CN103756277A - Conductive polycarbonate composite, preparation method and application thereof - Google Patents
Conductive polycarbonate composite, preparation method and application thereof Download PDFInfo
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- CN103756277A CN103756277A CN201310745756.4A CN201310745756A CN103756277A CN 103756277 A CN103756277 A CN 103756277A CN 201310745756 A CN201310745756 A CN 201310745756A CN 103756277 A CN103756277 A CN 103756277A
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Abstract
The invention belongs to the technical field of polycarbonate materials and discloses a conductive polycarbonate composite, a preparation method and an application thereof. The conductive polycarbonate composite comprises the following components in parts by weight: 100 parts of polycarbonate and 19-50 parts of conductive polyester master batch; the conductive polyester master batch comprises the following components in parts by weight: 10-30 parts of polyester, 1-5 parts of toughening agent, 8-15 parts of carbon black, 0.1-0.5 part of ester exchange inhibitor and 0-1 part of additive. The conductive polycarbonate composite, the preparation method and the application disclosed by the invention have the advantages that uniformly-dispersed master batches are obtained by utilizing selective dispersion of the carbon black in the polyester phase and firstly dispersing the carbon black in the polyester, and then are dispersed into polycarbonate, so that the dispersibility is improved, the used amount of the carbon black needed for building a conductive path is reduced; and the prepared conductive polycarbonate composite also has good conductivity under the low carbon-black filling amount, retains excellent mechanical property of the original polycarbonate resin, can be applied in the field of electronic appliances and is especially applicable to preparing conductive carrier belts for SMT (Surface Mount Technology) assembly in the electronic industry.
Description
Technical field
The invention belongs to polycarbonate material technical field, particularly a kind of low black loading, conductivity is good and mechanical property is excellent conductive polycarbonate composition and method of making the same and the application in electronic apparatus.
Background technology
In plastics, add conductive filler material (as graphitized carbon black, carbon fiber) be one of main method of preparing conductive plastics, but the loading level of generalized case conductive filler material is all larger, cause the mechanical property of material and machine-shaping property etc. to reduce more obvious, the consumption that therefore reduces conductive filler material is the important directions of preparing high-performance conductive plastics.Use the graphitized carbon black of super-high structure degree, as oil-absorption(number) index is greater than the superconduction carbon black of 300mL/100g, can less than 10%, reach conductive effect at content, but it is expensive, has limited its application.
Chinese patent CN101591469B discloses a kind of conductive polycarbonate/polybutylene terephthalate matrix material, use the graphitized carbon black of oil-absorption(number) 150mL/100g, when every 100 weight part polycarbonates of black loading add 21 weight part, the surface resistivity of matrix material can reach 10
5ohm-sq, but high carbon black-filled use, the mechanical property of reduction system, causes applying limited.
Summary of the invention
For the shortcoming that overcomes above-mentioned prior art is with not enough, primary and foremost purpose of the present invention is to provide a kind of low black loading, conductivity is good and mechanical property is excellent conductive polycarbonate composition.
Another object of the present invention is to provide the preparation method of a kind of above-mentioned low black loading, conductivity is good and mechanical property is excellent conductive polycarbonate composition.
Still a further object of the present invention is to provide the application in electronic apparatus of above-mentioned low black loading, conductivity is good and mechanical property is excellent conductive polycarbonate composition.
Object of the present invention realizes by following proposal:
Low black loading, the conductive polycarbonate composition that conductivity is good and mechanical property is excellent, the component that comprises following weight part meter:
100 parts of polycarbonate;
19～50 parts of conductive polyester master batches;
The component that described conductive polyester master batch comprises following weight part meter:
Preferably, the melt flow rate (MFR) of described polycarbonate (PC) is at 300 ℃, and 1.2Kg, is 5～30g/10min under ASTMD-1238 mensuration.
Preferably, described polyester is at least one in polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT) and polybutylene terephthalate (PBT).
