CN109749118A - A kind of preparation method of the high flame retardant polyureas aeroge based on ring phosphonitrile - Google Patents
A kind of preparation method of the high flame retardant polyureas aeroge based on ring phosphonitrile Download PDFInfo
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Abstract
The preparation method of the present invention relates to a kind of high flame retardant polyureas aeroge based on ring phosphonitrile.The present invention uses sol-gel process, i.e., using diamine, diisocyanate, six amino-benzene oxygen rings, three phosphonitrile as monomer synthesis of super branched polyurea polymer, forms polyureas wet gel by standing aging, utilize supercritical CO2Dry or freeze-drying method, prepares anti-flammability polyureas aeroge.The features such as present invention is adaptable extensively, reaction process is simple, obtained material has the structure of nano-scale, can be used as elastic conductor, micro-strip paster antenna, catalyst, water-oil separation film, high-performance adsorbent material etc..The present invention has expanded the application range of polyurea materials and aerogel material, improves the value of product, shortens manufacturing cycle, advances the process of its industrialization of marching toward.
Description
Technical field
The invention belongs to aerogel material preparation technical fields, and in particular to a kind of high flame retardant polyureas based on ring phosphonitrile
The preparation method of aeroge belongs to nano-porous materials preparation technical field, may be used as heat-barrier material, acoustic damping materials, fire-retardant
Material and catalyst carrier etc..
Background technique
Aeroge is the nano-porous materials for mutually assembling formation by colloidal particle or the high-polymer molecule, have low-density,
The excellent properties such as high porosity, lower thermal conductivity, high-specific surface area are widely used in heat-and sound-insulating material, catalyst carrier, filtering
The fields such as device.Aeroge divides according to chemical composition can be divided into inorganic aerogels, organic aerogel and inorganic-organic hybrid gas
Gel.The maximum feature that polymeric aerogels are different from inorganic aerogels is that polymer has flexible MOLECULE DESIGN, this makes
The performance for obtaining polymeric aerogels becomes to be easier to be controlled by people, can obtain more performances by the MOLECULE DESIGN of diversification
Diversification product.
1994, De VosR (US, 5484818 [P]) prepared polyureas aeroge for the first time, with outstanding mechanical property
It can be used widely with thermal stability and its unique porous structure in fields such as heat-insulated, sound insulating material, radiation shields.Je
(J Sol-Gel Sci Technol, 2008,49 (2): being 209) hard by presoma, polyamine of isocyanates to Kyun Lee etc.
Agent, triethylamine (TEA) are catalyst, obtain PUA wet gel under normal temperature and pressure conditions for the first time, then carry out supercritical CO2
It is dry, the PUA aeroge of high porosity, lower thermal conductivity (0.013 W/ (mK)), heat resistance good (~ 270 °C) is obtained, and
Polyureas aerogel heat-proof performance is studied.
However, most of polyureas aeroges are hydrocarbon organic structures, belong to inflammable or combustible material, the heat release rate in burning
Greatly, calorific value height, flame propagation speed, be not easy to extinguish, produce thick smoke and toxic gas etc., human life's safety and environment are protected
Shield constitutes potential threaten.
Summary of the invention
The preparation of the technical problem to be solved in the present invention is to provide a kind of high flame retardant polyureas aeroge based on ring phosphonitrile
Method, with solve the problems, such as traditional polyureas aerogel material poor fire, mechanical performance it is bad, using being restricted,
To solve, a kind of the technical solution adopted by the present invention are as follows: high flame retardant polyureas based on ring phosphonitrile
The preparation method of aeroge, specifically includes the following steps:
(1) under atmosphere of inert gases, diamine monomer and diisocyanate are dissolved in aprotic polar solvent, controlled
Solid content is 20% ~ 40%, and catalyst of triethylamine is added, and is stirred 2 ~ 8 hours at 15 ~ 50 °C, and obtaining isocyanates is end group
Polyureas oligomer solution A；
(2) six amino-benzene oxygen rings, three phosphonitrile monomer is added in the polyureas oligomer solution A in step (1), stirring 4 ~ 10 is small
When, add aprotic polar solvent in due course to keep the solid content of reaction system 5 ~ 10%, stand 24 under 15 ~ 50 °C ~
Polyureas wet gel B is obtained after 48 hours；
(3) the polyureas wet gel B in step (2) is used into supercritical CO2Dry or freeze-drying method, obtains polyureas gas
Gel.
