CN107337691B - A kind of new phosphorus-containing flame retardant and preparation method thereof - Google Patents
A kind of new phosphorus-containing flame retardant and preparation method thereof Download PDFInfo
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- CN107337691B CN107337691B CN201710514372.XA CN201710514372A CN107337691B CN 107337691 B CN107337691 B CN 107337691B CN 201710514372 A CN201710514372 A CN 201710514372A CN 107337691 B CN107337691 B CN 107337691B
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- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
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- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
Abstract
The present invention is a kind of new phosphorus-containing flame retardant and preparation method thereof, using one kettle way technique and Metal aluminum salt is used to use non-protonic solvent using phosphoryl chloride phosphorus oxychloride and benzoquinones analog derivative as base stock as catalyst, it reacts at room temperature for 24 hours, high yield obtains phosphonium flame retardant.The major advantage of this method has: relative to existing method, this method mild condition, a step is completed, and reduces the waste of cost of material and reaction generation.Have the characteristics that Atom economy and high efficiency simultaneously.
Description
[technical field]
The invention belongs to organic synthesis field, a kind of novel phosphorus fire retardant and preparation method thereof is related in particular to.
[background technique]
With the continuous development of China's material industry, fire retardant is in chemical material, electric appliance, communications and transportation, space flight and aviation, day
It is very extensive with being applied in the every field such as furniture.In general, fire retardant element classification can be divided into phosphorus system, boron system, halogen
Prime system, inorganic metal flame retardant etc..Wherein halogen based flame retardant, burning can generate a large amount of toxic gases, tight to environmental hazard
Weight.Inorganic metal based flame retardant, flame retarding efficiency is relatively low, its usual additive amount is bigger, but the content of fire retardant is excessively multipair
The performance of material has a great impact.Currently, continuous improvement of people's living standards, pushes fire retardant towards environmental protection, efficiently
Direction is developed.
Phosphorus flame retardant be it is a kind of have excellent performance, environmentally friendly fire retardant.It is widely used in plastics, fiber, coating etc.
Flame retardant treatment.That wherein application is more is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (abbreviation DOPO).Patent
103833947 A of CN discloses a kind of preparation method of the response type phosphonium flame retardant of polyurethane, passes through phosphorous-containing monomers 9,10-
It is derivative that the miscellaneous -10- phospha of dihydro-9-oxy-phenanthrene -10- oxide (DOPO) and unsaturated polybasic carboxylic acid or acid anhydrides form phosphorous-containing monomers
Object, and then esterification occurs with polyalcohol, obtain the halogen-free phosphorus-containing fire retardant agent of liquid.103866643 A of patent CN is disclosed
A kind of preparation method of composite flame-retardant agent, by adjusting triphenyl phosphate, pollopas, ammonium phosphate, pentaerythrite, sodium metasilicate etc.
A kind of composite flame-retardant agent for promoting paper fire retardancy is made in reaction raw materials proportion.
Although the synthetic method of phosphonium flame retardant are more, some shortcomings are still had, mainly there is the following aspects:
Method for synthesizing flame retardant is few, and step is more；It is at high cost, technology controlling and process is complicated, it is difficult to industrialized production.Therefore, develop it is a kind of simple,
The phosphonium flame retardant of efficient synthetic method synthesis high flame resistance, has important practical value.
[summary of the invention]
The purpose of the present invention is to provide a kind of new phosphorus-containing flame retardants and preparation method thereof, using one kettle way technique and make
Use Metal aluminum salt as catalyst, using phosphoryl chloride phosphorus oxychloride and benzoquinones analog derivative as base stock, using non-protonic solvent, in room temperature
For 24 hours, high yield obtains phosphonium flame retardant for lower reaction.The major advantage of this method has: relative to existing method, this method condition
Mildly, a step is completed, and reduces the waste of cost of material and reaction generation.Have Atom economy and high efficiency special simultaneously
Point.
To achieve the above object of the invention, the present invention proposes technical solution below:
The present invention with phosphoryl chloride phosphorus oxychloride analog derivative (I), benzoquinones analog derivative (II) be raw material, using Metal aluminum salt as catalyst,
With there are commonly solvents to make reaction dissolvent, reaction at a certain temperature, reacts certain time, and high yield obtains with high selectivity
To new phosphorus-containing flame retardant (III), structural formula is as follows:
Wherein, the R1、R2、R3、R4、R5Group is hydrogen, methyl, methoxyl group, isopropyl, nitro, cyano, hydroxyl, acetyl
One of base, sulfidomethyl, phenyl, hydroxyl, carboxyl, fluorine, chlorine, bromine.
In above-mentioned preparation method, which is characterized in that using phosphoryl chloride phosphorus oxychloride analog derivative, benzoquinones analog derivative as raw material, with metal
Aluminium salt is catalyst, with there are commonly solvents to make reaction dissolvent, is reacted at a certain temperature, reaction certain time, high yield,
New phosphorus-containing flame retardant is obtained with high selectivity.
In above-mentioned preparation method, which is characterized in that the R1、R2、R3Group be hydrogen, methyl, methoxyl group, nitro, cyano,
One of hydroxyl, fluorine, chlorine, bromine.
In above-mentioned preparation method, which is characterized in that the R4、R5Group be hydrogen, methyl, methoxyl group, tert-butyl, isopropyl,
One of nitro, cyano, allyl, hydroxyl, acetyl group, sulfidomethyl, phenyl, hydroxyl, carboxyl, fluorine, chlorine, bromine.
In above-mentioned preparation method, which is characterized in that the catalyst is AlCl3、AlBr3、Al(OH)3One of.
In above-mentioned preparation method, which is characterized in that mole additive amount of the catalyst is 0.01-0.20mol%.
In above-mentioned preparation method, which is characterized in that the solvent is toluene, acetonitrile, tetrahydrofuran (THF), dimethyl sulfoxide
(DMSO), one of n,N-Dimethylformamide (DMF).
In above-mentioned preparation method, which is characterized in that the condition of the catalysis reaction are as follows: react 0.5-24 at 0-120 DEG C
Hour.
[Detailed description of the invention]
It is that the present invention provides the synthesis path figure for catalyzing and synthesizing new phosphorus-containing flame retardant shown in Fig. 1.
[specific embodiment]
The synthesis path figure provided by the present invention for catalyzing and synthesizing new phosphorus-containing flame retardant, refers to attached drawing 1: by raw material chemical combination
Phosphoryl chloride phosphorus oxychloride, benzoquinones analog derivative, the Metal aluminum salt catalyst of object are placed in reaction vessel, solvent toluene are added, at 0-120 DEG C
It is reacted 0.5-24 hours under environment, after the reaction was completed, target compound chromatographic isolation obtains.
Below with reference to specific preparation example, the present invention will be further described:
Preparation example 1
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4、R5=H), 12mL toluene stirs reaction 24 hours at 25 DEG C, TLC tracking reaction to fully reacting.Reaction
As a result are as follows: product III (R1、R2、R3、R4、R5=H) yield be 96%.
The product that above-mentioned preparation example 1 synthesizes is done1H NMR analysis, as a result as follows:1H NMR(400MHz,CDCl3)δ7.86
(dd, J=12.5,7.5Hz, 1H), 7.57-7.54 (m, 2H), 7.50-7.47 (m, 4H), 7.07 (s, 1H), 6.86 (d, J=
8.7Hz, 1H), the 6.74 specific spectrograms of (d, J=8.8Hz, 1H) are as shown in Fig. 2.
The product that above-mentioned preparation example 1 synthesizes is done13C NMR analysis, as a result as follows:13C NMR(101MHz,CDCl3)δ
149.74,149.72,149.69,149.60,149.50,149.47,143.11,132.79,131.82,131.71,130.94,
129.56,128.83,128.69,121.80,120.48,116.96., specific spectrogram is as shown in Fig. 3.
The product that above-mentioned preparation example 1 synthesizes is done31P NMR analysis, as a result as follows:31P NMR(162MHz,CDCl3)δ
32.15. specific spectrogram is as shown in Fig. 4.
The product that above-mentioned preparation example 1 synthesizes is done into fusing point test analysis, measuring molten journey is 145-146 DEG C, is shown prepared
Fire retardant purity is high.
Phosphonium flame retardant obtained by above-described embodiment 1 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 2
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2=H；R3=Me),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R4、R5=H；R3=Me) yield be 99%.
Phosphonium flame retardant obtained by above-described embodiment 2 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 3
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=isopropyl；R5=Me), 12mL toluene stirs reaction 24 hours at 25 DEG C, and TLC tracking is reacted to anti-
It should be complete.Reaction result are as follows: product III (R1、R2、R3=H；R4=isopropyl；R5=Me) yield be 97%.
Phosphonium flame retardant obtained by above-described embodiment 3 is added in acrylic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 4
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R2、R3=H；R1=NO2)、
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R2、R3、R4、R5=H；R1=NO2) yield be 95%.
Phosphonium flame retardant obtained by above-described embodiment 4 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 5
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R3=H；R2=OH),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R3、R4、R5=H；R2=Me) yield be 94%.
Phosphonium flame retardant obtained by above-described embodiment 5 is added in phenolic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 6
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2=H；R3=OMe),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R4、R5=H；R3=OMe) yield be 98%.
Phosphonium flame retardant obtained by above-described embodiment 6 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 7
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=H；R5=Br), 12mL toluene stirs reaction 24 hours at 25 DEG C, TLC tracking reaction to fully reacting.
Reaction result are as follows: product III (R1、R2、R3、R4=H；R5=Br) yield be 91%.
Phosphonium flame retardant obtained by above-described embodiment 7 is added in ABS resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 8
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2=H；R3=Br),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R4、R5=H；R3=Br) yield be 96%.
Phosphonium flame retardant obtained by above-described embodiment 8 is added in acrylic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 9
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1=H；R2、R3=Br),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R4、R5=H；R2、R3The yield of=Br is 95%.
Phosphonium flame retardant obtained by above-described embodiment 9 is added in ABS resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 10
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R2、R3=H；R1=F),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R2、R3、R4、R5=H；R1=Me) yield be 98%.
Phosphonium flame retardant obtained by above-described embodiment 10 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 11
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4、R5=OH), 12mL toluene stirs reaction 24 hours at 25 DEG C, TLC tracking reaction to fully reacting.Reaction
As a result are as follows: product III (R1、R2、R3=H；R4、R5=OH) yield be 96%.
Phosphonium flame retardant obtained by above-described embodiment 11 is added in phenolic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 12
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R3=H；R2=Br),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R3、R4、R5=H；R2=Me) yield be 95%.
Phosphonium flame retardant obtained by above-described embodiment 12 is added in acrylic resin and carries out oxygen index (OI) test and vertical
Combustion rating test, is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm ×
3mm is measured according to UL94 standard using Vertical combustion instrument, and batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and hang down
The performance test specific experiment of straight combustion rating the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 13
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R2、R3=H；R1=Br),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R2、R3、R4、R5=H；R1=Me) yield be 95%.
Phosphonium flame retardant obtained by above-described embodiment 13 is added in ABS resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 14
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4、R5=Ph), 12mL toluene stirs reaction 24 hours at 25 DEG C, TLC tracking reaction to fully reacting.Reaction
As a result are as follows: product III (R1、R2、R3=H；R4、R5=Ph) yield be 95%.
Phosphonium flame retardant obtained by above-described embodiment 14 is added in acrylic resin and carries out oxygen index (OI) test and vertical
Combustion rating test, is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm ×
3mm is measured according to UL94 standard using Vertical combustion instrument, and batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and hang down
The performance test specific experiment of straight combustion rating the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 15
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R3=H；R2=Me),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R3、R4、R5=H；R2=Me) yield be 97%.
Phosphonium flame retardant obtained by above-described embodiment 15 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 16
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=H；R5=F), 12mL toluene stirs reaction 24 hours at 25 DEG C, TLC tracking reaction to fully reacting.Instead
Answer result are as follows: product III (R1、R2、R3、R4=H；R5=F) yield be 93%.
Phosphonium flame retardant obtained by above-described embodiment 16 is added in acrylic resin and carries out oxygen index (OI) test and vertical
Combustion rating test, is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm ×
3mm is measured according to UL94 standard using Vertical combustion instrument, and batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and hang down
The performance test specific experiment of straight combustion rating the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 17
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R3=H；R2=F),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R3、R4、R5=H；R2The yield of=F is 93%.
Phosphonium flame retardant obtained by above-described embodiment 17 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 18
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=H；R5=S-Me), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R3、R4=H；R5=S-Me) yield be 91%.
Phosphonium flame retardant obtained by above-described embodiment 18 is added in ABS resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 19
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2=H；R3=OH),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R4、R5=H；R3=OH) yield be 91%.
Phosphonium flame retardant obtained by above-described embodiment 19 is added in phenolic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 20
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=F；R5=C3H7), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R3=H；R4=F；R5=C3H7) yield be 92%.
Phosphonium flame retardant obtained by above-described embodiment 20 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 21
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2=H；R3=F),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R4、R5=H；R3=F) yield be 96%.
Phosphonium flame retardant obtained by above-described embodiment 21 is added in acrylic resin and carries out oxygen index (OI) test and vertical
Combustion rating test, is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm ×
3mm is measured according to UL94 standard using Vertical combustion instrument, and batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and hang down
The performance test specific experiment of straight combustion rating the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 22
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=H；R5=Cl), 12mL toluene stirs reaction 24 hours at 25 DEG C, TLC tracking reaction to fully reacting.
Reaction result are as follows: product III (R1、R2、R3、R4=H；R5=Cl) yield be 95%.
Phosphonium flame retardant obtained by above-described embodiment 22 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 23
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R2、R3=H；R1=Me),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R2、R3、R4、R5=H；R1=Me) yield be 98%.
Phosphonium flame retardant obtained by above-described embodiment 23 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 24
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=H；R5=COCH3), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R3=H；R4=H；R5=COCH3) yield be 97%.
Phosphonium flame retardant obtained by above-described embodiment 24 is added in ABS resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm × 3mm is pressed
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
The performance test specific experiment of grade the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 24
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2=H；R3=Cl),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R4、R5=H；R3=Cl) yield be 99%.
Phosphonium flame retardant obtained by above-described embodiment 24 is added in phenolic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 25
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=H；R5=COOH), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R3=H；R4=H；R5=COOH) yield be 95%.
Phosphonium flame retardant obtained by above-described embodiment 25 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 26
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R3=H；R2=OMe),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R3、R4、R5=H；R2=OMe) yield be 92%.
Phosphonium flame retardant obtained by above-described embodiment 26 is added in acrylic resin and carries out oxygen index (OI) test and vertical
Combustion rating test, is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm ×
3mm is measured according to UL94 standard using Vertical combustion instrument, and batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and hang down
The performance test specific experiment of straight combustion rating the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 27
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2、R3=H), 0.1mol
Benzoquinones II (R4=H；R5=S-Ph), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2、R3=H；R4=H；R5=S-Ph) yield be 99%.
Phosphonium flame retardant obtained by above-described embodiment 27 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 28
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R3=H；R2=Cl),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R3、R4、R5=H；R2=Cl) yield be 97%.
Phosphonium flame retardant obtained by above-described embodiment 28 is added in phenolic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 29
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1=H；R2、R3=Me),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R4、R5=H；R2、R3=Me) yield be 98%.
Phosphonium flame retardant obtained by above-described embodiment 29 is added in acrylic resin and carries out oxygen index (OI) test and vertical
Combustion rating test, is measured according to GB/T 2406-1993 standard using oxygen index instrument, and batten size 100mm × 6.5mm ×
3mm is measured according to UL94 standard using Vertical combustion instrument, and batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and hang down
The performance test specific experiment of straight combustion rating the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 30
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R2、R3=H；R1=Cl),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R2、R3、R4、R5=H；R1=Cl) yield be 95%.
Phosphonium flame retardant obtained by above-described embodiment 30 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 31
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2=H；R3=NO2)、
0.1mol benzoquinones II (R4、R5=F), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2=H；R3=NO2；R4、R5=F) yield be 91%.
Phosphonium flame retardant obtained by above-described embodiment 31 is added in phenolic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application
Preparation example 32
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R2、R3=H；R1=OMe),
0.1mol benzoquinones II (R4、R5=H), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R2、R3、R4、R5=H；R1=OMe) yield be 95%.
Phosphonium flame retardant obtained by above-described embodiment 32 is added in epoxy resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
Preparation example 38
0.15mol%AlCl is added in 100mL single-necked flask3, 0.1mol phosphoryl chloride phosphorus oxychloride I (R1、R2=H；R3=CH2CN)、
0.1mol benzoquinones II (R4、R5=Me), reaction stir 24 hours at 25 DEG C by 12mL toluene, and TLC tracking is reacted to having reacted
Entirely.Reaction result are as follows: product III (R1、R2=H；R3=CH2CN；R4、R5=Me；) yield be 94%.
Phosphonium flame retardant obtained by above-described embodiment 32 is added in phenolic resin and carries out oxygen index (OI) test and vertical combustion
Level estimate is burnt, is measured according to GB/T 2406-1993 standard using oxygen index instrument, batten size 100mm × 6.5mm × 3mm,
It is measured according to UL94 standard using Vertical combustion instrument, batten is having a size of 125mm × 13mm × 3mm.Limit oxygen index and vertical combustion
Burn grade performance test specific experiment the result is as follows:
Test result shows new phosphorus-containing flame retardant in limit oxygen index and vertical combustion two important flame retardant property indexs
Aspect has reached national standard, obtains good flame retardant effect, and dosage is few, is worthy of further application.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Cannot therefore and being interpreted as limitations on the scope of the patent of the present invention should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (4)
1. a kind of synthetic method of phosphonium flame retardant (III) is original with phosphoryl chloride phosphorus oxychloride analog derivative (I), benzoquinones analog derivative (II)
Material, with AlCl3For catalyst, reaction dissolvent is made with organic solvent, reaction is reacted certain time at a certain temperature, obtained phosphorous
Fire retardant (III)；Its structural formula I, II, III difference are as follows:
R1、R2、R3、R4、R5Group is hydrogen, methyl, methoxyl group, isopropyl, nitro, cyano, hydroxyl, acetyl group, sulfidomethyl, benzene
One of base, hydroxyl, carboxyl, fluorine, chlorine, bromine.
2. synthetic method according to claim 1, which is characterized in that mole additive amount of the catalyst is 0.01-
0.20mol%.
3. synthetic method according to claim 1, which is characterized in that the organic solvent is toluene, acetonitrile, tetrahydrofuran
(THF), one of dimethyl sulfoxide (DMSO), n,N-Dimethylformamide (DMF).
4. synthetic method according to claim 1, which is characterized in that the reaction are as follows: react 0.5-24 at 0-120 DEG C
Hour.
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