CN103122121A - Nano particle reinforced ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof - Google Patents
Nano particle reinforced ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a nano particle reinforced ABS (acrylonitrile butadiene styrene) composite material and belongs to the technical field of ABS composite materials. The preparation method provided by the invention comprises the following steps of: firstly coating nano particles by utilizing a surfactant to form surface modified nano particles and then carrying out melt blending on the surface modified nano particles with ABS by utilizing a double screw extruder to obtain ABS composite material aggregates, wherein the surface modified nano particles are organic montmorillonite, nano titanium dioxide and nano hydrotalcite. When the preparation method provided by the invention is applied to modification of recycled ABS, mechanical property and ageing resistance of the recycled ABS can be obviously improved, the properties of the modified ABS can meet and even be higher than the standard requirements of plastic parts for a motorcycle and an electric vehicle, and the modified ABS can replace a new ABS material.
Description
Technical field
The present invention relates to the technical field of ABS matrix material, more particularly, the present invention relates to a kind of nanoparticle reinforced ABS matrix material and preparation method thereof.
Background technology
ABS resin is the general name of the impact-resistant thermoplastic resin that is grouped into of vinyl cyanide, divinyl, three kinds of one-tenth of vinylbenzene, also claims abs polymer.ABS resin has had the advantage of three kinds of components concurrently, and wherein the vinylbenzene component provides good processing characteristics, and the vinyl cyanide component has been contributed intensity and the chemicals-resistant characteristic of resin, and the divinyl component has been brought good impact property for resin.Have the advantages such as good impact, processibility, dimensional stability, wear resistance and resistance to chemical attack due to ABS resin, it can be used under the environment of-40-100 ℃, therefore, ABS resin has been widely used in the various fields such as automobile, household electrical appliances, daily living article, sports goods and office appliance in recent years, for example dynamo-electric shell, air conditioning machinery, refrigerator lining, type-writer, camera housing, television cabin, safety helmet, antennafier, car light and plate, pipe, rod etc., wherein the consumption in electrical apparatus product accounts for 40%.
Certainly, ABS resin is not ternary simple interpolymer, but the microdispersed two-phase uneven texture of the rubbery polymer blends such as PB are arranged in AS resin external phase, because SAN has been grafted on elastomeric chain, has certain consistency between PB and SAN, the advantage of material competence exertion three components.On performance, ABS resin is closely linked the ABS molecular chain thereby can mutually assemble because the itrile group on vinyl cyanide has very strong polarity, and ABS intensity is very high, and density is little, and simultaneously, the polyhutadiene with rubber performance makes ABS have good toughness.
Yet the ubiquitous problem of aging of macromolecular material exists in ABS resin equally.There is carbon carbon duplex structure in polyhutadiene in ABS resin, and it is easily destroyed the generation free radical by the ultraviolet ray in solar ray, causes double bond content to reduce, and therefore can cause the shock strength of material obviously to reduce.And along with being widely used of terminal consumption product, correspondingly also there are a large amount of recuperable ABS resin, along with the surging of oil price with to the attention of environment, the recycling of ABS resin receives publicity, and a large amount of ABS production of articles commercial cities is wished to utilize and reclaimed ABS and reduce costs.Yet, for reclaiming ABS, be maximum problem because aging its mechanical property is significantly less than the ABS fresh feed.
Summary of the invention
In order to solve above-mentioned technical problem of the prior art, the object of the present invention is to provide a kind of nanoparticle reinforced ABS matrix material, it utilizes surface-modified nanoparticles to carry out to reclaiming ABS the nanoparticle reinforced ABS matrix material that blend prepares, not only improve intensity and the toughness of matrix material, and can also significantly improve the ageing resistance of its ABS.
