CN106633082B - A kind of macromolecular nitrogen based on three phosphonitrile of ring, phosphorus expanding fire retardant and preparation method thereof - Google Patents
A kind of macromolecular nitrogen based on three phosphonitrile of ring, phosphorus expanding fire retardant and preparation method thereof Download PDFInfo
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- CN106633082B CN106633082B CN201611269449.3A CN201611269449A CN106633082B CN 106633082 B CN106633082 B CN 106633082B CN 201611269449 A CN201611269449 A CN 201611269449A CN 106633082 B CN106633082 B CN 106633082B
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- fire retardant
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003063 flame retardant Substances 0.000 title claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011574 phosphorus Substances 0.000 title claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 35
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 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 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229920002379 silicone rubber Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical group C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 241001131796 Botaurus stellaris Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- -1 methyl phenyl vinyl Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
Classifications
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of macromolecular nitrogen based on three phosphonitrile of ring, phosphorus expanding fire retardant, belong to the synthesis field of fire retardant.The method for preparing the expanding fire retardant only needs a step, i.e., a certain amount of hexachlorocyclotriph,sphazene and dicyandiamide is reacted certain time under inert gas importing, and product is filtered, washing, and the processing such as dry obtains white powder, i.e. macromolecular nitrogen, phosphorus expanding fire retardant.The expanding fire retardant has the nitrogen and P elements of high level, it may make up the collaboration system of good flame-retardance energy, it shows excellent anti-flammability, can be used as addition type or reactive flame retardant is used in multiple polymers, to improve the flame retardant property of polymeric matrix.Present invention process working condition is simple, only needs single step reaction, and product purity and yield are higher, and last handling process is easy, has industrialization development potentiality.
Description
Technical field
The invention belongs to the synthesis fields of fire retardant, and in particular to a kind of macromolecular nitrogen based on three phosphonitrile of ring, phosphorus expansion
Fire retardant and preparation method thereof.
Background technique
Since 20th century, various high molecular material rapid developments, all kinds of new products emerge one after another, it has also become entire national
Economic, science and technology and the indispensable important materials of military project national defence every field.But most of high molecular material belongs to
Combustible material easily burns under the conditions ofs high temperature, heat source etc., causes fire, causes great casualties and property to damage to society
It loses.Therefore, the fire-retardant research of high molecular material, the concern especially with respect to the research of fire retardant and flame-retarded technology, by the whole world.
Currently on the market widely used halogenated flame retardant because its burn during use can give off poisonous gas and
Corrosive gas generates secondary murder by poisoning, and be faced with multi-party limitation: European Union RoSH instruction, WEEK instruct and will be in building materials etc.
New the fire retardant classification and testing standard etc. that industry is carried out.And construction material that China newly implements and its product burns performance etc.
Grade national standard, also limits the application of halogenated flame retardant.Domestic and international limitation of the laws and regulations to halogenated flame retardant, so that people
Demand to environment-friendly type non-bittern combustion inhibitor is increasingly strong.
Hexachlorocyclotriph,sphazene is a kind of novel flame retardant intermediate, has active P-Cl key, and Yi Fasheng addition replaces
Reaction, prepares new fire retardant.It is not halogen after chlorine atom is replaced by Halogen group in fire retardant based on the synthesis of three phosphonitrile of ring
Element, it is environmentally protective, and also nitrogen and the content of P elements are very high, may make up the collaboration system with good flame-retardance energy, separately
Outer reactivity is strong, easy functional modification, and type is more.Therefore, three phosphonitrile of ring synthesis fire retardant possess good thermal stability and
Anti-flammability has good market prospects, and is the perfect substitute products of halogenated flame retardant.
