CN101092553A - Method for preparing antistatic macromolecule material - Google Patents
Method for preparing antistatic macromolecule material Download PDFInfo
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- CN101092553A CN101092553A CN 200710042884 CN200710042884A CN101092553A CN 101092553 A CN101092553 A CN 101092553A CN 200710042884 CN200710042884 CN 200710042884 CN 200710042884 A CN200710042884 A CN 200710042884A CN 101092553 A CN101092553 A CN 101092553A
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Abstract
This invention discloses a method for preparing an antistatic polymer material, which is composed of thermoplastic resin, dispersant and conductive carbon black. The method comprises: (1) uniformly mixing dried thermoplastic resin and dispersant, adding into a Banbury mixer, melting, blending, adding conductive carbon black, and mixing; or (2) uniformly mixing dried thermoplastic resin, dispersant and conductive carbon black, adding into a Banbury mixer, and mixing to obtain the antistatic polymer material. During the mixing process, the dispersion stability of conductive carbon black in the matrix resin is enhanced by the dispersant. Uniformly dispersed conductive carbon black fine particles are advantageous for tunnel effect, thus the volume resistance of the material is reduced and maintained uniform and stable. The method is simple. Antistatic polymer material with variable volume resistance (105-1011) can be obtained by adjusting the addition amount of the dispersant with that of conductive carbon black maintained 10 parts.
Description
Technical field:
The present invention relates to a kind of preparation method's of macromolecular material, particularly a kind of antistatic macromolecule material preparation method.
Background technology:
Macromolecular material is widely used in the every field of national economy and people's daily life with its excellent cost performance.The volume specific resistance of most plastics is generally 10
17～10
19Ω cm has the excellent electric insulation performance, as polypropylene PP, polythene PE etc.But its insulativity can get into trouble in a lot of occasions sometimes, during as manufacturing PE, BOPP film, the electric shock phenomenon takes place easily; Static also can cause the easy dust suction of plastics, static sparking in addition can set off an explosion, accident such as fire, these have all greatly limited the application of plastics in industries such as electronics, petrochemical industry, medical treatment.Therefore the static hazard of elimination and minimizing plastics and goods thereof has become the important topic that current polymeric material field is badly in need of solution.
Adding static inhibitor or conductive filler material and reduce or eliminates accumulation of static electricity in plastic working and the use, can make the over-all properties of goods reach more satisfactory effect, is the method for using always at present.Because the graphitized carbon black raw material is easy to get, inexpensive, conductivity lasting stability, its volume resistance is 0.1～10
2Between the Ω cm, be natural semi-conductor, can adjust the conductivity of material significantly, therefore the research of the resin system that adds graphitized carbon black (CB) be subjected to extensive concern at home and abroad as conductive filler material.In order to promote graphitized carbon black under less addition, still can provide material effective static resistance, on the one hand, be similar to Progress in PolymerScience.1992,17 (2): 417-470 utilizes the various active group of carbon blacksurface such as carboxyl, hydroxyl, quinone oxygen base etc., and is very general with the method for improving the dispersiveness of graphitized carbon black in polymeric matrix at various superpolymer of its surface grafting or oligopolymer by chemical graft or physics grafted method; Thereby research on the other hand is to change the polarity of matrix resin to improve the consistency that material absorption sooty ability promotes carbon black and matrix resin by methods such as grafting, Polymer Degradation and Stability, 1997,55 (1): 115-121 just utilizes the ionizing radiation modified poly ethylene to promote the sooty consistency; Also have many researchs to form stability and the circulation ratio that network structure limits the motion raising conductive structure of graphitized carbon black particle by crosslinked polymer, Journal of AppliedPolymer Science, 2001,81:104-115 has reported polypropylene PP/ ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE)/CB compound system, can reduce the volume specific resistance of compound system by gamma-rays radiation crosslinking UHMWPE; Method is to improve the dispersiveness of graphitized carbon black by polynary complex matrix resin more at present, Journal of Electrostatics, 1999,47:201-214 has studied PP/ nylon (PA)/glass fibre (GF)/CB tetraplex can obtain the eliminostatic material when adding a small amount of CB.Chinese patent CN1312321A also provides a kind of and has prepared the method for antistatic material by PP/ ethylene-vinyl acetate copolymer (EVA)/CB.
