CN102229736A - Lightweight noise-reduction modified ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof - Google Patents

Lightweight noise-reduction modified ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof Download PDF

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Publication number
CN102229736A
CN102229736A CN201110176865XA CN201110176865A CN102229736A CN 102229736 A CN102229736 A CN 102229736A CN 201110176865X A CN201110176865X A CN 201110176865XA CN 201110176865 A CN201110176865 A CN 201110176865A CN 102229736 A CN102229736 A CN 102229736A
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noise reduction
modified abs
lightweight
abs material
lightweight noise
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CN102229736B (en
Inventor
周英辉
孙刚
李欣
李志平
程文超
陈延安
丁超
李国明
黄达
罗忠富
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Liaoning Jinfa Technology Co ltd
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Jiangsu Kingfa New Material Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a lightweight noise-reductio modified ABS (Acrylonitrile Butadiene Styrene) material which comprises the following raw materials in percentage by weight: 39-93.5% of ABS resin, 5-45% of inorganic filler, 1-10% of dispersing agent, 0.3-5% of coupling agent and 0.2-1% of antioxygen, wherein the inorganic filler is a hollow inorganic particle. Since the hollow inorganic particle is added to the formula of the material, the low density of the material is maintained while the mechanical property of the material is improved; meanwhile, the material is endowed with a certain noise reduction function because of the special hollow particle structure, therefore, the material has a very high application value in lightweight automobile manufacture, damping and noise reduction and the like. The lightweight noise-reduction modified ABS material is prepared by the step of processing the inorganic filler fed into a screw extruder respectively from multiple lateral feeding ports arranged at different positions, so that the hollow structure of the inorganic filler is not damaged when the inorganic filler is melt and extruded, the inorganic filler can be dispersed more evenly in a substrate, and the prepared material is endowed with better properties.

Description

A kind of lightweight noise reduction modified ABS material and preparation method thereof
Technical field
The present invention relates to a kind of lightweight noise reduction modified ABS material and preparation method thereof, can be applicable to automobile manufacturing field
Background technology
Resin has many good qualities vinyl cyanide (A)-divinyl (B)-vinylbenzene (S) terpolymer (hereinafter to be referred as ABS) as using very widely:
Vinyl cyanide (A) can be given material chemical resistance and certain surface hardness; Divinyl (B) can give toughness of material; Vinylbenzene (S) makes polymkeric substance have rigidity and certain fluidity.
In the modifying plastics industry, generally can use as inorganic minerals such as talcum powder, mica, lime carbonate, glass microballon, wollastonite, glass fibre and strengthen component as filling, improve the performance such as rigidity, thermotolerance, molding shrinkage, chemical resistant properties, surface gloss, incendivity of ABS material by blending and modifying, to satisfy the service requirements of final plastics.But since the density of these inorganic mineral fillers often the density than plastics is big, therefore in plastics, add the weight (the inorganic mineral filler content sees Table 1 to the influence of ABS density of material) that mineral filler can increase the finished product relatively.
Nowadays, Nonrenewable resources are more and more in short supply, also soar all the way based on a lot of derived product of oil such as the price of gasoline, diesel oil etc., call the cry of save energy more and more surging.The tare of automobile be directly connected to automobile unit's mileage oil consumption what, the lightweight of plastic component such as the integral part of bodywork parts such as collision bumper, flow deflector, outer plaque, dashboard, door-plate, column has become very important problem in the energy-saving and emission-reduction work now.Therefore, under the situation that guarantees the auto parts use properties, develop light weight or possess the material of other excellent properties simultaneously,, improve driver's driving comfort, have great using value and positive social effect to reduce the weight of car load component.
Table 1 inorganic mineral filler content is to the influence of ABS density of material
Figure 865467DEST_PATH_IMAGE001
Summary of the invention
Inventing technical problem to be solved is to overcome the deficiencies in the prior art, a kind of lightweight noise reduction modified ABS material is provided, it is when improving the mechanical property of materials, can not increase the density of material, even the density of reduction material, and when it is processed to automobile component, also have certain decrease of noise functions, can reduce the noise of experiencing when the driver travels, improve driver's driving comfort from vibration generations such as tire, windage, engine and other component.
The present invention also will provide a kind of preparation method of above-mentioned lightweight noise reduction modified ABS material simultaneously.
For solving above technical problem, the present invention takes following technical scheme:
A kind of lightweight noise reduction modified ABS material, by weight percentage, its composition of raw materials is as follows:
ABS resin 39% ~ 93.5%
Mineral filler 5% ~ 45%
Dispersion agent 1% ~ 10%
Coupling agent 0.3% ~ 5%
Oxidation inhibitor 0.2% ~ 1%
Described ABS resin is for the vinyl cyanide molar content accounts for 10% ~ 30%, the divinyl molar content accounts for 10% ~ 30%, the vinylbenzene molar content accounts for 40% ~ 60% acrylonitrile-butadiene-styrene terpolymer; Described mineral filler be size distribution between 5 microns ~ 20 microns, tap density is at 0.1g/cm 3 ~ 0.4g/cm 3 Between hollow inorganic particulate; Described dispersion agent is the maleic anhydride graft polyolefin elastomer; Described coupling agent is to contain amino silane coupling agent; Described oxidation inhibitor is the mixture of hindered phenol antioxygen and phosphorous acid ester.
The preparation method of lightweight noise reduction modified ABS material of the present invention is as follows:
Above-mentioned lightweight noise reduction modified ABS material is extruded by screw extrusion press and is processed to form; Described screw extrusion press has the main opening for feed that lays respectively at two ends and discharge port, between described main opening for feed and discharge port and a plurality of side opening for feeds at the described discharge port 1/5-4/5 screw extrusion press length of distance place, and described a plurality of side opening for feed is unequal to the distance of described discharge port; When extruding, ABS resin, dispersion agent, coupling agent and oxidation inhibitor with formula ratio mixes in super mixer earlier, to mix the gained material then feeds the screw extrusion press from main opening for feed, the mineral filler of formula ratio is divided into many parts, feeds the screw extrusion press from a plurality of side opening for feeds respectively; In the extrusion process, the control processing temperature is at 200 ℃ ~ 230 ℃.
Because the enforcement of above technical scheme, the present invention compared with prior art has plurality of advantages:
Lightweight noise reduction modified ABS material of the present invention adds the mineral filler of hollow granule type in the preparation prescription, can keep the lightweight of material when improving the mechanical property of materials, and the special construction of hollow granule makes also material have certain decrease of noise functions; The preparation method of lightweight noise reduction modified ABS material of the present invention, by mineral filler is extruded processing respectively from a plurality of side direction spouts feeding screw extrusion presss of different positions, can make mineral filler its hollow structure when melt extruding be difficult for destroyed, and it is more even that mineral filler is disperseed in matrix, makes prepared material property better.
Embodiment
Lightweight noise reduction modified ABS material of the present invention by weight percentage, is melt extruded through twin screw extruder by following component, is prepared from through the tablets press granulation again:
ABS resin 39% ~ 93.5%
Mineral filler 5% ~ 45%
Dispersion agent 1% ~ 10%
Coupling agent 0.3% ~ 5%
Oxidation inhibitor 0.2% ~ 1%
Described ABS resin is vinyl cyanide (A)-divinyl (B)-vinylbenzene (S) terpolymer, wherein, in molar content, vinyl cyanide accounts for 10%～30%, and divinyl accounts for 10%～30%, styrene comprise 40%～60%, be preferably vinyl cyanide and account for 15%～25%, divinyl accounts for 20%～30%, styrene comprise 45%～55%, and the ABS resin over-all properties is better under this proportioning.ABS resin used in the present invention can be selected Taiwan Qi Mei company production and selling: the ABS757(general purpose grade), ABS727(electroplates level), ABS777(is high temperature resistant level), the high flow stage of ABS756(), ABS765(prevent fires grade) and the ABS920(transparent stage) in one or more mixture.
Described mineral filler be size distribution between 5 microns ~ 20 microns, tap density is at 0.1g/cm 3 ~ 0.4g/cm 3 Between hollow inorganic particulate, be preferably hollow glass micropearl or hollow ceramic microspheres, concrete spendable commercial product comprises the hollow glass micropearl of 3M company (Minnesota Mining and Manufacturing Co., i.e. Minnesota ,USA mines and production company) production and selling.Because hollow inorganic particulate has the hollow structure of sealing, by its good distribution in matrix resin ABS, can realize the multi-functional of the final plastics that obtain, as reduce the density of ABS, improve material to the obstruct of noise and receptivity etc., it also can reach the basic function as mineral filler simultaneously, as increasing its shrinking percentage of rigidity, thermotolerance and reduction of ABS material.
Described dispersion agent is the maleic anhydride graft polyolefin elastomer; Be preferably one or more mixture of maleic anhydride grafted ethene-propylene-octene terpolymer, maleic anhydride grafted ethene-propylene-butadiene terpolymer, maleic anhydride graft styrene-butadiene copolymer, maleic anhydride graft hydrogenant ethylene-butadiene-styrene multipolymer, maleic anhydride grafting ratio requires between 0.65% ~ 0.95%.Elastomerics uses as toughner usually, and its adding can improve the shock resistance and the toughness of system greatly.The present invention adopts the polyolefin elastomer behind the maleic anhydride graft, main purpose be utilize its lower processing viscosity with and distinctive two-way avidity, improve the dispersion viscosity of ABS material system, guarantee that hollow inorganic particulate is in the course of processing, use extremely low shearing force can realize homodisperse, hollow structure is kept, also can play certain toughening effect simultaneously.Particularly, spendable commercially available prod comprises the FUSABOND 493D of du pont company production and selling.
Described coupling agent is amino silicane coupling agent commonly used.For the present invention, adopt and contain amino silane coupling agent, its effect is better than other coupling agents commonly used (as titanate coupling agent or aluminate coupling agent etc.).Amino silicane coupling agent can form avidity with the inorganic particulate surface, can form avidity with the matrix ABS resin again, it can form an interfacial layer that can transmit stress in the ABS system, strengthen the bonding strength between mineral filler and the organic resin, improve the performance of ABS material monolithic, simultaneously can also prevent that other medium to this contacting permeation, having improved interfacial state, help ageing-resistant, the proof stress and the chemical resistance of goods.Preferred use is two amino silicane coupling agents among the present invention, and it both can strengthen the bonding strength between hollow inorganic particulate and the ABS resin, can increase the bonding strength between hollow inorganic particulate and the dispersion agent again, had further strengthened the protection to hollow structure.Concrete spendable coupling agent comprises commercially available prod KH792.
Employed oxidation inhibitor is the composite mixture of Hinered phenols antioxidant and phosphorous acid ester among the present invention, specifically can use the Ethanox330 and the Ethanox368 of U.S. Ya Bao company production and selling to carry out composite.
Above-mentioned lightweight noise reduction modified ABS material is to melt extrude processing by screw extrusion press, forms through the tablets press granulation again; Described screw extrusion press has the main opening for feed that lays respectively at two ends and discharge port, between described main opening for feed and discharge port and a plurality of side opening for feeds at the described discharge port 1/5-4/5 screw extrusion press length of distance place, and described a plurality of side opening for feed is unequal to the distance of described discharge port; When extruding, ABS resin, dispersion agent, coupling agent and oxidation inhibitor with formula ratio mixes in super mixer earlier, to mix the gained material then feeds the screw extrusion press from main opening for feed, the mineral filler of formula ratio is divided into many parts, feeds the screw extrusion press from a plurality of side opening for feeds respectively; In the extrusion process, the control processing temperature is at 200 ℃ ~ 230 ℃.
Selection adds the mode of mineral filler by the side direction feeding in the ABS system, can reduce the destruction of the strong shearing of forcing machine inside to hollow mineral filler microtexture; Simultaneously, by mineral filler being divided into many parts at the different sections that melt extrude feedings respectively, also be for the strong shearing that further reduces forcing machine inside to the mineral filler structural damage, and it is more even that it is disperseed in matrix.
