CN104910539A - High-impact while household electrical appliance ABS composite material and preparation method therefor - Google Patents
High-impact while household electrical appliance ABS composite material and preparation method therefor Download PDFInfo
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Abstract
Provided are a high-impact while household electrical appliance ABS composite material and a preparation method therefor. The composite material is composed of 23-28 parts of butadiene-styrene-acrylonitrile graft copolymers, 68-73 parts of styrene-acrylonitrile copolymers, 0.1-0.3 part of magnesium stearate, 0.4-0.9 part of dethylene butylaerylate, 0.1-0.2 part of distearyl pentaerythritol diphosphite, 0.03-0.05 part of distearyl thiodipropionate, and 2-4 parts of surface modified titanium dioxide. Under prescribed technology conditions, titanium dioxide, nano calcium carbonate and barium sulfate are reacted in a mixed solution of titanate coupling agents, dimethicone, silane coupling agents and isopropanol, surface modified titanium dioxide is obtained and is fully mixed with butadiene-styrene-acrylonitrile graft copolymers, styrene-acrylonitrile copolymers and auxiliary agents, extrusion are granulation in an extruder are carried out and a high-impact while household electrical appliance ABS composite material is obtained. The impact strength is raised to more than 10%, and the whiteness exceeds 85.
Description
Technical field
The invention belongs to new chemical materials or polymeric material field, be specifically related to a kind of high-impact white domestic appliances ABS composite material and preparation method thereof.
Background technology
In recent years, along with the update of household appliances, also promote the market requirement of white domestic appliances.ABS resin is as the fifth-largest general-purpose plastics in the world and Plastics Toughening by Rubber the most widely, due to the combination of divinyl, vinylbenzene and vinyl cyanide three kinds of components, have complementary advantages, making ABS resin can carry out the adjustment of the multiple trade mark because producing actual needs, being widely used in HI high impact, high gloss, the several functions shaped material such as heat-resisting and fire-retardant.
Titanium dioxide is a kind of mineral filler with stable physics, chemical property and excellent whiteness, fills it in polymeric matrix, effectively can improve the whiteness of fluoropolymer resin.But untreated titanium dioxide is because of its surface attachment polar group (as-OH), cause it to be easy to produce agglomeration because of polar adsorption or the moisture absorption, titanium dioxide is difficult to disperse in organic medium, therefore have impact on its widespread use in the composite.Therefore how to improve the dispersiveness of inorganic particulate in organic substrate, the consistency improved between inorganic particulate and organic resin just becomes bottleneck prepared by matrix material.For different performance demand, multiple ABS composite material is had to be in the news.
The patented invention of CN 103214780 A discloses a kind of modified ABS power truck PP Pipe Compound and preparation method thereof.The composite nanoparticle of its application cats product modification zinc oxide and hydrotalcite, and part ABS reclaimed materials is added in the process of extruding pelletization, be intended to the weathering resistance can improving ABS product, and improve the recycle of ABS Product recycling material.A kind of high shading ABS composite material of patent CN 103333453 A disclosure of the invention and preparation method thereof.The patent proposes and one or both in barium sulfate or titanium dioxide are joined in the multiple commercially available ABS trade mark, carry out the preparation of high shading ABS composite material.Although this patent have selected the auxiliary agent such as multiple coupling agent, high glue powder toughner, but select existing commercially available ABS product to carry out the production of mixture, can not for ABS product latex particle size size, product melting index height, carry out the Molecular Structure Design between ABS product and mineral filler, therefore also exist unvanquishable restricted.
Summary of the invention
The present invention will solve prior art existing problems, one high-impact white domestic appliances ABS composite material and preparation method thereof is provided, to improve the dispersiveness of titanium dioxide in ABS matrix, guarantee that ABS resin impact property meets application needs, improve the thermostability of titanium dioxide, better dispersion effect, the production cost of titanium dioxide can be reduced again, decrease titanium dioxide reunite and cause the downslide rapidly of ABS composite product mechanical property, the ABS mixture obtained has higher impact property and thermostability, guarantee the relatively stable of chromatic aberration, meet the application needs of market high-impact white domestic appliances ABS.
The concrete technical scheme that the present invention adopts is, a kind of high-impact white domestic appliances ABS composite material, in mass parts, by butadiene-styrene-acrylonitrile graft copolymer 23 ~ 28 parts, styrene-acrylonitrile copolymer 68 ~ 73 parts, Magnesium Stearate 0.1 ~ 0.3 part, ethylene butyl acrylate 0.4 ~ 0.9 part, distearyl pentaerythrityl diphosphite 0.1 ~ 0.2 part, the two octadecyl ester 0.03 ~ 0.05 part of sulfuration dipropionic acid, finishing titanium dioxide 2 ~ 4 parts composition, titanium dioxide 36 ~ 60 parts in finishing titanium dioxide, 12 ~ 26 parts, barium sulfate, nanometer grade calcium carbonate 28 ~ 38 parts, titanate coupling agent 0.1 ~ 0.3 part, dimethyl silicone oil 0.2 ~ 0.4 part, silane coupling agent 0.1 ~ 0.4 part, Virahol 0.8 ~ 1.6 part, deionized water 150 ~ 250 parts, its preparation method is: titanium dioxide, nano-calcium carbonate and barium sulfate fully mix in high-speed kneading machine, cross 200 ~ 250 object sieves, obtaining mixing titanium oxide powder adds in Virahol and deionized water, stir under 40 ~ 50 DEG C of speed at 300 ~ 500r/min, add dimethyl silicone oil successively, silane coupling agent and titanate coupling agent, be warmed up to 60 DEG C of reaction 1.5 ~ 2h, obtain mixed with titanium white powder filtered on buchner funnel to be separated, and by 30 DEG C of washed with de-ionized water 2 times, dry in 70 DEG C of baking ovens, finishing titanium dioxide is obtained after grinding.
As above a kind of preparation method of high-impact white domestic appliances ABS composite material: primarily of following process and step composition:
(1) preparation of finishing titanium dioxide: titanium dioxide, nano-calcium carbonate and barium sulfate are fully mixed 3 ~ 5min in high-speed kneading machine, crosses 200 ~ 250 object sieves, obtains mixing titanium oxide powder; Described mixing titanium oxide powder is added in Virahol and deionized water, stir under 40 ~ 50 DEG C of speed at 300 ~ 500r/min, add dimethyl silicone oil, silane coupling agent and titanate coupling agent successively, be warmed up to 60 DEG C of reaction 1.5 ~ 2h, obtain mixed with titanium white powder; Described mixed with titanium white powder filtered on buchner funnel is separated, and by 30 DEG C of washed with de-ionized water 2 times, dries in 70 DEG C of baking ovens, after grinding, obtain finishing titanium dioxide; Wherein the mass fraction of each material is as follows: titanium dioxide 36 ~ 60 parts; 12 ~ 26 parts, barium sulfate; Nanometer grade calcium carbonate 28 ~ 38 parts; Titanate coupling agent 0.1 ~ 0.3 part; Dimethyl silicone oil 0.2 ~ 0.4 part; Silane coupling agent 0.1 ~ 0.4 part; Virahol 0.8 ~ 1.6 part; Deionized water 150 ~ 250 parts;
(2) preparation of high-impact white domestic appliances ABS composite material: butadiene-styrene-acrylonitrile graft copolymer, styrene-acrylonitrile copolymer, Magnesium Stearate, ethylene butyl acrylate, distearyl pentaerythrityl diphosphite, the two octadecyl ester of sulfuration dipropionic acid and finishing titanium dioxide are mixed in super mixer, join extruding pelletization in twin screw extruder, the cylindrical particle product of Φ 3mm × Φ 3mm is cut to after water cooling, injection moulding after dry, obtains high-impact white domestic appliances ABS composite material; Wherein the machine barrel transportation section of parallel dual-screw extruding machine, fluxing zone, metering zone, die head temperature are set to 180 ~ 190 DEG C, 190 ~ 200 DEG C, 190 ~ 200 DEG C, 200 ~ 210 DEG C respectively, and vacuumize process to machine barrel, vacuum tightness is 0.06 ± 0.01MPa simultaneously; Wherein the mass fraction of each component is: butadiene-styrene-acrylonitrile graft copolymer 23 ~ 28 parts, styrene-acrylonitrile copolymer 68 ~ 73 parts, Magnesium Stearate 0.1 ~ 0.3 part, ethylene butyl acrylate 0.4 ~ 0.9 part, distearyl pentaerythrityl diphosphite 0.1 ~ 0.2 part, the two octadecyl ester 0.03 ~ 0.05 part of sulfuration dipropionic acid, finishing titanium dioxide 2 ~ 4 parts.
