CN108929283A - A kind of synthetic method of high-purity crosslinking agent triallyl isocyanurate - Google Patents
A kind of synthetic method of high-purity crosslinking agent triallyl isocyanurate Download PDFInfo
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- CN108929283A CN108929283A CN201810768916.XA CN201810768916A CN108929283A CN 108929283 A CN108929283 A CN 108929283A CN 201810768916 A CN201810768916 A CN 201810768916A CN 108929283 A CN108929283 A CN 108929283A
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- 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
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Abstract
The invention discloses a kind of synthetic methods of high-purity crosslinking agent triallyl isocyanurate, by bromopropene, cyanuric acid, phase transfer catalyst and composite catalyst synthesize high-purity triallyl isocyanurate in polar organic solvent, the tail gas hydrogen bromide of generation is fully absorbed through the recirculated water of second level graphite parallel type film-falling absorption tower, it is made outside certain density hydrobromic acid and sells, synthetic reaction carries out in organic media rather than in the water-soluble middle liquid of strong basicity, the largely waste water containing organic matter and salt will not be generated, avoid the processing and disposition of high-concentration waste water and waste residue, final reaction solution obtains the high-purity TAIC of content >=99.0% after carrying out precipitation treatment.
Description
One, technical field
The present invention relates to a kind of preparation methods of fine chemicals, are exactly a kind of high-purity crosslinking agent triallyls
The synthetic method of chlorinated isocyanurates.
Two, background technique
Crosslinking agent TAIC is the abbreviation of English name Triallyl isocyanurate, and Chinese is that triallyl is different
Cyanurate or iso-cyanuric acid triallyl ester, scientific name 1,3,5- triallyl-guanamine, 4,6- triketones, structural formula
It is as follows:
Crosslinking agent TAIC is micro- yellow or colourless liquid (crystal), molecular formula C at room temperature12H15N3O3, molecular weight is
249.27, it is a kind of multi-olefin compound containing heteroaromatic, is divided into two kinds of specifications of technical grade and high-purity grade, technical grade TAIC is micro-
Yellow liquor body (crystal) content >=95.0%, fusing point are 17-21 DEG C, high-purity grade of TAIC colourless liquid (crystal) content >=99.0%,
Fusing point is 23-26 DEG C.
Technical grade TAIC main application: for a variety of thermoplastics (polyethylene, polyvinyl chloride, haloflex, EVA,
Polystyrene etc.) cross-linked modifier, heat resistance, solvent resistance, mechanical strength and the electrical property of product are remarkably improved after crosslinking
Energy；Auxiliary curing agent also as specific rubbers such as EP rubbers, various fluorubber, CPE can be significantly reduced vulcanization time, improve
Intensity, wearability, solvent resistance and corrosion resistance；As synthesis antipollution, intensity is big, large aperture, heat-resisting, acid and alkali-resistance propylene
The modifying agent of acid, the crosslinking agent of benzethylene type ion exchange resin and epoxy resin, polyphenyl dioctyl phthalate diallyl phthalate resin, can
Improve heat resistance, adhesiveness, mechanical strength and dimensional stability.
As crosslinking agent TAIC application range is gradually expanded, to product quality, more stringent requirements are proposed in market, technical grade
TAIC must can be applied to the bigger high-end field of added value by purification process.
The industrial production of TAIC is broadly divided into two kinds of process routes of cyanuric acid Aqueous phase and Zassol solvent method at present:
(1) it is water-soluble that a large amount of sodium hydroxide is added using cyanuric acid and chloropropene as reaction raw materials in cyanuric acid Aqueous phase in an aqueous medium
Liquid adjusts pH, makes isocyanuric acid that nucleophilic substitution occur with chloropropene and synthesizes TAIC.(2) Zassol solvent method, with Zassol
With chloropropene reaction raw materials, using higher boiling aprotic solvent as reaction medium, under high temperature and anhydrous condition, Zassol and chlorine third
Alkene is cyclized continuous two-step reaction synthesis TAIC through over-churning.
There is more disadvantage in route (1) cyanuric acid Aqueous phase and route (2) Zassol solvent method, need further to change
Into.
In alkaline water phase hydrolytic side reactions easily occur for reaction raw materials chloropropene in the cyanuric acid Aqueous phase of route (1),
It needs to be added excessive more chloropropene and participates in reaction, cause the unit consumption of chloropropene excessively high, one times or more more than reaction equivalent, water
The high-concentration waste water of side reaction and last neutralization reaction generation largely containing allyl alcohol, methacrylaldehyde, acrylic acid and salt is solved, is led
It causes waste water and Solid state fermentation cost is excessively high and reaction raw materials consumption is excessive.
