CN107501494A - A kind of phosphorous covalently organic frame nanometer sheet and preparation method thereof - Google Patents
A kind of phosphorous covalently organic frame nanometer sheet and preparation method thereof Download PDFInfo
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- CN107501494A CN107501494A CN201710849408.XA CN201710849408A CN107501494A CN 107501494 A CN107501494 A CN 107501494A CN 201710849408 A CN201710849408 A CN 201710849408A CN 107501494 A CN107501494 A CN 107501494A
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a kind of phosphorous covalently organic frame nanometer sheet and preparation method thereof, wherein phosphorous covalently organic frame nanometer sheet, it is characterised in that its general structure is as follows：Wherein, Z is phosphor-containing structure.The present invention is carried out organically-modified using phosphorus-containing compound to melamine/OPA COFs nanometer sheets so that COFs nanometer sheets can not only more highly effective flame-retardant epoxy resin, and can also improve the mechanical property of epoxy resin.
Description
Technical field
The present invention relates to a kind of phosphorous covalently organic frame nanometer sheet and preparation method thereof, belong to high polymer material technology neck
Domain.
Background technology
Covalent organic frame (Covalent Organic Frameworks:COFs) be passed through by organic structure ele it is strong
The two-dimentional or three-dimensional crystalline, porous material that covalent key connection is formed.Because it is special with the completely different structure of traditional organic material
Point, COFs are widely used in gas storage and separation, catalysis, chemical sensor, electrochemistry and clean energy resource aspect.While by
There is the three-layer laminated structure of class graphite in COFs, many scholars in the whole world are being directed to preparing COFs nanometer sheets now.
Xuan-He Liu in 2014 etc. exist《Small》4934-4939 pages of volume 10 is published on high starch breeding and prepares
COFs nanometer sheets.RyotaTanoue in 2011 etc. exists《ACS Nano》3923-3929 pages of volume 5 is published in self-control monocrystalline and makes
Golden face on prepare COFs nanometer sheets.But above-mentioned preparation process is complicated, yields poorly, raw material are also costly, greatly limit
Application of the COFs nanometer sheets in high molecule plastic is made.Melamine and adjacent benzene have been successfully prepared by ball-milling method at present
The COFs nanometer sheets of diformazan aldehyde radical, it is a certain degree of to solve above mentioned problem.It is but phosphorous with fire resistance on preparing
COFs nanometer sheets are rarely reported.Therefore, the preparation method for exploring the COFs nanometer sheets of the synthesis organic functional of cheap and simple is compeled
In the eyebrows and eyelashes.
The content of the invention
The present invention is intended to provide a kind of phosphorous covalently organic frame nanometer sheet and preparation method thereof, with melamine/adjacent benzene
Based on dicarbaldehyde COFs nanometer sheets, the organically-modified COFs nanometer sheets of novel phosphorus-containing are developed, it is retained script COFs materials
Possesses fire resistance while advantage.
The present invention phosphorous covalently organic frame nanometer sheet, its general structure is as follows：
Wherein, Z is phosphor-containing structure, specifically includes following structure：
The preparation method of the phosphorous covalently organic frame nanometer sheet of the present invention, comprises the following steps：
Step 1：The dimethyl sulfoxide solution (100ml) of the melamine containing 2.02g is added into the single-necked flask equipped with magneton,
Then the dimethyl sulfoxide solution (10ml) and aqueous acetic acid (40ml, 3M) of the OPA containing 3.22g are sequentially added, by single port
Flask vacuumizes, and is reacted 3 days under 135 DEG C, 0.1MPa, obtains COFs materials；
Step 2：The COFs materials that step 1 is obtained are scattered in a solvent, with 225rpm rotating speed wet method in ball mill
Ball milling 24 hours, upper strata suspension, as COFs nanometer sheets suspension are collected after centrifugation；
Step 3：Phosphorus-containing compound solution is added dropwise in the COFs nanometer sheet suspension that step 2 obtains, at 100-180 DEG C
React 12-24 hours, reaction centrifuges after terminating, and washs, obtains phosphorous COFs nanometer sheets.
In step 2, the solvent be selected from ethanol, chloroform, DMF (DMF), dioxane, tetrahydrofuran,
Acetone or dimethyl sulfoxide.
In step 2, the rotating speed of centrifugation is 3000-8000rpm.
In step 2, the concentration of COFs nanometer sheets suspension is 0.2-1wt% after ball milling.
In step 3, phosphorus-containing compound is with being 1 with the mass ratio of COFs nanometer sheets:1-10:1.
