CN106892943B - A kind of compound in triazine class, preparation method and applications - Google Patents
A kind of compound in triazine class, preparation method and applications Download PDFInfo
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- CN106892943B CN106892943B CN201710134793.XA CN201710134793A CN106892943B CN 106892943 B CN106892943 B CN 106892943B CN 201710134793 A CN201710134793 A CN 201710134793A CN 106892943 B CN106892943 B CN 106892943B
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- phosphorus oxychloride
- melamine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000003918 triazines Chemical class 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 52
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- -1 chlorinated phosphate ester Chemical class 0.000 claims description 8
- 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 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 10
- 239000003610 charcoal Substances 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 235000010290 biphenyl Nutrition 0.000 abstract description 2
- 239000004305 biphenyl Substances 0.000 abstract description 2
- 239000012452 mother liquor Substances 0.000 abstract description 2
- 239000012429 reaction media Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 238000002411 thermogravimetry Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000003245 coal Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000015689 metaplastic ossification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- MYOXMAQGEINAEF-UHFFFAOYSA-N [C].N1=NN=CC=C1 Chemical compound [C].N1=NN=CC=C1 MYOXMAQGEINAEF-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/56—Preparation of melamine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of compound in triazine class, preparation method and applications, with 2,2'- dihydroxybiphenyl, phosphorus oxychloride, triethylamine, melamine are primary raw material, a kind of novel compound in triazine class is made, it not only has charcoal source (biphenyl structural), but also there are also acid source (phosphoric acid structure) and gas sources (melamine), the carbon forming agent carbon-forming performance is good, thermal decomposition temperature is high, and with good stability, carbon left is big.Preparation method of the invention, reaction condition is mild, and side reaction is few, and operating process is simple, and reaction time greatly shortens, it is raw materials used safely, be easy to get, using water as reaction medium, avoid the use of organic solvent, simplify last handling process, be convenient for industrialized production.Solvent and mother liquor of the invention is recyclable to be applied, and technical operation flow is simple, avoids the disadvantages of prior art reaction time is too long and consumption of organic solvent is big.
Description
Technical field
The present invention relates to a kind of noval chemical compounds, and in particular to a kind of compound in triazine class, preparation method and applications.Belong to
Field of material technology.
Background technique
Expanding halide-free fire-retardant is a kind of nitrogenous, phosphorus composite flame-retardant agent, is mainly used for the fire-retardant of polyolefin, is in recent years
Carry out a kind of halogen-free flame retardants with fastest developing speed.When high molecular material heated combustion containing expanding halide-free fire-retardant, it can polymerize
Object surface forms one layer of uniform foam carbonaceous layer, the carbonaceous layer condensed phase play it is heat-insulated, oxygen barrier, press down cigarette and prevent molten drop
Effect, can effectively prevent the generation and diffusion of poison gas and corrosive gas, be a kind of very promising new flame retardant.
In general, expansion type flame retardant includes three parts, i.e., charcoal source (being often polyol, such as pentaerythrite),
Acid source (such as ammonium polyphosphate) and gas source (such as melamine).Carbon forming agent as most important group point in Intumscent Flame Retardant System it
One, solubility, thermal stability and application range and fire-retardant effect that expansion type flame retardant is largely determined at charcoal
Rate.Triazines macromolecular carbon forming agent is a kind of compound rich in tertiary carbon structure, has excellent foaming effect and at charcoal effect, and
And there is Halogen, low toxicity, decomposition temperature is high, the physical mechanical property of material is influenced it is small, it is impervious go out, flame retarding efficiency height etc. is excellent
Point, neat coal amout is excellent compared with traditional charcoal source, is not precipitated, resistance to migration, water-soluble low.
In recent years, the preparation of triazines macromolecular carbon forming agent and its patent in flame retardant area application constantly disclose, China
Ningbo Material Technology and Engineering Inst., the academy of sciences discloses the preparation method (patent of triazine hyperbranched macromolecular carbon forming agent
CN200910098421.1), diamino or dihydroxy compounds are mixed using one kettle way with non-proton organic solvent, is added
The aprotic organic solution and end-capping reagent of Cyanuric Chloride is added in catalyst in inert gas, prepares triazine hyperbranched big
Molecule carbon forming agent；The research institute also discloses the triazine carbon forming agent of the chain structure containing aromatic series and preparation method thereof (patent
It CN200910099717.5), is NH by general structure2-Ar-NH2, the aromatic dicarboxylic compound of HO-Ar-OH or HS-Ar-SH
Polycondensation obtains under the action of catalyst with monosubstituted Cyanuric Chloride；Shanghai Chemical Research Inst discloses one kind with Cyanuric Chloride and two
First amine is the method (patent CN200710170519.4) that reaction product prepares triazines carbon forming agent and halogen-free expansion fire retardant；
Guangzhou University discloses amido pyrrolotriazine derivatives macromolecular carbon forming agent and Flame Retardant Agent of Polypropylene preparation method (patent
CN201610509222.5), amido pyrrolotriazine derivatives are obtained using Cyanuric Chloride, the mixed amine containing alkylamine and acid binding agent as raw material
Macromolecular carbon forming agent.
Method made above all has that consumption of organic solvent big (predominantly acetone), environmental pollution is serious, and subsequent processing is tired
The disadvantages such as difficulty, product thermal stability is not high, and charcoal residual quantity is low, and reaction time is generally longer, at 20 hours or more.Therefore it grinds
Studying carefully the triazine derivative carbon forming agent that one kind is simple, efficient, performance is good has good application value.
Summary of the invention
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of compound in triazine class.
The present invention also provides a kind of above-mentioned preparation method and applications of compound in triazine class.
To achieve the above object, the present invention adopts the following technical solutions:
A kind of compound in triazine class, structural formula are as follows:
A kind of preparation method of above-mentioned compound in triazine class, comprising steps of
(1) under the action of triethylamine, condensation reaction occurs for 2,2'- dihydroxybiphenyls and phosphorus oxychloride, obtains 2,2 '-two
Phenylene chlorinated phosphate ester, reaction equation are as follows:
Hydrolysis occurs for (2) 2,2 '-diphenylene chlorinated phosphate esters, obtains containing 2,2 '-diphenylene dis
Salt-forming reaction then occurs with melamine for the reaction solution of ester to get product, and reaction equation is as follows:
Preferably, the specific method of step (1) is: being first uniformly mixed 2,2'- dihydroxybiphenyl with triethylamine, then stirs
It mixes down and phosphorus oxychloride is slowly added dropwise, temperature is adjusted after being added dropwise to -10~20 DEG C, is reacted 4~7 hours.
It is further preferred that using toluene as reaction dissolvent, for dissolving reaction mass and providing reaction environment, toluene
Mass ratio with 2,2'- dihydroxybiphenyl is 2~3.5:1, is still more preferably 2.3:1.
It is further preferred that the molar ratio of 2,2'- dihydroxybiphenyls, triethylamine and phosphorus oxychloride be 1~1.2:1.1~
1.3:1, further preferred 1.05:1.1:1.
It is further preferred that the time for adding of phosphorus oxychloride is 1~3 hour, it is still more preferably 1.5 hours.
It is further preferred that reaction temperature is 10 DEG C, the reaction time is 5 hours.
Preferably, the specific method of step (2) is: water and melamine is added, heating reflux reaction 3~5 hours, reacts
After cooling, filtering, it is dry to get product.
It is further preferred that the molar ratio of melamine and phosphorus oxychloride is 1:3~4, it is still more preferably 1:3.2,
The mass ratio of water and melamine is 800:37.9.
It is further preferred that using toluene as reaction dissolvent in step (1), before water and melamine is added, first
Revolving removes toluene.
It is further preferred that the reaction time is 3.5 hours.
It is dried in vacuo 6~20 hours it is further preferred that the drying is 80 DEG C.
A kind of above-mentioned compound in triazine class answering in the carbon forming agent for being used alone or as Intumscent Flame Retardant System
With.
Beneficial effects of the present invention:
The present invention, for primary raw material, is made a kind of new with 2,2'- dihydroxybiphenyl, phosphorus oxychloride, triethylamine, melamine
The compound in triazine class of type, it not only has charcoal source (biphenyl structural), but also there are also acid source (phosphoric acid structure) and gas source (melamines
Amine), the carbon forming agent carbon-forming performance is good, and thermal decomposition temperature is high, and with good stability, carbon left is big.
Preparation method of the invention, reaction condition is mild, and side reaction is few, and operating process is simple, and reaction time greatly shortens,
It is raw materials used safely, be easy to get, using water as reaction medium, avoid the use of organic solvent, simplify last handling process, be convenient for work
Industry metaplasia produces.Solvent and mother liquor of the invention is recyclable to be applied, and technical operation flow is simple, avoids the prior art reaction time
The disadvantages of too long and consumption of organic solvent is big.
Detailed description of the invention
Fig. 1 is the infrared spectrum of 1 gained compound in triazine class of the embodiment of the present invention.
Fig. 2 is the thermogravimetric analysis figure of embodiment 1, embodiment 2 and comparative example gained carbon forming agent.
Specific embodiment
The present invention will be further elaborated with reference to the accompanying drawings and examples, it should which explanation, following the description is only
It is not to be defined to its content to explain the present invention.
Embodiment 1:
Into the 2L four round flask with blender, thermometer and constant pressure funnel, add 188.0g (1mol) 2,
2'- dihydroxybiphenyl (99.0%), 433.0g toluene (99.5%), 132.9g (1.3mol) triethylamine (content 99.0%) are opened
Open stirring, for control temperature at 10 DEG C, phosphorus oxychloride 155.6g (1mol) (98.5%) is added dropwise in 1.0h, the reaction was continued 4h.Rotate first
Benzene, is added 800g water, 37.9g (0.3mol) melamine (99.8%), cooling, filtering, drying after 100 DEG C of back flow reaction 3h,
Product 801.1g is obtained, with phosphorus oxychloride collecting rate 96.0%, the neat coal amout that 500 DEG C of thermogravimetric analysis is 51.8%, thermal decomposition temperature
305℃。
Fig. 1 is the infrared spectrum of 1 gained compound in triazine class of embodiment, there is melamine group as can be seen from Figure 1
(1650~1000cm-1), biphenyl group (3500~2800cm-1) and phosphorus-oxygen groups (600~750cm-1), with target product
Structure is coincide.
Embodiment 2:
Into the 2L four round flask with blender, thermometer and constant pressure funnel, add 225.6g (1.2mol)
2,2'- dihydroxybiphenyls (99.0%), 433.0g toluene (99.5%), 112.4g (1.1mol) triethylamine (content 99.0%),
Stirring is opened, for control temperature at 10 DEG C, phosphorus oxychloride 155.6g (1mol) (98.5%) is added dropwise in 1.5h, the reaction was continued 5h.Revolving
Toluene, is added 800g water, 39.1g melamine (0.31mol) (99.8%), cooling after 100 DEG C of back flow reaction 3.5h, filtering,
Drying, obtains product 821.5g, with phosphorus oxychloride collecting rate 98.5%.The neat coal amout that 500 DEG C of thermogravimetric analysis is 50.2%, thermal decomposition
304 DEG C of temperature.
Embodiment 3:
Into the 2L four round flask with blender, thermometer and constant pressure funnel, add 188.0g (1mol) 2,
2'- dihydroxybiphenyl (99.0%), 433.0g toluene (99.5%), 102.2g (1mol) triethylamine (content 99.0%) are opened
Stirring, for control temperature at 10 DEG C, phosphorus oxychloride 155.6g (1mol) (98.5%) is added dropwise in 3h, the reaction was continued 7h.Toluene is rotated, is added
Enter 800g water, 37.9g (0.3mol) melamine (99.8%), cooling, filtering, drying after 100 DEG C of back flow reaction 5h obtain product
809.8g, with phosphorus oxychloride collecting rate 97.1%.The neat coal amout that 500 DEG C of thermogravimetric analysis be 50.2%, 304 DEG C of thermal decomposition temperature.
Embodiment 4:
Into the 2L four round flask with blender, thermometer and constant pressure funnel, add 197.0g (1.05) 2,
2'- dihydroxybiphenyl (99.0%), 433.0g toluene (99.5%), 112.4g (1.1mol) triethylamine (content 99.0%) are opened
Open stirring, for control temperature at 10 DEG C, phosphorus oxychloride 155.6g (1mol) (98.5%) is added dropwise in 1.5h, the reaction was continued 5h.Rotate first
Benzene, is added 800g water, 31.5g (0.25mol) melamine (99.8%), and cooling after 100 DEG C of back flow reaction 3.5h, is dried at filtering
It is dry, product 816.5g is obtained, with phosphorus oxychloride collecting rate 97.9%.
Embodiment 5:
In the 2L four round flask of thermometer and constant pressure funnel, add 188.0g (1mol) 2,2'- dihydroxybiphenyl
(99.0%), 433.0g toluene (99.5%), 132.9g (1.3mol) triethylamine (content 99.0%) open stirring, control temperature
For degree at 20 DEG C, phosphorus oxychloride 155.6g (1mol) (98.5%) is added dropwise in 1.0h, the reaction was continued 4h.Toluene is rotated, 800g water is added,
37.9g (0.3mol) melamine (99.8%), cooling, filtering, drying, obtain product 806.5g after 100 DEG C of back flow reaction 3h, with
Phosphorus oxychloride collecting rate 96.7%.
Embodiment 6:
Into the 2L four round flask with blender, thermometer and constant pressure funnel, add 188.0g (1mol) 2,
2'- dihydroxybiphenyl (99.0%), 658.0g toluene (99.5%), 132.9g (1.3mol) triethylamine (content 99.0%) are opened
Open stirring, for control temperature at 10 DEG C, phosphorus oxychloride 155.6g (1mol) (98.5%) is added dropwise in 1.0h, the reaction was continued 4h.Rotate first
Benzene, is added 800g water, 37.9g (0.3mol) melamine (99.8%), cooling, filtering, drying after 100 DEG C of back flow reaction 3h,
Product 803.1g is obtained, with phosphorus oxychloride collecting rate 96.3%.
Embodiment 7:
Into the 2L four round flask with blender, thermometer and constant pressure funnel, add 188.0g (1mol) 2,
2'- dihydroxybiphenyl (99.0%), 376.0g toluene (99.5%), 132.9g (1.3mol) triethylamine (content 99.0%) are opened
Open stirring, for control temperature at 10 DEG C, phosphorus oxychloride 155.6g (1mol) (98.5%) is added dropwise in 1.0h, the reaction was continued 4h.Rotate first
Benzene, is added 800g water, 37.9g (0.3mol) melamine (99.8%), cooling, filtering, drying after 100 DEG C of back flow reaction 3h,
Product 786.5g is obtained, with phosphorus oxychloride collecting rate 94.3%.
By the method for Examples 1 to 7, reaction condition milder, yield is improved, and simplifies last handling process, is convenient for work
Industry metaplasia produces.
Comparative example:
A kind of aromatic series chain structure triazines prepared by N-N- dimethyl acetamide, Cyanuric Chloride, diaminodiphenyl ether
Carbon forming agent, 500 DEG C of neat coal amouts of thermogravimetric analysis be 38.5%, 285 DEG C of thermal decomposition temperature.
Fig. 2 is the thermogravimetric analysis figure of embodiment 1, embodiment 2 and comparative example gained carbon forming agent.To find out in terms of Fig. 2, implement
The neat coal amout of 1 500 DEG C of gained carbon forming agent thermogravimetric analysis of example be 51.8%, 305 DEG C of thermal decomposition temperature；2 gained carbon forming agent of embodiment
The neat coal amout that 500 DEG C of thermogravimetric analysis be 50.2%, 304 DEG C of thermal decomposition temperature；And in comparative example 500 DEG C of carbon forming agent thermogravimetric analysis at
Charcoal amount be 38.5%, 285 DEG C of thermal decomposition temperature.Gained carbon forming agent carbon-forming performance of the invention is good, and carbon left is big, thermal decomposition temperature
Height, it is with good stability.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, based on the technical solutions of the present invention, those skilled in the art are not needed to make the creative labor and can be done
Various modifications or changes out are still within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of compound in triazine class, which is characterized in that comprising steps of
(1) under the action of triethylamine, condensation reaction occurs for 2,2'- dihydroxybiphenyls and phosphorus oxychloride, obtains 2,2 '-two sub- benzene
Base chlorinated phosphate ester, reaction equation are as follows:
Hydrolysis occurs for (2) 2,2 '-diphenylene chlorinated phosphate esters, obtains containing 2,2 '-diphenylene hydroxyl phosphates
Salt-forming reaction then occurs with melamine for reaction solution to get product, and reaction equation is as follows:
The specific method of step (1) is: being first uniformly mixed 2,2'- dihydroxybiphenyl with triethylamine, then the lower slowly drop of stirring
Add phosphorus oxychloride, temperature is adjusted after being added dropwise to -10~20 DEG C, is reacted 4~7 hours.
2. preparation method according to claim 1, which is characterized in that use toluene as reaction dissolvent, it is anti-for dissolving
It answers material and reaction environment is provided, toluene and 2, the mass ratio of 2'- dihydroxybiphenyl is 2~3.5:1.
3. preparation method according to claim 1, which is characterized in that 2,2'- dihydroxybiphenyls, triethylamine and phosphorus oxychloride
Molar ratio be 1~1.2:1.1~1.3:1.
4. preparation method according to claim 1, which is characterized in that the time for adding of phosphorus oxychloride is 1~3 hour.
5. preparation method according to claim 1, which is characterized in that the specific method of step (2) is: water and trimerization is added
Cyanamide heating reflux reaction 3~5 hours, cools down after reaction, filtering, dry to get product.
6. preparation method according to claim 5, which is characterized in that the molar ratio of melamine and phosphorus oxychloride is 1:3
~4.
7. preparation method according to claim 5, which is characterized in that use in step (1) toluene as reaction dissolvent,
It is added before water and melamine, first revolving removes toluene.
8. a kind of compound in triazine class that preparation method described in any one of claim 1~7 obtains is being used alone or is making
For the application in the carbon forming agent of Intumscent Flame Retardant System.
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| PCT/CN2017/108889 WO2018161619A1 (en) | 2017-03-07 | 2017-11-01 | Triazine compound, preparation method therefor, and application thereof |
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| DE3940765A1 (en) * | 1989-12-09 | 1991-06-13 | Hoechst Ag | METHOD FOR PRODUCING PURE CYCLIC PHOSPHORSAEUREDIARYLESTER |
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