol class nucleator（Millad 3988）, substituted aryl heterocycle
Phosphoric acid salt nucleator（ADK NA-21）And organic carboxyl acid salt nucleator（Millad NX8000K）.
In the present invention, in step (2), the organic solvent is 1-METHYLPYRROLIDONE, or resisted for permanent type macromolecule
The good solvent of electrostatic agent.
In the present invention, in step (3), the separation method is normal pressure suction filtration, vacuum decompression drying removal solvent；It is described to wash
The method of washing is：By the good solvent of permanent type Polymer-metallic Catalyst quantifying with 2~20 times of its meltage, wash 1~10 time.
Composite antistatic agent prepared by the present invention can be used for preparing antistatic macromolecule material, specifically can be using melting or molten
Liquid blending after, injection, molding or mixed solution knifing, pour film shaping.Wherein：
The specific preparation process of melt blending processing method is as follows：
Composite antistatic agent and high polymer material are dried in vacuo 12~48 hours at 80~120 DEG C, physical mixed is equal
After even, melt blending is carried out, blending temperature is 180~250 DEG C, shear rate is 5~120rpm, the blending time is 3~15 points
Clock；
Then, carry out molding and prepare test sample, molding temperature is 180~250 DEG C, and pressure is 25~45kg/cm2, survey
Sample coupon specification is the standard batten needed for 8~12cm of diameter, 0.5~3mm of thickness disk and other tests；
Solution blending processing method preparation process is as follows：
Composite antistatic agent and high polymer material are dried in vacuo 12~48 hours at a temperature of 80~120 DEG C respectively；Will
Quantitative composite antistatic agent is added to the 1-METHYLPYRROLIDONE of 2~15 times of mass ratioes and the in the mixed solvent of dimethylbenzene, ultrasound
Scattered 0.5~5 hour, 50~60kHz of working frequency, 100~200W of power, 25~60 DEG C of temperature obtain composite antistatic agent
Dispersed mixed solution；
Then, high polymer material is added in the mixed solution, continues stirring and dissolving 0.5~2 hour, whipping temp 25
~150 DEG C, 500~2000rpm of stir speed (S.S.) obtains the blend solution of composite antistatic agent and 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 is 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
Mass ratio with high polymer material is 1:1~1:50.Described high polymer material can be polypropylene（PP）.
The new permanent type Polymer-metallic Catalyst having been commercialized and nucleator are blended by physical blending process by the present invention,
A kind of new composite antistatic agent is prepared into, applied to antistatic macromolecule material.The NEW TYPE OF COMPOSITE antistatic additive has height
The permanent electrostatic safeguard function of molecule antistatic additive, electrostatic dissipation ability are influenceed the good characteristic such as smaller by the humidity of environment；Together
When, the composite antistatic agent changes the crystallization behavior of high polymer material by the nucleation of nucleator in component, accelerates knot
Brilliant speed, increase crystal density and promote fine grain size, so that it is interval to significantly reduce amorphous area, therefore, it is possible to have
Effect reduces the filling usage amount of Polymer-metallic Catalyst in high polymer material, further reduces production cost.The composite anti-static
Agent not give only high polymer material permanent antistatic performance, while enhancing the mechanical property of high polymer material, processing characteristics.
The cost of the NEW TYPE OF COMPOSITE antistatic additive is relatively low, and preparation method is simple, it is adaptable to industrialized production.
Brief description of the drawings
(a)-(f) is followed successively by PP, U3 and U3/PP, U3/NX8000K/PP, U3/3988/PP and U3/NA-21/ in Fig. 1
The outside drawing of PP composites.
Fig. 2 is PP materialsR v Relation between the loading of composite antistatic agent.Wherein, (a)-(d) curves are successively
For composite U3/PP, U3/NX8000K/PP, U3/NA-21/PP and U3/3988/PP.
(a)-(h) curves in Fig. 3 are followed successively by PP, U3, NX8000K, U3/NX8000K/PP, NA-21, U3/NA-21/
PP, 3988, U3/3988/PP infrared signature spectrogram.
(a)-(i) curves in Fig. 4 are followed successively by PP, U3 and U3/PP, NX8000K/PP, U3/NX8000K/PP, NA-21/
The wide-angle x-ray diffraction spectrogram of PP, U3/NA-21/PP, 3988/PP, U3/3988/PP composite（WAXD）.