The preparation method of above-mentioned a kind of high-impact white domestic appliances ABS composite material, the titanate coupling agent described in it is preferably titanate coupling agent.
The preparation method of above-described a kind of high-impact white domestic appliances ABS composite material, dimethyl-silicon oil viscosity is no more than 1000cp at 25 DEG C.
The preparation method of above-mentioned a kind of high-impact white domestic appliances ABS composite material, the mass ratio that its butadiene-styrene-acrylonitrile graft copolymer adopts middle divinyl, vinylbenzene and vinyl cyanide is: 52 ~ 60:23 ~ 32:14 ~ 18.
The preparation method of above-mentioned a kind of high-impact white domestic appliances ABS composite material, described in it, the particle diameter of butadiene-styrene-acrylonitrile graft copolymer is 280 ~ 320nm.
The preparation method of above-mentioned a kind of high-impact white domestic appliances ABS composite material, the percentage of grafting of its butadiene-styrene-acrylonitrile graft copolymer is 45% ~ 51%.
The preparation method of above-mentioned a kind of high-impact white domestic appliances ABS composite material, styrene-acrylonitrile copolymer described in it is at 220 DEG C, and the melting index under 10kg condition is greater than 30g/10min, N content >=7%, bonding acrylonitrile content is 23% ~ 26%, and number-average molecular weight is 70000 ~ 75000.
Compared with prior art, the present invention has following significantly positive effect:
(1) blending a small amount of barium sulfate and Nano particles of calcium carbonate in titanium dioxide in the present invention, barium sulfate effectively can to improve the whiteness of titanium dioxide on the one hand; On the other hand, Nano particles of calcium carbonate can improve the thermostability of titanium dioxide, obviously can reduce again the production cost of titanium dioxide.
(2) the present invention utilizes kinds of surface promoting agent to carry out finishing to titanium dioxide, barium sulfate and nano-calcium carbonate calcium compounds, consistency between the titanium dioxide of finishing and ABS resin polymkeric substance is better, there is better dispersion effect, decrease titanium dioxide reunite and cause the downslide rapidly of ABS composite product mechanical property, the ABS composite material of non-finishing titanium dioxide is added in contrast, and its shock strength is high by more than 10%.
(3) Task-size Controlling of butadiene-styrene-acrylonitrile graft copolymer in the present invention, can guarantee that the titanium dioxide of this multipolymer and finishing is under other auxiliary addition agent actings in conjunction, the ABS mixture obtained has higher impact property and whiteness.The impact property of the matrix material of gained, all more than 180J/m, reaches the performance index of high-impact ABS; Numerically see all more than 85 from whiteness, the Production requirement of white domestic appliances can be met.
Accompanying drawing explanation
Fig. 1 experimental example 1 does not add the ABS material profile scanning electromicroscopic photograph of titanium dioxide.
Fig. 2 experimental example 2 adds the ABS composite material profile scanning electromicroscopic photograph of non-finishing titanium dioxide.
Fig. 3 experimental example 3 high-impact white domestic appliances ABS composite material profile scanning electromicroscopic photograph.
Embodiment
With embodiment, the present invention is described below, but is not limited thereto.
embodiment 1 (not adding the ABS material of titanium dioxide)
Do not add the ABS material of titanium dioxide, its each component and mass fraction thereof are: Magnesium Stearate 0.3 part, ethylene butyl acrylate 0.5 part, distearyl pentaerythrityl diphosphite 0.15 part, the two octadecyl ester 0.05 part of sulfuration dipropionic acid, butadiene-styrene-acrylonitrile graft copolymer 28 parts, styrene-acrylonitrile copolymer 68 parts.Wherein the mass ratio of divinyl, vinylbenzene and vinyl cyanide is: 55:30:15; Styrene-acrylonitrile copolymer is at 220 DEG C, and the melting index under 10kg condition is 32.05g/10min, and N content is 7.2%, and bonding acrylonitrile content is 23%, and number-average molecular weight is 70000.
Preparation method:
280g butadiene-styrene-acrylonitrile graft copolymer, 680g styrene-acrylonitrile copolymer, 3g Magnesium Stearate, 5g ethylene butyl acrylate, 1.5g distearyl pentaerythrityl diphosphite, the two octadecyl ester of 0.5g sulfuration dipropionic acid are mixed in super mixer, join extruding pelletization in twin screw extruder, the cylindrical particle product of Φ 3mm × Φ 3mm is cut to after water cooling, injection moulding after dry, is not added titanium dioxide ABS material; Wherein the machine barrel transportation section of parallel dual-screw extruding machine, fluxing zone, metering zone, die head temperature are set to 190 DEG C, 200 DEG C, 200 DEG C, 210 DEG C respectively, and vacuumize process to machine barrel, vacuum tightness is 0.06MPa simultaneously.
experimental example 2 (adding the ABS composite material of non-finishing titanium dioxide)
The ABS composite material of non-finishing titanium dioxide, its each component and mass fraction thereof are: non-finishing titanium dioxide 3 parts, Magnesium Stearate 0.3 part, ethylene butyl acrylate 0.5 part, distearyl pentaerythrityl diphosphite 0.15 part, the two octadecyl ester 0.05 part of sulfuration dipropionic acid, butadiene-styrene-acrylonitrile graft copolymer 28 parts, styrene-acrylonitrile copolymer 68 parts.Wherein the mass ratio of divinyl, vinylbenzene and vinyl cyanide is: 55:30:15; Styrene-acrylonitrile copolymer is at 220 DEG C, and the melting index under 10kg condition is 32.05g/10min, and N content is 7.2%, and bonding acrylonitrile content is 23%, and number-average molecular weight is 70000.
Preparation method:
280g butadiene-styrene-acrylonitrile graft copolymer, 680g styrene-acrylonitrile copolymer, 3g Magnesium Stearate, 5g ethylene butyl acrylate, 1.5g distearyl pentaerythrityl diphosphite, the two octadecyl ester of 0.5g sulfuration dipropionic acid and the non-finishing titanium dioxide of 30g are mixed in super mixer, join extruding pelletization in twin screw extruder, the cylindrical particle product of Φ 3mm × Φ 3mm is cut to after water cooling, injection moulding after dry, obtains high-impact white domestic appliances ABS composite material; Wherein the machine barrel transportation section of parallel dual-screw extruding machine, fluxing zone, metering zone, die head temperature are set to 190 DEG C, 200 DEG C, 200 DEG C, 210 DEG C respectively, and vacuumize process to machine barrel, vacuum tightness is 0.06MPa simultaneously.
the following example of embodiment 3(is the ABS composite material of adding finishing titanium dioxide)
High-impact white domestic appliances ABS composite material, each component and mass fraction thereof are: finishing titanium dioxide 3 parts, Magnesium Stearate 0.3 part, ethylene butyl acrylate 0.5 part, distearyl pentaerythrityl diphosphite 0.15 part, the two octadecyl ester 0.05 part of sulfuration dipropionic acid, butadiene-styrene-acrylonitrile graft copolymer 28 parts, styrene-acrylonitrile copolymer 68 parts.Wherein the mass ratio of divinyl, vinylbenzene and vinyl cyanide is: 55:30:15; Styrene-acrylonitrile copolymer is at 220 DEG C, and the melting index under 10kg condition is 32.05g/10min, and N content is 7.2%, and bonding acrylonitrile content is 23%, and number-average molecular weight is 70000.
Preparation method:
15g titanium dioxide, 4.5g barium sulfate and 10.5g nano-calcium carbonate are joined in high-speed kneading machine and fully mixes 5min, cross 250 mesh sieve and obtain mixing titanium oxide powder; Described mixing titanium oxide powder is joined in the mixed solution of 1g Virahol and 150g deionized water, stir under 50 DEG C of speed at 500r/min, be added dropwise to 0.2g dimethyl silicone oil, 0.12g silane coupling agent and 0.18g chelating titanate coupling agent successively, be warming up to 60 DEG C of reaction 2h, obtain mixed with titanium white powder; Described modification titanium dioxide filtered on buchner funnel is separated, and by 30 DEG C of washed with de-ionized water 2 times, dries in 70 DEG C of baking ovens, after grinding, obtain finishing titanium dioxide; 280g butadiene-styrene-acrylonitrile graft copolymer, 680g styrene-acrylonitrile copolymer, 3g Magnesium Stearate, 5g ethylene butyl acrylate, 1.5g distearyl pentaerythrityl diphosphite, the two octadecyl ester of 0.5g sulfuration dipropionic acid and 30g finishing titanium dioxide are mixed in super mixer, join extruding pelletization in twin screw extruder, the cylindrical particle product of Φ 3mm × Φ 3mm is cut to after water cooling, injection moulding after dry, obtains high-impact white domestic appliances ABS composite material; Wherein the machine barrel transportation section of parallel dual-screw extruding machine, fluxing zone, metering zone, die head temperature are set to 190 DEG C, 200 DEG C, 200 DEG C, 210 DEG C respectively, and vacuumize process to machine barrel, vacuum tightness is 0.06MPa simultaneously.
