CN110092944A - The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO - Google Patents
The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO Download PDFInfo
- Publication number
- CN110092944A CN110092944A CN201910369146.6A CN201910369146A CN110092944A CN 110092944 A CN110092944 A CN 110092944A CN 201910369146 A CN201910369146 A CN 201910369146A CN 110092944 A CN110092944 A CN 110092944A
- Authority
- CN
- China
- Prior art keywords
- dps
- diphenyl sulphone
- flame retardant
- nitrogen phosphorus
- dopo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 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 30
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 24
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 claims abstract description 5
- 239000004814 polyurethane Substances 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- JYGYEBCBALMPDC-UHFFFAOYSA-N heptane;propan-2-one Chemical compound CC(C)=O.CCCCCCC JYGYEBCBALMPDC-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 11
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000003383 Atherton-Todd reaction Methods 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 17
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001385 heavy metal Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- -1 phosphorus series compound Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect 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
- C07F9/547—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
- C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention belongs to flame retardance of polymer fields, and in particular to the preparation method and applications of the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO.DOPO and 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s occur Atherton-Todd reaction and generate the phosphorus nitrogen sulphur synergistic fire retardant containing DOPO, diphenyl sulphone (DPS) structural unit.Applied to the macromolecules resin system such as polyurethane and ABS, with good with compatibility with polymer, storage stability is excellent, three kinds of phosphorous, nitrogen, sulphur elements simultaneously, has the effect of cooperative flame retardant in combustion, carbon yield is high, and when phosphorus content is 0.22 wt.% in resin system, vertical combustion grade reaches UL-94V-0 grades.Its cost of material is reasonable, and additive amount is few, and preparation process environmental protection is easy, easy to industrialized production.
Description
Technical field
The invention belongs to flame retardance of polymer fields, and in particular to sulphur-nitrogen-phosphorus containing double DOPO, diphenyl sulfone structural unit
The preparation method of ternary synergistic flame retardant, and it is applied to the flame-retardant modified of the macromolecule resins such as polyurethane, ABS.
Background technique
High polymer material is widely used in each department of the national economy such as industry, agricultural, military affairs, but most of high
Polymers belongs to petroleum base combustible material, and polarity oxygen index (OI) is lower than 21, and heat release rate is high when burning, and calorific value is big, flame propagation speed
Degree is fast, is not easy to extinguish, and generally can also produce thick smoke and toxic gas, grave danger caused by the security of the lives and property of people.
There are the secondary hazards such as thickness, the releasing of toxic or corrosive gas when traditional halogen fire proofing burns, to personal safety structure
At seriously threatening.Attention with the development and people of flame-retarded technology to environmental protection and personal safety, Halogen, low cigarette,
Less toxic, high-fire resistance environmental protection fire retarding agent has become research hotspot.Chinese patent CN 101278001A is using phosphorous acid and sub- phosphine
Fire retardant of the ester derivant of the phosphorous oxyacid of acid as polyurethane resin, when additive amount reaches 10wt.% or so, poly- ammonia
For the vertical combustion grade of ester resin up to UL-94V-0 grades, flame retardant property is suitable with DOPO.However, without rigidity in its molecular structure
Ring causes its thermal stability and chemical stability to decline, and synthesis technology is complicated, and industrialized production is difficult.For ABS fire retardant
System, Chinese patent CN 104277410A report the mixing flame-retardant system of a kind of bromide and antimony oxide, although ABS hangs down
Straight combustion rating reaches UL-94V-0 grades, but amount of flame-retardant agent reaches 12wt.% or more, and halogen and heavy metal form, and cause
Serious environmental pollution.
Derivative containing DOPO is fire-retardant since its thermal stability and chemical stability are high as a kind of novel flame redundant material
Performance is significant, and Halogen, it is smokeless, environmentally friendly, not easy to migrate, carbon yield is high the features such as, be macromolecule resin halogen-free flameproof in recent years
Research hotspot.At this stage, phosphorus-hydrogen bond active in DOPO molecular structure, is mainly prepared by nucleophilic displacement of fluorine mode and is contained
The fire retardant of DOPO structural unit.However, facile hydrolysis containing phosphorus series compound generates the toxic gases such as hydrogen phosphide, therefore actually answering
There is certain limitation in.Therefore, how to coordinate low phosphorus content and excellent flame retardancy, become technical bottleneck at this stage.In
103421212 A of state patent CN introduces hydroxyl in DOPO structure, and cured reaction-type flame-retarding can be participated in by being prepared for one kind
Agent, when epoxy resin vertical combustion grade reaches UL-94V-0 grades, effective phosphorus content is still higher than 1.8wt.%；Chinese patent CN
103865101 A introduce aromatic amine in DOPO, phosphorus nitrogen synergistic based flame retardant at preparation, although available phosphorus content is reduced to
0.75wt.%, but its synthesis technology complexity, purification difficult, it is difficult to industrialized production and application.On the other hand, sulfur-bearing based flame retardant,
With excellent fireproof performance, the advantages such as additive amount is few.Therefore, by closing the nuclear structure segment of DOPO, diphenyl sulfone
Reason assembling and modification, prepare phosphorus nitrogen and sulphur synergistic based flame retardant, solve that existing fire retardant performance is poor, phosphorus content is high, conjunction
At the technical problem of complex process.
Summary of the invention
The technical problem to be solved in the present invention is to provide sulphur-nitrogen containing double DOPO, diphenyl sulfone structural unit-phosphorus ternary associations
Imitate the preparation method of fire retardant；It is good with macromolecule resin compatibility that the based flame retardant has, and chemical and thermal stability is high, effective
When phosphorus content is 0.22wt.%, vertical combustion grade is up to UL-94V-0 grades.
To solve the above-mentioned problems, the technical scheme is that
DOPO and 3,3/,4,4/Tetramino diphenyl sulphone (DPS) occurs Atherton-Todd reaction and generates containing DOPO, diphenyl sulphone (DPS) structure
The phosphorus nitrogen sulphur synergistic fire retardant of unit, particular chemical formula are as follows:
The preparation method of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO, comprising the following steps:
DOPO (miscellaneous phenanthrene -10- the oxidation of the miscellaneous -10- phosphine of 9,10- dihydro-9-oxy is sequentially added in the container equipped with agitating device
Object), 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, carbon tetrachloride and solvent, stirring is uniformly mixed system, under conditions of ice bath,
Organic base is added into reaction system, reacts at room temperature, filtrate, filtrate is obtained by filtration after the reaction was completed in TLC tracking reaction process
After extraction is washed, is concentrated, normal heptane-acetone (V is addedNormal heptane∶VAcetone=1: 4) being allowed to precipitate, be dried in vacuo to obtain the diphenyl sulphone (DPS) containing DOPO
Nitrogen phosphorus sulphur synergistic fire retardant.
3,3 ', the 4,4 '-tetramino diphenyl sulphone (DPS), DOPO, carbon tetrachloride, organic base molar ratio be 1.0: (4.4~
6.0): (4.4~6.0): (4.4~6.0).
The solvent is methylene chloride, ethyl acetate, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, one in chloroform
Kind is a variety of.
The solvent usage is 4~8 times of DOPO mass.
The organic base is selected from one of trimethylamine, triethylamine, sodium methoxide, sodium ethoxide or a variety of.
Diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant prepared by the present invention containing DOPO has thermal stability and chemical stabilization
Property height, Halogen, suppression cigarette, with when macromolecule resin compatibility is good, effective phosphorus content is down to 0.22wt.%, vertical combustion grade can
Up to UL-94V-0 grades etc..
Compared with prior art, the beneficial effects of the present invention are:
(1) DOPO structural unit is introduced into diphenyl sulphone (DPS) molecule, simultaneously containing tri- kinds of element associations of S, N, P in molecular structure
Imitate fire-retardant, p and s element can promote to be formed layer of charcoal, and nitrogen, which generates ammonia after capable of burning, gas phase flame retardant effect, and synergistic effect overcomes
The deficiency of single ignition-proof element, improves heat resistance and high temperature charring rate, when effective phosphorus content is down to 0.22wt.%, high score
Subtree rouge vertical combustion grade is up to UL-94V-0 grades etc..
(2) preparation of this fire retardant is simple, and mild condition, raw material is easy to get, easy to industrialized production.
(3) the product thermostabilization that the present invention synthesizes is good, thermal stability with higher and hydrolytic resistance.
Specific embodiment
The invention will be further described with reference to embodiments, but the scope of protection of present invention is not limited to reality
Apply the range of example statement.
Embodiment 1:
In N2Under protection, 3,3 are added into the reaction flask equipped with mechanical agitator/,4,4/Tetramino diphenyl sulphone (DPS) 11.5g
(0.1mol), DOPO 95.2g (0.44mol), 67.7g (0.44mol) carbon tetrachloride and 350mL methylene chloride are added to reaction
In bottle, 30min is stirred.It is under condition of ice bath, the mixed solution of 60mL methylene chloride and 22.3g (0.22mol) triethylamine is slow
Slowly it is added dropwise in above-mentioned reaction flask, after being added dropwise to complete, room temperature reaction, TLC tracking reaction process is obtained by filtration after the reaction was completed
Filtrate.Normal heptane-acetone (V is added after extraction is washed, is concentrated in filtrateNormal heptane∶VAcetone=1: 4) being allowed to precipitating makes, and is dried in vacuo to obtain mesh
Mark compound, light yellow solid powder, yield 72.1%.
Diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic fire retardant produced by the present invention containing DOPO, initial decomposition temperature are about respectively 292 DEG C,
The carbon yield of 800 DEG C of fire retardants respectively reaches 31%, which has preferable thermal stability, and carbon yield is high, has preferable
Flame retardant effect.
The analysis result of fire retardant produced by the present invention is as follows:
Compound results of IR: FT-IR (KBr), v/cm-1:3273(N-H),3021(Ar-H),1416(P-
), Ph 1211 (P=O), 1129 (P-O-Ar).
Hydrogen nuclear magnetic resonance spectrum analysis result:1H NMR(DMSO-d6,400MHz):8.07-7.93(m,4H,ArH),7.75-
7.62(m,4H,ArH),7.58-7.52(m,5H,ArH),7.48-7.41(m,5H,ArH),7.36-7.31(m,5H,ArH),
7.29-7.23(m,5H,ArH),6.97-6.91(m,6H,ArH),6.86-6.75(m,5H,ArH),5.92(s,4H,N-H).
Embodiment 2:
The amount of DOPO increases to 103.8g (0.48mol), other same examples one, target compound yield 76.5%.
The amount of DOPO increases to 112.4g (0.52mol), other same examples one, target compound yield 81.3%.
The amount of DOPO increases to 121.1g (0.56mol), other same examples one, target compound yield 86.2%.
The amount of DOPO increases to 127.8g (0.60mol), other same examples one, target compound yield 75.8%.
Embodiment 3:
The amount of carbon tetrachloride increases to 73.9g (0.48mol), other same examples one, target compound yield 75.3%.
The amount of carbon tetrachloride increases to 80.1g (0.52mol), other same examples one, target compound yield 81.2%.
The amount of carbon tetrachloride increases to 86.2g (0.56mol), other same examples one, target compound yield 83.5%.
The amount of carbon tetrachloride increases to 92.3g (0.60mol), other same examples one, target compound yield 79.2%.
Embodiment 4:
The amount of triethylamine increases to 48.6g (0.48mol), other same examples one, target compound yield 74.5%.
The amount of triethylamine increases to 52.7g (0.52mol), other same examples one, target compound yield 76.3%.
The amount of triethylamine increases to 60.8g (0.56mol), other same examples one, target compound yield 76.1%.
Embodiment 5:
Alkali changes sodium methoxide, other same examples one, target compound yield 42.1% into.
Alkali changes sodium ethoxide, other same examples one, target compound yield 39.5% into.
Diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic fire retardant provided by the invention containing DOPO is as polyurethane, the flame-retardant additive of ABS
Application, the phosphorus content of the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO is 0.22wt.%~0.86wt.%,
Concrete application is as follows:
Batten is made according to insulating laminated sheet combustibility testing standard, is limited respectively with JF-3 type oxygen index measurer
Oxygen index (OI) (LOI) test, FZ-5401 type Vertical combustion instrument carry out the test of UL94 vertical combustion performance, measurement result such as following table 1-
2.Its limit oxygen index content is 21.7~39.1, and carbon yield is 23.8~34.3%.Contain in the flame retardant type macromolecule resin
When phosphorus amount is 0.22wt.%, vertical combustion grade is up to UL-94V-0 grades.
Flame retardant effect of the target compound of 1 embodiment of the present invention 1 of table synthesis as polyurethane flame-proof additive
Flame retardant effect of the target compound of 2 embodiment of the present invention 1 of table synthesis as ABS flame-retardant additive
Claims (7)
1. the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO, which is characterized in that chemical structural formula is as follows:
2. the preparation method of the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO, feature exist according to claim 1
In, the specific steps are as follows: the miscellaneous miscellaneous phenanthrene -10- of -10- phosphine of 9,10- dihydro-9-oxy is sequentially added in the container equipped with agitating device
Oxide, 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, carbon tetrachloride and solvent, stirring is uniformly mixed system, in the condition of ice bath
Under, organic base is added into reaction system, reacts at room temperature, filtrate is obtained by filtration after the reaction was completed in TLC tracking reaction process, filters
Normal heptane-acetone V is added after extraction is washed, is concentrated in liquidNormal heptane∶VAcetoneBe allowed to precipitate at=1: 4, is dried in vacuo to obtain-the 9- containing 9,10- dihydro
The diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic fire retardant of the miscellaneous phenanthrene -10- oxide of oxa- -10- phosphine.
3. the preparation method of the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO, feature exist according to claim 1
In, described 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, the miscellaneous phenanthrene -10- oxide of the miscellaneous -10- phosphine of 9,10- dihydro-9-oxy, carbon tetrachloride,
The molar ratio of organic base is 1.0: (4.4~6.0): (4.4~6.0): (4.4~6.0).
4. the preparation method of the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO, feature exist according to claim 1
In, the solvent be one of methylene chloride, ethyl acetate, acetonitrile, tetrahydrofuran, n,N-Dimethylformamide, chloroform or
It is a variety of.
5. the preparation method of the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO, feature exist according to claim 1
In the solvent usage is 4~8 times of the miscellaneous phenanthrene -10- oxide mass of the miscellaneous -10- phosphine of 9,10- dihydro-9-oxy.
6. the preparation method of the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO, feature exist according to claim 1
In the organic base is selected from one of trimethylamine, triethylamine, sodium methoxide, sodium ethoxide or a variety of.
7. the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant according to claim 1 containing DOPO is in polyurethane and ABS high score
Application on subtree resin system, the phosphorus content of the diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO are 0.22wt.%
~0.86wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910369146.6A CN110092944A (en) | 2019-05-05 | 2019-05-05 | The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910369146.6A CN110092944A (en) | 2019-05-05 | 2019-05-05 | The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110092944A true CN110092944A (en) | 2019-08-06 |
Family
ID=67446893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910369146.6A Pending CN110092944A (en) | 2019-05-05 | 2019-05-05 | The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110092944A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402550A (en) * | 2021-06-18 | 2021-09-17 | 中国科学技术大学 | Thiophosphonate-containing flame-retardant polyol, synthesis method thereof and application thereof in preparation of flame-retardant polyurethane flexible foam |
| CN115395174A (en) * | 2022-09-01 | 2022-11-25 | 欣旺达电动汽车电池有限公司 | Composite diaphragm, secondary battery and electric equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733024A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus/nitrogen/sulfur-containing flame retardant and preparation method thereof |
| CN108440598A (en) * | 2018-04-08 | 2018-08-24 | 三峡大学 | A kind of preparation method and applications of sulphur-nitrogen-phosphorus composite fire retardant |
| CN109265479A (en) * | 2018-08-21 | 2019-01-25 | 中北大学 | A kind of diaminodiphenylsulfone derivative flame retardant and its preparation method and application |
-
2019
- 2019-05-05 CN CN201910369146.6A patent/CN110092944A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733024A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus/nitrogen/sulfur-containing flame retardant and preparation method thereof |
| CN108440598A (en) * | 2018-04-08 | 2018-08-24 | 三峡大学 | A kind of preparation method and applications of sulphur-nitrogen-phosphorus composite fire retardant |
| CN109265479A (en) * | 2018-08-21 | 2019-01-25 | 中北大学 | A kind of diaminodiphenylsulfone derivative flame retardant and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402550A (en) * | 2021-06-18 | 2021-09-17 | 中国科学技术大学 | Thiophosphonate-containing flame-retardant polyol, synthesis method thereof and application thereof in preparation of flame-retardant polyurethane flexible foam |
| CN113402550B (en) * | 2021-06-18 | 2023-08-29 | 中国科学技术大学 | Flame-retardant polyol containing thiophosphonate, synthesis method thereof and application thereof in preparation of flame-retardant polyurethane soft foam |
| CN115395174A (en) * | 2022-09-01 | 2022-11-25 | 欣旺达电动汽车电池有限公司 | Composite diaphragm, secondary battery and electric equipment |
| CN115395174B (en) * | 2022-09-01 | 2023-06-06 | 欣旺达电动汽车电池有限公司 | Composite diaphragm, secondary battery and electric equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101921599B (en) | Bicyclic phosphate-based triazine derivative flame retardant and preparation method thereof | |
| CN101838538B (en) | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof | |
| CN101058730B (en) | Phosphorus-nitrogen type halogen-free ionic fire retardant, preparation method thereof and fire retarding polyvinyl alcohol material prepared from the same | |
| CN103113409B (en) | A kind of young laying ducks in cage containing triazine ring structure and preparation method thereof | |
| CN104558684A (en) | DOPO-containing dioxacaprophosphate flame retardant as well as preparation method and application thereof | |
| CN110357987B (en) | Intumescent flame retardant and preparation method thereof | |
| CN108440598B (en) | Preparation method and application of sulfur-nitrogen-phosphorus composite flame retardant | |
| CN110183727B (en) | Benzothiazole nitrogen phosphorus sulfur ternary synergistic flame retardant containing double DOPO units, and preparation method and application thereof | |
| CN109957114B (en) | Lignin intumescent flame retardant and preparation method thereof | |
| CN107573538A (en) | Phosphor nitrogen combustion inhibitor, preparation method and applications | |
| CN113214319B (en) | Quaternary phosphonium salt flame retardant and synthetic method and application thereof | |
| CN112409567B (en) | Preparation method of P-N type flame retardant based on DOPO | |
| CN104497041A (en) | Melamine aminotrimethylene phosphonate and preparation method thereof | |
| CN110092944A (en) | The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO | |
| CN110128702A (en) | Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications | |
| CN107056839B (en) | A kind of synthetic method of response type bicyclic phosphate fire retardant | |
| CN110128474B (en) | Preparation method and application of nitrogen-phosphorus-sulfur ternary synergistic flame retardant bis-DOPO thiazole compound | |
| CN109897219A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN109897224A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN104031090B (en) | A kind of preparation method of ring-type phosphorus nitrogen synergistic halogen-free flame retardants | |
| CN110105395A (en) | A kind of pyridine fire retardant and its preparation method and application | |
| CN107082909B (en) | A kind of preparation method and applications of the hydroquinone biphosphonate fire retardant containing DOPO | |
| CN106009039A (en) | Flame-retardant agent containing spirane structure and having antioxidant function and preparation method | |
| CN109897339A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN114634654A (en) | Efficient halogen-free phosphorus and nitrogen intumescent flame retardant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190806 |