CN103122121B - 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 composite material, more particularly, the present invention relates to a kind of nanoparticle reinforced ABS matrix material and preparation method thereof.
Background technology
The general name of the impact-resistant thermoplastic resin that ABS resin is vinyl cyanide, divinyl, vinylbenzene three kinds of one-tenth are grouped into, also claims abs polymer.ABS resin has had the advantage of three kinds of components concurrently, and wherein styrenic component provides good processing characteristics, and the intensity of vinyl cyanide component contributions resin and chemicals-resistant characteristic, butadiene component is then for resin brings good impact property.There is due to ABS resin the advantages such as good impact, processibility, dimensional stability, wear resistance and resistance to chemical attack, make it can use under the environment of-40-100 DEG C, 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, such as dynamo-electric shell, air conditioning machinery, refrigerator lining, type-writer, camera housing, television cabin, safety helmet, antennafier, car light and plate, pipe, rod etc., the consumption wherein in electrical apparatus product accounts for 40%.
Certainly, ABS resin is not ternary simple interpolymer, but have the rubbery polymers such as PB microdispersed two-phase uneven texture blend in AS resin external phase, because SAN has been grafted on elastomeric chain, there is certain consistency, the advantage of material competence exertion three components between PB and SAN.In performance, ABS resin has very strong polarity due to the itrile group on vinyl cyanide, and understand and mutually assemble thus be closely linked by ABS molecular chain, ABS intensity is very high, and density is little, and meanwhile, the polyhutadiene with rubber performance makes ABS have good toughness.
But the ubiquitous problem of aging of macromolecular material exists in ABS resin equally.There is carbon carbon duplex structure in the polyhutadiene in ABS resin, it easily destroy by the ultraviolet in solar ray generation free radical, cause double bond content to reduce, the shock strength of material therefore can be caused obviously to reduce.And along with widely using of terminal consumption product, correspondingly also there is a large amount of recuperable ABS resin, along with the surging of oil price and the attention to environment, the recycling of ABS resin receives publicity, and a large amount of ABS production of articles commercial cities wishes to utilize recovery ABS to reduce costs.But, for recovery ABS, be maximum problem because its mechanical property aging is significantly less than 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 the blended nanoparticle reinforced ABS matrix material prepared to recovery ABS, not only increase intensity and the toughness of matrix material, and the ageing resistance of its ABS can also be significantly improved.
In order to solve the problems of the technologies described above and realize goal of the invention, the invention provides following solution:
A preparation method for nanoparticle reinforced ABS matrix material, 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, makes tensio-active agent be coated on nanoparticle, form surface-modified nanoparticles; Described nanoparticle is selected from least one in organo montmorillonite (OMMT), nano titanium oxide and nano hydrotalcite (LDH);
(2) ABS composite material is prepared
Surface-modified nanoparticles and ABS are added melt blending in twin screw extruder according to the mass ratio of 1.0-5.0:24-45 and obtains ABS composite 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 40-60wt%, the content of 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 melt blending in twin screw extruder according to the mass ratio of 1.0-5.0:24-45:2.0-10.0 and obtains ABS composite material pellet.
Another aspect of the present invention also relates to the nanoparticle reinforced ABS matrix material prepared by above-mentioned preparation method.
Compared with prior art, the present invention has following beneficial effect:
(1) method of the present invention utilizes surface modification to cross organo montmorillonite, nano titanium oxide and nano hydrotalcite carry out modification to ABS; The present invention is by not only improving intensity and the toughness of ABS material to the selection of nanoparticles formulations, and beat all ageing resistance and the shock resistance significantly can also improving ABS, and then improves overall performance and the weather resistance of ABS material.
(2) method of the present invention is applied to the modification of the ABS material of recovery, utilizes 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 adding of composite nanoparticle can play obstruct and the effect of adsorb oxygen, the ager process of ABS material can be resisted.