In order to solve the problems of the technologies described above and realize goal of the invention, the invention provides following solution:
A kind of nanoparticle reinforced ABS composite manufacture method, it comprises the following steps:
(1) preparation of surface-modified nanoparticles
Nanoparticle, tensio-active agent and the organic antioxidant mass ratio according to 1.0:0.02-0.05:0.02-0.05 is fully mixed, tensio-active agent is coated on nanoparticle, form surface-modified nanoparticles; Described nanoparticle is selected from least a in organo montmorillonite (OMMT), nano titanium oxide and nano hydrotalcite (LDH);
(2) preparation ABS matrix material
Surface-modified nanoparticles and ABS are added according to the mass ratio of 1.0-5.0:24-45 in twin screw extruder, melt blending obtains ABS matrix material pellet.
Wherein, described nanoparticle is the mixture of organo montmorillonite (OMMT), nano titanium oxide and nano hydrotalcite (LDH); And in described nanoparticle, the content of organo montmorillonite is that the content of 40-60wt%, nano titanium oxide is 20-30wt%, and the nano hydrotalcite of surplus.
Wherein, the particle diameter of described nanoparticle is 5-100 nm.
Wherein, in step (2), surface-modified nanoparticles and ABS, ethylene-octene copolymer (POE) are added according to the mass ratio of 1.0-5.0:24-45:2.0-10.0 in twin screw extruder, melt blending obtains ABS matrix material pellet.
Another aspect of the present invention also relates to the nanoparticle reinforced ABS matrix material that is prepared by above-mentioned preparation method.
Compared with prior art, the present invention has following beneficial effect:
(1) method of the present invention utilizes organo montmorillonite, nano titanium oxide and the nano hydrotalcite that surface modification is crossed to carry out modification to ABS; The present invention has not only improved intensity and the toughness of ABS material by the selection to nanoparticles formulations, and beat all ageing resistance and the shock resistance that can also significantly improve ABS, and then has improved overall performance and the weather resistance of ABS material.
(2) modification of the method for the present invention ABS material that is applied to reclaim, utilize above-mentioned composite nano particle modified tensile strength and the shock strength that not only can improve material, and can significantly improve the dimensional stability of material product; And the adding to play and intercept and the effect of adsorb oxygen of composite nanoparticle, can resist the ager process of ABS material.
(3) the ABS plastic goods are through life-time service, particularly outdoor use, and easily deterioration by oxidation, cause mechanical property significantly to descend, thereby can not replace the ABS virgin material to be used for various goods manufacturings.And method of the present invention can be carried out toughness reinforcing, enhancing ageing resistance modification to it; and the material after modification can be applied to the parts manufacturings such as automobile, motorcycle, power truck and electrical equipment, electronics, instrument; realized reclaiming the recycle of ABS material, be conducive to environment protection and reduced the use of raw materials for plastics production.
Embodiment
Below with reference to embodiment, technical scheme of the present invention is further elaborated.
Nanoparticle reinforced ABS matrix material of the present invention, it is made by following steps:
(1) preparation of surface-modified nanoparticles
Being the nanoparticle of 5-100nm and tensio-active agent and organic antioxidant with median size adds in high-speed mixer according to the mass ratio of 1.0:0.02-0.05:0.02-0.05, be under the condition of 80-150 ℃ in temperature, stir 50-100 min, make tensio-active agent and nanoparticle Uniform Dispersion, and tensio-active agent is coated on nanoparticle, forms surface-modified nanoparticles; Described nanoparticle is comprised of organo montmorillonite (OMMT), nano titanium oxide and nano hydrotalcite (LDH);
(2) preparation ABS matrix material
Surface-modified nanoparticles, ABS resin and ethylene-octene copolymer (POE) are added melt blending in twin screw extruder according to the mass ratio of 1.0-5.0:24-45:0-10.0, wherein extrusion temperature is 210-235 ℃, screw speed is 100-210 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization.
In the present invention, the ABS resin of described ABS for reclaiming.
In the present invention, described organic antioxidant can be various known organic antioxidants; For example BHT (antioxidant BHT) or three nonylated phenyl phosphites (antioxidant TNP P)
In the present invention, described tensio-active agent can be various types of tensio-active agents, but cats product (polyethylene polyamines salt, ethanolamine salt or 2-alkylamino ethyl imidazol(e) quinoline) preferably, the applicant finds to use cats product not only to be conducive to the nanoparticle of surface modification is dispersed in the ABS material, but also be conducive to the antioxidant BHT that will use or antioxidant TNP P be adsorbed on nanoparticle around, make its stable existence in the polymeric system of ABS material, be conducive to keep the long-term antiageing effect of ABS.
