CN110483796A - ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant and preparation method thereof - Google Patents
ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant and preparation method thereof Download PDFInfo
- Publication number
- CN110483796A CN110483796A CN201910788681.5A CN201910788681A CN110483796A CN 110483796 A CN110483796 A CN 110483796A CN 201910788681 A CN201910788681 A CN 201910788681A CN 110483796 A CN110483796 A CN 110483796A
- Authority
- CN
- China
- Prior art keywords
- solution
- sulfonate sodium
- phosphonitrile
- benzenyl sulfonate
- hydroxy benzenyl
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardants and preparation method thereof, belong to fire proofing technical field.Fire retardant provided by the invention, temperature of initial decomposition are 380 DEG C ± 5 DEG C, and maximum rhermal decomposition rate remaining object amount at 560 DEG C or more, 800 DEG C is higher than 40%, have good thermal stability out.The preparation method comprises the following steps: being added to the hexachlorocyclotriph,sphazene solution that concentration is 5~40% in the solution A containing p-hydroxy benzenyl sulfonate sodium and acid binding agent, six p-hydroxy benzenyl sulfonate sodium ring of intermediate, three phosphonitrile is prepared；Cabaltous nitrate hexahydrate is mixed with six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile, is dissolved in solvent B, is denoted as solution C；2-methylimidazole is dissolved in solvent B, solution D is denoted as.Mixed solution C and solution D obtain required fire retardant by self assembly；Fire retardant of the invention is added in epoxy resin, polypropylene and polycarbonate, good fire-retardant, smoke suppressing effect is shown.
Description
Technical field
The present invention relates to a kind of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardants and preparation method thereof, belong to
In fire proofing technical field.
Background technique
With the progress and development of science and technology, high molecular material is in building, traffic, electric, communication and decoration etc.
Field has been widely used.But high molecular material generally belongs to inflammable, combustible material, oxygen index (OI) mostly 21% with
Under.In addition, high molecular material burning is generated with a large amount of dense smokes and toxic gas often, especially some toxic gases, as CO,
HCN、SO2、H2S、NH3, oxynitrides, hydrogen halides etc. can cause for several minutes when the concentration of these gases reaches several hundred a ppm
People is dead, this not only causes huge economic loss and casualties, also will affect the stabilization of society.In order to improve such feelings
Condition, scholars start to explore the flame-retardant modified of high molecular material, and various anti-flaming modified materials and fire retardant progress into public view
It is wild.
Fire retardant is to can reduce inflammable or combustible material flammability, self-extinguishment or smoke elimination, improves material flame resistance
A kind of functionalization auxiliary agent, had a vast market foreground in the every field such as chemical building material, clothing, food, lodging and transportion -- basic necessities of life, electronic apparatus.
Fire retardant can be divided into halogenated flame retardant, phosphorus flame retardant, nitrogenated flame retardant, silicon-series five-retardant, phosphorus-halogen by contained ignition-proof element
Several classes such as flame retardant, phosphorus-nitrogenated flame retardant.Traditional halogen containing flame-retardant releases toxic and corrosive gas when burning, and produces
Raw biggish smog, also results in " secondary disaster " while playing fire-retardant, thus gradually disabled.Each state is all being sought in recent years
Ask exploitation Halogen, low toxicity, smokeless, low pollution, low corrosion fire retardant, phosphorus, nitrogen expansion type combustion inhibitor and inorganic metal fire retardant
By attention.At present as a complete unit, phosphorus, nitrogen expansion type combustion inhibitor there are flame retarding efficiencies it is low, additive amount is big the problems such as, it is serious to limit
Its application is made.The study found that the metal ion of the divalent or variable valency that contain in inorganic metal fire retardant passes through free radical
Or molecular mechanisms of action can promote peroxide compound to degrade, to significantly promote into charcoal, can not only improve layer of charcoal
Quality and the cracking reaction route that polymer can be changed, so that the combustibility that polymer generates during cracking
Gas flow, which significantly reduces, reaches preferably flame retarding efficiency.Therefore, a kind of resistance for having both metal catalytic and phosphorus, nitrogen expansion synergistic is synthesized
Firing agent becomes an important directions of current new flame retardant development.
