CN109721839B - High-gloss low-linear-expansion-coefficient polypropylene composite material and preparation method thereof - Google Patents
High-gloss low-linear-expansion-coefficient polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a high-gloss low-linear-expansion-coefficient polypropylene composite material and a preparation method thereof, wherein the composite material is prepared from the following raw materials in parts by mass: 70-80 parts of polypropylene; 0-0.5 part of nucleating agent; 1-1.5 parts of a brightening agent; 15-20 parts of a filler; 0.1-0.3 part of antioxidant; 0.1-0.3 part of lubricant; 0-1 part of antibacterial agent; the mineral filler is composed of crystal whiskers, mica and nano montmorillonite; the whisker consists of calcium carbonate whisker, magnesium sulfate whisker and basalt whisker. The high-gloss low-linear-expansion-coefficient polypropylene composite material provided by the invention has high glossiness, can effectively reduce the linear expansion coefficient of the polypropylene material, has antibacterial performance, can well solve the phenomenon of serious shrinkage of the polypropylene material caused by post-crystallization in life, and has important practical benefits.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-gloss low-linear-expansion-coefficient polypropylene composite material and a preparation method thereof.
Background
The polypropylene resin raw material has good comprehensive mechanical property, high heat-resisting temperature, electric insulativity andthe acid-base composite material has the characteristics of excellent chemical stability to acid and base, wide production and processing window, low price and the like, so that the acid-base composite material is widely applied to the fields of automobile parts, household articles, electronic appliances and the like. However, since the gloss is low (about 80), the linear expansion coefficient is high (9.05X 10)-5and/K) and the antibacterial material has no antibacterial effect, so that the application of the antibacterial material in certain fields is limited, the low glossiness of the antibacterial material can not cover certain household appliance fields with high color requirements, such as washing machines, intelligent toilet covers and the like, and the linear expansion coefficient of the antibacterial material is high, so that when certain automobile large parts (such as automobile bumpers, door panels and the like) are produced, the parts shrink to different degrees due to the change of external temperature, and short plates are produced in the application aspect of the antibacterial material. In addition, as the health requirements of human beings are increased, the antibacterial awareness is increased more and more obviously, and the non-antibacterial property of the polypropylene material is concerned by consumers, so that the application of the polypropylene material is limited.
As for the preparation method of the polypropylene with low linear expansion coefficient, CN106317607A provides a polypropylene composite material with ultra-low linear expansion coefficient and a preparation method thereof, but the adopted inorganic filler Sc is2W3O12Has the characteristics of high price and the like, so that the application of the composite material is limited.
The invention aims to solve the main problem of how to obtain the antibacterial polypropylene composite material with high gloss and low linear expansion coefficient.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a high-gloss low-linear expansion coefficient polypropylene composite material which is prepared from the following raw materials in parts by mass:
the mineral filler is composed of crystal whiskers, mica and nano montmorillonite; the whisker consists of calcium carbonate whisker, magnesium sulfate whisker and basalt whisker.
Further, the mineral fillers are whiskers, mica and nano montmorillonite, and the weight ratio of the mineral fillers to the mineral fillers is 1: 1: (1-2) combining; in the whiskers, calcium carbonate whiskers, magnesium sulfate whiskers and basalt whiskers are mixed according to the weight ratio of 1: 1: 1, and (2) mixing the components in a ratio.
The crystal whisker is in a micro needle-like structure, is randomly distributed in the material to form a stacking structure, can greatly reduce the linear expansion coefficient of the polypropylene material, and does not influence the appearance and the glossiness of the material.
Further, the polypropylene is one or a combination of at least two of homo-polypropylene and co-polypropylene.
Further, the nucleating agent is one or the combination of at least two of alpha crystal form nucleating agent, dibenzylidene sorbitol and derivatives thereof, aryl phosphate salts and substituted aluminum benzoate salts, wherein the nucleating agent has the functions of promoting the material to form spherical crystals, improving the surface brightness of the material and reducing the using amount of the brightening agent.
Further, the brightening agent is one or the combination of at least two of benzalacetone, polyoxyethylene nonyl phenyl ether and sodium benzoate; the brightener can be uniformly dispersed on the surface after being heated in the plastic production process, so that the surface extruded by the plastic is very smooth, the abrasion of the machine is reduced, and the service life of the machine is prolonged.
Further, the antioxidant is one or at least two of hindered phenol antioxidant, thioester antioxidant and sulfite antioxidant.
Further, the lubricant is one or at least two of N, N' -ethylene bis stearamide, polyethylene wax, polypropylene wax, calcium stearate, zinc stearate and magnesium stearate.
Further, the antibacterial agent is one or a combination of at least two of silver ion antibacterial agents and inorganic antibacterial agents such as zinc oxide, copper oxide, ammonium dihydrogen phosphate, lithium carbonate and the like.
The invention also provides a preparation method of the high-gloss low-linear expansion coefficient polypropylene composite material, which comprises the following steps:
step a, weighing polypropylene, a nucleating agent, a brightening agent, mineral filling, an antioxidant, a lubricant and an antibacterial agent according to weight percentage;
b, adding all the materials in the step a into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
c, adding the premix obtained in the step b into a parallel double-screw extruder from a main feeding hopper, and shearing, melting, blending and extruding all component materials in the parallel double-screw extruder;
and d, cooling, drying and granulating the material strips from the neck mold of the parallel double-screw extruder to obtain the high-gloss low-linear expansion coefficient polypropylene composite material.
Further, the processing temperature of the double-screw extruder is 170-230 ℃.
Compared with the prior art, the high-gloss low-linear expansion coefficient polypropylene composite material provided by the invention has the following effects:
(1) the invention improves the condition of gloss reduction of the polypropylene material caused by the increase of the filling part by compounding the nucleating agent and the brightening agent;
(2) the phenomenon of higher linear expansion coefficient of the polypropylene material is reduced by adopting a nano composite modification method, the polypropylene material is dispersed into a polymer by utilizing a special effect after being reduced to a nano size, and the polypropylene resin is not only enhanced but also the linear expansion coefficient of the material can be greatly reduced by matching nano montmorillonite with crystal whisker.
(3) The material has an antibacterial effect through antibacterial modification.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the formulations (unit: parts by weight) of the following examples and comparative examples, as shown in the following table:
TABLE 1
In embodiments 1, 2, 3, and 4, the fillers are nano montmorillonite, mica, and whiskers, the whiskers are calcium carbonate whiskers, magnesium sulfate whiskers, and the basalt whiskers are in a ratio of 1: 1: 1, the filler in the comparative example 2 is calcium carbonate, and the filler in the comparative example 3 is only nano montmorillonite.
In each comparative example, the polypropylene used was homopolypropylene.
In each proportion and embodiment, the selected lubricants are calcium stearate, and the selected antioxidants are hindered phenol antioxidants 1010.
In the examples, the nucleating agent used was an alpha-crystal nucleating agent, and the brightening agents used were all benzylidene acetone brightening agents
The antimicrobial agent used in examples 1 and 2 was zinc oxide, and the antimicrobial agent used in examples 3 and 4 was zinc oxide.
Weighing all the raw materials according to the proportion in the examples and comparative examples in the table 1;
adding all the materials into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
adding the premix into a parallel double-screw extruder from a main feeding hopper, and shearing, melting, blending and extruding all component materials in the parallel double-screw extruder;
and cooling, drying and granulating the material strips discharged from the neck die of the parallel double-screw extruder to obtain samples of corresponding examples and comparative examples.
Wherein the processing temperature of the double-screw extruder is 170-230 ℃.
The composite material samples obtained above were subjected to the following performance tests:
the antibacterial test is carried out according to the Chinese national standard QB/T2591-
The gloss testing method is used for testing according to a plastic gloss standard GB8807-88CS-380, the photometers are calibrated and then respectively used for testing the comparative examples and the color plates made in the examples, finally the linear expansion coefficients of the conclusions are tested according to a national standard GB/T1036-2008, the linear expansion coefficients of the samples in the comparative examples and the examples are respectively tested, and the conclusions are obtained through comparison.
The test results are shown in the following table:
TABLE 2
It can be seen from examples 1, 2, 3 and 4 and comparative examples 1 and 2 that metals such as silver, copper and zinc (or ions thereof) are fixed on the surface of porous materials such as fluorite and silica gel to prepare the antibacterial agent by adding the antibacterial agent to the materials, utilizing the antibacterial capability of the metals such as silver and zinc and adopting methods such as physical adsorption ion exchange and the like, and then the antibacterial agent is added into corresponding products, so that the materials with antibacterial capability are obtained, the national requirements on antibacterial standards are met, and the application range of PP is expanded.
As can be seen from examples 1, 2, 3 and 4 and comparative examples 1 and 2, the normal PP-T20 has a coefficient of linear expansion of 8.28X 10 for the coefficient of linear expansion-5The linear expansion coefficient of the nano-montmorillonite/mica/mixed crystal whisker is reduced to the lowest by adopting a nano-composite modification method and mixing the nano-montmorillonite, the mica and the mixed crystal whisker in different proportionsTo 5X 10-5The reduction range of the/K is 39.6 percent, and the problem of unstable size of the PP material caused by high linear expansion coefficient in four seasons can be solved to a great extent.
It can be seen from examples 3 and 4 that, in the case of a constant total number of nucleating agents and brighteners, the gloss is improved in a ratio of brightener: the nucleating agent 2:1 is obviously better than the effect of the brightener when added separately, because the nucleating agent can promote the rapid crystallization in the material, the integral brightness of the material is increased while the material performance is maintained, the brightener is added for composite use, and the brightener is uniformly dispersed on the surface of the plastic by heating in the production process of the plastic, thereby achieving the effect of improving the surface gloss.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The high-gloss low-linear-expansion-coefficient polypropylene composite material is characterized by comprising the following raw materials in parts by mass:
70-80 parts of polypropylene
0 to 0.5 portion of nucleating agent
1-1.5 parts of brightener
15-20 parts of mineral filler
0.1 to 0.3 portion of antioxidant
0.1 to 0.3 portion of lubricant
0-1 part of antibacterial agent;
the mineral filler is composed of crystal whiskers, mica and nano montmorillonite; the whisker consists of calcium carbonate whisker, magnesium sulfate whisker and basalt whisker.
2. The high gloss low linear expansion coefficient polypropylene composite of claim 1, wherein: the mineral filler is whisker, mica and nano montmorillonite according to the weight ratio of 1: 1: (1-2) combining; in the whiskers, calcium carbonate whiskers, magnesium sulfate whiskers and basalt whiskers are mixed according to the weight ratio of 1: 1: 1, and (2) mixing the components in a ratio.
3. The high gloss low linear expansion coefficient polypropylene composite of claim 1, wherein: the polypropylene is one or a mixture of at least two of homo-polypropylene and co-polypropylene.
4. The high gloss low linear expansion coefficient polypropylene composite of claim 1, wherein: the nucleating agent is one or at least two combinations of alpha crystal form nucleating agents.
5. The high gloss low linear expansion coefficient polypropylene composite of claim 1, wherein: the brightener is one or a combination of at least two of benzalacetone, nonylphenol polyoxyethylene ether and sodium benzoate.
6. The high gloss low linear expansion coefficient polypropylene composite of claim 1, wherein: the antioxidant is one or the combination of at least two of hindered phenol antioxidant, thioester antioxidant and sulfite antioxidant.
7. The high gloss low linear expansion coefficient polypropylene composite of claim 1, wherein: the lubricant is one or the combination of at least two of N, N' -ethylene bis stearamide, polyethylene wax, polypropylene wax, calcium stearate, zinc stearate and magnesium stearate.
8. The high gloss low linear expansion coefficient polypropylene composite of claim 1, wherein: the antibacterial agent is one or the combination of at least two of silver ion antibacterial agents, zinc oxide, copper oxide, ammonium dihydrogen phosphate and lithium carbonate inorganic antibacterial agents.
9. The process for the preparation of a high gloss low linear expansion coefficient polypropylene composite according to any one of claims 1 to 8, characterized in that it comprises the following steps:
step a, weighing polypropylene, a nucleating agent, a brightening agent, a mineral filler, an antioxidant, a lubricant and an antibacterial agent according to weight percentage;
b, adding all the materials in the step a into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
c, adding the premix obtained in the step b into a parallel double-screw extruder from a main feeding hopper, and shearing, melting, blending and extruding all component materials in the parallel double-screw extruder;
and d, cooling, drying and granulating the material strips from the neck mold of the parallel double-screw extruder to obtain the high-gloss low-linear expansion coefficient polypropylene composite material.
10. The high gloss low linear expansion coefficient polypropylene composite of claim 8, wherein: the processing temperature of the double-screw extruder is 170-230 ℃.
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| CN111533988B (en) * | 2019-12-23 | 2022-03-29 | 会通新材料股份有限公司 | Good-appearance short-program-control oriented metallic silver polypropylene composite material and preparation method thereof |
| CN111533992B (en) * | 2020-04-30 | 2022-12-27 | 上海日之升科技有限公司 | High-gloss environment-friendly antibacterial polypropylene composite material and preparation method thereof |
| CN112175301B (en) * | 2020-10-22 | 2022-12-06 | 北方华锦化学工业股份有限公司 | Special antibacterial polypropylene material for washing machine and preparation method thereof |
| CN113698753A (en) * | 2021-09-22 | 2021-11-26 | 苏州纽微塑胶有限公司 | Raw material formula for producing automobile high-brightness appearance piece |
| CN115594917B (en) * | 2022-09-30 | 2023-10-20 | 武汉金发科技有限公司 | Polypropylene composite material with low linear expansion coefficient and preparation method thereof |
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