(A)-(C) in Fig. 5 is respectively DSC crystallization curves, melting curve and the crystallinity pair of PP, U3 and its composite
Compare block diagram.Wherein, (a)-(h) curves be followed successively by PP, U3/PP, NX8000K/PP, U3/NX8000K/PP, NA-21/PP,
U3/NA-21/PP、3988/PP、U3/3988/PP。
Fig. 6 is the scanning electron microscope (SEM) photograph (SEM) of PP and its composite.Wherein, (a)-(d) be followed successively by PP, NX8000K/PP,
U3/PP、U3/NX8000K/PP。
Fig. 7 is the polarized light microscopy figure of PP and its composite.Wherein, (a)-(d) is followed successively by PP, NX8000K/PP, U3/
PP、U3/NX8000K/PP。
Fig. 8 is the X-ray energy spectrogram of PP, U3 and its composite.Wherein, (a) and (b) is respectively U3/PP, U3/
NX8000K/PP electronic image；(c) and (d) be respectively U3/PP, U3/NX8000K/PP electronic image in oxygen element contain
Measure distribution map；（e）For carbon, oxygen element content balance figure in U3, U3/PP, U3/NX8000K/PP.
Fig. 9 is the tensile strength contrast block diagram of PP, U3 and its composite, wherein, (a)-(h) block diagrams are followed successively by
PP, U3/PP, NX8000K/PP, U3/NX8000K/PP, NA-21/PP, U3/NA-21/PP, 3988/PP and U3/3988/PP.
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 NX8000K（Physical features are as shown in table 1）With ion polymer type Polymer-metallic Catalyst U3（Physical features are such as
Shown in table 1）It is respectively put into vacuum drying chamber, in 80 DEG C of freeze-day with constant temperature 24 hours；The dried g of U3 12 are dissolved in
In 200ml 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 U3 solution；
The physical features of the polypropylene of table 1, nucleator and Polymer-metallic Catalyst
（2）Nucleator/U3 antistatic additive prepare composite antistatic agent
Dried NX8000K 0.5g are added in above-mentioned antistatic additive U3 solution, it is ultrasonic in ultrasonic disperse machine
120 minutes, working frequency 60kHz, power 150W, 25 DEG C of temperature；Then the mixed solution is continued into stirring and dissolving 48 hours, stirred
25 DEG C of temperature is mixed, stir speed (S.S.) 800rpm obtains NX8000K/U3 antistatic additive mixed solutions, it is separated, wash, done
It is dry.Vacuum drying 24 hours, temperature 60 C obtains NX8000K/U3 composite antistatic agents；
（3）Application of the composite antistatic agent in high polymer material
Applying step of the NX8000K/U3 composite antistatic agents of the present invention in PP is as follows：By 45.0g PP and
15 g composite antistatic agent physical mixeds, carry out melt blending, blending temperature be 180~250 DEG C, shear rate be 5~
120rpm, the blending time is 3~15 minutes；
Then carry out molding and prepare test specimens, molding temperature is 180~250 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)-(d) is respectively high polymer material PP, U3, composite U3/PP, U3/NX8000K/PP normal disc
Sample characteristics outside drawing.It is seen that after Polymer-metallic Catalyst U3 is blended into PP, composite is changed into transparent light
Yellow, and be blended into after the composite antistatic agent containing NX8000K, composite is still white, does not change Polymer-metallic Catalyst
U3 outward appearance uses characteristic.
Fig. 2 (a) and (b) are respectively composite U3/PP, U3/NX8000K/PPR V With permanent type polymeric antistatic
Change curve between agent U3, composite antistatic agent filling usage amount.PP and its composite sampleR v Test reference mark
Standard is GB/T1410-2006（CompositeR v ＜ 1012 Ohm.cm is anti-static material）, PP'sR V It is worth for 2.74 × 1017
ohm.cm.From Fig. 2 (a), U3 filling usage amount 25wt% and it is following when, compositeR V Value is between 1014 -
1017Between ohm/cm, too big change is had no, now composite inner is local does not form electric charge Percolation Network structure.Work as U3
Filling usage amount be 30 wt% when,R V It is worth for 8.2 × 1011 Ohm.cm, composite has antistatic effect, shows now
Matrices of composite material has formed diafiltration conductive network structure.Then, with the increase of U3 blending amounts, compositeR v Value
Change tends towards stability.Show the critical diafiltration conductive network loading of U3 in composite U3/PP in 30wt% or so.Similarly, such as
Shown in Fig. 2 (b), in composite U3/NX8000K/PP, during U3 filling usage amount 20wt%, compositeR V From 5.2 × 1015
Ohm.cm is down to 1.44 × 1013 Ohm.cm, shows that now composite inner locally initially forms electric charge Percolation Network structure.
