CN104910595A - High toughness polybutylece terephthalate/ acrylonitrile butadiene styrene (PBT/ABS) thermoplastic resin combination and preparation method thereof - Google Patents
High toughness polybutylece terephthalate/ acrylonitrile butadiene styrene (PBT/ABS) thermoplastic resin combination and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high toughness polybutylece terephthalate/ acrylonitrile butadiene styrene (PBT/ABS) thermoplastic resin combination and a preparation method thereof, which comprise following components with part by weight: PBT 50-75 parts, ABS 20-45 parts, acrylonitrile resin (SAN) 0-15 parts, reactive compatibilizer 1-5 parts, antioxidant 0.1-0.5 part and lubricant 0.1-0.5 part. The method for preparing the high toughness PBT/ABS thermoplastic resin combination comprises two steps: 1 the PBT and the reactive compatibilizer are fused, mixed and squeezed out to granulate firstly through a twin-screw extruder; and 2 particles which are prepared in the step 1, the ABS, the SAN, the antioxidant and the lubricant are fused, mixed and squeezed out to granulate and prepare to be resin combinations through the twin-screw extruder. The high toughness PBT/ABS thermoplastic resin combination and the preparation method thereof have the advantages that resin combinations which are prepared through the method have excellent mechanical properties, particularly has low temperuare impact toughness, and the gap impact strength of 1/8'Izod is equal or greater than 600J/m in -30 DEG C.
Description
[technical field]
The present invention relates to processing of high molecular material technical field, specifically, is a kind of high tenacity PBT/ABS resin combination and preparation method thereof.
[background technology]
Polybutylene terephthalate (PBT) is one of very important five large-engineering plastics of a class, has excellent electrical property, resistance toheat, processing characteristics and solvent resistance.Meanwhile, the mechanical property of PBT is very responsive to breach, and notched Izod impact strength is low.Therefore, to the toughening modifying of PBT be the important content of PBT high performance always.
Chinese patent CN101284932 discloses the method utilizing the activation expanding material of introducing 1 ~ 10% (polar polymer through reactive extrusion styrenic polymer) to prepare PBT/ABS alloy material.From mechanical property, its low temperature notched impact property is improved little, the low temperature impact strength at-20 DEG C of temperature only about ~ 15KJ/m
2.In fact, residual metal ions, acidic substance or other impurity etc. that leave in ABS rubber powder prepared by emulsion method can make the reaction between PBT and activation expanding material wayward, and the reactive functional groups generation self-crosslinking of activation expanding material also can be made to react.About a kind of mechanical property obviously can improving PBT/ABS resin combination, especially low-temperature impact toughness, " PBT/ABS resin combination of Izod notched Izod impact strength >=600J/m and preparation method thereof, yet there are no report to 1/8 at-30 DEG C of temperature.
[summary of the invention]
The object of the invention is for deficiency of the prior art, a kind of high tenacity PBT/ABS thermoplastic resin composition is provided.
Second object of the present invention provides the preparation method of a kind of high tenacity PBT/ABS thermoplastic resin composition.
For achieving the above object, the technical scheme that the present invention takes is: a kind of high tenacity PBT/ABS thermoplastic resin composition, and described composition comprises the following component counted by weight:
Polybutylene terephthalate (PBT) resin: 50 ~ 75 parts;
Styrene butadiene-vinyl cyanide (ABS) resin: 20 ~ 45 parts;
Styrene-acrylonitrile copolymer (SAN): 0 ~ 15 part;
Response type compatilizer: 1 ~ 5 part;
0.1 ~ 0.5 part, oxidation inhibitor;
Lubricant 0.1 ~ 0.5 part;
Wherein, described response type compatilizer is methyl methacrylate-glycidyl methacrylate-ethyl propenoate (MMA-GMA-EA) terpolymer, and wherein the percentage composition of GMA component is 5 ~ 20%.
Preferably, the limiting viscosity of described PBT is 0.6 ~ 1.5dl/gr.
Preferably, the rubber content of described ABS is 35 ~ 55%, and rubber size is 100 ~ 500nm.
