CN1074430C - Preparation of thermoplastic conductive composite material with high mechanical performance - Google Patents
Preparation of thermoplastic conductive composite material with high mechanical performanceInfo
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- CN1074430C CN1074430C CN97100447A CN97100447A CN1074430C CN 1074430 C CN1074430 C CN 1074430C CN 97100447 A CN97100447 A CN 97100447A CN 97100447 A CN97100447 A CN 97100447A CN 1074430 C CN1074430 C CN 1074430C
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Abstract
The present invention relates to a preparation method of a thermoplastic conductive composite material having high mechanical performance, which comprises the following steps: (1) a thermoplastic polymer is dissolved in an organic solvent; (2) a surface active agent, water and polyethylene glycol are added into the organic solution of the thermoplastic polymer to form emulsion; (3) phenylamine or derivatives thereof and a water solution of protonic acid are added into the emulsion; (4) an oxidizing agent solution is gradually added into the emulsion of the phenylamine and the polymer to carry out an oxidative polymerization reaction; (5) after the reaction is ended, a precipitating agent is added and heated to distill off the organic solvent; (6) the product is filtered and washed with water until the filter liquor does not contain SO4<2->; (7) alcohol is added into a filter cake at least one time, stirred, filtered and washed with water; (8) the filter cake cleanly washed is dried to obtain the thermoplastic conductive composite material having high mechanical performance. The tensile strength of the product obtained with the method of the present invention can reach 12.4 to 20.8 megapascals.
Description
The present invention relates to the manufacture method of thermoplastic conductive composite material, belong to C08G73/02, H01B1/00, H01B1/12 by the 6th edition International Classification of Patents.
In " preparation method of thermoplastic conductive composite material " of the disclosure of the Invention CN1127267A of the court, adopt emulsion polymerisation process to obtain the thermoplastic conductive macromolecular material, comprise and aniline or derivatives thereof and protonic acid are added the organic solvent that contains thermoplastic polymer (organic solvent is selected from chloroform, toluene, benzene, methylene dichloride, hexane, the mixture of hexanaphthene and above-mentioned all kinds of SOLVENTS) in, add the aqueous solution that contains tensio-active agent again, form emulsion, the aqueous solution that at room temperature in emulsion, adds oxygenant gradually, make aniline or derivatives thereof generation oxidative polymerization, generate the conducing composite material that doped polyaniline or derivatives thereof and thermoplastic polymer constitute.Be characterized in that specific conductivity is much higher than the standard machinery blend method, be easy to carry out melt-processed that processing temperature is low, electromagnetic interference shield effect is preferably arranged, have thermostability and environmental stability preferably, but that its weak point is a mechanical property is lower.
US5 in 1994 adds PEG when mentioning polymerization in 324, the 453 aniline emulsion oxypolymerization methods that propose and can obtain fibrous polyaniline, but its stability is bad, and the contriver does not provide mechanical performance data.
The method that the objective of the invention is to avoid above-mentioned weak point of the prior art and a kind of product mechanical property excellence is provided.
Purpose of the present invention can reach by following measure:
(1) thermoplastic polymer is dissolved in the organic solvent;
(2) in thermoplastic polymer organic solution, add tensio-active agent, water, and polyoxyethylene glycol, form emulsion;
(3) in emulsion, add aniline or derivatives thereof, protonic acid aqueous solution;
(4) add oxidizing agent solution in above-mentioned aniline and the polymer emulsion gradually and carry out oxidative polymerization;
(5) reaction adds precipitation agent after finishing, and heating steams organic solvent;
(6) product filters, and is washed to filtrate and does not contain SO
4 2-Till;
(7) filter cake at least once adds alcohols, stirs, and filters washing;
(8) filtration cakes torrefaction of Xi Jinging gets thermoplastic conductive composite material with high mechanical performance; Tensile strength by the inventive method products obtained therefrom can reach 12.4～20.8 MPas.
