CN106317107A - Preparation method of liquid flame retardant - Google Patents
Preparation method of liquid flame retardant Download PDFInfo
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- CN106317107A CN106317107A CN201610582275.XA CN201610582275A CN106317107A CN 106317107 A CN106317107 A CN 106317107A CN 201610582275 A CN201610582275 A CN 201610582275A CN 106317107 A CN106317107 A CN 106317107A
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- flame retardant
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- heating
- magnesium chloride
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 56
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 54
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 27
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 25
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 25
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 25
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 31
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000004044 response Effects 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- 239000008234 soft water Substances 0.000 claims description 7
- 238000012805 post-processing Methods 0.000 claims description 4
- 238000010411 cooking Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000005660 chlorination reaction Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- -1 wherein Chemical compound 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- ZDOGKMGVGXWLKK-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2,3,5,6-tetraphenylphenol Chemical compound C=1C=CC=CC=1C=1C(C=2C=CC=CC=2)=C(O)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C=1C(C)(C)C1=CC=C(O)C=C1 ZDOGKMGVGXWLKK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a liquid flame retardant. With cardanol and phosphorus oxychloride being reactants and magnesium chloride being a catalyst, a chemical reaction is carried out, the liquid flame retardant product is obtained after neutralizing, aftertreatment and other operation are carried out. The liquid flame retardant prepared through the method not only has the flame retardance of a traditional flame retardant, but also has the advantages of being convenient to use and accurate in metering due to the liquefied form; in addition, the preparation method makes a process route short, and is easy and convenient to operate, raw materials and the process are environmentally friendly, and the liquid flame retardant is suitable for industrial production, and therefore has good application prospects.
Description
Technical field
The invention belongs to chemical field, relate to the preparation method of a kind of auxiliary chemicals, particularly relate to a kind of liquid flame retardant
Preparation method.
Background technology
Fire-retardant science and technology is that fire preventing occurs in order to adapt to the needs that social safety produces and lives, and protects the people
Lives and properties and a science growing up.Fire retardant is flame-retarded technology application in real life, it be a kind of for
Improve the special auxiliary chemicals of flammable combustible material combustibility, be widely used in the fire-retardant processing of all kinds of finishing material.
Material after fire retardant is processed, when being attacked by extraneous burning things which may cause a fire disaster, it is possible to effectively stop, delay or terminate the biography of flame
Broadcast, thus reach fire-retardant effect.Fire retardant is commonly divided into following 4 classes: halogen-system fire retardant, phosphorus flame retardant, nitrogen system hinder
Combustion agent, phosphorus-halogenated flame retardant.
In numerous fire retardant kinds, halogen-system fire retardant with its good flame retardation effect, do not affect material physical and chemical performance and
It is widely used.But, the polymer amount of being fuming when burning adding halogen-system fire retardant greatly, easily releases corrosive gas
(such as HCl, HBr etc.) and harmful gas, easily cause secondary harm.Therefore, the fire retardant of the world today is studied towards Halogen
The direction changed is developed.Aluminium hydroxide, flame retardant of magnesium hydroxide application time be dependent on chemolysis heat absorption and release water outlet and
Play fire retardation, have avirulence, do not corrode processing equipment, decompose after generate aluminium oxide, magnesium oxide chemical property steady
Fixed, the most do not produce secondary harm.Along with the great personnel frequently occurring and thus bringing of fire incident and property
Loss, China is it has been specified that the electric wire used when building the important building such as subway must be halogen-free flame-retardant wire electricity
Cable, and along with improving constantly that people's environmental conservation and inherently safe are realized, the halogen-free flameproof of polymeric material is necessarily referred to as the present
After developing direction.In recent years, aluminium hydroxide (ATH) fire retardant be that in inorganic combustion inhibitor, most widely used general, consumption is maximum one
Kind, flame retardant of magnesium hydroxide is then one with fastest developing speed.Compared with aluminium hydroxide, the decomposition temperature of magnesium hydroxide is higher by one
A bit (aluminium hydroxide is about 220 DEG C, and magnesium hydroxide is then at 350 ~ 400 DEG C), it is more suitable for the processing request of some polymer, and
Also has the effect promoting polymer carbonization.Research to flame retardant of magnesium hydroxide is more the most in recent years, and application is the most continuous
Expand.
Phosphorus flame retardant is efficient as one, smokeless, low toxicity, free of contamination fire retardant, enjoys researcher to pay close attention to, exists
The aspects such as synthesis and application achieve prominent achievement.Elemental phosphorous is combustibles, but in resin, red phosphorus and other phosphorous interpolations
Agent mechanism is not the most simple oxidation, and phosphor-included additive mainly acts in condensed phase, and fire retardant mechanism is:
The first step
Formation phosphorylated ligand is as dehydrant, and promotes into charcoal, and the generation of charcoal reduces the conduction of heat from flame to condensed phase.
