CN103122061B - The method of a kind of direct preparation filling porous carbon material conductive polyester matrix material - Google Patents
The method of a kind of direct preparation filling porous carbon material conductive polyester matrix material Download PDFInfo
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- CN103122061B CN103122061B CN201110355842.5A CN201110355842A CN103122061B CN 103122061 B CN103122061 B CN 103122061B CN 201110355842 A CN201110355842 A CN 201110355842A CN 103122061 B CN103122061 B CN 103122061B
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- porous carbon
- carbonic acid
- ester
- carbon materials
- catalyzer
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Abstract
The present invention relates to a kind of method of direct synthesizing porous Carbon Materials electroconductibility polyester composite.The present invention adopts melt transesterification process, with porous carbon materials load basic cpd for catalyzer, with dihydroxy compound and carbonic diester based compound for conductive polycarbonate prepared by raw material.The filling quality per-cent of porous carbon materials just can obtain volume specific resistance and be less than 10 between 1% ~ 10%
3the product of Ω m.The method is simple, and carbon material consumption is little, can directly synthesize the polycarbonate material with better electrical property from raw material.
Description
Technical field
The present invention relates to a kind of preparation method of porous carbon materials conductive polyester, polyester monocase is together mixed with the porous carbon materials of supported catalyst, directly synthesizes macromolecule conducting material by melt transesterification process.
Background technology
This method of conductive polymer composites that conductive filler material preparation has lasting stability conductivity is added in polyester material, because technique is simple, lightweight, easy-formation, goods can once complete, resistivity is convenient to regulate and the advantage such as total cost is low, is widely used in recent years in many industries such as electronics, the energy, chemical industry, aerospace.Porous carbon materials not only has excellent conductivity, and also has very superior dimensional effect, is widely used in being filled in polyester material and prepares conducing composite material.Due to carbon black have cheap, practical, be widely used that (electrical resistivity range is 0 ~ 10
8between Ω cm), electroconductibility lasting stability, carbon black filled type conducting polymer composite is most widely used one in current conductive polymeric composite, not only can be used as eliminate and prevent polymer surface electrostatic, the aspects such as face dress heating element, electromagnetic wave shielding and high conductor electrode material can also be used as.Except carbon black, electrically conductive graphite, conductive carbon fibre are also the conductive fillers relatively commonly used, carbon nanotube as conductive filler, because its excellent dimensional effect becomes the focus studied now.
The preparation method of traditional compound-type conducting polyester has solution method and scorification two kinds.Porous carbon materials and the polyester simple blend required conductive fill agent content when reaching conductivity requirement is usually higher, causes the melt viscosity of compound system to increase, and processing characteristics and mechanical property are deteriorated, and cost increases.The people such as MosheNarkis by melt mixing methods, obtain 10 when black loading is more than 6% in " Newinjectionmoldableelectrostaticdissipative (ESD) compositesbasedonverylowcarbonblackloadings " literary composition
3the conductive polycarbonate of Ω cm; Mao Chengyu utilizes the mode of melting mixing in patent CN200910239056.1, obtains 5.7 × 10 with the black loading of 10%
6the conductive polycarbonate material of Ω cm; Bayer A.G by the method for melt blending, utilizes grafting effect being distributed to even carbon nanotube in polycarbonate of transesterification catalyst in patent DE20090611.Therefore, reduce the percolation threshold of conductive filler, under as far as possible low porous carbon materials consumption, prepare the important directions that high conductivity polyester composite is conductive polyester research.
Porous carbon materials load basic cpd is utilized to make catalyzer, by melt transesterification process direct synthesizing polyester class matrix material, not only eliminate repeat process complicated process, reduce costs, and porous carbon materials can be made fully to mix with polyester, the loading level of conductive filler can be reduced, also can reduce the impact of post-treatment process on polyester material performance, the conductive fill amount with 1% ~ 10% just obtains volume specific resistance lower than 10 simultaneously
3the conductive polyester material of Ω m.
Summary of the invention
The invention provides a kind of method preparing filling porous carbon material conductive polyester matrix material.Adopt alkaline metal salt to do on catalyst cupport to porous carbon materials and do conductive filler, with two ester group compounds and dihydroxy compound for raw material, when porous carbon materials loading level is 1% ~ 10% time, the volume specific resistance of the filling porous carbon material conductive polyester matrix material utilizing melt transesterification process to prepare can reach 10
3below Ω m.
Concrete technical scheme:
In the methods of the invention, two ester group compounds that can be used for preparing polyester can represent with general formula below:
Wherein R
1, R
2for hydrocarbyl group, can be aromaticity, the group of heteroatomic or pure alkyl.
Preferred diacyloxy diester compound includes but not limited to two (4-chloro-phenyl-) ester of diphenyl carbonate, carbonic acid two (methyl salicyl) ester, carbonic acid, two (O-Nitrophenylfluorone) ester of carbonic acid, two (4-tert-butyl-phenyl) ester of carbonic acid, carbonic acid dinaphthyl ester, two (biphenyl) ester of carbonic acid, carbonic acid two (o-methoxyphenyl) ester, dimethyl terephthalate (DMT), diethyl terephthalate, dibutyl terephthalate, dimethyl phthalate, and composition thereof.
Dihydroxy compound can represent with general formula below:
Wherein: R
3for hydrocarbyl group, wherein hydrocarbyl group can be aromaticity, heteroatomic or alkanes;
Preferred dihydroxyl includes but are not limited to ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 2,2-bis-(4-hydroxy phenyl) propane, 3,3-bis-(4-hydroxy phenyl) pentane, 2,2-bis-(3, the bromo-4-hydroxy phenyl of 5-bis-) propane, 2,2-bis-(3,5-dimethyl-4-hydroxy phenyl) propane, 2,2-bis-(3-methoxyl group-4-hydroxy phenyl) propane, 2,2-bis-(3,5-phenylbenzene-4-hydroxy phenyl) propane, and composition thereof.
Basic catalyst is any one in basic metal, alkaline-earth metal, the carbonate of transition metal, acetate, acetylacetonate and its oxyhydroxide.The feed postition of catalyzer loads on conductive filler, joins in that system of reaction together with carbon black.The mode of loading selected is pickling process, and the concentration of steeping fluid is selected at 0.01molL
-1~ 1.00molL
-1between, preferred 0.05molL
-1~ 0.5molL
-1between.Carbon black does conductive filler, and the specific surface area of carbon black is at 100m
2g
-1~ 1000m
2g
-1between.The mass percentage of carbon black is chosen as 0% ~ 10%, and preferably 1% ~ 8%.
The preparation method of described filling porous carbon material conductive polyester matrix material is that the porous carbon materials of the catalyzer by load does conductive filler and two ester group compounds together with dihydroxy compound by the direct compositing conducting polyester composite of melt transesterification process.Compared with the preparation method of conventional composite type electro-conductive material, eliminate a step Blending Processes, base material synthesis is replaced by a step with the filling of conductive agent, not only simplification of flowsheet, reduce costs, and make conductive agent disperse evenly, greatly reduce the loading level of porous carbon materials, decrease the impact of conductive agent on product mechanical property, obtain volume specific resistance when lower loading level lower than 10
3the conductive polyester matrix material of Ω m, present method is the preparation method of a novel very potential filling porous carbon material conductive polyester matrix material.
Embodiment
Further illustrate the present invention below by embodiment, but enforcement of the present invention is not limited to following examples:
Embodiment 1
The KOH solution 400.0mL of preparation 0.10mol/L, then joins in solution by 40.0g carbon black, at room temperature stirs 12h, suction filtration, washing, then obtain catalyzer at 100 DEG C of vacuum-drying 12h.
Take 43.2mmol dihydroxyphenyl propane and 46.7mmol diphenyl carbonate joins in three-necked flask, add 0.5g catalyzer, then divide transesterify and polycondensation two step of reaction reactions.
Use CH
2cl
2extract the PC in product, then utilize Ubbelohde viscometer to record viscosity-average molecular weight for 22803gmol according to " GB/T1632-93 dilute polymer viscosity number and For Intrinsic Viscosity Measurements "
-1.
The product obtained is made the disk that thickness is about 1.0mm, and the volume specific resistance recording sample with universal meter is 1.56 × 10
3Ω m.
Embodiment 2-6
Under the same terms, change catalyst levels, investigate its impact on the conductivity of product, test condition is identical with embodiment 1, the results are shown in table 1.
Table 1 conductive fill amount is on the impact of sample conductivity
Embodiment 7
The KOH solution 100.0mL of preparation 0.10mol/L, then joins in solution by 10.00g carbon nanotube, at room temperature stirs 12h, suction filtration, washing, then obtain catalyzer at 100 DEG C of vacuum-drying 12h.
Take 43.2mmol dihydroxyphenyl propane and 46.7mmol diphenyl carbonate joins in three-necked flask, add 1.5g catalyzer, then divide transesterify and polycondensation two step of reaction reactions.
Use CH
2cl
2extract the PC in product, then utilize Ubbelohde viscometer to record viscosity-average molecular weight for 20181gmol according to " GB/T1632-93 dilute polymer viscosity number and For Intrinsic Viscosity Measurements "
-1.
The product obtained is made the disk that thickness is about 1.0mm, and the volume specific resistance recording sample with universal meter is 4.14 × 10
3Ω m.
Embodiment 8
The ethylene glycol taking 51.5mmol dimethyl terephthalate (DMT) and 77.25mmol joins in three-necked bottle, adds catalyzer 0.35g obtained in embodiment 1, then divides transesterify and polycondensation two step of reaction reactions.
The product obtained is made the disk that thickness is about 1.0mm, and the volume specific resistance recording sample with universal meter is 2.87 × 10
4Ω m.
Embodiment 9
The LiACAC solution 400.0mL of preparation 0.10mol/L, then joins in solution by 40.0g carbon black, at room temperature stirs 12h, suction filtration, washing, then obtain catalyzer at 100 DEG C of vacuum-drying 12h.
Take 43.2mmol dihydroxyphenyl propane and 46.7mmol diphenyl carbonate joins in three-necked flask, add 1.75g catalyzer, then divide transesterify and polycondensation two step of reaction reactions.
Use CH
2cl
2extract the PC in product, then utilize Ubbelohde viscometer to record viscosity-average molecular weight for 22892gmol according to " GB/T1632-93 dilute polymer viscosity number and For Intrinsic Viscosity Measurements "
-1.
The product obtained is made the disk that thickness is about 1.0mm, and the volume specific resistance recording sample with universal meter is 7.39 × 10
3Ω m.
Comparative example 1
(viscosity-average molecular weight is 25223gmol by the obtained polycarbonate of the method for melt transesterification 0.30g carbon black to be added to 2.70g
-1) in, obtain product at 260 DEG C of mechanical stirring 1h.
Use CH
2cl
2extract the PC in product, then utilize Ubbelohde viscometer to record viscosity-average molecular weight for 15327gmol according to " GB/T1632-93 dilute polymer viscosity number and For Intrinsic Viscosity Measurements "
-1.
The product obtained is made the disk that thickness is about 1.0mm, and the volume specific resistance recording sample with universal meter is 706 Ω m.
Claims (2)
1. prepare a method for conductive polycarbonate, it is characterized in that: with porous carbon materials load basic cpd for catalyzer, with carbonic diester based compound and dihydroxy compound for raw material, directly prepare conductive polycarbonate by melt transesterification process; Described carbonic acid diester compound is diphenyl carbonate, carbonic acid (dimethyl salicyl) ester, two (4-chloro-phenyl-) ester of carbonic acid, two (O-Nitrophenylfluorone) ester of carbonic acid, two (4-tert-butyl-phenyl) ester of carbonic acid, carbonic acid dinaphthyl ester, two (biphenyl) ester of carbonic acid, two (o-methoxyphenyl) ester of carbonic acid; Described basic cpd is any one in basic metal, alkaline-earth metal, the carbonate of transition metal, acetate, acetylacetonate and its oxyhydroxide; The carrying method of porous carbon materials load basic cpd is pickling process, and dipping solution concentration is at 0.01molL
-1~ 1.00molL
-1between; Porous carbon materials is graphitized carbon black, and the mass percentage of porous carbon materials is chosen as 1% ~ 8%.
2. prepare the method for electroconductibility polyester according to claim 1, it is characterized in that: be pass through melt transesterification process, by reaction monomers and catalyzer melting mixing, through step-by-step decompression, intensification, under churned mechanically effect, directly prepare conductive polycarbonate, pressure range is between 10000Pa ~ 100Pa, temperature range is normal temperature to 300 DEG C, total reaction time 1 ~ 8 hour.
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| CN108841154A (en) * | 2018-04-18 | 2018-11-20 | 句容沣润塑料制品有限公司 | The preparation method of infant's plastic products |
| CN109679083A (en) * | 2018-12-31 | 2019-04-26 | 方万漂 | A kind of polycarbonate anti-static sheath material and preparation method thereof |
| CN112250577A (en) * | 2020-10-01 | 2021-01-22 | 银金达(上海)新材料有限公司 | Accelerated degradation catalyst and preparation method thereof |
| CN114316238B (en) * | 2021-12-10 | 2023-06-09 | 卓尔博（宁波）精密机电股份有限公司 | Bisphenol A type polycarbonate composite material for motor housing and preparation method thereof |
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| CN1167664C (en) * | 2002-08-28 | 2004-09-22 | 天津大学 | Catalytic synthesis of methyl phenyl oxalate and phenostal by using load metal oxide |
| US20050070658A1 (en) * | 2003-09-30 | 2005-03-31 | Soumyadeb Ghosh | Electrically conductive compositions, methods of manufacture thereof and articles derived from such compositions |
| CN1562952A (en) * | 2004-04-08 | 2005-01-12 | 天津大学 | Method for catalyzer synthesizing methyl-phenyl-oxalate and phenostal |
| CN101255115A (en) * | 2008-03-26 | 2008-09-03 | 中国科学院成都有机化学有限公司 | Method for synthesizing long-chain alkyl carbonate by transesterification |
| CN101759987B (en) * | 2009-12-28 | 2012-10-10 | 毛澄宇 | Conductive polycarbonate mixture and preparation method thereof |
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Address after: 610041 Chengdu hi tech Zone, East Road, high tech building Co-patentee after: Jiangsu oxiranchem Co., Ltd. Patentee after: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences Address before: 610041 Chengdu hi tech Zone, East Road, high tech building Co-patentee before: Oxiranchem (Yangzhou) Co., Ltd. Patentee before: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences |