CN109206636A - One kind hollow beads containing boron bakelite resin and preparation method thereof - Google Patents
One kind hollow beads containing boron bakelite resin and preparation method thereof Download PDFInfo
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- CN109206636A CN109206636A CN201810845619.0A CN201810845619A CN109206636A CN 109206636 A CN109206636 A CN 109206636A CN 201810845619 A CN201810845619 A CN 201810845619A CN 109206636 A CN109206636 A CN 109206636A
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- boron bakelite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
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Abstract
The present invention provides a kind of boron bakelite resin hollow beads and preparation method thereof, belong to technical field of polymer materials, and phenol, boric acid, basic catalyst and formaldehyde are mixed and carries out polycondensation reaction by the present invention, obtain boron bakelite resin；After obtained boron bakelite resin, inner nuclear material, dispersion stabilizer, amine curing agent and water are mixed, cross-linking reaction is carried out, mixed liquor is obtained；The inner nuclear material is the oil-based liquid that boiling point is greater than water；Obtained mixed liquor is subjected to crosslinking curing, filtering and calcination processing, obtains hollow beads containing boron bakelite resin.The Shell Materials for the hollow beads containing boron bakelite resin that the present invention obtains are containing boron bakelite resin, and high fixing carbon imparts the excellent thermal stability of hollow beads.Embodiment statistics indicate that, at 800 DEG C, the carbon yields of the hollow beads containing boron bakelite resin that the application obtains is 61~63%.
Description
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of hollow beads containing boron bakelite resin and its preparation
Method.
Background technique
Hollow phenolic resin microbeads are that a kind of kernel is air or other gases, outer layer are the hollow structure material of phenolic resin
Material.Since its interior media is gas, structure closing has the characteristics that density is small, thermal conductivity is low, excellent heat stability, therefore
Hollow phenolic resin microbeads be often used as filler assign composite material light, it is heat-insulated the features such as, be widely used in thermal protection
Field.
Common hollow phenolic resin microbeads preparation method has foaming, spray drying process, phase transition method, suspension polymerization
Deng, can prepare partial size be nanoscale or micron-sized hollow beads.Basic principle is under alkaline condition, using phenol, isophthalic
Diphenol and paraformaldehyde, formalin or water soluble phenol resin are raw material, with other liquid immiscible with phenolic resin
Body or solid material are core, or foaming agent is used to generate gas as core, solidify crosslinked phenolic resin and form stable shell, then
Core is removed by the means such as calcining or dissolving, to obtain phenolic resin hollow beads.
Current hollow phenolic microballon is prepared mostly using phenolic resin as raw material by raw material of phenolic resin
Hollow phenolic resin microbeads, though have good hot property, with the development of the high-tech sectors such as aerospace, without
Method meets the needs of to its thermal stability.
Summary of the invention
In view of this, the present invention mentions it is an object of that present invention to provide hollow beads containing boron bakelite resin and preparation method thereof
The hollow beads containing boron bakelite resin supplied have excellent thermal stability.
The present invention provides a kind of preparation methods of hollow beads containing boron bakelite resin, comprising the following steps:
1) phenol, boric acid, basic catalyst and formaldehyde are mixed and carries out polycondensation reaction, obtained containing boron bakelite resin；It is described
Formaldehyde is added in the form of paraformaldehyde or formalin.
2) step 1) is obtained mixed containing boron bakelite resin, inner nuclear material, dispersion stabilizer, amine curing agent and water
After conjunction, mixed liquor is obtained；The inner nuclear material is the oil-based liquid that boiling point is greater than water；
3) mixed liquor for obtaining the step 2) successively carries out crosslinking curing, filtering, calcination processing, obtains containing boron phenolic
Resin hollow beads.
Preferably, the temperature of polycondensation reaction is 80~100 DEG C in the step 1), and the time of polycondensation reaction is 6~8h.
Preferably, step 1) the neutral and alkali catalyst is NaOH, NH3·H2O, barium hydroxide or magnesia.
