CN106147184B - Low content carbon nanotubes makrolon composite anti-static masterbatch and preparation method thereof - Google Patents
Low content carbon nanotubes makrolon composite anti-static masterbatch and preparation method thereof Download PDFInfo
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- CN106147184B CN106147184B CN201510173507.1A CN201510173507A CN106147184B CN 106147184 B CN106147184 B CN 106147184B CN 201510173507 A CN201510173507 A CN 201510173507A CN 106147184 B CN106147184 B CN 106147184B
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Abstract
The invention discloses a kind of low content carbon nanotubes makrolon composite anti-static masterbatch, and it includes the following components calculated by weight：15 parts of carbon nanotubes, 5 10 parts of dispersant, spherical 0.5 5 parts of dispersion aids, 5 10 parts of volume eliminant, 03 parts of auxiliary agent, 75 85 parts of makrolon.Meanwhile the invention also discloses the preparation methods of the antistatic master batch.The antistatic master batch of the present invention has excellent antistatic effect, and sheet resistance can reach 104Ω to 103The order of magnitude of Ω, particularly smaller or equal than 103The order of magnitude of Ω, and only need to add a small amount of conductive agent at low cost.Meanwhile the electric conductivity of the product formed after the masterbatch secondary operation using the present invention is compared with the masterbatch will not there were significant differences.In addition antistatic master batch preparation process of the invention is simple to operation, of low cost, suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of functional master batch for plastic processing, more particularly to a kind of poly- carbonic acid of low content carbon nanotubes
Ester composite anti-static masterbatch and preparation method thereof.
Technical background
Makrolon is a kind of common engineering plastics, as most fast general of growth rate in five large-engineering plastics
Engineering plastics.At present, the three of makrolon big application fields are glazing, auto industry and electronics, electrical equipment industry, secondly
The also office equipments such as industrial machinery part, CD, packaging, computer, medical treatment and health care, film, leisure and protective equipment
Deng.In practical applications, part polycarbonate products need to have antistatic property again on its original base (if as anti-quiet
Electric material uses, and sheet resistance need to be down to 106~109Ω), but makrolon has good insulating properties in itself, needs therefore
The substances such as conductive agent are added wherein.The antistatic master batch based on makrolon is generally added with a large amount of conductions on the market at present
Agent, but its conductive capability is still weaker.Recently, researcher attempts to be added into carbon nanotubes as conductive agent in masterbatch, but
It is that scattered in masterbatch of carbon nanotubes is a kind of weak balance of static state, once masterbatch carries out secondary operation, temperature rise, molecule heat
Movement aggravation, then the dispersity of carbon nanotubes will be destroyed and reunited again, so as to masterbatch electric conductivity occur
The shortcomings of good, but product electric conductivity is poor.
The content of the invention
It is a primary object of the present invention to provide a kind of low content carbon nanotubes makrolon composite anti-static masterbatch and its
Preparation method, with overcome the deficiencies in the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of low content carbon nanotubes makrolon composite anti-static masterbatch, it includes calculated by weight such as the following group
Point：1-5 parts of carbon nanotubes, 5-10 parts of dispersant, spherical 0.5-5 parts of dispersion aids, 5-10 parts of volume eliminant, 0-3 parts of auxiliary agent,
75-85 parts of makrolon.
Further, the carbon nanotubes preferably uses multi-walled carbon nanotube, but not limited to this.
Further, the dispersant is preferably from polyether polyol or epoxy resin, but not limited to this.
Further, the spherical dispersion aids includes nano silicon dioxide, nano-calcium carbonate, talcum powder or nano-hollow
Glass microballoon, but not limited to this.
Further, the polyester elastomer of the preferably self-contained phenyl ring of the volume eliminant, such as terephthalic acid (TPA) fourth two
Alcohol ester, but not limited to this.
Further, the auxiliary agent includes antioxidant, lubricant, fire retardant or one kind or more in other processing aids
Kind, and it is without being limited thereto.
Further, the makrolon may be selected from the poly- carbon of modification of the makrolon or industrialized production of industrialized production
Acid esters, and it is without being limited thereto.