Inert gas of the present invention is preferably any one in nitrogen or argon gas.
Diamine monomer of the present invention is preferred are as follows:
(PDA)、(ODA)、(BPA)、(SDA)、(DDS)、
(DDB)、(DADB)、
(DDBB)、(DDBZ)、
(DDBA)、(FDDB)、(FDDBB)、(FABA)、
(FBZ)、(FOBA) any one in.
Aprotic polar solvent of the present invention is preferably N,N-dimethylformamide (DMF), N, N- dimethyl second
Amide (DMAc), N-Methyl pyrrolidone (NMP), any one in dimethyl sulfoxide (DMSO).
Diisocyanate of the present invention is preferred are as follows:
(2,4-TDI),(2,6-TDI),(MDI),(HDI),(HMDI),(IPDI)
In any one.
Six amino-benzene oxygens ring, three phosphonitrile monomer of the present invention is preferred are as follows:
Diisocyanate of the present invention: aromatic diamine: six amino-benzene oxygen rings, three phosphonitrile: the molar ratio of triethylamine is preferably
(n+1): n:2/6 ~ (2/6) * 3:2 (n+1)/3 ~ 2 (n+1), wherein n is the arbitrary integer in 5 ~ 30.
Supercritical CO of the present invention2Drying means, step are using non-proton in acetone displacement polyureas wet gel
Property polar solvent, then utilize supercritical CO2Drying mode removes acetone, obtains polyureas aeroge.
Freeze-drying method of the present invention, step are to utilize the tert-butyl alcohol and methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, third
Aprotic polar solvent and catalyst in the mixed solvent M displacement polyureas wet gel of ketone and water finally use the pure of the tert-butyl alcohol
Solvent carries out solvent and replaces to obtain the polyureas wet gel using the tert-butyl alcohol as solvent, is dried and is gathered between -50 ~ 20 °C
Urea aeroge, wherein the volume fraction of the tert-butyl alcohol is 0% ~ 100% in mixed solvent M.
The present invention assigns polyureas phosphorus-nitrogen cooperative flame retardant effect, passes through using six amino-benzene oxygen rings, three phosphonitrile monomer as raw material
Supercritical CO_2 drying technology or freeze-drying prepare anti-flammability polyureas aeroge, it has lightweight, heat-insulated, fire-retardant, mechanicalness
The excellent feature of energy.
The present invention is applied widely, low in cost, reaction time is short, low-density, the high flame retardant of possible industry amplification are poly-
Urea aeroge and preparation method thereof.Its basic ideas is the polyureas oligomer generated using diamine and diisocyanate, then
Polyureas wet gel is obtained after adding six amino-benzene oxygen rings, three phosphonitrile, then passes through supercritical CO2Dry or freeze drying process
Polyureas aeroge is obtained, can be used as novel heat-insulated, sound insulation, fire-retardant, catalyst carrier material.