Second step
Phosphoric acid can absorb heat, because it prevent that CO is oxidized to CO2, reduces heating process.
3rd step
Condensed phase is formed the protective layer of the vitreous or liquid of thin layer, therefore reduces oxygen diffusion and gas phase with solid
Heat between Xiang and quality transmission, it is suppressed that char combustion process, reduce phosphonium flame retardant decomposes and occur to change as follows:
Phosphorus flame retardant → phosphoric acid partially → phosphoric acid → poly-Metaphosphoric acid, poly-Metaphosphoric acid is the most volatile stable compound, has strong dehydration
Property, at polymer table compound and air exclusion；The substantial amounts of heat of moisture sorption of abjection, makes polymer surfaces fire retardant decomposes
Discharging volatility phosphide, show through mass spectral analysis, pure hydrogen atom concentration is substantially reduced, and shows that PO captures H, i.e. PO
+H·=HPO。
In recent years, phosphonium flame retardant is most widely used general, one that consumption is maximum in inorganic combustion inhibitor, the most right
The research of phosphonium flame retardant is more, and application the most constantly expands.
In prior art, the fire retardant of common polymer, is mostly pressed powder or granule, and solid flame retardant ring
Safeguarding grades is the lowest, and cost is high；Unlike this, liquid flame retardant, particularly Halogen liquid flame retardant, such as tetraphenyl (bisphenol-A) two phosphorus
Acid esters (BDP) and tetraphenyl resorcinol diphosphate (RDP), can reach the requirement of environmental protection.
Therefore, for the research staff of this area, develop a kind of more environmentally-friendly liquid flame retardant and preparation side thereof
Method is undoubtedly one of emphasis of fire retardant R&D work.
Summary of the invention
For shortcomings and deficiencies present in above-mentioned prior art, in conjunction with above-mentioned reason, inventor have developed a kind of ring
The preparation method of the liquid flame retardant of border friendly, described preparation method is with Cardanol, phosphorus oxychloride as reactant, with chlorination
Magnesium is catalyst, the reaction of cooking different foods in one pot carried out in reaction vessel.Wherein, the Cardanol used, belong to pure natural raw material, no
Can cause environment pollution or poison.Additionally, described preparation method is without using solvent, it is possible to reduce energy consumption and produce into
This, avoided solvent contamination simultaneously.
Preferably, the preparation method of aforesaid liquid fire retardant comprises the following steps:
(1) in reaction vessel, add Cardanol, phosphorus oxychloride and magnesium chloride, use gradient increased temperature reacting by heating, keep reaction
System pressure-fired；Then, reaction system is imposed negative pressure, reacting by heating, until reaction is completely；
(2) reaction system is neutralized process；
(3) post processing, prepares described liquid flame retardant.
It is further preferred that the step (1) in above-mentioned preparation method is: add Cardanol, trichlorine oxygen in reaction vessel
Phosphorus and magnesium chloride, wherein, the mol ratio of Cardanol, phosphorus oxychloride and magnesium chloride is 3.00 ~ 3.40:0.8 ~ 1.2:0.01 ~ 0.04；
Keep reaction system pressure-fired；First, first stage reacting by heating is carried out: reaction temperature is 50 ~ 60 DEG C, 2 hours response time；
Then, then through 4 hours gradient increased temperatures to 150 DEG C；Carrying out second stage reacting by heating, reaction temperature is 148 ~ 150 DEG C, during reaction
Between 2 hours；Then, reaction system is imposed negative pressure, and keeps this negative pressure, carry out phase III reacting by heating 2 in 128 ~ 130 DEG C
Hour；Wherein, the hydrogen chloride gas that first stage, second stage and phase III reacting by heating produce respectively is all discharged into chlorination
Hydrogen absorption system.
It is further preferred that in above-mentioned preparation method, the mol ratio of Cardanol, phosphorus oxychloride and magnesium chloride is
3.02:1:0.02。
It is further preferred that the step (2) in above-mentioned preparation method is: be subsequently added into the sodium hydrate aqueous solution of 32wt%
Being neutralized, wherein, the mole of sodium hydroxide is 4 times of magnesium chloride mole；Then, adding weight is described sodium hydroxide
The soft water that aqueous solution weight is 9 times, cleans material, and carries out a point water.
It is further preferred that the step (3) in above-mentioned preparation method is: dehydration, then filter, prepare described liquid flame-proof
Agent.
It is further preferred that the operation temperature of described dehydration is 100 ~ 110 DEG C, operation pressure is-90 ~-95kpa.
It is further preferred that described filtration uses single bag type filter in 1 μm aperture to implement.
It is further preferred that in above-mentioned preparation method, described pressure-fired is 10kpa ~ 15kpa, described negative pressure is-
75kpa ~-85kpa.What deserves to be explained is, pressure listed in the present invention is gauge pressure.
Preparation method of the present invention, with Cardanol, phosphorus oxychloride as reactant, carries out chemistry with magnesium chloride for catalyst
Reaction, then passes through the operations such as neutralization, post processing, i.e. obtains liquid flame retardant product.Prepare according to the method for the invention
Liquid flame retardant, not only has a fire resistance that conventional flame retardant is had, and because it has easy to use, meter for liquid
Measure characteristic accurately；Additionally, preparation method process route provided by the present invention is short, easy and simple to handle, technique environmental protection, be suitable to
Industrialized production, thus, there is good application prospect.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further elaborated, but the present invention is not limited to following embodiment party
Formula.
The invention provides the preparation method of a kind of liquid flame retardant, it is characterised in that described preparation method is with Fructus anacardii
Phenol, phosphorus oxychloride are reactant, with magnesium chloride as catalyst, and the reaction of cooking different foods in one pot carried out in reaction vessel.
In a preferred embodiment, the preparation method of described liquid flame retardant comprises the following steps:
(1) in reaction vessel, add Cardanol, phosphorus oxychloride and magnesium chloride, use gradient increased temperature reacting by heating, keep reaction
System pressure-fired；Then, reaction system is imposed negative pressure, reacting by heating, until reaction is completely；
(2) reaction system is neutralized process；
(3) post processing, prepares described liquid flame retardant.
In a further preferred embodiment, the step (1) in described preparation method is: add in reaction vessel
Cardanol, phosphorus oxychloride and magnesium chloride, wherein, the mol ratio of Cardanol, phosphorus oxychloride and magnesium chloride be 3.00 ~ 3.40:0.8 ~
1.2:0.01 ~ 0.04；Keep reaction system pressure-fired；First, carry out first stage reacting by heating: reaction temperature is 50 ~ 60 DEG C,
2 hours response time；Then, then through 4 hours gradient increased temperatures to 150 DEG C；Carrying out second stage reacting by heating, reaction temperature is
148 ~ 150 DEG C, 2 hours response time；Then, reaction system is imposed negative pressure, and keeps this negative pressure, carry out in 128 ~ 130 DEG C
Phase III reacting by heating 2 hours；Wherein, the chlorination that first stage, second stage and phase III reacting by heating produce respectively
Hydrogen is all discharged into chlorine hydride absorption system.
In one further preferred embodiment, the mol ratio of Cardanol, phosphorus oxychloride and magnesium chloride is 3.02:1:
0.02。
In a further preferred embodiment, the step (2) in described preparation method is: be subsequently added into 32wt%'s
Sodium hydrate aqueous solution is neutralized, and wherein, the mole of sodium hydroxide is 4 times of magnesium chloride mole；Then, weight is added
For the soft water of described sodium hydrate aqueous solution weight 9 times, clean material, and carry out a point water.
In a further preferred embodiment, the step (3) in described preparation method is: dehydration, then filters, system
Obtain described liquid flame retardant.
In one further preferred embodiment, the operation temperature of described dehydration is 100 ~ 110 DEG C, operates pressure
For-90 ~-95kpa.
In one further preferred embodiment, described filtration uses single bag type filter in 1 μm aperture to implement.
In one further preferred embodiment, described pressure-fired is 10kpa ~ 15kpa, and described negative pressure is-75kpa
~-85kpa。
Step in the preparation method of following liquid flame retardant is conventional method if no special instructions, described raw material such as without
Special instruction all can be either commercially available from open.
Embodiment 1
(1) in reaction vessel, Cardanol, phosphorus oxychloride and magnesium chloride, wherein, Cardanol, phosphorus oxychloride and magnesium chloride are added
Mol ratio is 3.12:0.9:0.02；The pressure-fired keeping reaction system is 10kpa ~ 15kpa(G)；First, carry out the first stage
Reacting by heating: reaction temperature is 50 ~ 55 DEG C, 2 hours response time；Then, then through 4 hours gradient increased temperatures to 150 DEG C；Carry out
Two-stage heat reacts, and reaction temperature is 148 ~ 150 DEG C, 2 hours response time；Then, reaction system is imposed-75kpa ~-
Negative pressure 85kpa(G), and keep this negative pressure, carry out phase III reacting by heating 2 hours in 128 ~ 130 DEG C；Wherein, the first rank
The hydrogen chloride gas that section, second stage and phase III reacting by heating produce respectively is all discharged into chlorine hydride absorption system.
