CN103694679A - TLCP (Thermotropic Liquid Crystal Polyester)-reinforced conductive TiO2/PA composite material - Google Patents

TLCP (Thermotropic Liquid Crystal Polyester)-reinforced conductive TiO2/PA composite material Download PDF

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Publication number
CN103694679A
CN103694679A CN201310695783.5A CN201310695783A CN103694679A CN 103694679 A CN103694679 A CN 103694679A CN 201310695783 A CN201310695783 A CN 201310695783A CN 103694679 A CN103694679 A CN 103694679A
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Prior art keywords
tlcp
conductive
composite material
matrix material
tio2
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CN201310695783.5A
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Inventor
陈超
郭建鹏
金幸�
孟成铭
杨涛
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Shanghai Rizhisheng New Technology Development Co Ltd
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Shanghai Rizhisheng New Technology Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention relates to a TLCP (Thermotropic Liquid Crystal Polyester)-reinforced conductive TiO2/PA composite material. The composite material comprises the following components by weight percent: 30% to 80% of polyamide, 1% to 30% of conductive TiO2, 5% to 40% of TLCP and 0.01% to 10% of aiding agent. The TLCP is successfully applied to the conductive TiO2/PA composite material, so that the high machining fluidity of the conductive TiO2/PA composite material is achieved. Thus, the conductive TiO2/PA composite material is suitable for machining of thin-walled parts, and has the good mechanical property. Meanwhile, the characteristics of other conductive polyamide materials (such as carbon black or materials in which carbon fibers are added) which are less prone to color blending and poor in temperature endurance and selectivity (functions cannot be exerted well unless the good compatibility exists between macromolecular materials and a basal body) are successfully overcome due to the application of the conductive TiO2.

