CN103146052A - Modified glass fiber reinforced polypropylene nano material and preparation method - Google Patents
Modified glass fiber reinforced polypropylene nano material and preparation method Download PDFInfo
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- CN103146052A CN103146052A CN2013100696634A CN201310069663A CN103146052A CN 103146052 A CN103146052 A CN 103146052A CN 2013100696634 A CN2013100696634 A CN 2013100696634A CN 201310069663 A CN201310069663 A CN 201310069663A CN 103146052 A CN103146052 A CN 103146052A
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Abstract
The invention relates to a modified glass fiber reinforced polypropylene nano material and a preparation method, belonging to the field of high-molecular materials. The preparation method comprises the following steps of: preparing SiO2/PMMA (polymethyl methacrylate) filler by a chemical dispersion method; and preparing the glass fiber reinforced polypropylene nano material through a melt blending method by taking the nano SiO2/PMMA filler as filler and adopting polypropylene resin, glass fiber and an antioxidant. The glass fiber reinforced polypropylene nano material provided by the invention has the benefits that by adding the glass fiber and the nano material, the strength of the polypropylene material is enhanced; and the toughness of the polypropylene material is guaranteed by wrapping nano SiO2 with PMMA.
Description
Technical field
The present invention relates to a kind of modification fiber glass reinforced polypropylene nano material and preparation method, belong to polymeric material field.
Background technology
Polypropylene has many premium propertiess as a kind of general-purpose plastics, but, poor heat resistance low because of physical strength, the reason such as contraction deformation is large and creep resistance is poor are restricted it in actual applications, can not use as high performance engineering plastics.Therefore, polypropylene is carried out modification, making its through engineering approaches is an important research topic.Adopt that the elastomer blended and fiber of rubber-like, filler blending method strengthen, during tenacity-increased profax, toughness and intensity are difficult to take into account simultaneously.Nanoparticle provides new way for polyacrylic modification.What mostly report in document is take nanometer SiO2 as packing material, and add coupling agent with the reunion of minimizing nanoparticle and improve filler and the consistency of basal body interface, but because the effect of small molecules coupling agent is limited, modified effect is subjected to restriction to a certain extent.
Summary of the invention
For solving the deficiencies in the prior art, the object of the invention is to overcome the defective of prior art, a kind of modification fiber glass reinforced polypropylene nano material and preparation method who adopts the glass-reinforced polypropylene nano material, guarantees simultaneously toughness of material is provided.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
Modification fiber glass reinforced polypropylene nano material is characterized in that, by following composition by weight melt blending form:
Wherein nanometer SiO2/PMMA filler is formed by PMMA clad nano SiO2, and nanometer SiO2/PMMA filler also is doped into coupling agent.
Aforesaid modification fiber glass reinforced polypropylene nano material, described acrylic resin is homopolymer type or copolymer type, the melt mass flow rate of acrylic resin is between 5～80g/10min.
Aforesaid modification fiber glass reinforced polypropylene nano material, in described nanometer SiO2/PM MA filler, the parts by weight of component are:
SiO2 40-60 part PMMA 40-60 part coupling agent 5-10 part.
Aforesaid modification fiber glass reinforced polypropylene nano material, described coupling agent is silane, titanic acid ester, phosphoric acid ester or chromium complex.
Aforesaid modification fiber glass reinforced polypropylene nano material, described antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, 2,6-ditertbutylparacresol, 4,4'-thiobis (the 6-tertiary butyl-3-(methyl) phenol) one or more.
The method of aforesaid modification fiber glass reinforced polypropylene nano material comprises the steps:
1) prepare nanometer SiO2/PMMA filler with chemical dispersion method;
2) with nanometer SiO2/PMMA filler as filler, join same acrylic resin, glass fibre, antioxidant and prepare the fiber glass reinforced polypropylene nano material by melt-blending process.
The method of aforesaid modification fiber glass reinforced polypropylene nano material, the solvent that described chemical dispersion method uses is toluene or ethanol.
The method of aforesaid modification fiber glass reinforced polypropylene nano material is in step 2) in, with the weight fraction counting, nanometer SiO2/PMMA filler accounts for 2-5 part, and acrylic resin accounts for 60-75 part, glass fibre 20-30 part, antioxidant 0.3-1 part.
The method of aforesaid modification fiber glass reinforced polypropylene nano material, step 2) described melt blending temperature is the 150-300 degree.
Usefulness of the present invention is: fiber glass reinforced polypropylene nano material of the present invention, by increasing glass fibre and adding nano material, the intensity of Reinforced Polypropylene material; By making the PMMA clad nano
SiO2 has guaranteed the toughness of polypropylene material.
Embodiment
Carry out each composition of proportioning by the weight shown in table 1.
Each composition weight of table 1 embodiment 1-4
Composition weight according to each embodiment in table 1 prepares modification fiber glass reinforced polypropylene nano material, and detailed process is as follows:
Chemical dispersion method prepares nanometer SiO2/PMMA filler: chemical dispersion mainly adopts coupling agent to come modified Nano SiO2/PMMA, make its surperficial hydroxyl and coupling agent generation chemical action, reduce its surperficial wetting ability, improve surface hydrophobicity, reduce the purpose of reuniting to reach.Coupling agent commonly used is silane coupling agent.Usually people have two kinds with the method for coupling agent treatment nanometer SiO2/PMMA, and its key distinction is that the selection of solvent is different.The toluene solvant method is with a certain amount of pretreated nanometer SiO2 and PMMA, adds the flask take toluene as solvent, adds the coupling agent after hydrolysis, and high temperature flows a few hours next time, then washs respectively rear drying with methyl alcohol and hexyl ether.The alcohol solvent method adds pretreated nanometer SiO2 and PMMA after usually the second alcohol and water being mixed with certain proportion, stirred for several hour, and high speed centrifugation separates.The difference of two kinds of methods can be with mechanism different explain of coupling agent from nanometer SiO2 effect: produce the hydroxyl generation hydrogen bond action on hydroxyl and nanometer SiO2 in method 1 after the hydrolysis of the alkoxyl group of coupling agent, the step effect of then at high temperature spouting generates the structure of si one 0-si, and nanometer SiO2 is to be connected by Si one 0 one Si keys with coupling agent.And the rear unsaturated hydroxyl generation hydrogen bond action that produces on hydroxyl and nanometer SiO2 of the alkoxyl group of coupling agent hydrolysis in method 2, the mode of connection more complicated of its nanometer SiO2 and coupling agent may be the mixing effect of all kinds of hydrogen bonds and Si-o-Si.
Wherein nanometer SiO2/PMMA prepares like this: with 1g nanometer SiO2(specific surface area greater than 600m/g, median size 80nm, Haitai Nano Material Co., Ltd., Nanjing) with 1mL methyl methacrylate (MMA, close europeanized reagent company limited of Tianjin section) mix, at 30 ℃ of lower ultra-sonic dispersion 2h or 5h; Add initiator Diisopropyl azodicarboxylate (Dongxing, Shenyang chemical reagent work) in solution after ultra-sonic dispersion, be warming up to 80 ℃, cause MMA radical polymerization occurs; With the polymerisate suction filtration, use washed with de-ionized water, filter cake is dry 24h under 80 ℃, the powder that obtains is nanometer SiO2/PMMA, is designated as nanometer SiO2/PMMA(t), t represents the ultra-sonic dispersion time.
Modification fiber glass reinforced polypropylene preparations of nanomaterials: add a certain amount of nanometer SiO2/PMMA filler in acrylic resin, glass fiber resin, it is in the torque rheometer of 180 ℃ that mixture is joined temperature in batches, mixing rate is 32r/min, after torque is stable, mix 15min, the gained Polypropylene Nanocomposites carries out compressing tablet under 180 ℃ with vulcanizing press.
According to standard GB/T 13525/T-92 test mechanical performance, according to GB1634 test thermostability and ageing-resistant performance, concrete test result sees Table 2.
The performance of each embodiment of table 2 and contrast
Wherein, Comparative Examples is fiber glass reinforced polypropylene material of the prior art.
This shows, the mechanical property of modification fiber glass reinforced polypropylene nano material of the present invention is superior, having reached the performance of the polypropylene material that adopts the glass fibre modification, even performance is more excellent, thermostability might as well, ageing-resistant performance is superior, intensity is high, and good toughness illustrates that it has taken into account toughness and intensity simultaneously.
Above demonstration and described ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand, and above-described embodiment does not limit the present invention in any form, and all employings are equal to replaces or technical scheme that the mode of equivalent transformation obtains, all drops in protection scope of the present invention.
Claims (9)
1. modification fiber glass reinforced polypropylene nano material, is characterized in that, by following composition by weight melt blending form:
Acrylic resin 60-75 part
Glass fibre 20-30 part
Nanometer SiO2/PMMA filler 2-5 part
Antioxidant 0.3-1 part,
Wherein nanometer SiO2/PMMA filler is formed by PMMA clad nano SiO2, and nanometer SiO2/PMMA filler also is doped into coupling agent.
2. modification fiber glass reinforced polypropylene nano material according to claim 1, it is characterized in that: described acrylic resin is homopolymer type or copolymer type, and the melt mass flow rate of acrylic resin is between 5 ~ 80 g/10min.
3. modification fiber glass reinforced polypropylene nano material according to claim 2, is characterized in that, in described nanometer SiO2/PMMA filler, the parts by weight of component are:
SiO2 40-60 part PMMA 40-60 part coupling agent 5-10 part.
4. modification fiber glass reinforced polypropylene nano material according to claim 3, it is characterized in that: described coupling agent is silane, titanic acid ester, phosphoric acid ester or chromium complex.
5. modification fiber glass reinforced polypropylene nano material according to claim 3, it is characterized in that: described antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, 2,6-ditertbutylparacresol, 4,4'-thiobis (the 6-tertiary butyl-3-(methyl) phenol) one or more.
6. prepare the method for the described modification fiber glass reinforced polypropylene of claim 1-5 any one nano material, comprise the steps:
1) prepare nanometer SiO2/PMMA filler with chemical dispersion method;
2) with nanometer SiO2/PMMA filler as filler, join same acrylic resin, glass fibre, antioxidant and prepare the fiber glass reinforced polypropylene nano material by melt-blending process.
7. the method for modification fiber glass reinforced polypropylene nano material according to claim 6, it is characterized in that: the solvent that described chemical dispersion method uses is toluene or ethanol.
8. the method for modification fiber glass reinforced polypropylene nano material according to claim 6, is characterized in that: in step 2) in, count with weight fraction, nanometer SiO2/PMMA filler accounts for 2-5 part, acrylic resin accounts for 60-75 part, glass fibre 20-30 part, antioxidant 0.3-1 part.
9. the method for modification fiber glass reinforced polypropylene nano material according to claim 6, is characterized in that: step 2) described melt blending temperature is the 150-300 degree.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356509A (en) * | 2014-11-10 | 2015-02-18 | 杭州金州高分子科技有限公司 | High-hardness scratch-resistant high-gloss modified polypropylene (PP) material |
| CN105037920A (en) * | 2015-03-25 | 2015-11-11 | 银禧工程塑料（东莞）有限公司 | High-blackness polypropylene composition and preparation method thereof |
| CN105623097A (en) * | 2016-03-02 | 2016-06-01 | 北京航天试验技术研究所 | Nanometer-material-compounded long-glass-fiber-reinforced polypropylene material and preparing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020775A (en) * | 2007-03-15 | 2007-08-22 | 复旦大学 | High strength and high toughness modified poly-propylene material |
| CN101671461A (en) * | 2009-09-27 | 2010-03-17 | 华中科技大学 | Silica hybrid microspheres polymer composites and preparation method thereof |
-
2013
- 2013-03-05 CN CN2013100696634A patent/CN103146052A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020775A (en) * | 2007-03-15 | 2007-08-22 | 复旦大学 | High strength and high toughness modified poly-propylene material |
| CN101671461A (en) * | 2009-09-27 | 2010-03-17 | 华中科技大学 | Silica hybrid microspheres polymer composites and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356509A (en) * | 2014-11-10 | 2015-02-18 | 杭州金州高分子科技有限公司 | High-hardness scratch-resistant high-gloss modified polypropylene (PP) material |
| CN105037920A (en) * | 2015-03-25 | 2015-11-11 | 银禧工程塑料（东莞）有限公司 | High-blackness polypropylene composition and preparation method thereof |
| CN105037920B (en) * | 2015-03-25 | 2017-07-28 | 银禧工程塑料（东莞）有限公司 | A kind of high blackness polypropene composition and preparation method thereof |
| CN105623097A (en) * | 2016-03-02 | 2016-06-01 | 北京航天试验技术研究所 | Nanometer-material-compounded long-glass-fiber-reinforced polypropylene material and preparing method thereof |
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Application publication date: 20130612 |