Further, the sheet resistance of the masterbatch is less than 104Ω。
The preparation method of the low content carbon nanotubes makrolon composite anti-static masterbatch includes：Take carbon nanotubes 1-5
Part, 5-10 parts of dispersant, spherical 0.5-5 parts of dispersion aids, 5-10 parts of volume eliminant, 0-3 parts of auxiliary agent and makrolon 75-85
After part is sufficiently mixed, is squeezed out and be granulated with double screw extruder, obtain the antistatic master batch.
Further, the preparation method can include：First at least part material, particularly makrolon are dried, then
Each component is sufficiently mixed, double screw extruder is then added in and squeezes out, dried again after cooling and dicing.
For example, among an embodiment, the Screw Extrusion temperature used can be 250 DEG C -280 DEG C.Certainly, use
Screw Extrusion temperature can also make choice according to the specific trade mark of polycarbonate matrix.
In another example among an embodiment, can by makrolon first in 120 DEG C of vacuum drying ovens it is dry 4 it is small when, then
Dispensing is sufficiently mixed with other components.
Compared with prior art, advantages of the present invention includes：
(1) in antistatic master batch of the invention, by using the spherical dispersion aids with bigger serface, can cause
Carbon nanotubes is enriched in spherical dispersion aids surface and forms bridge joint, and highly effective conductive network is formed in matrix, thus
Without carbon nanotubes is handled or modified, and the usage amount of carbon nanotubes can be reduced so that conductive capability is obtained into one
The promotion of step, sheet resistance is from the 10 of commercial like product5Ω or 106Ω, which is promoted to arrive, is less than or equal to 103Ω；
(2) in antistatic master batch of the invention, because employing volume eliminant simultaneously, obtained masterbatch is in secondary operation
In the process, will not because of temperature raise cause molecular thermalmotion aggravate and so that the dispersity of carbon nanotubes is laid equal stress on by destruction
Kainogenesis is reunited, after secondary operation product electric conductivity will not there were significant differences；
(3) antistatic master batch preparation process of the invention is simple to operation, of low cost, suitable for large-scale production.
Specific embodiment
Technical scheme is described further with reference to several embodiments.The skilled practitioner
According to foregoing invention content makes present invention non-intrinsically safe modifications and adaptations in technique or on formula, this hair is still fallen within
Bright protection domain.
Embodiment 1
The polycarbonate anti-static masterbatch of the low content carbon nanotubes includes the following component calculated in parts by weight：
4 parts of multi-walled carbon nanotube (CNTs, average length 861nm)
5 parts of bisphenol A epoxide resin
1 part of nano silicon dioxide (spherical, average grain diameter 637nm)
10 parts of polybutylene terephthalate (PBT) (PBT, Changchun chemical industry 100-211M)
0.5 part of antioxidant 1010
79.5 parts of makrolon (PC, South Korea LG 1201-15).
The preparation method of the masterbatch includes：First by makrolon when 120 DEG C of vacuum drying 4 are small, then by itself and its
Its raw material carries out physical mixed by above proportioning, then with twin-screw extrusion and is granulated, and extrusion temperature is 265 DEG C, rotating speed 250r/
min。
Embodiment 2
The polycarbonate anti-static masterbatch of the low content carbon nanotubes includes the following component calculated in parts by weight：
5 parts of multi-walled carbon nanotube (CNTs, average length 861nm)
4,110 5 parts of polyethers
1 part of talcum powder (49 μm of average grain diameter)
10 parts of polybutylene terephthalate (PBT) (Changchun chemical industry 100-211M)
0.5 part of antioxidant 1010
78.5 parts of makrolon (South Korea LG 1201-15)
The preparation method of the polycarbonate anti-static masterbatch of the low content carbon nanotubes includes：Makrolon is existed first
When 120 DEG C of vacuum drying 4 are small, it is then subjected to physical mixed with other raw materials by above proportioning, then with twin-screw extrusion simultaneously
It is granulated, 265 DEG C of extrusion temperature, rotating speed 250r/min.
Embodiment 3
The polycarbonate anti-static masterbatch of the low content carbon nanotubes includes the following component calculated in parts by weight：
1 part of multi-walled carbon nanotube (CNTs, average length 861nm)
8 parts of bisphenol A epoxide resin
5 parts of nano-calcium carbonate (spherical, average grain diameter 107nm)
5 parts of polybutylene terephthalate (PBT) (PBT, Changchun chemical industry 100-211M)
0.5 part of antioxidant 1010
80.5 parts of makrolon (PC, South Korea LG 1201-15).