Purpose of the present invention can also reach by following measure: promptly wash used alcohols low-carbon alcohol and be selected from methyl alcohol, ethanol, propyl alcohol, its mixture of butanols or the aqueous solution.
The present invention is further explained below in conjunction with embodiment.
Embodiment 2 at room temperature is dissolved in 160 gram high-impact polystyrenes [HIPS] in 600 milliliters the benzene in reactor, adds polyoxyethylene glycol 200 10 grams after the dissolving, and sodium laurylsulfonate 190 grams add 250 milliliters of the ethanol of 800 milliliters in water and 95%, form emulsion.139.5 gram aniline are added in the hydrochloric acid soln that 400 ml concns are 6 mol, and this solution is joined in the above-mentioned emulsion.Drip 750 milliliters of the aqueous solution containing 342 gram ammonium persulphates gradually, drip and finish the back room temperature continuation reaction 1.5 hours, 1.5 add 1200 milliliters of 95% ethanol with volume pump after hour, progressively improve temperature to 60～75 ℃ of reactor, benzene distillation is come out, reaction product is transferred in the container after suction filtration, washing, add 800 milliliter 95% ethanolic soln again, and stirred suction filtration 1 hour, wash once, reaction product is dry under 60～100 ℃ condition again.Sample carries out hot-forming to the said products under 170 ℃, the condition of 15 MPas, the four point probe specific conductivity of the sheet material that obtains is 2.6 Siemens/cm, the sheet material of its 1 mm thick Electromagnetic Interference shielding efficiency in the range of frequency of 30～1500MHz is 12.6～16.4 decibels, the sheet material of 3 mm thick electromagnetic interference shield efficient in identical range of frequency is 20.0～27.1 decibels, and the sheet material of 5 mm thick Electromagnetic Interference shielding efficiency in identical range of frequency is 27.2～34.2 decibels.In injection temperature is that 180 ℃, injection pressure are 4 MPas, dwell time to be that 50 seconds and mould temperature are injection molding under 40 ℃ the condition, and the tensile strength of injection batten is 15.2 MPas.
Embodiment 3 at room temperature, in reactor, 320 gram high-impact polystyrenes [HIPS] are dissolved in 1200 milliliters the benzene, add polyoxyethylene glycol 200 10 grams after the dissolving, sodium lauryl sulphate 202 grams, 250 milliliters of ethanol that add 1200 milliliters in water and 95% form emulsion.83.7 gram aniline are added in the hydrochloric acid soln that 250 ml concns are 6 mol, and this solution is joined in the above-mentioned emulsion.Drip 450 milliliters of the aqueous solution containing 205 gram ammonium persulphates gradually, drip and finish the back room temperature continuation reaction 2 hours, add 1200 milliliters of 95% ethanol with volume pump after 2 hours, progressively improve temperature to 60～75 ℃ of reactor, benzene distillation is come out, reaction product is transferred in the container after suction filtration, washing, add 800 milliliter 95% ethanolic soln again, and stirred suction filtration 1 hour, wash once, reaction product is dry under 60～100 ℃ condition again.Sample injection temperature be 180 ℃, injection pressure be 4 MPas, dwell time are 50 seconds and mould temperature be 40 ℃ condition under injection molding, the tensile strength of injection batten is 19.6 MPas.
Embodiment 4 preparation methods add 800 milliliters in water with embodiment 3 in forming emulsion, the protonic acid of employing is tosic acid 190 grams.Sample is that 180 ℃, injection pressure are 4 MPas, dwell time to be that 50 seconds and mould temperature are injection molding under 40 ℃ the condition in injection temperature, and the tensile strength of injection batten is 15.1 MPas.