In step 3, the phosphorus-containing compound is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), Asia
Diethyl phosphate, dimethylphosphite, dibutyl phosphite, diphenyl phosphite or dialkyl phosphite.It is described to contain phosphatization
Polymer solution solvent for use is methanol, ethanol, ether, chloroform, N, N-dimethylformamide or dioxane.The phosphorous chemical combination
The concentration of thing solution is 0.2-2mol/L.
In step 3, the rotating speed of centrifugation is 1500-8000rpm；Solvent for use is methanol, tetrahydrofuran, third during washing
One or more in ketone, dichloromethane.
Compared with prior art, beneficial effects of the present invention are embodied in：
If the 1, above-mentioned phosphorus-containing compound is directly added into epoxy resin and carries out in-situ polymerization, the crosslinking that can reduce epoxy resin is close
Degree, damage the mechanical performance of epoxy resin.The present invention is received using above-mentioned phosphorus-containing compound to melamine/OPA COFs
Rice piece carries out organically-modified so that COFs nanometer sheets can not only more highly effective flame-retardant epoxy resin, and can also improve asphalt mixtures modified by epoxy resin
The mechanical property of fat.
2nd, COFs of the present invention is prepared easy, and raw material is easy to get, and greatly reduces COFs cost of manufacture.
3rd, the phosphorous COFs nanometer sheets synthesis technique that prepared by the present invention is simple, and the phosphorus-containing compound of reaction is participated in by adjusting
Content and species, can effectively adjust the phosphorus content of obtained modification COFs materials, be provided to be further organically-modified
May.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of DOPO-COFs nanometer sheets in embodiment 1.
Fig. 2 is the x-ray photoelectron energy spectrum diagram of DOPO-COFs nanometer sheets in embodiment 1.
Fig. 3 is DOPO-COFs nanometer sheet transmission electron microscope photos in embodiment 1.
Fig. 4 is the heat release rate curve of the epoxy resin of embodiment 6 and its nano composite material.
Fig. 5 is the dynamic mechanical analysis curve of the epoxy resin of embodiment 6 and its nano composite material.
Embodiment
Technical scheme is described in further detail below in conjunction with accompanying drawing and specific embodiment.
Embodiment 1：The preparation of COFs nanometer sheets
1st, the dimethyl sulfoxide solution 100ml, Ran Houyi of the melamine containing 2.02g are added into the single-necked flask equipped with magneton
The secondary dimethyl sulfoxide solution 10ml and aqueous acetic acid (40ml, 3M) for adding the OPA containing 3.22g, single-necked flask is taken out very
Sky, reacted 3 days under 135 DEG C, 0.1MPa, obtain COFs materials；
2nd, the COFs materials that step 1 obtains are dispersed in DMF, turned in ball mill with 225rpm
Fast wet ball grinding 24 hours, upper strata suspension, as COFs nanometer sheets suspension are collected after centrifugation.
Embodiment 2：The preparation of DOPO-COFs nanometer sheets
4.6g DOPO are dissolved in DMF, are then added drop-wise to 200g 0.2wt%'s at 130 DEG C
In COFs nanometer sheet suspension, reacted 12 hours after completion of dropwise addition；Reaction centrifuges reaction solution 10 points at 1500 rpm after terminating
Clock, supernatant liquid is filtered, products therefrom is washed successively with acetone, chloroform, methanol, obtains DOPO-COFs nanometer sheets.
Fig. 1 is the infrared spectrogram of DOPO-COFs nanometer sheets in embodiment 1.In COFs infrared spectrum, 3401,
1726 and 1350cm-1The peak at place is aromatic ring stretching vibration respectively, unreacted aldehyde radical stretching vibration and-NH- stretching vibrations.COFs
In 1209 and 810cm-1The key at place is the aromatics stretching vibration of C-N keys.In DOPO infrared spectrum, in 2437,1143 Hes
1117cm-1The peak at place corresponds respectively to the stretching vibration of P-H keys, P=O stretching vibrations and P-O-Ph stretching vibrations.In DOPO-
In the infrared spectrum of COFs nanometer sheets, P-H is disappeared, and illustrates that DOPO and COFs nanometer sheets are reacted.DOPO-COFs simultaneously
P=O keys and P-O-Ph keys are found that in the infared spectrum of nanometer sheet, illustrates to successfully synthesize DOPO-COFs nanometer sheets.