The features such as present invention is adaptable extensively, reaction process is simple, obtained material has the knot of nano-scale
Structure can be used as elastic conductor, micro-strip paster antenna, catalyst, water-oil separation film, high-performance adsorbent material etc..The present invention expands
The application range of polyurea materials and aerogel material, improves the value of product, shortens manufacturing cycle, advance it and march toward
The process of industrialization.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph of embodiment sample；
Fig. 2 is the Fourier Transform Infrared Spectroscopy figure of embodiment sample.By attached drawing 2 it is found that in 2246 cm-1Neighbouring isocyanic acid
Ester group characteristic absorption peak completely disappears, and shows that reaction is very complete.In the uptake zone N-H (3200 ~ 3500 cm-1) ' observe 3292
cm-1The N-H stretching vibration absworption peak of neighbouring hydrogen bond association, 1638 cm-1Absorption peak belongs to the flexible vibration of hydrogen bond association allophanyl
Dynamic peak, in 1512 cm-1The bands of a spectrum at place are the characteristic peaks of HN-CO-NH.According to the presence of these characteristic peaks, it was demonstrated that sample has
The feature structure of aromatic polyureas.On the other hand, in 1182 cm-1For the absorption peak of P=N, 1277 cm-1For P-N absorption
Peak, both for the characteristic peak of ring phosphonitrile.
Specific embodiment
Below in conjunction with examples of implementation, the present invention is described in further detail, and cannot understand and protect model to the present invention
The limitation enclosed.
Embodiment 1
Under nitrogen atmosphere, PDA (0.540 g, 5 mmol) and 2,4-TDI (1.044 g, 6 mmol) are dissolved in DMF, are controlled
Solid content processed is 20%, is added catalyst of triethylamine (0.404 g, 4 mmol), stirs 2 hours under 15 °C, obtain isocyanates
For the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile monomer is added in polyureas oligomer solution A
(0.258 g, 0.33 mmol) stirs 4 hours, adds DMF in due course to keep the solid content of reaction system 5%, under 15 °C
Polyureas wet gel B is obtained after standing 24 hours；It carries out 3 solvents to polyureas wet gel B with acetone to replace, 8 hours every time, most
After carry out supercritical CO2It is dry, obtain polyureas aeroge.The limit oxygen index of gained polyureas aeroge is 52%, density 0.10
g/cm3, specific surface area is 352 m2/ g, thermal conductivity are 0.018 W/ (mK).
Embodiment 2
Under nitrogen atmosphere, PDA (3.240 g, 30 mmol) and 2,4-TDI (5.394 g, 31 mmol) are dissolved in DMAc,
Controlling solid content is 40%, is added catalyst of triethylamine (2.121 g, 21 mmol), stirs 8 hours under 50 °C, obtain isocyanide
Acid esters is the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile list is added in polyureas oligomer solution A
Body (0.783 g, 1 mmol) stirs 10 hours, adds DMAc in due course to keep the solid content of reaction system 10%, at 50 °C
Lower standing obtained polyureas wet gel B after 48 hours；It is displacement polyureas wet gel B with the mixed solvent of the tert-butyl alcohol and methanol, wherein
The volume fraction of the tert-butyl alcohol is 0 ~ 100%, then using the tert-butyl alcohol as solvent displacement wet gel, obtain for the polyureas of t-butanol solvent it is wet
Gel is freeze-dried under -50 °C, obtains urea aeroge.The limit oxygen index of gained polyureas aeroge is 52%, density
For 0.12 g/cm3, specific surface area is 331 m2/ g, thermal conductivity are 0.023 W/ (mK).
Embodiment 3
Under nitrogen atmosphere, ODA (1.000 g, 5 mmol) and 2,4-TDI (1.044 g, 6 mmol) are dissolved in DMF, are controlled
Solid content processed is 20%, is added catalyst of triethylamine (1.121 g, 12 mmol), stirs 2 hours under 15 °C, obtain isocyanic acid
Ester is the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile monomer is added in polyureas oligomer solution A
(0.258 g, 0.33 mmol) stirs 4 hours, adds DMF in due course to keep the solid content of reaction system 5%, under 15 °C
Polyureas wet gel B is obtained after standing 24 hours；It carries out 3 solvents to polyureas wet gel B with acetone to replace, 8 hours every time, most
After carry out supercritical CO2It is dry, obtain polyureas aeroge.The limit oxygen index of gained polyureas aeroge is 51%, density 0.13
g/cm3, specific surface area is 363 m2/ g, thermal conductivity are 0.021 W/ (mK).
