CN104356495B

CN104356495B - A kind of conductive POE and preparation method thereof

Info

Publication number: CN104356495B
Application number: CN201410566889.XA
Authority: CN
Inventors: 王玉庭; 邹全亮
Original assignee: Dongguan Decheng Plastic Technology Co Ltd
Current assignee: Dongguan Decheng Plastic Technology Co Ltd
Priority date: 2014-10-22
Filing date: 2014-10-22
Publication date: 2017-09-26
Anticipated expiration: 2034-10-22
Also published as: CN104356495A

Abstract

The invention provides a kind of conductive POE and preparation method thereof, the percentage by weight that the conductive POE is accounted for by each component is mainly prepared by the following raw material：50 70%POE, 5 10%LLDPE, 15 35% conductive blacks, 2 5% white oils, 2 5% surfactants, 0.5 2% lubricant and 0.3 0.5% antioxidant.The present invention is then mixed the conductive black handled well with POE by being pre-processed to raw material conductive black, and then banburying is molded, and conductive POE is made in extruding pelletization, and the conductive POE has≤80 Ω low-resistance value and excellent mechanical property.

Description

A kind of conductive POE and preparation method thereof

Technical field

The invention belongs to conductive material technical field, it is related to a kind of conductive POE and preparation method thereof.

Background technology

In recent years, the research for high-conductivity polymer material is very active, and it can be used as the environmental protection of combined through ground wire Anti-corrosion of metal material, the conductive plastics of Cable-like Conductive Plastics Anodes electric wire of type conductive high polymer sheath material and other earth cables The materials such as clad, require that its resistance is smaller for this high-conductivity polymer material, with fabulous electric conductivity and well The feature of environmental protection and anti-corrosive properties, in addition it is also necessary to have excellent mechanical mechanics property and processing characteristics.

POE is a kind of ethylene octane copolymer, can be used as thermoplastic elastomer (TPE), can be used as the anti-impact modifier of plastics again And toughener, it is widely used in industrial the modified toughened of automobile special material, electric wire, medical tool, household electrical appliance and packs thin The various fields such as film.Current numerous studies are directed to POE being applied to conductive material, expect to obtain electric conductivity and mechanical property Good conductive material, to be preferably applied for the fields such as electric wire, electric elements, electrode material and sensor.

CN101696289A discloses environment-friendly high-conductive plastic jacket material and preparation method thereof, the high-conductive plastic jacket Material includes base-material POE (8180), POE (8750), thermoplastic elastomer SEBS (YH-403), superconductive carbon black, dispersant, stearic acid Zinc Zn-St, paraffin, rheological agent, antioxidant and POE (DF0540), are mixed by weight ratio, are plastified and are squeezed through double screw extruder Go out, single screw extrusion machine granulation is made, and wherein base-material various composition weight is：34-39 parts of POE (8180), POE (8750) 9-15 parts, it is 8-15 parts of thermoplastic elastomer SEBS (YH-403), 25-30 parts of superconductive carbon black, 2-5 parts of dispersant, stearic Sour 0.1-0.5 parts of zinc Zn-St, 1-5 parts of paraffin, 0.2-0.8 parts of rheological agent, 0.1-0.5 parts of antioxidant and POE (DF0540) 1.5-4.5 part.This invention is using three kinds of trade mark POE as raw material, and thermoplastic elastomer is modifying agent, adds 25-30 parts of superconductive carbon blacks And other auxiliary agents such as dispersant, lubricant, rheological agent, the high-conductive plastic jacket material being made has preferable electric conductivity and stretching Performance, it is disadvantageous in that：Manufacturing process is complicated, and product quality is difficult to control between batch, is not easy to produce in enormous quantities.

The content of the invention

It is a kind of with low resistance and excellent it is an object of the invention to be provided using a kind of better simply preparation method Mechanical property conductive POE.

To achieve these goals, the present invention uses following technical scheme：

On the one hand, the invention provides a kind of conductive POE, the percentage by weight accounted for by each component is main by the following raw material system It is standby to obtain：

Wherein, each component percentage by weight sum is 100%.

