CN101302323A - Toughened and reinforced ABS material and preparation thereof - Google Patents
Toughened and reinforced ABS material and preparation thereof Download PDFInfo
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- CN101302323A CN101302323A CNA200810067342XA CN200810067342A CN101302323A CN 101302323 A CN101302323 A CN 101302323A CN A200810067342X A CNA200810067342X A CN A200810067342XA CN 200810067342 A CN200810067342 A CN 200810067342A CN 101302323 A CN101302323 A CN 101302323A
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Abstract
The invention discloses a toughened and reinforced ABS material and a method for preparing the same. The toughened and reinforced ABS material is prepared by the following compositions by weight percentage: 55 to 75 percent of acrylonitrile-butadiene-styrene copolymers, 5 to 15 percent of toughening agent, 10 to 30 percent of reinforcing agent, 3.0 to 7.0 percent of compatilizer, 0.3 to 0.5 percent of coupling agent, 0.1 to 1.0 percent of antioxidant and 0.3 to 0.7 percent of glass-fiber exposure resistant agent. The method effectively improves the impact strength and the toughness of a whole system through addition of the toughening agent into an ABS and GF system. During the process of fusing and extruding the toughened and reinforced ABS, the toughening agent is uniformly distributed in ABS resins; when the material or a molded piece is impacted, the toughening agent which is uniformly dispersed in the ABS resins can effectively absorb the impact energy in time so as to improve the toughness of the reinforced ABS and make the molded piece achieve the effect that the molded piece can not be cracked when a self-tapping screw is tightened.
Description
[technical field]
The present invention relates to technical field of polymer materials, relate in particular to a kind of toughened and reinforced ABS material and preparation method thereof.This kind alloy can be applicable to electrical and electronic component, and office equipment parts and shell, laptop computer and notebook computer casing and other need certain intensity need beat in the product of self-tapping screw again.
[background technology]
Acrylonitrile-butadiene-styrene copolymer (ABS) is a kind of increasingly extensive engineering plastics of using, ABS has good rigidly, shock strength height, low temperature resistant, chemical proofing, physical strength and electric property are good, heat-resisting, surface hardness is high, be easy to processing, finish size stability and surface luster are good, make glass easily and strengthen the easy application of product, painted, can also carry out metallize, plating, welding and secondary processing such as bonding.But its some shortcoming is low as the ABS intensity of enhancing modified not, and poor heat resistance etc. have all restricted its application in a lot of fields.The modification of co-blended aurification is a kind of important means of ABS modification, and it makes the ABS performance excellent more, thereby has widened its Application Areas.
Fiber glass reinforced ABS is one of industrialized ABS modified product early, and fiber glass reinforced ABS is present most important reinforced ABS material.With respect to ABS, it has improved fatigue strength and the hardness of ABS on performance.Tensile strength, flexural strength, modulus in flexure, compressive strength, wear resistance, reduction water-absorbent, creep, heat-drawn wire and the molding shrinkage of ABS have been improved simultaneously.Very big to the demand that strengthens glass ABS in the market, domestic considerable enterprise has also done a lot of research work on the one hand at this, obtains sizable progress and achievement.
The weak point of fiber glass reinforced ABS is the poor toughness of material, and easy explosion when playing self-tapping screw has limited the application of fiber glass reinforced ABS in some field.
[summary of the invention]
The technical problem to be solved in the present invention is, it is poor to overcome traditional fiber glass reinforced ABS toughness of material, the defective that shock strength is not high provides the toughened and reinforced ABS material of a kind of shock strength height, good toughness, and the preparation method of this kind toughened and reinforced ABS material also will be provided simultaneously.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is that a kind of toughened and reinforced ABS material is prepared from by following component by weight percentage:
Acrylonitrile-butadiene-styrene copolymer 55～75%;
Toughner 5～15%;
Toughener 10～30%;
Compatilizer 3.0～7.0%;
Coupling agent 0.3～0.5%;
Oxidation inhibitor 0.1～1.0%;
Anti-glass emergence on the surface agent 0.3～0.7%.
By 91%～97% high glue powder, 0.5～2% coupling agent and 2%～7% compatilizer are prepared from by weight percentage for above-described toughened and reinforced ABS material, described toughner.Described compatilizer is SMA resin system vinylbenzene (S)-maleic anhydride (MA) multipolymer.Described toughener is a glass fibre reinforcement.Described oxidation inhibitor comprises phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester 0.05-0.5% and phosphite ester kind antioxidant (2,4 di-tert-butyl-phenyl) tris phosphite 0.05-0.5%.The modified product that described anti-glass emergence on the surface agent is an ethylene bis stearamide.