Embodiment 4
Under nitrogen atmosphere, BPA (5.520 g, 30 mmol) and 2,6-TDI (5.394 g, 31 mmol) are dissolved in NMP,
Controlling solid content is 40%, is added catalyst of triethylamine (6.262 g, 62 mmol), stirs 2 hours under 50 °C, obtain isocyanide
Acid esters is the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile list is added in polyureas oligomer solution A
Body (0.783 g, 1 mmol) stirs 10 hours, adds NMP in due course to keep the solid content of reaction system 10%, at 50 °C
Lower standing obtained polyureas wet gel B after 48 hours；It is displacement polyureas wet gel B with the mixed solvent of the tert-butyl alcohol and ethyl alcohol, wherein
The volume fraction of the tert-butyl alcohol is 0 ~ 100%, then using the tert-butyl alcohol as solvent displacement wet gel, obtain for the polyureas of t-butanol solvent it is wet
Gel is freeze-dried under -50 °C, obtains polyureas aeroge.The limit oxygen index of gained polyureas aeroge is 50%, close
Degree is 0.11 g/cm3, specific surface area is 332 m2/ g, thermal conductivity are 0.023 W/ (mK).
Embodiment 5
Under nitrogen atmosphere, SDA (1.080 g, 5 mmol) and 2,6-TDI (1.044 g, 6 mmol) are dissolved in NMP, are controlled
Solid content processed is 20%, is added catalyst of triethylamine (0.404 g, 4 mmol), stirs 2 hours under 15 °C, obtain isocyanates
For the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile monomer is added in polyureas oligomer solution A
(0.258 g, 0.33 mmol) stirs 4 hours, adds NMP in due course to keep the solid content of reaction system 5%, under 15 °C
Polyureas wet gel B is obtained after standing 24 hours；It carries out 3 solvents to polyureas wet gel B with acetone to replace, 8 hours every time, most
After carry out supercritical CO2It is dry, obtain polyureas aeroge.The limit oxygen index of gained polyureas aeroge is 54, density 0.012
g/cm3, specific surface area is 361 m2/ g, thermal conductivity are 0.023 W/ (mK).
Embodiment 6
Under nitrogen atmosphere, DDS (7.440 g, 30 mmol) and MDI (7.750 g, 31 mmol) are dissolved in DMSO, are controlled
Solid content is 40%, is added catalyst of triethylamine (6.262 g, 62 mmol), stirs 8 hours under 50 °C, obtain isocyanates
For the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile monomer is added in polyureas oligomer solution A
(0.783 g, 1 mmol) stirs 10 hours, adds DMSO in due course to keep the solid content of reaction system 10%, under 50 °C
Polyureas wet gel B is obtained after standing 48 hours；It is displacement polyureas wet gel B with the mixed solvent of the tert-butyl alcohol and 1- propyl alcohol, wherein
The volume fraction of the tert-butyl alcohol is 0 ~ 100%, then using the tert-butyl alcohol as solvent displacement wet gel, obtain for the polyureas of t-butanol solvent it is wet
Gel is freeze-dried under 20 °C, obtains polyureas aeroge.
Embodiment 7
Under argon atmosphere, DDB (1.460 g, 5 mmol) and HDI (1.008 g, 6 mmol) are dissolved in NMP, control is solid
Content is 20%, is added catalyst of triethylamine (1.121 g, 12 mmol), stirs 2 hours under 15 °C, obtaining isocyanates is
The polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile monomer is added in polyureas oligomer solution A
(0.258 g, 0.33 mmol) stirs 4 hours, adds aprotic polar solvent in due course to keep the solid content of reaction system
5%, polyureas wet gel B is obtained after standing 24 hours under 15 °C；3 solvent replacements are carried out to polyureas wet gel B with acetone,
8 hours every time, finally carry out supercritical CO2It is dry, obtain polyureas aeroge.