Preferably, the relative molecular mass of described san copolymer is 4 ~ 40 × 104g/mol, and acrylonitrile content is 18 ~ 34%.
Preferably, described oxidation inhibitor is one or more in Hinered phenols antioxidant or phosphite ester kind antioxidant.
Preferably, described lubricant comprises one or more in pentaerythritol stearate, polyethylene wax, ethylene bis stearamide, stearate or dimethylsilane.
For realizing above-mentioned second object, the technical scheme that the present invention takes is: the preparation method of thermoplastic resin composition according to claim 1, comprises the following steps:
(1) by polybutylene terephthalate resin and response type compatilizer MMA-GMA-EA through twin screw extruder melt blending, extruding pelletization;
(2) particle step (1) prepared prepares resin combination with styrene butadiene-acrylonitrile resin, styrene-acrylonitrile copolymer, oxidation inhibitor, lubricant through twin screw extruder melt blending, extruding pelletization again.
The complete processing of described step (1) is as follows: twin screw extruder one to two district temperature arrange 180-190 DEG C, three to four district 210-220 DEG C, five to seven district 220-230 DEG C, eight to ten district 210-220 DEG C, screw speed 100 ~ 300rpm.
The complete processing of described step (2) is as follows: twin screw extruder one to two district temperature arrange 180-190 DEG C, three to four district 210-220 DEG C, five to seven district 220-230 DEG C, eight to ten district 210-220 DEG C, screw speed 400 ~ 600rpm.
The invention has the advantages that:
The present invention first from material properties, by two technology points: (1) controls the ratio of reactive functional groups in activation expanding material; (2) first response type compatilizer and PBT are first carried out melt blending, reactive extrursion makes after it loses activity, again with ABS melt blending, obviously can improve the mechanical property of PBT/ABS resin combination, especially low-temperature impact toughness, " Izod notched Izod impact strength >=the 600J/m of 1/8 at-30 DEG C of temperature.
[embodiment]
Below in conjunction with embodiment, embodiment provided by the invention is elaborated.
The invention provides a kind of high tenacity PBT/ABS thermoplastic resin composition, described composition comprises the following component counted by weight:
Polybutylene terephthalate (PBT) resin: 50 ~ 75 parts;
Styrene butadiene-vinyl cyanide (ABS) resin: 20 ~ 45 parts;
Styrene-acrylonitrile copolymer (SAN): 0 ~ 15 part;
Response type compatilizer: 1 ~ 5 part;
0.1 ~ 0.5 part, oxidation inhibitor;
Lubricant 0.1 ~ 0.5 part;
Preferably, response type compatilizer is methyl methacrylate-glycidyl methacrylate-ethyl propenoate (MMA-GMA-EA) terpolymer, and wherein the percentage composition of GMA component is 5 ~ 20%.
Preferably, the limiting viscosity of PBT is 0.6 ~ 1.5dl/gr.
Preferably, the rubber content of ABS is 35 ~ 55%, and rubber size is 100 ~ 500nm.
Preferably, the relative molecular mass of san copolymer is 4 ~ 40 × 10
4g/mol, acrylonitrile content is 18 ~ 34%.
Preferably, oxidation inhibitor is one or more in Hinered phenols antioxidant or phosphite ester kind antioxidant.
Preferably, lubricant comprises one or more in pentaerythritol stearate, polyethylene wax, ethylene bis stearamide, stearate or dimethylsilane.
The preparation method of described thermoplastic resin composition comprises following steps:
(1) by PBT and response type compatilizer (MMA-GMA-EA) through twin screw extruder melt blending, extruding pelletization.Complete processing is as follows: twin screw extruder one to two district temperature arrange 180-190 DEG C, three to four district 210-220 DEG C, five to seven district 220-230 DEG C, eight to ten district 210-220 DEG C, screw speed 100 ~ 300rpm;
(2) particle step (1) prepared prepares resin combination with ABS, SAN, oxidation inhibitor, lubricant through twin screw extruder melt blending, extruding pelletization again.Complete processing is as follows: twin screw extruder one to two district temperature arrange 180-190 DEG C, three to four district 210-220 DEG C, five to seven district 220-230 DEG C, eight to ten district 210-220 DEG C, screw speed 400 ~ 600rpm.