Above-described toughened and reinforced ABS material can be prepared from by following compositions in weight percentage:
Acrylonitrile-butadiene-styrene copolymer 60～70%;
Toughner 7～10%;
Toughener 15～25%;
Compatilizer 5.0～6.0%;
Coupling agent 0.3～0.5%;
Oxidation inhibitor 0.3～0.5%;
Anti-glass emergence on the surface agent 0.5～0.6%;
Above percentage ratio is weight percent.
The preparation method of above-described toughened and reinforced ABS material, this preparation method may further comprise the steps:
Step 1: take by weighing each component by above-mentioned weight percent;
Step 2: with the acrylonitrile-butadiene-styrene copolymer is matrix, adds toughner, toughener, compatilizer, coupling agent, oxidation inhibitor, anti-glass emergence on the surface agent and an amount of dispersion agent and mixes in high-speed mixer;
Step 3: each component that will mix places twin screw extruder, through the melting mixing extruding pelletization.
The preparation method of above-described toughened and reinforced ABS material, this twin screw extruder one district's temperature: 170～180 ℃, two district's temperature: 180～190 ℃, three district's temperature: 200～210 ℃, four district's temperature: 210～220 ℃, five district's temperature: 200～210 ℃, six district's temperature: 190～200 ℃, residence time 1-2 minute, engine speed: 300-350rpm.In step 2, in high-speed mixer, mixed 3-5 minute.
The preparation method of above-described toughened and reinforced ABS material, also comprise the toughner making step: by weight percentage with 91%～97% high glue powder, 0.5～2% coupling agent and 2%～7% compatilizer are put into high mixer, heat temperature raising is to 60-70 ℃ while mixing, high-speed mixing 15-25 minute, its mixture is put into the forcing machine extruding pelletization, make toughner.
The present invention improves the shock strength and the toughness of whole system effectively by add a certain proportion of toughner in the system of ABS+GF.Its mechanism is that toughened and reinforced ABS is in melt extruding process, toughner can be distributed in the middle of the ABS resin uniformly, when this material or product are subjected to impacting, be dispersed in the central toughner of ABS resin and can absorb ballistic energy timely and effectively, thereby improve the toughness of reinforced ABS, make product reach when playing self-tapping screw not can explosion effect.
[embodiment]
In following examples of the present invention, acrylonitrile-butadiene-styrene copolymer (ABS) resin relative density is 1.00～1.05, and fusing point is 175-185 ℃; Compatilizer is SMA resin system vinylbenzene (S)-maleic anhydride (MA) multipolymer.Toughener is a glass fibre reinforcement; Coupling agent is organo silane coupling agent KH550.Oxidation inhibitor comprises phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester 0.05-0.5% and phosphite ester kind antioxidant (2,4 di-tert-butyl-phenyl) tris phosphite 0.05-0.5%.Anti-glass emergence on the surface agent is the modified product of ethylene bis stearamide.
Toughner making method of the present invention is as follows: by weight percentage with 91%～97% high glue powder, 0.5～2% coupling agent and 2%～7% compatilizer are put into high mixer, heat temperature raising is to 60-70 ℃ while mixing, high-speed mixing 15-25 minute, its mixture is put into the forcing machine extruding pelletization, the toughner relative density of making is 0.80～0.90, and fusing point is 160～170 ℃.High glue powder is the acrylonitrile-butadiene-phenylethene grafted copolymer of high rubber content (＞50%), as the B415 of Crompton Blendex, and the HR181 of the tall and erect wound in Dongguan etc.The embodiment that toughner is made is as follows: will contain 95% high glue powder, 1% coupling agent and 4% compatilizer are put into high mixer, the heat temperature raising to 65 ℃ while mixing, and high-speed mixing 20 minutes is put into the forcing machine extruding pelletization with its mixture, makes toughner.
Embodiment 1
With its acrylonitrile-butadiene-styrene copolymer of resin (ABS) weight ratio be: 55%; The toughner weight ratio is: 10%; Toughener glass fibre weight ratio is: 30%; Compatilizer (SMA) weight ratio is: 3.0%; Coupling agent (KH-550) weight ratio is: 0.5%; Oxidation inhibitor (1010) weight ratio is: 0.4%; Oxidation inhibitor 168 weight ratios are: 0.4%; Anti-glass emergence on the surface agent (TAF) weight ratio is: 0.7%.In high-speed mixer, mixed 4 minutes;
Each component that mixes places twin screw extruder, through the melting mixing extruding pelletization;
This twin screw extruder one district's temperature: 170～180 ℃, two district's temperature: 180～190 ℃, three district's temperature: 200～210 ℃, four district's temperature: 210～220 ℃, five district's temperature: 200～210 ℃, six district's temperature: 190～200 ℃, residence time 1-2 minute, engine speed: 300-350rpm.