(3) ABS plastic goods are through life-time service, particularly outdoor use, oxidizable aging, cause mechanical property significantly to decline, and ABS virgin material thus can not be replaced for various goods manufacture.And method of the present invention can carry out toughness reinforcing, enhancing ageing resistance modification to it; and modified material can be applied to the parts manufacture such as automobile, motorcycle, power truck and electrical equipment, electronics, instrument; achieve and reclaim the recycle of ABS material, be conducive to environment protection and decrease 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 up of following steps:
(1) preparation of surface-modified nanoparticles
Be that the nanoparticle of 5-100nm and tensio-active agent and organic antioxidant add in high-speed mixer according to the mass ratio of 1.0:0.02-0.05:0.02-0.05 by median size, be under the condition of 80-150 DEG C in temperature, stir 50-100 min, make tensio-active agent and nanoparticle dispersed, and make tensio-active agent be coated on nanoparticle, form surface-modified nanoparticles; Described nanoparticle is made up of organo montmorillonite (OMMT), nano titanium oxide and nano hydrotalcite (LDH);
(2) ABS composite material is prepared
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 DEG C, screw speed is 100-210 rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization.
In the present invention, described ABS is the ABS resin reclaimed.
In the present invention, described organic antioxidant can be various known organic antioxidants; Such as BHT (antioxidant BHT) or three nonylated phenyl phosphorous acid esters (antioxidant TNP P)
In the present invention, described tensio-active agent can be various types of tensio-active agent, but preferably cats product (polyethylene polyamines salt, ethanolamine salt or 2-alkylaminoethyl tetrahydroglyoxaline), applicant finds to use cats product to be not only conducive to the nanoparticle of surface modification to be dispersed in ABS material, but also be conducive to used antioxidant BHT or antioxidant TNP P to be adsorbed on around nanoparticle, make its stable existence in the polymeric system of ABS material, be conducive to the chronic anti-aging effect keeping ABS.
The inventive process provides approach recovery ABS material being carried out to modification, 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 adding of composite nanoparticle can play obstruct and the effect of adsorb oxygen, can resist and delay the aging of ABS resin.Modified material can be applied to the parts manufacture such as automobile, motorcycle, power truck and electrical equipment, electronics, instrument, achieves the recycle of the ABS material of recovery, is conducive to environment protection and decreases the use of raw materials for plastics production.
Embodiment 1
Being that the nanoparticle of 5-100nm, oleic acid and antioxidant BHT add in high-speed mixer according to the mass ratio of 1.0:0.02:0.02 by median size, is under the condition of 100-120 DEG C in temperature, stirs 50-100 min, forms surface-modified nanoparticles; Described nanoparticle is made up of the nano titanium oxide of OMMT, 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 DEG C, screw speed is 120-150 rpm, and obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Embodiment 2
Being that the nanoparticle of 5-100nm, oleic acid and antioxidant BHT add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02 by median size, is under the condition of 120-150 DEG C in temperature, stirs 75-100 min, forms surface-modified nanoparticles; Described nanoparticle is made up of the nano titanium oxide of OMMT, 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 DEG C, screw speed is 120-150 rpm, and obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Embodiment 3
Being that the nanoparticle of 5-100nm, stearic acid and antioxidant BHT add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02 by median size, is under the condition of 120-150 DEG C in temperature, stirs 75-100 min, forms surface-modified nanoparticles; Described nanoparticle is made up of the nano titanium oxide of OMMT, 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 DEG C, screw speed is 120-150 rpm, and obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Embodiment 4
By median size be the nanoparticle of 5-100nm, polyethylene polyamines salt and antioxidant BHT according to 1.0:0.05: mass ratio add in high-speed mixer, be under the condition of 120-150 DEG C in temperature, stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is made up of the nano titanium oxide of OMMT, 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 DEG C, screw speed is 120-150 rpm, and obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Embodiment 5
Be that the nanoparticle of 5-100nm, ethanolamine salt and antioxidant TNP P add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02 by median size, be under the condition of 100-120 DEG C in temperature, stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is made up of the nano titanium oxide of OMMT, 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 DEG C, screw speed is 120-150 rpm, and obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Embodiment 6
Be that the nanoparticle of 5-100nm and 2-alkylaminoethyl tetrahydroglyoxaline and antioxidant TNP P add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02 by median size, be under the condition of 100-120 DEG C in temperature, stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is made up of the nano titanium oxide of OMMT, 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 DEG C, screw speed is 120-150 rpm, and obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Embodiment 7