Fig. 2 is the x-ray photoelectron energy spectrum diagram of DOPO-COFs nanometer sheets in embodiment 1.The DOPO-COFs nanometers measured
The phosphorus content of piece is 0.69at%, and the DOPO of load accounts for the 11.6wt% of total DOPO-COFs nanometers tablet quality.Also illustrate simultaneously
DOPO-COFs nanometer sheets synthesize successfully.
Fig. 3 is DOPO-COFs nanometer sheet transmission electron microscope photos in embodiment 1.As can be seen from the figure come, DOPO-COFs
The size of nanometer sheet is probably hundreds of nanometers to several microns.
Embodiment 3：The preparation of phosphorous COFs nanometer sheets
0.4g diethyl phosphites are dissolved in dioxane, are then added drop-wise to 200g 0.5wt%'s at 180 DEG C
In COFs nanometer sheet suspension, reacted 18 hours after completion of dropwise addition；Reaction centrifuges reaction solution 10 points at 3,000 rpm after terminating
Clock, supernatant liquid is filtered, products therefrom is washed successively with acetone, chloroform, methanol, obtains phosphorous COFs nanometer sheets.
Embodiment 4：The preparation of phosphorous COFs nanometer sheets
20g dibutyl phosphites are dissolved in DMF, are then added drop-wise to 200g at 100 DEG C
In 0.1wt% COFs nanometer sheet suspension, reacted 24 hours after completion of dropwise addition；React reaction solution after terminating in 8000rpm
Lower centrifugation 10 minutes, supernatant liquid is filtered, products therefrom is washed, obtains phosphorous COFs nanometers successively with acetone, chloroform, methanol
Piece.
Embodiment 5：The preparation of phosphorous COFs nanometer sheets
2g diphenyl phosphites are dissolved in DMF, 200g 0.5wt% are then added drop-wise at 160 DEG C
COFs nanometer sheet suspension in, reacted 12 hours after completion of dropwise addition；React and reaction solution is centrifuged 10 under 4000rpm after terminating
Minute, supernatant liquid is filtered, products therefrom is washed successively with acetone, chloroform, methanol, obtains phosphorous COFs nanometer sheets.
Embodiment 6：The preparation of phosphorous COFs nanometer sheets
6g DOPO are dissolved in dioxane, the COFs nanometer sheets that 200g 0.5wt% are then added drop-wise at 145 DEG C are hanged
In supernatant liquid, reacted 15 hours after completion of dropwise addition；Reaction centrifuges reaction solution 10 minutes at 3,000 rpm after terminating, by upper liquid
Body is filtered, and products therefrom is washed successively with acetone, chloroform, methanol, obtains phosphorous COFs nanometer sheets.
Embodiment 7：Performance comparision
By 1.6g DOPO-COFs nanometer sheets, 0.186g DOPO and 1.414g COFs (DOPO：COFs=11.6：
88.4), 1.6g COFs nanometer sheets distinguish ultrasonic disperse in 50ml tetrahydrofuran solutions, are then respectively adding 40g epoxy resin
In, mechanical agitation is finally separately added into 8.4g MDAs in 8 hours to remove tetrahydrofuran at 80 DEG C, at 100 DEG C
With 150 DEG C at be incubated 2h respectively.Obtained epoxide resin nano compound is subjected to taper calorimetric and dynamic mechanical analysis test, ground
Study carefully its burning behavior and mechanical property.
Fig. 4 is the heat release rate curve of the epoxy resin of embodiment 6 and its nano composite material.Add 3.2wt%
The HRR peak value of epoxy resin reduces by 18.4% after DOPO-COFs nanometer sheets.Compared with control sample, HRR peak
Value is also decreased obviously.The DOPO-COFs nanometer sheets for illustrating to prepare possess fire resistance.
Fig. 5 is the dynamic mechanical analysis result of the epoxy resin of embodiment 6 and its nano composite material.It is obvious that add
After DOPO-COFs nanometer sheets, the mechanics ability of epoxy resin significantly improves.
Claims (10)
1. a kind of phosphorous covalently organic frame nanometer sheet, it is characterised in that its general structure is as follows：
Wherein, Z is phosphor-containing structure.