When U3 filling usage amount increases to 25wt%, matrices of composite material forms global diafiltration conductive network structure, i.e., critical diafiltration
Conductive network loading is in 25wt% or so, also, the continuation increase of the filling usage amount with U3, compositeR v Value after
It is continuous to be reduced to 1.13 × 109 Ohm.cm, with U3'sR v Value 3.25 × 108 Ohm.cm is closer to.This shows that NX8000K's adds
Enter, significantly reduce the critical diafiltration conductive network usage amount of U3 in PP matrixes.
(a)-(d) curves in Fig. 3 are respectively PP, U3, NX8000K, composite U3/NX8000K/PP infrared signature
Collection of illustrative plates, the collection of illustrative plates shows to contain PP, U3, NX8000K characteristic peak in composite U3/NX8000K/PP, between the two
Have been carried out preferably blending.(a)-(e) curves in Fig. 4 are respectively PP, U3, U3/PP, NX8000K/PP, U3/
The diffraction maximum of 14.2 °, 16.8 ° and 18.8 ° or so appearance corresponds to PP alpha-crystal form spy in NX8000K/PP WAXD collection of illustrative plates, figure
Diffraction maximum is levied, the diffraction of 110,040,130 crystal faces is corresponded respectively to.As seen from the figure, the WAXD spectrograms of all composites
Diffraction maximum and pure PP are completely the same, and this shows that U3, NX8000K are blended into after PP and does not change its crystal habit.
In Fig. 5 (A)-(C)（a）- (d) curves are respectively PP and composite U3/PP, NX8000K/PP, U3/
NX8000K/PP DSC crystallization curves, melting curve and crystallinity contrast block diagram.It can be seen that composite U3/
NX8000K/PP crystallization peak temperature, melting temperature, crystallinity are all remarkably higher than PP, U3/PP respective value, and are less than
NX8000K/PP respective value.This shows in composite antistatic agent that NX8000K has played nucleation, improves PP, U3/
PP crystallinity, to significantly reduce its amorphous area interval, reduce further U3 critical diafiltration conductive network loading；Together
When, in composite U3/NX8000K/PP, due to space steric effect of the U3 molecules in PP matrixes, reduce to a certain degree
NX8000K nucleation efficiencies.
Fig. 6, Fig. 7 are respectively scanning electron microscope (SEM) photograph (SEM), the polarized light microscopy figure of PP and its composite, and (a)-(d) is followed successively by
PP、NX8000K/PP、U3/PP、U3/NX8000K/PP.Fig. 8 is the X-ray energy spectrogram of PP, U3 and its composite.Wherein,
(a)-(b) is respectively U3/PP, U3/NX8000K/PP electronic image；(c)-(d) is respectively U3/PP, U3/NX8000K/PP
Electronic image in oxygen element content distribution figure；（e）For carbon, oxygen element content balance in U3, U3/PP, U3/NX8000K/PP
Figure.NX8000K/PP has effectively played nucleation in Fig. 6-8, composite antistatic agent, improves PP, U3/PP
Crystal density and promote fine grain size, improve ordering degree, so as to significantly reduce offices of the U3 in PP matrixes
Portion's enrichment, reunion, reduce further its critical diafiltration conductive network loading.
(a)-(d) block diagrams in Fig. 9 are followed successively by PP, U3/PP, NX8000K/PP, U3/NX8000K/PP tensile strength
Comparison diagram.As seen from the figure, U3 is introduced in PP matrixes, tensile strength is significantly reduced, and NX8000K/U3 composite antistatic agents are common
It is mixed into PP matrixes, tensile strength, which has, to be significantly improved, the draftability of composite can be strengthened by showing NX8000K introducing
Energy.
