CN101891936B - Preparation method of composite material based on epoxy resin and phosphazene nanotubes - Google Patents
Preparation method of composite material based on epoxy resin and phosphazene nanotubes Download PDFInfo
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- CN101891936B CN101891936B CN2010102423055A CN201010242305A CN101891936B CN 101891936 B CN101891936 B CN 101891936B CN 2010102423055 A CN2010102423055 A CN 2010102423055A CN 201010242305 A CN201010242305 A CN 201010242305A CN 101891936 B CN101891936 B CN 101891936B
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Abstract
The invention relates to a preparation method of a composite material based on epoxy resin and phosphazene nanotubes, which belongs to the technical field of nano materials. The preparation method comprises the following steps: under ultrasonic conditions, adding acid binding agent into tetrahydrofuran; adding 4,4'-dihydroxy-diphenyl sulfone and hexachlorocyclotriphosphazene to carry out condensation reaction; adding epoxy chloropropane; dropwise adding sodium hydroxide water solution; heating to carry out water bath reaction, thereby obtaining epoxide group modified phosphazene nanotubes; adding the epoxide group modified phosphazene nanotubes into the acetone dissolved epoxy resin, adding epoxy resin curing agent, carrying out ultrasonic dispersion, removing acetone in a vacuum drying oven at low temperature, and pouring the mixture into a die; and curing at high temperature to obtain the composite material based on epoxy resin and phosphazene nanotubes. The epoxy resin composite material has the advantages of high shock resistance, tensile property and thermal stability.
Description
Technical field
What the present invention relates to is a kind of method of technical field of nano material, specifically is a kind of preparation method of the matrix material based on epoxy resin and phosphazene nanotubes.
Background technology
Epoxy resin has good thermotolerance, electrical insulating property, dielectric properties and good adhesive property, thereby is widely used in fields such as electronic package material, coating, sizing agent.But because epoxy resin exists born matter crisp problem, particularly shock resistance and tensile property relatively poor, make its application receive certain restriction, the mechanical property that therefore improves it is key very.
Up to the present, both at home and abroad,, be broadly divided into two types: nano level and non-nano level according to the size of property-modifying additive in the improving one's methods of epoxy resin mechanical property.The research of the additive of non-nano level early as is adopted rubber toughenedly, but this method descends the strength of materials, rigidity; And for example adopt filler to strengthen, then toughness of material can descend again.Nano level property-modifying additive has nano silicon, nano-calcium carbonate, nano aluminium oxide, organo montmorillonite, carbon nanofiber, carbon nanotube etc., and these additives can to a certain degree improve the mechanical property of epoxy resin.Wherein, especially carbon nanotube becomes the focus that people study with its particular performances, is considered to have much a type nano granular that improves the epoxy resin mechanical property of potentiality.Yet the carbon nanotube production cost is higher; In the time of in adding resin matrix to, be prone to produce and reunite, disperse unequal unfavorable phenomenon; In addition, because non-activity point on the carbon nanotube must carry out pre-treatment for it before joining resin matrix, and this process need is made troubles to production technique through complicated multistep chemical reaction; According to another bibliographical information, complicated modification also can produce the structure of carbon nanotube and destroy, and makes it lose original excellent properties.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of preparation method of the matrix material based on epoxy resin and phosphazene nanotubes is provided; Add the preparation technology of the epoxy resin composite material of phosphazene nanotubes modification, the epoxy resin composite material for preparing has favorable shock resistance, tensile property, thermostability.
The present invention realizes through following technical scheme, the present invention includes following steps:
Step 1, under ultrasound condition, in THF, add acid-binding agent, add 4 subsequently; 4 '-dihydroxy diphenylsulphone and hexachlorocyclotriphosphazene carry out condensation reaction; Add epoxy chloropropane again, splash into aqueous sodium hydroxide solution, obtain the phosphazene nanotubes that epoxide group is modified through the water-bath of heating.
Described acid binding agent is a triethylamine.
Described 4, the mol ratio of 4 '-dihydroxy diphenylsulphone, hexachlorocyclotriphosphazene and epoxy chloropropane is 4: 1: 8.
Described condensation reaction is specially: 40 degrees centigrade were reacted 4 hours down.
The weight percent concentration of described aqueous sodium hydroxide solution is 30%.
The described water-bath of heating is meant: reaction is 4 hours in 60 degrees centigrade of water-baths;
The structural formula of the phosphazene nanotubes that described epoxide group is modified is following:
Step 2, the phosphazene nanotubes that resulting epoxide group is modified add in the epoxy resin of acetone solution; Add epoxy curing agent; Through behind the ultra-sonic dispersion in vacuum drying oven low temperature remove acetone; Then mixture is poured in the mould, behind hot setting, obtained matrix material based on epoxy resin and phosphazene nanotubes.
Described epoxy curing agent is 4,4 '-MDA;
Described hot setting is specially: 100 degrees centigrade 2 hours, 150 degrees centigrade 3 hours, 250 degrees centigrade 3 hours.
Compared with prior art; The present invention has following beneficial effect: the prepared phosphazene nanotubes of the present invention has reactive group; Can obtain having the phosphazene nanotubes that epoxide group is modified through single step reaction, method is simple, cost is lower and pattern is controlled, productive rate is higher; Its reaction is added in the epoxy resin-base; The matrix material based on epoxy resin and phosphazene nanotubes that success prepares has the favorable mechanical performance; When the interpolation quality percentage composition of phosphazene nanotubes is 0.1%; The shock strength of material has improved 76.7%, and tensile strength has improved 25.4%; Simultaneously, owing to contain abundant phosphorus, nitrogen element in the phosphazene nanotubes, the residual rate of thermogravimetric analysis display material in the time of 800 degrees centigrade has significant lifting, and the mass loss rate of material has decline to a certain degree; Find also that through research when the addition of phosphazene nanotubes was little, their disperse phase in epoxy resin-base can effectively play the toughness reinforcing effect of enhancing when evenly.
Description of drawings
Fig. 1 prepares the process route chart of the phosphazene nanotubes of epoxide group modification for the present invention;
Fig. 2 is phosphazene nanotubes and Fourier's infrared spectrum of the phosphazene nanotubes of epoxide group modification of the hydroxyl of embodiment 1 preparation.
Fig. 3 is the sem photograph of the phosphazene nanotubes modified of the epoxide group of embodiment 1 preparation;
Fig. 4 is the sem photograph of the epoxy resin of the phosphazene nanotubes modification of embodiment 1-4 preparation;
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.Following examples all are that synthetic route specifies with Fig. 1.
Embodiment 1
Step 1 in the single port flask of the THF that fills 10000 weight parts, adds the triethylamine of 87 weight parts under the 50W ultrasound condition; Add 4 of 144 weight parts subsequently, the hexachlorocyclotriphosphazene of 4 '-dihydroxy diphenylsulphone and 50 weight parts, 40 degrees centigrade were reacted 4 hours down; The epoxy chloropropane that adds 900 weight parts again splashes into the aqueous sodium hydroxide solution of the concentration 30% of 400 weight parts, and reaction is 4 hours in 60 degrees centigrade of water-baths; With THF, water, washing with alcohol, filtration; Drying obtains the phosphazene nanotubes that epoxide group is modified, productive rate 83%.
Step 2 joins 8000 parts by weight of epoxy resin E618 in the acetone of 6000 weight parts, and the phosphazene nanotubes that the epoxide group of 11 weight parts is modified adds wherein, adds 4 of 3000 weight parts again; 4 '-MDA; Under ultrasonic 240W condition, disperseed 90 minutes, 30 degrees centigrade of placements were removed organic solvent in 6 hours in vacuum drying oven, then mixture were poured in the iron mould; 100 degrees centigrade 2 hours; 150 degrees centigrade 3 hours, 250 degrees centigrade 3 hours, obtain matrix material based on epoxy resin and phosphazene nanotubes.
Embodiment 2
Step 1 in the single port flask of the THF that fills 20000 weight parts, adds the triethylamine of 174 weight parts under the 50W ultrasound condition; Add 4 of 288 weight parts subsequently, the hexachlorocyclotriphosphazene of 4 '-dihydroxy diphenylsulphone and 100 weight parts, 40 degrees centigrade were reacted 4 hours down; The epoxy chloropropane that adds 1800 weight parts again splashes into the aqueous sodium hydroxide solution of the concentration 30% of 800 weight parts, and reaction is 6 hours in 60 degrees centigrade of water-baths; With THF, water, washing with alcohol, filtration; Drying obtains the phosphazene nanotubes that epoxide group is modified, productive rate 78%.
Step 2 joins 8000 parts by weight of epoxy resin E618 in the acetone of 5000 weight parts, and the phosphazene nanotubes that the epoxide group of 5.5 weight parts is modified adds wherein, adds 4 of 3000 weight parts again; 4 '-MDA; Under ultrasonic 240W condition, disperseed 90 minutes, 30 degrees centigrade of placements were removed organic solvent in 6 hours in vacuum drying oven, then mixture were poured in the iron mould; 100 degrees centigrade 2 hours; 150 degrees centigrade 3 hours, 250 degrees centigrade 3 hours, obtain matrix material based on epoxy resin and phosphazene nanotubes.
Embodiment 3
Step 1 in the single port flask of the THF that fills 10000 weight parts, adds the triethylamine of 174 weight parts under the 50W ultrasound condition; Add 4 of 288 weight parts subsequently, the hexachlorocyclotriphosphazene of 4 '-dihydroxy diphenylsulphone and 100 weight parts, 40 degrees centigrade were reacted 4 hours down; The epoxy chloropropane that adds 1800 weight parts again splashes into the aqueous sodium hydroxide solution of the concentration 30% of 800 weight parts, and reaction is 4 hours in 60 degrees centigrade of water-baths; With THF, water, washing with alcohol, filtration; Drying obtains the phosphazene nanotubes that epoxide group is modified, productive rate 81%.
Step 2 joins 8000 parts by weight of epoxy resin E618 in the acetone of 8000 weight parts, and the phosphazene nanotubes that the epoxide group of 55 weight parts is modified adds wherein, adds 4 of 3000 weight parts again; 4 '-MDA; Under ultrasonic 240W condition, disperseed 90 minutes, 30 degrees centigrade of placements were removed organic solvent in 8 hours in vacuum drying oven, then mixture were poured in the iron mould; 100 degrees centigrade 2 hours; 150 degrees centigrade 3 hours, 250 degrees centigrade 3 hours, obtain matrix material based on epoxy resin and phosphazene nanotubes.
Embodiment 4
Step 1 in the single port flask of the THF that fills 40000 weight parts, adds the triethylamine of 344 weight parts under the 50W ultrasound condition; Add 4 of 576 weight parts subsequently, the hexachlorocyclotriphosphazene of 4 '-dihydroxy diphenylsulphone and 200 weight parts, 40 degrees centigrade were reacted 4 hours down; The epoxy chloropropane that adds 3600 weight parts again splashes into the aqueous sodium hydroxide solution of the concentration 30% of 1600 weight parts, and reaction is 8 hours in 60 degrees centigrade of water-baths; With THF, water, washing with alcohol, filtration; Drying obtains the phosphazene nanotubes that epoxide group is modified, productive rate 88%.
Step 2 joins 8000 parts by weight of epoxy resin E618 in the acetone of 10000 weight parts, and the phosphazene nanotubes that the epoxide group of 225 weight parts is modified adds wherein, adds 4 of 3000 weight parts again; 4 '-MDA; Under ultrasonic 240W condition, disperseed 90 minutes, 30 degrees centigrade of placements were removed organic solvent in 10 hours in vacuum drying oven, then mixture were poured in the iron mould; 100 degrees centigrade 2 hours; 150 degrees centigrade 3 hours, 250 degrees centigrade 3 hours, obtain matrix material based on epoxy resin and phosphazene nanotubes.
The implementation result of embodiment:
Fig. 2 is phosphazene nanotubes and Fourier's infrared spectrum of the phosphazene nanotubes of epoxide group modification of the hydroxyl of embodiment 1 preparation.A represents the infrared spectrum of the phosphazene nanotubes of hydroxyl, and B represents the infrared spectrum of the phosphazene nanotubes of epoxide group modification.3100cm
-1What (h) locate is the absorption peak of hydroxyl; 1590cm
-1(a) and 1480cm
-1(b) be the absorption peak of phenyl ring; 1294cm
-1(c) and 1150cm
-1(e) be the absorption peak of O=S=O; 1187cm
-1(d) be the absorption peak of P=N; 940cm
-1(f) be the absorption peak of P-O-Ar; 875cm
-1(g) be the absorption peak of P-N.3100cm
-1(h) absorption peak of locating hydroxyl disappears 908cm
-1The absorption peak and the 2925cm of place's epoxide group
-1And 2865cm
-1The absorption peak of place's methylene radical has proved that phosphazene nanotubes successfully modified by epoxide group.
Fig. 3 amplifies 10000 times figure for the sem photograph .a of the phosphazene nanotubes that the epoxide group of embodiment 1 preparation is modified, and b amplifies 50000 times figure.The length of the phosphazene nanotubes that epoxide group is modified approximately is several microns, and external diameter is between 80 to 90 nanometers.The surface of nanotube smoothly is owing to have the small molecules of epoxide group is connected on nanotube through chemical bond-linking surface inadequately; Intersperse on nanotube; When the preparation matrix material; Nanotube is exactly to react through the amino in these epoxide groups and the solidifying agent, and nanotube is well combined with resin matrix, strengthens toughness reinforcing effect thereby play.
Fig. 4 is the sem photograph of the epoxy resin of the phosphazene nanotubes modification of embodiment 1-4 preparation.It is 0.05%, 0.1%, 0.5%, 2% that a, b, c, d represent the nanotube addition respectively.When the addition of nanotube was 0.05% and 0.1%, their dispersions in epoxy resin-base were very even; And when addition was 0.5%, most of nanotube still presented uniform dispersion, but some reunion occurred, can see micron-sized agglomerating particles; When addition continued to increase to 2%, agglomeration was more obvious, and blocky coacervate just becomes the defective of matrix material, in Mechanics Performance Testing, shows.
The mechanical property of the epoxy resin of the phosphazene nanotubes modification of table 1 embodiment 1-4 preparation
Can find that from the data of table 1 there be close getting in touch in the distribution in epoxy resin-base of the mechanical property of matrix material and nanotube.At addition is 0.1% o'clock, and the matrix material that obtains has best shock strength and tensile strength.
Claims (4)
1. the preparation method based on the matrix material of epoxy resin and phosphazene nanotubes is characterized in that, may further comprise the steps:
Step 1, under ultrasound condition, in THF, add acid binding agent, add 4 subsequently; 4 '-dihydroxy diphenylsulphone and hexachlorocyclotriphosphazene carry out condensation reaction; Add epoxy chloropropane again, splash into aqueous sodium hydroxide solution, obtain the phosphazene nanotubes that epoxide group is modified through the water-bath of heating;
Described 4, the mol ratio of 4 '-dihydroxy diphenylsulphone, hexachlorocyclotriphosphazene and epoxy chloropropane is 4: 1: 8;
Described condensation reaction is specially: 40 degrees centigrade were reacted 4 hours down;
The weight percent concentration of described aqueous sodium hydroxide solution is 30%;
The described water-bath of heating is meant: reaction is 4 hours in 60 degrees centigrade of water-baths;
Step 2, the phosphazene nanotubes that resulting epoxide group is modified add in the epoxy resin of acetone solution; Add epoxy curing agent; Through behind the ultra-sonic dispersion in vacuum drying oven low temperature remove acetone; Then mixture is poured in the mould, behind hot setting, obtained matrix material based on epoxy resin and phosphazene nanotubes;
Described hot setting is specially: 100 degrees centigrade 2 hours, 150 degrees centigrade 3 hours, 250 degrees centigrade 3 hours.
2. the preparation method of the matrix material based on epoxy resin and phosphazene nanotubes according to claim 1 is characterized in that described acid binding agent is a triethylamine.
3. the preparation method of the matrix material based on epoxy resin and phosphazene nanotubes according to claim 1 is characterized in that, the structural formula of the phosphazene nanotubes that described epoxide group is modified is following:
4. the preparation method of the matrix material based on epoxy resin and phosphazene nanotubes according to claim 1 is characterized in that described epoxy curing agent is 4,4 '-MDA.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103694632A (en) * | 2013-11-27 | 2014-04-02 | 浙江工业大学之江学院工业研究院 | Preparation method of epoxy resin composite material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104109346B (en) * | 2013-04-22 | 2017-08-18 | 中国石油化工股份有限公司 | The seismic physical model material and preparation method of a kind of silicon powder modified epoxy |
| CN104250425B (en) * | 2013-06-26 | 2017-06-16 | 中国石油化工股份有限公司 | The seismic physical model material and preparation method of a kind of silica nanometer powder modified epoxy |
| CN105348489A (en) * | 2015-12-16 | 2016-02-24 | 太仓康盛化工有限公司 | Self-emulsified epoxy resin curing agent |
| CN106008918B (en) * | 2016-06-29 | 2018-03-20 | 江苏傲伦达科技实业股份有限公司 | A kind of epoxy resin containing sulfone |
| CN111217986B (en) * | 2020-02-23 | 2021-08-10 | 北京化工大学 | Preparation method of hydroxy sulfone type halogen-free cyclophosphazene flame-retardant and toughened epoxy resin |
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| CN101070389A (en) * | 2007-06-21 | 2007-11-14 | 上海交通大学 | Hollow micro-ball containing phosphazene and preparing method |
| CN101092484A (en) * | 2007-06-21 | 2007-12-26 | 上海交通大学 | Surface modified microballons of containing phosphazene, and preparation method |
| CN101659677A (en) * | 2009-09-17 | 2010-03-03 | 上海交通大学 | Triphosphazene epoxy resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070389A (en) * | 2007-06-21 | 2007-11-14 | 上海交通大学 | Hollow micro-ball containing phosphazene and preparing method |
| CN101092484A (en) * | 2007-06-21 | 2007-12-26 | 上海交通大学 | Surface modified microballons of containing phosphazene, and preparation method |
| CN101659677A (en) * | 2009-09-17 | 2010-03-03 | 上海交通大学 | Triphosphazene epoxy resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694632A (en) * | 2013-11-27 | 2014-04-02 | 浙江工业大学之江学院工业研究院 | Preparation method of epoxy resin composite material |
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