CN110183831A - Preparation method and application of metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame-retardant material - Google Patents
Preparation method and application of metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame-retardant material Download PDFInfo
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- CN110183831A CN110183831A CN201910431900.4A CN201910431900A CN110183831A CN 110183831 A CN110183831 A CN 110183831A CN 201910431900 A CN201910431900 A CN 201910431900A CN 110183831 A CN110183831 A CN 110183831A
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- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000003063 flame retardant Substances 0.000 title claims abstract description 19
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000012621 metal-organic framework Substances 0.000 title abstract description 5
- -1 modified graphite carbon nitride Chemical class 0.000 title abstract 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 239000004809 Teflon Substances 0.000 claims description 9
- 229920006362 Teflon® Polymers 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame retardant material. The composite flame-retardant material mainly comprises the following raw materials in parts by weight: 96-100 parts of unsaturated polyester, 10-20 parts of melamine, 5 parts of terephthalic acid, 2 parts of ferric chloride hexahydrate and 2 parts of initiator. And (3) fully mixing a proper amount of metal organic framework modified graphite carbon nitride, an initiator and unsaturated polyester resin, and then curing and molding to obtain the product. The invention has the advantages that: (1) the metal organic framework modified graphite carbon nitride can be successfully synthesized only by a hydrothermal method, and has the advantages of simple synthesis route, low raw material cost and mild reaction conditions; (2) the compatibility of the provided composite flame-retardant material between graphite carbon nitride and unsaturated polyester is poor; (3) the composite flame retardant material has low addition amount of the flame retardant and small influence on mechanical properties. And no toxic gas is generated during combustion, thereby being green and environment-friendly. (4) Compared with pure unsaturated polyester resin, the provided composite flame retardant material has better flame retardant property and thermal stability.
Description
Technical field
The invention belongs to carbon material hydridization flame-retardant high-molecular technical fields, and in particular to a kind of metal organic frame modification nitrogen
Change carbon/unsaturated polyester resin composite flame-proof material preparation method and applications.
Background technique
Unsaturated polyester resin is using most extensively because of its at low cost, easy processing, excellent corrosion resistance and electrical property
One of thermosetting resin.However, unsaturated polyester resin and its composite material can generate a large amount of smog in burning, especially
When halogen flame is used as additive, toxic gas, such as hydrogen chloride, hydrogen bromide and carbon monoxide can be supervened.Therefore,
In order to expand the application range of unsaturated polyester resin, it is desirable that people develop environmental protection and efficient unsaturated polyester resin flame-retardant is multiple
Condensation material.
Recently, two-dimension nano materials cause extensive concern in the preparation and application of ignition resistant polymeric composite.
Wherein, graphitic nitralloy carbon has excellent thermal stability and photostability.Also, graphitic nitralloy carbon synthetic route is convenient, raw material
It is at low cost.But the compatibility of graphitic nitralloy carbon and unsaturated polyester resin is poor.On the other hand, metal organic framework itself
Porous structure can promote the thermal stability of polymer composites.Therefore, it is organic to develop a kind of novel metal by the present invention
Backbone modification graphitic nitralloy carbon fire proofing, and unsaturated polyester resin composite flame-proof material is prepared, improve unsaturated polyester (UP) tree
The flame retardant property and thermal stability of resin composite material.
Patent CN101386669A discloses a kind of reaction-type flame-retarding unsaturated polyester resin composite material, but synthetic route
Raw material that are complicated and needing are excessive.It is fire-retardant unsaturated poly- that CN101544815A and CN103524975A discloses two kinds of Compositional types
Ester resin composite materials, but two patent additive amounts are all excessive.Metal organic frame modification graphitic nitralloy carbon provided by the invention/
Unsaturated polyester (UP) composite flame-proof material synthetic route is simpler, and fire retardant additive amount is low.
Summary of the invention
In order to solve deficiency in the prior art, the object of the present invention is to provide a kind of metal organic frames to modify graphite nitrogen
Change carbon/unsaturated polyester resin composite flame-proof material and preparation method thereof.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of metal organic frame modification graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material, the unsaturation
Polyester resin composite flame-proof material is mainly composed of the following raw materials by weight: 96~100 parts of unsaturated polyester (UP), melamine 10~
20 parts, 5 parts of terephthalic acid (TPA), 2 parts of ferric chloride hexahydrate, 2 parts of initiator.