Embodiment 8
Under argon atmosphere, DADB (11.040 g, 30 mmol) and HMDI (8.112 g, 31 mmol) are dissolved in DMSO,
Controlling solid content is 40%, is added catalyst of triethylamine (2.121 g, 21 mmol), stirs 2 hours under 50 °C, obtain isocyanide
Acid esters is the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile list is added in polyureas oligomer solution A
Body (0.783 g, 1 mmol) stirs 10 hours, adds DMSO in due course to keep the solid content of reaction system 10%, at 50 °C
Lower standing obtained polyureas wet gel B after 48 hours；It is displacement polyureas wet gel B with the mixed solvent of the tert-butyl alcohol and 2- propyl alcohol,
The volume fraction of the middle tert-butyl alcohol is 0 ~ 100%, then using the tert-butyl alcohol as solvent displacement wet gel, obtains the polyureas for t-butanol solvent
Wet gel is freeze-dried under 20 °C, obtains polyureas aeroge.
Embodiment 9
Under argon atmosphere, DDBB (2.590 g, 5 mmol) and HMDI (1.572 g, 6 mmol) are dissolved in NMP, are controlled
Solid content is 20%, is added catalyst of triethylamine (1.121 g, 12 mmol), stirs 2 hours under 15 °C, obtain isocyanates
For the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile monomer is added in polyureas oligomer solution A
(0.258 g, 0.33 mmol) stirs 4 hours, adds NMP in due course to keep the solid content of reaction system 5%, under 15 °C
Polyureas wet gel B is obtained after standing 24 hours；It carries out 3 solvents to polyureas wet gel B with acetone to replace, 8 hours every time, most
After carry out supercritical CO2It is dry, obtain polyureas aeroge.
Embodiment 10
Under argon atmosphere, DDBZ (1.980 g, 5 mmol) and HMDI (1.572 g, 6 mmol) are dissolved in NMP, are controlled
Solid content is 20%, is added catalyst of triethylamine (0.404 g, 4 mmol), stirs 2 hours under 15 °C, obtaining isocyanates is
The polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile monomer is added in polyureas oligomer solution A
(0.258 g, 0.33 mmol) stirs 4 hours, adds NMP in due course to keep the solid content of reaction system 5%, under 15 °C
Polyureas wet gel B is obtained after standing 24 hours；It carries out 3 solvents to polyureas wet gel B with acetone to replace, 8 hours every time, most
After carry out supercritical CO2It is dry, obtain polyureas aeroge.
Embodiment 11
Under argon atmosphere, DDBA (12.300 g, 30 mmol) and IPDI (6.882 g, 31 mmol) are dissolved in DMSO,
Controlling solid content is 40%, is added catalyst of triethylamine (2.121 g, 21 mmol), stirs 8 hours under 50 °C, obtain isocyanide
Acid esters is the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile list is added in polyureas oligomer solution A
Body (0.783 g, 1 mmol) stirs 10 hours, adds DMSO in due course to keep the solid content of reaction system 10%, at 50 °C
Lower standing obtained polyureas wet gel B after 48 hours；It is displacement polyureas wet gel B with the mixed solvent of the tert-butyl alcohol and 2- propyl alcohol,
The volume fraction of the middle tert-butyl alcohol is 0 ~ 100%, then using the tert-butyl alcohol as solvent displacement wet gel, obtains the polyureas for t-butanol solvent
Wet gel is freeze-dried under 20 °C, obtains polyureas aeroge.