Description

The conduction TiO that a kind of TLCP strengthens 2/ PA matrix material
Technical field
The present invention relates to technical field of composite materials, specifically, is the conduction TiO strengthening about a kind of TLCP 2/ PA matrix material.
Background technology
Nylon has good mechanical property, and wear-resisting, oil resistant, resistance to solvent, self-lubricity, be one of broad-spectrum engineering plastics.Along with the continuous expansion of its Application Areas, the application aspect electronic apparatus also constantly increases, and accordingly the requirement of its conductivity is improved constantly.The volume specific resistance of common polymeric amide is > 10 all 15Ω, but at present due to the market requirement, much require material itself to have good antistatic effect, or conductive effect, so that material can be used in electromagnetic shielding field or require anlistatig occasion.
The preparation of polyamide electroconductive matrix material mainly realizes by adding various conductive filler materials, the most frequently used conductive filler material is carbon black or carbon fiber at present, as Chinese Patent Application No. a kind of high tenacity electroconductive nylon matrix material that is 201210388292.1 and preparation method thereof, Chinese Patent Application No. is that low interpolation electroconductive nylon 6 matrix materials of a kind of low cost of CN201310117659.0 and preparation method thereof are all as filler, to improve the electroconductibility of polymeric amide by adding graphitized carbon black, although it has added other in addition as additional conductive agent, but graphitized carbon black plays a major role in system the inside.Along with Nano-technology Development, carbon nanotube and Graphene are also applied to electrically conductive polyamide matrix material as a kind of filler, but its effect is bad, only have with carbon black and carbon fiber and mix use, could obtain good electroconductibility.Above-mentioned electrically conductive polyamide material, although there is good electroconductibility, its have inevitable shortcoming be exactly color can only be that black and processing characteristics are poor, in process of production seriously polluted.
Another kind of conventional conductive filler material is high score subclass additive, if Chinese Patent Application No. is 200710172871.1 1 kinds of flame-retardant antistatic reinforced nylon 6 compositions and preparation method, if Chinese Patent Application No. is 201110298092.2 1 kinds of Antistatic nylon materials and preparation method thereof, in use there are a lot of shortcomings in this static inhibitor, as antistatic effect lack permanent, add decomposes in man-hour etc.
TiO 2itself does white pigment as a kind of filler is conventional, is widely used in the industries such as coating, plastics, rubber, medicine, food.Itself is also non-conductive, and to after its surface modification, it has good electroconductibility, and its resistivity only has 1-10 Ω.At electromagnetic shielding, antistatic and surface heater field has potential application widely.Therefore the present invention has utilized the high conductivity of conductive titanate dioxide and the advantage of its widespread use aspect pigment, has overcome the shortcoming of above-mentioned conductive filler material.
Thermotropic liquid crystal (TLCP) polymer is comprised of rodlike molecule, and under molten state, molecule parllel is arranged, and is only subject to very little shearing force just can make molecule arrange in the same direction.Even if so it has had certain order under liquid state.Blend melt is when processing shear-stress hemostasis or extrusion moulding, and liquid crystal microcell is orientated to microfibrillar structure, and this structure can be effectively frozen in goods process of cooling.This liquid still remains unchanged in cooling rear molecular arrangement, so the intensity in this direction, Young's modulus are also larger.Because molecule has above-mentioned this specific character arranging, even if be that the material of non-enhancing grade also produces self-enhancement effect, and other materials only has by glass or fine intensity and the Young's modulus that could improve material such as strengthen of carbon.
Liquid crystal polymer can play the dual function of processing aid and toughener, and the relative melt flow lubricate of aligned liquid-crystal reduces melt viscosity.This processing to improvement thermoplastic composite is very helpful, and is applicable to processing thin-walled parts.
Summary of the invention
The conduction TiO that provides a kind of TLCP to strengthen is provided for deficiency of the prior art 2/ PA matrix material.
For achieving the above object, the technical scheme that the present invention takes is:
The conduction TiO that a kind of TLCP strengthens 2/ PA matrix material, described matrix material component and weight percentage:
Polymeric amide: 30-80%,
Conduction TiO 2: 1-30%,
TLCP?：5%-40%，
Auxiliary agent: 0.01%-10%.
Described polymeric amide be selected from following PA-66, PA-6, PA610, PA1010, PA1012, PA612, PA46, MXD6 one or more.
Described conduction TiO 2for the nanometer with conducting function through the coated processing in surface or micron TiO 2powder, its coating layer is SnO 2doping Sb 2o 5conductive layer.Or produce and the conduction TiO of additive method manufacture by implantation shooting method 2.
Described TLCP is the backbone chain type TLCP of the rigid rod of polyester one class.
Auxiliary agent is high score subclass conductive auxiliary agent and conventional lubricants, oxidation inhibitor and some auxiliary agents of improving the weather-proof and processing characteristics of material.
The invention has the advantages that: the present invention is by conjunction with above-mentioned feature, successfully TLCP is used for conducting electricity TIO 2/ PA matrix material, gives its good intensity and forming process type, simultaneously due to conduction TIO 2application, successfully overcome other electrically conductive polyamide materials (carbon black or carbon fiber add class) and be difficult for color matching or temperature tolerance, the feature of poor selectivity (high score subclass needs and matrix has good consistency just can better play a role).
Embodiment
Below embodiment provided by the invention is elaborated.
Embodiment 1:
By following formula
Nylon 66: 64%
Conduction TiO 2: 18%
TLCP：15%
Electrically conductive polyaniline: 2%
Irgasfos 168: 0.5%
Oxidation inhibitor 1098:0.5%
Take sample, then material is put into low speed mixer and stir 5min.Each component mixes, according to the form below Temperature Setting extruder temperature, and engine speed is set 35Hz, and through extruding pelletization, then injection moulding batten is tested its electroconductibility and mechanical property.
Figure 2013106957835100002DEST_PATH_IMAGE001
It should be noted that: described conduction TiO 2for the nanometer with conducting function through the coated processing in surface or micron TiO 2powder, its coating layer is SnO 2doping Sb 2o 5conductive layer.Or produce and the conduction TiO of additive method manufacture by implantation shooting method 2(as the FT-1000 of Japanese Shi Yuan company, FT-3000 series).Described TLCP is the backbone chain type TLCP (as the Zenite series of Du Pont) of the rigid rod of polyester one class.
Embodiment 2:
By following formula
Nylon 66: 74%
Conduction TiO 2: 18%
TLCP：?5%
Electrically conductive polyaniline: 2%
Irgasfos 168: 0.5%
Oxidation inhibitor 1098:0.5%
Take sample, then material is put into low speed mixer and stir 5min.Each component mixes, according to the form below Temperature Setting extruder temperature, and engine speed is set 35Hz, and through extruding pelletization, then injection moulding batten is tested its electroconductibility and mechanical property.
Embodiment 3:
By following formula
Nylon 66: 39%
Nylon 6: 10%
Conduction TiO 2: 30%
TLCP：20%
Irgasfos 168: 0.5%
Oxidation inhibitor 1098:0.5%
Take sample, then material is put into low speed mixer and stir 5min.Each component mixes, according to the form below Temperature Setting extruder temperature, and engine speed is set 35Hz, and through extruding pelletization, then injection moulding batten is tested its electroconductibility and mechanical property.
Embodiment 4:
By following formula
Nylon 66: 34%
Nylon 6: 10%
Conduction TiO 2: 20%
TLCP：35%
Irgasfos 168: 0.5%
Oxidation inhibitor 1098:0.5%
Take sample, then material is put into low speed mixer and stir 5min.Each component mixes, according to the form below Temperature Setting extruder temperature, and engine speed is set 35Hz, and through extruding pelletization, then injection moulding batten is tested its electroconductibility and mechanical property.
Figure 2013106957835100002DEST_PATH_IMAGE004
The performance data of each embodiment 1-4 sees the following form:
Figure 2013106957835100002DEST_PATH_IMAGE005
The conduction TiO that the TLCP of embodiment of the present invention 1-4 strengthens 2/ PA matrix material is compared and is had good fluidity with the electroconductive nylon matrix material of prior art, easily the advantage of color matching.Its melting index ratio is in the situation that same carbon black or carbon fiber addition improve more than 5%, and volume specific resistance improves 3% left and right, and more easily color matching.
Embodiment 5-10:
Figure 2013106957835100002DEST_PATH_IMAGE006
Figure 2013106957835100002DEST_PATH_IMAGE007
By above table formula, take sample, then material is put into low speed mixer and stir 5min.Each component mixes, according to the form below Temperature Setting extruder temperature, and engine speed is set 35Hz, and through extruding pelletization, then injection moulding batten is tested its electroconductibility and mechanical property.
Figure 2013106957835100002DEST_PATH_IMAGE008
The performance data of each embodiment sees the following form:
Figure 2013106957835100002DEST_PATH_IMAGE009
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the inventive method; can also make some improvement and supplement, these improvement and supplement and also should be considered as protection scope of the present invention.

Claims (6)

1. the conduction TiO that a TLCP strengthens 2/ PA matrix material, is characterized in that, described matrix material component and weight percentage are as follows:
Polymeric amide: 30-80%,
Conduction TiO 2: 1-30%,
TLCP?：5%-40%，
Auxiliary agent: 0.01%-10%.
2. matrix material according to claim 1, is characterized in that, described polymeric amide be selected from following PA-66, PA-6, PA610, PA1010, PA1012, PA612, PA46, MXD6 one or more.
3. matrix material according to claim 1, is characterized in that, described conduction TiO 2for the nanometer with conducting function through the coated processing in surface or micron TiO 2powder, its coating layer is SnO 2doping Sb 2o 5conductive layer.
4. matrix material according to claim 1, is characterized in that, described TLCP is the backbone chain type TLCP of the rigid rod of polyester one class.
5. matrix material according to claim 1, is characterized in that, described auxiliary agent is high score subclass conductive auxiliary agent and conventional lubricants, oxidation inhibitor and some auxiliary agents of improving the weather-proof and processing characteristics of material.
6. matrix material according to claim 5, is characterized in that, described high score subclass conductive auxiliary agent is polyaniline, Polythiophene one class.
CN201310695783.5A 2013-12-18 2013-12-18 TLCP (Thermotropic Liquid Crystal Polyester)-reinforced conductive TiO2/PA composite material Pending CN103694679A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5744271A (en) * 1995-09-28 1998-04-28 Fuji Electric Co., Ltd. Photoconductor for electrophotography
CN1259971A (en) * 1997-08-27 2000-07-12 大冢化学株式会社 Printing sheets
WO2004024821A1 (en) * 2002-09-13 2004-03-25 Dsm Ip Assets B.V. Moulding composition comprising nylon-6 and a fibrous reinforcing agent
CN1815373A (en) * 2005-02-01 2006-08-09 光华开发科技股份有限公司 Bottom coating for photoelectric photoreceptor and its forming method and photoelectric photoreceptor
CN1993633A (en) * 2004-08-02 2007-07-04 富士胶片株式会社 Optical film, producing method therefor, polarizing plate and image display apparatus
CN101260233A (en) * 2008-04-18 2008-09-10 北京工业大学 Special-purpose nylon material for automobile intake manifold and processing method thereof
CN102219994A (en) * 2011-05-24 2011-10-19 华南理工大学 Heat conducting nanometer material and preparation method and application thereof
CN102585488A (en) * 2011-01-13 2012-07-18 上海杰事杰新材料(集团)股份有限公司 High temperature-resistant nylon/thermotropic liquid crystal polymer blend and preparation method for blend

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5744271A (en) * 1995-09-28 1998-04-28 Fuji Electric Co., Ltd. Photoconductor for electrophotography
CN1259971A (en) * 1997-08-27 2000-07-12 大冢化学株式会社 Printing sheets
WO2004024821A1 (en) * 2002-09-13 2004-03-25 Dsm Ip Assets B.V. Moulding composition comprising nylon-6 and a fibrous reinforcing agent
CN1993633A (en) * 2004-08-02 2007-07-04 富士胶片株式会社 Optical film, producing method therefor, polarizing plate and image display apparatus
CN1815373A (en) * 2005-02-01 2006-08-09 光华开发科技股份有限公司 Bottom coating for photoelectric photoreceptor and its forming method and photoelectric photoreceptor
CN101260233A (en) * 2008-04-18 2008-09-10 北京工业大学 Special-purpose nylon material for automobile intake manifold and processing method thereof
CN102585488A (en) * 2011-01-13 2012-07-18 上海杰事杰新材料(集团)股份有限公司 High temperature-resistant nylon/thermotropic liquid crystal polymer blend and preparation method for blend
CN102219994A (en) * 2011-05-24 2011-10-19 华南理工大学 Heat conducting nanometer material and preparation method and application thereof

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Application publication date: 20140402