Method of the present invention provides the approach that carries out modification to reclaiming the ABS material, and method of the present invention not only can improve tensile strength and the shock strength of material, and can significantly improve the dimensional stability of material product; And the adding to play and intercept and the effect of adsorb oxygen of composite nanoparticle, can resist and delay the aging of ABS resin.Material after modification can be applied to the parts manufacturings such as automobile, motorcycle, power truck and electrical equipment, electronics, instrument, realized the recycle of the ABS material that reclaims, is conducive to environment protection and reduced the use of raw materials for plastics production.
Embodiment 1
The nanoparticle, oleic acid and the antioxidant BHT that with median size are 5-100nm add in high-speed mixer according to the mass ratio of 1.0:0.02:0.02, in temperature are under the condition of 100-120 ℃, to stir 50-100 min, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of OMMT, the 30wt% of 40wt%, the LDH of 30wt%; Then the ABS of surface-modified nanoparticles and recovery is added melt blending in twin screw extruder according to the mass ratio of 1:15, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization, and its performance sees Table 1.
Embodiment 2
The nanoparticle, oleic acid and the antioxidant BHT that with median size are 5-100nm add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02, in temperature are under the condition of 120-150 ℃, to stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of OMMT, the 25wt% of 50wt%, the LDH of 25wt%; Then the ABS1 of surface-modified nanoparticles and recovery is added melt blending in twin screw extruder according to the mass ratio of 1:10, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization, and its performance sees Table 1.
Embodiment 3
The nanoparticle, stearic acid and the antioxidant BHT that with median size are 5-100nm add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02, in temperature are under the condition of 120-150 ℃, to stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of OMMT, the 25wt% of 50wt%, the LDH of 25wt%; Then the ABS of surface-modified nanoparticles and recovery is added melt blending in twin screw extruder according to the mass ratio of 1:10, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization, and its performance sees Table 1.
Embodiment 4
With median size be nanoparticle, polyethylene polyamines salt and the antioxidant BHT of 5-100nm according to 1.0:0.05: mass ratio add in high-speed mixer, be under the condition of 120-150 ℃, to stir 75-100 min in temperature, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of OMMT, the 25wt% of 50wt%, the LDH of 25wt%; Then the ABS1 of surface-modified nanoparticles and recovery is added melt blending in twin screw extruder according to the mass ratio of 1:10, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization, and its performance sees Table 1.
Embodiment 5
The nanoparticle, ethanolamine salt and the antioxidant TNP P that with median size are 5-100nm add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02, be under the condition of 100-120 ℃ in temperature, stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of OMMT, the 25wt% of 50wt%, the LDH of 25wt%; Then the ABS of surface-modified nanoparticles and recovery is added melt blending in twin screw extruder according to the mass ratio of 1.0:10.0, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization, and its performance sees Table 1.
Embodiment 6
Being the nanoparticle of 5-100nm and 2-alkylamino ethyl imidazol(e) quinoline and antioxidant TNP P with median size adds in high-speed mixer according to the mass ratio of 1.0:0.05:0.02, be under the condition of 100-120 ℃ in temperature, stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of OMMT, the 25wt% of 50wt%, the LDH of 25wt%; Then the ABS of surface-modified nanoparticles and recovery is added melt blending in twin screw extruder according to the mass ratio of 1.0:10.0, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization, and its performance sees Table 1.
Embodiment 7
Being the nanoparticle of 5-100nm and 2-alkylamino ethyl imidazol(e) quinoline and antioxidant TNP P with median size adds in high-speed mixer according to the mass ratio of 1.0:0.05:0.02, be under the condition of 100-120 ℃ in temperature, stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of OMMT, the 25wt% of 50wt%, the LDH of 25wt%; Then the ABS of surface-modified nanoparticles, recovery and POE are added melt blending in twin screw extruder according to the mass ratio of 1:10:2, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance sees Table 1.