Embodiment 12
Under argon atmosphere, FDDB (2.140 g, 5 mmol) and IPDI (1.332 g, 6 mmol) are dissolved in NMP, are controlled
Solid content is 20%, is added catalyst of triethylamine (1.121 g, 12 mmol), stirs 2 hours under 15 °C, obtain isocyanates
For the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile monomer is added in polyureas oligomer solution A
(0.258 g, 0.33 mmol) stirs 4 hours, adds NMP in due course to keep the solid content of reaction system 5%, under 15 °C
Polyureas wet gel B is obtained after standing 24 hours；It carries out 3 solvents to polyureas wet gel B with acetone to replace, 8 hours every time, most
After carry out supercritical CO2It is dry, obtain polyureas aeroge.
Embodiment 13
Under argon atmosphere, FDDBB (15.120 g, 30 mmol) and 2,4-TDI (5.394 g, 31 mmol) are dissolved in DMSO
In, control solid content is 40%, is added catalyst of triethylamine (6.262 g, 62 mmol), stirs 2 hours, obtain under 50 °C
Isocyanates is the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphorus is added in polyureas oligomer solution A
Nitrile monomer (0.783 g, 1 mmol) stirs 8 hours, adds DMSO in due course to keep the solid content of reaction system 10%, 50
Polyureas wet gel B is obtained after standing 48 hours under °C；It is displacement polyureas wet gel B with the mixed solvent of the tert-butyl alcohol and acetone,
The volume fraction of the middle tert-butyl alcohol is 0 ~ 100%, then using the tert-butyl alcohol as solvent displacement wet gel, obtains the polyureas for t-butanol solvent
Wet gel is freeze-dried under 20 °C, obtains polyureas aeroge.
Embodiment 14
Under argon atmosphere, FABA (3.270 g, 5 mmol) and 2,4-TDI (1.044 g, 6 mmol) are dissolved in NMP,
Controlling solid content is 20%, is added catalyst of triethylamine (1.121 g, 12 mmol), and addition catalyst of triethylamine (0.404 g, 4
Mmol), stirred 2 hours under 15 °C, obtain the polyureas oligomer solution A that isocyanates is end group；In polyureas oligomer
It is added in solution A six amino-benzene oxygen rings, three phosphonitrile monomer (0.258 g, 0.33 mmol), stirs 4 hours, add NMP in due course
To keep the solid content of reaction system 5%, polyureas wet gel B is obtained after standing 24 hours under 15 °C；With acetone to polyureas
Wet gel B carries out 3 solvent replacements, 8 hours every time, finally carries out supercritical CO2It is dry, obtain polyureas aeroge.
Embodiment 15
Under argon atmosphere, FBZ (15.960 g, 30 mmol) and 2,4-TDI (5.394 g, 31 mmol) are dissolved in DMSO
In, control solid content is 40%, is added catalyst of triethylamine (2.121 g, 21 mmol), stirs 2 hours, obtain under 50 °C
Isocyanates is the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphorus is added in polyureas oligomer solution A
Nitrile monomer (0.783 g, 1 mmol) stirs 8 hours, adds DMSO in due course to keep the solid content of reaction system 10%, 50
Polyureas wet gel B is obtained after standing 48 hours under °C；It is displacement polyureas wet gel B with the mixed solvent of the tert-butyl alcohol and acetone,
The volume fraction of the middle tert-butyl alcohol is 0 ~ 100%, then using the tert-butyl alcohol as solvent displacement wet gel, obtains the polyureas for t-butanol solvent
Wet gel is freeze-dried under 20 °C, obtains polyureas aeroge.
Embodiment 16
Under argon atmosphere, FOBA (2.730 g, 5 mmol) and 2,4-TDI (1.044 g, 6 mmol) are dissolved in NMP,
Controlling solid content is 20%, is added catalyst of triethylamine (1.121 g, 12 mmol), stirs 2 hours under 15 °C, obtain isocyanide
Acid esters is the polyureas oligomer solution A of end group；Six amino-benzene oxygen rings, three phosphonitrile list is added in polyureas oligomer solution A
Body (0.258 g, 0.33 mmol) stirs 4 hours, adds NMP in due course to keep the solid content of reaction system 5%, at 15 °C
Lower standing obtained polyureas wet gel B after 24 hours；It carries out 3 solvents to polyureas wet gel B with acetone to replace, 8 hours every time,
Finally carry out supercritical CO2It is dry, obtain polyureas aeroge.
