CN103709381B - The preparation method of a kind of phenol-biphenyl type resol tiny balloon - Google Patents
The preparation method of a kind of phenol-biphenyl type resol tiny balloon Download PDFInfo
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- CN103709381B CN103709381B CN201410008165.3A CN201410008165A CN103709381B CN 103709381 B CN103709381 B CN 103709381B CN 201410008165 A CN201410008165 A CN 201410008165A CN 103709381 B CN103709381 B CN 103709381B
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Abstract
The invention discloses a kind of phenol-biphenyl type resol tiny balloon and preparation method thereof, this preparation method is by after phenol-biphenyl type resol, Cellmic C 121, acetone, vulkacit H and fluorocarbon surfactant mixing, be added drop-wise to stirring reaction in methyl-silicone oil, cooling, washing, drying, solidification, to obtain final product; The method is simple, with low cost, obtained tiny balloon dimensional stabilizing is controlled, hollow rate is high, and maintain the advantages such as high temperature resistant, high carbon residue that phenol-biphenyl type resol has itself, thermo-oxidative stability be excellent, the numerous areas such as naval vessel, Aeronautics and Astronautics can be widely used in, be applicable to applying on a large scale.
Description
Technical field
The present invention relates to the preparation method of a kind of phenol-biphenyl type resol tiny balloon, belong to polymer modification field.
Background technology
Resol tiny balloon is a kind of kernel is air or other gas, the outer material with special construction for resol.Hollow Phenolic Micro-Spheres has the various features such as density is low, specific surface area is large, thermal conductivity is low, excellent heat stability, the covering impact of performance are good, achieves application in a lot of fields.Resol tiny balloon can be used as the opacifying property pigment of polymkeric substance, antiultraviolet additive, Feel Modifzers, light heat insulating material, the body material of ion exchange resin and the lightweight additives of plastic foam material; also resol hollow microsphere can be coated in space flight device surface and be used as resistance to ablation layer; the huge heat produced after can effectively completely cutting off spacecraft and atmospheric layer severe friction, the normal work of protection spacecraft internals.The preparation method of the resol tiny balloon of current bibliographical information mainly contains template, emulsion method, spray-drying process, phase separation method, foaming etc., the polymer microballoon field developed by traditional resol has extensive work, and resol tiny balloon is applied widely in fields such as traffic, building, industry, national defence.
Along with developing rapidly of aerospace cause, traditional novalac polymer microballoon can not meet the requirements at the higher level of the performances such as ablation resistant material thermotolerance, ablation resistance.Therefore, the Design & preparation of the special type phenolic resinous polymer microballoon of the novel high-performance particularly special type phenolic resinous polymer microballoon of high temperature resistant, resistance to ablation becomes the important directions of high-performance polymer hollow microsphere exploitation.
Summary of the invention
The present invention is directed to the defect that novalac polymer microballoon traditional in prior art exists, object is to provide the preparation method preparing phenol-biphenyl type resol tiny balloon that a kind of process is simple, reaction conditions is easily controlled, microspherulite diameter is controlled, the tiny balloon cost that the method obtains is low, hollow rate is good, good in thermal property, applied range.
The invention provides the preparation method of a kind of phenol-biphenyl type resol tiny balloon, this preparation method is by after phenol-biphenyl type resol, Cellmic C 121, acetone, vulkacit H and fluorocarbon surfactant mixing, be added drop-wise to stirring reaction 10 ~ 60min in the methyl-silicone oil of 130 ~ 200 DEG C, cooling, washing, drying, solidification, to obtain final product; Wherein, the mol ratio of phenol-biphenyl type resol, Cellmic C 121 and acetone is 1:0.10 ~ 0.35:5 ~ 15; The mass ratio of phenol-biphenyl type resol, vulkacit H and fluorocarbon surfactant is 1:0.01 ~ 0.25:0.05 ~ 0.3.
Described phenol-biphenyl type resol molecular weight is Mn=600.
Phenol in described preparation method-biphenyl type resol: Cellmic C 121: the mol ratio of acetone is preferably 1:0.15 ~ 0.25:7 ~ 12.
Phenol in described preparation method-biphenyl type resol: vulkacit H: the mass ratio of tensio-active agent is preferably 1:0.06 ~ 0.25:0.09 ~ 0.20.
In described methyl-silicone oil, stirring reaction temperature is 150 ~ 170 DEG C.
The described stirring reaction time is 20 ~ 40min.
Described mixing is by ultrasonic disperse process 20 ~ 40min.
Described rate of addition is 30 ~ 40/min.