Preferably, the molar ratio of phenol, boric acid and formaldehyde is 1:0.1~0.25:1.3~2 in the step 1), and alkalinity is urged
Agent dosage is the 0.5%~5.0% of phenol quality.
Preferably, inner nuclear material is octane, nonane, decane, toluene, dimethylbenzene or methyl-silicone oil in the step 2).
Preferably, dispersion stabilizer is polyacrylic acid, polyvinyl alcohol, hydroxymethyl cellulose or poly- methyl in the step 2)
Acrylamide.
Preferably, which is characterized in that described to contain boron bakelite resin, inner nuclear material, dispersion stabilizer, amine curing agent and water
Amount ratio be 15~25g:8~25g:16g~27g:1.5~2.5g:100mL.
Preferably, the temperature of cross-linking and curing reaction is 80~90 DEG C in the step 3), time of crosslinking curing is 2~
3h, the pH value of crosslinking curing are 1~2.
Preferably, the calcining in the step 3) successively includes the first calcining, the second calcining and third calcining；
The temperature of first calcining is 80~110 DEG C, and the time of the first calcining is 4~10h；
The temperature of second calcining is 130~150 DEG C, and the time of the second calcining is 2~3h；
The temperature of the third calcining is 170~180 DEG C, and the time of third calcining is 2~3h.The present invention also provides upper
The hollow beads containing boron bakelite resin that preparation method is prepared are stated, the shell of the hollow beads is containing boron bakelite resin, wall
Thickness is 7 μm~40 μm, and kernel gas is air, and the partial size of the hollow beads containing boron bakelite resin is 0.2mm~1.2mm.
Advantageous effects: the present invention provides a kind of preparation method of hollow beads containing boron bakelite resin, the present invention will
Phenol, boric acid, basic catalyst and formaldehyde mixing carry out polycondensation reaction, obtain containing boron bakelite resin；It will obtain containing boron phenolic
Cross-linking reaction is carried out after resin, inner nuclear material, dispersion stabilizer, amine curing agent and water mixing, obtains mixed liquor；The kernel
Material is the oil-based liquid that boiling point is greater than water；Mixed liquor is successively subjected to crosslinking curing, filtering, calcination processing, obtains boracic phenol
Urea formaldehyde hollow beads.The Shell Materials for the hollow beads containing boron bakelite resin that the present invention obtains are containing boron bakelite resin, height
Carbon yield imparts the excellent thermal stability of hollow beads.Embodiment statistics indicate that, at 800 DEG C, boracic that the present invention obtains
The carbon yield of phenolic resin hollow beads is 61~63%.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 1；PF is
Phenolic resin microballon, BPF are microballon containing boron bakelite resin；
Fig. 2 is the scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin in embodiment 1；
Fig. 3 is the thermogravimetric curve figure of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 1；PF
For phenolic resin microballon, BPF is microballon containing boron bakelite resin；
Fig. 4 is the infrared spectrogram of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 2；PF is
Phenolic resin microballon, BPF are microballon containing boron bakelite resin；
Fig. 5 is the scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin in embodiment 2；
Fig. 6 is the thermogravimetric curve figure of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 2；PF
For phenolic resin microballon, BPF is microballon containing boron bakelite resin；
Fig. 7 is the infrared spectrogram of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 3；PF is
Phenolic resin microballon, BPF are microballon containing boron bakelite resin；
Fig. 8 is the scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin in embodiment 3；
Fig. 9 is the thermogravimetric curve figure of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 3；PF
For phenolic resin microballon, BPF is microballon containing boron bakelite resin；
Specific embodiment
The present invention provides a kind of preparation methods of hollow beads containing boron bakelite resin, comprising the following steps:
1) phenol, boric acid, basic catalyst and formaldehyde are mixed and carries out polycondensation reaction, obtained containing boron bakelite resin；It is described
Formaldehyde is added in the form of paraformaldehyde or formalin；
2) step 1) is obtained mixed containing boron bakelite resin, inner nuclear material, dispersion stabilizer, amine curing agent and water
After conjunction, mixed liquor is obtained；The inner nuclear material is the oil-based liquid that boiling point is greater than water；
3) mixed liquor for obtaining the step 2) successively carries out crosslinking curing, filtering, calcination processing, obtains containing boron phenolic
Resin hollow beads.