embodiment 4
High-impact white domestic appliances ABS composite material, each component and mass fraction thereof are: finishing titanium dioxide 3 parts, Magnesium Stearate 0.3 part, ethylene butyl acrylate 0.45 part, distearyl pentaerythrityl diphosphite 0.2 part, the two octadecyl ester 0.05 part of sulfuration dipropionic acid, butadiene-styrene-acrylonitrile graft copolymer 25 parts, styrene-acrylonitrile copolymer 71 parts, wherein the mass ratio of divinyl, vinylbenzene and vinyl cyanide is: 56:26:18; Styrene-acrylonitrile copolymer is at 220 DEG C, and the melting index under 10kg condition is 30.85g/10min, and N content is 7.8%, and bonding acrylonitrile content is 25%, and number-average molecular weight is 74500.
Preparation method: 15g titanium dioxide, 9g nano-calcium carbonate and 6g barium sulfate are fully mixed 4min in high-speed kneading machine, crosses 250 object sieves, obtains mixing titanium oxide powder; Described mixing titanium oxide powder is joined in 1g Virahol and 150g deionized water, stir under 45 DEG C of speed at 350r/min, add 0.2g dimethyl silicone oil, 0.12g silane coupling agent and 0.18g chelating titanate coupling agent successively, be warmed up to 60 DEG C of reaction 2h, obtain mixed with titanium white powder; Described titanium dioxide filtered on buchner funnel is separated, and by 30 DEG C of washed with de-ionized water 2 times, dries in 70 DEG C of baking ovens, after grinding, obtain finishing titanium dioxide; 250g butadiene-styrene-acrylonitrile graft copolymer, 710g styrene-acrylonitrile copolymer, 3g Magnesium Stearate, 4.5g ethylene butyl acrylate, 2g distearyl pentaerythrityl diphosphite, the two octadecyl ester of 0.5g sulfuration dipropionic acid and 30g finishing titanium dioxide are mixed in super mixer, join extruding pelletization in twin screw extruder, the cylindrical particle product of Φ 3mm × Φ 3mm is cut to after water cooling, injection moulding after dry, obtains high-impact white domestic appliances ABS composite material; Wherein the machine barrel transportation section of parallel dual-screw extruding machine, fluxing zone, metering zone, die head temperature are set to 185 DEG C, 195 DEG C, 195 DEG C, 205 DEG C respectively, and vacuumize process to machine barrel, vacuum tightness is 0.06MPa simultaneously.
embodiment 5
High-impact white domestic appliances ABS composite material, each component and mass fraction thereof are: finishing titanium dioxide 2.5 parts, Magnesium Stearate 0.3 part, ethylene butyl acrylate 0.45 part, distearyl pentaerythrityl diphosphite 0.2 part, the two octadecyl ester 0.05 part of sulfuration dipropionic acid, butadiene-styrene-acrylonitrile graft copolymer 26 parts, styrene-acrylonitrile copolymer 70.5 parts.Wherein the mass ratio of divinyl, vinylbenzene and vinyl cyanide is: 52:32:16; Styrene-acrylonitrile copolymer is at 220 DEG C, and the melting index under 10kg condition is 31.84g/10min, and N content is 7.4%, and bonding acrylonitrile content is 26%, and number-average molecular weight is 73000.
Preparation method:
12.5g titanium dioxide, 6.25g barium sulfate and 6.25g nano-calcium carbonate are joined in high-speed kneading machine and fully mixes 4min, cross 250 mesh sieve and obtain mixing titanium oxide powder; Described mixing titanium oxide powder is joined in the mixed solution of 1.5g Virahol and 150g deionized water, stir under 40 DEG C of speed at 400r/min, add 0.1g dimethyl silicone oil, 0.2g silane coupling agent and 0.2g chelating titanate coupling agent successively, be warming up to 60 DEG C of reaction 2h, obtain mixed with titanium white powder; Described modification titanium dioxide filtered on buchner funnel is separated, and by 30 DEG C of washed with de-ionized water 2 times, dries in 70 DEG C of baking ovens, after grinding, obtain finishing titanium dioxide; 260g butadiene-styrene-acrylonitrile graft copolymer, 705g styrene-acrylonitrile copolymer, 3g Magnesium Stearate, 4.5g ethylene butyl acrylate, 2g distearyl pentaerythrityl diphosphite, the two octadecyl ester of 0.5g sulfuration dipropionic acid and 25g finishing titanium dioxide are mixed by super mixer, join extruding pelletization in twin screw extruder, the cylindrical particle product of Φ 3mm × Φ 3mm is cut to after water cooling, injection moulding after dry, obtains high-impact white domestic appliances ABS composite material; Wherein the machine barrel transportation section of parallel dual-screw extruding machine, fluxing zone, metering zone, die head temperature are set to 190 DEG C, 200 DEG C, 200 DEG C, 210 DEG C respectively, and vacuumize process to machine barrel, vacuum tightness is 0.06MPa simultaneously.
