CN105732717A - Imidazolium liquid flame-retardant agent containing caged phosphate structure and preparation method thereof - Google Patents
Imidazolium liquid flame-retardant agent containing caged phosphate structure and preparation method thereof Download PDFInfo
- Publication number
- CN105732717A CN105732717A CN201610218246.5A CN201610218246A CN105732717A CN 105732717 A CN105732717 A CN 105732717A CN 201610218246 A CN201610218246 A CN 201610218246A CN 105732717 A CN105732717 A CN 105732717A
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- solvent
- liquid type
- ion liquid
- type fire
- 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.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012757 flame retardant agent Substances 0.000 title abstract description 26
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 title abstract 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 title abstract 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000003063 flame retardant Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 96
- -1 imidazole ion Chemical class 0.000 claims description 63
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 54
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 35
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 22
- 241000272517 Anseriformes Species 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- 150000003851 azoles Chemical class 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 abstract description 63
- 239000000463 material Substances 0.000 abstract description 29
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 229920000515 polycarbonate Polymers 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 125000003944 tolyl group Chemical group 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 description 25
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- OWNSZSBRIOHAAJ-UHFFFAOYSA-N 1-chlorosulfonyloxybutane Chemical class CCCCOS(Cl)(=O)=O OWNSZSBRIOHAAJ-UHFFFAOYSA-N 0.000 description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 5
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 5
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 5
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- MDLHEADEPQXWHI-UHFFFAOYSA-N benzene;furan Chemical compound C=1C=COC=1.C1=CC=CC=C1 MDLHEADEPQXWHI-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002341 toxic gas Substances 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
- C07F9/547—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
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- 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
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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)
- Fireproofing Substances (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The general structural formula of an imidazolium liquid flame-retardant agent containing a caged phosphate structure disclosed in the invention is shown in the description, wherein X is an alkyl group, a phenyl group or a phosphate group of C=1-20, Y is an alkyl group, a phenyl group or a tolyl group of C=1-20, and the limit oxygen index of polycarbonate after the flame-retardant agent is used for polycarbonate can be increased by 4.5-6 units compared with pure polycarbonate.The invention further discloses a preparation method of the flame-retardant agent.The imidazolium liquid flame-retardant agent containing the caged phosphate structure does not contain halogen, is high in decomposition temperature, can be independently used, and is little in addition amount and good in flame-retardant effect.Oxidation decomposition occurring in the processing process of the flame-retardant agent can be effectively avoided, and adverse effects on mechanical properties of a material can be reduced.The preparation method is easy to operate, cost is low, a product obtained through reaction is high in yield, the reaction raw material substituted imidazole can be recycled and reused, and environmental protection and energy conservation are achieved.
Description
Technical field
The invention belongs to imidazole ion liquid type fire retardant and preparation method thereof, relate in particular to a kind of containing young laying ducks in cage knot
The preparation method of the imidazole ion liquid type fire retardant of structure.
Background technology
Ionic liquid as an eco-friendly compound of class, because there is uniqueness and the physicochemical properties of excellence in recent years
To development at full speed be widely applied, as it is almost without vapour pressure, the most volatile, liquid journey wide ranges, Heat stability is good,
Thermal capacity is big, electrochemical window width, the feature such as non-combustible, is referred to as " green solvent " that can substitute conventional organic solvents.
The more important thing is that the molecule designability of ionic liquid is strong, can be by the alkyl chain length of regulation cation, change alkyl substituent
Kind, selecting suitable anion to regulate physical property and the chemical property of ionic liquid, this makes us can be according to tool
The needs of body design " functional ionic liquids ".At present ionic liquid in synthesis, catalysis, isolation technics, electrochemistry, divide
Analysis chemistry and the most a lot of research of nanometer material science aspect, and ionic liquid is as the plasticizer of macromolecular material, dispersion
The report of the functional aid such as agent, fire retardant also day animando.
Patent CN102924749A reports a kind of Ionic liquid-type phosphate fire retardant of research synthesis, and is answered
Join and add in polypropylene (PP) for expanding fire retardant, obtain preferable flame retardant effect.But, in that patent, closed
The ion liquid type fire retardant become needs to quote a certain amount of halogen and can reach corresponding effect, and along with macromolecular material
The expansion of application, people are more and more higher to the requirement of fire retardant and fire proofing, and halogenated flame retardant is because of the process in burning
Middle meeting discharges a large amount of dense smoke and the corrosivity toxic gas such as two English, benzene furan, is the most gradually used by restriction.And should
The fire retardant that patent is reported needs to coordinate ammonium polyphosphate, tetramethylolmethane and tripolycyanamide to be re-dubbed expansion type flame retardant to be added
Just playing preferable flame retardant effect in material, be used alone the unsatisfactory of effect, it is certain that this makes it have in the application
Restricted.
Summary of the invention
It is an object of the invention to for prior art exist defect, first provide a kind of imidazoles containing young laying ducks in cage structure from
Sub-liquid type fire retardant, this fire retardant does not contains halogen, has the thermal stability of excellence.