(2) sodium hydrate aqueous solution being subsequently added into 32wt% is neutralized, and wherein, the mole of sodium hydroxide is chlorination
4 times of magnesium mole；Then, add the soft water that weight is described sodium hydrate aqueous solution weight 9 times, clean material three times, and
Carry out a point water；
(3) at 100 DEG C and-90kpa(G) under the conditions of be dehydrated, then use single bag type filter in 1 μm aperture to filter, prepare
Described liquid flame retardant product.
Embodiment 2
(1) in reaction vessel, Cardanol, phosphorus oxychloride and magnesium chloride, wherein, Cardanol, phosphorus oxychloride and magnesium chloride are added
Mol ratio is 3.02:1:0.02；The pressure-fired keeping reaction system is 10kpa ~ 15kpa(G)；First, carrying out the first stage adds
Thermal response: reaction temperature is 55 ~ 60 DEG C, 2 hours response time；Then, then through 4 hours gradient increased temperatures to 150 DEG C；Carry out second
Stepwise heating reacts, and reaction temperature is 148 ~ 150 DEG C, 2 hours response time；Then, reaction system is imposed-75kpa ~-
Negative pressure 85kpa(G), and keep this negative pressure, carry out phase III reacting by heating 2 hours in 128 ~ 130 DEG C；Wherein, the first rank
The hydrogen chloride gas that section, second stage and phase III reacting by heating produce respectively is all discharged into chlorine hydride absorption system.
(2) sodium hydrate aqueous solution being subsequently added into 32wt% is neutralized, and wherein, the mole of sodium hydroxide is chlorination
4 times of magnesium mole；Then, add the soft water that weight is described sodium hydrate aqueous solution weight 9 times, clean material three times, and
Carry out a point water；
(3) at 110 DEG C and-93kpa(G) under the conditions of be dehydrated, then use single bag type filter in 1 μm aperture to filter, prepare
Described liquid flame retardant product.
Embodiment 3
(1) in reaction vessel, Cardanol, phosphorus oxychloride and magnesium chloride, wherein, Cardanol, phosphorus oxychloride and magnesium chloride are added
Mol ratio is 3.30:1.1:0.04；The pressure-fired keeping reaction system is 10kpa ~ 15kpa(G)；First, carry out the first stage
Reacting by heating: reaction temperature is 50 ~ 56 DEG C, 2 hours response time；Then, then through 4 hours gradient increased temperatures to 150 DEG C；Carry out
Two-stage heat reacts, and reaction temperature is 150 DEG C, 2 hours response time；Then, reaction system is imposed-75kpa ~-85kpa
(G) negative pressure, and keep this negative pressure, carry out phase III reacting by heating 2 hours in 128 ~ 130 DEG C；Wherein, the first stage,
The hydrogen chloride gas that two-stage and phase III reacting by heating produce respectively is all discharged into chlorine hydride absorption system.
(2) sodium hydrate aqueous solution being subsequently added into 32wt% is neutralized, and wherein, the mole of sodium hydroxide is chlorination
4 times of magnesium mole；Then, add the soft water that weight is described sodium hydrate aqueous solution weight 9 times, clean material three times, and
Carry out a point water；
(3) at 106 DEG C and-95kpa(G) under the conditions of be dehydrated, then use single bag type filter in 1 μm aperture to filter, prepare
Described liquid flame retardant product.
Embodiment 4
(1) in reaction vessel, Cardanol, phosphorus oxychloride and magnesium chloride, wherein, Cardanol, phosphorus oxychloride and magnesium chloride are added
Mol ratio is 3.40:1.2:0.03；The pressure-fired keeping reaction system is 10kpa ~ 15kpa(G)；First, carry out the first stage
Reacting by heating: reaction temperature is 58 ~ 60 DEG C, 2 hours response time；Then, then through 4 hours gradient increased temperatures to 150 DEG C；Carry out
Two-stage heat reacts, and reaction temperature is 148 ~ 150 DEG C, 2 hours response time；Then, reaction system is imposed-75kpa ~-
Negative pressure 85kpa(G), and keep this negative pressure, carry out phase III reacting by heating 2 hours in 128 ~ 130 DEG C；Wherein, the first rank
The hydrogen chloride gas that section, second stage and phase III reacting by heating produce respectively is all discharged into chlorine hydride absorption system.
(2) sodium hydrate aqueous solution being subsequently added into 32wt% is neutralized, and wherein, the mole of sodium hydroxide is chlorination
4 times of magnesium mole；Then, add the soft water that weight is described sodium hydrate aqueous solution weight 9 times, clean material three times, and
Carry out a point water；
(3) at 101 DEG C and-95kpa(G) under the conditions of be dehydrated, then use single bag type filter in 1 μm aperture to filter, prepare
Described liquid flame retardant product.
Being described in detail the specific embodiment of the present invention above, but it is intended only as example, the present invention does not limit
It is formed on particular embodiments described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and
Substitute the most all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Amendment, all should contain within the scope of the invention.
Claims (9)
1. the preparation method of a liquid flame retardant, it is characterised in that described preparation method be with Cardanol, phosphorus oxychloride be anti-
Answer thing, with magnesium chloride as catalyst, the reaction of cooking different foods in one pot carried out in reaction vessel.
Preparation method the most according to claim 1, it is characterised in that comprise the following steps:
(1) in reaction vessel, add Cardanol, phosphorus oxychloride and magnesium chloride, use gradient increased temperature reacting by heating, keep reaction
System pressure-fired；Then, reaction system is imposed negative pressure, reacting by heating, until reaction is completely；
(2) reaction system is neutralized process；
(3) post processing, prepares described liquid flame retardant.
Preparation method the most according to claim 2, it is characterised in that step (1) is:
Cardanol, phosphorus oxychloride and magnesium chloride, wherein, rubbing of Cardanol, phosphorus oxychloride and magnesium chloride is added in reaction vessel
Your ratio is 3.00 ~ 3.40:0.8 ~ 1.2:0.01 ~ 0.04；Keep reaction system pressure-fired；First, first stage heating is carried out anti-
Should: reaction temperature is 50 ~ 60 DEG C, 2 hours response time；Then, then through 4 hours gradient increased temperatures to 150 DEG C；Carry out second stage
Reacting by heating, reaction temperature is 148 ~ 150 DEG C, 2 hours response time；Then, reaction system is imposed negative pressure, and keeps this to bear
Pressure, carries out phase III reacting by heating 2 hours in 128 ~ 130 DEG C；Wherein, first stage, second stage and phase III heating
The hydrogen chloride gas that reaction produces respectively is all discharged into chlorine hydride absorption system.
Preparation method the most according to claim 3, it is characterised in that the mol ratio of Cardanol, phosphorus oxychloride and magnesium chloride
For 3.02:1:0.02.
Preparation method the most according to claim 2, it is characterised in that step (2) is:
The sodium hydrate aqueous solution being subsequently added into 32wt% is neutralized, and wherein, the mole of sodium hydroxide is magnesium chloride mole
4 times；Then, add the soft water that weight is described sodium hydrate aqueous solution weight 9 times, clean material, and carry out a point water.
Preparation method the most according to claim 2, it is characterised in that step (3) is:
Dehydration, then filters, and prepares described liquid flame retardant.
Preparation method the most according to claim 6, it is characterised in that the operation temperature of described dehydration is 100 ~ 110 DEG C, behaviour
Making pressure is-90 ~-95kpa.
Preparation method the most according to claim 6, it is characterised in that described filtration uses single bag type filter in 1 μm aperture
Implement.
9. according to the preparation method according to any one of claim 2 ~ 8, it is characterised in that described pressure-fired be 10kpa ~
15kpa, described negative pressure is-75kpa ~-85kpa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373484A (en) * | 2018-02-25 | 2018-08-07 | 李嘉顺 | A kind of phosphorous anacardol polyglycidyl ether and preparation method thereof |
| CN109251471A (en) * | 2018-09-05 | 2019-01-22 | 中国林业科学研究院林产化学工业研究所 | Tricresyl phosphate cashew nut phenolic ester plasticized modifier and preparation method and applications |
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| CN102268036A (en) * | 2011-05-24 | 2011-12-07 | 江苏常余化工有限公司 | Preparation method of tert-butyl triphenyl phosphate |
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| CN102268036A (en) * | 2011-05-24 | 2011-12-07 | 江苏常余化工有限公司 | Preparation method of tert-butyl triphenyl phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108373484A (en) * | 2018-02-25 | 2018-08-07 | 李嘉顺 | A kind of phosphorous anacardol polyglycidyl ether and preparation method thereof |
| CN109251471A (en) * | 2018-09-05 | 2019-01-22 | 中国林业科学研究院林产化学工业研究所 | Tricresyl phosphate cashew nut phenolic ester plasticized modifier and preparation method and applications |
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