According to the present invention, employed super mixer rotating speed is at 650 ~ 1300 rev/mins in the specific implementation process; Employed forcing machine is a twin screw extruder, side opening for feed on the fuselage has two, one of them distance to discharge port is 1/5 ~ 3/5 screw extrusion press length, another distance to discharge port is 3/5 ~ 4/5 screw extrusion press length, extrude and add man-hour, the mineral filler of formula ratio evenly is divided into two parts, two side opening for feeds from the different positions section add respectively, the screw speed of twin screw extruder is controlled at 250 ~ 300 rev/mins, barrel zone temperature is controlled at 200 ℃ ~ 230 ℃, and the water temperature of supporting tank is greatly between 25 ℃ ~ 50 ℃; The rotating speed of employed tablets press is at 500 ~ 800 rev/mins.
The testing standard of the physical and mechanical properties of gained lightweight noise reduction modified ABS material of the present invention is as shown in table 2:
The test event of table 2 Material Physics mechanical property and corresponding testing method
The present invention will be further described in detail below in conjunction with specific embodiment, but be not limited to these embodiment.
Embodiment 1
The prescription of present embodiment lightweight noise reduction modified ABS material is listed in table 3-1:
Table 3-1
Figure 125864DEST_PATH_IMAGE003
Embodiment 2
The prescription of present embodiment lightweight noise reduction modified ABS material is listed in table 3-2:
Table 3-2
Figure 618025DEST_PATH_IMAGE004
Embodiment 3
The prescription of present embodiment lightweight noise reduction modified ABS material is listed in table 5-3:
Table 3-3
Figure 735017DEST_PATH_IMAGE005
Embodiment 4
The prescription of present embodiment lightweight noise reduction modified ABS material is listed in table 3-4:
Table 3-4
Embodiment 5
The prescription of present embodiment lightweight noise reduction modified ABS material is listed in table 3-5:
Table 3-5
Figure 466661DEST_PATH_IMAGE007
Embodiment 6
The prescription of present embodiment lightweight noise reduction modified ABS material is listed in table 3-6:
Table 3-6
Figure 801827DEST_PATH_IMAGE008
Embodiment 7
The prescription of present embodiment lightweight noise reduction modified ABS material is listed in table 3-7:
Table 3-7
Figure 593066DEST_PATH_IMAGE009
More than each embodiment all adopt identical preparation method and processing condition to prepare lightweight noise reduction modified ABS material.
The physical parameter of above embodiment 1 ~ embodiment 7 prepared lightweight noise reduction modified ABS materials is listed in table 4:
Table 4
Figure 671880DEST_PATH_IMAGE010
Can find out from table 4, gained ABS material of the present invention all has lower density and mechanical property preferably, it has very high using value for automobile lightweight manufacturing, can be used for making bumper, wheel cover, outer casing, dashboard, door-plate, column backplate, flow deflector and other interior trim backplates, vehicle body sound-absorbing module, air-conditioning system assembly or the like.
" scope " disclosed herein is with the form of the lower limit and the upper limit.Can be respectively one or more lower limits and one or more upper limit.Given range limits by a selected lower limit and a upper limit.The border that the selected lower limit and the upper limit define special scope.All can carry out restricted portion by this way and comprise with capable of being combined, and promptly any lower limit can be combined to form a scope with any upper limit.For example, listed the scope of 60-120 and 80-110, be interpreted as that the scope of 60-110 and 80-120 also reckons with at special parameter.In addition, if if the minimum extent value of listing 1 and 2 and listed maximum range value 3,4 and 5, then Xia Mian scope could all reckon with: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless have other the explanation, each components contents scope of composition with and preferable range between can be combined to form new technical scheme mutually.
In the present invention, unless other explanations are arranged, the technical characterictic of each technical scheme can be combined to form new technical scheme mutually.For concise and to the point purpose, the applicant has omitted the specific descriptions of these combinations in specification sheets, but can think that the open scope of this specification sheets has specifically comprised these technical schemes that obtain by combination.
In the present invention, unless other explanations are arranged, all " parts " and percentage ratio (%) all refer to weight percentage.
In the present invention, unless other explanations are arranged, the percentage ratio sum of each component is 100% in all compositions.