embodiment 6
High-impact white domestic appliances ABS composite material, each component and mass fraction thereof are: finishing titanium dioxide 2 parts, Magnesium Stearate 0.25 part, ethylene butyl acrylate 0.6 part, distearyl pentaerythrityl diphosphite 0.12 part, the two octadecyl ester 0.03 part of sulfuration dipropionic acid, butadiene-styrene-acrylonitrile graft copolymer 23 parts, styrene-acrylonitrile copolymer 74 parts.Wherein the mass ratio of divinyl, vinylbenzene and vinyl cyanide is: 56:28:16; Styrene-acrylonitrile copolymer is at 220 DEG C, and the melting index under 10kg condition is 31.56g/10min, and N content is 7.5%, and bonding acrylonitrile content is 24%, and number-average molecular weight is 72500.
Preparation method:
10g titanium dioxide, 6g nano-calcium carbonate and 4g barium sulfate are fully mixed 5min in high-speed kneading machine, crosses 200 object sieves, obtain mixing titanium oxide powder; Described mixing titanium oxide powder is joined in 1g Virahol and 150g deionized water, stir under 50 DEG C of speed at 300r/min, add 0.2g dimethyl silicone oil, 0.15g silane coupling agent and 0.15g chelating titanate coupling agent successively, be warmed up to 60 DEG C of reaction 1.5h, obtain mixed with titanium white powder; Described mixed with titanium white powder filtered on buchner funnel is separated, and by 30 DEG C of washed with de-ionized water 2 times, dries in 70 DEG C of baking ovens, after grinding, obtain finishing titanium dioxide; 230g butadiene-styrene-acrylonitrile graft copolymer, 740g styrene-acrylonitrile copolymer, 2.5g Magnesium Stearate, 6g ethylene butyl acrylate, 1.2g distearyl pentaerythrityl diphosphite, the two octadecyl ester of 0.3g sulfuration dipropionic acid and 20g finishing titanium dioxide are mixed in super mixer, join extruding pelletization in twin screw extruder, the cylindrical particle product of Φ 3mm × Φ 3mm is cut to after water cooling, injection moulding after dry, obtains high-impact white domestic appliances ABS composite material; Wherein the machine barrel transportation section of parallel dual-screw extruding machine, fluxing zone, metering zone, die head temperature are set to 180 ~ 190 DEG C, 190 ~ 200 DEG C, 190 ~ 200 DEG C, 200 ~ 210 DEG C respectively, and vacuumize process to machine barrel, vacuum tightness is 0.05MPa simultaneously.
the performance index of table 1. high-impact white domestic appliances ABS composite material
As can be seen from Table 1, the impact property of the matrix material of gained, all more than 180J/m, reaches the performance index of high-impact ABS; Numerically see all more than 85 from whiteness, the Production requirement of white domestic appliances can be met.Contrast experiment's example 1 does not add the ABS material of titanium dioxide, and its whiteness is far below matrix material; And contrast experiment's example 2, add the ABS composite material of non-finishing titanium dioxide, its impact property reduces clearly, far below the ABS composite material of finishing titanium dioxide.
From the profile scanning photo of the product of ABS shown in Fig. 1, do not find titanium dioxide particle, be simple aggregation thing section picture; When with the addition of after not by the titanium dioxide of finishing, in fig. 2, the existence of titanium dioxide particle can be seen, and there is this obvious agglomeration, affect the impact property of matrix material; The profile scanning electromicroscopic photograph of the matrix material prepared according to experimental example 3 of the present invention as shown in Figure 3, wherein the titanium dioxide of finishing has better dispersiveness, have no obvious agglomeration to occur, therefore ensure that the excellent properties of high-impact white domestic appliances ABS composite material.The dispersion state similar to Fig. 3 can show in experimental example 4-6, shows the superiority of high-impact white domestic appliances ABS composite material performance of the present invention.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For the person of ordinary skill of the art, can according to technical scheme of the present invention and inventive concept, make corresponding change and substitute, and performance or purposes identical, all should be considered as protection scope of the present invention.