Route (2) Zassol solvent method is cyclized two step successive reactions and synthesizes TAIC through over-churning, i.e., it is different first to generate allyl
Cyanate, then high temperature cyclization form tripolymer product, exist be cyclized halfway phenomenon in the reaction, and there are more in product
Dimer impurity, and the high temperature precipitation of higher cyclisation temperature and high boiling solvent can all cause product to occur to divide at high temperature
Solution and polymerization reaction generate more impurity, so that product purity is a greater impact, limit product in the use of high-end field.Together
When due to needing to generate isocyanates intermediate in reaction process, to prevent it from reacting with water needs in entire reaction process
Stringent anhydrous state and high boiling solvent precipitation is kept to need to keep high vacuum state for a long time, these working conditions pair
The shortcomings that equipment requirement is higher, and there are operating condition harshnesses, and operating flexibility is small, and energy consumption is high, is not easy to production operation.
Three, summary of the invention
The present invention is high for the existing synthetic method chloropropene unit consumption of TAIC, generates waste water, waste residue amount is big and product is pure
Spend the defects of low, energy consumption is high, it is desirable to provide a kind of synthetic method of environmental type, the technical problem to be solved is that pass through to close
At the high-purity TAIC of content >=99.0% can be obtained after, separation and precipitation.
The technical program be using cyanuric acid and bromopropene as raw material, be provided with the synthesis reaction vessel of device for absorbing tail gas in
Synthetic reaction is carried out in organic solvent, synthetic reaction formula is as follows:
The technical program includes mixing, reaction, degassing, washing, separation and precipitation each unit process, the area with the prior art
It is not the cyanuric acid of purity >=98.5%, phase transfer catalyst and catalysts to be added in organic solvent to be stirred first
And it is warming up to 70-80 DEG C, the bromopropene of purity >=99.0% is then added dropwise, continues to stir at 70-80 DEG C after being added dropwise anti-
It answers 3-5 hours.It is bubbled degassing, after reaction to drive away bromination hydrogen remaining in reaction solution；It adds water and stirs and washes after degassing
Wash away water-solubility impurity；It finally stands, be layered, dividing and go water phase, obtaining organic phase；Organic phase precipitation recycles organic solvent, obtains
To the high-purity TAIC of content >=99.0%.
The organic solvent is selected from 1,2- dichloroethanes, chloroform, ethyl acetate, dimethyl sulfoxide or acetonitrile.It is preferred that 1,2-
Dichloroethanes.
Cyanuric acid and bromopropene can be calculated by theoretical amount, i.e., molar ratio is that the ratio of 1:3 feeds intake.For convenience of operation, with pure
The cyanuric acid and purity >=99.0% bromopropene quality of degree >=98.5% are haggled over for convenience.In mass, the two mass ratio is
1:2.7-2.8.
The phase transfer catalyst is selected from quaternary ammonium salt, such as benzyltriethylammoinium chloride, benzyltrimethylammonium chloride, three pungent
One or more of methyl ammonium, tetrabutylammonium chloride or tetrabutylammonium bromide.It is preferred that tetrabutylammonium bromide.Phase transfer
The dosage of catalyst is the 1.5-2.5% of cyanuric acid quality.
The catalysts are selected from the triethylamine and stannous chloride composite catalyst that mass ratio is 1:1.Its dosage is
The 1.5-2.5% of cyanuric acid quality.
This synthetic reaction carries out in organic media, it is therefore prevented that bromopropene and water are under high temperature, alkaline condition in water phase
The phenomenon that hydrolytic side reactions occur, consumption of raw materials is made largely to exceed theoretical amount, makes the unit consumption of bromopropene close to theoretical equivalence, avoids
Largely containing allyl alcohol, methacrylaldehyde, acrylic acid high-concentration waste water generation, react environmental protection and economy, meet environmentally protective
The requirement of synthesis technology.
The hydrogen bromide tail gas that reaction generates is fully absorbed through second level graphite parallel type falling liquid film water absorption tower, and is followed by adjusting
Ring absorbs the flow of water, and the hydrobromic acid that required concentration can be made is for sale, avoids generation salt object during the reaction
Matter substantially reduces the generation of solid salt waste, increases economic benefit and social benefit.