Phenol, boric acid, basic catalyst and formaldehyde are mixed and carry out polycondensation reaction by the present invention, are obtained containing boron bakelite resin.
In the present invention, the temperature of the polycondensation reaction is preferably 80~100 DEG C, and more preferably 85~95 DEG C；The contracting
The time of poly- reaction is preferably 6~8h, more preferably 7h.
In the present invention, the basic catalyst is preferably NaOH, NH3·H2O, barium hydroxide or magnesia.
In the present invention, the molar ratio of the phenol, boric acid and formaldehyde is preferably 1:0.1~0.25:1.3~2, more preferably
For 1:0.2:1.4, the basic catalyst dosage is the 0.5%~5.0% of phenol quality, more preferably 3.5%.
In the present invention, the phenol, boric acid, basic catalyst and formaldehyde hybrid mode are preferably first by phenol and boric acid
It is warming up to 90~160 DEG C of progress esterifications after mixing and obtains phenyl-borate reaction solution, then by the phenyl-borate reaction solution
It is mixed after being cooled to polycondensation reaction temperature with basic catalyst and formaldehyde.
In the present invention, when the formaldehyde is formalin, concentration 37%.
In the present invention, the time of the esterification is preferably 4~6h, more preferably 5h.
The present invention is not particularly limited the rate of heating and cooling, selects heating well known to those skilled in the art and incites somebody to action
Warm rate.
It obtains containing after boron bakelite resin, the present invention will be obtained containing boron bakelite resin, inner nuclear material, dispersion stabilizer, amine
After class curing agent and water mixing, mixed liquor is obtained；The inner nuclear material is the oil-based liquid that boiling point is greater than water.
In the present invention, the regulator of the pH value is preferably hydrochloric acid, sulfuric acid or phosphoric acid.
In the present invention, the inner nuclear material is preferably octane, nonane, decane, toluene, dimethylbenzene or methyl-silicone oil.
In the present invention, the dispersion stabilizer is preferably polyacrylic acid, polyvinyl alcohol, hydroxymethyl cellulose or poly- methyl
Acrylamide.
In the present invention, the amine curing agent is preferably hexa, triethanolamine, melamine or aniline.
In the present invention, the quality of the amine curing agent is preferably the 8~16% of boracic phenolic resin quality, more preferably
It is 10~15%.
In the present invention, the dosage containing boron bakelite resin, inner nuclear material, dispersion stabilizer, amine curing agent and water
Than for 15~25g:8~25g:16g~27g:1.5~2.5g:100mL, more preferably 18~20g:15~20g:20~25g:
1.8~2.0g:100mL.
In the present invention, it is described containing boron bakelite resin, inner nuclear material, dispersion stabilizer, amine curing agent and water mixing
Method preferably first will inner nuclear material, dispersion stabilizer and water mix after stir at room temperature, then after being mixed with containing boron bakelite resin
It is warming up to cross-linking reaction temperature, curing agent is then added under stiring.
In the present invention, the rate of the stirring is preferably 300r/min~600r/min, and more preferably 400r/min~
500r/min, the time of the stirring are preferably 10~15min, more preferably 13min.
After obtaining mixed liquor, obtained mixed liquor is successively carried out crosslinking curing, filtering and calcination processing by the present invention, is obtained
Hollow beads containing boron bakelite resin.
In the present invention, the crosslinking curing temperature is preferably 80~90 DEG C, and more preferably 85 DEG C；The cured time
Preferably 2~3h, more preferably 2.5h.
It in the present invention, further preferably include that the reaction solution after solidifying successively is cooled down, filtered and forged after the solidification
It burns.