Claims (8)
1. a high-impact white domestic appliances ABS composite material, in mass parts butadiene-styrene-acrylonitrile graft copolymer 23 ~ 28 parts, styrene-acrylonitrile copolymer 68 ~ 73 parts, Magnesium Stearate 0.1 ~ 0.3 part, ethylene butyl acrylate 0.4 ~ 0.9 part, distearyl pentaerythrityl diphosphite 0.1 ~ 0.2 part, the two octadecyl ester 0.03 ~ 0.05 part of sulfuration dipropionic acid, finishing titanium dioxide 2 ~ 4 parts, titanium dioxide 36 ~ 60 parts in finishing titanium dioxide, 12 ~ 26 parts, barium sulfate, nanometer grade calcium carbonate 28 ~ 38 parts, titanate coupling agent 0.1 ~ 0.3 part, dimethyl silicone oil 0.2 ~ 0.4 part, silane coupling agent 0.1 ~ 0.4 part, Virahol 0.8 ~ 1.6 part, deionized water 150 ~ 250 parts, its preparation method is: titanium dioxide, nano-calcium carbonate and barium sulfate fully mix 3 ~ 5min in high-speed kneading machine, cross 200 ~ 250 object sieves, obtaining mixing titanium oxide powder adds in Virahol and deionized water, stir under 40 ~ 50 DEG C of speed at 300 ~ 500r/min, add dimethyl silicone oil successively, silane coupling agent and titanate coupling agent, be warmed up to 60 DEG C of reaction 1.5 ~ 2h, obtain mixed with titanium white powder filtered on buchner funnel to be separated, and by 30 DEG C of washed with de-ionized water 2 times, dry in 70 DEG C of baking ovens, finishing titanium dioxide is obtained after grinding.
2. the preparation method of the high-impact white domestic appliances ABS composite material of a kind of claim 1 as claimed in claim 1, is made up of following process and step:
(1) titanium dioxide, nano-calcium carbonate and barium sulfate are fully mixed 3 ~ 5min in high-speed kneading machine, cross 200 ~ 250 object sieves, obtain mixing titanium oxide powder; Described mixing titanium oxide powder is added in Virahol and deionized water, stir under 40 ~ 50 DEG C of speed at 300 ~ 500r/min, add dimethyl silicone oil, silane coupling agent and titanate coupling agent successively, be warmed up to 60 DEG C of reaction 1.5 ~ 2h, obtain mixed with titanium white powder; Described mixed with titanium white powder filtered on buchner funnel is separated, and by 30 DEG C of washed with de-ionized water 2 times, dries in 70 DEG C of baking ovens, after grinding, obtain finishing titanium dioxide; Wherein the mass fraction of each material is as follows: titanium dioxide 36 ~ 60 parts, 12 ~ 26 parts, barium sulfate, nanometer grade calcium carbonate 28 ~ 38 parts, titanate coupling agent 0.1 ~ 0.3 part, dimethyl silicone oil 0.2 ~ 0.4 part, silane coupling agent 0.1 ~ 0.4 part, Virahol 0.8 ~ 1.6 part, deionized water 150 ~ 250 parts;
(2) butadiene-styrene-acrylonitrile graft copolymer, styrene-acrylonitrile copolymer, Magnesium Stearate, ethylene butyl acrylate, distearyl pentaerythrityl diphosphite, the two octadecyl ester of sulfuration dipropionic acid and finishing titanium dioxide are mixed in super mixer, join extruding pelletization in twin screw extruder, the cylindrical particle product of Φ 3mm × Φ 3mm is cut to after water cooling, injection moulding after dry, obtains high-impact white domestic appliances ABS composite material; Wherein the machine barrel transportation section of parallel dual-screw extruding machine, fluxing zone, metering zone, die head temperature are set to 180 ~ 190 DEG C, 190 ~ 200 DEG C, 190 ~ 200 DEG C, 200 ~ 210 DEG C respectively, and vacuumize process to machine barrel, vacuum tightness is 0.06 ± 0.01MPa simultaneously; Wherein the mass fraction of each component is: butadiene-styrene-acrylonitrile graft copolymer 23 ~ 28 parts, styrene-acrylonitrile copolymer 68 ~ 73 parts, Magnesium Stearate 0.1 ~ 0.3 part, ethylene butyl acrylate 0.4 ~ 0.9 part, distearyl pentaerythrityl diphosphite 0.1 ~ 0.2 part, the two octadecyl ester 0.03 ~ 0.05 part of sulfuration dipropionic acid, finishing titanium dioxide 2 ~ 4 parts as obtained in step (1).