Described phenol-biphenyl type resol prepares by the following method: by phenol, 4,4 '-dichloromethyl biphenyl, methyl alcohol, concentrated hydrochloric acid mix with mol ratio 1:0.15 ~ 0.35:0.20 ~ 0.35:0.05 ~ 0.15, at 80 ~ 100 DEG C of stirring reaction 240 ~ 360min, cooling, namely obtains phenol-biphenyl type resol.
Described fluorocarbon surfactant can be the FY-F501 branched chain type perfluoroalkyl polyoxy Vinyl Ether nonionogenic tenside of Guangzhou Fu Yuangui Science and Technology Ltd. production, the H30 fluorochemical surfactant etc. of Zichuan, Zibo City Huahai chemical plant production.
The preparation method of phenol of the present invention-xenol urea formaldehyde tiny balloon comprises the following steps:
Step (one): by phenol, 4,4 '-dichloromethyl biphenyl, methyl alcohol and concentrated hydrochloric acid are the proportioning mixing of 1:0.15 ~ 0.35:0.20 ~ 0.35:0.05 ~ 0.15 in molar ratio, constant temperature 240 ~ 360min be heated to 80 ~ 100 DEG C under at the uniform velocity agitation condition at, to pour into after beaker in vacuum drying oven, be cooled to room temperature, obtain phenol-biphenyl type resol (BN);
Step (two): by phenol-biphenyl type resol, Cellmic C 121, acetone, vulkacit H and fluorocarbon surfactant mixing, wherein, the mol ratio of phenol-biphenyl type resol, Cellmic C 121 and acetone is 1:0.10 ~ 0.35:5 ~ 15; The mass ratio of phenol-biphenyl type resol, vulkacit H and fluorocarbon surfactant is 1:0.01 ~ 0.25:0.05 ~ 0.3, after mixed solution ultrasonic disperse 20 ~ 40min, be that 30 ~ 40/min is added drop-wise in the methyl-silicone oil of 130 ~ 200 DEG C with speed, stirring reaction 10 ~ 60min, cool rear sherwood oil and acetone cleaning, under the condition of 50 DEG C, dry 10 ~ 14h, puts into baking oven and solidifies, obtain phenol-biphenyl type resol tiny balloon.
Beneficial effect of the present invention: the present invention is by controlling phenol-biphenyl type resol, Cellmic C 121, acetone, the conditions such as the proportioning of vulkacit H and fluorocarbon surfactant and blowing temperature, the phenol of particle diameter between 450 ~ 950 μm-xenol urea formaldehyde tiny balloon can be obtained, and obtained phenol-xenol urea formaldehyde tiny balloon is spherical regular, hollow rate is high, its floatability can reach more than 91%, simultaneously, the good in thermal property of phenol-xenol urea formaldehyde tiny balloon, the carbon yield of 900 DEG C of nitrogen atmospheres can reach 70%, decomposition temperature is high, under nitrogen atmosphere, the decomposition temperature of 5wt% is at 450 DEG C, can meeting spatial aircraft, guided missile, rockets etc. are to ablation requirement, in addition, preparation method's technique of the present invention is simple, reaction conditions is easily controlled, and the cheaper starting materials of employing, greatly reduces production cost.
Accompanying drawing explanation
The BN resin and 4 that [Fig. 1] obtains for embodiment 1, the FT-IR spectrogram of 4 '-dichloromethyl biphenyl raw material.
The SEM figure of phenol-biphenyl type resol tiny balloon that [Fig. 2] obtains for embodiment 1.
The SEM figure of phenol-biphenyl type resol tiny balloon that [Fig. 3] obtains for embodiment 2.
The SEM figure of phenol-biphenyl type resol tiny balloon that [Fig. 4] obtains for embodiment 3.
The TGA figure of phenol-biphenyl type resol tiny balloon that [Fig. 5] obtains for embodiment 1.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of limit the scope of the invention.
Embodiment 1
Step (one): add 4 in the 250mL four-hole boiling flask with whipping appts and reflux condensing tube, 4 '-dichloromethyl biphenyl 20.20g, methyl alcohol 2.26g, continue to pass into nitrogen, add phenol 22.59g and mass concentration is 37% hydrochloric acid 2.25g, back flow reaction 6h at 95 DEG C, after reaction terminates, be warming up to 170 DEG C of underpressure distillation removing excessive phenols, pour product in bottle while hot into, after putting into vacuum drying oven cooling, namely obtain light brown resin B N.