Summary of the invention
The purpose of the present invention is to provide a kind of macromolecular nitrogen based on three phosphonitrile of ring, phosphorus expanding fire retardant and its preparation sides
Method.The fire retardant is halogen-free and two kinds of nitrogen, phosphorus constituent content height, may make up the collaboration system with good flame-retardance energy, resistance
It fires high-efficient, meets the requirement of laws and regulations and people to ecological environmental protection, in combustion, greatly reduce corrosivity gas
The release of body and toxic gas has the characteristics of low toxicity, low cigarette, is a kind of ideal environmental type fire retardant.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of macromolecular nitrogen based on three phosphonitrile of ring, phosphorus expanding fire retardant, the macromolecular nitrogen, phosphorus expanding fire retardant have with
Flowering structure:
The preparation method of a kind of macromolecular nitrogen based on three phosphonitrile of ring, phosphorus expanding fire retardant, the preparation method is only
A step is needed to obtain three phosphorus of chlordene ring specifically includes the following steps: hexachlorocyclotriph,sphazene and dicyandiamide are dissolved in solvent respectively
Nitrile solution and dicyandiamide solution；Acid binding agent is added into dicyandiamide solution again, hexachlorocyclotriph,sphazene solution is then added dropwise, in inertia
Gas imports lower reaction, and product is filtered, washed, is dried, and obtains white powder, i.e. macromolecular nitrogen, phosphorus expanding fire retardant.
Preferably, the synthetic route of this method is as follows:
Preferably, the molar ratio of the hexachlorocyclotriph,sphazene and dicyandiamide is 1:4-1:8.
Preferably, the solvent be n,N-Dimethylformamide, dimethyl sulfoxide, n,N-dimethylacetamide, toluene and
Any one or more in methylene chloride.
Preferably, the temperature of the reaction is 50-120 DEG C.
Preferably, the time of the reaction is 5-10h.
Preferably, the inert gas is argon gas, helium or nitrogen.
Preferably, the acid binding agent is pyridine, triethylamine, imidazoles, any one or more in 4-dimethylaminopyridine.
Preferably, the solvent of the washing is any one in dimethyl sulfoxide, ethyl alcohol, methylene chloride and deionized water
Or it is a variety of.
Compared with prior art, the invention has the advantages that and technical effect:
1, macromolecular nitrogen of the invention, phosphorus expanding fire retardant can be used as a kind of addition type or reactive flame retardant for difference
Polymeric matrix in, do not migrate in a polymer matrix, avoid " bloom " phenomenon.
2, macromolecular nitrogen of the invention, phosphorus expanding fire retardant is halogen-free and two kinds of nitrogen, phosphorus constituent content height, may make up tool
There is the collaboration system of good flame-retardance energy, flame retarding efficiency is high, has the advantages of Halogen, low cigarette, low toxicity, high-efficiency environment friendly, is conducive to
Sustainable development has a good application prospect.
3, macromolecular nitrogen of the invention, the preparation method of phosphorus expanding fire retardant are simple, only need single step reaction, and react item
Part is mild, easily controllable, without complicated aftertreatment technology, is convenient for industrialized realization.
Detailed description of the invention
Fig. 1 is the infrared spectrum of macromolecular nitrogen in embodiment 1, phosphorus expanding fire retardant.
Fig. 2 is the thermogravimetric curve of macromolecular nitrogen in embodiment 2, phosphorus expanding fire retardant.
Fig. 3 is macromolecular nitrogen in embodiment 3, phosphorus expanding fire retardant31P nmr spectrum.
Specific embodiment
In order to preferably describe and understand the present invention, below with reference to embodiment and attached drawing to specific implementation of the invention make into
One step explanation, but the scope of protection of present invention is not limited to the scope of the embodiments.