More preferably, described polyester is polybutylene terephthalate.
Preferably, the oil-absorption(number) of described carbon black is 100～300mL/100g, according to ASTM standard D2414, measures.
Preferably, described toughner is selected from least one in ethylene-methyl methacrylate butyl ester-glycidyl acrylate terpolymer and ethylene-methyl acrylate copolymer.
Described ester exchange inhibitor is phosphite ester compound, is preferably tricresyl phosphite (TPP).
Preferably, described auxiliary agent is at least one in oxidation inhibitor and lubricant.
Wherein, described oxidation inhibitor is at least one in hindered phenol compound, phosphite ester compound and organosulfur oxidation inhibitor.Preferably, described oxidation inhibitor is at least one in antioxidant 1010, irgasfos 168.
Described lubricant is preferably at least one in low molecule ester class, metal soap, stearic acid complex ester class and amides.
The present invention also provides the preparation method of a kind of above-mentioned low black loading, conductivity is good and mechanical property is excellent conductive polycarbonate composition, comprises following concrete steps:
(1), after 10～30 weight part polyester, 1～5 weight part toughner, 8～15 weight part carbon blacks, 0.1～0.5 weight part ester exchange inhibitor and 0～1 weight part auxiliary agent are mixed, melt extrude, granulation, obtain conductive polyester master batch;
(2) the conductive polyester master batch and 100 weight part polycarbonates that 19～50 weight part steps (1) are prepared mix, and melt extrude, granulation, obtain conductive polycarbonate composition.
The condition melt extruding described in step (1) is 220～240 ℃.
The condition melt extruding described in step (2) is 240～260 ℃.
In preparation process of the present invention, when keeping conductive polycarbonate composition superior electrical conductivity energy, reduce the consumption of carbon black, improved the overall performance of composition.
Conductive polycarbonate composition of the present invention still can have good electroconductibility under low carbon black filled consumption, and retain the good mechanical property of former polycarbonate resin, can be applicable to field of electronics, be particularly useful for making the conduction carrier band of electron trade SMT assembling use.
Mechanism of the present invention is:
The present invention utilizes carbon black at polyester such as polybutylene terephthalates, to have good selectivity in mutually to disperse, pass through two-step approach, reduce the consumption of setting up the required carbon black of conductive path, the polycarbonate compositions preparing still can have good electroconductibility under low carbon black filled consumption, retains again the good mechanical property of former polycarbonate resin.When keeping superior electrical conductivity energy in preparation process, reduce the consumption of carbon black, improved the overall performance of composition.The polyester such as polycarbonate and polybutylene terephthalate can connect transesterification reaction under molten state, and add carbon black, add rear system viscosity to increase, melt extruding in process, suffered shearing is stronger, transesterification reaction degree increases, material degradation possibility is increased, have a strong impact on the performance of material; The present invention passes through two-step approach, by the polyester such as ester exchange inhibitor and polybutylene terephthalate melting mixing in advance, complexing residual catalyzer during the polyester such as synthetic polybutylene terephthalate, contingent transesterification reaction while being conducive to suppress the polyester such as a rear step polybutylene terephthalate and polycarbonate mixing, keeps the original performance of material.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) conductive polycarbonate composition of the present invention had both had superior electrical conductivity energy, retained again the good mechanical property of former polycarbonate resin.
(2) the present invention prepares conductive polycarbonate composition by two-step approach, and carbon black is disperseed mutually at polyester in advance, guarantees, under conductivity prerequisite that conductive polycarbonate composition is good, to reduce the consumption of carbon black.
(3) in two-step approach of the present invention, use in advance titanium class catalyzer residual in the effective complexing polyester of ester exchange inhibitor, the transesterification reaction degree occurring while reducing polyester and polycarbonate blending, has improved the overall performance of composition.