Step (two): add 5g BN resin in 200mL beaker, 6g acetone, 0.65g FY-F501,0.30g vulkacit H and 0.22g Cellmic C 121 is added after being stirred to dissolving, dissolve, stir after ultrasonic 30min, take off and leave standstill 48h in vacuum drying oven, as the masterbatch preparing microballoon after taking out.50mL methyl-silicone oil is added in 1L beaker, magnetic agitation is opened after being heated to 170 DEG C, control rotating speed is evenly added in beaker by masterbatch by the rate of addition of 30 droplets/point simultaneously, along with the whipping agent resin that reduces foaming also starts to solidify gradually, stop after 15min stirring, taking-up beaker cools, after cooling by the microballoon careful collection that swims on methyl-silicone oil out, put into 50mL sherwood oil supersound process 30min, after suction filtration, microballoon is poured into and take advantage of ultrasonic 30min in the beaker of 50mL acetone, be positioned over dry 2h after fixing in 50 DEG C of vacuum drying ovens after suction filtration and can obtain final product microballoon.
Obtained phenol-xenol urea formaldehyde tiny balloon is detected: show that median size is 750 μm by metallography microscope sem observation, statistics; Show that microballoon its floatability is 92.71% through the floating experiment of dehydrated alcohol 24h; Be 70% at the carbon yield of 900 DEG C of nitrogen atmospheres.
Embodiment 2
Step (one): add 4 in the 250mL four-hole boiling flask with whipping appts and reflux condensing tube, 4 '-dichloromethyl biphenyl 20.20g, methyl alcohol 2.26g, continue to pass into nitrogen, add phenol 22.59g and mass concentration is 37% hydrochloric acid 2.25g, back flow reaction 6h at 95 DEG C, after reaction terminates, be warming up to 170 DEG C of underpressure distillation removing excessive phenols, pour product in bottle while hot into, after putting into vacuum drying oven cooling, namely obtain light brown resin B N.
Step (two): add 5g BN resin in 200mL beaker, 5.5g acetone, 0.50g FY-F501,0.70g vulkacit H and 0.18g Cellmic C 121 is added after being stirred to dissolving, dissolve, stir after ultrasonic 30min, take off and leave standstill 48h in vacuum drying oven, as the masterbatch preparing microballoon after taking out.50mL methyl-silicone oil is added in 1L beaker, magnetic agitation is opened after being heated to 160 DEG C, control rotating speed is evenly added in beaker by masterbatch by the rate of addition of 35 droplets/point simultaneously, along with the whipping agent resin that reduces foaming also starts to solidify gradually, stop after 15min stirring, taking-up beaker cools, after cooling by the microballoon careful collection that swims on methyl-silicone oil out, put into 50mL sherwood oil supersound process 30min, after suction filtration, microballoon is poured into and take advantage of ultrasonic 30min in the beaker of 50mL acetone, be positioned over dry 2h after fixing in 50 DEG C of vacuum drying ovens after suction filtration and can obtain final product microballoon.
Obtained phenol-xenol urea formaldehyde tiny balloon is detected: show that median size is 770 μm by metallography microscope sem observation, statistics; Show that microballoon its floatability is 93.42% through the floating experiment of dehydrated alcohol 24h; Be 70% at the carbon yield of 900 DEG C of nitrogen atmospheres.
Embodiment 3
Step (one): add 4 in the 250mL four-hole boiling flask with whipping appts and reflux condensing tube, 4 '-dichloromethyl biphenyl 20.20g, methyl alcohol 2.26g, continue to pass into nitrogen, add phenol 22.59g and mass concentration is 37% hydrochloric acid 2.25g, back flow reaction 6h at 95 DEG C, after reaction terminates, be warming up to 170 DEG C of underpressure distillation removing excessive phenols, pour product in bottle while hot into, after putting into vacuum drying oven cooling, namely obtain light brown resin B N.
Step (two): add 5g BN resin in 200mL beaker, 4.0g acetone, 0.45g H30,1.00g vulkacit H and 0.14g Cellmic C 121 is added after being stirred to dissolving, dissolve, stir after ultrasonic 30min, take off and leave standstill 48h in vacuum drying oven, as the masterbatch preparing microballoon after taking out.50mL methyl-silicone oil is added in 1L beaker, magnetic agitation is opened after being heated to 150 DEG C, control rotating speed is evenly added in beaker by masterbatch by the rate of addition of 40 droplets/point simultaneously, along with the whipping agent resin that reduces foaming also starts to solidify gradually, stop after 15min stirring, taking-up beaker cools, after cooling by the microballoon careful collection that swims on methyl-silicone oil out, put into 50mL sherwood oil supersound process 30min, after suction filtration, microballoon is poured into and take advantage of ultrasonic 30min in the beaker of 50mL acetone, be positioned over dry 2h after fixing in 50 DEG C of vacuum drying ovens after suction filtration and can obtain final product microballoon.