Embodiment 5 preparation methods are with embodiment 3, high-impact polystyrene is 240 grams, the solvent benzol of dissolving high-impact polystyrene is 900 milliliters, emulsifying agent sodium laurylsulfonate 190 grams, sample is at 170 ℃, carry out hot-forming under the condition of 15 MPas, the four point probe specific conductivity of the sheet material that obtains is 0.1 Siemens/cm, the sheet material of its 1 mm thick Electromagnetic Interference shielding efficiency in the range of frequency of 30～1500MHz is 3.8～7.9 decibels, the sheet material of 3 mm thick electromagnetic interference shield efficient in identical range of frequency is 7.3～10.2 decibels. in injection temperature is 180 ℃, injection pressure is 4 MPas, dwell time is that 50 seconds and mould temperature are injection molding under 40 ℃ the condition, and the tensile strength of injection batten is 19.6 MPas.
Embodiment 6 at room temperature, in reactor, 160 gram high-impact polystyrenes [HIPS] are dissolved in 600 milliliters the benzene, add polyoxyethylene glycol 200 10 grams after the dissolving, sodium laurylsulfonate 190 grams, the ethanol that adds 1000 milliliters in water and 250 milliliter 95%, violent stirring forms emulsion.111.6 gram aniline are added in the hydrochloric acid soln that 300 ml concns are 6 mol, and this solution is joined in the above-mentioned emulsion.Drip 600 milliliters of the aqueous solution containing 274 gram ammonium persulphates gradually, drip and finish the back room temperature continuation reaction 2 hours, add 1000 milliliters of 95% ethanol with volume pump after 2 hours, progressively improve temperature to 60～75 ℃ of reactor, benzene distillation is come out, reaction product is transferred in the container after suction filtration, washing, add 800 milliliter 95% ethanolic soln again, and stirred suction filtration 1 hour, wash once, reaction product is dry under 60～100 ℃ condition again.Sample carries out hot-forming to the said products under 170 ℃, the condition of 15 MPas, the four point probe specific conductivity of the sheet material that obtains is 1.25 Siemens/cm, the sheet material of its 1 mm thick Electromagnetic Interference shielding efficiency in the range of frequency of 30～1500MHz is 10.8～14.3 decibels, the sheet material of 3 mm thick electromagnetic interference shield efficient in identical range of frequency is 13.5～15.5 decibels, and the sheet material of 5 mm thick electromagnetic interference shield efficient in identical range of frequency is 20.5～24.3 decibels.Sample is that 180 ℃, injection pressure are 4 MPas, dwell time to be that 50 seconds and mould temperature are injection molding under 40 ℃ the condition in injection temperature, and the tensile strength of injection batten is 14.5 MPas
Embodiment 7 preparation methods are with embodiment 3, final product washs with 800 ml methanol, sample carries out hot-forming to the said products under 170 ℃, the condition of 15 MPas, the four point probe specific conductivity of the sheet material that obtains is 0.12 Siemens/cm, injection temperature be 180 ℃, injection pressure be 4 MPas, dwell time are 50 seconds and mould temperature be 40 ℃ condition under injection molding, the tensile strength of injection batten is 18.6 MPas.
Embodiment 8 preparation methods are with embodiment 3, but when forming emulsion, do not add polyoxyethylene glycol 200 and ethanol, sample carries out hot-forming to the said products under 170 ℃, the condition of 15 MPas, the four point probe specific conductivity of the sheet material that obtains is 0.2 Siemens/cm, sample injection temperature be 180 ℃, injection pressure be 4 MPas, dwell time are 50 seconds and mould temperature be 40 ℃ condition under injection molding, the tensile strength of injection batten is 19.3 MPas.
Add PEG when being done the visible polymerization of thermal weight loss heating curve (Fig. 1 and Fig. 2) by embodiment 7 and embodiment 8 samples the performance of product is not made significant difference, thermostability is good.Comparative Examples 1 at room temperature is dissolved in 240 gram high-impact polystyrenes [HIPS] in 900 milliliters the benzene in reactor, and the dissolving back adds 83.7 gram aniline, mix, and above-mentioned mixing solutions is added to contains sodium laurylsulfonate 96 gram in totally 1500 milliliters the water, violent stirring forms emulsion.Drip the saturated solution that contains tosic acid 171, ammonium persulphate 205 grams gradually, drip and finish the back room temperature continuation reaction 4 hours, after finishing, reaction adds 900 milliliters of 95% ethanol, progressively improve temperature to 60～80 ℃ of reactor, benzene distillation is come out, reaction product through suction filtration, wash and do not have SO in the filtrate
4 2-Till, product carries out drying again.Sample carries out hot-forming under 170 ℃, the condition of 15 MPas to the said products, the four point probe specific conductivity of the sheet material that obtains is 0.1 Siemens/cm, and its tensile strength is 3.8 MPas.Comparative Examples 2 at room temperature, in reactor, 240 gram butadiene-styrene block copolymers [SBS] are dissolved in 900 milliliters the benzene, the dissolving back adds 83.7 gram aniline and 171 gram tosic acid, mix, in above-mentioned mixing solutions, add 600 milliliters in Sodium dodecylbenzene sulfonate 209 grams and water, violent stirring forms emulsion.Drip the saturated solution of ammonium persulphate 205 grams gradually, drip to finish the back and continue reaction 4 hours, add 900 milliliters of 95% ethanol after reaction finishes, progressively improve temperature to 60～80 ℃ of reactor in room temperature, benzene distillation is come out, reaction product through suction filtration, wash and do not have SO in the filtrate
4 2-Till, product carries out drying again.Sample carries out hot-forming under 170 ℃, the condition of 15 MPas to the said products, the four point probe specific conductivity of the sheet material that obtains is 0.2 Siemens/cm, and its tensile strength is 2.1 MPas.Comparative Examples 3 at room temperature, in reactor, 240 gram butadiene-styrene block copolymers [SBS] are dissolved in 900 milliliters the benzene, the dissolving back adds 83.7 gram aniline and 250 ml concns are 6 mol hydrochloric acid, mix, in above-mentioned mixing solutions, add 600 milliliters in Sodium dodecylbenzene sulfonate 209 grams and water, violent stirring forms emulsion.Drip the saturated solution of ammonium persulphate 205 grams gradually, drip to finish the back and continue reaction 4 hours, add 900 milliliters of 95% ethanol after reaction finishes, progressively improve temperature to 60～80 ℃ of reactor in room temperature, benzene distillation is come out, reaction product through suction filtration, wash and do not have SO in the filtrate
4 2-Till, product carries out drying again.Sample carries out hot-forming under 170 ℃, the condition of 15 MPas to the said products, the four point probe specific conductivity of the sheet material that obtains is 0.06 Siemens/cm, and its tensile strength is 4.4 MPas.Embodiment 1～8, Comparative Examples 1～3 data are listed on the summary sheet, as seen by the inventive method, the tensile strength of conducing composite material significantly improves: the tensile strength of Comparative Examples conducing composite material is generally in 2.1～4.4 MPas, and can reach 12.4～20.8 MPas by the tensile strength of the conducing composite material of the inventive method gained, specific conductivity and electromagnetic wave shielding efficient are quite or omit.
Embodiment and Comparative Examples data summary table
Claims (6)
1. the manufacture method of a thermoplastic conductive composite material with high mechanical performance, may further comprise the steps: (1) thermoplastic polymer is dissolved in the organic solvent; (2) in thermoplastic polymer organic solution, add tensio-active agent, water, and polyoxyethylene glycol, form emulsion; (3) in emulsion, add aniline or derivatives thereof, protonic acid aqueous solution; (4) add oxidizing agent solution in above-mentioned aniline and the polymer emulsion gradually and carry out oxidative polymerization; (5) reaction adds precipitation agent after finishing, and heating steams organic solvent; (6) product filters, and is washed to filtrate and does not contain SO
4 2-Till; (7) filter cake at least once adds alcohols, stirs, and filters washing; (8) filtration cakes torrefaction of Xi Jinging gets thermoplastic conductive composite material with high mechanical performance; After it is characterized in that oxidation products steams organic solvent, filtration, washing, at least once obtain finished product with alcohols washing, stirring, washing, drying.
2. by the manufacture method of claim 1, it is characterized in that washing used alcohols is low-carbon alcohol.
3. by the method for claim 1 or 2, it is characterized in that low-carbon alcohol is 95% (volume) aqueous ethanolic solution.
4. by the manufacture method of claim 1, it is characterized in that protonic acid is 6M HCl.
5. by the manufacture method of claim 1, it is characterized in that tensio-active agent is sodium lauryl sulphate, sodium laurylsulfonate.
6. by the manufacture method of claim 1, it is characterized in that adding in the thermoplastic polymer emulsion Macrogol 200,95% (volume) ethanol, tensio-active agent and aqueous oxidizing agent solution and carry out oxidative polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100447A CN1074430C (en) | 1997-02-04 | 1997-02-04 | Preparation of thermoplastic conductive composite material with high mechanical performance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100447A CN1074430C (en) | 1997-02-04 | 1997-02-04 | Preparation of thermoplastic conductive composite material with high mechanical performance |
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| Publication Number | Publication Date |
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| CN1190110A CN1190110A (en) | 1998-08-12 |
| CN1074430C true CN1074430C (en) | 2001-11-07 |
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| CN97100447A Expired - Fee Related CN1074430C (en) | 1997-02-04 | 1997-02-04 | Preparation of thermoplastic conductive composite material with high mechanical performance |
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| CN103159953B (en) * | 2013-04-02 | 2015-05-13 | 东华大学 | Method for preparing conductive polymer based electromagnetic composite material |
| CN106757786A (en) * | 2016-12-09 | 2017-05-31 | 彭州市运达知识产权服务有限公司 | A kind of PAn conducting membrane and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731408A (en) * | 1985-12-20 | 1988-03-15 | Polaroid Corporation | Processable conductive polymers |
| WO1989001694A1 (en) * | 1987-08-07 | 1989-02-23 | Allied-Signal Inc. | Thermally stable forms of electrically conductive polyaniline |
| US5006278A (en) * | 1987-01-12 | 1991-04-09 | Allied-Signal | Solution processible forms of electrically conductive polyaniline and the method of manufacture of electroconductive articles therefrom |
| JPH04170493A (en) * | 1990-11-02 | 1992-06-18 | Mitsubishi Paper Mills Ltd | Antistatic composition |
| US5324453A (en) * | 1992-08-07 | 1994-06-28 | Neste Oy | Electrically conducting polyaniline: method for emulsion polymerization |
| CN1127267A (en) * | 1995-08-29 | 1996-07-24 | 北京燕山石油化工公司研究院 | Preparing method for thermoplastic conductive composite material |
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1997
- 1997-02-04 CN CN97100447A patent/CN1074430C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731408A (en) * | 1985-12-20 | 1988-03-15 | Polaroid Corporation | Processable conductive polymers |
| US5006278A (en) * | 1987-01-12 | 1991-04-09 | Allied-Signal | Solution processible forms of electrically conductive polyaniline and the method of manufacture of electroconductive articles therefrom |
| WO1989001694A1 (en) * | 1987-08-07 | 1989-02-23 | Allied-Signal Inc. | Thermally stable forms of electrically conductive polyaniline |
| JPH04170493A (en) * | 1990-11-02 | 1992-06-18 | Mitsubishi Paper Mills Ltd | Antistatic composition |
| US5324453A (en) * | 1992-08-07 | 1994-06-28 | Neste Oy | Electrically conducting polyaniline: method for emulsion polymerization |
| CN1127267A (en) * | 1995-08-29 | 1996-07-24 | 北京燕山石油化工公司研究院 | Preparing method for thermoplastic conductive composite material |
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| CN1190110A (en) | 1998-08-12 |
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