CN105086375B - The preparation method of epoxy resin poromerics - Google Patents
The preparation method of epoxy resin poromerics Download PDFInfo
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- CN105086375B CN105086375B CN201510486424.8A CN201510486424A CN105086375B CN 105086375 B CN105086375 B CN 105086375B CN 201510486424 A CN201510486424 A CN 201510486424A CN 105086375 B CN105086375 B CN 105086375B
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Abstract
The invention discloses a kind of preparation method of epoxy resin poromerics, epoxy foams material abscess-size for solving existing method preparation is big, the technical problem that quantity is few.Technical scheme is, using bisphenol A type epoxy resin, the methylimidazole of 2 ethyl 4 as raw material, the uniform epoxy resin poromerics of structure have been prepared after the compressing of precured sheet, gas saturation, high temperature foaming and solidify afterwards processing.The present invention is with environment-friendly supercritical CO2For foaming agent, due to supercritical CO2Fluid has preferable solvability and diffusion, and the average cell size of prepared epoxy resin poromerics is reduced to 5.84~20.2 μm by 100 μm of technical background, and minimum has reached 5.84 μm.Cell density is by the 10 of technical background6Individual/cm3Increase to 1.09 × 108~1.47 × 109Individual/cm3, up to 1.47 × 109Individual/cm3。
Description
Technical field
The present invention relates to a kind of preparation method of poromerics, more particularly to a kind of preparation side of epoxy resin poromerics
Method.
Background technology
Microporous polymer refer to abscess-size for 10 μm or so, cell density be about 109Individual/cm3Foamable polymer material
Material.The features such as microporous polymer has light weight, impact strength height, fatigue life length, good heat endurance, is future polymer foam
The Main way of Material Field development.Epoxy resin has excellent heat resistance and mechanical property, is widely used in foamed material
Preparation.At this stage, the preparation method of epoxy foams material mainly has chemical blowing process, physical blowing method and tiny balloon
Method.Epoxy foams material abscess-size prepared by the above method is larger, abscess negligible amounts, and not reaching poromerics will
Ask.
Document 1 " Authorization Notice No. is CN101302304B Chinese invention patent " discloses a kind of epoxy resin-matrix foaming
The preparation method of material.This method by control reaction condition realize epoxy chemical blowing and curing molding collaboration control
System, it is 2.7 and the epoxy foams material with good water resistance and chemical resistance to have prepared expansion ratio.But
Foaming agent selected by the patent is CBA, and abscess-size is more than 100 μm.
Document 2 " application publication number is CN104530463A Chinese invention patent " discloses a kind of epoxy foams modeling
The preparation method of material.This method adds foam stabiliser, antioxidant and solidification in the epoxy using water as physical blowing agent
Agent obtains pre-composition, it is foamed after prepared low-density epoxy resin foam plastics.However, using water as foaming, influence bubble
The dimensional stability of foam plastics, and foam size does not reach poromerics requirement.
Document 3 " application publication number is CN103910974A Chinese invention patent " discloses a kind of tiny balloon ring type filling
Oxygen tree fat composite foam material and preparation method thereof.Report and hollow glass micropearl is filled in liquid-state epoxy resin, through secondary
The epoxy foams material of hole-closing structure has been prepared after deaeration, solidification.Because tiny balloon size is 100-2000 μm, make
The epoxy foams material abscess-size that must be prepared is more than 100 μm, does not reach the requirement of poromerics.
Although the above method has successfully prepared epoxy foams material, density of material is reduced, possesses certain answer
With value, but the material abscess-size prepared is more than 100 μm, and abscess quantity is less than 106Individual/cm3, it is impossible to it is referred to as fine-celled foam
Material, and product properties controllability and repeatability are low.