Aforesaid method has in theory been obtained certain success, but the uncertainty of the complicacy of technology and modified effect influences the development of industry always.Progress in Organic Coatings, 2002,45 (2-3): 249-257 improve graphitized carbon black dispersed and stable in solution system by outer adding assistant, the research of this respect and use comparative maturity, this method is simple, is popular in the coating and printing ink industry.But in plastic working, dispersion agent uses seldom separately, usually needs more composite coupling agents, expanding material or lubricant to improve the dispersion of fillers such as carbon black, and this has not only increased the complicacy of technology, and final material property is affected.Also be so in antistatic macromolecule material,, reach certain antistatic property, often need higher carbon black addition because dispersion efficiency is not high.Chinese patent CN1858098A provides a kind of anti-electrostatic flame-retardant polyvinyl, except using the paucidisperse agent, has still used coupling agent inevitably, and the addition of carbon black in final material is also greater than 10 parts.
Summary of the invention:
The purpose of this invention is to provide a kind of antistatic macromolecule material, it uses dispersion agent, with easy method, with less graphitized carbon black addition, makes macromolecular material obtain good antistatic or eliminostatic performance.
The preparation method of a kind of antistatic macromolecule material of the present invention is as follows, below all represents with mass parts:
(1) dispersant of the thermoplastic resin that 100 parts of thorough dryings are crossed and 0.2～10 part evenly adds in the Banbury mixer back, at melt blending 1～2 minute under 140～270 ℃ the processing temperature and under 20～100rpm rotor speed, add 2～10 parts of graphitized carbon blacks then, banburying 4～10 minutes obtains a kind of antistatic macromolecule material;
Or (2) thermoplastic resin that 100 parts of thorough dryings are crossed, 0.2～10 part dispersion agent and 2～10 parts of graphitized carbon blacks are mixed together even back and add in the Banbury mixer, banburying is 4～10 minutes under 140～270 ℃ processing temperatures and 20～100rpm rotor speed, obtains a kind of antistatic macromolecule material.
The thermoplastic resin that the present invention uses is polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polycarbonate (PC), polyester (PBT or PET), polyamide (PA), polyphenylene sulfide (PPS), polyphenylene oxide (PPO), polymethylmethacrylates (PMMA) etc., its melting index is 0.5～60g/10min.
The dispersion agent that the present invention uses is to contain the phospholipid natural polymer, synthetic macromolecules such as the polyamino salt of long-chain polyester, polyamino amidophosphoric acid salt; Preferably modification amide polyesters oligopolymer.
The oil-absorption(number) of the graphitized carbon black that the present invention uses is 85～380ml/100g.
In a kind of antistatic material preparation of the present invention, selected dispersion agent has higher surface activity and suitable polarity, be applied in various kinds of resin/graphitized carbon black compound system affinity matrix well, when reducing surface energy, can firmly adsorb graphitized carbon black again, promote the stably dispersing of graphitized carbon black in matrix resin.The present invention utilizes the characteristics of dispersion agent, and graphitized carbon black can be disperseed more equably with littler size in resin system, and the distributed dimension of graphitized carbon black particle reaches nano level.Be evenly distributed and be more conducive between the tiny graphitized carbon black particle volume resistance of macromolecular material is reduced and keep evenly stablizing by tunnel effect.
Technology of the present invention is simple, adds the graphitized carbon black less than 10 parts in thermoplastic resin, as long as can obtain volume specific resistance from 10 by the consumption that changes dispersion agent
5～10
11Antistatic or the eliminostatic macromolecular material that changes, and not limited by the resin polar.Relation between carbon black addition and the macromolecular material volume specific resistance obtains easily, thereby is easy to realize the stable of technology.
Description of drawings:
Fig. 1 is the stereoscan photograph of the product that obtains of Comparative Examples 2.
Fig. 2 is the stereoscan photograph of the product that obtains of embodiment 2.
Embodiment:
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
The thermoplastic resin that uses in following examples has
Polypropylene (PP), Co-polypropylene, Panjin ethene limited liability company produces, and the trade mark is F401, and melting index is 2.67g/10min;
Polyethylene (PE), linear low density polyethylene (LLDPE), petrochemical industry limited liability company of Shanghai match section produces, and the trade mark is LL0220AA, and melting index is 3.31g/10min;
Polycarbonate (PC), LG Dow Polycarbonate Ltd. produces, and the trade mark is CALIBRE
*, melting index is 30g/10min.
The graphitized carbon black that uses in following examples is Cabot Co.,Ltd's product, and the trade mark is Vulcan XC-72, and the DBP oil-absorption(number) is 168.6ml/100g.
The dispersion agent that uses in following examples is Shanghai Glenn chemical company product, and the trade mark is respectively Altfona3020 (a kind of special modification polyamino amidophosphoric acid salt) and Altfona3050 (a kind of modification amide polyesters oligopolymer).
Embodiment 1-2 (adopting above-mentioned preparation method (1)):
Polypropylene (F401), dispersion agent (Altfona3050 or Altfona3020) and graphitized carbon black (the DBP absorption value is 168.6ml/100g) that thorough drying is crossed add in the Haake torque rheometer in the ratio in the table 1, banburying 10min under the rotor speed of 190 ℃ processing temperatures and 64rpm obtains the Anti-static PP macromolecular material.The Anti-static PP macromolecular material that banburying obtains is at preheating 15mins on the press of 15MPa, under 190 ℃ of temperature, hot pressing 10min, and the 5min that colds pressing again makes the test piece of the thick 10*10mm size of 1mm.According to GB1410-78 standard testing volume specific resistance, the results are shown in Table 1.
Comparative Examples 1-2 is respectively the sample that does not add graphitized carbon black and dispersion agent, and other preparations and test condition are with embodiment 1-2, and the volume specific resistance test result sees Table 1.
The prescription and the volume specific resistance of table 1 Anti-static PP macromolecular material
| Prescription (mass fraction) | Volume specific resistance (Ω cm) | ||||
| PP | CB | Altfona3020 | Altfona3050 | ||
| Embodiment 1 | 100 | 8 | 2 | 1.94×10 10 | |
| Embodiment 2 | 100 | 8 | 2 | 1.08×10 6 | |
| Comparative Examples 1 | 100 | 8.25×10 16 | |||
| Comparative Examples 2 | 100 | 8 | 6.00× 10 12 | ||
As can be seen from Table 1, when in PP, adding 8 parts of graphitized carbon blacks, add dispersant A ltfona3020 and can make the volume specific resistance of macromolecular material reduce by 6 orders of magnitude, can do antistatic material and use; Add dispersant A ltfona3050 and can make the volume specific resistance of macromolecular material reduce by 10 orders of magnitude, can do the eliminostatic material and use; And the volume specific resistance of macromolecular material that does not add dispersion agent is 10
12The order of magnitude, still can not reach anlistatig purpose.Fig. 1 is the stereoscan photograph of the product that obtains of Comparative Examples 2, amplifies 8,000 times.As can be seen from Figure 1, do not add in the graphitized carbon black/PP compound system of dispersion agent, carbon black dispersion is bad, and a large amount of carbon blacks are distributed among the PP with the form of agglomerate, do not reach the effect that reduces material volume resistivity; Fig. 2 is the stereoscan photograph of the product that obtains of embodiment 2, amplifies 10,000 times.As can be seen from Figure 2, added in graphitized carbon black/PP compound system of dispersant A ltfona3050, can observed bigger graphitized carbon black particle also less than 500nm, more graphitized carbon black particle is evenly dispersed among the PP with more tiny size.Graphitized carbon black distributes tiny more, even more, and then the graphitized carbon black spacing of particle is approaching more, the just easy more volume resistance reduction that makes material by tunnel effect.
Embodiment 3-5 (adopting above-mentioned preparation method (1)):
Linear low density polyethylene (LL0220AA), dispersion agent (Altfona3050) and graphitized carbon black (the DBP absorption value is 168.6ml/100g) that thorough drying is crossed add in the Haake torque rheometer in the ratio in the table 2, banburying 10min under the rotor speed of 160 ℃ processing temperatures and 64rpm obtains antistatic PE macromolecular material.The antistatic PE macromolecular material that banburying obtains is at preheating 15mins on the press of 15MPa, under 160 ℃ of temperature, hot pressing 10min, and the 5min that colds pressing again makes the test piece of the thick 10*10mm size of 1mm.According to GB1410-78 standard testing volume specific resistance, the results are shown in Table 2.