2. phosphorous covalently organic frame nanometer sheet according to claim 1, it is characterised in that Z specifically includes following structure：
3. the preparation method of the phosphorous covalently organic frame nanometer sheet described in a kind of claim 1, it is characterised in that including as follows
Step：
Step 1：The dimethyl sulfoxide solution of the melamine containing 2.02g is added into the single-necked flask equipped with magneton, is then added successively
Dimethyl sulfoxide solution and the concentration for entering the OPA containing 3.22g are 3M aqueous acetic acid 40ml, and single-necked flask is vacuumized,
Reacted 3 days under 135 DEG C, 0.1MPa, obtain COFs materials；
Step 2：The COFs materials that step 1 is obtained are scattered in a solvent, with 225rpm rotating speed wet ball grinding in ball mill
24 hours, upper strata suspension, as COFs nanometer sheets suspension are collected after centrifugation；
Step 3：Phosphorus-containing compound solution is added dropwise in the COFs nanometer sheet suspension that step 2 obtains, reacted at 100-180 DEG C
12-24 hours, reaction centrifuge after terminating, and wash, obtain phosphorous COFs nanometer sheets.
4. preparation method according to claim 3, it is characterised in that：
In step 2, the solvent is selected from ethanol, chloroform, DMF, dioxane, tetrahydrofuran, acetone or two
First sulfoxide.
5. preparation method according to claim 3, it is characterised in that：
In step 2, the rotating speed of centrifugation is 3000-8000rpm.
6. preparation method according to claim 3, it is characterised in that：
In step 2, the concentration of COFs nanometer sheets suspension is 0.2-1wt% after ball milling.
7. preparation method according to claim 3, it is characterised in that：
In step 3, phosphorus-containing compound is with being 1 with the mass ratio of COFs nanometer sheets:1-10:1.
8. preparation method according to claim 3, it is characterised in that：
In step 3, the phosphorus-containing compound is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorous acid diethyl
Ester, dimethylphosphite, dibutyl phosphite, diphenyl phosphite or dialkyl phosphite.
9. preparation method according to claim 3, it is characterised in that：
In step 3, the phosphorus-containing compound solution solvent for use be methanol, ethanol, ether, chloroform, DMF or
Dioxane；The concentration of the phosphorus-containing compound solution is 0.2-2mol/L.
10. preparation method according to claim 3, it is characterised in that：
In step 3, the rotating speed of centrifugation is 1500-8000rpm；During washing solvent for use be methanol, tetrahydrofuran, acetone,
One or more in dichloromethane.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109294506A (en) * | 2018-10-15 | 2019-02-01 | 山东腾熙新材料有限公司 | A kind of conductive adhesive film and preparation method thereof |
| CN111320872A (en) * | 2020-04-15 | 2020-06-23 | 盐城申源塑胶有限公司 | Red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property and preparation method thereof |
| CN111318266A (en) * | 2020-02-14 | 2020-06-23 | 南京师范大学 | Two-dimensional covalent organic framework modified ion exchange resin and preparation method and application thereof |
| WO2021037273A1 (en) * | 2019-08-30 | 2021-03-04 | 厦门大学 | Covalent organic frame flame retardant having schiff base-containing vanillin group, and preparation method therefor |
| WO2021109993A1 (en) * | 2019-12-02 | 2021-06-10 | 厦门大学 | Preparation method for organic phosphine grafted hollow metal organic framework material and use thereof |
| CN113801463A (en) * | 2021-09-06 | 2021-12-17 | 宁波葆尔新材料有限公司 | Anti-condensation material and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294506A (en) * | 2018-10-15 | 2019-02-01 | 山东腾熙新材料有限公司 | A kind of conductive adhesive film and preparation method thereof |
| WO2021037273A1 (en) * | 2019-08-30 | 2021-03-04 | 厦门大学 | Covalent organic frame flame retardant having schiff base-containing vanillin group, and preparation method therefor |
| WO2021109993A1 (en) * | 2019-12-02 | 2021-06-10 | 厦门大学 | Preparation method for organic phosphine grafted hollow metal organic framework material and use thereof |
| CN111318266A (en) * | 2020-02-14 | 2020-06-23 | 南京师范大学 | Two-dimensional covalent organic framework modified ion exchange resin and preparation method and application thereof |
| CN111318266B (en) * | 2020-02-14 | 2022-01-28 | 南京师范大学 | Two-dimensional covalent organic framework modified ion exchange resin and preparation method and application thereof |
| CN111320872A (en) * | 2020-04-15 | 2020-06-23 | 盐城申源塑胶有限公司 | Red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property and preparation method thereof |
| CN111320872B (en) * | 2020-04-15 | 2023-04-25 | 盐城申源塑胶有限公司 | Red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property and preparation method thereof |
| CN113801463A (en) * | 2021-09-06 | 2021-12-17 | 宁波葆尔新材料有限公司 | Anti-condensation material and preparation method thereof |
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