(4) conductive polycarbonate composition of the present invention has excellent conductivity and mechanical property, can be applicable to field of electronics, is particularly useful for making the conduction carrier band of electron trade SMT assembling use.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiments of the invention adopt following raw material:
Polycarbonate, supports purchased from Korea S three, trade mark TRIREX3025PJ, and melting index is about 10g/min;
Polybutylene terephthalate, purchased from Yizheng Fiber Optical plant company limited, the trade mark is PBT L2100, viscosity is 0.8dL/g;
Carbon black, purchased from winning wound Degussa, trade mark HIBLACK420B, DBP value is 153mL/100g;
Toughner EMA, purchased from U.S. DuPont company, trade mark ELVALOY1125AC;
Anti-oxidant Irganox 1010, purchased from Ciba company, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Lubricant is pentaerythritol stearate, and purchased from LOZA company, the trade mark is GLYCOLUBE-P.
Tensile property test is undertaken by ASTM D638, specimen size 160*12.7*3.2mm, and draw speed is 10mm/min; Flexural strength is undertaken by ASTM D790, specimen size 64*12.7*3.2mm, and rate of bending is 2mm/min, span is 51.2mm; Socle girder notched Izod impact strength is undertaken by ASTM D256, specimen size 64*10.2*3.2mm;
Electroconductibility is measured according to ASTM standard D257; Surface resistivity is larger, and material electroconductibility is poorer.
Embodiment 1: the preparation of conductive polycarbonate composition
The carbon black of the toughner of the polybutylene terephthalate of 15 weight parts, 3 weight parts, 8 weight parts, 0.1 weight part ester exchange inhibitor, 0.1 weight part oxidation inhibitor, the lubricant of 0.2 weight part, after mixing in input mixing machine, in twin screw extruder, extruding pelletization at the temperature of 220～240 ℃, obtains conductive polyester master batch.
Again conductive polyester master batch is mixed with the polycarbonate of 100 weight parts, at the temperature of 240～260 ℃, melt extrude, granulation, obtain conductive polycarbonate composition.
Embodiment 2: the preparation of conductive polycarbonate composition
The carbon black of the toughner of 30 weight part polybutylene terephthalates, 1 weight part, 15 weight parts, 0.5 weight part ester exchange inhibitor, 0.1 weight part oxidation inhibitor, 0.2 weight part lubricant, after mixing in input mixing machine, in twin screw extruder, extruding pelletization at the temperature of 220～240 ℃, obtains conductive polyester master batch.
Again conductive polyester master batch is mixed with the polycarbonate of 100 weight parts, at the temperature of 240～260 ℃, melt extrude, granulation, obtain conductive polycarbonate composition.
Embodiment 3: the preparation of conductive polycarbonate composition
The ester exchange inhibitor of the carbon black of the toughner of the polybutylene terephthalate of 10 weight parts, 5 weight parts, 10 weight parts, 0.5 weight part, the oxidation inhibitor of 0.1 weight part, the lubricant of 0.2 weight part, after mixing in input mixing machine, in twin screw extruder, extruding pelletization at the temperature of 220～240 ℃, obtains conductive polyester master batch.
Again conductive polyester master batch is mixed with the polycarbonate of 100 weight parts, at the temperature of 240～260 ℃, melt extrude, granulation, obtain conductive polycarbonate composition.
Comparative example 1: single stage method is prepared conductive polycarbonate composition
The toughner of the polybutylene terephthalate of 15 weight parts, 3 weight parts, the carbon black of 8 weight parts, the ester exchange inhibitor of 0.1 weight part, the oxidation inhibitor of 0.1 weight part, the lubricant of 0.2 weight part, after the polycarbonate of 100 weight parts drops into and mixes in mixing machine, in twin screw extruder, extruding pelletization at the temperature of 220～240 ℃, obtains conductive polycarbonate composition.