Embodiment 2
（1）The preparation of permanent type Polymer-metallic Catalyst solution
By NA-21（Physical features are as shown in table 1）With ion polymer type Polymer-metallic Catalyst U3（Physical features such as table
Shown in 1）It is respectively put into vacuum drying chamber, in 80 DEG C of freeze-day with constant temperature 24 hours；The dried g of U3 12 are dissolved in 200ml
In organic solvent 1-METHYLPYRROLIDONE, ultrasound 120 minutes in ultrasonic disperse machine, working frequency 60kHz, power 150W, temperature
25 DEG C of degree；Then the solution is continued into stirring and dissolving 2 hours, obtains antistatic additive U3 solution；
（2）Nucleator/U3 antistatic additive prepare composite antistatic agent
Dried NA-21 0.25g are added in above-mentioned antistatic additive U3 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 of temperature, stir speed (S.S.) 800rpm obtains NA-21/U3 antistatic additive mixed solutions, and it is separated, washed, is dried.
Vacuum drying 24 hours, temperature 60 C obtains NA-21/U3 composite antistatic agents；
（3）Application of the composite antistatic agent in high polymer material
Applying step of the NA-21/U3 composite antistatic agents of the present invention in PP is as follows：By 45.0g PP and 15
G composite antistatic agent physical mixeds, carry out melt blending, and blending temperature is 180~250 DEG C, and shear rate is 5~120rpm,
The blending time is 3~15 minutes；
Then carry out molding and prepare test specimens, molding temperature is 180~250 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)-(c),（e）Respectively high polymer material PP, U3, composite U3/PP, U3/NA-21/PP standard round
Disk sample characteristics outside drawing.It is seen that after Polymer-metallic Catalyst U3 is blended into PP, composite is changed into transparent
It is faint yellow, and be blended into after the composite antistatic agent containing NX8000K, composite is still white, does not change polymeric antistatic
Agent U3 outward appearance uses characteristic.
Fig. 2 (a) and (c) are respectively composite U3/PP, U3/NA-21/PPR v With permanent type Polymer-metallic Catalyst
Change curve between U3, composite antistatic agent filling usage amount.PP and its composite sampleR v Test reference standard
For GB/T1410-2006（CompositeR v ＜ 1012 Ohm.cm is anti-static material）, PP'sR v It is worth for 2.74 × 1017
ohm.cm.Fig. 2 (a) shows, U3 filling usage amount 25wt% and it is following when, compositeR v Value is between 1014 ~
1017Between ohm/cm, too big change is had no, now composite inner is local does not form electric charge Percolation Network structure.Work as U3
Filling usage amount be 30 wt% when,R v It is worth for 8.2 × 1011 Ohm.cm, composite has antistatic effect, shows now
Matrices of composite material has formed diafiltration conductive network structure.Then, with the increase of U3 blending amounts, compositeR v Value
Change tends towards stability.Show the critical diafiltration conductive network loading of U3 in composite U3/PP in 30wt% or so.Similarly, such as
Shown in Fig. 2 (c), in composite U3/NA-21/PP, during U3 filling usage amount 20wt%, compositeR V From 1.06 × 1016
Ohm.cm is down to 1.48 × 1013 Ohm.cm, shows that now composite inner locally initially forms electric charge Percolation Network structure.
When U3 filling usage amount increases to 25wt%, matrices of composite material forms global diafiltration conductive network structure, i.e., critical diafiltration
Conductive network loading is in 25wt% or so, also, the continuation increase of the filling usage amount with U3, compositeR v Value after
It is continuous to be down to 2.04 × 109 Ohm.cm, with U3'sR v Value 3.25 × 108 Ohm.cm is closer to.This shows that NA-21 addition has
Reduce to effect the critical diafiltration conductive network usage amount of U3 in PP matrixes.