Be that the nanoparticle of 5-100nm and 2-alkylaminoethyl tetrahydroglyoxaline and antioxidant TNP P add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02 by median size, be under the condition of 100-120 DEG C in temperature, stir 75-100 min, form surface-modified nanoparticles; Described nanoparticle is made up of the nano titanium oxide of OMMT, 25wt% of 50wt%, the LDH of 25wt%; Then ABS and POE of surface-modified nanoparticles, recovery is added melt blending in twin screw extruder according to the mass ratio of 1:10:2, wherein extrusion temperature is 210-235 DEG C, screw speed is 120-150 rpm, obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Embodiment 8
Being that the nanoparticle of 5-100nm, stearic acid and antioxidant TNP P add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02 by median size, is under the condition of 120-150 DEG C in temperature, stirs 75-100 min, forms surface-modified nanoparticles; Described nanoparticle is made up of the nano titanium oxide of OMMT, 25wt% of 50wt%, the LDH of 25wt%; Then ABS and POE of surface-modified nanoparticles and recovery is added melt blending in twin screw extruder according to the mass ratio of 1:10:2, wherein extrusion temperature is 190-220 DEG C, screw speed is 120-150 rpm, obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Comparative example 1
Be that the nano-OMMT particle of 5-100nm and oleic acid and organic antioxidant BHT agent add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02 by median size, be under the condition of 100-120 DEG C 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 DEG C, screw speed is 120-150 rpm, obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Comparative example 2
Be that the nanoparticle of 5-100nm and oleic acid and organic antioxidant BHT agent add in high-speed mixer according to the mass ratio of 1.0:0.05:0.02 by median size, be under the condition of 100-120 DEG C in temperature, stir 50-100 min, form surface-modified nanoparticles; Described nanoparticle is made up 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 DEG C, screw speed is 120-150 rpm, and obtain nanoparticle reinforced ABS matrix material after extruding pelletization, its performance is in table 1.
Table 1 product technology performance table
The technical feature of the recovery ABS used 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 embodiment part is elaborated technical scheme of the present invention by embodiment, but those of ordinary skill in the art is to be understood that and without departing from the scope of the present disclosure, can adopts equivalent replacement 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 departing from invention essence, within the protection domain being all interpreted as having dropped on application claims.
Claims (7)
1. a preparation method for nanoparticle reinforced ABS matrix material, 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, makes tensio-active agent be coated on nanoparticle, form surface-modified nanoparticles; Described nanoparticle is the mixture of organo montmorillonite, nano titanium oxide and nano hydrotalcite; And in described nanoparticle, the content of organo montmorillonite is 40-60wt%, the content of nano titanium oxide is 20-30wt%, and surplus is nano hydrotalcite;
(2) ABS composite material is prepared
Surface-modified nanoparticles and ABS are added melt blending in twin screw extruder according to the mass ratio of 1-5:24-45 and obtains ABS composite material pellet.
2. preparation method according to claim 1, is characterized in that: the particle diameter of described nanoparticle is 5-100nm.
3. preparation method according to claim 1, is characterized in that: described ABS is the ABS reclaimed.
4. preparation method according to claim 1, it is characterized in that in step (2), surface-modified nanoparticles and ABS, ethylene-octene copolymer are added melt blending in twin screw extruder according to the mass ratio of 1-5:24-45:2-10 and obtains ABS composite material pellet.
5. preparation method according to claim 1, is characterized in that comprising the following steps:
(1) preparation of surface-modified nanoparticles
Be that the nanoparticle of 5-100nm, tensio-active agent and organic antioxidant add in high-speed mixer according to the mass ratio of 1.0:0.02-0.05:0.02-0.05 by median size, be under the condition of 80-150 DEG C in temperature, stir 50-100min, make tensio-active agent and nanoparticle dispersed, and make tensio-active agent be coated on nanoparticle, form surface-modified nanoparticles;
(2) ABS composite material is prepared
Surface-modified nanoparticles, 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 DEG C, screw speed is 60-210rpm, obtains nanoparticle reinforced ABS matrix material after extruding pelletization.
6. preparation method according to claim 5, is characterized in that: described tensio-active agent is cats product, and described cats product is selected from the one in polyethylene polyamines salt, ethanolamine salt or 2-alkylaminoethyl tetrahydroglyoxaline.
7. preparation method according to claim 6, is characterized in that: described tensio-active agent is 2-alkylaminoethyl tetrahydroglyoxaline.
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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 |
| 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 |
| 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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