Embodiment 2
With its acrylonitrile-butadiene-styrene copolymer of resin (ABS) weight ratio be: 50%; The toughner weight ratio is: 15%; Toughener glass fibre weight ratio is: 30%; Compatilizer (SMA) weight ratio is: 4.0%; Coupling agent (KH-550) weight ratio is: 0.3%; Oxidation inhibitor (1010) weight ratio is: 0.05%; Oxidation inhibitor 168 weight ratios are: 0.05%; Anti-glass emergence on the surface agent (TAF) weight ratio is: 0.6%.In high-speed mixer, mixed 4 minutes;
Each component that mixes is placed twin screw extruder, through the melting mixing extruding pelletization;
This twin screw extruder one district's temperature: 170～180 ℃, two district's temperature: 180～190 ℃, three district's temperature: 200～210 ℃, four district's temperature: 210～220 ℃, five district's temperature: 200～210 ℃, six district's temperature: 190～200 ℃, residence time 1-2 minute, engine speed: 300-350rpm.
Embodiment 3
To set acrylonitrile-butadiene-styrene copolymer (ABS) weight ratio is: 65%; The toughner weight ratio is: 8%; Toughener glass fibre weight ratio is: 20%; Compatilizer (SMA) weight ratio is: 5.0%; Coupling agent (KH-550) weight ratio is: 0.4%; Oxidation inhibitor (1010) weight ratio is: 0.5%; Oxidation inhibitor 168 weight ratios are: 0.5%; Anti-glass emergence on the surface agent (TAF) weight ratio is: 0.6%; Above percentage ratio is weight percent.In high-speed mixer, mixed 4 minutes;
The raw material that mixes is placed twin screw extruder, through the melting mixing extruding pelletization;
This twin screw extruder one district's temperature: 170～180 ℃, two district's temperature: 180～190 ℃, three district's temperature: 200～210 ℃, four district's temperature: 210～220 ℃, five district's temperature: 200～210 ℃, six district's temperature: 190～200 ℃, residence time 1-2 minute, engine speed: 300-350rpm.
Embodiment 4
With its acrylonitrile-butadiene-styrene copolymer of resin (ABS) weight ratio be: 63%; The toughner weight ratio is: 9.5%; Toughener glass fibre weight ratio is: 20%; Compatilizer (SMA) weight ratio is: 6.0%; Coupling agent (KH-550) weight ratio is: 0.4%; Oxidation inhibitor (1010) weight ratio is: 0.3%; Oxidation inhibitor 168 weight ratios are: 0.3%; Anti-glass emergence on the surface agent (TAF) weight ratio is: 0.5%; Above percentage ratio is weight percent.In high-speed mixer, mixed 4 minutes;
The raw material that mixes is placed twin screw extruder, through the melting mixing extruding pelletization;
This twin screw extruder one district's temperature: 170～180 ℃, two district's temperature: 180～190 ℃, three district's temperature: 200～210 ℃, four district's temperature: 210～220 ℃, five district's temperature: 200～210 ℃, six district's temperature: 190～200 ℃, residence time 1-2 minute, engine speed: 300-350rpm.
Embodiment 5
With its acrylonitrile-butadiene-styrene copolymer of resin (ABS) weight ratio be: 77%; The toughner weight ratio is: 5.5%; Toughener glass fibre weight ratio is: 10%; Compatilizer (SMA) weight ratio is: 6.0%; Coupling agent (KH-550) weight ratio is: 0.4%; Oxidation inhibitor (1010) weight ratio is: 0.3%; Oxidation inhibitor 168 weight ratios are: 0.3%; Anti-glass emergence on the surface agent (TAF) weight ratio is: 0.5%; Above percentage ratio is weight percent.In high-speed mixer, mixed 4 minutes;
The raw material that mixes is placed twin screw extruder, through the melting mixing extruding pelletization;
This twin screw extruder one district's temperature: 170～180 ℃, two district's temperature: 180～190 ℃, three district's temperature: 200～210 ℃, four district's temperature: 210～220 ℃, five district's temperature: 200～210 ℃, six district's temperature: 190～200 ℃, residence time 1-2 minute, engine speed: 300-350rpm.