Comparative Examples 3-4 is respectively the sample that does not add graphitized carbon black and dispersion agent, and other preparations and test condition are with embodiment 3-5, and the volume specific resistance test result sees Table 2.
The prescription and the volume specific resistance of the antistatic PE macromolecular material of table 2
| Prescription (mass fraction) | Volume specific resistance (Ω cm) | |||
| PE | CB | Altfona3050 | ||
| Embodiment 3 | 100 | 8 | 2 | 1.85×10 11 |
| Embodiment 4 | 100 | 8 | 4 | 1.33×10 8 |
| Embodiment 5 | 100 | 10 | 0.6 | 8.50×10 10 |
| Comparative Examples 3 | 100 | 3.31×10 16 | ||
| Comparative Examples 4 | 100 | 8 | 1.06×10 14 | |
As can be seen from Table 2, when in PE, adding 8 parts of graphitized carbon blacks, add dispersant A ltfona3050 and can make the volume specific resistance of macromolecular material reduce by 5～8 orders of magnitude, can do antistatic material and use; And the volume specific resistance of macromolecular material that does not add dispersion agent is 10
14The order of magnitude, still can not reach anlistatig purpose.Comparative example 4 and 5 as can be seen, the volume specific resistance that the consumption (embodiment 4) that increases dispersion agent can more effective reduction material than the consumption (embodiment 5) that increases graphitized carbon black.
Embodiment 6-7 (adopting above-mentioned preparation method (2)):
Polycarbonate (the CALIBRE that thorough drying is crossed
*), dispersion agent (Altfona3050 or Altfona3020) adds in the Haake torque rheometer in the ratio in the table 2, melt blending under 240 ℃ the processing temperature and under the rotor speed of 64rpm 1 minute, by the amount in the table 2 graphitized carbon black (the DBP absorption value is 168.6ml/100g) is added banburying 10min in the Haake torque rheometer again, obtain the antistatic PC macromolecular material.The antistatic PC macromolecular material that banburying obtains is at preheating 15mins on the press of 15MPa, under 240 ℃ of temperature, hot pressing 10min, and the 5min that colds pressing again makes the test piece of the thick 10*10mm size of 1mm.According to GB1410-78 standard testing volume specific resistance, the results are shown in Table 3.
Comparative Examples 5-6 is respectively the sample that does not add graphitized carbon black and dispersion agent, and other preparations and test condition are with embodiment 6-7, and the volume specific resistance test result sees Table 3.
The prescription and the volume specific resistance of table 3 antistatic PC macromolecular material
| Prescription (mass fraction) | Volume specific resistance (Ω cm) | ||||
| PC | CB | Altfona3050 | Altfona3020 | ||
| Embodiment 6 | 100 | 8 | 2 | 1.06×10 6 | |
| Embodiment 7 | 100 | 8 | 2 | 2.62×10 5 | |
| Comparative Examples 5 | 100 | 1.32×10 16 | |||
| Comparative Examples 6 | 100 | 8 | 2.97×10 11 | ||
As can be seen from Table 3, when in PC, adding 8 parts of graphitized carbon blacks, add dispersant A ltfona3050 or Altfona3020 and can make the volume specific resistance of macromolecular material reduce by 10～11 orders of magnitude, can do the eliminostatic material and use.
Claims (5)
1. the preparation method of an antistatic macromolecule material is characterized in that the preparation method is as follows:
(1) dispersant of the thermoplastic resin that 100 parts of thorough dryings are crossed and 0.2～10 part evenly adds in the Banbury mixer back, at melt blending 1～2 minute under 140～270 ℃ the processing temperature and under 20～100rpm rotor speed, add 2～10 parts of graphitized carbon blacks then, banburying 4～10 minutes obtains a kind of antistatic macromolecule material; Or (2) thermoplastic resin that 100 parts of thorough dryings are crossed, 0.2～10 part dispersion agent and 2～10 parts of graphitized carbon blacks are mixed together even back and add in the Banbury mixer, banburying is 4～10 minutes under 140～270 ℃ processing temperatures and 20～100rpm rotor speed, obtains a kind of antistatic macromolecule material.
2. according to the preparation method of right 1 described a kind of antistatic macromolecule material, it is characterized in that described dispersion agent is polyamino salt, polyamino amidophosphoric acid salt or the modification amide polyesters oligopolymer that contains phospholipid natural polymer, long-chain polyester.
3. according to the preparation method of right 1 described a kind of antistatic macromolecule material, it is characterized in that dispersion agent is preferably modification amide polyesters oligopolymer.
4. according to the preparation method of right 1 described a kind of antistatic macromolecule material, it is characterized in that thermoplastic resin is a polypropylene, polyethylene, polyvinyl chloride, polystyrene, polycarbonate, polyester, polymeric amide, polyphenylene sulfide, polyphenylene oxide or polymethylmethacrylate; Its melting index is 0.5～60g/10min.
5. according to the preparation method of right 1 described a kind of antistatic macromolecule material, the oil-absorption(number) that it is characterized in that graphitized carbon black is 85～380ml/100g.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225217B (en) * | 2008-02-03 | 2010-06-16 | 惠州鑫长风电子有限公司 | Material for manufacturing computer fan |
| CN101948614A (en) * | 2009-07-08 | 2011-01-19 | 帝人化成株式会社 | The moulding product that form by conductive resin composition |
| CN102304272A (en) * | 2011-04-03 | 2012-01-04 | 广东生益科技股份有限公司 | Black halogen-free flame-retardant epoxy resin composition and cover film prepared from same |
| CN102414282A (en) * | 2009-04-24 | 2012-04-11 | 狮王株式会社 | Polar dispersion composition of carbon black |
| CN103319765A (en) * | 2012-03-22 | 2013-09-25 | 金发科技股份有限公司 | Conductive barrier polyethylene composition, its preparation method and application |
| CN109691274A (en) * | 2017-10-23 | 2019-04-30 | (株)张自动化 | Seeder with Electro-static Driven Comb function |
| CN111269697A (en) * | 2020-03-29 | 2020-06-12 | 连云港中意航空材料有限公司 | Method for synthesizing high-molecular abrasive and antistatic agent |
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2007
- 2007-06-28 CN CN 200710042884 patent/CN101092553A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225217B (en) * | 2008-02-03 | 2010-06-16 | 惠州鑫长风电子有限公司 | Material for manufacturing computer fan |
| CN102414282A (en) * | 2009-04-24 | 2012-04-11 | 狮王株式会社 | Polar dispersion composition of carbon black |
| CN102414282B (en) * | 2009-04-24 | 2014-03-12 | 狮王株式会社 | Polar dispersion composition of carbon black |
| CN101948614A (en) * | 2009-07-08 | 2011-01-19 | 帝人化成株式会社 | The moulding product that form by conductive resin composition |
| CN101948614B (en) * | 2009-07-08 | 2014-07-02 | 帝人化成株式会社 | Molding made from conductive resin composition |
| CN102304272A (en) * | 2011-04-03 | 2012-01-04 | 广东生益科技股份有限公司 | Black halogen-free flame-retardant epoxy resin composition and cover film prepared from same |
| CN103319765A (en) * | 2012-03-22 | 2013-09-25 | 金发科技股份有限公司 | Conductive barrier polyethylene composition, its preparation method and application |
| CN103319765B (en) * | 2012-03-22 | 2015-12-16 | 金发科技股份有限公司 | A kind of conduction, barrier polyethylene composition and its preparation method and application |
| CN109691274A (en) * | 2017-10-23 | 2019-04-30 | (株)张自动化 | Seeder with Electro-static Driven Comb function |
| CN111269697A (en) * | 2020-03-29 | 2020-06-12 | 连云港中意航空材料有限公司 | Method for synthesizing high-molecular abrasive and antistatic agent |
| CN113024966A (en) * | 2021-01-28 | 2021-06-25 | 宁波贝拓电气有限公司 | Shell for photoelectric switch and preparation method thereof |
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