Comparative example 2: the preparation of conductive polycarbonate material
15 weight part polycarbonates, 3 weight part toughner, 8 weight part carbon blacks, 0.1 weight part oxidation inhibitor, 0.2 weight part lubricant, after mixing in input mixing machine, in twin screw extruder, extruding pelletization at the temperature of 220～240 ℃, obtains conductive polycarbonate master batch.
Again the above-mentioned conductive polycarbonate master batch preparing is mixed with 85 weight part polycarbonates, at the temperature of 240～260 ℃, melt extrude, granulation, obtain conductive polycarbonate material.
The conductive polycarbonate composition that embodiment 1～3 and comparative example 1～2 are prepared carries out performance measurement, the results are shown in Table 1.
The performance perameter of table 1 conductive polycarbonate composition
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Tensile strength (MPa) | 58 | 61 | 55 | 50 | 54 |
| Flexural strength (MPa) | 85 | 92 | 82 | 75 | 80 |
| Modulus in flexure (MPa) | 2586 | 2750 | 2450 | 2850 | 2351 |
| Notched Izod impact strength (J/m) | 262 | 152 | 247 | 65 | 280 |
| Surface resistivity (ohm-sq) | 10 5 | 10 3 | 10 5 | ＞10 12 | ＞10 12 |
From embodiment 1, can find out with comparative example 1, it is good that the electroconductibility of polycarbonate compositions prepared by two-step approach obviously prepares than single stage method, utilize carbon black to be chosen in advance the dispersion of the polyester phases such as polyethylene terephthalate, reduce the amount of the required carbon black of Establishing conductive path, reached the object of using the carbon black of low filling content to obtain the material that conductive effect is good; Simultaneously the two-step approach residual titanium class catalyzer of polyester that made in advance the effective complexing of ester exchange inhibitor, makes the conductive polycarbonate composition properties of preparation more excellent.Similarly from embodiment 1, can find out with comparative example 2, carbon black has in mutually optionally better dispersed at polyester such as the preferred polyethylene terephthalates of the present invention, and this only uses polycarbonate to realize.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a conductive polycarbonate composition, is characterized in that the component that comprises following weight part meter:
100 parts of polycarbonate;
19～50 parts of conductive polyester master batches;
The component that described conductive polyester master batch comprises following weight part meter:
2. conductive polycarbonate composition according to claim 1, is characterized in that: the melt flow rate (MFR) of described polycarbonate, at 300 ℃, is 5～30g/10min under 1.2Kg.
3. conductive polycarbonate composition according to claim 1, is characterized in that: described polyester is at least one in polyethylene terephthalate, Poly(Trimethylene Terephthalate) and polybutylene terephthalate.
4. conductive polycarbonate composition according to claim 1, is characterized in that: the oil-absorption(number) of described carbon black is 100～300mL/100g.
5. conductive polycarbonate composition according to claim 1, is characterized in that: described ester exchange inhibitor is phosphite ester compound.
6. conductive polycarbonate composition according to claim 1, is characterized in that: described toughner is at least one in ethylene-methyl methacrylate butyl ester-glycidyl acrylate terpolymer and ethylene-methyl acrylate copolymer; Described auxiliary agent is at least one in oxidation inhibitor and lubricant.
7. conductive polycarbonate composition according to claim 1, is characterized in that: described polyester is polybutylene terephthalate; Described ester exchange inhibitor is tricresyl phosphite.
8. according to a preparation method for the conductive polycarbonate composition described in claim 1～7 any one, it is characterized in that comprising following concrete steps:
(1), after 10～30 weight part polyester, 1～5 weight part toughner, 8～15 weight part carbon blacks, 0.1～0.5 weight part ester exchange inhibitor and 0～1 weight part auxiliary agent are mixed, melt extrude, granulation, obtain conductive polyester master batch;
(2) the conductive polyester master batch and 100 weight part polycarbonates that 19～50 weight part steps (1) are prepared mix, and melt extrude, granulation, obtain conductive polycarbonate composition.