The content of the invention
In order to which the epoxy foams material abscess-size for overcoming the shortcomings of existing method preparation is big, quantity is few, the present invention
A kind of preparation method of epoxy resin poromerics is provided.This method using bisphenol A type epoxy resin, the methylimidazole of 2- ethyls -4 as
Raw material, even structure has been prepared after the compressing of precured sheet, gas saturation, high temperature foaming and solidify afterwards processing
Epoxy resin poromerics.The present invention is with environment-friendly supercritical CO2For physical blowing agent, diffusion rate is very fast, nucleation
Point is more, has finally prepared the uniform epoxy resin poromerics of structure.
The technical solution adopted for the present invention to solve the technical problems：A kind of preparation method of epoxy resin poromerics,
It is characterized in comprising the following steps：
Step 1: by epoxide number be 0.11~0.14eq/100g bisphenol A type epoxy resin and 2- ethyl -4- methyl miaows
Azoles is according to mass ratio 20:1 is added in dichloromethane, and mixed solution is obtained after being stirred 1~3 hour on magnetic stirring apparatus, will be mixed
Close solution to be placed in vacuum drying oven after vacuum drying, obtain epoxy powder, gained sample is labeled as A；
Suppressed 10~30 minutes under 18~22MPa pressure Step 2: sample A is placed in 90~110 DEG C of hot press,
Then room temperature is naturally cooled to, gained sample is labeled as B；
Step 3: sample B is placed in autoclave, supercritical CO is passed through2Fluid simultaneously controls temperature, make sample B 36~
45 DEG C, pressurize 24~72 hours in 8~10MPa autoclave, pressurize terminate rear quick pressure releasing, and gained sample is labeled as C；
Foamed 5~15 seconds Step 4: sample C is placed in 110~130 DEG C of constant temperature silicone oil bath, foaming will examination after terminating
Sample is placed in cooling and shaping in ice-water bath, and gained sample is labeled as D；
Step 5: sample D is placed in baking oven, 1.5~2.5 hours are incubated at 75~85 DEG C, then heat to 105~
115 DEG C are incubated 1.5~2.5 hours, then heat to 135~145 DEG C and are incubated 1.5~2.5 hours, natural cooling obtains asphalt mixtures modified by epoxy resin
Fat poromerics.
The beneficial effects of the invention are as follows：This method is using bisphenol A type epoxy resin, the methylimidazole of 2- ethyls -4 as raw material, warp
The uniform epoxy of structure has been prepared after crossing the compressing of precured sheet, gas saturation, high temperature foaming and solidify afterwards processing
Resin poromerics.The present invention is with environment-friendly supercritical CO2For physical blowing agent, comparatively fast, nucleating point is more for diffusion rate,
Finally the uniform epoxy resin poromerics of structure is prepared.Due to supercritical CO2Fluid have preferable solvability and
Diffusion so that material has reached 4%~5.5% in gas saturation stage adsorbance, is formd enough initial stage in foaming
Nucleating point, so as to reduce abscess-size, improve cell density.Epoxy resin poromerics prepared by the present invention is averaged
Abscess-size is reduced to 5.84~20.2 μm by 100 μm of technical background, and minimum has reached 5.84 μm.Cell density is carried on the back by technology
The 10 of scape6Individual/cm3Increase to 1.09 × 108~1.47 × 109Individual/cm3, up to 1.47 × 109Individual/cm3。
The present invention is elaborated with reference to the accompanying drawings and detailed description.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of epoxy resin poromerics prepared by the inventive method.
Embodiment
Embodiment 1：
(1) epoxide number is pressed for 0.11~0.14eq/100g bisphenol A type epoxy resin and 2-ethyl-4-methylimidazole
According to mass ratio 20:1 adds in dichloromethane, obtains mixed solution after being stirred 1 hour on magnetic stirring apparatus, mixed solution is put
After being dried in vacuo in vacuum drying oven, epoxy powder is obtained, gained sample is labeled as A；
(2) sample A is placed in 90 DEG C of hot press and suppressed 30 minutes under 18MPa pressure, then naturally cool to room
Temperature, gained sample is labeled as B；
(3) sample B is placed in autoclave, is passed through supercritical CO2Fluid simultaneously controls temperature, makes sample B in 36 DEG C, 9MPa
Autoclave in pressurize 72 hours, pressurize terminates rear quick pressure releasing, and gained sample is labeled as C；
(4) sample C is placed in 120 DEG C of constant temperature silicone oil bath and foamed 15 seconds, foaming is placed in ice-water bath after terminating and cooled down
Sizing, gained sample is labeled as D；
(5) sample D is placed in baking oven, 2.5 hours is incubated at 75 DEG C, then heated to 105 DEG C and be incubated 2.5 hours, so
After be warming up to 135 DEG C be incubated 2.5 hours, natural cooling obtains epoxy resin poromerics.
It will be seen from figure 1 that epoxy resin poromerics abscess is presented uniform spherical, cell size distribution is in micron order
Not, average cell size is 9.66 μm, and cell density is 1.07 × 109Individual/cm3。
After tested, the average cell size of epoxy resin poromerics manufactured in the present embodiment is 9.66 μm, cell density
For 1.07 × 109Individual/cm3。
Embodiment 2：
(1) epoxide number is pressed for 0.11~0.14eq/100g bisphenol A type epoxy resin and 2-ethyl-4-methylimidazole
According to mass ratio 20:1 adds in dichloromethane, obtains mixed solution after being stirred 2 hours on magnetic stirring apparatus, mixed solution is put
After being dried in vacuo in vacuum drying oven, epoxy powder is obtained, gained sample is labeled as A；
(2) sample A is placed in 100 DEG C of hot press and suppressed 15 minutes under 20MPa pressure, then naturally cool to room
Temperature, gained sample is labeled as B；
(3) sample B is placed in autoclave, is passed through supercritical CO2Fluid simultaneously controls temperature, make sample B 40 DEG C,
Pressurize 24 hours in 10MPa autoclave, pressurize terminates rear quick pressure releasing, and gained sample is labeled as C；
(4) sample C is placed in 110 DEG C of constant temperature silicone oil bath and foamed 15 seconds, foaming is placed in ice-water bath after terminating and cooled down
Sizing, gained sample is labeled as D；
(5) sample D is placed in baking oven, 2 hours is incubated at 80 DEG C, then heated to 110 DEG C and be incubated 2 hours, Ran Housheng
Warm to 140 DEG C are incubated 2 hours, and natural cooling obtains epoxy resin poromerics.
After tested, the average cell size of epoxy resin poromerics manufactured in the present embodiment is 7.96 μm, cell density
For 1.42 × 109Individual/cm3。
Embodiment 3：
(1) epoxide number is pressed for 0.11~0.14eq/100g bisphenol A type epoxy resin and 2-ethyl-4-methylimidazole
According to mass ratio 20:1 adds in dichloromethane, obtains mixed solution after being stirred 2 hours on magnetic stirring apparatus, mixed solution is put
After being dried in vacuo in vacuum drying oven, epoxy powder is obtained, gained sample is labeled as A；
(2) sample A is placed in 110 DEG C of hot press and suppressed 10 minutes under 20MPa pressure, then naturally cool to room
Temperature, gained sample is labeled as B；
(3) sample B is placed in autoclave, is passed through supercritical CO2Fluid simultaneously controls temperature, makes sample B in 40 DEG C, 8MPa
Autoclave in pressurize 48 hours, pressurize terminates rear quick pressure releasing, and gained sample is labeled as C；
(4) sample C is placed in 130 DEG C of constant temperature silicone oil bath and foamed 5 seconds, foaming is placed in cool down in ice-water bath after terminating to be determined
Type, gained sample is labeled as D；
(5) sample D is placed in baking oven, 2 hours is incubated at 80 DEG C, then heated to 110 DEG C and be incubated 2 hours, Ran Housheng
Warm to 140 DEG C are incubated 2 hours, and natural cooling obtains epoxy resin poromerics.
After tested, the average cell size of epoxy resin poromerics manufactured in the present embodiment is 5.84 μm, cell density
For 1.47 × 109Individual/cm3。
Embodiment 4：
(1) epoxide number is pressed for 0.11~0.14eq/100g bisphenol A type epoxy resin and 2-ethyl-4-methylimidazole
According to mass ratio 20:1 adds in dichloromethane, obtains mixed solution after being stirred 3 hours on magnetic stirring apparatus, mixed solution is put
After being dried in vacuo in vacuum drying oven, epoxy powder is obtained, gained sample is labeled as A；
(2) sample A is placed in 100 DEG C of hot press and suppressed 15 minutes under 22MPa pressure, then naturally cool to room
Temperature, gained sample is labeled as B；
(3) sample B is placed in autoclave, is passed through supercritical CO2Fluid simultaneously controls temperature, makes sample B in 45 DEG C, 8MPa
Autoclave in pressurize 24 hours, pressurize terminates rear quick pressure releasing, and gained sample is labeled as C；
(4) sample C is placed in 130 DEG C of constant temperature silicone oil bath and foamed 10 seconds, sample is placed in ice-water bath by foaming after terminating
Middle cooling and shaping, gained sample is labeled as D；
(5) sample D is placed in baking oven, 1.5 hours is incubated at 85 DEG C, then heated to 115 DEG C and be incubated 1.5 hours, so
After be warming up to 145 DEG C be incubated 1.5 hours, natural cooling obtains epoxy resin poromerics.
After tested, the average cell size of epoxy resin poromerics manufactured in the present embodiment is 20.2 μm, cell density
For 1.09 × 108Individual/cm3。
Claims (1)
1. a kind of preparation method of epoxy resin poromerics, it is characterised in that comprise the following steps：
Step 1: epoxide number is pressed for 0.11~0.14eq/100g bisphenol A type epoxy resin and 2-ethyl-4-methylimidazole
According to mass ratio 20:1 adds in dichloromethane, obtains mixed solution after being stirred 1~3 hour on magnetic stirring apparatus, will mix molten
Liquid is placed in vacuum drying oven after vacuum drying, obtains epoxy powder, and gained sample is labeled as A；
Step 2: sample A is placed in 90~110 DEG C of hot press into compacting 10~30 minutes under 18~22MPa pressure, then
Room temperature is naturally cooled to, gained sample is labeled as B；
Step 3: sample B is placed in autoclave, supercritical CO is passed through2Fluid simultaneously controls temperature, make sample B 36~45 DEG C, 8
Pressurize 24~72 hours in~10MPa autoclave, pressurize terminates rear quick pressure releasing, and gained sample is labeled as C；
Foamed 5~15 seconds Step 4: sample C is placed in 110~130 DEG C of constant temperature silicone oil bath, foaming puts sample after terminating
The cooling and shaping in ice-water bath, gained sample is labeled as D；
Step 5: sample D is placed in baking oven, 1.5~2.5 hours are incubated at 75~85 DEG C, 105~115 DEG C are then heated to
Insulation 1.5~2.5 hours, then heats to 135~145 DEG C and is incubated 1.5~2.5 hours, it is micro- that natural cooling obtains epoxy resin
Porous materials.
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| CN105086375B true CN105086375B (en) | 2017-09-15 |
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| CN106398122B (en) * | 2016-10-13 | 2018-06-08 | 常州大学 | A kind of graphene epoxy resin composite foam material and preparation method thereof |
| CN109897209B (en) * | 2019-03-25 | 2021-08-20 | 西北工业大学 | Preparation method of epoxy resin microporous material with bimodal distribution |
| CN110028763B (en) * | 2019-04-12 | 2021-08-06 | 西北工业大学 | Preparation method of low-density high-rate epoxy resin microporous material |
| CN110524781A (en) * | 2019-09-02 | 2019-12-03 | 厦门市锋特新材料科技有限公司 | A kind of TPU sheet foaming process |
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| CN101357996B (en) * | 2008-09-12 | 2010-12-15 | 中国科学院广州化学研究所 | Multi-microporous epoxy thermosetting resin, preparation method and application thereof |
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