Embodiment 1
9.7g dicyandiamide is added to the 500ml four-hole boiling flask equipped with blender, reflux condensing tube, inert gas ingress pipe
In, dimethyl sulfoxide is added makees 10g pyridine is added after solvent is dissolved and make acid binding agent, helium injection gas and after being warming up to 50 DEG C will
10g hexachlorocyclotriph,sphazene is dissolved in n,N-Dimethylformamide to be added dropwise in four-hole boiling flask with dropping funel again, control temperature
Degree is cooled to room temperature after reaction, after filtering, is washed three times with 200ml dimethyl sulfoxide, 80 DEG C in 50 DEG C of reaction 10h
Lower drying can obtain macromolecular nitrogen, phosphorus expanding fire retardant.The INFRARED SPECTRUM of macromolecular nitrogen manufactured in the present embodiment, phosphorus expanding fire retardant
Figure is as shown in Figure 1, in 3300cm-1Bimodal being obviously reduced and in 514cm of place's division-1Basic disappearance, illustrate chlordene ring three
Chlorine on phosphonitrile is replaced by amino, in addition in 2220cm-1, 2152cm-1Place be C ≡ N key stretching vibration peak disappear and
1540cm-1Left and right broad peak and 810cm-1There are three cyanogen heterocycle spies and make peak, illustrating to react between cyano generates three cyanogen rings.By
Goal response known to infrared spectrum successfully occurs.Gained macromolecular nitrogen, phosphorus expanding fire retardant are applied to silicon rubber flame-retardant system
In, 70.5:27.5:2 in mass ratio by methyl vinyl silicone rubber, macromolecular nitrogen, phosphorus expanding fire retardant, dimethyl -2 2,5-,
5- bis(t-butylperoxy) hexane is kneaded 20min at 25 DEG C in open mill, then with compression molding instrument at 100 DEG C into
Row compression molding 20min obtains flame-proof silicon rubber.Table 1 is the data about pure silicon rubber and flame-proof silicon rubber flame retardant property.
Table 1
From table 1 it can be found that compared with pure silicon rubber, it is added to the fire-retardant silicon of macromolecular nitrogen, phosphorus expanding fire retardant
Rubber has better flame resistance.
Embodiment 2
14.5g dicyandiamide is added to equipped with blender, reflux condensing tube, tetra- mouthfuls of 500ml burnings of inert gas ingress pipe
In bottle, addition toluene makees addition 15g triethylamine after solvent is dissolved and makees acid binding agent, after leading to nitrogen and being warming up to 80 DEG C, by 10g
Hexachlorocyclotriph,sphazene, which is dissolved in toluene, is added dropwise to four-hole boiling flask with dropping funel again, controls temperature in 80 DEG C of reaction 9h, instead
It is cooled to room temperature after answering, after filtering, is washed three times with 200ml ethyl alcohol and 200ml deionized water, it is dry at 80 DEG C
Obtain macromolecular nitrogen, phosphorus expanding fire retardant.Thermogravimetric curve such as Fig. 2 of macromolecular nitrogen manufactured in the present embodiment, phosphorus expanding fire retardant
It is shown.As shown in Figure 2,700 DEG C of fire retardant of quality remnants are 30.1%, it is seen that flame retarding efficiency is high.
Embodiment 3
19.3g dicyandiamide is added to equipped with blender, reflux condensing tube, tetra- mouthfuls of 500ml burnings of inert gas ingress pipe
In bottle, addition n,N-Dimethylformamide does addition 15g imidazoles after solvent is dissolved and makees acid binding agent, and logical argon gas is simultaneously warming up to
After 120 DEG C, 10g hexachlorocyclotriph,sphazene is dissolved in dimethyl sulfoxide and is added dropwise to four-hole boiling flask with dropping funel again, controlled
Temperature is cooled to room temperature after reaction in 120 DEG C of reaction 5h, after filtering, with 200ml dimethyl sulfoxide and 200ml go from
Three times, drying can obtain macromolecular nitrogen, phosphorus expanding fire retardant to sub- water washing at 80 DEG C.Macromolecular nitrogen manufactured in the present embodiment, phosphorus
Expanding fire retardant31P nmr spectrum is as shown in Figure 3.31P NMR (ppm, soild), δ=16.51-19.53ppm.By institute
Macromolecular nitrogen, phosphorus expanding fire retardant are applied to silicon rubber flame-retardant system, 68.5:29.5:2 in mass ratio is by methyl phenyl vinyl
Base silicon rubber, macromolecular nitrogen, phosphorus expanding fire retardant, 2,4- dichlorobenzoperoxide are kneaded in open mill at 25 DEG C
Then 20min carries out compression molding 15min with compression molding instrument at 120 DEG C and obtains flame-proof silicon rubber.Table 1 is about pure
The data of silicon rubber and flame-proof silicon rubber flame retardant property.
Table 1
From table 1 it can be found that compared with pure silicon rubber, it is added to the fire-retardant silicon of macromolecular nitrogen, phosphorus expanding fire retardant
Rubber has better flame resistance.
Claims (9)
1. a kind of macromolecular nitrogen based on three phosphonitrile of ring, phosphorus expanding fire retardant, which is characterized in that the macromolecular nitrogen, phosphorus expansion resistance
Combustion agent has a structure that
2. the method for preparing a kind of macromolecular nitrogen based on three phosphonitrile of ring described in claim 1, phosphorus expanding fire retardant, feature
It is, comprising the following steps: hexachlorocyclotriph,sphazene and dicyandiamide are dissolved in solvent respectively, obtain hexachlorocyclotriph,sphazene solution and double
Cyanamide solution；Acid binding agent is added into dicyandiamide solution again, hexachlorocyclotriph,sphazene solution is then added dropwise, under inert gas importing
Reaction, product are filtered, washed, are dried, and white powder, i.e. macromolecular nitrogen, phosphorus expanding fire retardant are obtained；
The acid binding agent is pyridine, triethylamine, imidazoles, any one or more in 4-dimethylaminopyridine.
3. preparation method according to claim 2, which is characterized in that the synthetic route of this method is as follows:
4. preparation method according to claim 2, which is characterized in that the hexachlorocyclotriph,sphazene and feeding intake for dicyandiamide are rubbed
You are than being 1:4-1:8.
5. preparation method according to claim 2, which is characterized in that the solvent is n,N-Dimethylformamide, diformazan
Any one or more in base sulfoxide, DMAC N,N' dimethyl acetamide, toluene and methylene chloride.
6. preparation method according to claim 2, which is characterized in that the temperature of the reaction is 50-120 DEG C.
7. preparation method according to claim 2, which is characterized in that the time of the reaction is 5-10h.
8. preparation method according to claim 2, which is characterized in that the inert gas is argon gas, helium or nitrogen.
9. preparation method according to claim 2, which is characterized in that the solvent of the washing be dimethyl sulfoxide, ethyl alcohol,
Any one or more in methylene chloride and deionized water.
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| CN106633082B true CN106633082B (en) | 2019-08-20 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103751943A (en) * | 2014-01-13 | 2014-04-30 | 西安坚瑞安全应急设备有限责任公司 | Fire extinguishing composition containing nitrogenous organic compound |
| CN104292504A (en) * | 2014-10-14 | 2015-01-21 | 河北大学 | Phosphonitrile fire retardant and preparation method and application thereof |
| CN104725428A (en) * | 2014-10-12 | 2015-06-24 | 青岛科技大学 | Melamine modified polyamino cyclotriphosphazene and preparation method thereof |
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| CN103751943A (en) * | 2014-01-13 | 2014-04-30 | 西安坚瑞安全应急设备有限责任公司 | Fire extinguishing composition containing nitrogenous organic compound |
| CN104725428A (en) * | 2014-10-12 | 2015-06-24 | 青岛科技大学 | Melamine modified polyamino cyclotriphosphazene and preparation method thereof |
| CN104292504A (en) * | 2014-10-14 | 2015-01-21 | 河北大学 | Phosphonitrile fire retardant and preparation method and application thereof |
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| 环三磷腈类阻燃剂的合成及应用研究进展;游歌云 程之泉 彭浩 贺红武;《应用化学》;20140930;全文 |
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