Embodiment 6
With its acrylonitrile-butadiene-styrene copolymer of resin (ABS) weight ratio be: 75%; The toughner weight ratio is: 5%; Toughener glass fibre weight ratio is: 12%; Compatilizer (SMA) weight ratio is: 7.0%; Coupling agent (KH-550) weight ratio is: 0.4%; Oxidation inhibitor (1010) weight ratio is: 0.15%; Oxidation inhibitor 168 weight ratios are: 0.15%; Anti-glass emergence on the surface agent (TAF) weight ratio is: 0.3%; Above percentage ratio is weight percent.In high-speed mixer, mixed 4 minutes;
The raw material that mixes is placed twin screw extruder, through the melting mixing extruding pelletization;
This twin screw extruder one district's temperature: 170～180 ℃, two district's temperature: 180～190 ℃, three district's temperature: 200～210 ℃, four district's temperature: 210～220 ℃, five district's temperature: 200～210 ℃, six district's temperature: 190～200 ℃, residence time 1-2 minute, engine speed: 300-350rpm.
Performance evaluation mode and implementation standard:
With the particle finished as stated above in 80～90 ℃ convection oven dry 4 hours in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injector, and the injection mold temperature control is at 80 ℃.
The tensile property test is undertaken by ISO 527-2, and specimen size is 150 * 10 * 4, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80 * 10 * 4, and draw speed is 2mm/min, and span is 64mm, and simple beam impact strength is undertaken by ISO 179, and specimen size is 55 * 6 * 4, and notch depth is 1/3rd of a sample thickness; The test of ash is undertaken by the testing method of ISO 3451.
Comprehensive mechanical performance is passed judgment on by the numerical value of tensile strength, elongation at break, flexural strength, modulus in flexure, shock strength and the flame retardant resistance of test gained.
Table 1: the formula table of embodiment 1-6
| Component % | Manufacturer | Model | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| ABS | LG | 121H | 55 | 50 | 65 | 63 | 77 | 75 |
| Toughner | Self-control | 10 | 15 | 8 | 9.5 | 5.5 | 5 | |
| Glass | Megalith | 988 | 30 | 30 | 20 | 20 | 10 | 12 |
| SMA | Last maritime affairs must reach | M14 | 3 | 4 | 5 | 6 | 6.0 | 7 |
| Coupling agent | The bright section of Nanjing Holley | KH550 | 0.5 | 0.3 | 0.4 | 0.4 | 0.4 | 0.4 |
| Oxidation inhibitor | Jin Haiyabao | 1010 | 0.4 | 0.05 | 0.5 | 0.3 | 0.3 | 0.15 |
| Oxidation inhibitor | Jin Haiyabao | 168 | 0.4 | 0.05 | 0.5 | 0.3 | 0.3 | 0.15 |
| Anti-glass emergence on the surface agent | Suzhou Xingtai state light | TAF | 0.7 | 0.6 | 0.6 | 0.5 | 0.5 | 0.3 |
Table 2: the fiber glass reinforced ABS material property contrast table of embodiment 1-6 and prior art
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Fiber glass reinforced ABS |
| Tensile strength (mpa) | 92 | 90 | 75 | 73 | 65 | 63 | 72 |
| Elongation at break (%) | 3 | 3 | 4.5 | 4.5 | 6 | 6 | 2.5 |
| Flexural strength (mpa) | 115 | 112 | 100 | 98 | 87 | 85 | 125 |
| Modulus in flexure (mpa) | 5500 | 5300 | 4000 | 3900 | 3200 | 3000 | 3800 |
| Shock strength (KJ/m2) | 15 | 15 | 16 | 16 | 17 | 17 | 12 |
| Toughness | Good | Good | Remarkably | Remarkably | Remarkably | Remarkably | Difference |
| Floating fine | Not obvious | Not obvious | Not obvious | Not obvious | Not obvious | Not obvious | Seriously |
| Ash | 30 | 30 | 20 | 20 | 10 | 12 | 20 |
Can learn from the data of table 1 and table 2:
1) along with the attenuating of glass, the shock strength of material is improved, the trend that toughness increases;
2) along with the increase of toughner, the shock strength of material is improved, the trend that toughness increases;
3) along with the increase of compatilizer, the shock strength of material is improved, the trend that toughness increases.
It is low that the present invention has overcome traditional fiber glass reinforced ABS material impact intensity, the defective of poor toughness, the invention has the beneficial effects as follows: the good toughness of product, the shock strength height, intensity height, chemical resistant properties are good, dimensional stability reaches low warpage properties well, guaranteeing to strengthen the original inflexible of glass ABS material simultaneously, can improve the toughness and the impact property that strengthen glass ABS significantly, can be widely used in electrical and electronic component, office equipment parts and shell, laptop computer and notebook computer casing and other need certain intensity need beat in the product of self-tapping screw again.