In the present invention, the cooling is preferably cooled to room temperature.The present invention is not particularly limited cooling rate, choosing
With cooling rate well known to those skilled in the art.
The present invention is not particularly limited the method for filtering, selects filter method well known to those skilled in the art.
In the present invention, the calcining preferably includes the first calcining, the second calcining and third calcining.
In the present invention, the temperature of first calcining is preferably 80~110 DEG C, and more preferably 100 DEG C；First calcining
Time is preferably 4~10h, more preferably 6h.The present invention is not particularly limited the heating rate for being warming up to the first calcination temperature,
Select heating rate well known to those skilled in the art.
In the present invention, the temperature of second calcining is preferably 130~150 DEG C, and more preferably 140 DEG C；Second calcining
Time be preferably 2~3h, more preferably 2.5h.The present invention does not have special limit to the heating rate for being warming up to the first calcination temperature
It is fixed, select heating rate well known to those skilled in the art.
In the present invention, the temperature of the third calcining is preferably 170~180 DEG C, and more preferably 175 DEG C；Third calcining
Time be preferably 2~3h, more preferably 2.5h.The present invention does not have special limit to the heating rate for being warming up to the first calcination temperature
It is fixed, select heating rate well known to those skilled in the art.
The present invention removes inner nuclear material by calcining, obtains hollow beads containing boron bakelite resin.
The present invention also provides the hollow beads containing boron bakelite resin that above-mentioned preparation method is prepared, the hollow beads
Shell be containing boron bakelite resin, wall thickness is 7 μm~40 μm, and kernel gas is air, the hollow beads containing boron bakelite resin
Partial size be 0.2mm~1.2mm.
In the present invention, the wall thickness is preferably 10~30 μm, and more preferably 15~20 μm.
In the present invention, the wall thickness is adjusted by additional amount containing boron bakelite resin, and additional amount containing boron bakelite resin is higher,
The wall thickness is bigger.
In the present invention, the partial size containing the hollow beads containing boron bakelite resin is preferably 0.5mm~1.0mm.
In the present invention, the partial size is adjusted by stirring rate, and stirring rate is bigger, and partial size is smaller.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
Raw material:
Method:
Phenol, boric acid are added in the there-necked flask of installation thermometer, condensing unit, agitating device, control temperature 100
DEG C, 6h is reacted, basic catalyst and paraformaldehyde are added at 80 DEG C, can be obtained in 100 DEG C of reaction 6h containing boron bakelite resin.
Then by deionized water, methyl-silicone oil, polyvinyl alcohol be added to synthesis containing in boron bakelite resin, stirring rate control exists
15mins is stirred at room temperature in 500r/min, is uniformly dispersed.PH=1 is adjusted with dilute hydrochloric acid, adds hexa, and will
Temperature rises to 80 DEG C, and after 80 DEG C of reaction 2h, cooling, filtering obtains after 110 DEG C/6hr+130 DEG C/2h+180 DEG C/2h calcining
Hollow beads containing boron bakelite resin.
The performance indicator of the obtained hollow beads containing boron bakelite resin is as follows:
800 DEG C of average grain diameter=280 μm wall thickness=9 μm carbon yield=61.7%
Yield=51% (with the microballon Mass Calculation after drying)
Fig. 1 is the infrared spectrogram of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 1；By scheming
1 it is found that 1360cm-1Place is the stretching vibration absworption peak of B-O key, illustrates to contain in phenolic resin and contains boron element, and is drawn with B-O key
Enter in phenolic resin.
Fig. 2 is the scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin in embodiment 1；
Left figure is the complete scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin, and right figure is broken containing boron bakelite resin
Hollow beads scanning electron microscope (SEM) photograph.
As shown in Figure 2, embodiment 1 prepare the shape of hollow beads containing boron bakelite resin it is largely spherical in shape, sphericity compared with
Good, average grain diameter is 280 μm, and wall thickness is 9 μm.