Embodiment 8
The nanoparticle, stearic acid and the antioxidant TNP P that with median size are 5-100nm add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02, in temperature are under the condition of 120-150 ℃, to stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of OMMT, the 25wt% of 50wt%, the LDH of 25wt%; Then the ABS of surface-modified nanoparticles and recovery and POE are added melt blending in twin screw extruder according to the mass ratio of 1:10:2, wherein extrusion temperature is 190-220 ℃, screw speed is 120-150 rpm, obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance sees Table 1.
Comparative Examples 1
Being the nano-OMMT particle of 5-100nm and oleic acid and organic antioxidant BHT agent with median size adds in high-speed mixer according to the mass ratio of 1.0:0.05:0.02, be under the condition of 100-120 ℃ in temperature, stir 50-100 min, form surface-modified nanoparticles; Then the ABS of surface-modified nanoparticles and recovery and ethylene-octene copolymer (POE) are added melt blending in twin screw extruder according to the mass ratio of 1:10:2, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance sees Table 1.
Comparative Examples 2
Being the nanoparticle of 5-100nm and oleic acid and organic antioxidant BHT agent with median size adds in high-speed mixer according to the mass ratio of 1.0:0.05:0.02, be under the condition of 100-120 ℃ in temperature, stir 50-100 min, form surface-modified nanoparticles; Described nanoparticle is comprised of the nano titanium oxide of 50wt% and the nano silicon of 50wt%; Then the ABS of surface-modified nanoparticles and recovery is added melt blending in twin screw extruder according to the mass ratio of 1:10, wherein extrusion temperature is 210-235 ℃, screw speed is 120-150 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization, and its performance sees Table 1.
Table 1 product technology performance table
The technical feature of the recovery ABS that uses in the present invention is as shown in table 2:
Table 2
Wherein, vicat softening temperature (VST) carries out according to the regulation of GB1633; Tensile yield strength carries out according to the regulation of GB/T1040.2-2006; Rockwell hardness carries out according to the regulation of GB/T 3398-2008.
Although the embodiment part elaborates technical scheme of the present invention by embodiment, but those of ordinary skill in the art is to be understood that and can breaking away from scope disclosed by the invention, can adopt to be equal to and replace or the enforcement of equivalent transformation form.Therefore, protection scope of the present invention is not limited to the specific embodiment of embodiment part, as long as no the embodiment that breaks away from invention essence, within all being interpreted as having dropped on the protection domain of requirement of the present invention.
Claims (10)
1. nanoparticle reinforced ABS composite manufacture method is characterized in that comprising the following steps:
(1) preparation of surface-modified nanoparticles
Nanoparticle, tensio-active agent and the organic antioxidant mass ratio according to 1.0:0.02-0.05:0.02-0.05 is fully mixed, tensio-active agent is coated on nanoparticle, form surface-modified nanoparticles; Described nanoparticle is selected from least a in organo montmorillonite, nano titanium oxide and nano hydrotalcite;
(2) preparation ABS matrix material
Surface-modified nanoparticles and ABS are added according to the mass ratio of 1-5:24-45 in twin screw extruder, melt blending obtains ABS matrix material pellet.
2. preparation method claimed in claim 1, is characterized in that described nanoparticle is the mixture of organo montmorillonite, nano titanium oxide and nano hydrotalcite; And in described nanoparticle, the content of organo montmorillonite is that the content of 40-60wt%, nano titanium oxide is 20-30wt%, and the nano hydrotalcite of surplus.
3. preparation method according to claim 1 and 2, it is characterized in that: the particle diameter of described nanoparticle is 5-100 nm.
4. preparation method according to claim 1 and 2, is characterized in that: the ABS of described ABS for reclaiming.
5. preparation method according to claim 1 and 2, it is characterized in that in step (2), surface-modified nanoparticles and ABS, ethylene-octene copolymer are added according to the mass ratio of 1-5:24-45:2-10 in twin screw extruder, melt blending obtains ABS matrix material pellet.