The initiator is benzoyl peroxide.
A kind of above-mentioned metal organic frame modification graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material preparation side
Method mainly comprises the steps that
(1) it weighs melamine to be added in ceramic crucible with cover, and is calcined 4 hours at 550 DEG C using Muffle furnace,
After natural cooling, using agate mortar by yellow product grind into powder, graphitic nitralloy carbon is obtained;
(2) terephthalic acid (TPA) is added in n,N-Dimethylformamide, stirring is sufficiently dissolved until terephthalic acid (TPA), is obtained
To solution A;
(3) graphitic nitralloy carbon is added in solution A, stirs 5 minutes, obtains solution B;
(4) ferric chloride hexahydrate is added in solution B, stirs 30 minutes, obtains solution C;
(5) solution C is introduced into the steel autoclave of teflon lined, heats 12 hours, is cooled at 150 DEG C
After room temperature, slurries are centrifuged to and are used respectively n,N-Dimethylformamide, ethyl alcohol and deionized water washing, then dry in 80 DEG C of vacuum
It is 12 hours dry in case, obtain particle A;
(6) particle A is annealed 2 hours in 350 DEG C of air, obtains metal organic frame modification graphitic nitralloy carbon;
(7) metal organic frame is modified into graphitic nitralloy carbon, initiator benzoyl peroxide is added to unsaturated polyester (UP) tree
In rouge, stirs 20~60 minutes, obtain solution D after mixing;
(8) solution D is poured into Teflon mould, drying box is put into after injection molding, obtains belonging to organic after solidification demoulding
Frame modifies graphitic nitralloy carbon/unsaturated polyester (UP) composite flame-proof material.
The step (1), (2), (3), (4) described stirring are magnetic agitation.
The revolving speed of the step (7) stirring is 500~700 revs/min.
The additive amount of the modified hydridization carbosphere in surface is the 4% of unsaturated polyester resin weight in the step (7);Cause
The additive amount of agent is the 2% of unsaturated polyester resin weight.
Condition of cure described in the step (8) are as follows: constant temperature 60 minutes under the conditions of 80 DEG C, constant temperature 180 divides under the conditions of 110 DEG C
Clock.
Compared with prior art, the present invention has the advantage that:
(1) metal organic frame modification graphitic nitralloy carbon provided by the invention only needs hydro-thermal method that can synthesize success, synthesizes
Route is simple, reaction condition is mild.
(2) raw material needed for metal organic frame provided by the invention modification graphitic nitralloy carbon is few, and raw material sources extensively,
It is low in cost, it is suitble to large-scale industrial production.
(3) metal organic frame provided by the invention modifies graphitic nitralloy carbon thermal stability with higher itself and at charcoal
Performance can increase substantially the thermal stability of unsaturated polyester resin.
(4) metal organic frame provided by the invention modifies graphitic nitralloy carbon, for purer graphitic nitralloy carbon, improve with
Compatibility between unsaturated polyester resin.
(5) metal organic frame provided by the invention modifies graphitic nitralloy carbon/unsaturated polyester (UP) flame retardant composite material, fire-retardant
The additive amount of agent is low, smaller to Effect on Mechanical Properties.And toxic gas is not generated when burning, it is environmentally protective.
Detailed description of the invention
Fig. 1 is the FTIR spectrum figure of embodiment 1,2 and 3.
Fig. 2 is the X-ray diffractogram of embodiment 1,2 and 3.
Fig. 3 is thermogravimetric curve of the embodiment 1,2 and 3 in nitrogen atmosphere.
Fig. 4 be thermogravimetric (left side) of the unsaturated polyester resin composite material that provides of embodiment 4,5 and 6 in nitrogen atmosphere and
Thermal weight loss rate curve (right side).
Fig. 5 is the total heat release figure that embodiment 4,5 and 6 provides.