It should be noted that, in following examples and comparative example, starting material used are:
PBT selects the PBT GX121 of Yizheng Fiber Optical plant, and limiting viscosity is 0.98dl/gr;
ABS selects the P/D150F of Korea S Jin Hu, and rubber content is 50%, rubber size 350nm;
SAN selects the NF2200 of platform, AN=26%, and molecular weight is 12.7 × 10
4g/mol;
MMA-GMA-EA selects the content of GMA component to be 10%;
Phosphite ester kind antioxidant IG-168 selected by oxidation inhibitor;
Pentaerythritol stearate PETS selected by lubricant.
Embodiment 1 raw material forms
Polybutylene terephthalate (PBT) resin: 50 parts;
Styrene butadiene-vinyl cyanide (ABS) resin: 34 parts;
Styrene-acrylonitrile copolymer (SAN): 15 parts;
Response type compatilizer MMA-GMA-EA:1 part;
0.1 part, oxidation inhibitor;
Lubricant 0.1 part.
Embodiment 2 raw material forms
Polybutylene terephthalate (PBT) resin: 75 parts;
Styrene butadiene-vinyl cyanide (ABS) resin: 20 parts;
Response type compatilizer MMA-GMA-EA:5 part;
0.3 part, oxidation inhibitor;
Lubricant 0.5 part.
Embodiment 3 raw material forms
Polybutylene terephthalate (PBT) resin: 45 parts;
Styrene butadiene-vinyl cyanide (ABS) resin: 45 parts;
Styrene-acrylonitrile copolymer (SAN): 7 parts;
Response type compatilizer MMA-GMA-EA:3 part;
0.5 part, oxidation inhibitor;
Lubricant 0.2 part.
Embodiment 4 raw material forms
Polybutylene terephthalate (PBT) resin: 55 parts;
Styrene butadiene-vinyl cyanide (ABS) resin: 25 parts;
Styrene-acrylonitrile copolymer (SAN): 10 parts;
Response type compatilizer MMA-GMA-EA:5 part;
03 part, oxidation inhibitor;
Lubricant 0.3 part.
Embodiment 5 preparation method
The preparation method of the PBT/ABS resin combination of embodiment 1 ~ 4, comprises the following steps:
(1) raw material drying: first PBT, ABS and SAN are positioned over dry more than 6h in the baking oven of 80 DEG C;
(2) master batch is prepared: by PBT, MMA-GMA-EA, oxidation inhibitor, the first premix of lubricant 5 ~ 10 minutes, to be melt extruded through twin screw extruder by mixed starting material, granulation.Twin screw extruder one to ten district temperature arranges and is respectively 180,190,210,220,220,220,220,210,210,210 DEG C, screw speed 300rpm;
(2) prepare resin combination: particle prepared by the first step again with ABS, SAN, oxidation inhibitor, the first premix of lubricant 5 ~ 10 minutes, then prepare resin combination through twin screw extruder melt blending, extruding pelletization.Twin screw extruder one to ten district temperature arranges and is respectively 180,190,210,220,220,220,220,210,210,210 DEG C, screw speed 500rpm.
Comparative example 1
Polybutylene terephthalate (PBT) resin: 50 parts;
Styrene butadiene-vinyl cyanide (ABS) resin: 34 parts;
Styrene-acrylonitrile copolymer (SAN): 15 parts;
Response type compatilizer MMA-GMA-EA:1 part;
0.1 part, oxidation inhibitor;
Lubricant 0.1 part.
Preparation method comprises the following steps:
(1) raw material drying: first PBT, ABS and SAN are positioned over dry more than 6h in the baking oven of 80 DEG C;
(2) resin combination is prepared: by PBT, ABS, SAN, MMA-GMA-EA, oxidation inhibitor, the first premix of lubricant 5 ~ 10 minutes, then prepare resin combination through twin screw extruder melt blending, extruding pelletization.Twin screw extruder one to ten district temperature arranges and is respectively 180,190,210,220,220,220,220,210,210,210 DEG C, screw speed 500rpm.