The two of the purpose of the present invention are to provide the preparation side of the above-mentioned imidazole ion liquid type fire retardant containing young laying ducks in cage structure
Method.
The imidazole ion liquid type fire retardant containing young laying ducks in cage structure that the present invention provides, it is characterised in that its general structure is such as
Under:
In formula, X is the alkyl of C=1-20, phenyl or phosphate-based, and the most phosphate-based structure is as follows:
Y is the alkyl of C=1-20, phenyl or p-methylphenyl, is applied in Merlon by this fire retardant, is 0.1～5wt% at addition
Time, its limited oxygen index is 29.5～32.0%.
The alkyl of the preferred C=1-8 of Y described in above fire retardant or p-methylphenyl.
The preparation method of the above-mentioned imidazole ion liquid type fire retardant containing young laying ducks in cage structure that the present invention provides, its feature exists
As follows in processing step and the condition of the method:
1) at N2Under protection, by 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] octane (PEPA) and tiing up
Acid agent is sequentially added in solvent I, and stirring is slowly added dropwise substituted sulfonic acid chlorine after dissolving mix homogeneously to major part PEPA again, and
Reacting 6-15h at 25-50 DEG C, reaction is distilled off solvent I after terminating, more scrubbed, obtain intermediate after drying, its
Middle acid binding agent and PEPA mol ratio are 1-1.2:1；PEPA is 1:1-1.5 with the mol ratio of replacement sulfonic acid chloride, and it reacted
Journey is as follows:
2) gained intermediate is first dissolved completely in solvent II, is subsequently adding substituted imidazole, and at N2It is warming up under protection
60-85 DEG C of reaction 48-72h, is distilled off solvent II, scrubbed, after drying, wherein substituted imidazole and intermediate
Mol ratio is 1-1.2:1；Its course of reaction is as follows:
Solvent I used in said method is any one in dichloromethane, acetone or oxolane.
Solvent II used in said method is in acetone, acetonitrile, 1-Methylimidazole., 1-ethyl imidazol(e) or 1-propyl imidazole
Any one.
Acid binding agent used in said method is triethylamine or pyridine.
The structural formula replacing sulfonic acid chloride used in said method is:
In formula, Y is alkyl or the p-methylphenyl of the alkyl of C=1-20, phenyl or p-methylphenyl, preferably C=1-8.
The structural formula of substituted imidazole used in said method is:
In formula, X is the alkyl of C=1-20, phenyl or phosphate-based, and the most phosphate-based structure is as follows:
The present invention compared with prior art, has the advantage that
1, without halogen in the structure of the imidazole ion liquid type fire retardant containing young laying ducks in cage structure provided due to the present invention,
Thus this fire retardant can meet the requirement of environmental protection sustainable development now, have a good application prospect；
2, containing sulfonic acid in the anion of the imidazole ion liquid type fire retardant containing young laying ducks in cage structure provided due to the present invention
Root, thus in makrolon material, have only to add minimal amount of (0.1wt%) fire retardant i.e. can reach preferable fire-retardant effect
Really, the negative effect that material mechanical performance is brought by additive flame retardant is decreased.
3, there is the thermal stability of excellence owing to the present invention containing the imidazole ion liquid type fire retardant of young laying ducks in cage structure,
Its decomposition temperature is all more than the processing temperature of the major part macromolecular materials such as Merlon, thus can be prevented effectively from it in processing
During oxidation Decomposition occurs, so that losing excellent anti-flammability.
4, the imidazole ion liquid type fire retardant containing young laying ducks in cage structure provided due to the present invention can individually make in use
With, it is not necessary to carry out compounding just there is preferable anti-flammability with other flame-retardant composition, thus both avoided and found its matched
Its flame-retardant composition carries out the trouble compounded, and can reduce again the restriction of actual application.
5, the preparation method technological operation that the present invention provides is simple, with low cost, and reaction products therefrom yield is high, reacts former
Material substituted imidazole is recyclable again with, environmental protection and saving.
Accompanying drawing explanation
Fig. 1 be the anion prepared by present example 1 be pyrovinic acid root glyoxaline ion liquid type fire retardant (brief note
For [Pmim] CH3SO3)1H NMR spectra.In figure, the chemical shift of each hydrogen atom is specific as follows: (δH,(CD3)2SO):
9.1(1H,s,NCHN),7.7(1H,s,CCHNCH3),7.6(1H,s,CCHNCH2),4.7(6H,d,OCH2),4.3(2H,s,
NCH2),3.8(3H,s,NCH3),2.3(3H,s,SCH3), it can be seen that the structure of this target product and expected structure one
Cause.
Fig. 2 be the anion prepared by the embodiment of the present invention 1 be the glyoxaline ion liquid type fire retardant of pyrovinic acid root13C
NMR spectra.In figure, the chemical shift of each carbon atom is specific as follows: (δc,(CD3)2SO):138.5(N-CH2-N),
124.4(CH3-N-CH2),123.7(N-CH2-CH2),75.9(O-CH2),45.9(N-CH2-C4),40.3(CH3SO3),37.3
and 36.9(C4diffierent conformation),36.4(N-CH3), it can be seen that the structure of this target product and expection
Structure is consistent.