Fig. 3 is the thermogravimetric curve figure of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 1, by
Known to Fig. 3；Hollow beads containing boron bakelite resin have superior thermal stability in embodiment 1.
Embodiment 2
Raw material:
Method:
Phenol, boric acid are added in the there-necked flask of installation thermometer, condensing unit, agitating device, control temperature 150
DEG C, 4h is reacted, basic catalyst and formaldehyde are added at 80 DEG C, heat preservation 8h can be obtained containing boron bakelite resin.Then will go from
Sub- water, octane, polyacrylic acid be added to synthesis containing in boron bakelite resin, stirring rate control is stirred at room temperature in 400r/min
12mins is mixed, is uniformly dispersed.PH=1 is adjusted with dilute hydrochloric acid, adds triethanolamine, and temperature is risen to 90 DEG C, it is anti-at 90 DEG C
After answering 2h, cooling, filtering obtains hollow beads containing boron bakelite resin after 110 DEG C/6hr+130 DEG C/2h+180 DEG C/2h solidification.
The performance indicator of the obtained hollow beads containing boron bakelite resin is as follows:
800 DEG C of average grain diameter=400 μm wall thickness=18 μm carbon yield=62.1%
Yield=54% (with the microballon Mass Calculation after drying)
Fig. 4 is the infrared spectrogram of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 2, by scheming
4 it is found that 1360cm-1Place is the stretching vibration absworption peak of B-O key, illustrates to contain in phenolic resin and contains boron element, and is drawn with B-O key
Enter in phenolic resin.
Fig. 5 is the scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin in embodiment 2；
Left figure is the complete scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin, and right figure is broken containing boron bakelite resin
Hollow beads scanning electron microscope (SEM) photograph.
As shown in Figure 5, the most of shape spherical in shape of the shape of hollow beads containing boron bakelite resin prepared by embodiment 2, sphericity
Preferably, average grain diameter is 400 μm, and wall thickness is 18 μm.
Fig. 6 is the thermogravimetric curve figure of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 2, by
Known to Fig. 6；Hollow beads containing boron bakelite resin have superior thermal stability in embodiment 2.
Embodiment 3
Raw material:
Method:
Phenol, boric acid are added in the there-necked flask of installation thermometer, condensing unit, agitating device, control temperature 120
DEG C, 5h is reacted, basic catalyst and formaldehyde are added at 80 DEG C, can be obtained in 90 DEG C of reaction 7h containing boron bakelite resin.Then
By deionized water, toluene, hydroxymethyl cellulose be added to synthesis containing in boron bakelite resin, stirring rate is controlled in 320r/
10min is stirred at room temperature in min, is uniformly dispersed.PH=2 is adjusted with dilute hydrochloric acid, adds melamine, and temperature is risen to
90 DEG C, after 90 DEG C of reaction 3h, cooling, filtering is obtained after 110 DEG C/6hr+130 DEG C/2h+180 DEG C/2h solidification containing boron phenolic
Resin hollow beads.
Product performance indicator:
800 DEG C of average grain diameter=800 μm wall thickness=31 μm carbon yield=62.5%
Yield=53% (with the microballon Mass Calculation after drying)
Fig. 7 is the infrared spectrogram of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 3, by scheming
7 it is found that 1360cm-1Place is the stretching vibration absworption peak of B-O key, illustrates to contain in phenolic resin and contains boron element, and is drawn with B-O key
Enter in phenolic resin.
Fig. 8 is the scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin in embodiment 3；
Left figure is the complete scanning electron microscope (SEM) photograph of hollow beads containing boron bakelite resin, and right figure is broken containing boron bakelite resin
Hollow beads scanning electron microscope (SEM) photograph.
As shown in Figure 8, embodiment 2 prepare the shape of hollow beads containing boron bakelite resin it is largely spherical in shape, sphericity compared with
Good, average grain diameter is 800 μm, and wall thickness is 31 μm.