Comparative example 2
Polybutylene terephthalate (PBT) resin: 55 parts;
Styrene butadiene-vinyl cyanide (ABS) resin: 25 parts;
Styrene-acrylonitrile copolymer (SAN): 10 parts;
Response type compatilizer MMA-GMA-EA:5 part;
0.3 part, oxidation inhibitor;
Lubricant 0.3 part.
Preparation method comprises the following steps:
(1) raw material drying: first PBT, ABS and SAN are positioned over dry more than 6h in the baking oven of 80 DEG C;
(2) resin combination is prepared: by PBT, ABS, SAN, MMA-GMA-EA, oxidation inhibitor, the first premix of lubricant 5 ~ 10 minutes, then prepare resin combination through twin screw extruder melt blending, extruding pelletization.Twin screw extruder one to ten district temperature arranges and is respectively 180,190,210,220,220,220,220,210,210,210 DEG C, screw speed 500rpm.
Embodiment 6 performance evaluation mode and implementation criteria thereof
Resin combination prepared by embodiment and comparative example is positioned over dry more than 6h in 80 DEG C of baking ovens, removing moisture; Then carry out injection molding and prepare sample.Physical property measurement follows following test method: based on ASTMD-256 standard test normal temperature (23 DEG C) and low temperature (-30 DEG C) 1/8 " Izod notched Izod impact strength; Based on tensile strength and the tension set of ASTM D-638 standard test 50mm/min.
The performance of the raw material weight number of embodiment 1 ~ 4 and comparative example 1 ~ 2 and the resin combination of preparation thereof is listed in the table below 1.
Table 1
As can be seen from the experimental result of embodiment 1 ~ 4, the PBT/ABS thermoplastic resin composition prepared according to the present invention, has excellent mechanical property, especially low temperature notched impact property.By embodiment compared with comparative example, utilize first response type compatilizer and PBT are first carried out melt blending, reactive extrursion makes after it loses activity, again with the method for ABS melt blending, the mechanical property of PBT/ABS resin combination obviously can be improved, especially low-temperature impact toughness.
In sum, the present invention is first from the raw-material attribute of understanding, residual metal ions, acidic substance or other impurity etc. that leave in ABS rubber powder prepared by emulsion method can make the reaction between PBT and activation expanding material wayward, and the reactive functional groups generation self-crosslinking of activation expanding material also can be made to react.By two technology points: (1) controls the ratio of reactive functional groups in activation expanding material; (2) first response type compatilizer and PBT are first carried out melt blending, reactive extrursion make after it loses activity, then with ABS melt blending, obviously can improve the mechanical property of PBT/ABS resin combination, especially low-temperature impact toughness.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the inventive method; can also make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.
Claims (9)
1. a high tenacity PBT/ABS thermoplastic resin composition, is characterized in that, described composition comprises the following component counted by weight:
Polybutylene terephthalate resin: 50 ~ 75 parts;
Styrene butadiene-acrylonitrile resin: 20 ~ 45 parts;
Styrene-acrylonitrile copolymer: 0 ~ 15 part;
Response type compatilizer: 1 ~ 5 part;
0.1 ~ 0.5 part, oxidation inhibitor;
Lubricant 0.1 ~ 0.5 part;
Wherein, described response type compatilizer is methyl methacrylate-glycidyl methacrylate-ethyl propenoate terpolymer MMA-GMA-EA, and wherein the percentage composition of GMA component is 5 ~ 20%.
2. thermoplastic resin composition according to claim 1, is characterized in that, the limiting viscosity of described polybutylene terephthalate resin is 0.6 ~ 1.5dl/gr.
3. thermoplastic resin composition according to claim 1, is characterized in that, the rubber content of described styrene butadiene-acrylonitrile resin is 35 ~ 55%, and rubber size is 100 ~ 500nm.
4. thermoplastic resin composition according to claim 1, is characterized in that, the relative molecular mass of described styrene-acrylonitrile copolymer is 4 ~ 40 × 104g/mol, and acrylonitrile content is 18 ~ 34%.