9. the preparation method of conductive polycarbonate composition according to claim 8, is characterized in that: the condition melt extruding described in step (1) is 220～240 ℃; The condition melt extruding described in step (2) is 240～260 ℃.
10. the application in electronic apparatus according to the conductive polycarbonate composition described in claim 1～7 any one.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384213A (en) * | 2018-03-22 | 2018-08-10 | 疆合材料科技（苏州）有限公司 | A kind of polycarbonate composite material of high conductivity and preparation method thereof |
| CN111117200A (en) * | 2020-02-17 | 2020-05-08 | 江苏新奥碳纳米材料应用技术研究院有限公司 | Graphene reinforced polycarbonate conductive composite material and preparation method thereof |
| CN111592746A (en) * | 2020-05-06 | 2020-08-28 | 宁波浙铁大风化工有限公司 | Ceramic white filled laser-engravable polycarbonate compound and preparation method thereof |
| CN112266597A (en) * | 2020-10-20 | 2021-01-26 | 浙江洁美电子科技股份有限公司 | Conductive polycarbonate composition for carrier tape and carrier tape prepared from conductive polycarbonate composition |
| CN115572467A (en) * | 2022-09-28 | 2023-01-06 | 江苏金发科技新材料有限公司 | Polyester composition and preparation method and application thereof |
| EP4141073A1 (en) * | 2021-08-31 | 2023-03-01 | SHPP Global Technologies B.V. | Filled conductive compositions with improved conductivity |
| CN116769295A (en) * | 2023-06-29 | 2023-09-19 | 浦江亿通塑胶电子有限公司 | Conductive PC (polycarbonate) for conductive carrier tape sheet and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384213A (en) * | 2018-03-22 | 2018-08-10 | 疆合材料科技（苏州）有限公司 | A kind of polycarbonate composite material of high conductivity and preparation method thereof |
| CN111117200A (en) * | 2020-02-17 | 2020-05-08 | 江苏新奥碳纳米材料应用技术研究院有限公司 | Graphene reinforced polycarbonate conductive composite material and preparation method thereof |
| CN111592746A (en) * | 2020-05-06 | 2020-08-28 | 宁波浙铁大风化工有限公司 | Ceramic white filled laser-engravable polycarbonate compound and preparation method thereof |
| CN112266597A (en) * | 2020-10-20 | 2021-01-26 | 浙江洁美电子科技股份有限公司 | Conductive polycarbonate composition for carrier tape and carrier tape prepared from conductive polycarbonate composition |
| CN112266597B (en) * | 2020-10-20 | 2023-06-23 | 浙江洁美电子科技股份有限公司 | Conductive polycarbonate composition for carrier tape and carrier tape prepared from conductive polycarbonate composition |
| EP4141073A1 (en) * | 2021-08-31 | 2023-03-01 | SHPP Global Technologies B.V. | Filled conductive compositions with improved conductivity |
| WO2023031828A1 (en) * | 2021-08-31 | 2023-03-09 | Shpp Global Technologies B.V. | Filled conductive compositions with improved electrical conductivity |
| CN115572467A (en) * | 2022-09-28 | 2023-01-06 | 江苏金发科技新材料有限公司 | Polyester composition and preparation method and application thereof |
| CN115572467B (en) * | 2022-09-28 | 2024-01-12 | 江苏金发科技新材料有限公司 | Polyester composition and preparation method and application thereof |
| CN116769295A (en) * | 2023-06-29 | 2023-09-19 | 浦江亿通塑胶电子有限公司 | Conductive PC (polycarbonate) for conductive carrier tape sheet and preparation method thereof |
| CN116769295B (en) * | 2023-06-29 | 2024-02-23 | 浦江亿通塑胶电子有限公司 | Conductive PC (polycarbonate) for conductive carrier tape sheet and preparation method thereof |
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Application publication date: 20140430 |