(a), (b) in Fig. 3,（e）、（f）Curve be respectively PP, U3, NA-21, composite U3/NA-21/PP it is infrared
Characteristic spectrum, by collection of illustrative plates it can be seen that containing PP, U3, NA-21 characteristic peak in composite U3/NA-21/PP, both
Between have been carried out preferably blending.(a)-(c) in Fig. 4,（f）、（g）Curve be respectively PP, U3, U3/PP, NA-21/PP,
The diffraction maximum of 14.2 °, 16.8 ° and 18.8 ° or so appearance corresponds to PP alpha-crystal form spy in U3/NA-21/PP WAXD collection of illustrative plates, figure
Diffraction maximum is levied, the diffraction of 110,040,130 crystal faces is corresponded respectively to.As seen from the figure, the WAXD spectrograms of all composites
Diffraction maximum and pure PP are completely the same, and this shows that U3, NX8000K are blended into after PP and does not change its crystal habit.
Fig. 5 (A)-（C）In（a）、(b)、（e）、（f）Curve is respectively PP and composite U3/PP, NA-21/PP, U3/
NA-21/PP DSC crystallization curves, melting curve and crystallinity contrast block diagram.In figure, composite U3/NA-21/PP knot
Brilliant peak temperature, melting temperature, crystallinity are all remarkably higher than PP, U3/PP respective value, and are less than NA-21/PP respective counts
Value.This shows in composite antistatic agent that NA-21 has played nucleation, improves PP, U3/PP crystallinity, is effectively reduced
Its amorphous area is interval, so as to reduce further U3 critical diafiltration conductive network loading.Meanwhile, in composite U3/
In NA-21/PP, due to space steric effect of the U3 molecules in PP matrixes, NA-21 nucleation efficiencies are reduced to a certain degree.
(a), (c), (e) in Fig. 9,（f）Block diagram is followed successively by PP, U3/PP, NA-21/PP, U3/NA-21/PP stretching
Intensity contrast figure.As seen from the figure, U3 is introduced in PP matrixes, tensile strength is significantly reduced, and NA-21/U3 composite antistatic agents
It is blended into PP matrixes, tensile strength, which has, to be significantly improved, the draftability of composite can be strengthened by showing NA-21 introducing
Energy.
Embodiment 3
（1）The preparation of permanent type Polymer-metallic Catalyst solution
By 3988 and ion polymer type Polymer-metallic Catalyst U3（Physical features are as shown in table 1）Vacuum is respectively put into do
In dry case, in 80 DEG C of freeze-day with constant temperature 24 hours；The dried g of U3 12 are dissolved in 200ml organic solvent N- crassitudes
In ketone, ultrasound 120 minutes, working frequency 60kHz, power 150W, 25 DEG C of temperature in ultrasonic disperse machine；Then the solution is held
Continuous stirring and dissolving 2 hours, obtains antistatic additive U3 solution；
（2）Nucleator/U3 antistatic additive prepare composite antistatic agent
Dried 3988 0.45g is added in above-mentioned antistatic additive U3 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 of temperature, stir speed (S.S.) 800rpm obtains 3988/U3 antistatic additive mixed solutions, and it is separated, washed, is dried.Very
Sky is dried 24 hours, and temperature 60 C obtains 3988/U3 composite antistatic agents；
（3）Application of the composite antistatic agent in high polymer material
Applying step of the 3988/U3 composite antistatic agents of the present invention in PP is as follows：By 45.0g PP and 15 g
Composite antistatic agent physical mixed, carries out melt blending, and blending temperature is 180~250 DEG C, and shear rate is 5~120rpm, altogether
Do time as 3~15 minutes；
Then carry out molding and prepare test specimens, molding temperature is 180~250 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)-(c),（f）Respectively high polymer material PP, U3, composite U3/PP, U3/3988/PP standard round
Disk sample characteristics outside drawing.It is seen that after Polymer-metallic Catalyst U3 is blended into PP, composite is changed into transparent
It is faint yellow, and be blended into after the composite antistatic agent containing 3988, composite is still white, does not change Polymer-metallic Catalyst U3
Outward appearance use characteristic.