Fig. 9 is the thermogravimetric curve figure of the hollow beads containing boron bakelite resin in phenolic resin microballon and embodiment 3,
As shown in Figure 9；Hollow beads containing boron bakelite resin have superior thermal stability in embodiment 3.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of hollow beads containing boron bakelite resin, comprising the following steps:
1) phenol, boric acid, basic catalyst and formaldehyde are mixed and carries out polycondensation reaction, obtained containing boron bakelite resin；The formaldehyde
It is added in the form of paraformaldehyde or formalin；
2) it is mixed what the step 1) obtained containing boron bakelite resin, inner nuclear material, dispersion stabilizer, amine curing agent and water
To mixed liquor；The inner nuclear material is the oil-based liquid that boiling point is greater than water；
3) mixed liquor that the step 2) obtains successively is subjected to crosslinking curing, filtering, calcination processing are obtained containing boron bakelite resin
Hollow beads.
2. preparation method according to claim 1, which is characterized in that in the step 1) temperature of polycondensation reaction be 80~
100 DEG C, the time of polycondensation reaction is 6~8h.
3. preparation method according to claim 1, which is characterized in that step 1) the neutral and alkali catalyst be NaOH,
NH3·H2O, barium hydroxide and magnesia.
4. preparation method according to any one of claims 1 to 3, which is characterized in that phenol, boric acid in the step 1)
Molar ratio with formaldehyde is 1:0.1~0.25:1.3~2, and basic catalyst dosage is the 0.5%~5.0% of phenol quality.
5. preparation method according to claim 1, which is characterized in that in the step 2) inner nuclear material be octane, nonane,
Decane, toluene, dimethylbenzene or methyl-silicone oil.
6. preparation method according to claim 1, which is characterized in that dispersion stabilizer is polypropylene in the step 2)
Acid, polyvinyl alcohol, hydroxymethyl cellulose or polymethacrylamide.
7. according to claim 1, preparation method described in 5~6 any one, which is characterized in that boracic phenol in the step 2)
Urea formaldehyde, inner nuclear material, dispersion stabilizer, amine curing agent and water amount ratio be 15~25g:8~25g:16g~27g:
1.5~2.5g:100mL.
8. preparation method according to claim 1, which is characterized in that crosslinking curing temperature is 80~90 in the step 3)
DEG C, the time of crosslinking curing is 2~3h, and the pH value of crosslinking curing is 1~2.
9. preparation method according to claim 1, which is characterized in that the calcining in the step 3) successively includes first forging
It burns, the second calcining and third are calcined；
The temperature of first calcining is 80~110 DEG C, and the time of the first calcining is 4~10h；
The temperature of second calcining is 130~150 DEG C, and the time of the second calcining is 2~3h；
The temperature of the third calcining is 170~180 DEG C, and the time of third calcining is 2~3h.
10. the hollow beads containing boron bakelite resin that claim 1~9 any one preparation method obtains, which is characterized in that described
The shell of hollow beads is containing boron bakelite resin, and wall thickness is 7 μm~40 μm, and kernel gas is air, described to contain boron bakelite resin
The partial size of hollow beads is 0.2mm~1.2mm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144052A (en) * | 2019-05-28 | 2019-08-20 | 沙县宏盛塑料有限公司 | A kind of preparation method of the phenolic resin bilayer microballoon of boron cladding |
| CN110144046A (en) * | 2019-05-28 | 2019-08-20 | 沙县宏盛塑料有限公司 | A kind of preparation method of boracic phenolic resin microspheres and carbosphere |
| CN110354768A (en) * | 2019-07-19 | 2019-10-22 | 西北工业大学深圳研究院 | A kind of thermosetting phenolic resin hollow microsphere of silicon boron modification and its preparation method and application |
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| CN110354768A (en) * | 2019-07-19 | 2019-10-22 | 西北工业大学深圳研究院 | A kind of thermosetting phenolic resin hollow microsphere of silicon boron modification and its preparation method and application |
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