Fig. 3 be the anion prepared by the embodiment of the present invention 1 be the heat of the glyoxaline ion liquid type fire retardant of pyrovinic acid root
Weight analysis curve.It can be seen that [Pmim] CH3SO3Temperature of initial decomposition be 339 DEG C, maximum weightless temperature
TmaxBeing 368 DEG C, thermal weight loss speed peak value is 11.6%/min, the carbon residue when 700 DEG C is up to 36.6%, and himself is described
Become charcoal the best.
Detailed description of the invention
Embodiment is given below so that the invention will be further described.Be necessary it is pointed out here that, following example can not be managed
Solve as limiting the scope of the invention, if the person skilled in the art in this field according to the invention described above content to the present invention
Make some nonessential improvement and adjustment, still fall within scope.
What deserves to be explained is: the limited oxygen index of following example products obtained therefrom is made into 120 × 6.5 × 3.2mm3
Standard batten, according to ASTM D2863-97 standard, measures on HC-2 oxygen index instrument.
Embodiment 1
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent triethylamine are added sequentially in dichloromethane, room
Stirring 10min at temperature 25 DEG C, then drip the methylsufonyl chloride of 0.5mol, time for adding controls 1.5h, 25 after dripping
Reacting 6h at DEG C, reaction is distilled off dichloromethane after terminating, more scrubbed, obtain intermediate after drying, yield 85%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent 1-Methylimidazole., is subsequently adding the 1-Methylimidazole. of 0.5mol,
And at N2Being warming up to 85 DEG C of stirring reaction 48h under protection, distillation is except solvent 1-Methylimidazole., residue washed with acetone 3-4
Secondary, it is dried to obtain the glyoxaline ion liquid type fire retardant that anion is pyrovinic acid root, yield is 76%.Its structural formula is such as
Under:
3) obtained flame-retardant agent is carried out blended obtaining with the addition of 0.5wt% with Merlon (PC) in torque rheometer
Fire retardation PC material, its limited oxygen index is 30.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 4.5 units.
Embodiment 2
1) at N2Under protection, 0.5mol PEPA and 0.6mol acid binding agent triethylamine are sequentially added in acetone, room temperature 25
Stirring 20min at DEG C, then drip the paratoluensulfonyl chloride of 0.75mol, time for adding controls 3h, after dripping at 25 DEG C
Reaction 8h, reaction is distilled off acetone after terminating, more scrubbed, obtain intermediate, yield 88% after drying, its structure is such as
Under:
2) gained 0.5mol intermediate is dissolved in solvent 1-Methylimidazole., is subsequently adding the 1-Methylimidazole. of 0.6mol,
And at N2Being warming up to 83 DEG C of stirring reaction 58h under protection, distillation is except solvent 1-Methylimidazole., residue washed with acetone 3-4
Secondary, it is dried to obtain the glyoxaline ion liquid type fire retardant that anion is p-methyl benzenesulfonic acid root, yield is 72%.Its structural formula
As follows:
3) obtained flame-retardant agent is carried out blended obtaining with the addition of 0.1wt% with Merlon (PC) in torque rheometer
Fire retardation PC material, its limited oxygen index is 30.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 4.5 units.
Embodiment 3
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent triethylamine are sequentially added in dichloromethane, room temperature
Stirring 10min at 25 DEG C, then drip the 1-butyl sulfochlorides of 0.52mol, time for adding controls 1.5h, 26 after dripping
Reacting 6h at DEG C, reaction is distilled off dichloromethane after terminating, more scrubbed, obtain white intermediate after drying, yield 78%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent 1-Methylimidazole., is subsequently adding the 1-Methylimidazole. of 0.5mol,
And at N2It is warming up to 80 DEG C of stirring reaction 50h under protection, solvent 1-Methylimidazole., residue washed with acetone are distilled off
3-4 time, being dried to obtain the glyoxaline ion liquid type fire retardant that anion is butyl sulfonic acid root, yield is 75%.Its structure
Formula is as follows:
3) carry out being blended in torque rheometer with the addition of 1wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 30.5%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.0 units.
Embodiment 4
1) at N2Under protection, 0.5mol PEPA and 0.55mol acid binding agent triethylamine are added sequentially in dichloromethane,
Stirring 10min at room temperature 25 DEG C, then drip the 1-octyl group sulfonic acid chloride of 0.58mol, time for adding controls 1.5h, after dripping
Reacting 6h at 28 DEG C, reaction is distilled off dichloromethane after terminating, more scrubbed, obtain white intermediate after drying, receive
Rate 81%, its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent 1-Methylimidazole., is subsequently adding the 1-Methylimidazole. of 0.55mol,
And at N2It is warming up to 85 DEG C of stirring reaction 48h under protection, solvent 1-Methylimidazole., residue washed with acetone are distilled off
3-4 time, being dried to obtain the glyoxaline ion liquid type fire retardant that anion is octyl sulfonic acid root, yield is 78%.Its structure
Formula is as follows:
3) carry out being blended in torque rheometer with the addition of 1wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.5 units.