Obtained phenol-xenol urea formaldehyde tiny balloon is detected: show that median size is 770 μm by metallography microscope sem observation, statistics; Show that microballoon its floatability is 91.79% through the floating experiment of dehydrated alcohol 24h; Be 70% at the carbon yield of 900 DEG C of nitrogen atmospheres.
Comparative example 1
Step (one): add 4 in the 250mL four-hole boiling flask with whipping appts and reflux condensing tube, 4 '-dichloromethyl biphenyl 20.20g, methyl alcohol 2.26g, continue to pass into nitrogen, add phenol 22.59g and mass concentration is 37% hydrochloric acid 2.25g, back flow reaction 6h at 95 DEG C, after reaction terminates, be warming up to 170 DEG C of underpressure distillation removing excessive phenols, pour product in bottle while hot into, after putting into vacuum drying oven cooling, namely obtain light brown resin B N.
Step (two): add 5g BN resin in 200mL beaker, 6g acetone, 0.65g FY-F501,0.30g vulkacit H and 0.45g Cellmic C 121 is added after being stirred to dissolving, dissolve, stir after ultrasonic 30min, take off and leave standstill 48h in vacuum drying oven, as the masterbatch preparing microballoon after taking out.50mL methyl-silicone oil is added in 1L beaker, magnetic agitation is opened after being heated to 170 DEG C, control rotating speed is evenly added in beaker by masterbatch by the rate of addition of 30 droplets/point simultaneously, along with the whipping agent resin that reduces foaming also starts to solidify gradually, stop after 15min stirring, taking-up beaker cools, after cooling by the microballoon careful collection that swims on methyl-silicone oil out, put into 50mL sherwood oil supersound process 30min, after suction filtration, microballoon is poured into and take advantage of ultrasonic 30min in the beaker of 50mL acetone, be positioned over dry 2h after fixing in 50 DEG C of vacuum drying ovens after suction filtration and can obtain final product microballoon.
Obtained phenol-xenol urea formaldehyde tiny balloon is detected: show that median size is 930 μm by metallography microscope sem observation, statistics; Show that microballoon its floatability is 34.72% through the floating experiment of dehydrated alcohol 24h; Be 70% at the carbon yield of 900 DEG C of nitrogen atmospheres.
Comparative example 2
Step (one): add 4 in the 250mL four-hole boiling flask with whipping appts and reflux condensing tube, 4 '-dichloromethyl biphenyl 20.20g, methyl alcohol 2.26g, continue to pass into nitrogen, add phenol 22.59g and mass concentration is 37% hydrochloric acid 2.25g, back flow reaction 6h at 95 DEG C, after reaction terminates, be warming up to 170 DEG C of underpressure distillation removing excessive phenols, pour product in bottle while hot into, after putting into vacuum drying oven cooling, namely obtain light brown resin B N.
Step (two): add 5g BN resin in 200mL beaker, 5.5g acetone, 0.20g H30,0.70g vulkacit H and 0.18g Cellmic C 121 is added after being stirred to dissolving, dissolve, stir after ultrasonic 30min, take off and leave standstill 48h in vacuum drying oven, as the masterbatch preparing microballoon after taking out.50mL methyl-silicone oil is added in 1L beaker, magnetic agitation is opened after being heated to 160 DEG C, control rotating speed is evenly added in beaker by masterbatch by the rate of addition of 35 droplets/point simultaneously, along with the whipping agent resin that reduces foaming also starts to solidify gradually, stop after 15min stirring, taking-up beaker cools, after cooling by the microballoon careful collection that swims on methyl-silicone oil out, put into 50mL sherwood oil supersound process 30min, after suction filtration, microballoon is poured into and take advantage of ultrasonic 30min in the beaker of 50mL acetone, be positioned over dry 2h after fixing in 50 DEG C of vacuum drying ovens after suction filtration and can obtain final product microballoon.
Obtained phenol-xenol urea formaldehyde tiny balloon is detected: show that median size is 840 μm by metallography microscope sem observation, statistics; Show that microballoon its floatability is 51.39% through the floating experiment of dehydrated alcohol 24h; Be 70% at the carbon yield of 900 DEG C of nitrogen atmospheres.