Summary of the invention
That the purpose of the present invention is to solve existing fire retardants is inefficient, smoke suppressing effect is unobvious, thermal stability
The problem of difference, and a kind of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant is provided and preparation method thereof.
The purpose of the present invention is what is be achieved through the following technical solutions.
ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, specific surface area < 1250.8m2·g-1, hole
Hold < 0.142mLg-1, average pore size < 2.375nm, temperature of initial decomposition is 380 DEG C ± 5 DEG C, and maximum rhermal decomposition rate exists
Remaining object amount is higher than 40% at 560 DEG C or more, 800 DEG C, is one kind using ZIF-67 as frame, six para hydroxybenzene sulphurs are adulterated in frame
The purple powder shape fire retardant of sour three phosphonitrile of sodium ring.
The preparation method of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, the specific steps are as follows:
Step 1: hexachlorocyclotriph,sphazene is dissolved in solvent A, three phosphorus of chlordene ring that mass concentration is 5~40% is obtained
Nitrile solution, is placed in dropping funel.
Step 2: p-hydroxy benzenyl sulfonate sodium and acid binding agent are added sequentially in four-hole boiling flask under the protection of nitrogen, add
Enter solvent A, at 20~40 DEG C after stirring to solution clarification, obtains the solution that p-hydroxy benzenyl sulfonate sodium mass concentration is 5~30%
A.45~50 DEG C are warming up to, one gained hexachlorocyclotriph,sphazene solution of a dropping step, time for adding was controlled at 5~80 minutes, was added dropwise
After be warming up to assigned temperature, after being stirred at reflux 6~24 hours stop stirring.Reaction solution is filtered, by filter residue with third
After ketone and distilled water replace washing 3~5 times, it is transferred in convection oven and is dried 10 hours in 60~100 DEG C, it is right to obtain intermediate six
Three phosphonitrile of sodium hydroxybenzenesulfonate ring.
Step 3: 1:(2~8 in molar ratio): (0.01~0.07) weighs cabaltous nitrate hexahydrate, 2-methylimidazole and step
Two resulting six p-hydroxy benzenyl sulfonate sodiums ring, three phosphonitriles.Cabaltous nitrate hexahydrate and six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile are mixed
It closes, is dissolved in solvent B, is denoted as solution C；2-methylimidazole is dissolved in solvent B, solution D is denoted as.Solution C and solution D are placed in
In ultrasonic water bath pot, ultrasonic disperse 5~after forty minutes, solution D is poured into solution C, is stirred at room temperature 16~24 hours at room temperature
Stop stirring afterwards.It is centrifuged with the revolving speed of 10000rad/min, after washing 3~5 times with solvent B, product is moved in convection oven
It is 8 hours dry in 80 DEG C, obtain ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant.
Step 1: solvent A described in two is one of tetrahydrofuran, anhydrous acetonitrile or dioxane；
Acid binding agent described in step 2 is one of triethylamine, cerium chloride and pyridine；
The molar ratio of hexachlorocyclotriph,sphazene described in step 2, p-hydroxy benzenyl sulfonate sodium and acid binding agent is 1:(6.5~8):
(6~10)；
The selection of assigned temperature described in step 2 and the selection of solvent A are related, when solvent A selects tetrahydrofuran, temperature
Degree is 62~66 DEG C；When solvent A selects anhydrous acetonitrile, temperature is 80~85 DEG C；When solvent A selects dioxane, temperature
It is 98~102 DEG C；
Solvent B described in step 3 is one of acetone, ethyl alcohol, methanol or N,N-dimethylformamide；
The mass concentration of cabaltous nitrate hexahydrate is 2- methyl miaow in 0.5~20%, solution D in solution C described in step 3
The mass concentration of azoles is 0.5~25%；
Beneficial effect
1, a kind of ZIF-67 provided by the invention adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, initial decomposition temperature
Degree is 380 DEG C ± 5 DEG C, and maximum rhermal decomposition rate remaining object amount at 560 DEG C or more, 800 DEG C is higher than 40%, is shown good
Thermal stability.
2, a kind of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant provided by the invention is added to epoxy
In resin, polypropylene and polycarbonate, good fire-retardant, smoke suppressing effect is shown.
