CN109265479A - A kind of diaminodiphenylsulfone derivative flame retardant and its preparation method and application - Google Patents
A kind of diaminodiphenylsulfone derivative flame retardant and its preparation method and application Download PDFInfo
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- CN109265479A CN109265479A CN201810955839.9A CN201810955839A CN109265479A CN 109265479 A CN109265479 A CN 109265479A CN 201810955839 A CN201810955839 A CN 201810955839A CN 109265479 A CN109265479 A CN 109265479A
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- diaminodiphenylsulfone
- flame retardant
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- derivative flame
- derivative
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 89
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical class C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 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 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 15
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical class C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims description 14
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 235000019504 cigarettes Nutrition 0.000 abstract description 5
- 230000000979 retarding effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000001629 suppression Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JBCUKQQIWSWEOK-UHFFFAOYSA-N 2-(benzenesulfonyl)aniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 JBCUKQQIWSWEOK-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004786 cone calorimetry Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- -1 phosphorous diaminodiphenylsulfone derivative Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-C aromatic linkage)
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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)
- 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 belongs to chemical fire retardant fields, and in particular to a kind of diaminodiphenylsulfone derivative flame retardant and its preparation method and application.The molecular structural formula of the diaminodiphenylsulfone derivative flame retardant is as follows:The diaminodiphenylsulfone derivative flame retardant has many advantages, such as that structure novel, nontoxic, suppression cigarette, flame retarding efficiency are high.Meanwhile the preparation method synthesis technology of the diaminodiphenylsulfone derivative flame retardant is simple, easily operated, is suitable for popularization and application.
Description
Technical field
The invention belongs to fire-retardant FRW technical fields, and in particular to a kind of diaminodiphenylsulfone derivative flame retardant and its
Preparation method and application.
Background technique
The advantages that polycarbonate (PC) is colorless and transparent because having, heat distortion temperature height, good stability of the dimension, shock resistance, and
Application field is extensive.PC itself has certain flame retardant property, but apparent drip phenomenon (UL94V-2 grades) can occur when burning
And with a large amount of black smoke, so that greatly limiting it uses field.It must be mentioned to meet the application requirement of certain special dimensions
Its high flame retardant property inhibits molten drop.
Currently, improving the flame retardant property of PC by the way of adding fire retardant into PC, inhibiting the molten of PC burning generation
Drop.The existing fire retardant for PC, though certain flame retardant effect can be obtained, there are still certain defects.Such as, organic phosphorus
Though fire retardant flame retarding efficiency is higher, additive amount is larger, leads to the obvious variation of the transparency of fire proofing and heat distortion temperature drops
It is low；Though sulfonate salt flame additive amount is small, flame retarding efficiency is very high, general additive amount is less than 1wt.%, it is not able to satisfy thin-walled
Sample it is fire-retardant；Silicon-series five-retardant can assign the excellent flame retardant property of fire retardation PC material, hot-working character and cold temperature impact
Can, but its additive amount it is big, it is expensive and make the fire proofing transparency decline.
Summary of the invention
To solve the above problems, the present invention proposes a kind of diaminodiphenylsulfone derivative flame retardant and preparation method thereof and answers
With.The diaminodiphenylsulfone derivative flame retardant has many advantages, such as that structure novel, nontoxic, suppression cigarette, flame retarding efficiency are high.Meanwhile
The preparation method synthesis technology of the diaminodiphenylsulfone derivative flame retardant is simple, easily operated, is suitable for popularization and application.
The present invention is achieved by the following technical solutions:
A kind of diaminodiphenylsulfone derivative flame retardant, abbreviation TPDDS, the diaminodiphenylsulfone derivative flame retardant
Molecular structural formula is as follows:
Further, the diaminodiphenylsulfone derivative flame retardant is that phosphorous diaminodiphenylsulfone derivative is fire-retardant
Agent.
Further, the diaminodiphenylsulfone derivative flame retardant is by diaminodiphenylsulfone (DDS) and chlorophosphate
Diphenyl ester reacts under catalysts conditions to be obtained.