Comparative example 3
Step (one): add 4 in the 250mL four-hole boiling flask with whipping appts and reflux condensing tube, 4 '-dichloromethyl biphenyl 20.20g, methyl alcohol 2.26g, continue to pass into nitrogen, add phenol 22.59g and mass concentration is 37% hydrochloric acid 2.25g, back flow reaction 6h at 95 DEG C, after reaction terminates, be warming up to 170 DEG C of underpressure distillation removing excessive phenols, pour product in bottle while hot into, after putting into vacuum drying oven cooling, namely obtain light brown resin B N.
Step (two): add 5g BN resin in 200mL beaker, 4.0g acetone, 0.45g H30,1.00g vulkacit H and 0.14g Cellmic C 121 is added after being stirred to dissolving, dissolve, stir after ultrasonic 30min, take off and leave standstill 48h in vacuum drying oven, as the masterbatch preparing microballoon after taking out.50mL methyl-silicone oil is added in 1L beaker, magnetic agitation is opened after being heated to 220 DEG C, control rotating speed is evenly added in beaker by masterbatch by the rate of addition of 40 droplets/point simultaneously, along with the whipping agent resin that reduces foaming also starts to solidify gradually, stop after 15min stirring, taking-up beaker cools, after cooling by the microballoon careful collection that swims on methyl-silicone oil out, put into 50mL sherwood oil supersound process 30min, after suction filtration, microballoon is poured into and take advantage of ultrasonic 30min in the beaker of 50mL acetone, be positioned over dry 2h after fixing in 50 DEG C of vacuum drying ovens after suction filtration and can obtain final product microballoon.
Obtained phenol-xenol urea formaldehyde tiny balloon is detected: show that median size is 980 μm by metallography microscope sem observation, statistics; Show that microballoon its floatability is 29.88% through the floating experiment of dehydrated alcohol 24h; Be 70% at the carbon yield of 900 DEG C of nitrogen atmospheres.
Claims (6)
1. the preparation method of phenol-biphenyl type resol tiny balloon, it is characterized in that, after phenol-biphenyl type resol, Cellmic C 121, acetone, vulkacit H and fluorocarbon surfactant mixing, be added drop-wise to the drop rate of 30 ~ 40/min in the methyl-silicone oil of 130 ~ 200 DEG C by magnetic stirrer stirring reaction 20 ~ 40min, cooling, washing, dry, solidification, to obtain final product; Wherein, the mol ratio of phenol-biphenyl type resol, Cellmic C 121 and acetone is 1:0.10 ~ 0.35:5 ~ 15; The mass ratio of phenol-biphenyl type resol, vulkacit H and fluorocarbon surfactant is 1:0.01 ~ 0.25:0.05 ~ 0.3.
2. preparation method as claimed in claim 1, is characterized in that, phenol-biphenyl type resol: Cellmic C 121: the mol ratio of acetone is 1:0.15 ~ 0.25:7 ~ 12.
3. preparation method as claimed in claim 1, is characterized in that, phenol-biphenyl type resol: vulkacit H: the mass ratio of tensio-active agent is 1:0.06 ~ 0.25:0.09 ~ 0.20.
4. preparation method as claimed in claim 1, it is characterized in that, in described methyl-silicone oil, stirring reaction temperature is 150 ~ 170 DEG C.
5. preparation method as claimed in claim 1, it is characterized in that, described mixing is by ultrasonic disperse process 20 ~ 40min.
6. preparation method as claimed in claim 1, it is characterized in that, described phenol-biphenyl type resol prepares by the following method: by phenol, 4,4 '-dichloromethyl biphenyl, methyl alcohol, concentrated hydrochloric acid mix with mol ratio 1:0.15 ~ 0.35:0.20 ~ 0.35:0.05 ~ 0.15, at 80 ~ 100 DEG C of stirring reaction 240 ~ 360min, cooling, to obtain final product.
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| CN104592717B (en) * | 2015-02-03 | 2017-11-17 | 中南大学 | One inter-species acetylenylbenzene azo biphenyl type phenol formaldehyde foam and preparation method thereof |
| CN104558533B (en) * | 2015-02-03 | 2017-02-01 | 中南大学 | M-acetylenyl benzeneazo biphenyl phenolic resin and preparation method thereof |
| CN106328390A (en) * | 2016-08-30 | 2017-01-11 | 中国科学院山西煤炭化学研究所 | Method for preparing active carbon microspheres with high specific capacitance in large scale |
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| CN102627927B (en) * | 2012-03-26 | 2013-12-04 | 黑龙江省科学院石油化学研究院 | Medium temperature curing high temperature resistant phenolic adhesive |
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