Fig. 6 is that metal organic frame modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material preparation flow
Figure.
Specific embodiment
The present invention is done below with reference to specific embodiment and more comprehensively, is meticulously described, but protection scope of the present invention
It is not limited to embodiment in detail below.
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
With reference to the accompanying drawings and examples, the technical solution used to invention is further elaborated.
Embodiment 1
The preparation of graphitic nitralloy carbon, specifically comprises the following steps:
10 parts of melamines are added in ceramic crucible with cover, and are calcined 4 hours at 550 DEG C using Muffle furnace,
After natural cooling, using agate mortar by yellow product grind into powder, graphitic nitralloy carbon is obtained.
It will be seen from figure 1 that embodiment 1 is in 1200-1700cm-1Between have multiple characteristic peaks.Wherein, 1235,
1317 and 1407cm-1The characteristic peak at place is attributed to the stretching vibration of the connection unit of C-N (- C)-C or C-NH-C.In 1638 Hes
1458cm-1The characteristic peak at place is the stretching vibration of C-N and C=N in CN heterocycle.Furthermore it is possible to by 888 and 805cm-1The two of place
A characteristic peak is that the exemplary bent of triazine ring is vibrated.In Fig. 2, there are two peaks at 27.4 and 13.9 ° in embodiment 1.Its
In, the strong peak at 27.4 ° is the characteristic interlayer accumulation peak of aromatic systems, and the weak peak at 13.9 ° is related with interlayer accumulation.
It may indicate that embodiment 1 is successfully prepared combined with Figure 1 and Figure 2,.
Show that embodiment 1 only has one thermal degradation stage in Fig. 3.As it can be seen from table 1 embodiment 1 can be with thermostabilization
Until T0.1=638 DEG C (temperature of 10% weight loss), illustrate that embodiment 1 is heat-staple when temperature is lower than 600 DEG C.
Embodiment 2
The preparation of ferrous metal organic frame, specifically comprises the following steps:
(1) 5g terephthalic acid (TPA) is added in 100mL n,N-Dimethylformamide, magnetic agitation is until terephthaldehyde
After completely dissolution, ferric chloride hexahydrate is added in above-mentioned solution for acid, is stirred 30 minutes, is obtained solution A.
(2) solution A is introduced into the steel autoclave of teflon lined, heats 12 hours, is cooled at 150 DEG C
After room temperature, slurries are centrifuged to and are used respectively n,N-Dimethylformamide, ethyl alcohol and deionized water washing, then dry in 80 DEG C of vacuum
It is 12 hours dry in case, obtain particle A;
(3) particle A is annealed 2 hours in 350 DEG C of air, obtains ferrous metal organic frame.
It will be seen from figure 1 that observing six characteristic peaks at 1522,1382,1015,754 and 536cm-1 1625.Position
In 1625,1522,1382 and 1015cm-1Vibration of the characteristic peak at place from carboxylate groups.754 and 536cm-1Characteristic peak
The stretching vibration of the C-H bending vibration and Fe-O that are belonging respectively in terephthalic acid (TPA) ligand phenyl ring.The XRD diagram of Fig. 2 it can be found that
There are multiple peaks in embodiment 2, these peaks are all the typical peaks of embodiment 2.It can be seen that embodiment 2 from Fig. 1 and Fig. 2 to prepare
Success.
Embodiment 2 shows 3 main zero-g periods in Fig. 3.Due to the evaporation of solvent, the first stage occurs in 50-
Between 150 DEG C.The decomposition of terephthalic acid (TPA) ligand leads to the second weight loss stage between 350-550 DEG C.Phase III
Thermal degradation be 600 DEG C after form unbodied iron oxide.