A kind of preparation method of diaminodiphenylsulfone derivative flame retardant proposed by the present invention, the preparation method include:
Step 1, under conditions of catalyst, pH value are 7~9, the acetonitrile solution of chlorinated diphenyl phosphate is slowly dropped into two
It is reacted in the anhydrous acetonitrile of aminodiphenyl sulfone, obtains thick solid；
Step 2, it after the thick solid is first washed with HCl solution, then is washed until described thick with NaOH solution
Solid is in neutrality；
Step 3, neutral thick solid step 2 obtained is dissolved in methanol, obtains solution B；Stir institute in side
It states solution B side and is poured slowly into CaCl2In solution, precipitate A is precipitated, the precipitate A is obtained by filtration；
Step 4, it uses first alcohol and water to recrystallize to improve product purity the precipitate A, the diamino is precipitated
Diphenyl sulfone derivative fire retardant.
Further, the chemical name of the diaminodiphenylsulfone derivative flame retardant (abbreviation TPDDS) are as follows: four (hexichol
Base phosphate) four phosphamide of -4,4 '-diphenyl sulfone.
Further, diaminodiphenylsulfone described in step 1 and the chlorinated diphenyl phosphate are molten in acetonitrile solvent
Xie Du higher.
Further, the preparation method of the anhydrous acetonitrile of diaminodiphenylsulfone described in step 1 are as follows: in stirring, add
Under conditions of the solidifying reflux of hot and cold, after the diaminodiphenylsulfone and catalyst are mixed, anhydrous acetonitrile is added, it is sufficiently molten
Solution.
Further, catalyst described in step 1 is 4-dimethylaminopyridine.
Further, temperature when reacting described in step 1 is 70~80 DEG C.
Further, diaminodiphenylsulfone described in step 1 and the molar ratio of the chlorinated diphenyl phosphate are 1:5~8.
Further, reaction described in step 1 adjusts the pH value of reaction using n,N-diisopropylethylamine.
Further, reaction described in step 1 detects extent of reaction with thin-layered chromatography, is examined using the thin-layered chromatography
When surveying extent of reaction, solvent is used as using methanol and toluene, the volume ratio of the methanol and the toluene is 1:4~8.
Further, the reaction equation of reaction described in step 1 are as follows:
Further, HCl solution concentration described in step 2 is 0.01mol/L~0.3mol/L.
Further, NaOH solution concentration described in step 2 is 0.01mol/L~0.3mol/L；It is washed using NaOH solution
It washs, can remove some impurity and excessive chlorinated diphenyl phosphate for being dissolved in alkalinity, to avoid impurity that may be present under
The influence of single step reaction.
Further, CaCl described in step 32The concentration of solution is 0.02mol/L~0.5mol/L, CaCl2Coagulation is played to make
With the precipitate A being precipitated from solution.
Further, the precipitate A is brown solid.
The present invention also provides a kind of diaminodiphenylsulfone derivative flame retardant answering in the poly- carbonic acid resin (PC) of bisphenol A-type
With.
The present invention has following advantageous effects:
(1) contain phosphorus, nitrogen, a variety of ignition-proof elements of sulphur, tool in diaminodiphenylsulfone derivative flame retardant structure of the invention
Have the advantages that structure novel, nontoxic, suppression cigarette, flame retarding efficiency are high.
(2) when additive amount is only 2%, LOI value is had reached diaminodiphenylsulfone derivative flame retardant of the invention
34.3%, dosage is few, at low cost.
(3) the preparation method synthesis technology of diaminodiphenylsulfone derivative flame retardant of the invention is simple, easily operated, fits
In popularization and application.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for the diaminodiphenylsulfone derivative flame retardant that the embodiment of the present invention 1 is prepared.
Fig. 2A be the diaminodiphenylsulfone derivative flame retardant that is prepared of the embodiment of the present invention 1 in air atmosphere
TGA figure.
Fig. 2 B be the diaminodiphenylsulfone derivative flame retardant that is prepared of the embodiment of the present invention 1 in air atmosphere
DTG figure.
Fig. 3 A be the diaminodiphenylsulfone derivative flame retardant that is prepared of the embodiment of the present invention 1 in a nitrogen atmosphere
TGA figure.
Fig. 3 B be the diaminodiphenylsulfone derivative flame retardant that is prepared of the embodiment of the present invention 1 in a nitrogen atmosphere
DTG figure.
Fig. 4 A is the TGA figure of the PC and PC/TPDDS system that is prepared of the embodiment of the present invention 1 in air atmosphere.
Fig. 4 B is the DTG figure of the PC and PC/TPDDS system that is prepared of the embodiment of the present invention 1 in air atmosphere.
Fig. 5 A is the TGA figure of the PC and PC/TPDDS system that is prepared of the embodiment of the present invention 1 in a nitrogen atmosphere.
For PC the and PC/TPDDS system that the embodiment of the present invention 1 is prepared, DTG schemes Fig. 5 B in a nitrogen atmosphere.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments and specification
The present invention is explained in further detail in attached drawing.It should be appreciated that specific embodiment described herein is used only for explaining this
Invention, is not intended to limit the present invention.
On the contrary, the present invention covers any substitution done on the essence and scope of the present invention being defined by the claims, repairs
Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to of the invention thin
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
The present invention can also be understood completely in description.
Embodiment 1
The present embodiment is related to a kind of diaminodiphenylsulfone derivative flame retardant, abbreviation TPDDS, and the diaminodiphenylsulfone is spread out
The molecular structural formula of biological fire retardant is as follows:
A kind of preparation method of diaminodiphenylsulfone derivative flame retardant, the preparation method include:
Step 1, under conditions of stirring, heating and condensing reflux, diaminodiphenylsulfone and 4-dimethylaminopyridine (are urged
Agent) it is completely dissolved in anhydrous acetonitrile, the anhydrous acetonitrile of diaminodiphenylsulfone is made；Again by chlorinated diphenyl phosphate
Anhydrous acetonitrile, which is slowly dropped into above-mentioned solution, to be reacted, and thick solid is obtained；
Step 2, after thick solid described in step 1 first being washed with HCl solution, then with NaOH solution wash until its
It is in neutrality；
Step 3, neutral thick solid step 2 obtained is dissolved in methanol, is delayed when stirring the solution B
Slowly CaCl is poured into2In solution, precipitate A is precipitated, the precipitate A is obtained after filtering；
Step 4, recrystallization purification is carried out to the precipitate A using first alcohol and water, it is derivative that the diaminodiphenylsulfone is precipitated
Object fire retardant.
The reaction equation of reaction described in step 1 are as follows:
The present embodiment is described in detail using experiment below.
Experiment content: 2.48g (0.01mol) diaminodiphenylsulfone and 0.12g 4-dimethylaminopyridine (catalyst) are set
In the 250mL with mechanical stirring and condensation reflux unit dry four-hole boiling flask, then 100mL anhydrous acetonitrile is poured into, sufficiently
Stirring and dissolving, and solution is gradually heated to 70~80 DEG C.13.43g (0.05mol) chlorinated diphenyl phosphate is dissolved in 100mL
In anhydrous acetonitrile, it is slowly dropped to constant pressure funnel in above-mentioned four-hole boiling flask；In reaction process, with N, N- bis- is different
Propylethylamine adjusts pH=7~9 of reaction, and (solvent is methanol: toluene=1:(4 with thin-layered chromatography detection extent of reaction
~8), volume ratio).
To after reaction, remove solvent with Rotary Evaporators, obtain thick solid.The thick solid is first used
The HCl solution washing of 0.01mol/L three times, then wash up to the thick solid with the NaOH solution of 0.01mol/L and to be in
Property.The thick solid is dissolved in 30mL methanol, solution B is obtained, the solution B is poured slowly into while stirring
The CaCl of 0.05mol/L2In solution, precipitate A is precipitated in coagulation, and the precipitate A is brown solid.The precipitate A is obtained after filtering,
Again with methanol and water recrystallize precipitate A, obtain target product diaminodiphenylsulfone derivative flame retardant, it may be assumed that four (hexichol
Base phosphate) -4,4 '-diphenyl sulfone, four phosphamide (TPDDS), yield 67%.
Structural characterization data are as follows, and specific spectrogram is as shown in FIG. 1 to 3.
Fig. 1 show the infrared spectrogram of the diaminodiphenylsulfone derivative flame retardant of the present embodiment.It can be obtained by Fig. 1:
3100cm-1And 3063cm-1Place is C-H stretching vibration peak on phenyl ring；1591cm-1And 1488cm-1Place is that the stretching, extension of phenyl ring skeleton is shaken
Dynamic absorption peak；1400cm-1Place is the stretching vibration absworption peak of N-C key in Ar-NH-R；1297cm-1And 1158cm-1Place is O=S
The stretching vibration peak of=O key；1194cm-1Place is the vibration absorption peak of P=O；1099cm-1And 1070cm-1Place is that P-N key is flexible
Vibration absorption peak.
Using AVANCE type III Bruker-600, with Acetone-d6Make solvent to carry out synthesized target product
Nucleus magnetic hydrogen spectrum analysis.By nucleus magnetic hydrogen spectrum analysis it is found that target product diaminodiphenylsulfone derivative flame retardant1H-NMR data
It is as follows: δ=8.0663ppm (unimodal, SO2- Ar-H (α-H), 4H), δ=7.5142ppm (unimodal, SO2-Ar-H (β-H), 4H),
δ=7.2075-7.3762ppm (doublet, H-Ar-O-P, 40H), δ=2.8217ppm (water peak in reagent), δ=
(2.0702ppm reagent peak).
Using AVANCE type III Bruker-600, with Acetone-d6Make solvent to carry out synthesized target product
Nuclear-magnetism phosphorus spectrum analysis.By nuclear-magnetism phosphorus spectrum analysis it is found that target product diaminodiphenylsulfone derivative flame retardant31P-NMR data
It is as follows: δ=- 11.74ppm.
The thermal stability for the diaminodiphenylsulfone derivative flame retardant that the preparation method of the present embodiment is obtained below and
Flame retardant property is studied, as shown in Fig. 2A~Fig. 5 B.
1. the thermal stability of diaminodiphenylsulfone derivative flame retardant is studied
Fig. 2A and Fig. 2 B and Fig. 3 A and Fig. 3 B is diaminodiphenylsulfone derivative flame retardant under air and nitrogen atmosphere, with
The TGA and corresponding DTG curve that the heating rate of 10 DEG C/min measures.
Table 1 gives main thermal degradation parameter.Definition: TonsetIt is corresponded to when weightlessness 5% in thermal decomposition process for material
Temperature, TmaxCorresponding temperature, carbon left when Char is 800 DEG C when thermal weight loss maximum for material generation.
1 diaminodiphenylsulfone derivative flame retardant of table thermal degradation parameter in air and nitrogen atmosphere
It is listed in Table 1 below by Fig. 2A, Fig. 2 B, the resulting partial data of Fig. 3 A and Fig. 3 B.As shown in Table 1, diaminodiphenylsulfone
T of the derivative flame retardant under air and nitrogen atmosphereonsetRespectively 339.8 DEG C, 346.8 DEG C show that fire retardant has well
Thermal stability.Relative to 240~270 DEG C of processing temperature of PC, fire retardant will not be thermally decomposed when PC is processed, and can satisfy
The processing conditions of PC.Continue to increase with temperature, carbon left point of the fire retardant under air and nitrogen atmosphere, at 800 DEG C
Not Wei 8.5%, 23.4%, show that fire retardant is more stable at charcoal.Either under nitrogen or air atmosphere, fire retardant is sent out
Raw step degradation.But compared with thermal degradation under nitrogen atmosphere, the aerial T of fire retardantonset、TmaxAnd 800 DEG C residual
Charcoal amount all reduces.The reason is that pyrolysis not only occurs for fire retardant, but also oxidative decomposition occurs in the presence of oxygen,
To accelerate the decomposition of fire retardant.
2. the flame retardant property research of diaminodiphenylsulfone derivative flame retardant
The present embodiment be diaminodiphenylsulfone derivative flame retardant is directly compounded other any auxiliary agents are not added with PC, thus
Test the flame retardant property of its fire retardant.Concrete operations are as follows:
PC and diaminodiphenylsulfone derivative flame retardant are placed in 110 DEG C of air dry ovens dry 8h, then by PC and
Diaminodiphenylsulfone derivative flame retardant is squeezed out again with double screw extruder after being pre-mixed in different ratios, is cooling, is granulated, spiral shell
Bar revolving speed is 85r/min.Pellet obtained is placed in 110 DEG C of air dry ovens dry 8h.According to GB/T 25156-2010,
Experimental standard batten is made with injection molding machine.
The LOI value of test batten is all made of the standard testing of ISO 4589-2-1996 and obtains, batten specification be 120mm ×
10mm×4mm.Vertical burn test is measured by U.S.'s UL94 standard, and batten specification is 120mm × 13mm × 3.2mm.It adopts
It with FTT-0242 cone calorimetry, is tested by ISO-5660-1 standard, heat radiation power is 35kW/m2, specification 100mm
×100mm×3.2mm.Test result is as follows for it shown in table 2:
The fire-retardant and cone of the PC/TPDDS system of the different adding proportion of table 2 measures test result
Note: pk-SPR refers to maximum raw cigarette rate.COY refers to the amount of the CO discharged in the unit time.
The LOI value that pure PC is concluded that by limit oxygen index and vertical burn test is 26.5%, UL94 vertical combustion
Grade is UL94V-2.With the increase of TPDDS additive amount, the LOI value of composite material is gradually increased.As addition 0.25wt.%
When TPDDS, the LOI value of composite material is 30.4%, and by UL94V-1 grades, when additive amount is 2wt.%, LOI value
Reach 34.3%.Thus illustrate that TPDDS can be good at improving the LOI value of composite material, show preferable flame retardant effect.By
The pk-SPR value of PC/TPDDS composite material is it is found that TPDDS has certain suppression cigarette effect.By PC/TPDDS composite material
COY value is it is found that TPDDS makes the amount of CO reduce 14%.Also, the yield of CO can be used as smoke toxicity during PC base burn
Evaluation index.
Table 3PC and PC/TPDDS system thermal degradation performance parameter under air and carbon yield
Table 3 lists thermal stability data of the PC and PC/TPDDS system in air atmosphere.As shown in Table 3, with
The increase of TPDDS additive amount, the T of PC/TPDDS composite materialonsetAnd TmaxAll it increased.The reason is that diaminodiphenylsulfone
The effect of the diphenyl sulfone of high thermal stability in derivative flame retardant molecule, improves the overall stability of PC substrate.PC/
Carbon left at 800 DEG C of TPDDS composite material significantly improves, and its Vmax2It is substantially reduced, the reason is that in fire retardant TPDDS
Under the action of, the decomposition rate that the degradation of PC substrate generates the better layer of charcoal of stability and slows down layer of charcoal improves carbon left.
In air atmosphere for PC and PC/TPDDS system, heating rate is the TGA and DTG of 10 DEG C/min to Fig. 4 A and Fig. 4 B
Curve.By Fig. 4 A and Fig. 4 B it is found that in air, the degradation of two steps, first stage master occur for PC and PC/TPDDS composite material
The thermal degradation of PC substrate occurs, PC substrate carries out the chain rupture of isopropylidene key, the hydrolysis or alcoholysis of carbonic acid ester bond, carbonic acid ester bond
Rearrangement to form ehter bond and cross-linking reaction, to form protectiveness layer of charcoal.In addition, being also known as by Fig. 4 A and Fig. 4 B, composite material
The purer PC's of remaining layer of charcoal is more in the first stage.And second stage is then that the first stage carbon residue of generation is further in air
Thermal oxide is decomposed.
Table 4PC and PC/TPDDS system thermal degradation performance parameter under a nitrogen and carbon yield
Table 4 lists thermal stability data of the PC and PC/TPDDS system in nitrogen atmosphere.As shown in Table 4, compared to
The V of pure PCmax, the V of PC/TPDDS composite materialmaxValue increases.The reason is that fire retardant can promote after its composite material starts decomposition
It decomposes into PC substrate and Quick cross-linking generates stable layer of charcoal at charcoal, is covered in substrate surface and hinders heat and oxygen to not
The propagation for firing substrate, plays the role of heat-insulated oxygen-impermeable, slows down the rapid burning of substrate, to improve flame retardant property.
In a nitrogen atmosphere for PC and PC/TPDDS system, heating rate is the TGA and DTG of 10 DEG C/min to Fig. 5 A and Fig. 5 B
Curve.By Fig. 5 A, Fig. 5 B and table 4 it is found that in a nitrogen atmosphere, step degradation occurs for pure PC and PC/TPDDS composite material.
Embodiment 2
A kind of diaminodiphenylsulfone derivative flame retardant that the present embodiment is related to and preparation method thereof, the diamino being prepared
The physico-chemical property of base diphenyl sulfone derivative fire retardant is substantially the same manner as Example 1, only unlike:
The dosage of chlorinated diphenyl phosphate is 16.12g, the molar ratio of the diaminodiphenylsulfone and chlorinated diphenyl phosphate
For 1:6, yield are as follows: 67.1%.
Embodiment 3
A kind of diaminodiphenylsulfone derivative flame retardant that the present embodiment is related to and preparation method thereof, the diamino being prepared
The physico-chemical property of base diphenyl sulfone derivative fire retardant is substantially the same manner as Example 1, only unlike:
The dosage of chlorinated diphenyl phosphate is 18.80g, i.e., mole of described diaminodiphenylsulfone and chlorinated diphenyl phosphate
Than for 1:7, yield are as follows: 67%.
Embodiment 4
A kind of diaminodiphenylsulfone derivative flame retardant that the present embodiment is related to and preparation method thereof, the diamino being prepared
The physico-chemical property of base diphenyl sulfone derivative fire retardant is substantially the same manner as Example 1, only unlike:
The dosage of chlorinated diphenyl phosphate is 21.49g, i.e., mole of described diaminodiphenylsulfone and chlorinated diphenyl phosphate
Than for 1:8, yield are as follows: 66.8%.
Claims (10)
1. a kind of diaminodiphenylsulfone derivative flame retardant, which is characterized in that the diaminodiphenylsulfone derivative flame retardant
Molecular structural formula is as follows:
2. a kind of preparation method of diaminodiphenylsulfone derivative flame retardant according to claim 1, which is characterized in that institute
Stating preparation method includes:
Step 1, under conditions of catalyst, pH value are 7~9, the acetonitrile solution of chlorinated diphenyl phosphate is slowly dropped into diamino
It is reacted in the anhydrous acetonitrile of diphenyl sulphone (DPS), obtains thick solid；
Step 2, it after the thick solid is first washed with HCl solution, then is washed until the thick solid with NaOH solution
It is in neutrality；
Step 3, neutral thick solid step 2 obtained is dissolved in methanol, obtains solution B；Side stirring is described molten
The side liquid B is poured slowly into CaCl2In solution, precipitate A is precipitated in coagulation, and the precipitate A is obtained by filtration；
Step 4, recrystallization purification is carried out to the precipitate A using first alcohol and water, the diaminodiphenylsulfone derivative resistance is precipitated
Fire agent.
3. a kind of preparation method of diaminodiphenylsulfone derivative flame retardant according to claim 2, which is characterized in that step
Diaminodiphenylsulfone described in rapid 1 and the molar ratio of chlorinated diphenyl phosphate are 1:5~8.
4. a kind of preparation method of diaminodiphenylsulfone derivative flame retardant according to claim 2, which is characterized in that step
Rapid 1 catalyst is 4-dimethylaminopyridine.
5. a kind of preparation method of diaminodiphenylsulfone derivative flame retardant according to claim 2, which is characterized in that step
Reaction described in rapid 1 uses N, and N- diisopropylethylamine adjusts the pH value of reaction.
6. a kind of preparation method of diaminodiphenylsulfone derivative flame retardant according to claim 2, which is characterized in that step
The reaction equation of rapid 1 reaction are as follows:
7. a kind of preparation method of diaminodiphenylsulfone derivative flame retardant according to claim 2, which is characterized in that step
HCl solution concentration described in rapid 2 is 0.01mol/L~0.3mol/L.
8. a kind of preparation method of diaminodiphenylsulfone derivative flame retardant according to claim 2, which is characterized in that step
NaOH solution concentration described in rapid 2 is 0.01mol/L~0.3mol/L.
9. a kind of preparation method of diaminodiphenylsulfone derivative flame retardant according to claim 2, which is characterized in that step
CaCl described in rapid 32The concentration of solution is 0.02mol/L~0.5mol/L.
10. a kind of diaminodiphenylsulfone derivative flame retardant according to claim 1 is in the poly- carbonic acid resin of bisphenol A-type
Using.
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