6. preparation method according to claim 1 and 2 is characterized in that comprising the following steps:
(1) preparation of surface-modified nanoparticles
Being the nanoparticle of 5-100nm and tensio-active agent and organic oxidation-resistant agent with median size adds in high-speed mixer according to the mass ratio of 1.0:0.01-0.05:0-0.05, be under the condition of 80-150 ℃ in temperature, stir 50-100 min, make tensio-active agent and nanoparticle Uniform Dispersion, and tensio-active agent is coated on nanoparticle, forms surface-modified nanoparticles; Described nanoparticle is comprised of organo montmorillonite, nano titanium oxide and nano hydrotalcite;
(2) preparation ABS matrix material
Surface-modified nanoparticles and ABS and optional ethylene-octene copolymer are added melt blending in twin screw extruder according to the mass ratio of 1.0-5.0:24-45:0-10.0, wherein extrusion temperature is 210-235 ℃, screw speed is 60-210 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization.
7. preparation method according to claim 6, it is characterized in that: described organic antioxidant is BHT or three nonylated phenyl phosphites.
8. preparation method according to claim 7, it is characterized in that: described tensio-active agent is cats product, and described cats product is selected from a kind of in polyethylene polyamines salt, ethanolamine salt or 2-alkylamino ethyl imidazol(e) quinoline.
9. preparation method according to claim 8, it is characterized in that: described tensio-active agent is 2-alkylamino ethyl imidazol(e) quinoline.
10. a nanoparticle reinforced ABS matrix material, is characterized in that being prepared by the described preparation method of claim 1-9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106751402A (en) * | 2016-12-21 | 2017-05-31 | 马鞍山瑞美塑业有限公司 | A kind of mobile air conditioner chassis high-strength plastic preparation method for material |
| CN107163488A (en) * | 2017-06-09 | 2017-09-15 | 东莞市联洲知识产权运营管理有限公司 | A kind of hydrotalcite-modified ABS composite material of high-weatherability |
| CN108219349A (en) * | 2016-12-14 | 2018-06-29 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing modified ABS resin and preparation method thereof |
| CN109248710A (en) * | 2018-09-25 | 2019-01-22 | 中国科学院福建物质结构研究所 | A kind of composition and preparation method thereof of doping vario-property layered double-hydroxide |
| CN114437496A (en) * | 2022-03-09 | 2022-05-06 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
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| CN101016401A (en) * | 2007-03-02 | 2007-08-15 | 浙江大学 | Injection moulding composition based on reclaiming ABS |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101016401A (en) * | 2007-03-02 | 2007-08-15 | 浙江大学 | Injection moulding composition based on reclaiming ABS |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219349A (en) * | 2016-12-14 | 2018-06-29 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing modified ABS resin and preparation method thereof |
| CN106751402A (en) * | 2016-12-21 | 2017-05-31 | 马鞍山瑞美塑业有限公司 | A kind of mobile air conditioner chassis high-strength plastic preparation method for material |
| CN107163488A (en) * | 2017-06-09 | 2017-09-15 | 东莞市联洲知识产权运营管理有限公司 | A kind of hydrotalcite-modified ABS composite material of high-weatherability |
| CN109248710A (en) * | 2018-09-25 | 2019-01-22 | 中国科学院福建物质结构研究所 | A kind of composition and preparation method thereof of doping vario-property layered double-hydroxide |
| CN109248710B (en) * | 2018-09-25 | 2021-06-22 | 中国科学院福建物质结构研究所 | Doped modified layered double hydroxide composition and preparation method thereof |
| CN114437496A (en) * | 2022-03-09 | 2022-05-06 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
| CN114437496B (en) * | 2022-03-09 | 2024-01-02 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
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Denomination of invention: Nano particle reinforced ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof Effective date of registration: 20160624 Granted publication date: 20141224 Pledgee: Industrial Commercial Bank of China Ltd Taizhou Huangyan branch Pledgor: Zhejiang Yulong Technology Development Co., Ltd. Registration number: 2016330000036 |
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