CN109020909A - A kind of preparation method of three (2,3- dibromopropyl) fulminuric acid esters - Google Patents
A kind of preparation method of three (2,3- dibromopropyl) fulminuric acid esters Download PDFInfo
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- CN109020909A CN109020909A CN201810690526.5A CN201810690526A CN109020909A CN 109020909 A CN109020909 A CN 109020909A CN 201810690526 A CN201810690526 A CN 201810690526A CN 109020909 A CN109020909 A CN 109020909A
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- Prior art keywords
- preparation
- dibromopropyl
- reaction
- acid ester
- bromine
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- -1 2,3- dibromopropyl Chemical group 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HQWDILUMZXPFNW-UHFFFAOYSA-N 2-cyano-2-nitroacetamide Chemical class NC(=O)C(C#N)[N+]([O-])=O HQWDILUMZXPFNW-UHFFFAOYSA-N 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims abstract description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000009413 insulation Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000012044 organic layer Substances 0.000 claims abstract description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001953 recrystallisation Methods 0.000 claims abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to one kind three (2,3- dibromopropyl) fulminuric acid ester preparation method, steps are as follows for the preparation method: (1) triallyl isocyanurate (TAIC) and reaction dissolvent being added in reaction kettle according to the ratio, be warming up to after certain temperature and a certain amount of bromine is added dropwise while stirring；(2) for a period of time, 20% solution of sodium bisulfite is then added in insulation reaction after dripping off bromine, until the reddish brown decoloration of reaction system；(3) it then stands liquid separation and goes out organic layer, after being cooled to 0-10 DEG C, instill quantitative recrystallisation solvent while stirring, the form precipitating for making product to crystallize, through being dried under reduced pressure to obtain product after filtering.Preparation method of the invention has the characteristics of product yield is high, good product quality, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of new flame retardant three (2,3- dibromopropyl) fulminuric acid ester.
Background technique
Three (2,3- dibromopropyl) fulminuric acid esters, English name Tri(2,3-dibromopropyl)
Isocyanurate (abbreviation TBC) is a kind of addition type bromine system new flame retardant with triazine ring, not soluble in water, pure and mild
Alkane dissolves in aromatic hydrocarbons, halogenated hydrocarbons and ketone etc..With good flame retardation effect, volatility is low, compatibility is good, durable, water-fast and nontoxic
Etc. characteristics.It is now widely used in polyolefin, polyvinyl chloride, polyurathamc, ABS, unsaturated polyester (UP), various synthetic rubber and conjunction
At the fire-retardant of the products such as fiber.
Three (2,3- dibromopropyl) fulminuric acid esters (TBC) are by triallyl isocyanurate (TAIC) and bromine parent
Electric addition reaction is prepared.TAIC is containing there are three the high polymer monomer of allyl, being a kind of widely used fine chemistry industry
Product, it can cooperate the organic peroxides such as DCP for polyolefin, polyvinyl chloride, polyester, polyamide, EP rubbers, silicon rubber
The crosslinking of equal thermoplastic materials；Its unique triazine structure, the heat resistance, mechanical strength and oil resistant that can improve crosslinked products are resistance to
Gas.Its triazine ring is a conjugated system, and resonance stability is lower than phenyl ring, at normal temperature, the double bond on TAIC allyl
It can produce addition reaction with bromine, generate the TAIC hexabromide-TBC of saturation.But the TBC that addition reaction generates is produced
Object is highly viscous shape, to be sold as product, post-processes the separation method to have had, uses suitable solvent in this preparation method
Crystallization Separation is carried out, product purity height and crystal form are good, are to implement industrialized ideal method.
Summary of the invention
It is an object of the invention to improve the prior art, provide a kind of new flame retardant three (2,3- dibromopropyl) different trimerization
The preparation method of cyanate.
The present invention improves technical solution used by its technical problem:
A kind of preparation method of three (2,3- dibromopropyl) fulminuric acid esters, steps are as follows for the preparation method:
(1) triallyl isocyanurate (TAIC) and reaction dissolvent are added in reaction kettle according to the ratio, are warming up to certain temperature
A certain amount of bromine is added dropwise while stirring afterwards；
(2) for a period of time, 20% solution of sodium bisulfite is then added in insulation reaction after dripping off bromine, until reaction system is reddish brown
Decoloration；
(3) it then stands liquid separation and goes out organic layer, after being cooled to 0-10 DEG C, instill quantitative recrystallisation solvent while stirring, make product
It is precipitated in the form of crystallization, through being dried under reduced pressure to obtain product after filtering.
Preferably, the triallyl isocyanurate (TAIC) and its weight proportion of bromine are 1:2~1:3.
Preferably, the reaction dissolvent is methylene chloride, chloroform and 1, and one kind of 2- dichloroethanes, dosage is three allyls
1~3 times of base chlorinated isocyanurates (TAIC) weight.
Preferably, the recrystallisation solvent is one of n-hexane, normal heptane and petroleum ether, and dosage is reaction dissolvent weight
1~4 times of amount.
Preferably, reaction temperature is 10-50 DEG C.
Preferably, crystallization temperature is 0-10 DEG C.
The characteristics of product yield is high the beneficial effects of the present invention are: preparation method of the invention has, good product quality, fits
Close industrialized production.
Specific embodiment
Below with reference to embodiment, the content of the present invention will be explained in more detail.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, and all equipment and raw material etc. are equal
It is commercially available or the industry is common.Method in following embodiments is unless otherwise instructed the routine of this field
Method.
Embodiment 1
In flask of the 250ml with stirring, thermometer dropping funel and reflux condenser, 49.8g triallyl isocyanide urine is added
Acid esters (TAIC) and 90g1,2- dichloroethanes, are warming up to 40 DEG C, and 100g bromine is added dropwise in stirring, adds rear insulation reaction 30
Minute, 20% solution of sodium bisulfite is then added dropwise, until the reddish brown decoloration of system, then liquid separation goes out organic layer, is cooled to 10
DEG C or less start to instill 150g normal heptane, make product and be precipitated in the form that crystallizes, white products are dried under reduced pressure to obtain after filtering
68.5g.Bromine number 65.4,105.8-109.7 DEG C of fusing point.
Embodiment 2
In flask of the 250ml with stirring, thermometer dropping funel and reflux condenser, 49.8g triallyl isocyanide urine is added
Acid esters (TAIC) and 90g chloroform, are warming up to 35 DEG C, and 100g bromine is added dropwise in stirring, adds rear insulation reaction 30 minutes, then
20% solution of sodium bisulfite is added dropwise, until the reddish brown decoloration of system, then liquid separation goes out organic layer, is cooled to 10 DEG C or less and opens
Begin to instill 150g petroleum ether, makes product and be precipitated in the form crystallized, white products 69.0g is dried under reduced pressure to obtain after filtering.Bromine number
65.2,105.4-109.5 DEG C of fusing point.
Embodiment 3
In flask of the 1000ml with stirring, thermometer dropping funel and reflux condenser, 199.2g triallyl isocyanide is added
Urate (TAIC) and 400g1,2- dichloroethanes, are warming up to 40 DEG C, and 400g bromine is added dropwise in stirring, adds rear insulation reaction
30 minutes, 20% solution of sodium bisulfite is then added dropwise, until the reddish brown decoloration of system, then liquid separation goes out organic layer, is cooled to
10 DEG C or less start to instill 800g normal heptane, make product and are precipitated in the form crystallized, white products are dried under reduced pressure to obtain after filtering
275g.Bromine number 65.1,105.4-108.9 DEG C of fusing point.
Embodiment 4
In flask of the 5L with stirring, thermometer dropping funel and reflux condenser, 0.996kg triallyl isocyanuric acid is added
Ester (TAIC) and 1.5kg chloroform, are warming up to 35-37 DEG C, and 2kg bromine is added dropwise in stirring, adds rear insulation reaction 30 minutes, so
20% solution of sodium bisulfite is added dropwise afterwards, until the reddish brown decoloration of system, then liquid separation goes out organic layer, is cooled to 10 DEG C or less
Start to instill 3kg petroleum ether, makes product and be precipitated in the form crystallized, white products 1.40kg is dried under reduced pressure to obtain after filtering.Bromine number
65.3,105.2-109.1 DEG C of fusing point.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (6)
- The preparation method of one kind three 1. (2,3- dibromopropyl) fulminuric acid ester, which is characterized in that the preparation method step It is as follows:(1) triallyl isocyanurate and reaction dissolvent are added in reaction kettle according to the ratio, are warming up to certain temperature back and stir It mixes side and a certain amount of bromine is added dropwise；(2) for a period of time, 20% solution of sodium bisulfite is then added in insulation reaction after dripping off bromine, until reaction system is reddish brown Decoloration；(3) it then stands liquid separation and goes out organic layer, after being cooled to 0-10 DEG C, instill quantitative recrystallisation solvent while stirring, make product It is precipitated in the form of crystallization, through being dried under reduced pressure to obtain product after filtering.
- 2. a kind of preparation method of three (2,3- dibromopropyl) fulminuric acid ester according to claim 1, feature exist In the triallyl isocyanurate and bromine weight proportion are 1:2~1:3.
- 3. a kind of preparation method of three (2,3- dibromopropyl) fulminuric acid ester according to claim 1, feature exist In the reaction dissolvent is methylene chloride, chloroform and 1, and one kind of 2- dichloroethanes, dosage is triallyl isocyanurate 1~3 times of weight.
- 4. a kind of preparation method of three (2,3- dibromopropyl) fulminuric acid ester according to claim 1, feature exist In the recrystallisation solvent is one of n-hexane, normal heptane and petroleum ether, and dosage is 1~4 times of reaction dissolvent weight.
- 5. a kind of preparation method of three (2,3- dibromopropyl) fulminuric acid ester according to claim 1, feature exist In reaction temperature is 10-50 DEG C.
- 6. a kind of preparation method of three (2,3- dibromopropyl) fulminuric acid ester according to claim 1, feature exist In crystallization temperature is 0-10 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810690526.5A CN109020909A (en) | 2018-06-28 | 2018-06-28 | A kind of preparation method of three (2,3- dibromopropyl) fulminuric acid esters |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810690526.5A CN109020909A (en) | 2018-06-28 | 2018-06-28 | A kind of preparation method of three (2,3- dibromopropyl) fulminuric acid esters |
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| Publication Number | Publication Date |
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| CN109020909A true CN109020909A (en) | 2018-12-18 |
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| CN201810690526.5A Pending CN109020909A (en) | 2018-06-28 | 2018-06-28 | A kind of preparation method of three (2,3- dibromopropyl) fulminuric acid esters |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776438A (en) * | 2019-03-27 | 2019-05-21 | 山东润科化工股份有限公司 | A kind of heat-staple TBC method for synthesizing flame retardant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694186A (en) * | 2014-01-06 | 2014-04-02 | 中国石油大学(华东) | Production method of tri (2,3-dibromo propyl) isocyanurate |
-
2018
- 2018-06-28 CN CN201810690526.5A patent/CN109020909A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694186A (en) * | 2014-01-06 | 2014-04-02 | 中国石油大学(华东) | Production method of tri (2,3-dibromo propyl) isocyanurate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776438A (en) * | 2019-03-27 | 2019-05-21 | 山东润科化工股份有限公司 | A kind of heat-staple TBC method for synthesizing flame retardant |
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Application publication date: 20181218 |
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