3. the preparation method of a kind of high-impact white domestic appliances ABS composite material as claimed in claim 2, titanate coupling agent described in it is preferably chelating titanate coupling agent.
4. the preparation method of a kind of high-impact white domestic appliances ABS composite material as claimed in claim 2, it is characterized in that, described dimethyl-silicon oil viscosity is no more than 1000cp at 25 DEG C.
5. the preparation method of a kind of high-impact white domestic appliances ABS composite material as claimed in claim 2, the mass ratio of its divinyl, vinylbenzene and vinyl cyanide is: 52 ~ 60:23 ~ 32:14 ~ 18.
6. the preparation method of a kind of high-impact white domestic appliances ABS composite material as claimed in claim 2, described in it, the particle diameter of butadiene-styrene-acrylonitrile graft copolymer is 280 ~ 320nm.
7. the preparation method of a kind of high-impact white domestic appliances ABS composite material as claimed in claim 2, the percentage of grafting of the butadiene-styrene-acrylonitrile graft copolymer described in it is 45% ~ 51%.
8. the preparation method of a kind of high-impact white domestic appliances ABS composite material according to claim 2, styrene-acrylonitrile copolymer described in it is at 220 DEG C, melting index under 10kg condition is greater than 30g/10min, N content >=7%, bonding acrylonitrile content is 23% ~ 26%, and number-average molecular weight is 70000 ~ 75000.
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| CN105331242A (en) * | 2015-11-27 | 2016-02-17 | 常熟市晓轶金属配件厂 | Cam for textile machinery |
| CN105713335A (en) * | 2015-09-18 | 2016-06-29 | 怀宁县明发塑业有限责任公司 | Nano modified high-impact-resistance ABS composite plastic |
| CN105860421A (en) * | 2016-06-12 | 2016-08-17 | 欧振云 | High-impact-resistant ABS composite material |
| CN106398104A (en) * | 2016-12-12 | 2017-02-15 | 广东威林工程塑料股份有限公司 | Weather-resistant, bending-resistant, high-gloss and low-light-transmittance ABS material and preparation method thereof |
| CN106967256A (en) * | 2017-03-01 | 2017-07-21 | 中国石油天然气股份有限公司吉林石化分公司 | A kind of oil resistivity PET/ABS composites and preparation method thereof |
| CN107903742A (en) * | 2017-12-07 | 2018-04-13 | 南京中贝电子有限公司 | A kind of aqueous, environmental protective three-proofing coating |
| CN109438866A (en) * | 2018-10-16 | 2019-03-08 | 吉林化工学院 | 3D printing carbon fiber/ABS composite material and preparation method thereof |
| CN116120678A (en) * | 2023-02-27 | 2023-05-16 | 吉林化工学院 | ABS resin for 3D printing and preparation method thereof |
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| CN105713335A (en) * | 2015-09-18 | 2016-06-29 | 怀宁县明发塑业有限责任公司 | Nano modified high-impact-resistance ABS composite plastic |
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| CN106967256A (en) * | 2017-03-01 | 2017-07-21 | 中国石油天然气股份有限公司吉林石化分公司 | A kind of oil resistivity PET/ABS composites and preparation method thereof |
| CN107903742A (en) * | 2017-12-07 | 2018-04-13 | 南京中贝电子有限公司 | A kind of aqueous, environmental protective three-proofing coating |
| CN109438866A (en) * | 2018-10-16 | 2019-03-08 | 吉林化工学院 | 3D printing carbon fiber/ABS composite material and preparation method thereof |
| CN109438866B (en) * | 2018-10-16 | 2021-04-09 | 吉林化工学院 | Carbon fiber/ABS composite material for 3D printing and preparation method thereof |
| CN116120678A (en) * | 2023-02-27 | 2023-05-16 | 吉林化工学院 | ABS resin for 3D printing and preparation method thereof |
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