The preparation method of the masterbatch includes：First by makrolon when 120 DEG C of vacuum drying 4 are small, then by itself and its
Its raw material carries out physical mixed by above proportioning, then with twin-screw extrusion and is granulated, and extrusion temperature is 265 DEG C, rotating speed 250r/
min。
Embodiment 4
The polycarbonate anti-static masterbatch of the low content carbon nanotubes includes the following component calculated in parts by weight：
5 parts of multi-walled carbon nanotube (CNTs, average length 861nm)
5 parts of bisphenol A epoxide resin
1 part of hollow glass micropearl (spherical, average grain diameter 223nm)
10 parts of polybutylene terephthalate (PBT) (PBT, Changchun chemical industry 100-211M)
0.5 part of antioxidant 1010
78.5 parts of makrolon (PC, South Korea LG 1201-15).
The preparation method of the masterbatch includes：First by makrolon when 120 DEG C of vacuum drying 4 are small, then by itself and its
Its raw material carries out physical mixed by above proportioning, then with twin-screw extrusion and is granulated, and extrusion temperature is 265 DEG C, rotating speed 250r/
min。
Vulcanizing press pressing plate will be used after particle drying after above-mentioned pelletizing, its sheet resistance is tested using sheet resistance instrument
As a result it is as shown in table 1 below.
The sheet resistance test result of 1 embodiment 1-2 products of table
| Sample | Sheet resistance Ω |
| Embodiment 1 | 5.8*102 |
| Embodiment 2 | 2.3*103 |
| Embodiment 3 | 9.8*103 |
| Embodiment 4 | 4.1*102 |
Embodiment 1,2 gained masterbatch are molded by injection molding machine, 270 DEG C of injection temperature, 120 DEG C of mould temperature, after injection molding
Sheet resistance test is carried out to it, test result is as shown in table 2 below.
The sheet resistance test result of 2 embodiment 1-2 products of table
| Sample | Sheet resistance Ω |
| Embodiment 1 is molded batten | 7.6*103 |
| Embodiment 2 is molded batten | 6.7*103 |
| Embodiment 3 is molded batten | 1.3*104 |
| Embodiment 4 is molded batten | 8.1*103 |
Reference examples 1：
The antistatic master batch includes the following component calculated in parts by weight：
4 parts of multi-walled carbon nanotube (CNTs, average length 861nm)
5 parts of bisphenol A epoxide resin
1 part of nano silicon dioxide (spherical, average grain diameter 637nm)
0.5 part of antioxidant 1010
89.5 parts of makrolon (PC, South Korea LG 1201-15).
The preparation method of the masterbatch includes：First by makrolon when 120 DEG C of vacuum drying 4 are small, then by itself and its
Its raw material carries out physical mixed by above proportioning, then with twin-screw extrusion and is granulated, and extrusion temperature is 265 DEG C, rotating speed 250r/
min。
Reference examples 2：
The antistatic master batch includes the following component calculated in parts by weight：
4 parts of multi-walled carbon nanotube (CNTs, average length 861nm)
5 parts of bisphenol A epoxide resin
10 parts of polybutylene terephthalate (PBT) (PBT, Changchun chemical industry 100-211M)
0.5 part of antioxidant 1010
80.5 parts of makrolon (PC, South Korea LG 1201-15).
The preparation method of the masterbatch includes：First by makrolon when 120 DEG C of vacuum drying 4 are small, then by itself and its
Its raw material carries out physical mixed by above proportioning, then with twin-screw extrusion and is granulated, and extrusion temperature is 265 DEG C, rotating speed 250r/
min。
Vulcanizing press pressing plate will be used after particle drying after above-mentioned pelletizing, its sheet resistance is tested using sheet resistance instrument
The results are shown in table below.