In the present invention, unless other explanations are arranged, numerical range " a-b " expression a represents that to the breviary of any real number combination between the b wherein a and b are real numbers.For example the whole real numbers between " 0-5 " have all been listed in numerical range " 0-5 " expression herein, and " 0-5 " just the breviary of these combinations of values represents.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention

Claims (9)

1. lightweight noise reduction modified ABS material, it is characterized in that: by weight percentage, the composition of raw materials of described lightweight noise reduction modified ABS material is as follows:
ABS resin 39% ~ 93.5%
Mineral filler 5% ~ 45%
Dispersion agent 1% ~ 10%
Coupling agent 0.3% ~ 5%
Oxidation inhibitor 0.2% ~ 1%
Described ABS resin is for the vinyl cyanide molar content accounts for 10% ~ 30%, the divinyl molar content accounts for 10% ~ 30%, the vinylbenzene molar content accounts for 40% ~ 60% acrylonitrile-butadiene-styrene terpolymer; Described mineral filler be size distribution between 5 microns ~ 20 microns, tap density is at 0.1g/cm 3 ~ 0.4g/cm 3 Between hollow inorganic particulate; Described dispersion agent is the maleic anhydride graft polyolefin elastomer; Described coupling agent is to contain amino silane coupling agent; Described oxidation inhibitor is the mixture of hindered phenol antioxygen and phosphorous acid ester.
2. lightweight noise reduction modified ABS material according to claim 1 is characterized in that: described mineral filler is hollow glass micropearl or hollow ceramic microspheres.
3. lightweight noise reduction modified ABS material according to claim 1 is characterized in that: described dispersion agent is one or more a mixture of maleic anhydride grafted ethene-propylene-octene terpolymer, maleic anhydride grafted ethene-propylene-butadiene terpolymer, maleic anhydride graft styrene-butadiene copolymer, maleic anhydride graft hydrogenant ethylene-butadiene-styrene multipolymer.
4. lightweight noise reduction modified ABS material according to claim 3, it is characterized in that: the maleic anhydride grafting ratio of described dispersion agent is between 0.65% ~ 0.95%.
5. lightweight noise reduction modified ABS material according to claim 1 is characterized in that: described coupling agent is two amino silicane coupling agents.
6. the preparation method of a lightweight noise reduction modified ABS material as claimed in claim 1, it is characterized in that: described lightweight noise reduction modified ABS material is extruded by screw extrusion press and is processed to form; Described screw extrusion press has the main opening for feed that lays respectively at two ends and discharge port, between described main opening for feed and discharge port and a plurality of side opening for feeds at the described discharge port 1/5-4/5 screw extrusion press length of distance place, and described a plurality of side opening for feed is unequal to the distance of described discharge port; When extruding, ABS resin, dispersion agent, coupling agent and oxidation inhibitor with formula ratio mixes in super mixer earlier, to mix the gained material then feeds the screw extrusion press from main opening for feed, the mineral filler of formula ratio is divided into many parts, feeds the screw extrusion press from a plurality of side opening for feeds respectively; In the extrusion process, the control processing temperature is at 200 ℃ ~ 230 ℃.
7. preparation method according to claim 6, it is characterized in that: described side opening for feed has two, one of them distance to described discharge port is 1/5 ~ 3/5 screw extrusion press length, and another distance to described discharge port is 3/5 ~ 4/5 screw extrusion press length.
8. preparation method according to claim 6 is characterized in that: described screw extrusion press is a twin screw extruder, extrudes to add man-hour, and the screw speed of described twin screw extruder is controlled at 250 ~ 300 rev/mins, and barrel zone temperature is controlled at 200 ℃ ~ 230 ℃.
9. lightweight noise reduction modified ABS material as claimed in claim 1 is in the application of automobile manufacturing field.
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CN103524997A (en) * 2013-10-08 2014-01-22 青岛颐世保塑料有限公司 Modified ABS hollow glass bead filling material
CN104403220A (en) * 2014-12-17 2015-03-11 天津金发新材料有限公司 Low-odor, anti-static and anti-bacterial glass fiber reinforced AS (acrylonitrile-styrene) composition and preparation method thereof
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