Embodiment 5
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent triethylamine are added sequentially in dichloromethane, 30
Stirring 10min at DEG C, then drip the methylsufonyl chloride of 0.5mol, time for adding controls 1.5h, after dripping at 30 DEG C
Reaction 8h, reaction is distilled off dichloromethane after terminating, more scrubbed, obtain white intermediate after drying, yield 82%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent 1-ethyl imidazol(e), is subsequently adding the 1-ethyl imidazol(e) of 0.5mol,
And at N2It is warming up to 84 DEG C of stirring reaction 50h under protection, solvent 1-ethyl imidazol(e), residue washed with acetone are distilled off
3-4 time, being dried to obtain the glyoxaline ion liquid type fire retardant that anion is pyrovinic acid root, yield is 69%.Its structure
Formula is as follows:
3) obtained flame-retardant agent is carried out blended obtaining with the addition of 0.8wt% with Merlon (PC) in torque rheometer
Fire retardation PC material, its limited oxygen index is 29.5%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 4.0 units.
Embodiment 6
1) at N2Under protection, 0.5mol PEPA and 0.6mol acid binding agent triethylamine are added sequentially in acetone, room temperature 30
Stirring 20min at DEG C, then drip the paratoluensulfonyl chloride of 0.75mol, time for adding controls 3h, after dripping at 30 DEG C
Reaction 10h, reaction is distilled off acetone after terminating, more scrubbed, obtain white intermediate after drying, yield 88%, its
Structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent-ethyl imidazol(e), is subsequently adding the 1-ethyl imidazol(e) of 0.6mol, and
At N2It is warming up to 80 DEG C of stirring reaction 60h under protection, solvent 1-ethyl imidazol(e), residue washed with acetone 3-4 are distilled off
Secondary, it is dried to obtain the glyoxaline ion liquid type fire retardant that anion is p-methyl benzenesulfonic acid root, yield 78%.Its structural formula is such as
Under:
3) carry out being blended in torque rheometer with the addition of 1wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.5 units.
Embodiment 7
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent triethylamine are added sequentially in dichloromethane, 35
Stirring 10min at DEG C, then drip the 1-butyl sulfochlorides of 0.5mol, time for adding controls 1.5h, at 35 DEG C after dripping
Lower reaction 8h, reaction is distilled off dichloromethane after terminating, more scrubbed, obtain white intermediate after drying, yield 83%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent 1-ethyl imidazol(e), is subsequently adding the 1-ethyl imidazol(e) of 0.5mol,
And at N2It is warming up to 85 DEG C of stirring reaction 65h under protection, solvent 1-ethyl imidazol(e), residue washed with acetone are distilled off
3-4 time, it is dried to obtain the glyoxaline ion liquid type fire retardant that anion is butyl sulfonic acid root, yield 67%.Its structural formula
As follows:
3) carry out being blended in torque rheometer with the addition of 1wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.5 units.
Embodiment 8
1) at N2Under protection, 0.5mol PEPA and 0.52mol acid binding agent triethylamine are added sequentially in dichloromethane,
Stirring 10min at 35 DEG C, then drip the 1-octyl group sulfonic acid chloride of 0.65mol, time for adding controls 1.5h, 35 after dripping
Reacting 8h at DEG C, reaction is distilled off dichloromethane after terminating, more scrubbed, obtain white intermediate after drying, yield 79%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent 1-ethyl imidazol(e), is subsequently adding the 1-ethyl imidazol(e) of 0.52mol,
And at N2It is warming up to 80 DEG C of stirring reaction 48h under protection, solvent 1-ethyl imidazol(e), residue washed with acetone are distilled off
3-4 time, being dried to obtain the glyoxaline ion liquid type fire retardant that anion is octyl sulfonic acid root, yield is 75%.Its structure
Formula is as follows:
3) carry out being blended in torque rheometer with the addition of 2wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 30.5%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.0 units.
Embodiment 9
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent triethylamine are added sequentially in dichloromethane, 40
Stirring 10min at DEG C, then drip the methylsufonyl chloride of 0.5mol, time for adding controls 1.5h, after dripping at 40 DEG C
Reaction 8h, reaction is distilled off dichloromethane after terminating, more scrubbed, obtain white intermediate after drying, yield 76%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetone, is subsequently adding the 1-1-Butyl-1H-imidazole of 0.5mol, and
N2It is warming up to 60 DEG C of stirring reaction 70h under protection, solvent 1-1-Butyl-1H-imidazole be distilled off, residue washed with acetone 3-4 time,
Being dried to obtain the glyoxaline ion liquid type fire retardant that anion is pyrovinic acid root, yield is 71%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 3wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.0 units.