The present invention can also overcome the floating fine serious defective of traditional glass enhancing glass ABS material surface by the content of control compatilizer and anti-glass emergence on the surface agent in addition, guaranteeing that glass strengthens the rigidity of glass ABS material, improve product toughness and impact property, under the prerequisite of warpage properties, improve the surface floating fiber effect of toughened and reinforced ABS material, further enlarged the range of application of reinforced ABS material.
Claims (10)
1, a kind of toughened and reinforced ABS material is characterized in that: by weight percentage by with
Following component is prepared from:
Acrylonitrile-butadiene-styrene copolymer 55～75%;
Toughner 5～15%;
Toughener 10～30%;
Compatilizer 3.0～7.0%;
Coupling agent 0.3～0.5%;
Oxidation inhibitor 0.1～1.0%;
Anti-glass emergence on the surface agent 0.3～0.7%.
2, toughened and reinforced ABS material according to claim 1 is characterized in that: by 91%～97% high glue powder, 0.5～2% coupling agent and 2%～7% compatilizer are prepared from described toughner by weight percentage.
3, toughened and reinforced ABS material according to claim 2 is characterized in that: described compatilizer is SMA resin system vinylbenzene (S)-maleic anhydride (MA) multipolymer, and described toughener is a glass fibre reinforcement.
4, toughened and reinforced ABS material according to claim 2, it is characterized in that: described oxidation inhibitor comprises phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester 0.05-0.5% and phosphite ester kind antioxidant (2,4 di-tert-butyl-phenyl) tris phosphite 0.05-0.5%.
5, toughened and reinforced ABS material according to claim 1 is characterized in that: the modified product that described anti-glass emergence on the surface agent is an ethylene bis stearamide.
6, toughened and reinforced ABS material according to claim 1 is characterized in that: be prepared from by following compositions in weight percentage:
Acrylonitrile-butadiene-styrene copolymer 60～70%;
Toughner 7～10%;
Toughener 15～25%;
Compatilizer 5.0～6.0%;
Coupling agent 0.3～0.5%;
Oxidation inhibitor 0.3～0.5%;
Anti-glass emergence on the surface agent 0.5～0.6%;
Above percentage ratio is weight percent.
7, a kind of preparation method of toughened and reinforced ABS material as claimed in claim 1 is characterized in that: this preparation method may further comprise the steps:
Step 1: take by weighing each component by above-mentioned weight percent;
Step 2: with the acrylonitrile-butadiene-styrene copolymer is matrix, adds toughner, toughener, compatilizer, coupling agent, oxidation inhibitor, anti-glass emergence on the surface agent and an amount of dispersion agent and mixes in high-speed mixer;
Step 3: each component that will mix places twin screw extruder, through the melting mixing extruding pelletization.
8, the preparation method of toughened and reinforced ABS material according to claim 7, it is characterized in that: this twin screw extruder one district's temperature: 170～180 ℃, two district's temperature: 180～190 ℃, three district's temperature: 200～210 ℃, four district's temperature: 210～220 ℃, five district's temperature: 200～210 ℃, six district's temperature: 190～200 ℃, residence time 1-2 minute, engine speed: 300-350rpm.
9, the preparation method of toughened and reinforced ABS material according to claim 8 is characterized in that: in the step 2, mixed 3-5 minute in high-speed mixer.
10, according to the preparation method of the described toughened and reinforced ABS material of arbitrary claim in the claim 7 to 9, it is characterized in that: comprise the toughner making step: by weight percentage with 91%～97% high glue powder, 0.5～2% coupling agent and 2%～7% compatilizer are put into high mixer, heat temperature raising is to 60-70 ℃ while mixing, high-speed mixing 15-25 minute, its mixture is put into the forcing machine extruding pelletization, make toughner.
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| CN105504659A (en) * | 2016-01-26 | 2016-04-20 | 中国石油集团东北炼化工程有限公司吉林设计院 | High-impact-strength ABS material used at -40 DEG C and preparation method thereof |
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| CN106519554A (en) * | 2016-11-25 | 2017-03-22 | 佛山市南海承骏科技有限公司 | ABS (acrylonitrile-butadiene-styrene) flexibilizer and preparation method thereof |
| CN106519554B (en) * | 2016-11-25 | 2019-02-12 | 佛山市南海承骏科技有限公司 | A kind of ABS toughener and preparation method thereof |
| CN114591577A (en) * | 2022-03-04 | 2022-06-07 | 武汉金发科技有限公司 | Interface modifier and preparation method and application thereof |
| CN114591577B (en) * | 2022-03-04 | 2023-09-26 | 武汉金发科技有限公司 | Interface modifier and preparation method and application thereof |
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