Embodiment 3
Ferrous metal organic frame modifies the preparation of graphitic nitralloy carbon, specifically comprises the following steps:
(1) 5g terephthalic acid (TPA) and 0.6g graphitic nitralloy carbon are added in 100mL n,N-Dimethylformamide, magnetic force
Stirring until terephthalic acid (TPA) after completely dissolution, ferric chloride hexahydrate is added in above-mentioned solution, magnetic force stir 30 points
Clock obtains solution A;
(2) solution A is introduced into the steel autoclave of teflon lined, is heated 12 hours at 150 DEG C, is cooled to room
Slurries are centrifuged and are used respectively n,N-Dimethylformamide, ethyl alcohol and deionized water washing by Wen Hou, then in 80 DEG C of vacuum drying oven
Middle drying 12 hours, obtains particle A;
(3) particle A is annealed 2 hours in 350 DEG C of air, obtains ferrous metal organic frame modification graphitic nitralloy carbon.
It is corresponding with embodiment 1 and embodiment 2 that embodiment 3 is located at the characteristic peak in Fig. 1 and Fig. 2, illustrates prepared by embodiment 3
Success.
Embodiment 3 mainly shows the weightlessness in two stages in Fig. 3.First stage occurs between 350-500 DEG C, this
It is attributable to the decomposition of terephthalic acid (TPA) ligand.Then temperature, which increases, leads to the distillation of graphitic nitralloy carbon to occur second and lose
The weight stage.Also, as it can be seen from table 1 the T of embodiment 30.1Than 1 low 175 DEG C of embodiment.Meanwhile compared with Example 1, real
The residual quantity for applying example 3 increases 21.9wt%, shows the more thermostabilization than embodiment 1 of embodiment 3.
Embodiment 4
The preparation of pure unsaturated polyester resin, specifically comprises the following steps:
2g benzoyl peroxide is added in 98g unsaturated polyester resin, is stirred 60 minutes with 700 revs/min, observation
After being completely dissolved to benzoyl peroxide, solution is poured into Teflon mould, 80 DEG C constant temperature 1 hour, 110 DEG C of constant temperature
3h, cooling and demolding after taking-up.
Thermogravimetric curve of the embodiment 4 under stream of nitrogen gas is as shown in figure 4, corresponding data are shown in Table 2.Embodiment 4 only shows
A zero-g period out, T0.1And Tmax(the corresponding temperature of maximum heat weight loss rate) is respectively 339 and 430 DEG C, finally at 800 DEG C
When only remain 10.6wt% carbon residue.Embodiment 4 total heat release be it is highest in embodiment 4,5 and 6, reach 131.9kW/m2,
Illustrate that embodiment 4 discharges most heats in burning, i.e. the risk of embodiment 4 in a fire is just maximum.
Embodiment 5
The preparation of graphitic nitralloy carbon/unsaturated polyester resin composite material, specifically comprises the following steps:
4g graphitic nitralloy carbon is added in 94g unsaturated polyester resin, is stirred 20 minutes, is added with 700 revs/min
2g benzoyl peroxide continues stirring 40 minutes.Solution is poured into Teflon mould, 80 DEG C constant temperature 1 hour, 110
DEG C constant temperature 3h, cooling and demolding after taking-up.
Thermogravimetric curve of the embodiment 5 under stream of nitrogen gas is as shown in figure 4, corresponding data are shown in Table 2.Graphitic nitralloy carbon/no
The T of saturated polyester resin composite material0.1、TmaxCarbon residue with 500 DEG C is all higher than embodiment 4.But since graphitic nitralloy carbon exists
Temperature is higher than 600 DEG C and starts to distil, and graphitic nitralloy carbon/unsaturated polyester resin composite material is caused to be lower than in 800 DEG C of carbon residue
Embodiment 4.The total heat release of embodiment 5 reduces 1.8kW/m for embodiment 42, illustrate the addition of graphitic nitralloy carbon
The fire risk of unsaturated polyester resin can slightly be reduced.
Embodiment 6
Ferrous metal organic frame modify the preparation of carbonitride/unsaturated polyester resin flame-retardant composite material, specifically include as
Lower step:
4g ferrous metal organic frame modification graphitic nitralloy carbon is added in 94g unsaturated polyester resin, with 700 revs/min
Clock stirs 20 minutes, adds 2g benzoyl peroxide, continues stirring 40 minutes.Solution is poured into Teflon mould,
80 DEG C constant temperature 1 hour, 110 DEG C of constant temperature 3h, cooling and demolding after taking-up.
Thermogravimetric curve of the embodiment 6 under stream of nitrogen gas is as shown in figure 4, corresponding data are shown in Table 2.The T of embodiment 60.1With
TmaxIt is reduced with the addition of ferrous metal organic frame modification carbonitride, but the carbon residue at 500 and 800 DEG C of embodiment 6 increases
Add.This can illustrate that embodiment 6 is more stable than embodiment 4 and embodiment 5.The total heat of embodiment 6 is discharged relative to embodiment 4
With 5 for reduce 10.2% and 9.0%, illustrate ferrous metal organic frame modification carbonitride can reduce unsaturated polyester resin
Fire risk improves the flame retardant property of unsaturated polyester resin.
The Thermogravimetric Data of above-described embodiment 1,2 and 3 in a nitrogen atmosphere is as shown in table 1:
Thermogravimetric Data under 1 embodiment of table, 1,2,3 nitrogen atmosphere
The thermogravimetric of unsaturated polyester resin flame-retardant composite material in a nitrogen atmosphere obtained by above-described embodiment 4,5 and 6
It is as shown in table 2 with total heat release data:
Claims (6)
1. a kind of metal organic frame modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material, which is characterized in that institute
Unsaturated polyester resin composite flame-proof material is stated mainly to be composed of the following raw materials by weight: 96~100 parts of unsaturated polyester (UP), trimerization
10~20 parts of cyanamide, 5 parts of terephthalic acid (TPA), 2 parts of ferric chloride hexahydrate, 2 parts of initiator.
2. the modified hydridization carbosphere/unsaturated polyester (UP) flame retardant composite material in surface according to claim 1, feature exist
In the initiator is benzoyl peroxide.
3. a kind of metal organic frame described in claim 1 modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material
The preparation method of material, which is characterized in that mainly comprise the steps that
(1) it weighs melamine to be added in ceramic crucible with cover, and is calcined 4 hours at 550 DEG C using Muffle furnace, in nature
After cooling, using agate mortar by yellow product grind into powder, graphitic nitralloy carbon is obtained;
(2) terephthalic acid (TPA) is added in n,N-Dimethylformamide, stirring is sufficiently dissolved until terephthalic acid (TPA), is obtained molten
Liquid A;
(3) graphitic nitralloy carbon is added in solution A, stirs 5 minutes, obtains solution B;
(4) ferric chloride hexahydrate is added in solution B, stirs 30 minutes, obtains solution C;
(5) solution C is introduced into the steel autoclave of teflon lined, heats 12 hours, is cooled to room temperature at 150 DEG C
Afterwards, slurries are centrifuged to and are used respectively n,N-Dimethylformamide, ethyl alcohol and deionized water washing, then in 80 DEG C of vacuum drying oven
It is 12 hours dry, obtain particle A;
(6) particle A is annealed 2 hours in 350 DEG C of air, obtains metal organic frame modification graphitic nitralloy carbon;
(7) metal organic frame modification graphitic nitralloy carbon, initiator benzoyl peroxide are added in unsaturated polyester resin,
Stirring 20~60 minutes, obtains solution D after mixing;
(8) solution D is poured into Teflon mould, drying box is put into after injection molding, obtain belonging to organic frame after solidification demoulding
Modify graphitic nitralloy carbon/unsaturated polyester (UP) composite flame-proof material.
4. metal organic frame according to claim 3 modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material
The preparation method of material, which is characterized in that step (1), (2), (3), (4) described stirring are magnetic agitation, step (7) described stirring
Revolving speed be 500~700 revs/min.
5. metal organic frame according to claim 3 modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material
The preparation method of material, which is characterized in that the additive amount of metal organic frame modification graphitic nitralloy carbon is unsaturated poly- in step (7)
The 4% of ester weight resin;The additive amount of initiator is the 2% of unsaturated polyester resin weight.
6. metal organic frame according to claim 3 modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material
The preparation method of material, which is characterized in that condition of cure described in step (8) are as follows: constant temperature 60 minutes under the conditions of 80 DEG C, 110 DEG C of items
Constant temperature 180 minutes under part.
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