3, a kind of ZIF-67 provided by the invention adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, is with ZIF-67
For frame structure, six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile is adulterated in structure, preparation method is simple, easily-controlled reaction conditions.
4, a kind of ZIF-67 provided by the invention adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, passes through six pairs of hydroxyls
Three phosphonitrile of base benzene sulfonic acid sodium salt ring participates in ZIF-67 nucleation, growth, makes to adulterate the ZIF- after six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile
67 Kong Rong and aperture increases, exposed catalytic site increase, and are conducive to the flame retardant effect for improving material.
5, a kind of ZIF-67 provided by the invention adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, can significantly improve
Acid source and the unmatched problem of gas source ratio in six p-hydroxy benzenyl sulfonate sodium tricyclic phosphonitriles, and in the bimetallic of metallic cobalt and sodium
Under catalytic action, carbon residue intensity is significantly improved, to improve flame retarding efficiency.
Specific embodiment
Embodiment is provided below in conjunction with experimental result of the present invention with the invention will be further described:
Embodiment 1:
ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, specific surface area 1158.6m2·g-1, hole
Holding is 0.109mLg-1, average pore size 2.021nm, temperature of initial decomposition be 384 DEG C, maximum rhermal decomposition rate at 561 DEG C,
Remaining object amount is 40.21% at 800 DEG C, is one kind using ZIF-67 as frame, six p-hydroxy benzenyl sulfonate sodium rings three are adulterated in frame
The purple powder shape fire retardant of phosphonitrile.
The preparation method of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, the specific steps are as follows:
Step 1: 1:6.8:6 weighs 5.01g (14.41mmol) hexachlorocyclotriph,sphazene, 19.22g in molar ratio
(97.99mmol) p-hydroxy benzenyl sulfonate sodium and 12.05mL (86.46mmol, 8.75g) triethylamine.Hexachlorocyclotriph,sphazene is dissolved
To 20mL tetrahydrofuran, the hexachlorocyclotriph,sphazene solution that mass concentration is 21.96% is obtained, is placed in dropping funel.
Step 2: installing thermometer, condenser pipe, agitating paddle, air inlet pipe and device for absorbing tail gas.In the protection of nitrogen
Under, p-hydroxy benzenyl sulfonate sodium and triethylamine are sequentially added in the four-hole boiling flask of 500mL, and the tetrahydrofuran of 200mL is added, 40
At DEG C after stirring to solution clarification, the solution A that p-hydroxy benzenyl sulfonate sodium mass concentration is 9.33% is obtained, is warming up to 50 DEG C.Drop
Add hexachlorocyclotriph,sphazene solution obtained by step 1, is warming up to 66 DEG C after being added dropwise within 20 minutes, stops after being stirred at reflux 16 hours
Stirring.Reaction solution is filtered, after filter residue acetone and distilled water are alternately washed 3 times, is transferred in convection oven in 100
DEG C dry 10 hours, obtain six p-hydroxy benzenyl sulfonate sodium ring of intermediate, three phosphonitrile, yield 93.32%, purity 97.88%.
Step 3: 1:3:0.05 weighs 4.35g (14.95mmol) cabaltous nitrate hexahydrate, 3.68g in molar ratio
Six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile of (44.85mmol) 2-methylimidazole and 0.98g (0.75mmol) above-mentioned steps two.It will
Cabaltous nitrate hexahydrate is mixed with six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile, is dissolved in 200mL methanol, and cabaltous nitrate hexahydrate matter is obtained
Measure the solution C that concentration is 2.66%；2-methylimidazole is dissolved in 200mL methanol, obtaining 2-methylimidazole mass concentration is
2.27% solution D.Solution C and solution D are placed in ultrasonic water bath pot, after forty minutes, solution D is fallen for ultrasonic disperse at room temperature
Enter in solution C, stops stirring after being stirred at room temperature 20 hours.It is centrifuged with the revolving speed of 10000rad/min, after washing 3 times with methanol,
Product is moved in convection oven and is dried 8 hours in 80 DEG C, it is fire-retardant to obtain ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile
Agent.
Fire retardant in the present embodiment is applied in bisphenol A type epoxy resin (E-44), 4,4'- diaminodiphenylmethane
As curing agent, fire retarding epoxide resin is prepared.Combustion testing the results show that when fire retardant additive amount be 5% when, limit oxygen index
Up to 29.8%, vertical combustion grade reaches UL-94V-0 grades, and heat release rate peak value, total heat release are opposite with total smoke release
Pure epoxy resin declines 50.36%, 29.28% and 32.21% respectively, CO, CO2Burst size declines, and meets the fire-retardant ring of industry
The application requirement of oxygen resin.
Embodiment 2:
ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, specific surface area 1162.7m2·g-1, hole
Holding is 0.113mLg-1, average pore size 2.042nm, temperature of initial decomposition is 383 DEG C, and maximum rhermal decomposition rate is 563 DEG C,
Remaining object amount is 40.36% at 800 DEG C, is one kind using ZIF-67 as frame, six p-hydroxy benzenyl sulfonate sodium rings three are adulterated in frame
The purple powder shape fire retardant of phosphonitrile.
The preparation method of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, the specific steps are as follows:
Step 1: 1:7.2:7 weighs 5.16g (14.84mmol) hexachlorocyclotriph,sphazene, 20.96g in molar ratio
(106.85mmol) p-hydroxy benzenyl sulfonate sodium and 14.48mL (103.88mmol, 10.51g) triethylamine.Hexachlorocyclotriph,sphazene is molten
Solution obtains the hexachlorocyclotriph,sphazene solution that mass concentration is 24.62%, is placed in dropping funel to 20mL anhydrous acetonitrile.
Step 2: installing thermometer, condenser pipe, agitating paddle, air inlet pipe and device for absorbing tail gas.In the protection of nitrogen
Under, p-hydroxy benzenyl sulfonate sodium and triethylamine are sequentially added in the four-hole boiling flask of 500mL, and the anhydrous acetonitrile of 200mL is added, 40
At DEG C after stirring to solution clarification, the solution A that p-hydroxy benzenyl sulfonate sodium mass concentration is 11.06% is obtained, is warming up to 50 DEG C.Drop
Add hexachlorocyclotriph,sphazene solution obtained by step 1, is warming up to 83 DEG C after being added dropwise within 25 minutes, stops after being stirred at reflux 16 hours
Stirring.Reaction solution is filtered, after filter residue acetone and distilled water are alternately washed 3 times, is transferred in convection oven in 100
DEG C dry 10 hours, obtain six p-hydroxy benzenyl sulfonate sodium ring of intermediate, three phosphonitrile, yield 93.68%, purity 97.94%.
Step 3: 1:4:0.05 weighs 4.40g (15.12mmol) cabaltous nitrate hexahydrate, 4.96g in molar ratio
Six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile of (60.48mmol) 2-methylimidazole and 0.99g (0.76mmol) above-mentioned steps two.It will
Cabaltous nitrate hexahydrate is mixed with six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile, is dissolved in 200mL acetone, and cabaltous nitrate hexahydrate matter is obtained
Measure the solution C that concentration is 2.70%；2-methylimidazole is dissolved in 200mL acetone, obtaining 2-methylimidazole mass concentration is
3.05% solution D.Solution C and solution D are placed in ultrasonic water bath pot, after forty minutes, solution D is fallen for ultrasonic disperse at room temperature
Enter in solution C, stops stirring after being stirred at room temperature 20 hours.It is centrifuged with the revolving speed of 10000rad/min, after acetone washing 3 times,
Product is moved in convection oven 80 DEG C in 8 hours dry, it is fire-retardant to obtain ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile
Agent.
Fire retardant in the present embodiment is applied in bisphenol A type epoxy resin (E-51), 4,4'- diaminodiphenylmethane
As curing agent, fire retarding epoxide resin is prepared.Combustion testing the results show that when fire retardant additive amount be 5% when, limit oxygen index
Up to 30.1%, vertical combustion grade reaches UL-94V-0 grades, and heat release rate peak value, total heat release are opposite with total smoke release
Pure epoxy resin decline 48.26%, 28.36% and 32.36%, CO, CO2Burst size declines, and meets industrial flame retardant epoxy tree
The application requirement of rouge.