Fig. 2 (a) and (d) are respectively composite U3/PP, U3/3988/PPR v With permanent type Polymer-metallic Catalyst
Change curve between U3, composite antistatic agent filling usage amount.PP and its composite sampleR v Test reference standard
For GB/T1410-2006（CompositeR v ＜ 1012 Ohm.cm is anti-static material）, PP'sR v It is worth for 2.74 × 1017
ohm.cm.Fig. 2 (a) shows, U3 filling usage amount 25wt% and it is following when, compositeR v Value is between 1014 ~
1017Between ohm/cm, too big change is had no, now composite inner is local does not form electric charge Percolation Network structure.Work as U3
Filling usage amount be 30 wt% when,R v It is worth for 8.2 × 1011 Ohm.cm, composite has antistatic effect, shows now
Matrices of composite material has formed diafiltration conductive network structure.Then, with the increase of U3 blending amounts, compositeR v Value
Change tends towards stability.Show the critical diafiltration conductive network loading of U3 in composite U3/PP in 30wt% or so.Similarly, such as
Shown in Fig. 2 (d), in composite U3/3988/PP, during U3 filling usage amount 20wt%, compositeR V From 1.2 ×
1016Ohm.cm is down to 8.78 × 1013 Ohm.cm, shows that now composite inner locally initially forms electric charge Percolation Network knot
Structure.When U3 filling usage amount increases to 25wt%, matrices of composite material forms global diafiltration conductive network structure, i.e., critical
Conductive network loading is percolated in 25wt% or so, also, the continuation increase of the filling usage amount with U3, compositeR v
Value continues to be down to 1.39 × 109 Ohm.cm, with U3'sR v Value 3.25 × 108 Ohm.cm is closer to.This shows, 3988 plus
Enter, significantly reduce the critical diafiltration conductive network usage amount of U3 in PP matrixes.
(a), (b) in Fig. 3,（g）、（h）Curve is respectively PP, U3,3988, composite U3/3988/PP infrared spy
Collection of illustrative plates is levied, the collection of illustrative plates shows to contain PP, U3,3988 characteristic peak in composite U3/3988/PP, has entered between the two
Preferable blending is gone.(a)-(c) in Fig. 4,（h）、（i）Curve is respectively PP, U3, U3/PP, 3988/PP, U3/3988/PP
WAXD collection of illustrative plates, the diffraction maximums of 14.2 °, 16.8 ° and 18.8 ° or so appearance correspond to PP alpha-crystal form characteristic diffraction peak in figure, point
Not Dui Yingyu 110,040,130 crystal faces diffraction.As seen from the figure, the diffraction maximum of the WAXD spectrograms of all composites and pure PP
Completely the same, this shows that U3,3988 are blended into after PP and does not change its crystal habit.
In Fig. 5 (A)-(C)（a）、（b）、（g）、（h）Curve is respectively PP and its composite U3/PP, 3988/PP, U3/
3988/PP DSC crystallization curves, melting curve and crystallinity contrast block diagram.In figure, composite U3/3988/PP crystallization
Peak temperature, melting temperature, crystallinity are all remarkably higher than PP, U3/PP respective value, and are less than 3988/PP respective value.This
Show in composite antistatic agent, 3988 have played nucleation, improve PP, U3/PP crystallinity, to significantly reduce its non-
Crystalline region is interval, reduce further U3 critical diafiltration conductive network loading.Meanwhile, in composite U3/3988/PP,
Due to space steric effect of the U3 molecules in PP matrixes, 3988 nucleation efficiencies are reduced to a certain degree.
(a), (c), (g) in Fig. 9,（h）The stretching that block diagram is followed successively by PP, U3/PP, 3988/PP, U3/3988/PP is strong
Spend comparison diagram.As seen from the figure, U3 is introduced in PP matrixes, tensile strength is significantly reduced, and NA-21/U3 composite antistatic agents are common
It is mixed into PP matrixes, tensile strength, which has, to be significantly improved, the tensile property of composite can be strengthened by showing 3988 introducing.