The higher bromopropene of activity is used in crosslinking agent TAIC synthesis for the first time as reaction raw materials, the bond energy of C-Br is
The C-Cl bond energy of 276KJ/mol, chloropropene are 327KJ/mol, and the C-Br bond energy of bromopropene is smaller, reactivity ratio's chloropropene
By force, it easily reacts with isocyanuric acid and sloughs bromination hydrogen molecule, obtain product TAIC.
The boiling point of bromopropene is 71 DEG C, and chloropropene boiling point is 44 DEG C, and bromopropene boiling point is higher, under higher reaction temperatures not
Meeting transient evaporation is detached from reaction system, is conducive to bromopropene and cyanuric acid haptoreaction at relatively high temperatures.
80-100 DEG C of reaction dissolvent boiling point, moderate boiling point, temperature is excessively high when avoiding the occurrence of high boiling solvent precipitation makes product
There is the phenomenon that decomposition and polymerization side reactions.
Reaction uses quaternary ammonium salt-type phase transfer catalyst and accelerates the reaction rate between solid-liquid two-phase raw material.
Reaction uses that (the two weight ratio can be effective for the 1:1) composite catalyst formed by triethylamine and stannous chloride
Polarize isocyanuric acid, increases its reactivity, it is promoted to react with bromopropene.
This synthetic method yield is high, in terms of raw material bromopropene, yield >=92%；One-step synthesis just obtains content >=99.0%
High-purity TAIC product, do not need to purify, so that it may directly apply to electronic material, medical macromolecular materials, special cable, half
The high added values such as conductor, liquid crystal, solar battery and high-end product field, such as the closed material of printed wiring board,
To prevent liquids and gases substance from entering inside of electronic component.
Four, specific embodiment
Non-limiting examples are described below:
1. the clear water circulating pump of second level graphite parallel type film-falling absorption tower is opened, to equipped with thermometer, propeller agitator
In (120 revs/min of revolution) and the 1000L glassed steel reaction vessels of reflux condenser, 350kg1,2- dichloroethanes, 123kg is added
Cyanuric acid, 2kg tetrabutylammonium bromide, 1.1kg triethylamine, 1.1kg stannous chloride are heated to 70 DEG C, are slowly added dropwise under stirring
343kg bromopropene about needs 2 hours or so.After being added dropwise, 70 DEG C continuation insulation reaction 5 hours, react the hydrogen bromide of generation
Gas is absorbed as hydrobromic acid through the clear water of second level graphite parallel type film-falling absorption tower, after reaction, is passed through compressed air and drives out of
Remaining bromination hydrogen in reaction system, adds 200kg water, and the water-solubility impurity in stirring and dissolving reaction system is stood
After layering, organic phase is evaporated under reduced pressure, solvent is removed, obtains 218.2 kilograms of TAIC product, content 99.3%, yield 93% (with
Bromopropene meter).
2. the clear water circulating pump of second level graphite parallel type film-falling absorption tower is opened, to equipped with thermometer, propeller agitator
In (120 revs/min of revolution) and the 1000L glassed steel reaction vessels of reflux condenser, 350kg1,2- dichloroethanes, 125kg is added
Cyanuric acid, 2.5kg benzyltriethylammoinium chloride, 1.5kg triethylamine, 1.5kg stannous chloride are heated to 75 DEG C, slowly under stirring
Be added dropwise 348kg bromopropene, about need 3 hours or so, after being added dropwise, 75 DEG C continuation insulation reaction 4 hours, react the bromine of generation
Change hydrogen and be absorbed as hydrobromic acid through the clear water of second level graphite parallel type film-falling absorption tower, after reaction, is passed through compressed air
It drives bromination hydrogen remaining in reaction system out of, adds 200kg water, the water-solubility impurity in stirring and dissolving reaction system,
After stratification, organic phase is evaporated under reduced pressure, solvent is removed, obtains 219.9 kilograms of TAIC product, content 99.2%, yield
92.3% (in terms of bromopropene).
3. the clear water circulating pump of second level graphite parallel type film-falling absorption tower is opened, to equipped with thermometer, propeller agitator
In (120 revs/min of revolution) and the 1000L glassed steel reaction vessels of reflux condenser, addition 380kg 1,2- dichloroethanes,
128kg cyanuric acid, 3.1kg tetrabutylammonium bromide, 1.3kg triethylamine, 1.3kg stannous chloride are heated to 80 DEG C, slowly under stirring
Be added dropwise 352kg bromopropene, about need 3.5 hours or so, after being added dropwise, 80 DEG C continuation back flow reaction 3 hours, react generation
Bromination hydrogen is absorbed as hydrobromic acid through the clear water of second level graphite parallel type film-falling absorption tower, after reaction, it is empty to be passed through compression
Gas drives bromination hydrogen remaining in reaction system out of, adds 200kg water, and the water solubility in stirring and dissolving reaction system is miscellaneous
After stratification, organic phase is evaporated under reduced pressure for matter, removes solvent, obtains 224.1 kilograms of TAIC product, content 99.4%, yield
93.2% (in terms of bromopropene).
Cyanogen urea content >=98.5%, granularity >=100 mesh, white solid powder.
Bromopropene content >=99.0%, 71.3 DEG C of boiling point, colourless transparent liquid.
Product TAIC content is analyzed using liquid chromatogram external standard method, 1120 liquid chromatogram of liquid chromatograph model Agilent
Instrument.
Claims (6)
1. a kind of synthetic method of high-purity crosslinking agent triallyl isocyanurate is used using cyanuric acid and bromopropene as raw material
The synthesis reaction vessel for being provided with device for absorbing tail gas is reacted in organic solvent, including mixing, reaction, degassing, washing, point
From with precipitation each unit process, it is characterised in that: the reaction is first to urge the cyanuric acid of content >=98.5%, phase transfer
Agent and catalysts, which are added in organic solvent, to be stirred and is warming up to 70-80 DEG C, and content >=99.0% is then added dropwise
Bromopropene continues to be stirred to react at 70-80 DEG C 3-5 hours after being added dropwise；The ratio of cyanuric acid and bromopropene 1:3 in molar ratio
Example feeds intake, and the phase transfer catalyst is quaternary ammonium salts, and dosage is the 1.5-2.5% of cyanuric acid quality, and the reaction is urged
Agent is composite catalyst, and dosage is the 1.5-2.5% of cyanuric acid quality.
2. synthetic method according to claim 1, it is characterised in that: the organic solvent is selected from 1,2- dichloroethanes,
Chloroform, ethyl acetate, dimethyl sulfoxide or acetonitrile.
3. synthetic method according to claim 1 or 2.It is characterized by: the organic solvent is 1,2- dichloroethanes.
4. synthetic method according to claim 1, it is characterised in that: the phase transfer catalyst is selected from
Benzyltriethylammoinium chloride, benzyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium chloride, tetrabutyl bromine
Change one or more of ammonium.
5. synthetic method according to claim 1 or 4, it is characterised in that: the phase transfer catalyst is tetrabutyl bromine
Change ammonium.
6. synthetic method according to claim 1, the catalysts are the triethylamine and chlorination that mass ratio is 1:1
Cuprous composite catalyst.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6248671A (en) * | 1985-08-26 | 1987-03-03 | Res Inst For Prod Dev | Production of alkenyl isocyanurate |
| CN102887868A (en) * | 2012-09-18 | 2013-01-23 | 杭州科利化工股份有限公司 | Preparation method of triallyl isocyanurate |
| CN103906753A (en) * | 2011-11-01 | 2014-07-02 | 韩国生产技术研究院 | Isocyanurate epoxy compound having alkoxysilyl group, method of preparing same, composition including same, cured product of the composition, and use of the composition |
| CN105425542A (en) * | 2014-09-12 | 2016-03-23 | 奇美实业股份有限公司 | Photosensitive resin composition for color filter and application thereof |
| CN106810505A (en) * | 2017-03-02 | 2017-06-09 | 江苏华星新材料科技股份有限公司 | The technique that a kind of isocyanuric acid prepares Triallyl isocyanurate |
-
2018
- 2018-07-13 CN CN201810768916.XA patent/CN108929283B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6248671A (en) * | 1985-08-26 | 1987-03-03 | Res Inst For Prod Dev | Production of alkenyl isocyanurate |
| CN103906753A (en) * | 2011-11-01 | 2014-07-02 | 韩国生产技术研究院 | Isocyanurate epoxy compound having alkoxysilyl group, method of preparing same, composition including same, cured product of the composition, and use of the composition |
| CN102887868A (en) * | 2012-09-18 | 2013-01-23 | 杭州科利化工股份有限公司 | Preparation method of triallyl isocyanurate |
| CN105425542A (en) * | 2014-09-12 | 2016-03-23 | 奇美实业股份有限公司 | Photosensitive resin composition for color filter and application thereof |
| CN106810505A (en) * | 2017-03-02 | 2017-06-09 | 江苏华星新材料科技股份有限公司 | The technique that a kind of isocyanuric acid prepares Triallyl isocyanurate |
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