CN104419193B

CN104419193B - PPO/PA6 alloy material used for electrostatic coating and preparation method thereof

Info

Publication number: CN104419193B
Application number: CN201310367459.0A
Authority: CN
Inventors: 贾中秋; 马庆丰; 宋阳
Original assignee: Heilongjiang Xinda Enterprise Group Co Ltd
Current assignee: Heilongjiang Xinda Enterprise Group Co Ltd
Priority date: 2013-08-22
Filing date: 2013-08-22
Publication date: 2017-03-22
Anticipated expiration: 2033-08-22
Also published as: CN104419193A

Abstract

The invention relates to a conductive PPO/PA6 alloy material with high temperature resistance used for electrostatic coating and a preparation method thereof. The material is the high-temperature resistance conductive fiber-modified PPO/PA6 alloy material. Innovation of the preparation technology of alloy material embody that a chemical dipping method is used for coating a layer nickel-doped alumina on the surface of silicon oxide fiber to prepare the high-temperature resistance conductive fiber, supercritical CO2 is employed as a carrier for uniformly grafting an aluminic acid ester coupling agent on the high-temperature resistance conductive fiber surface, then blending extrusion is carried out with a PPO/PA6 alloy formula system through a double screw extruder, and steps of drawing bars, cooling and granulating can be carried out to obtain the modified PPO/PA6 alloy. In the automobile industry on-line spraying technology, compared with a traditional PPO/PA6, the modified PPO/PA6 alloy material has conductivity and high heat resistance performance, the electrostatic coating process can be directly carried out without a conductive priming paint, the product enables party-line production with metal parts, so that production cost and energy consumption can be reduced.

Description

A kind of PPO/PA6 alloy materials suitable for electrostatic spraying and preparation method thereof

Technical field

The present invention relates to polymeric material field, and in particular to one kind can be used for electrostatic spraying, high temperature resistant conduction PPO/PA6 Alloy material and preparation method, can be while carry out body panels PPO/PA6 of on-line spray with body in white in being applied to automobile industry The part such as alloy material, such as mud guard, beater or beat-up.

Background technology

During automobile production, vehicle body spraying cost accounts for vehicle body cost and is about 50%, therefore, body panels are same with body in white Shi Jinhang on-line spray, can paint this by saving spray in a large number, but adopt on-line spray technique, and PPO/PA6 alloy materials are on the one hand Need the baking temperature of resistance to electrophoresis（200～210 DEG C）；Another aspect PPO/PA6 alloy need to possess the conducting function needed for electrophoresis, pass The PPO/PA6 alloy materials of system can not take into account electric conductivity and thermostability simultaneously, and conductive using high temperature resistant obtained in the present invention PPO/PA6 alloy materials can overcome disadvantages mentioned above, and type part prepared by the material can be without the need for spraying conductive primer can be directly in advance Carry out electrostatic spraying, same production line can spray metal part also sprayable plastic components, reduce cost and the energy disappear Consumption, and the heterochromia caused because of different processing technique can be avoided.

The content of the invention

The present invention is prepared for one kind and can directly carry out electrostatic spraying operation, and the conductive PPO/PA6 alloy materials of high temperature resistant should Material prepare type part for automobile industry on-line spray technique when, can with the same wire spraying of metal mold part, initially with change Learn infusion process and high temperature resistant conductive fibre is prepared in one layer of nickel doped aluminium of silicon oxide fibre surface-coated, at the Jing coupling agents of surface It is modified Jing after check rod, cooling, pelletizing by double screw extruder blending extrusion with PPO/PA6 alloy formulas system after reason PPO/PA alloy materials.The alloy material not only has preferable mechanical property, and with good electric conductivity, antioxidation Property, high temperature resistant.

Technical scheme：

Step one：At 25～70 DEG C, normal pressure, under conditions of high-speed stirred 24h, using method of chemical immersion in silicon oxide fibre The precursor of one layer of nickel doped aluminium of surface-coated, then carries out heat treatment, and temperature range is 450～1000 DEG C, is prepared resistance to Nickel doped aluminium/the silicon oxide fibre of high-temperature electric conduction；

Step 2：At 70～100 DEG C, under conditions of 25MPa, in supercritical CO₂It is aluminate coupling agent is equal in reactor The even surface for being grafted on silicon oxide fibre；

Step 3：Proportioning mix homogeneously in high-speed mixer is pressed after each component in above-mentioned formula is dried, will mixing Material be added to double screw extruder in carry out melting extrusion；Extrusion temperature scope is 250～270 DEG C；Engine speed is 300 ～600rpm；Feeding rotating speed is 20～45 rpm；The mixture of extrusion is water cooled, dry in vacuum drying oven after pelletize, so The blend being baked is molded into into standard sample bar at 250～270 DEG C afterwards.

Instantiation：

With reference to specific embodiment, the present invention is described in more detail, but the invention is not limited in following enforcement respectively Example：

Present embodiment uses section grand double screw extruder and extra large day injection machine again, primary raw material nylon 6 resin, characteristic Viscosity 2.48dL/g；Polyphenylene oxide resin, intrinsic viscosity are 0.50 dL/g；Bulking agent uses Maleated SEBS；Toughener uses SBS； Fiberfill fibers use homemade high temperature resistant conductive fibre；Antioxidant includes 1010,168（Li Anlong）；Twin-screw extruder barrel One area's temperature of temperature：230～240 DEG C, two area's temperature：240～250 DEG C, three area's temperature：250～260 DEG C, four area's temperature：250 ～260 DEG C, five area's temperature：240～250 DEG C, six area's temperature：230～240 DEG C, pressure is 10～15MPa, and screw slenderness ratio is 35～40,400～600r/min of engine speed.Each component is uniformly mixed according to a ratio and is placed in double screw extruder, Jing meltings Mixing extruding pelletization.Gained pellet 120 DEG C of 8～10h of forced air drying of Jing again, are molded into the performance test sample of standard on injection machine Bar, injection temperature are 250～270 DEG C.After sample molding in temperature it is（23±2℃）, humidity be（50±5）Put in the environment of % Put（24±1）h.

Each embodiment physical property is tested by following standard, and concrete examination criteria is as follows：

Tensile strength GB/T1040-1992

Bending strength GB/T9341-2000

Bending moduluses GB/T9341-2000

Simply supported beam notch impact strength GB/T1043-1993

Heat distortion temperature ASTM D648（0.45MPa）

Specific insulation IEC 60093

The corresponding formula of 1 each embodiment of table

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					Raw material	Consumption（Part）	Consumption（Part）	Consumption（Part）	Consumption（Part）
PPO	25	30	35	40
					PA6	60	50	40	30
Bulking agent	0.3	0.3	0.3	0.3
					Toughener	4	4	4	4
Self-control fiber	10	15	20	25
					1010	0.2	0.2	0.2	0.2
168	0.4	0.4	0.4	0.4

The corresponding physical property of 2 each embodiment sample of table

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					Impact strength KJ/m²	6.27	8.02	7.68	6.15
Tensile strength MPa	103.58	124.18	122.69	94.35
					Bending strength MPa	139.26	191.22	172.78	141.56
Bending moduluses MPa	4160	4879	4690	4250
					Heat distortion temperature DEG C	202	215	221	203
Specific insulation Ω cm	0.68×10^{- 3}	1.3×10^{- 3}	0.77×10^{- 3}	0.83×10^{- 3}

As known from Table 2, MODIFIED PP O/PA6 alloy material has higher heat distortion temperature, and its specific insulation exists 10^{- 3}The Ω cm orders of magnitude, show that the material has conducting function.MODIFIED PP O/PA6 alloy material prepared by the present invention not only has There is preferable mechanical property, and with good electric conductivity, non-oxidizability, high temperature resistant is same in automotive body panels and body in white When on-line spray when, type part prepared by the MODIFIED PP O/PA6 alloy material can take into account electric conductivity and thermostability simultaneously, greatly reduce Production cost and energy consumption.

Claims

1. a kind of PPO/PA6 alloy materials suitable for electrostatic spraying, by weight percentage, its formula composition is as follows：

High temperature resistant conductive fibre 10～25%

PA6 30～60%

PPO 25～40%

Toughener 2～5%

Bulking agent 0.2～0.4%

Auxiliary agent 0.1～1%；

The auxiliary agent is antioxidant；

The high temperature resistant conductive fibre draw ratio is 24:1～28:1, using method of chemical immersion in silicon oxide fibre surface-coated one Layer nickel doped aluminium precursor, then heat treatment is carried out, temperature is 450～1000 DEG C, and the conductive nickel doping oxygen of high temperature resistant is obtained Change aluminum/silicon oxide fibre.

2. PPO/PA6 alloy materials according to claim 1, it is characterised in that：In supercritical CO₂Environment in, by aluminic acid Ester coupling agent is equably grafted on the conductive nickel doped aluminium/silicon oxide fibre surface of the high temperature resistant.