Embodiment 10
1) at N2Under protection, 0.5mol PEPA and 0.6mol acid binding agent triethylamine are added sequentially in acetone, 40 DEG C
Lower stirring 20min, then drip the paratoluensulfonyl chloride of 0.75mol, time for adding controls 3h, anti-at 40 DEG C after dripping
Answering 10h, reaction is distilled off acetone after terminating, more scrubbed, obtain white intermediate, yield 86%, its knot after drying
Structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetone, is subsequently adding the 1-1-Butyl-1H-imidazole of 0.6mol, and
N2It is warming up to 62 DEG C of stirring reaction 68h under protection, solvent 1-1-Butyl-1H-imidazole be distilled off, residue washed with acetone 3-4 time,
Being dried to obtain the glyoxaline ion liquid type fire retardant that anion is p-methyl benzenesulfonic acid root, yield is 75%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 3wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 30.5%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.0 units.
Embodiment 11
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent triethylamine are added sequentially in acetone, 43 DEG C
Lower stirring 10min, then drip the 1-butyl sulfochlorides of 0.55mol, time for adding controls 1.5h, after dripping at 43 DEG C
Reaction 8h, reaction is distilled off acetone after terminating, more scrubbed, obtain white intermediate, yield 82%, its knot after drying
Structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetone, is subsequently adding the 1-1-Butyl-1H-imidazole of 0.5mol, and
N2It is warming up to 65 DEG C of stirring reaction 60h under protection, solvent acetone, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is butyl sulfonic acid root, yield is 72%.Its structural formula is as follows:
3) obtained flame-retardant agent is carried out blended obtaining with the addition of 2.5wt% with Merlon (PC) in torque rheometer
Fire retardation PC material, its limited oxygen index is 30.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 4.5 units.
Embodiment 12
1) at N2Under protection, 0.5mol PEPA and 0.58mol acid binding agent triethylamine are added sequentially in dichloromethane, 45
Stirring 10min at DEG C, then drip the 1-octyl group sulfonic acid chloride of 0.62mol, time for adding controls 1.5h, at 45 DEG C after dripping
Lower reaction 8h, reaction is distilled off dichloromethane after terminating, more scrubbed, obtain white intermediate after drying, yield 78%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetone, is subsequently adding the 1-1-Butyl-1H-imidazole of 0.58mol, and
N2It is warming up to 62 DEG C of stirring reaction 70h under protection, solvent acetone, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is octyl sulfonic acid root, yield is 76%.Its structural formula is as follows:
3) obtained flame-retardant agent is carried out blended obtaining with the addition of 2.5wt% with Merlon (PC) in torque rheometer
Fire retardation PC material, its limited oxygen index is 30.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 4.5 units.
Embodiment 13
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent pyridine are added sequentially in oxolane, 50 DEG C
Lower stirring 10min, then drip the methylsufonyl chloride of 0.5mol, time for adding controls 1.5h, anti-at 50 DEG C after dripping
Answering 10h, reaction is distilled off oxolane after terminating, more scrubbed, obtain white intermediate after drying, yield 86%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetone, is subsequently adding the 1-phenylimidazole of 0.5mol, and
N2It is warming up to 62 DEG C of stirring reaction 68h under protection, solvent acetone, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is pyrovinic acid root, yield is 75%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 3wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 29.5%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 4.0 units.
Embodiment 14
1) at N2Under protection, 0.5mol PEPA and 0.6mol acid binding agent pyridine are added sequentially in oxolane, 50 DEG C
Lower stirring 20min, then drip the paratoluensulfonyl chloride (being dissolved in oxolane ketone) of 0.75mol, time for adding controls 3h,
Reacting 12h after dripping at 50 DEG C, reaction is distilled off oxolane after terminating, more scrubbed, obtain white after drying
Intermediate, yield 88%, its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetone, is subsequently adding the 1-phenylimidazole of 0.6mol, and
N2It is warming up to 60 DEG C of stirring reaction 72h under protection, solvent acetone, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is p-methyl benzenesulfonic acid root, yield is 75%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 5wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.5 units.
Embodiment 15
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent pyridine are added sequentially in oxolane, 48 DEG C
Lower stirring 10min, then drip the butyl sulfochlorides of 0.5mol, time for adding controls 1.5h, anti-at 48 DEG C after dripping
Answering 10h, reaction is distilled off oxolane after terminating, more scrubbed, obtain white intermediate after drying, yield 78%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetone, is subsequently adding the 1-phenylimidazole of 0.5mol, and
N2It is warming up to 62 DEG C of stirring reaction 65h under protection, solvent acetone, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is butyl sulfonic acid root, yield is 68%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 5wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.5 units.
Embodiment 16
1) at N2Under protection, 0.5mol PEPA and 0.55mol acid binding agent pyridine are added sequentially in oxolane, 48
Stirring 10min at DEG C, then drip the octyl group sulfonic acid chloride of 0.7mol, time for adding controls 1.5h, after dripping at 48 DEG C
Reaction 10h, reaction is distilled off oxolane after terminating, more scrubbed, obtain white intermediate after drying, yield 72%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetone, is subsequently adding the 1-phenylimidazole of 0.55mol, and
N2It is warming up to 60 DEG C of stirring reaction 68h under protection, solvent acetone, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is octyl sulfonic acid root, yield is 76%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 3wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.5%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 6.0 units.
