CN103231485A - Preparation method and rheological property test method of reinforced toughened nylon 11 ternary composite material - Google Patents
Preparation method and rheological property test method of reinforced toughened nylon 11 ternary composite material Download PDFInfo
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- CN103231485A CN103231485A CN2013100703799A CN201310070379A CN103231485A CN 103231485 A CN103231485 A CN 103231485A CN 2013100703799 A CN2013100703799 A CN 2013100703799A CN 201310070379 A CN201310070379 A CN 201310070379A CN 103231485 A CN103231485 A CN 103231485A
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Abstract
The invention discloses a preparation method and a rheological property test method of a reinforced toughened nylon 11 ternary composite material. The reinforced toughened nylon 11 ternary composite material is a PA11/HGB/POE-g-MAH ternary composite material. The preparation method comprises the following steps of continuously baking PA11 in a vacuum oven at a temperature of 80 DEG C for more than 12h, then accurately weighing HGB according to requirements, adding the weighed HGB and the PA11 into a silane coupling agent dissolved by ethanol, uniformly stirring by a glass rod, drying in air for next use, and carrying out extrusion granulation of the PA11-treated HGB and POE-g-MAH by a double-screw extruder at a temperature of 200 to 240 DEG C at a screw rotating speed of 90rpm. The PA11/HGB/POE-g-MAH ternary composite material is prepared by a melt blending method. The preparation method realizes influence caused by POE-g-MAH content on composite material rheological properties and lays a solid foundation for preparation of nylon 11 composite materials having better performances.
Description
Technical field
The present invention relates to a kind of preparation and rheology testing that strengthens tenacity increased nylon 11 trielement composite materials, be specifically related to a kind of research and rheology testing of PA11/HGB/POE-g-MAH trielement composite material.
Background technology
Along with the develop rapidly of society with science and technology, oneself can not satisfy the situation of development day by day the performance of homogenous material, and high performance, multifunction and compoundization have become the inexorable trend of material development.Nylon 11 is with respect to other poly-phthalein amine material, though have that water absorption rate is low, oil resistivity good, low temperature resistant, elastic memory good, stress cracking resistance good, be easy to advantages such as processing.But oneself can not satisfy various products to the specific (special) requirements of material property the performance of pure nylon 11, and its higher relatively market price has also limited the further expansion of its application.Chinese scholars is a lot of to the research of modified nylon, and especially based on the study on the modification of nylon 6 and nylon 66, and the nylon 11 study on the modification is less relatively.The foreign study emphasis concentrates on crystal structure, crystal phase transition and the piezoelectric property of nylon 11; Domesticly aspect above-mentioned, also carried out many research.Yet the alloy research at nylon 11 plasticising, enhancing, aspect such as toughness reinforcing is then all less relatively, also lacks at present and effectively improves one's methods.
Therefore, to prepare the importance of high-performance and functionalization nylon 11 base alloy material more and more obvious for the method by physics or chemical modification.
Summary of the invention
At the problems referred to above, the purpose of the embodiment of the invention is to provide a kind of toughness reinforcing nylon 11 modified composite material that strengthens,
The embodiment of the invention is achieved in that a kind of preparation method of PA11/HGB/POE-g-MAH trielement composite material, and this preparation method may further comprise the steps:
To dry by the fire continuously in the vacuum drying oven of PA11 under 80 ℃ more than the 12h, after the baking material was finished, accurate weighing HGB added in the silane coupler with the ethanol dissolving then as requested, stirs with glass bar, dries stand-by;
With PA11 and the HGB after handling and POE-g-MAH through double screw extruder at 200 ℃ of-240 ℃ of following extruding pelletizations, screw speed is 90rpm.
Further, this preparation method further comprises the rheology testing method of PA11/POE-g-MAH/HGB composite:
Take by weighing the sample about 2g, it is packed in the barrel of preset temperature, compacting, constant temperature 10min is 2.45 * 10
4Pa, 3.68 * 10
4Pa, 4.90 * 10
4Pa, 6.13 * 10
4Pa, 7.35 * 10
4Under the shear stress of Pa, by extruding in the capillary, electronic recorder records temperature and the rate of extrusion of melt automatically with material.
Further, described rheology testing method adopts XLY-II type flow graph, capillary diameter d=1.0mm, and draw ratio L/D=40, inlet angle is 90 °.
Further, described experimental technique condition is:
The raw material drying condition: the composite pellet is cooled to room temperature at 80 ℃ of vacuum drying 12h;
Experimental temperature: 220 ℃, 230 ℃, 240 ℃, 250 ℃.
This method has prepared the PA11/POE-g-MAH/HGB trielement composite material by adopting melt-blending process, has obtained the content of POE-g-MAH to the influence of composite rheological characteristic energy, lays a solid foundation for preparing the better nylon 11 composite of performance.The mechanical property such as hot strength, impact strength, hardness that is added with the nylon 11 of glass microballoon and elastomer POE-g-MAH is improved, and can prevent the material aging that caused by light and heat; Along with the increase of glass microballoon content, the Martin heat resistance temperature of material improves.The performance of successful improvement nylon 11 also can be used in industrial development in a large number, and it will bring huge opportunity to China's nylon aspect development, and bring effective economic worth.
Description of drawings
The lg γ of the PA11/POE-g-MAH/HGB composite that Fig. 1 provides for the embodiment of the invention
W～lg τ
WCurve map;
The lg γ of the PA11/POE-g-MAH/HGB composite of the different POE-g-MAH content that Fig. 2 provides for the embodiment of the invention
W～lg η a curve map;
The lg η a of the PA11/POE-g-MAH/HGB composite of the different POE-g-MAH content that Fig. 3 provides for the embodiment of the invention～1/T figure.
The specific embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
Glass microballoon is glass (or pottery) spheroid of diameter in several microns to several millimeters particle size range, branch solid, hollow, porous glass beads is arranged, have good in optical property, sphere lens characteristic, characteristics such as shock resistance is strong, rollability good, thermal conductivity factor is low, light weight, be widely used in fields such as urban transportation sign, mark of car, retroeflection curtain, injection technology, packing material, insulation material.
Glass microballoon is glass (or pottery) spheroid of diameter in several microns to several millimeters particle size range, branch solid, hollow, porous glass beads is arranged, have good in optical property, sphere lens characteristic, characteristics such as shock resistance is strong, rollability good, thermal conductivity factor is low, light weight, be widely used in fields such as urban transportation sign, mark of car, retroeflection curtain, injection technology, packing material, insulation material.
Adopt HGB, elastomer POE-g-MAH is respectively as rigidity and elastic particle, jointly PA11 is strengthened with toughness reinforcing, research HGB and elastomeric content and order by merging are to the rule that influences of composite property, in the hope of keep the strength and stiffness of material in the impact resistance that improves material.
The present invention is further illustrated below in conjunction with drawings and Examples.
1.PA11/POE-g-MAH/HGB the preparation of trielement composite material
To dry by the fire continuously in the vacuum drying oven of PA11 under 80 ℃ more than the 12h, after the baking material was finished, accurate weighing HGB added in the silane coupler with the ethanol dissolving then as requested, stirs with glass bar, dries stand-by.With PA11, at 200 ℃ of-240 ℃ of following extruding pelletizations, screw speed is 90rpm through double screw extruder for the HGB after the processing and POE-g-MAH.
2.PA11/POE-g-MAH/HGB the rheology testing of composite
Flow graph: XLY-II type, science and education instrument plant of Jilin University, capillary diameter d=1.0mm, draw ratio L/D=40, inlet angle is 90 °, so do not make the Begley entrance correction.
2.1 experimental technique condition
The raw material drying condition: the composite pellet is cooled to room temperature at 80 ℃ of vacuum drying 12h;
Experimental temperature: 220 ℃, 230 ℃, 240 ℃, 250 ℃;
Experimental technique: take by weighing the sample about 2g, it is packed in the barrel of preset temperature, compacting, constant temperature 10min is 2.45 * 10
4Pa, 3.68 * 10
4Pa, 4.90 * 10
4Pa, 6.13 * 10
4Pa, 7.35 * 10
4Under the shear stress of Pa, by extruding in the capillary, electronic recorder records temperature and the rate of extrusion of melt automatically with material.
3. result
3.1 the rheological curve of the trielement composite material of different POE-g-MAH content
Fig. 1 is the lg τ of the PA11/POE-g-MAH/HGB composite of different POE-g-MAH content
w～lg γ
wCurve map.As seen from Figure 1, in the certain shear scope, the curve of gained presents good linear relationship.The POE-g-MAH that adds different content can not change the pseudoplastic behavior feature of co-mixing system.With the increase of shear stress, shear rate increases.
The non-newtonian index of the PA11/POE-g-MAH/HGB trielement composite material of the different POE-g-MAH content of table 1
Table 1 is listed the non-newtonian index (n) of the PA11/POE-g-MAH/HGB composite of different POE-g-MAH content.Can be used to judge the difference degree of fluid and Newton type fluid, in essence, what the n value reflected is that apparent viscosity is to the sensitivity of shear stress or shear rate.It is 1 more big that non-newtonian index departs from, and non-Newtonianism is more strong, and apparent viscosity is more responsive to shear stress.
3.2 the melt viscosity of the PA11/POE-g-MAH/HGB composite of different POE-g-MAH content
As can be seen from Figure 2, when uniform temperature, apparent viscosity improves with shear rate and descends, and this is non-newtonian fluid " shear force is thinning " phenomenon.It can also be seen that from figure in the time of 230 ℃, POE-g-MAH adds reduces the viscosity of composite, the content of the POE-g-MAH of trielement composite material was less than 30% o'clock, the apparent viscosity of composite reduces, and the content of POE-g-MAH was greater than 30% o'clock, and the composite apparent viscosity increases.
3.3 the viscous flow activation energy of the PA11/POE-g-MAH/HGB composite of different POE-g-MAH content
Concerning most polymers, when melt temperature during far above glass transition temperature, the relation of their apparent viscosity and temperature can satisfy Arrhenius equation: η=Aexp (E/RT) approx.Map with the 1/T of ln η, can obtain viscous flow activation energy by straight slope.
Fig. 3 is the lg η a～1/T curve map of PA11/POE-g-MAH/HGB composite under constant τ w.The slope of figure cathetus has represented the size of viscous flow activation energy Δ E, and the height of viscous flow activation energy has reflected the sensitiveness of apparent melt viscosity to temperature, reflected in essence big molecule do " snakelike " motion forward the wriggling unit size.
The viscous flow activation energy of PA11/POE-g-MAH/HGB composite is listed in table 2, and as can be seen from Table 2, the adding of POE-g-MAH reduces the viscous flow activation energy of composite, and namely the PA11/HGB/POE-g-MAH trielement composite material is the strongest to the sensitiveness of temperature.This is because the adding of POE-g-MAH has increased the molecule chain flexibility, makes its viscosity temperature become insensitive, so viscous flow activation energy reduces.
The viscous flow activation energy of the trielement composite material of the different POE-g-MAH content of table 2
Claims (4)
1. the preparation method of a PA11/HGB/POE-g-MAH trielement composite material is characterized in that, this preparation method may further comprise the steps:
To dry by the fire continuously in the vacuum drying oven of PA11 under 80 ℃ more than the 12h, after the baking material was finished, weighing HGB added in the silane coupler with the ethanol dissolving then as requested, stirs with glass bar, dries stand-by;
At 200 ℃ of-240 ℃ of following extruding pelletizations, screw speed is 90rpm, is injected into the standard testing batten with injector then through double screw extruder for HGB after PA11 handled and POE-g-MAH.
2. preparation method as claimed in claim 1 is characterized in that, this preparation method further comprises
The rheology testing method of PA11/POE-g-MAH/HGB composite:
Take by weighing the sample about 2g, it is packed in the barrel of preset temperature, compacting, constant temperature 10min is 2.45 * 10
4Pa, 3.68 * 10
4Pa, 4.90 * 10
4Pa, 6.13 * 10
4Pa, 7.35 * 10
4Under the shear stress of Pa, by extruding in the capillary, electronic recorder records temperature and the rate of extrusion of melt automatically with material.
3. preparation method as claimed in claim 2 is characterized in that, described rheology testing method adopts XLY-II type flow graph, capillary diameter d=1.0mm, and draw ratio L/D=40, inlet angle is 90 °.
4. preparation method as claimed in claim 2 is characterized in that, the experimental technique condition of described rheology testing method is:
The raw material drying condition: the composite pellet is cooled to room temperature at 80 ℃ of vacuum drying 12h;
Experimental temperature: 220 ℃, 230 ℃, 240 ℃, 250 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110057717A (en) * | 2019-04-19 | 2019-07-26 | 深圳大学 | The method for building up of high polymer molten viscous flow activation energy model based on characteristic size |
| CN110595952A (en) * | 2019-09-10 | 2019-12-20 | 吴宗周 | Method for measuring and calculating viscous flow activation energy of high polymer material |
| CN111793354A (en) * | 2020-07-27 | 2020-10-20 | 苏州赛迪斯新材料科技有限公司 | Nylon 11-based film and preparation method and application thereof |
-
2013
- 2013-03-06 CN CN201310070379.9A patent/CN103231485B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| 丁雪佳等: "空心玻璃微珠填充尼龙6的研究", 《塑料》, vol. 32, no. 2, 30 April 2003 (2003-04-30) * |
| 孙向东等: "空心玻璃微珠填充MC尼龙复合材料的研究", 《工程塑料应用》, vol. 33, no. 1, 10 January 2005 (2005-01-10), pages 7 - 10 * |
| 李迎春: "纳米蒙脱土填充尼龙11共混复合体系强韧化研究", 《中国博士学位论文全文数据库工程科技Ⅱ辑》, 15 June 2011 (2011-06-15), pages 59 - 62 * |
| 王志强等: "尼龙11/空心玻璃微珠复合材料流变行为研究", 《工程塑料应用》, vol. 40, no. 3, 10 March 2012 (2012-03-10), pages 83 - 85 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110057717A (en) * | 2019-04-19 | 2019-07-26 | 深圳大学 | The method for building up of high polymer molten viscous flow activation energy model based on characteristic size |
| CN110057717B (en) * | 2019-04-19 | 2021-06-11 | 深圳大学 | Method for establishing polymer melt viscous flow activation energy model based on characteristic dimension |
| CN110595952A (en) * | 2019-09-10 | 2019-12-20 | 吴宗周 | Method for measuring and calculating viscous flow activation energy of high polymer material |
| CN110595952B (en) * | 2019-09-10 | 2022-05-10 | 吴宗周 | Method for measuring and calculating viscous flow activation energy of high polymer material |
| CN111793354A (en) * | 2020-07-27 | 2020-10-20 | 苏州赛迪斯新材料科技有限公司 | Nylon 11-based film and preparation method and application thereof |
| CN111793354B (en) * | 2020-07-27 | 2023-05-05 | 苏州赛迪斯新材料科技有限公司 | Nylon 11-based film and preparation method and application thereof |
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