Claims (7)
1. the preparation method of a kind of nucleator and high molecular composite antistatic agent, it is characterised in that concretely comprise the following steps：
（1）The drying process of nucleator and Polymer-metallic Catalyst
Nucleator and permanent type Polymer-metallic Catalyst are respectively put into vacuum drying chamber, at a temperature of 60~120 DEG C, constant temperature
Dry 12~48 hours；
（2）The preparation of Polymer-metallic Catalyst solution
Dried Polymer-metallic Catalyst is dissolved in organic solvent, ultrasound 5~60 minutes in ultrasonic disperse machine, work
50~60kHz of frequency, 100~200W of power, temperature are 25~60 DEG C；Then, the mixed solution is persistently stirred and heats 0.5
It is completely dissolved it within~2 hours, heating-up temperature is 80~120 DEG C, obtains Polymer-metallic Catalyst solution；
（3）The preparation of composite antistatic agent
Dried nucleator is added in Polymer-metallic Catalyst solution, ultrasound 5~60 minutes in ultrasonic disperse machine, work
50~60kHz of frequency, 100~200W of power, temperature are 25~60 DEG C；Then, that the mixed solution is persistently stirred into 0.5~2 is small
When be completely dissolved it, whipping temp is 25~120 DEG C, and 500~2000rpm of stir speed (S.S.) obtains nucleator and macromolecule anti-
The mixed solution of electrostatic agent；
The mixed solution of nucleator and Polymer-metallic Catalyst is separated, washed, and vacuum is done at a temperature of 40~80 DEG C
Dry 12~72 hours, obtain nucleator and high molecular composite antistatic agent；
Wherein, step（1）Described in permanent type Polymer-metallic Catalyst be IPE U3；The nucleator is dibenzyl sorbitol
One kind in class nucleator, substituted aromatic heterocyclic phosphate class nucleator or organic carboxyl acid salt nucleator；The nucleator with
The quality proportioning of permanent type Polymer-metallic Catalyst is 1:20~1:1000.
2. the preparation method of nucleator as claimed in claim 1 and high molecular composite antistatic agent, it is characterised in that step
（2）In, the organic solvent be 1-METHYLPYRROLIDONE, or Polymer-metallic Catalyst other good solvents.
3. the preparation method of nucleator as claimed in claim 1 and high molecular composite antistatic agent, it is characterised in that step
（3）In, the separation method is normal pressure suction filtration, vacuum decompression drying removal solvent；The washing methods is：By composite anti-static
The good solvent of agent is quantified with 2~20 times of its meltage, is washed 1~10 time.
4. nucleator and high molecular composite antistatic agent that the preparation method according to one of claim 1-3 is obtained.
5. application of the composite antistatic agent as claimed in claim 4 in antistatic macromolecule material is prepared.
6. application of the composite antistatic agent according to claim 5 in antistatic macromolecule material is prepared, its feature exists
After by composite antistatic agent and high polymer material by melt blending, injection, molding or mixed solution knifing, film shaping is poured；
Melt blending processing method is comprised the following steps that：
Composite antistatic agent and high polymer material are dried in vacuo 12~48 hours at 80~120 DEG C, physical mixed is uniform
Afterwards, melt blending is carried out, blending temperature is 180~250 DEG C, shear rate is 5~120rpm, the blending time is 3~15 minutes；
Then, carry out molding and prepare test sample, molding temperature is 180~250 DEG C, and pressure is 25~45kg/cm2, test sample
Specification is the standard batten needed for 8~12cm of diameter, 0.5~3mm of thickness disk and other tests；
Or, composite antistatic agent and high polymer material are used after solution blending, injection, molding or mixed solution knifing, poured
Film is molded；Solution blending processing method is comprised the following steps that：
Composite antistatic agent and high polymer material are dried in vacuo 12~48 hours at a temperature of 80~120 DEG C respectively；Will be quantitative
Composite antistatic agent is added to the 1-METHYLPYRROLIDONE of 2~15 times of mass ratioes and the in the mixed solvent of dimethylbenzene, ultrasonic disperse
0.5~5 hour, 50~60kHz of working frequency, 100~200W of power, 25~60 DEG C of temperature obtained composite antistatic agent uniform
Dispersion mixing solution；
High polymer material is added in above-mentioned mixed solution, continues stirring and dissolving 0.5~2 hour, whipping temp 25~150
DEG C, 500~2000rpm of stir speed (S.S.) obtains the blend solution of composite antistatic agent/high polymer material；
With will the mixed solution carry out pouring film or knifing in a mold, will load mixed liquor mould carry out the vacuum drying demoulding
After produce test sample, vacuum drying temperature is 60~120 DEG C, and drying time is 2~48 hours.
7. application of the composite antistatic agent according to claim 6 in antistatic macromolecule material is prepared, its feature exists
In composite antistatic agent and high polymer material mass ratio be 1:1~1:50；Described high polymer material is polypropylene.
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