The sheet resistance test result of 3 reference examples 1-2 products of table
| Sample | Sheet resistance Ω |
| Reference examples 1 | 7.8*104 |
| Reference examples 2 | 1.1*106 |
Compared with embodiment 1-2, the sheet resistance of reference examples 1-2 is higher, and the surface of reference examples 1 is relatively rough,
Extrusion has some setbacks.In addition, reference examples 1,2 gained masterbatch are molded by injection molding machine, 270 DEG C of injection temperature, 120 DEG C of mould temperature, note
It is moulded into after type and carries out sheet resistance test to obtaining injection batten, it is found that its sheet resistance has greatly compared with embodiment 1-2 products
Width improves.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all
The equivalent change or modification that Spirit Essence is made according to the present invention, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of low content carbon nanotubes makrolon composite anti-static masterbatch, it is characterised in that comprising calculate by weight as
Lower component：1-5 parts of carbon nanotubes, 5-10 parts of dispersant, spherical 0.5-5 parts of dispersion aids, 5-10 parts of volume eliminant, auxiliary agent 0-
3 parts, 75-85 parts of makrolon；Wherein carbon nanotubes is enriched in spherical dispersion aids surface and forms bridge joint and described antistatic
Conductive network is formed in masterbatch, and the sheet resistance of the masterbatch is less than 104Ω。
2. low content carbon nanotubes makrolon composite anti-static masterbatch according to claim 1, which is characterized in that described
Carbon nanotubes uses multi-walled carbon nanotube.
3. low content carbon nanotubes makrolon composite anti-static masterbatch according to claim 1, which is characterized in that described
Dispersant is at least selected from polyether polyol or epoxy resin.
4. low content carbon nanotubes makrolon composite anti-static masterbatch according to claim 1, which is characterized in that described
Spherical dispersion aids includes nano silicon dioxide, nano-calcium carbonate, talcum powder or nano-hollow glass microballoon.
5. low content carbon nanotubes makrolon composite anti-static masterbatch according to claim 1, which is characterized in that described
Volume eliminant includes the polyester elastomer containing phenyl ring.
6. low content carbon nanotubes makrolon composite anti-static masterbatch according to claim 1, which is characterized in that described
Auxiliary agent includes antioxidant, lubricant or fire retardant.
7. low content carbon nanotubes makrolon composite anti-static masterbatch according to claim 1, which is characterized in that described
Makrolon includes the makrolon of industrialized production or the modified polycarbonate of industrialized production.
8. the preparation side of low content carbon nanotubes makrolon composite anti-static masterbatch as any one of claim 1-7
Method, it is characterised in that including：Take 1-5 parts of carbon nanotubes, 5-10 parts of dispersant, spherical 0.5-5 parts of dispersion aids, volume eliminant
After 75-85 parts of 5-10 parts, 0-3 parts of auxiliary agent and makrolon are sufficiently mixed, are squeezed out and be granulated with double screw extruder, described in acquisition
Antistatic master batch.
9. the preparation method of low content carbon nanotubes makrolon composite anti-static masterbatch according to claim 8, feature
It is, the Screw Extrusion temperature used is 250 DEG C -280 DEG C.
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| CN107227011A (en) * | 2017-05-31 | 2017-10-03 | 宁波海雨新材料科技有限公司 | A kind of CNT denatured conductive makrolon and preparation method thereof |
| CN112266596A (en) * | 2020-10-16 | 2021-01-26 | 厦门华晔精密模具有限公司 | Conductive polycarbonate composite material and preparation method thereof |
| CN115386213B (en) * | 2022-08-29 | 2024-05-03 | 南京聚隆科技股份有限公司 | High light absorption material and preparation method thereof |
| CN116102866B (en) * | 2022-12-30 | 2024-06-18 | 金发科技股份有限公司 | Voltage-resistant and antistatic PC composition and preparation method and application thereof |
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| CN102558917A (en) * | 2011-12-30 | 2012-07-11 | 苏州工业园区润佳工程塑料有限公司 | Wrapped conducting nano material, conducting nano composite material and preparation method for wrapped conducting nano material and conducting nano composite material |
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| WO2014186460A1 (en) * | 2013-05-14 | 2014-11-20 | Eaton Corporation | Multi additive multifunctional composite for use in a non-metallic fuel conveyance system |
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| CN102558917A (en) * | 2011-12-30 | 2012-07-11 | 苏州工业园区润佳工程塑料有限公司 | Wrapped conducting nano material, conducting nano composite material and preparation method for wrapped conducting nano material and conducting nano composite material |
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Effective date of registration: 20200106 Address after: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Patentee after: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien Address before: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Co-patentee before: Ningbo Haiyu Advanced Materials Technology Co., Ltd. Patentee before: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien |