CN102391473A - Preparation method for anhydride cured epoxy resin/palygorskite nanocomposite material - Google Patents
Preparation method for anhydride cured epoxy resin/palygorskite nanocomposite material Download PDFInfo
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- CN102391473A CN102391473A CN2011102593046A CN201110259304A CN102391473A CN 102391473 A CN102391473 A CN 102391473A CN 2011102593046 A CN2011102593046 A CN 2011102593046A CN 201110259304 A CN201110259304 A CN 201110259304A CN 102391473 A CN102391473 A CN 102391473A
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Abstract
The invention relates to a preparation method for an anhydride cured epoxy resin/palygorskite nanocomposite material. The preparation method comprises the following steps of: grinding palygorskite into mineral powder; performing calcining activation treatment on the palygorskite mineral powder; heating and liquefying epoxy resin; adding the palygorskite in an amount which is 1 to 8 percent of the mass of the epoxy resin, mixing and stirring; adding an anhydride curing agent in an amount which is 20 to 40 percent of the mass of the epoxy resin; stirring the obtained mixture; and vacuumizing, degassing and the like to obtain the composite material. The product is generally used for casting or encapsulating electronic and electrical products, and heating and curing. The preparation method has the advantages of obviously improving the toughness of an epoxy resin anhydride cured material and obviously improving mechanical properties and heat stability, and is easy to implement and low in cost.
Description
Technical field
The present invention relates to the preparation method of a kind of acid anhydride curable epoxy resin/polygorskite nano composite material.
Background technology
Epoxy resin has good machinery, performance such as electric, bonding, is widely used in fields such as coating, matrix material, high-performance tackiness agent, electrically insulating material; But often there are problems such as bubble, crackle, brittle failure in epoxy resin cure.Especially there are deadly defects such as fragility is big, easy to crack in epoxy resin/anhydride-cured system.At present mainly epoxy resin is carried out modification through the material that adds elastomerics or have a soft molecular structure; But these methods are improving the epoxy resin flexible simultaneously; Mechanical modulus and thermotolerance (Zhao Shiqi, 1998, the insulating material communication of cured article have often been reduced; Xu Li, 2008, the Guangzhou chemistry; Chinese invention patent, application number 200810202164.7).Jia Runping etc. (2010, new carbon) are organic monomer with the maleic anhydride, and are carbon nano-tube modified through plasma-induced graft polymerization method; Be applied to epoxy resin solidifying system; Prepare the carbon nano tube/epoxy resin nano composite material, toughness, the intensity of made matrix material are improved, but the preparation process is complicated; And a large amount of synthetic agents that adopt costliness, cost is higher.
Polygorskite (being also referred to as attapulgite) is a kind of chain layer silicate mineral of 2:1 type; Its structural unit layer connects through the top oxo bridge and forms chain stratiform pore passage structure.Polygorskite has the nano pore of one dimension, boundling shape, and the diameter of its single nanofiber is approximate number nanometer (with place of production difference to some extent) only, and length then can reach several microns.This natural slope mineral wool in detail has been used in the inorganic nano composite material preparation, and it is used and mainly concentrates on polymeric amide (bad bodyguard congruence, 2006, engineering plastics application; Chinese invention patent ZL200510095548.X), polyaniline (Yao is superfine, 2010, silicate journal), Vestolen PP 7052 polymeric systems such as (Li Likun etc., 2008, polymer journals).
Polygorskite is used for the amine curing system more in epoxy resin composite material.Sun Yanyan etc. (2011, plastics industry) add in the amine cured epoxy resin system through with after the pre-treatment of polygorskite silane coupling agent, improve the avidity between polygorskite and epoxy resin-base, thereby improve the toughness of synthetic materials, and thermostability also slightly improves.
At present, still the no-trump polygorskite directly is used for the research report or the patented technology of acid anhydride curable epoxy resin system.
The content of invention
The objective of the invention is to overcome in the present acid anhydride curable epoxy resin material; The synthetic materials of introducing with high costs; And mineral filler such as smectite can't effectively significantly improve the shortcoming of synthetic materials toughness, mechanical property and thermostability simultaneously; Propose a kind of employing high-specific surface area, high surface, the polygorskite of high length-diameter ratio is as functional stuffing, the method for acid anhydride curable epoxy resin/polygorskite matrix material that preparation toughness, intensity and thermostability significantly improve simultaneously.
The main technical schemes that realizes the object of the invention is to remove polygorskite planar water and zeolite water through the calcination activation treatment; Make polygorskite outside surface hydroxyl and anhydride curing agent that addition reaction more effectively take place; Impel the anhydride curing agent carboxyl and the epoxy resin epoxy group(ing) generation addition reaction of opening again, make between polygorskite and epoxy resin-base to combine with chemical bond.This good interface effect helps improving the over-all properties of matrix material greatly.
Realize the concrete technical scheme of the object of the invention: the preparation method of a kind of acid anhydride curable epoxy resin/polygorskite nano composite material comprises the following steps: successively
1) polygorskite is ground to form breeze, cross 200 mesh sieves;
2) the polygorskite breeze is carried out calcining and activating and handled 30-120 minute, temperature is 150 ℃ to 400 ℃;
3) epoxy resin-base is heated to 80 ℃ and makes it liquefaction, polygorskite thorough mixing, the stirring with it after the adding calcination; The add-on of polygorskite is the 1-8% of epoxy resin quality;
4) add anhydride curing agent in the mixture in step 3), its add-on is the 20-40% of epoxy resin quality; The gained mixture was stirred 1-3 hour down at 80-100 ℃; Vacuumize degassing was handled 5-30 minute then; Be warmed up to 120 again and spend stirring reaction 0.5-1.5 hour at a slow speed, vacuumize degassing handled 5-10 minute matrix material (acid anhydride curable epoxy resin/polygorskite nano composite material).
This product generally is used for casting or packaging electronic, electric product and is heating and curing; Then the gained casting material is injected mould if process the sample of test performance, solidified 2-4 hour down at 120-180 ℃.
Above said anhydride curing agent comprise pyromellitic dianhydride dianhydride, Tetra hydro Phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, alkylene Succinic anhydried, Pyroglutaric acid, dodecenylsuccinic acid acid anhydride, gather the nonane diacid acid anhydride, gather the combination between certain herbaceous plants with big flowers dicarboxylic anhydride and the different acid anhydrides.
Above said epoxy resin refer to bisphenol A epoxide resin.
Above said polygorskite purity more than 90%.
Advantage of the present invention and positively effect are: at first handle through calcining and activating, promote the chemical action of polygorskite surface hydroxyl and epoxy resin-base, increase the affinity and the interface compatibility of itself and epoxy resin-base; Secondly, utilize the enhanced characteristic of polygorskite nanofiber, improve toughness and intensity; Once more, polygorskite need not to carry out the organically-modified over-all properties that can realize improving matrix material as functional stuffing; It is given prominence to and is also advantageous in that compound method is simple in addition, low production cost, and production process is environmentally friendly.
In sum, the present invention has significantly improved the mechanical property and the thermostability of matrix material when significantly improving epoxy resin anhydride-cured toughness of material.Secondly implementation method of the present invention is simple, with low cost, can have a extensive future.In addition, comparing other, to adopt organo-clay mineral be the matrix material (if you would take off the stone ring epoxy resin composite material) of filler, and the prepared polygorskite epoxy resin composite material cost of present method is lower, and thermostability improves more remarkable.
This product generally is used for the casting and the encapsulation of Electrical and Electronic product.
The practical implementation method:
To further specify the present invention among the following embodiment, but to not restriction of the present invention.
Embodiment one,
The polygorskite raw material is from Xuyi Jiangsu, and purity 96%, 180 is spent calcination activation treatment 1 hour hour.Take by weighing E44 epoxy resin 31.1g, join in the 100ml beaker, be heated to 80 ℃; Official mountain, Mingguang City polygorskite through purifying of adding 1% is 0.311g, stirs ultrasonic 30 minutes 10 minutes; The pyromellitic dianhydride that adds epoxy resin quality 20% is 6.22g, and stirring reaction is 60 minutes fast, vacuum outgas 10 minutes; Be warmed up to 120 ℃ of stirring reactions 90 minutes at a slow speed, vacuum outgas 8 minutes is used for casting or packaging electronic electric product and is heating and curing.For test casting material performance, inject mould, 130 ℃ solidified 2 hours.The pure acid anhydride curable epoxy resin material sample of preparation uses the same method.Adopt DMA dynamic mechanical spectrometer, shock-testing machine, universal testing machine, TG thermogravimetric analyzer etc. that pure acid anhydride curable epoxy resin material sample and acid anhydride curable epoxy resin/polygorskite composite sample are tested.The result shows: the impact property of pure acid anhydride curable epoxy resin material is 3.6KJ/m
2, bending property 63.96MPa, 101.8 ℃ of second-order transition temperatures, 320 ℃ of initial heat decomposition temperatures, Young's modulus is respectively 1116MPa and 44.6MPa with 150 ℃ the time at 80 ℃.The impact property of adding 1% polygorskite-acid anhydride curable epoxy resin matrix material is 4.1KJ/m
2, bending property 94.47MPa, 120.8 ℃ of second-order transition temperatures, 343 ℃ of initial heat decomposition temperatures, Young's modulus is respectively 1815MPa and 60.9MPa with 150 ℃ the time at 80 ℃.
Embodiment two,
The polygorskite raw material is from Mingguang City, Anhui, and purity 95%, 300 is spent calcination activation treatment 1 hour.Take by weighing E44 epoxy resin 30.1g, add the 100ml beaker, be heated to 80 ℃; Official mountain, Mingguang City polygorskite through purifying of adding 2% is 0.602g, stirs ultrasonic 30 minutes 10 minutes; Adding pyromellitic dianhydride is 6.02g, and stirring reaction is 60 minutes fast, vacuum outgas 10 minutes; Be warmed up to 120 ℃ of stirring reactions 120 minutes at a slow speed, vacuum outgas 6 minutes is used for casting or packaging electronic electric product and is heating and curing.For test casting material performance, inject mould, 130 ℃ solidified 2 hours.The pure acid anhydride curable epoxy resin material sample of preparation uses the same method.Adopt DMA dynamic mechanical spectrometer, shock-testing machine, universal testing machine, TG thermogravimetric analyzer etc. that pure acid anhydride curable epoxy resin material sample and acid anhydride curable epoxy resin/polygorskite composite sample are tested.The result shows: the impact property of pure acid anhydride curable epoxy resin material is 3.6KJ/m
2, bending property 63.96MPa, 101.8 ℃ of second-order transition temperatures, 320 ℃ of initial heat decomposition temperatures, Young's modulus is respectively 1116MPa and 44.6MPa with 150 ℃ the time at 80 ℃.The impact property of adding 2% polygorskite-acid anhydride curable epoxy resin matrix material is 5.3KJ/m
2, bending property 105.48MPa, 145.8 ℃ of second-order transition temperatures, 340 ℃ of initial heat decomposition temperatures, Young's modulus is respectively 1716MPa and 75.14MPa with 150 ℃ the time at 80 ℃.
Embodiment three,
The polygorskite raw material is from Mingguang City, Anhui, and purity 95%, 200 is spent calcination activation treatment 1 hour.Take by weighing E44 epoxy resin 30.5g, add the 100ml beaker, be heated to 80 ℃; Add official mountain, Mingguang City polygorskite 0.915g, stirred ultrasonic 30 minutes 10 minutes through purifying; Adding pyromellitic dianhydride is 9.15g, and stirring reaction is 60 minutes fast, vacuum outgas 10 minutes; Be warmed up to 120 ℃ of stirring reactions 85 minutes at a slow speed, vacuum outgas 10 minutes is used for casting or packaging electronic electric product and is heating and curing.For test casting material performance, inject mould, 130 ℃ solidified 2 hours.The pure acid anhydride curable epoxy resin material sample of preparation uses the same method.Adopt DMA dynamic mechanical spectrometer, shock-testing machine, universal testing machine, TG thermogravimetric analyzer etc. that pure acid anhydride curable epoxy resin material sample and acid anhydride curable epoxy resin/polygorskite composite sample are tested.The result shows: the impact property of pure acid anhydride curable epoxy resin material is 3.6KJ/m
2, bending property 63.96MPa, 101.8 ℃ of second-order transition temperatures, 320 ℃ of initial heat decomposition temperatures, Young's modulus is respectively 1116MPa and 44.6MPa with 150 ℃ the time at 80 ℃.The impact property of adding 3% polygorskite-acid anhydride curable epoxy resin matrix material is 4.9KJ/m
2, bending property 82.78MPa, 156.6 ℃ of second-order transition temperatures, 345 ℃ of initial heat decomposition temperatures, Young's modulus is respectively 1754MPa and 264.6MPa with 150 ℃ the time at 80 ℃.
Claims (4)
1. the preparation method of acid anhydride curable epoxy resin/polygorskite nano composite material comprises the following steps: successively
1) polygorskite is ground to form breeze, cross 200 mesh sieves;
2) the polygorskite breeze is carried out calcining and activating and handled 30-120 minute, temperature is 150 ℃ to 400 ℃;
3) epoxy resin-base is heated to 80 ℃ and makes it liquefaction, polygorskite thorough mixing, the stirring with it after the adding calcination; The add-on of polygorskite is the 1-8% of epoxy resin quality;
4) add anhydride curing agent in the mixture in step 3), its add-on is the 20-40% of epoxy resin quality; With the institute
Get mixture and stirred 1-3 hour down at 80-100 ℃, vacuumize degassing was handled 5-30 minute then, was warmed up to 120 again
Spend stirring reaction 0.5-1.5 hour at a slow speed, vacuumize degassing is handled and was formed matrix material in 5-10 minute.
2. according to the preparation method of a kind of acid anhydride curable epoxy resin/polygorskite nano composite material described in the claim 1, it is characterized in that said anhydride curing agent comprises pyromellitic dianhydride dianhydride, Tetra hydro Phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, alkylene Succinic anhydried, Pyroglutaric acid, dodecenylsuccinic acid acid anhydride, gathers the nonane diacid acid anhydride, gathers the combination between certain herbaceous plants with big flowers dicarboxylic anhydride and the different acid anhydrides.
3. according to the preparation method of a kind of acid anhydride curable epoxy resin/polygorskite nano composite material described in the claim 1, it is characterized in that said epoxy resin refers to bisphenol A epoxide resin.
4. according to the preparation method of a kind of acid anhydride curable epoxy resin/polygorskite nano composite material described in the claim 1, its
Characteristic is that said polygorskite purity is more than 90%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403274A (en) * | 2014-11-21 | 2015-03-11 | 芜湖市宝艺游乐科技设备有限公司 | High-thermal-stability epoxy resin composite material and manufacturing method thereof |
| CN106280279A (en) * | 2016-08-10 | 2017-01-04 | 袁春华 | A kind of preparation method of high heat conduction epoxy molding plastic |
| CN106883378A (en) * | 2017-04-16 | 2017-06-23 | 西北师范大学 | The preparation and the application in epoxy resin is prepared of the organic inorganic hybridization curing agent with fire resistance |
| CN108912608A (en) * | 2018-06-29 | 2018-11-30 | 江苏德溢利新材料科技有限公司 | A kind of the glass reinforced plastic photovoltaic bracket and its processing technology of modification |
| CN109111693A (en) * | 2018-06-29 | 2019-01-01 | 江苏德溢利新材料科技有限公司 | A kind of glass reinforced plastic photovoltaic bracket that high-ductility is weather-proof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298509A (en) * | 2008-06-18 | 2008-11-05 | 西北师范大学 | Nanometer grade paligorskite-flame retardant epoxide resin composite material |
| CN102101962A (en) * | 2010-12-15 | 2011-06-22 | 常州大学 | Polyaniline epoxy anti-corrosive paint and preparation method thereof |
-
2011
- 2011-09-02 CN CN 201110259304 patent/CN102391473B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298509A (en) * | 2008-06-18 | 2008-11-05 | 西北师范大学 | Nanometer grade paligorskite-flame retardant epoxide resin composite material |
| CN102101962A (en) * | 2010-12-15 | 2011-06-22 | 常州大学 | Polyaniline epoxy anti-corrosive paint and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403274A (en) * | 2014-11-21 | 2015-03-11 | 芜湖市宝艺游乐科技设备有限公司 | High-thermal-stability epoxy resin composite material and manufacturing method thereof |
| CN106280279A (en) * | 2016-08-10 | 2017-01-04 | 袁春华 | A kind of preparation method of high heat conduction epoxy molding plastic |
| CN106883378A (en) * | 2017-04-16 | 2017-06-23 | 西北师范大学 | The preparation and the application in epoxy resin is prepared of the organic inorganic hybridization curing agent with fire resistance |
| CN106883378B (en) * | 2017-04-16 | 2019-03-29 | 西北师范大学 | The preparation of hybrid inorganic-organic curing agent with flame retardant property and preparing the application in epoxy resin |
| CN108912608A (en) * | 2018-06-29 | 2018-11-30 | 江苏德溢利新材料科技有限公司 | A kind of the glass reinforced plastic photovoltaic bracket and its processing technology of modification |
| CN109111693A (en) * | 2018-06-29 | 2019-01-01 | 江苏德溢利新材料科技有限公司 | A kind of glass reinforced plastic photovoltaic bracket that high-ductility is weather-proof |
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