Embodiment 17
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent pyridine are added sequentially in oxolane, 50 DEG C
Lower stirring 10min, then drip the methylsufonyl chloride of 0.5mol, time for adding controls 1.5h, anti-at 50 DEG C after dripping
Answering 12h, reaction is distilled off oxolane after terminating, more scrubbed, obtain white intermediate after drying, yield 72%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetonitrile, is subsequently adding the 1-phosphate ester imidazoles of 0.5mol, and
N2It is warming up to 78 DEG C of stirring reaction 60h under protection, solvent acetonitrile, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is pyrovinic acid root, yield is 75%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 5wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 5.5 units.
Embodiment 18
1) at N2Under protection, 0.5mol PEPA and 0.6mol acid binding agent pyridine are added sequentially in oxolane, 50
Stirring 20min at DEG C, then drip the paratoluensulfonyl chloride (being dissolved in oxolane ketone) of 0.75mol, time for adding controls
3h, reacts 15h at 50 DEG C after dripping, reaction is distilled off oxolane after terminating, more scrubbed, obtain after drying
White intermediate, yield 88%, its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetonitrile, is subsequently adding the 1-phosphate ester imidazoles of 0.6mol, and
N2It is warming up to 72 DEG C of stirring reaction 76h under protection, solvent acetonitrile, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is p-methyl benzenesulfonic acid root, yield is 75%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 5wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 32.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 6.5 units.
Embodiment 19
1) at N2Under protection, 0.5mol PEPA and 0.5mol acid binding agent pyridine are added sequentially in oxolane, 50
Stirring 10min at DEG C, then drip the butyl sulfochlorides of 0.5mol, time for adding controls 1.5h, anti-at 50 DEG C after dripping
Answering 12h, reaction is distilled off oxolane after terminating, more scrubbed, obtain white intermediate after drying, yield 77%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetonitrile, is subsequently adding the 1-phosphate ester imidazoles of 0.5mol, and
N2It is warming up to 78 DEG C of stirring reaction 60h under protection, solvent acetonitrile, residue washed with acetone 3-4 time is distilled off, is dried
Obtaining the glyoxaline ion liquid type fire retardant that anion is butyl sulfonic acid root, yield is 75%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 3wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 32.0%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 6.5 units.
Embodiment 20
1) at N2Under protection, 0.5mol PEPA and 0.58mol acid binding agent pyridine are added sequentially in oxolane, 50
Stirring 10min at DEG C, then drip the octyl group sulfonic acid chloride of 0.73mol, time for adding controls 1.5h, after dripping at 50 DEG C
Reaction 12h, reaction is distilled off oxolane after terminating, more scrubbed, obtain white intermediate after drying, yield 72%,
Its structure is as follows:
2) gained 0.5mol intermediate is dissolved in solvent acetonitrile, is subsequently adding the 1-phosphate ester imidazoles of 0.58mol, and
At N2It is warming up to 80 DEG C of stirring reaction 60h under protection, solvent acetonitrile, residue washed with acetone 3-4 time is distilled off, does
Dry obtaining the glyoxaline ion liquid type fire retardant that anion is octyl sulfonic acid root, yield is 75%.Its structural formula is as follows:
3) carry out being blended in torque rheometer with the addition of 5wt% and Merlon (PC) by obtained flame-retardant agent and obtain
Fire retardation PC material, its limited oxygen index is 31.5%, contrasts with the oxygen index (OI) 25.5% of pure PC and improves 6.0 units.
Claims (10)
1. the imidazole ion liquid type fire retardant containing young laying ducks in cage structure, it is characterised in that the knot of this fire retardant
Structure formula is as follows:
In formula, X is the alkyl of C=1-20, phenyl or phosphate-based, and the most phosphate-based structure is as follows:
Y is the alkyl of C=1-20, phenyl or p-methylphenyl, is applied in Merlon by this fire retardant, at addition is
When 0.1～5wt%, its limited oxygen index is 29.5～32.0%.
Imidazole ion liquid type fire retardant containing young laying ducks in cage structure the most according to claim 1, its feature
It is alkyl or p-methylphenyl that the Y described in the general structure of this fire retardant is C=1-8.