POE of the present invention is ethene and the thermoplastic elastic of octene in-situ polymerization formation under metallocene catalyst catalysis Body, is characterized in：(1) the flexible chain coiled structure of octene and the ethylene chain of crystallization make it existing excellent as physical crosslinking point Toughness have good processability again.(2) there is no unsaturated double-bond in POE molecular structures, with excellent ageing-resistant performance. (3) POE narrow molecular weight distributions are good with compatible polyolefin with preferable mobility.(4) good mobility can improve and fill out The dispersion effect of material, while can also improve the weld mark strength of product.

The present invention can choose suitable POE according to the requirement of product hardness and be used as base material.Preferably, the POE is U.S. Du Pont of state 1450, Dupont 8100, Dupont 8200, Dupont 8999, Exxon Mobil 0203, Exxon Mobil 0210th, Exxon Mobil 3000, Exxon Mobil 6202, Exxon Mobil 6102, Tao Shi 8100, Tao Shi 8003, Tao Shi 7370, Tao Shi 1450, Mitsui chemistry DF710, Mitsui chemistry DF740, Mitsui chemistry DF810 and Mitsui chemistry One kind or at least two mixture in DF910.

POE accounts for 50-70% in conductive POE of the present invention, such as 50%, 52%, 54%, 55%th, 57%, 59%, 60%, 62%, 64%, 65%, 66%, 67%, 68%, 69% or 70%.

LLDPE of the present invention is LLDPE, and preferred melt flow index is less than 2 or film-grade LLDPE, it is preferable that the LLDPE is Mitsui 2020L, Mitsui 3021F, Mitsui 3520F, Mitsubishi 3100H, Mitsubishi F30H, LG-DOW 1220 and one kind or at least two mixture in LG-DOW 1221.

The soft durometers for acting as adjusting POE of LLDPE in the present invention, if product hardness is too high, reduction LLDPE's Consumption, consumption that is on the contrary then improving LLDPE.In the present invention in order that obtaining the conductive POE has preferable hardness by LLDPE Weight percent content control in 5-10%, such as 5%, 5.4%, 5.8%, 6%, 6.2%, 6.5%, 6.8%, 7%, 7.2%th, 7.5%, 7.8%, 8%, 8.2%, 8.4%, 8.6%, 8.8%, 9%, 9.2%, 9.4%, 9.6%, 9.8% or 10%.

Conductive black of the present invention preferably high structure high electric conductivity carbon black, it is preferable that the conductive black is led for Cabot Electric carbon BP 2000, Cabot conductive black Vxc72R, Cabot conductive black Vxc72, win wound Degussa conductive black Printex XE2-B, win wound Degussa conductive black HIBLACK 420B, win wound Degussa conductive black Printex L6, win Create Degussa conductive black Printex L, win wound Degussa conductive black Hiblack 40B2, section qin EC-300J, section qin EC- The conductive charcoal of 600JD, Czech's Type B superconductive carbon black and Colombia of U.S. Conductex 7055Ultra and Colombia of the U.S. One kind or at least two mixture in black 7067.

Conductive black accounts for 15-35% in conductive POE of the present invention, such as 15%, 16%, 18%th, 20%, 22%, 24%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35%.

White oil of the present invention is technical white oil, the technical white oil of preferably No. 15 or more than No. 15, and in the present invention White oil accounts for 2-5% in the conductive POE, such as 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.3%th, 3.5%, 3.7%, 3.9%, 4%, 4.2%, 4.4%, 4.6%, 4.8% or 5%.

Surfactant (dispersant) of the present invention is compound for multi-functional coupling dispersant or two or more dispersants Thing, preferably ethylene bis stearamide (EBS) and silane coupler or the compound of aluminate coupling agent.In conduction of the present invention Surfactant accounts for 2-5% in POE, such as 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.3%th, 3.5%, 3.7%, 3.9%, 4%, 4.2%, 4.4%, 4.6%, 4.8% or 5%.

Lubricant of the present invention is one in Tissuemat E, zinc stearate, magnesium stearate, calcium stearate and barium stearate Kind or at least two mixture.Polyethylene (PE) wax can for Clariant wax powder PE520, Honeywell 6A waxes, husky rope wax and The one kind covered in denier E waxes or at least two mixture.The shared percentage by weight of lubricant in conductive POE of the present invention For 0.5-2%, such as 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2%.