5. thermoplastic resin composition according to claim 1, is characterized in that, described oxidation inhibitor is one or more in Hinered phenols antioxidant or phosphite ester kind antioxidant.
6. thermoplastic resin composition according to claim 1, is characterized in that, described lubricant comprises one or more in pentaerythritol stearate, polyethylene wax, ethylene bis stearamide, stearate or dimethylsilane.
7. the preparation method of thermoplastic resin composition according to claim 1, is characterized in that, comprises the following steps:
(1) by polybutylene terephthalate resin and response type compatilizer MMA-GMA-EA through twin screw extruder melt blending, extruding pelletization;
(2) particle step (1) prepared prepares resin combination with styrene butadiene-acrylonitrile resin, styrene-acrylonitrile copolymer, oxidation inhibitor, lubricant through twin screw extruder melt blending, extruding pelletization again.
8. the preparation method of thermoplastic resin composition according to claim 7, it is characterized in that, the complete processing of described step (1) is as follows: twin screw extruder one to two district temperature arrange 180-190 DEG C, three to four district 210-220 DEG C, five to seven district 220-230 DEG C, eight to ten district 210-220 DEG C, screw speed 100 ~ 300rpm.
9. the preparation method of thermoplastic resin composition according to claim 7, it is characterized in that, the complete processing of described step (2) is as follows: twin screw extruder one to two district temperature arrange 180-190 DEG C, three to four district 210-220 DEG C, five to seven district 220-230 DEG C, eight to ten district 210-220 DEG C, screw speed 400 ~ 600rpm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108070196A (en) * | 2016-11-18 | 2018-05-25 | 合肥市和裕达塑业有限公司 | A kind of anticorrosive, high-low temperature resistant ABS material and its preparation method and application |
| CN110003602A (en) * | 2019-04-13 | 2019-07-12 | 苏州旭光聚合物有限公司 | A kind of automobile modified ABS composite material |
| CN112759908A (en) * | 2020-12-24 | 2021-05-07 | 上海金发科技发展有限公司 | Scratch-repairable high-gloss ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof |
| CN114836002A (en) * | 2022-07-04 | 2022-08-02 | 金发科技股份有限公司 | High-toughness high-magnetic-attraction ABS alloy and preparation method and application thereof |
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| CN101440196A (en) * | 2007-11-19 | 2009-05-27 | 上海日之升新技术发展有限公司 | Reinforced environmental-protecting flame-retardant PBT and ABS alloy material |
| CN103524990A (en) * | 2012-07-03 | 2014-01-22 | 青岛欣展塑胶有限公司 | PBT/ABS (polybutylene terephthalate/acrylonitrile-butadiene-styrene) alloy material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101440196A (en) * | 2007-11-19 | 2009-05-27 | 上海日之升新技术发展有限公司 | Reinforced environmental-protecting flame-retardant PBT and ABS alloy material |
| CN103524990A (en) * | 2012-07-03 | 2014-01-22 | 青岛欣展塑胶有限公司 | PBT/ABS (polybutylene terephthalate/acrylonitrile-butadiene-styrene) alloy material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108070196A (en) * | 2016-11-18 | 2018-05-25 | 合肥市和裕达塑业有限公司 | A kind of anticorrosive, high-low temperature resistant ABS material and its preparation method and application |
| CN110003602A (en) * | 2019-04-13 | 2019-07-12 | 苏州旭光聚合物有限公司 | A kind of automobile modified ABS composite material |
| CN112759908A (en) * | 2020-12-24 | 2021-05-07 | 上海金发科技发展有限公司 | Scratch-repairable high-gloss ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof |
| CN112759908B (en) * | 2020-12-24 | 2023-02-10 | 上海金发科技发展有限公司 | Scratch-repairable high-gloss ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof |
| CN114836002A (en) * | 2022-07-04 | 2022-08-02 | 金发科技股份有限公司 | High-toughness high-magnetic-attraction ABS alloy and preparation method and application thereof |
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