3. the preparation side of the imidazole ion liquid type fire retardant containing young laying ducks in cage structure described in a claim 1
Method, it is characterised in that processing step and the condition of the method are as follows:
1) at N2Under protection, by 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] octane and acid binding agent
Being sequentially added in solvent I, stirring is to major part 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] octane
Being slowly added dropwise substituted sulfonic acid chlorine after dissolving mix homogeneously again, and react 6-15h at 25-50 DEG C, reaction is steamed after terminating
Evaporate removing solvent I, more scrubbed, obtain intermediate after drying, wherein acid binding agent and 1-epoxide phospha-4-methylol
-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane mol ratio is 1-1.2:1；1-epoxide phospha-4-methylol-2,6,7-trioxa is double
Ring [2.2.2] octane is 1:1-1.5 with the mol ratio of replacement sulfonic acid chloride；
2) gained intermediate is first dissolved completely in solvent II, is subsequently adding substituted imidazole, and at N2Under protection
It is warming up to 60-80 DEG C of reaction 48-72h, solvent II be distilled off, scrubbed, after drying, wherein replace miaow
Azoles is 1-1.2:1 with the mol ratio of intermediate.
The preparation side of the imidazole ion liquid type fire retardant containing young laying ducks in cage structure the most according to claim 3
Method, it is characterised in that the structural formula replacing sulfonic acid chloride used in the method is:
In formula, Y is the alkyl of C=1-20, phenyl or p-methylphenyl.
The preparation side of the imidazole ion liquid type fire retardant containing young laying ducks in cage structure the most according to claim 3
Method, it is characterised in that the structural formula replacing sulfonic acid chloride used in the method is:
In formula, Y is alkyl or the p-methylphenyl of C=1-8.
6. according to the imidazole ion liquid type fire retardant containing young laying ducks in cage structure described in claim 3 or 4 or 5
Preparation method, it is characterised in that the structural formula of substituted imidazole used in the method is:
In formula, X is the alkyl of C=1-20, phenyl or phosphate-based, and the most phosphate-based structure is as follows:
7. according to the imidazole ion liquid type fire retardant containing young laying ducks in cage structure described in claim 3 or 4 or 5
Preparation method, it is characterised in that acid binding agent used in the method is triethylamine or pyridine.
The preparation side of the imidazole ion liquid type fire retardant containing young laying ducks in cage structure the most according to claim 6
Method, it is characterised in that acid binding agent used in the method is triethylamine or pyridine.
9. according to the imidazole ion liquid type fire retardant containing young laying ducks in cage structure described in claim 3 or 4 or 5
Preparation method, it is characterised in that solvent I used used in the method is dichloromethane, acetone or tetrahydrochysene furan
Any one in muttering；Solvent II used is acetone, acetonitrile, 1-Methylimidazole., 1-ethyl imidazol(e) or 1-propyl imidazole
In any one.
The preparation of the imidazole ion liquid type fire retardant containing young laying ducks in cage structure the most according to claim 8
Method, it is characterised in that solvent I used used in the method is in dichloromethane, acetone or oxolane
Any one；Solvent II used is appointing in acetone, acetonitrile, 1-Methylimidazole., 1-ethyl imidazol(e) or 1-propyl imidazole
A kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610218246.5A CN105732717B (en) | 2016-04-08 | 2016-04-08 | Imidazole ion liquid type fire retardant of the structure containing young laying ducks in cage and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610218246.5A CN105732717B (en) | 2016-04-08 | 2016-04-08 | Imidazole ion liquid type fire retardant of the structure containing young laying ducks in cage and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105732717A true CN105732717A (en) | 2016-07-06 |
| CN105732717B CN105732717B (en) | 2017-10-03 |
Family
ID=56252973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610218246.5A Active CN105732717B (en) | 2016-04-08 | 2016-04-08 | Imidazole ion liquid type fire retardant of the structure containing young laying ducks in cage and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732717B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106422410A (en) * | 2016-09-18 | 2017-02-22 | 四川大学 | Preparation method and application of tentacle type amino acid supported ionic liquid |
| CN107652468A (en) * | 2017-10-17 | 2018-02-02 | 四川大学 | Imidazole sulfonic acid ionic liquid fire retardant, preparation method and application containing DOPO |
| CN109134929A (en) * | 2018-08-24 | 2019-01-04 | 北京理工大学 | A kind of loop coil expanding fire retardant and preparation method thereof |
| CN109749044A (en) * | 2018-11-29 | 2019-05-14 | 四川大学 | The pure and mild fire-retardant anti-static polyurethane elastomer prepared therefrom of phosphorus contained multicomponent and their preparation method |
| CN115011113A (en) * | 2019-12-18 | 2022-09-06 | 江苏集萃先进高分子材料研究所有限公司 | Flame-retardant material and preparation method thereof |