Antioxidant of the present invention is BASF irgasfos 168 and/or BASF antioxidant 1010.Led of the present invention Antioxidant accounts for 0.3-0.5% in electric POE, such as 0.3%, 0.32%, 0.35%, 0.38%, 0.4%th, 0.42%, 0.44%, 0.46%, 0.48% or 0.5%.

On the other hand, the invention provides a kind of conductive POE preparation method, comprise the following steps：

(1) conductive black is pre-processed：Conductive black is put into high mixer, 10min is preheated in 300r/min, water removal is gone Part, then add white oil, surfactant, lubricant and antioxidant, high speed 1500r/min processing 15-25min by formula ratio；

(2) conduction POE preparation：The conductive black handled well is mixed by formula ratio with POE and LLDPE, Ran Houmi Type is smelt, finished product is made in extruding pelletization.

The invention has the advantages that：The present invention will be then handled well by the way that conductive black is pre-processed Conductive black is mixed with POE and LLDPE, and then banburying is molded, extruding pelletization, and it is 50- to prepare containing percentage by weight 70%POE, 5-10%LLDPE, 15-35% conductive black, 2-5% white oils, 2-5% surfactants, 0.5-2% lubricants and The conductive POE of 0.3-0.5% antioxidant, preparation technology is simple, and cost is low, and obtained conductive POE has≤80 Ω electricity Resistance, and tensile strength, in more than 9MPa, elongation at break >=500%, melting means is 30-40g/10min, and density is in 1.09- 1.12g/cm³, and hardness is more than 70A, illustrates the conductive POE products in tensile strength, hardness, toughness, ageing-resistant stability In terms of all there is relatively excellent performance.

Embodiment

Technical scheme is further illustrated below by embodiment.Those skilled in the art should be bright , the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.

Embodiment 1

In the present embodiment in order to prepare conductive POE, mainly included using the percentage by weight accounted for by each component following former The formula of material：

After selected said components formula, then prepare by following steps conductive POE：(1) conductive black is pre-processed：It will lead Electric carbon black is put into high mixer, and 10min is preheated in 300r/min, removes moisture content, adds white oil, surface by formula described above afterwards Activating agent, lubricant and antioxidant, high speed 1500r/min processing 15-25min；(2) conduction POE preparation：Will by above-mentioned formula The conductive black handled well is mixed with POE and LLDPE, then using banbury banburying shaping, then using single screw rod or Person's double screw extruder is granulated, and conductive POE finished products are made.

Embodiment 2

Embodiment 3

Embodiment 4

National Standard Method according to table 1 determined under the conditions of shown experiment test conduction POE obtained by embodiment 1-4 into The resistance value of product is simultaneously surveyed respectively to mechanical property parameters such as its tensile strength, elongation at break, melting means, density and hardness Examination.Test result is as shown in table 1.

The embodiment 1-4 of table 1 measurement result

From measurement result it is known that the present invention is by the way that conductive black is pre-processed, then by the conduction handled well Carbon black is mixed with POE and LLDPE, is molded using banbury banburying, then using single screw rod or double screw extruder granulation system The standby conductive POE for obtaining each component containing following weight percent content：50-70%POE, 5-10%LLDPE, 15-35% Conductive black, 2-5% white oils, 2-5% surfactants, 0.5-2% lubricants and 0.3-0.5% antioxidant.It is prepared by the present invention The Ω of obtained conductive POE resistance value≤80, and tensile strength is in more than 9MPa, elongation at break >=500%, and melting means is 30-40g/10min, density is in 1.09-1.12g/cm³, and hardness is more than 70A, this illustrates that the conductive POE products are strong in stretching All there is relatively more excellent performance in terms of degree, hardness, toughness, ageing-resistant stability.Therefore, the conductive POE materials have excellent Good conduction and mechanical property, is expected to obtain preferably in fields such as electric wire, electric elements, electrode material and sensors Using.

Applicant states that the present invention illustrates conductive POE of the present invention and preparation method thereof, but this by above-described embodiment Invention is not limited to above-described embodiment, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Affiliated skill The technical staff in art field is it will be clearly understood that any improvement in the present invention, equivalence replacement to each raw material of product of the present invention and auxiliary The addition of co-ingredients, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.

Claims

1. a kind of conductive POE, it is characterised in that the percentage by weight that the conductive POE is accounted for by each component is prepared by the following raw material Obtain：

The preparation method of the conductive POE comprises the following steps：

(1) conductive black is pre-processed：Conductive black is put into high mixer, 10min is preheated in 300r/min, moisture content is removed, so Afterwards white oil, surfactant, lubricant and antioxidant, high speed 1500r/min processing 15-25min are added by formula ratio；

(2) conduction POE preparation：The carbon black handled well is mixed by formula ratio with POE and LLDPE, then banburying is molded, and is squeezed Go out granulation, finished product is made.

2. a kind of conductive POE, it is characterised in that the percentage by weight that the conductive POE is accounted for by each component is prepared by the following raw material Obtain：

The preparation method of the conductive POE comprises the following steps：

3. a kind of conductive POE, it is characterised in that the percentage by weight that the conductive POE is accounted for by each component is prepared by the following raw material Obtain：

The preparation method of the conductive POE comprises the following steps：

4. a kind of conductive POE, it is characterised in that the percentage by weight that the conductive POE is accounted for by each component is prepared by the following raw material Obtain：

The preparation method of the conductive POE comprises the following steps：

5. the conductive POE according to any one of claim 1-4, it is characterised in that the POE is that ethene and octene are in situ It polymerize the thermoplastic elastomer (TPE) formed.

6. conductive POE according to claim 5, it is characterised in that the POE is Dupont 1450, Dupont 8100th, Dupont 8200, Dupont 8999, Exxon Mobil 0203, Exxon Mobil 0210, Exxon Mobil 3000, Exxon Mobil 6202, Exxon Mobil 6102, Tao Shi 8100, Tao Shi 8003, Tao Shi 7370, Tao Shi 1450, Mitsui Learn DF710, Mitsui chemistry DF740, Mitsui chemistry DF810 and one kind in Mitsui chemistry DF910 or at least Two kinds of mixture.

7. the conductive POE according to any one of claim 1-4, it is characterised in that the LLDPE is melt flow index Less than 2 or film-grade LLDPE.

8. the conductive POE according to any one of claim 1-4, it is characterised in that the LLDPE is Mitsui 2020L, Mitsui 3021F, Mitsui 3520F, Mitsubishi 3100H, Mitsubishi F30H, LG-DOW 1220 and U.S. One kind or at least two mixture in state Tao Shi 1221.

9. the conductive POE according to any one of claim 1-4, it is characterised in that the conductive black is that high structure is special Conductive black.

10. conductive POE according to claim 9, it is characterised in that the conductive black is Cabot conductive black BP2000, Cabot conductive black Vxc72R, Cabot conductive black Vxc72, win wound Degussa conductive black Printex Degussa is created in XE2-B, win wound Degussa conductive black HIBLACK 420B, win wound Degussa conductive black Printex L6, win Conductive black Printex L, win wound Degussa conductive black Hiblack 40B2, section qin EC-300J, section qin EC-600JD, victory In gram Type B superconductive carbon black and the Ultra of Colombia of U.S. Conductex 7055 and Colombia of U.S. conductive black 7067 One kind or at least two mixture.

11. the conductive POE according to any one of claim 1-4, it is characterised in that the white oil is technical white oil.

12. the conductive POE according to any one of claim 1-4, it is characterised in that the white oil is the work of more than No. 15 Industry white oil.

13. the conductive POE according to any one of claim 1-4, it is characterised in that the surfactant is multi-functional It is coupled the compound of dispersant or two or more dispersants.

14. conductive POE according to claim 13, it is characterised in that the surfactant is ethylene bis stearamide With silane coupler or the compound of aluminate coupling agent.

15. the conductive POE according to any one of claim 1-4, it is characterised in that the lubricant be Tissuemat E, One kind or at least two mixture in zinc stearate, magnesium stearate, calcium stearate and barium stearate.

16. conductive POE according to claim 15, it is characterised in that the Tissuemat E be Clariant wax powder PE520, Honeywell 6A waxes, husky rope wax and the one kind covered in denier E waxes or at least two mixture.

17. the conductive POE according to any one of claim 1-4, it is characterised in that the antioxidant is BASF antioxygen Agent 168 and/or BASF antioxidant 1010.

18. the preparation method of the conductive POE according to any one of claim 1-17, it is characterised in that including following step Suddenly：