Claims (8)
1. a kind of preparation method of the high flame retardant polyureas aeroge based on ring phosphonitrile, specifically includes the following steps:
(1) under atmosphere of inert gases, diamine monomer and diisocyanate are dissolved in aprotic polar solvent, controlled
Solid content is 20 ~ 40%, and catalyst of triethylamine is added, stirs 2 ~ 8 hours under 15 ~ 50 °C, and obtaining isocyanates is terminal groups
The polyureas oligomer solution A of group；
(2) six amino-benzene oxygen rings, three phosphonitrile monomer is added in the polyureas oligomer solution A in step (1), stirring 4 ~ 10 is small
When, add aprotic polar solvent in due course to keep the solid content of reaction system 5 ~ 10%, stand 24 under 15 ~ 50 °C ~
Polyureas wet gel B is obtained after 48 hours；
(3) the polyureas wet gel B in step (2) is used into supercritical CO2Dry or freeze-drying method, obtains polyureas airsetting
Glue.
2. according to the method described in claim 1, it is characterized by: the inert gas is any one in nitrogen or argon gas
Kind.
3. according to the method described in claim 1, it is characterized by: the diamine is
(PDA)、(ODA)、(BPA)、(SDA)、(DDS)、
(DDB)、(DADB)、
(DDBB)、(DDBZ)、
(DDBA)、(FDDB)、(FDDBB)、(FABA)、
(FBZ)、(FOBA) any one in.
4. according to the method described in claim 1, it is characterized by: aprotic polar solvent in the step (1) is N,
Dinethylformamide DMF, DMAC N,N' dimethyl acetamide DMAc, N-Methyl pyrrolidone NMP, appointing in dimethyl sulfoxide DMSO
It anticipates one kind.
5. according to the method described in claim 1, it is characterized by: the diisocyanate in the step (2) is
(2,4-TDI),(2,6-TDI),(HDI),(HMDI),(IPDI),(MDI) appointing in
It anticipates one kind.
6. according to the method described in claim 1, it is characterized by: six amino-benzene oxygen rings, three phosphonitrile in the step (2)
Monomer is
。
7. according to the method described in claim 1, it is characterized by: supercritical CO in the step (3)2Drying means step is
Using the aprotic polar solvent in acetone displacement polyureas wet gel, supercritical CO is then utilized2Drying mode removes acetone,
Obtain polyureas aeroge.
8. according to the method described in claim 1, it is characterized by: freeze-drying method step is to utilize in the step (3)
The tert-butyl alcohol and the aprotic in the mixed solvent M displacement polyureas wet gel of methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, acetone and water
Polar solvent and catalyst, finally with the pure solvent of the tert-butyl alcohol carry out solvent replace to obtain it is wet solidifying by the polyureas of solvent of the tert-butyl alcohol
Glue is dried to obtain polyureas aeroge between -50 DEG C ~ 20 DEG C, wherein the volume fraction of the tert-butyl alcohol is in mixed solvent M
0%~100%。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110872370A (en) * | 2019-12-05 | 2020-03-10 | 齐鲁工业大学 | Application of low-phosphorus cross-linking agent in preparation of polyurethane film |
| CN113583177A (en) * | 2021-08-17 | 2021-11-02 | 安徽天润化学工业股份有限公司 | Preparation method and application of temperature-resistant and salt-resistant six-arm star polyacrylamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113583177A (en) * | 2021-08-17 | 2021-11-02 | 安徽天润化学工业股份有限公司 | Preparation method and application of temperature-resistant and salt-resistant six-arm star polyacrylamide |
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