Embodiment 3:
ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, specific surface area 1155.9m2·g-1, hole
Holding is 0.112mLg-1, average pore size 2.032nm, temperature of initial decomposition is 385 DEG C, and maximum rhermal decomposition rate is 565 DEG C,
Remaining object amount is 40.07% at 800 DEG C, is one kind using ZIF-67 as frame, six p-hydroxy benzenyl sulfonate sodium rings three are adulterated in frame
The purple powder shape fire retardant of phosphonitrile.
The preparation method of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, the specific steps are as follows:
Step 1: 1:7.6:8 weighs 10.08g (28.99mmol) hexachlorocyclotriph,sphazene, 43.22g in molar ratio
(220.32mmol) p-hydroxy benzenyl sulfonate sodium and 32.33mL (231.92mmol, 23.47g) triethylamine.Hexachlorocyclotriph,sphazene is molten
Solution obtains the hexachlorocyclotriph,sphazene solution that mass concentration is 24.18%, is placed in dropping funel to 40mL anhydrous acetonitrile.
Step 2: installing thermometer, condenser pipe, agitating paddle, air inlet pipe and device for absorbing tail gas.In the protection of nitrogen
Under, p-hydroxy benzenyl sulfonate sodium and triethylamine are sequentially added in the four-hole boiling flask of 1L, and the anhydrous acetonitrile of 400mL is added, 40 DEG C
After lower stirring to solution clarification, the solution A that p-hydroxy benzenyl sulfonate sodium mass concentration is 11.29% is obtained, is warming up to 50 DEG C.It is added dropwise
Hexachlorocyclotriph,sphazene solution obtained by step 1, is warming up to 83 DEG C after being added dropwise within 20 minutes, stops stirring after being stirred at reflux 20 hours
It mixes.Reaction solution is filtered, after filter residue acetone and distilled water are alternately washed 3 times, is transferred in convection oven in 100 DEG C
It is 10 hours dry, obtain six p-hydroxy benzenyl sulfonate sodium ring of intermediate, three phosphonitrile, yield 94.02%, purity 97.79%.
Step 3: 1:5:0.05 weighs 8.76g (30.10mmol) cabaltous nitrate hexahydrate, 12.36g in molar ratio
Six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile of (150.50mmol) 2-methylimidazole and 1.97g (1.51mmol) above-mentioned steps two.
Cabaltous nitrate hexahydrate is mixed with six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile, is dissolved in 400mL acetone, obtains cabaltous nitrate hexahydrate
The solution C that mass concentration is 2.69%；2-methylimidazole is dissolved in 400mL acetone, obtaining 2-methylimidazole mass concentration is
3.77% solution D.Solution C and solution D are placed in ultrasonic water bath pot, after forty minutes, solution D is fallen for ultrasonic disperse at room temperature
Enter in solution C, stops stirring after being stirred at room temperature 20 hours.It is centrifuged with the revolving speed of 10000rad/min, after acetone washing 3 times,
Product is moved in convection oven and is dried 8 hours in 80 DEG C, it is fire-retardant to obtain ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile
Agent.
Fire retardant in the present embodiment is applied in polypropylene, combustion testing is the results show that when fire retardant additive amount is
When 10%, limit oxygen index is up to 28.9%, and vertical combustion grade reaches UL-94V-0 grades, and heat release rate peak value, total heat are released
It puts and declines 36.9%, 29.8% and 30.48% respectively with respect to virgin pp with total smoke release, CO, CO2Burst size declines,
Meet the application requirement of industrial polypropylene flame redardant.
Embodiment 4:
ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, specific surface area 1148.9m2·g-1, hole
Holding is 0.115mLg-1, average pore size 2.084nm, temperature of initial decomposition is 384 DEG C, and maximum rhermal decomposition rate is 566 DEG C,
Remaining object amount is 40.58% at 800 DEG C, is one kind using ZIF-67 as frame, six p-hydroxy benzenyl sulfonate sodium rings three are adulterated in frame
The purple powder shape fire retardant of phosphonitrile.
The preparation method of ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, the specific steps are as follows:
Step 1: 1:8:9 weighs 10.16g (29.22mmol) hexachlorocyclotriph,sphazene, 45.85g in molar ratio
(233.76mmol) p-hydroxy benzenyl sulfonate sodium and 36.65mL (262.98mmol, 26.61g) triethylamine.Hexachlorocyclotriph,sphazene is molten
Solution obtains the hexachlorocyclotriph,sphazene solution that mass concentration is 19.63%, is placed in dropping funel to 40mL dioxane.
Step 2: installing thermometer, condenser pipe, agitating paddle, air inlet pipe and device for absorbing tail gas.In the protection of nitrogen
Under, p-hydroxy benzenyl sulfonate sodium and triethylamine are sequentially added in the four-hole boiling flask of 1L, and the dioxane of 400mL is added, 40 DEG C
After lower stirring to solution clarification, the solution A that p-hydroxy benzenyl sulfonate sodium mass concentration is 9.39% is obtained, is warming up to 50 DEG C.It is added dropwise
Hexachlorocyclotriph,sphazene solution obtained by step 1, temperature stops stirring to 98 DEG C after being added dropwise within 25 minutes after being stirred at reflux 20 hours.
Reaction solution is filtered, after filter residue acetone and distilled water are alternately washed 3 times, is transferred in convection oven dry in 100 DEG C
Dry 10 hours, obtain six p-hydroxy benzenyl sulfonate sodium ring of intermediate, three phosphonitrile, yield 94.36%, purity 98.12%.
Step 3: 1:6:0.05 weighs 8.92g (30.65mmol) cabaltous nitrate hexahydrate, 15.10g in molar ratio
Six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile of (183.90mmol) 2-methylimidazole and 2.00g (1.53mmol) above-mentioned steps two.
Cabaltous nitrate hexahydrate is mixed with six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile, is dissolved in 400mL methanol, obtains cabaltous nitrate hexahydrate
The solution C that mass concentration is 2.72%；2-methylimidazole is dissolved in 400mL methanol, obtaining 2-methylimidazole mass concentration is
4.55% solution D.Solution C and solution D are placed in ultrasonic water bath pot, after forty minutes, solution D is fallen for ultrasonic disperse at room temperature
Enter in solution C, stops stirring after being stirred at room temperature 20 hours.It is centrifuged with the revolving speed of 10000rad/min, after washing 3 times with methanol,
Product is moved in convection oven and is dried 8 hours in 80 DEG C, it is fire-retardant to obtain ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile
Agent.
Fire retardant in the present embodiment is applied in polycarbonate, combustion testing is the results show that work as fire retardant additive amount
When being 5%, limit oxygen index is up to 32.5%, and vertical combustion grade reaches UL-94V-0 grades, and heat release rate peak value, total heat are released
It puts and declines 47.21%, 30.21% and 33.69% respectively with the relatively pure polycarbonate of total smoke release, CO, CO2Burst size under
Drop meets the application requirement of industrial fire-retardant polycarbonate.
Above-described specific descriptions have carried out further specifically the purpose of invention, technical scheme and beneficial effects
It is bright, it should be understood that the above is only a specific embodiment of the present invention, the protection model being not intended to limit the present invention
It encloses, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection scope within.
Claims (7)
1.ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant, it is characterised in that: is one kind using ZIF-67 as frame
Frame adulterates the purple powder shape fire retardant of six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile in frame；The specific surface area < of fire retardant
1250.8m2·g-1, Kong Rong < 0.142mLg-1, average pore size < 2.375nm, temperature of initial decomposition is 380 DEG C ± 5 DEG C, most
Big rhermal decomposition rate remaining object amount at 560 DEG C or more, 800 DEG C is higher than 40%.
2. the method for preparing ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant as described in claim 1, special
Sign is: specific step is as follows:
Step 1: hexachlorocyclotriph,sphazene is dissolved in solvent A, it is molten to obtain the hexachlorocyclotriph,sphazene that mass concentration is 5~40%
Liquid is placed in dropping funel；
Step 2: p-hydroxy benzenyl sulfonate sodium and acid binding agent are added sequentially in four-hole boiling flask under the protection of nitrogen, it is added molten
Agent A obtains solution A at 20~40 DEG C after stirring to solution clarification；The mass concentration of p-hydroxy benzenyl sulfonate sodium in the solution A
It is 5~30%；45~50 DEG C are warming up to, one gained hexachlorocyclotriph,sphazene solution of a dropping step, time for adding is controlled at 5~80 points
Clock is warming up to assigned temperature after being added dropwise, and stops stirring after being stirred at reflux 6~24 hours；Reaction solution is filtered, will be filtered
After slag acetone and distilled water replace washing 3~5 times, it is transferred in convection oven and is dried 10 hours in 60~100 DEG C, obtained intermediate
Six p-hydroxy benzenyl sulfonate sodium ring of body, three phosphonitrile；The molar ratio of the hexachlorocyclotriph,sphazene, p-hydroxy benzenyl sulfonate sodium and acid binding agent
For 1:(6.5~8): (6~10)；
Step 3: 1:(2~8 in molar ratio): (0.01~0.07) weighs cabaltous nitrate hexahydrate, 2-methylimidazole and step 2 institute
Six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile obtained；Cabaltous nitrate hexahydrate is mixed with six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile, it is molten
In solvent B, it is denoted as solution C；2-methylimidazole is dissolved in solvent B, solution D is denoted as；Solution C and solution D are placed in ultrasound
In water-bath, ultrasonic disperse 5~after forty minutes, solution D is poured into solution C, is stopped after being stirred at room temperature 16~24 hours at room temperature
Only stir；It is centrifuged with the revolving speed of 10000rad/min, after washing 3~5 times with solvent B, product is moved in convection oven in 80
DEG C dry 8 hours, obtain ZIF-67 doping six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant.
3. method as claimed in claim 2, it is characterised in that: the solvent A is tetrahydrofuran, anhydrous acetonitrile or dioxy six
Ring.
4. method as claimed in claim 2, it is characterised in that: acid binding agent described in step 2 is triethylamine, cerium chloride or pyridine.
5. method as claimed in claim 2, it is characterised in that: the selection of assigned temperature described in step 2 and the selection of solvent A
Related, when solvent A selects tetrahydrofuran, temperature is 62~66 DEG C；When solvent A selects anhydrous acetonitrile, temperature is 80~85
℃；When solvent A selects dioxane, temperature is 98~102 DEG C.
6. method as claimed in claim 2, it is characterised in that: solvent B described in step 3 is acetone, ethyl alcohol, methanol or N, N-
Dimethylformamide.
7. method as claimed in claim 2, it is characterised in that: the quality of cabaltous nitrate hexahydrate is dense in solution C described in step 3
Degree is 0.5~20%, 2-methylimidazole mass concentration is 0.5~25% in solution D.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910788681.5A CN110483796A (en) | 2019-08-26 | 2019-08-26 | ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910788681.5A CN110483796A (en) | 2019-08-26 | 2019-08-26 | ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110483796A true CN110483796A (en) | 2019-11-22 |
Family
ID=68553949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910788681.5A Pending CN110483796A (en) | 2019-08-26 | 2019-08-26 | ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483796A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592657A (en) * | 2020-05-29 | 2020-08-28 | 福建师范大学 | Phosphorus-modified ZIF-8 material and preparation method and application thereof |
| CN113045766A (en) * | 2021-03-24 | 2021-06-29 | 湖北中烟工业有限责任公司 | Novel cigarette fire retardant and preparation method and application thereof |
| CN115287895A (en) * | 2022-10-09 | 2022-11-04 | 南通缘棉家纺有限公司 | Bacteriostatic mite-killing fabric based on plant fibers and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752637A (en) * | 2018-08-01 | 2018-11-06 | 河北大学 | A kind of ZIF-8 encapsulation hexachlorocyclotriph,sphazene fire retardant, preparation method and application and fire retarding epoxide resin |
| CN109796629A (en) * | 2017-11-17 | 2019-05-24 | 南开大学 | Novel N-P-S expansion type phosphor flame retardant and preparation method thereof |
-
2019
- 2019-08-26 CN CN201910788681.5A patent/CN110483796A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796629A (en) * | 2017-11-17 | 2019-05-24 | 南开大学 | Novel N-P-S expansion type phosphor flame retardant and preparation method thereof |
| CN108752637A (en) * | 2018-08-01 | 2018-11-06 | 河北大学 | A kind of ZIF-8 encapsulation hexachlorocyclotriph,sphazene fire retardant, preparation method and application and fire retarding epoxide resin |
Non-Patent Citations (1)
| Title |
|---|
| LI AIJIAO ET AL.: "Fabrication of zeolitic imidazolate frameworks on layered double hydroxide", 《COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592657A (en) * | 2020-05-29 | 2020-08-28 | 福建师范大学 | Phosphorus-modified ZIF-8 material and preparation method and application thereof |
| CN113045766A (en) * | 2021-03-24 | 2021-06-29 | 湖北中烟工业有限责任公司 | Novel cigarette fire retardant and preparation method and application thereof |
| CN113045766B (en) * | 2021-03-24 | 2022-04-29 | 湖北中烟工业有限责任公司 | Cigarette fire retardant and preparation method and application thereof |
| CN115287895A (en) * | 2022-10-09 | 2022-11-04 | 南通缘棉家纺有限公司 | Bacteriostatic mite-killing fabric based on plant fibers and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110483796A (en) | ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant and preparation method thereof | |
| WO2020182111A1 (en) | Molybdenum disulfide hybrid flame retardant coated with phosphorus-nitrogen-zinc two-dimensional supramolecule and application thereof | |
| CN110423354B (en) | ZIF-67@ ZIF-8 doped polycyclotriphosphazene flame retardant and preparation method thereof | |
| CN108794745B (en) | Schiff base charring agent containing triazine ring and synthesis method thereof | |
| CN105542160A (en) | Single-component phosphor-nitrogen double-ring cage-shaped macromolecular intumescent flame retardant as well as preparation method and application thereof | |
| CN103756013B (en) | Flame-retardant modified APP and its preparation method and application | |
| CN101974167A (en) | Intumescent flame retardant and synthesis method thereof | |
| CN110467820A (en) | A kind of hydrophobic type metal organic frame poly- (three phosphonitrile-co- bisphenol AF of ring) fire retardant and preparation method thereof | |
| CN104478934B (en) | Containing a fire retardant for the ring three phosphonitrile phenanthrene of oneself interior phosphoric acid ester of two oxygen heterocycle, preparation method and application | |
| CN113248716B (en) | Flame-retardant co-curing agent and preparation method thereof, and intrinsic high-thermal-conductivity/flame-retardant liquid crystal epoxy resin material and preparation method thereof | |
| CN108707906A (en) | A kind of high temperature compound corrosion inhibitor and preparation method thereof suitable for mild steel | |
| CN110452547B (en) | ZIF-67\ polysulfone sphere flame retardant and preparation method thereof | |
| CN102827373A (en) | Preparation method of phosphorus-nitrogen intumescent flame retardant | |
| CN103102483A (en) | Higher molecular weight type intumescent flame retardant containing triazine structure and synthetic method thereof | |
| CN110467747A (en) | The fire-retardant complex compound of metal ion and preparation method with schiff bases structure | |
| CN106188620B (en) | Expansion type flame retardant based on star-like pyrrolotriazine derivatives and preparation method thereof | |
| CN110128474B (en) | Preparation method and application of nitrogen-phosphorus-sulfur ternary synergistic flame retardant bis-DOPO thiazole compound | |
| CN109111571A (en) | Containing triazine-phosphorus schiff bases fire retardant and its synthetic method | |
| CN106220665B (en) | Expansion type flame retardant of star-like pyrrolotriazine derivatives and preparation method thereof | |
| CN110092944A (en) | The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO | |
| CN109111570A (en) | Linear phosphorous schiff bases carbon forming agent and its synthetic method | |
| CN106349503B (en) | Expansion type flame retardant of pentaerythritol derivative and preparation method thereof | |
| CN107082909B (en) | A kind of preparation method and applications of the hydroquinone biphosphonate fire retardant containing DOPO | |
| CN106986896B (en) | Star-like boron phosphazene derivative expansion type flame retardant and preparation method thereof | |
| CN108384001A (en) | Primary amine blocking modification macro molecular triazine carbon forming agent 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 |
Application publication date: 20191122 |
|
| RJ01 | Rejection of invention patent application after publication |