| CN116574369A (en) * | 2023-05-15 | 2023-08-11 | 东莞金熙特高分子材料实业有限公司 | Modified polyamide PA flame-retardant material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110073331A1 (en) * | 2009-08-11 | 2011-03-31 | H & C Scientific Resources International, LLC | Ionic Liquid Flame Retardants |
| CN102924749A (en) * | 2012-10-18 | 2013-02-13 | 合肥工业大学 | Ionic liquid-type phosphate fire retardant and preparation method thereof |
-
2016
- 2016-04-08 CN CN201610218246.5A patent/CN105732717B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110073331A1 (en) * | 2009-08-11 | 2011-03-31 | H & C Scientific Resources International, LLC | Ionic Liquid Flame Retardants |
| CN102924749A (en) * | 2012-10-18 | 2013-02-13 | 合肥工业大学 | Ionic liquid-type phosphate fire retardant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAOGUAN GUI ET AL.: ""Synergistic effect of graphene and an ionic liquid containing phosphonium on the thermal stability and flame retardancy of polylactide"", 《RSC ADV.》 * |
| XUEFENG YANG ET AL.: ""Synthesis of a novel ionic liquid containing phosphorus and its application in intumescent flame retardant polypropylene system"", 《POLYM. ADV. TECHNOL.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106422410A (en) * | 2016-09-18 | 2017-02-22 | 四川大学 | Preparation method and application of tentacle type amino acid supported ionic liquid |
| CN107652468A (en) * | 2017-10-17 | 2018-02-02 | 四川大学 | Imidazole sulfonic acid ionic liquid fire retardant, preparation method and application containing DOPO |
| CN109134929A (en) * | 2018-08-24 | 2019-01-04 | 北京理工大学 | A kind of loop coil expanding fire retardant and preparation method thereof |
| CN109749044A (en) * | 2018-11-29 | 2019-05-14 | 四川大学 | The pure and mild fire-retardant anti-static polyurethane elastomer prepared therefrom of phosphorus contained multicomponent and their preparation method |
| CN109749044B (en) * | 2018-11-29 | 2021-05-21 | 四川大学 | Phosphorus-containing polyol, flame-retardant antistatic polyurethane elastomer prepared from phosphorus-containing polyol and preparation method of flame-retardant antistatic polyurethane elastomer |
| CN115011113A (en) * | 2019-12-18 | 2022-09-06 | 江苏集萃先进高分子材料研究所有限公司 | Flame-retardant material and preparation method thereof |
| CN115011113B (en) * | 2019-12-18 | 2023-07-21 | 江苏集萃先进高分子材料研究所有限公司 | Flame-retardant material and preparation method thereof |
| CN116574369A (en) * | 2023-05-15 | 2023-08-11 | 东莞金熙特高分子材料实业有限公司 | Modified polyamide PA flame-retardant material and preparation method thereof |
| CN116574369B (en) * | 2023-05-15 | 2024-04-02 | 东莞金熙特高分子材料实业有限公司 | Modified polyamide PA flame-retardant material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105732717B (en) | 2017-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105732717A (en) | Imidazolium liquid flame-retardant agent containing caged phosphate structure and preparation method thereof | |
| Min et al. | Synthesis and properties of ionic liquids: imidazolium tetrafluoroborates with unsaturated side chains | |
| EP2274291B1 (en) | Reactive ionic liquids | |
| CN104900879B (en) | A kind of flame retardant type sodium-ion battery electrolyte and its application | |
| CN101882696B (en) | Nonaqueous electrolyte material of fluorosulfonylimide lithium and application thereof | |
| CN107652468B (en) | Imidazole sulfonic acid ionic liquid fire retardant, preparation method and application containing DOPO | |
| EP2535328B1 (en) | Fluoroalkane derivative, gelling agent and gel composition | |
| CN103980313A (en) | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof | |
| US6743947B1 (en) | Electrochemically stable onium salts and electrolytes containing such for electrochemical capacitors | |
| Zhou et al. | A new class of hydrophobic ionic liquids: Trialkyl (2-methoxyethyl) ammonium perfluoroethyltrifluoroborate | |
| CN102924749B (en) | Ionic liquid-type phosphate fire retardant and preparation method thereof | |
| EP2945956A1 (en) | Low symmetry molecules and phosphonium salts, methods of making and devices formed there from | |
| JP2009054884A (en) | Nonaqueous electrolyte for capacitor and nonaqueous electrolyte capacitor having same | |
| Mei et al. | Synthesis of new fluorine-containing room temperature ionic liquids and their physical and electrochemical properties | |
| CN102344510A (en) | Preparation method of three-source-in-one expansion type fire retardant | |
| JP5856916B2 (en) | Lower fluorinated phosphate ammonium salt | |
| CN105336506B (en) | A kind of nonflammable electrolytic solution for super capacitor | |
| CN107879976B (en) | Ionic liquid compound and preparation method thereof, ionic liquid polymer and polymer solid electrolyte containing polymer | |
| CN106188130A (en) | A kind of preparation method of fluorine-containing phosphate ester | |
| CN102277176A (en) | Chloroalkyl polyphosphate ester fire retardant and synthetic technology thereof | |
| CN103755604B (en) | Hydrogen fluorine ether sulfone compound and preparation method thereof, lithium-ion battery electrolytes | |
| CN110128474A (en) | The preparation method and applications of the double DOPO thiazolium compounds of nitrogen phosphorus sulphur synergistic flame retardant | |
| Xiong et al. | Novel deep eutectic electrolyte induced by Na··· N interactions for sodium batteries | |
| EP2752409B1 (en) | Double-center bipyridyl cationic ionic liquid, preparation method therefor and use thereof | |
| KR20150008353A (en) | Ionic liquids having bisfluorosulfonylimide anion for electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |