CN101328153B - Preparation of tris(tri-bromophenoxy) triazine by nonsolvent method - Google Patents
Preparation of tris(tri-bromophenoxy) triazine by nonsolvent method Download PDFInfo
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- CN101328153B CN101328153B CN2008100623007A CN200810062300A CN101328153B CN 101328153 B CN101328153 B CN 101328153B CN 2008100623007 A CN2008100623007 A CN 2008100623007A CN 200810062300 A CN200810062300 A CN 200810062300A CN 101328153 B CN101328153 B CN 101328153B
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Abstract
The invention relates to a method for preparing three (tribromo- phenoxy) triazine by a nonsolvent method. The method solves the technical problems that an organic solvent is not used in the process of preparing the product and the pollution to the environment is reduced. The method comprises the following steps that: 1) at a temperature of below 5 DEG C, a catalyst and 30 to 70 percent of the weight of a reducing agent are dissolved in water, cyanuric chloride is added and scatters rapidly to form an even suspending liquid; and 2) a bromol sodium water solution is added drop by drop, the temperature is raised with the dropping process to the reflux temperature and is kept. Meanwhile, the remained reducing agent is added, the mixture is stirred and filtered so that the three (tribromo- phenoxy) triazine with a shape of filter cake is obtained; and the filter cake is added with a Na2CO3 aqueous with a concentration between 0.01 and 5 percent, and the product is obtained by ball milling, filtering, washing and drying.
Description
Technical field
The present invention relates to the preparation method of three (tribromophenoxy) triazine.
Background technology
Three (tribromophenoxy) triazine is a kind of additive flame retardant of excellent performance of brominated nitrogen, and purposes is very extensive, is mainly used in thermoplastics and the rubber, also can be used for thermosetting resin.Its molecular structure is as follows:
This structure has excellent thermostability and light stability, the consistency good with resin.The fire-retardant product that three (tribromophenoxy) triazine obtains is excellent in cushion effect, tint permanence good by adding, do not influence thermoplastics weather resisteant, have persistent antistatic property and processing characteristics good, this fire retardant has obtained being extensive use of in recent years.
Existing multinomial both at home and abroad synthetic patent and application patent about this fire retardant.See French Patent (FR1566675) in 1969 the earliest about the patent of three (tribromophenoxy) triazine, it is proved to be a kind of fire retardant of excellent property in this patent, and synthetic patent sees United States Patent (USP) (US3843650) and Japanese Patent (JP 47-25232) in 1974 the earliest, these two pieces of patents have adopted cyanuric chloride have been dissolved in a kind of ketone or the cyclic ether solvents, and the method that adds bromophenisic acid salt brine solution or ethanolic soln is again synthesized.In recent ten years, people adjust solvent kind and water and solvent ratios by updating catalyst technology, and modes such as reactant ratio are improved the synthesis technique of three (tribromophenoxy) triazine, and have applied for relevant patent.
Since the appearance of three (tribromophenoxy) triazine, although people update its synthesis technique, but under existing catalyst technology, for guaranteeing yield and product purity, all be unable to do without solvent, generally adopt phase-transfer catalyst at present, with methylene dichloride, chloroform, trichloroethane, tetracol phenixin, benzene, toluene, ethylbenzene, p-Xylol, tetrachloroethane, chlorobenzene, ketones etc. are as solvent, or and water formation mixed solvent.Wherein the synthetic patent of chlorinated solvents is maximum, as the several synthetic patent of Japanese DKS company (JP3034972, US 5498714, US 5965731 etc.) all use methylene dichloride as solvent in, methylene dichloride exists volatile, is difficult for decomposing, and is serious to the destruction of atmospheric ozone layer.And contain benzene solvent is one of strong carcinogen.
Make solvent with ketone such as acetone first among the patent US 5965731 of the Albemarle Corporation company of the U.S. in 1999.By contrast, though ketones solvent is slightly little to the influence of environment, still exists after all, moreover in security, also have hidden danger.
The present invention is reaction medium with water, adopts synthetic three (tribromophenoxy) triazine of composite catalyzing technology.
Three (tribromophenoxy) triazine of the present invention preparation can be used for PS (styrene resin), ABS resin, and PC (polycarbonate), ABS/PC alloy, PBT, PET, PETG, Resins, epoxy etc. fire-retardant also can be used for preparing the flame retardant solution of textiles.
Summary of the invention
The technical issues that need to address of the present invention are not with an organic solvent, to reduce the pollution to environment in the preparation process of product.
Three (tribromophenoxy) of the present invention triazine preparation method is characterized in that, may further comprise the steps;
1) below 5 ℃, the reductive agent that adds catalyzer, 30～70% weight dissolves in water, adds cyanuric chloride and disperses to form unit for uniform suspension fast;
2) drip the bromophenisic acid sodium water solution, progressively be warmed up to reflux temperature with the dropping process, remaining reductive agent is added in insulation simultaneously, stirs, and filters, and obtains three (tribromophenoxy) triazine, becomes filter cake shape;
Described cyanuric chloride: the mol ratio of bromophenisic acid sodium is 1: 2.90～3.20 (be preferably 1: 3.00～3.10); Described catalyzer is to be made up of phase-transfer catalyst and acid binding agent, and wherein the phase-transfer catalyst add-on is 0.01%～6.0% (being preferably 0.1%～6.0%) of bromophenisic acid sodium weight; The acid binding agent add-on is 0.01%～8.0% (being preferably 0.1%～8.0%) of bromophenisic acid sodium weight; It is 0.01%～5.0% (being preferably 0.01～3.0%) of bromophenisic acid sodium weight that reductive agent adds total amount;
Reactive material---bromophenisic acid sodium and the cyanuric chloride concentration in water is 12～50%;
Described reductive agent is selected from one or more in S-WAT, sodium bisulfite, the hydrazine hydrate;
Described phase-transfer catalyst comprises quaternary amine, quaternary amine alkali and season phosphine alkali, specifically be selected from tetramethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyl tributyl ammonium chloride, benzyl tributyl brometo de amonio, dimethyl diethyl brometo de amonio, the phenyl triethyl ammonium chloride, phenyl triethyl brometo de amonio, phenyl tripropyl ammonium chloride, phenyl tripropyl brometo de amonio, phenyl tributyl ammonium chloride, phenyl tributyl brometo de amonio, the phenyl trimethyl ammonium chloride, the phenyl trimethylammonium bromide, (R)-(3-carboxyl-2-hydroxypropyl) trimethylammonium hydroxide inner salt, N-methyl-N, N-two (octadecyl)-N-(3-sulfo group propyl group) ammonium hydroxide inner salt, (R)-(3-carboxyl-2-hydroxypropyl) trimethylammonium hydroxide hydrochloride, methyltributylammonichloride chloride, the methyl tributyl brometo de amonio, methyl tributyl ammonium hydroxide, the phenyl trimethyl ammonium chloride, the phenyl trimethylammonium bromide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, benzyltrimethylammonium hydroxide, tetramethyl-hydroxide phosphine, tetraethyl-hydroxide phosphine, tetrapropyl hydroxide phosphine, the tetrabutylammonium hydroxide phosphine, benzyl triphenyl hydroxide phosphine, methyl triphenyl hydroxide phosphine, in ethyl triphenyl hydroxide phosphine or the propyl group triphenyl hydroxide phosphine one or more;
Described acid binding agent is selected from one or more in triethylamine, trolamine, pyridine or the morpholine.
As preferably, reactive material---bromophenisic acid sodium and the cyanuric chloride concentration in water is 15～45%.
The present invention the 1st) in the step,, need prevent that hydrolysis from taking place guaranteeing that cyanuric chloride disperses simultaneously.
Cyanuric chloride is very slow at hydrolysis reaction below 5 ℃, and main side reaction is as follows:
The starting temperature of above-mentioned reaction 1 is below 5 ℃, and reaction 2 reduces temperature and can effectively suppress hydrolysis about 25 ℃.
The present invention the 2nd) in the step: under certain temperature range, cyanuric chloride and bromophenisic acid sodium in water, carry out replacement(metathesis)reaction under catalyzer, the reductive agent effect, prepare three (tribromophenoxy) triazine.
When the present invention directly reacted in water, the replacement(metathesis)reaction of the hydrolysis of cyanuric chloride and bromophenisic acid sodium and cyanuric chloride was competition mutually, and catalysis technique is crucial.The phase transfer of technology that conventional art adopts is ineffective owing to the organic solvent phase that does not have traditional sense in the present invention.The present invention has adopted the composite catalyzing technology, brings into play katalysis by the method that acid binding agent and phase-transfer catalyst combine.
General viewpoint thinks that phase-transfer catalyst plays a role, be that a reactant dissolves in water, another is in organic solvent, phase-transfer catalyst is as a bridge that transmits between solvent phase and water, reactant enters in the different media in help water or the solvent phase, and driving a reaction carries out like this.
Phase-transfer catalyst effect of the present invention is interpreted as, acid binding agent and cyanuric chloride particle surface-the Cl chelating, form organic phase on the cyanuric chloride surface, acid binding agent helps HCl to the water transmission simultaneously, acting in conjunction by phase-transfer catalyst and acid binding agent, reduce steric hindrance, improved reaction efficiency.
With step 2) filter cake shape three (tribromophenoxy) triazine that obtains, adding concentration is the Na of 0.01～5% (being preferably 0.1～3%)
2CO
3The aqueous solution, ball milling filters, washing, the dry product that gets; Na
2CO
3Solution: the weight ratio of filter cake be 0.5～20: 1 (be preferably 1～10: 1), 10～90 ℃ of ball milling temperature (being preferably 30～60 ℃), the ball milling time is 0.1～10 hour (0.5～5 hour).
Three (tribromophenoxy) triazine of the present invention's preparation can be used on the glass fibre enhancing or does not have glass-fiber-reinforced polyester in preparation, described polyester is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), a kind of in the amorphism polyethylene terephthalate (PETG); Polystyrene (PS), polycarbonate (PC), ABS, PC/ABS alloy; Polymeric amide, described is polyamide 6 (PA6), uses as fire retardant in polyamide 66 (PA66) and both mixing and/or the multipolymer, reaches different fire-retardant requirements according to different additions.
The present invention directly adopts water as reaction medium, makes to be reflected in the water to carry out.Its advantage is to have overcome original employing organic solvent or organic solvent and water mixed solution as various drawbacks that reaction medium brought; And equipment is simple, and technological operation is convenient.
Embodiment
Specific embodiments of the invention below are described, but the present invention is not limited to these embodiment.
Embodiment 1
In 500 liters of reactors, add 200 liters of entry, phase-transfer catalyst benzyl tributyl brometo de amonio 820 grams, acid binding agent pyridine 2450 grams, reductive agent S-WAT 410 gram stirs and is cooled to 3 ℃, adds 14.1 kilograms of the cyanuric chlorides of 98% purity, stir after 10 minutes fast, treat temperature-stable at 5 ℃, totally 204.3 kilograms of the bromophenisic acid sodium water solutions of the continuous dropping of beginning 40% concentration, and heat up gradually.
Temperature-rise period is as follows: be raised to 35 ℃ in 1.5 hours, and dripped 68.1 kilograms of bromophenisic acid sodium water solutions; Continue to heat up, be raised to 70 ℃ in about 2 hours, drip 68.1 kilograms of bromophenisic acid sodium water solutions; Continue to heat up and keep dropping, be raised to more than 95 ℃, and drip remaining bromophenisic acid sodium water solution, and add the remaining reductive agent 4100 grams 10% sulfite at concentration lower aqueous solution at 2 hours.Keep refluxing 2 hours, be cooled to 60 ℃, filter, obtain three (tribromophenoxy) triazine filter cake.
The Na that filter cake is added 300 kilogram of 1% concentration under 50 ℃
2CO
3Ball milling 1.5 hours filters, and washes 2 times, and drying obtains white products, yield 97% (in cyanuric chloride).
The product melting range: 225～227 ℃, bromine content is 67.1%, free bromine≤5ppm.
Embodiment 2
In 500 liters of reactors, add 200 liters of entry, benzyl tributyl brometo de amonio 794 grams, S-WAT 397 grams, pyridine 2382 gram stirs and is cooled to 3 ℃, adds 14.1 kilograms of the cyanuric chlorides of 98% concentration, stir after 10 minutes fast, treat temperature-stable at 5 ℃, totally 198.4 kilograms of the bromophenisic acid sodium water solutions of the continuous dropping of beginning 40% concentration, and heat up gradually.
Temperature-rise period is as follows: be raised to 35 ℃ in 1.5 hours, and dripped 66.1 kilograms of bromophenisic acid sodium water solutions; Continue to heat up, be raised to 70 ℃ in about 2 hours, drip 66.1 kilograms of bromophenisic acid sodium water solutions; Continue to heat up and keep dropping, be raised to more than 95 ℃ at 2 hours, and drip remaining bromophenisic acid sodium water solution, and add 3970 grams, the 10% sulfite at concentration lower aqueous solution.
Keep refluxing 2 hours, be cooled to 60 ℃, filter, add the Na of 300 kilogram of 1% concentration
2CO
3Ball milling 1.5 hours filters, and washes 2 times, and drying obtains white products, yield 95% (in cyanuric chloride).
The product melting range: 221～226 ℃, bromine content is 66.2%, free bromine≤5ppm.
Embodiment 3
In 500 liters of reactors, add 200 liters of entry, methyl tributyl brometo de amonio 574 grams, S-WAT 287 grams, pyridine 1715 gram stirs and is cooled to 3 ℃, adds 9.9 kilograms of the cyanuric chlorides of 98% concentration, stir after 10 minutes fast, treat temperature-stable at 5 ℃, totally 143 kilograms of the bromophenisic acid sodium water solutions of the continuous dropping of beginning 40% concentration, and heat up gradually.
Temperature-rise period is as follows: be raised to 35 ℃ in 1.5 hours, and dripped 46.7 kilograms of bromophenisic acid sodium water solutions; Continue to heat up, be raised to 70 ℃ in about 2 hours, drip 46.7 kilograms of bromophenisic acid sodium water solutions; Continue to heat up and keep dropping, be raised to more than 95 ℃ at 2 hours, and drip remaining bromophenisic acid sodium water solution, and add 2870 grams, the 10% sulfite at concentration lower aqueous solution.
Keep refluxing 2 hours, be cooled to 60 ℃, filter, add 300 kilograms of 1%Na
2CO
3Ball milling 1.5 hours filters, and washes 2 times, and drying obtains white products, yield 97.3% (in cyanuric chloride).
The product melting range: 226～228 ℃, bromine content is 66.7%, free bromine≤5ppm.
Embodiment 4
Substantially the same manner as Example 1, benzyl tributyl brometo de amonio 1640 grams.
Yield 97% (in cyanuric chloride).The product melting range: 225～227 ℃, bromine content is 67.0%, free bromine≤5ppm.
Embodiment 5
Substantially the same manner as Example 1, add pyridine 4085 grams.
Yield 97.4% (in cyanuric chloride).The product melting range: 226～227 ℃, bromine content is 67.4%, free bromine≤5ppm.
Embodiment 6
Substantially the same manner as Example 1, add trolamine 2450 grams.
Yield 95.8% (in cyanuric chloride).The product melting range: 223～227 ℃, bromine content is 66.5%, free bromine≤5ppm.
Embodiment 7
Substantially the same manner as Example 1, add tetrabutylammonium hydroxide phosphine 820 grams.
Yield 94.9% (in cyanuric chloride).The product melting range: 222～228 ℃, bromine content is 65.9%, free bromine≤5ppm.
Embodiment 8
Substantially the same manner as Example 1, be not incubated.
Yield 95.9% (in cyanuric chloride).The product melting range: 223～227 ℃, bromine content is 65.7%, free bromine≤5ppm.
Embodiment 9
Substantially the same manner as Example 1, do not adopt 1%Na
2CO
3Ball milling 1.5 hours, direct filtration.
Yield 97.2% (in cyanuric chloride).The product melting range: 225～227 ℃, bromine content is 67.1%, free bromine 19ppm.
Application Example
On twin screw following prescription is carried out extruding pelletization processing, three (tribromophenoxy) triazine that adopts embodiment 1 to obtain obtains the flame retardant plastics mixture according to following surface compositions.In the above-mentioned prescription, add oxidation inhibitor 0.2% 1010,0.1% PEQ in addition; Lubricant EBS 0.2%; UV stablizer 0.1%.
| Numbering | Polymkeric substance | Glass fibre | Three (tribromophenoxy) triazine | Antimonous oxide | Flame retardant resistance |
| X-1 | PBT | 30％ | 15 | 5 | UL94-V0(0.8mm) |
| X-2 | PBT | 30％ | 12 | 4 | UL94-V0(1.6mm) |
| X-3 | PBT | 0 | 16 | 5 | UL94-V0(0.8mm) |
| X-4 | PET | 0 | 18 | 6 | UL94-V0(0.8mm) |
| X-5 | PETG | 0 | 18 | 6 | UL94-V0(1.6mm) |
| X-6 | PC | 0 | 5 | 0 | UL94-V0(0.8mm) |
| X-7 | HIPS | 0 | 15 | 6 | UL94-V0(0.8mm) |
| X-8 | PC∶ABS＝70∶30 | 0 | 12 | 4 | UL94-V0(0.8mm) |
| X-9 | ABS | 0 | 15 | 6 | UL94-V0(1.6mm) |
| X-10 | PA6 | 0 | 9 | 3 | UL94-V0(1.6mm) |
| X-11 | PA66 | 0 | 8 | 3 | UL94-V0(0.8mm) |
Claims (6)
1. (tribromophenoxy) triazine preparation method is characterized in that, may further comprise the steps;
1) below 5 ℃, the reductive agent that adds catalyzer, 30～70% weight dissolves in water, adds cyanuric chloride and disperses to form unit for uniform suspension fast;
2) drip the bromophenisic acid sodium water solution, progressively be warmed up to reflux temperature with the dropping process, remaining reductive agent is added in insulation simultaneously, stirs, and filters, and obtains three (tribromophenoxy) triazine, becomes filter cake shape;
Described cyanuric chloride: the mol ratio of bromophenisic acid sodium is 1: 2.90～3.20; Described catalyzer is to be made up of phase-transfer catalyst and acid binding agent, and wherein the phase-transfer catalyst add-on is 0.01%～6.0% of a bromophenisic acid sodium weight; The acid binding agent add-on is 0.01%～8.0% of a bromophenisic acid sodium weight; It is 0.01%～5.0% of bromophenisic acid sodium weight that reductive agent adds total amount;
Bromophenisic acid sodium and the cyanuric chloride concentration in water is 12～50%;
Described reductive agent is selected from one or more in S-WAT, sodium bisulfite, the hydrazine hydrate;
Described phase-transfer catalyst is selected from tetramethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyl tributyl ammonium chloride, benzyl tributyl brometo de amonio, dimethyl diethyl brometo de amonio, the phenyl triethyl ammonium chloride, phenyl triethyl brometo de amonio, phenyl tripropyl ammonium chloride, phenyl tripropyl brometo de amonio, phenyl tributyl ammonium chloride, phenyl tributyl brometo de amonio, the phenyl trimethyl ammonium chloride, the phenyl trimethylammonium bromide, (R)-(3-carboxyl-2-hydroxypropyl) trimethylammonium hydroxide inner salt, N-methyl-N, N-two (octadecyl)-N-(3-sulfo group propyl group) ammonium hydroxide inner salt, (R)-(3-carboxyl-2-hydroxypropyl) trimethylammonium hydroxide hydrochloride, methyltributylammonichloride chloride, the methyl tributyl brometo de amonio, methyl tributyl ammonium hydroxide, the phenyl trimethyl ammonium chloride, the phenyl trimethylammonium bromide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, benzyltrimethylammonium hydroxide, tetramethyl-hydroxide phosphine, tetraethyl-hydroxide phosphine, tetrapropyl hydroxide phosphine, the tetrabutylammonium hydroxide phosphine, benzyl triphenyl hydroxide phosphine, methyl triphenyl hydroxide phosphine, in ethyl triphenyl hydroxide phosphine or the propyl group triphenyl hydroxide phosphine one or more;
Described acid binding agent is selected from one or more in triethylamine, trolamine, pyridine or the morpholine.
2. three (tribromophenoxy) according to claim 1 triazine preparation method is characterized in that it is 0.01～3.0% of bromophenisic acid sodium weight that described reductive agent adds total amount; The phase-transfer catalyst add-on is 0.1%～6.0% of a bromophenisic acid sodium weight, and the acid binding agent add-on is 0.1%～8.0% of a bromophenisic acid sodium weight.
3. three (tribromophenoxy) according to claim 1 and 2 triazine preparation method is characterized in that described bromophenisic acid sodium: the mol ratio of cyanuric chloride=3.00～3.10: 1, and bromophenisic acid sodium and the cyanuric chloride concentration in water is 15～45%.
4. three (tribromophenoxy) according to claim 1 and 2 triazine preparation method is characterized in that step 2) in the heating-up time be 0.1～15 hour, soaking time is 0.05～8 hour.
5. three (tribromophenoxy) according to claim 3 triazine preparation method is characterized in that step 2) in the heating-up time be 0.1～15 hour, soaking time is 0.05～8 hour.
6. three (tribromophenoxy) according to claim 1 and 2 triazine preparation method is characterized in that step 2) filter cake shape three (tribromophenoxy) triazine that obtains, add concentration and be 0.01～5% Na
2CO
3The aqueous solution, ball milling filters, washing, the dry product that gets; Na
2CO
3Solution: the weight ratio of filter cake is 0.5～20: 1,10～90 ℃ of ball milling temperature, and the ball milling time is 0.1～10 hour.
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| CN106916338A (en) * | 2017-04-25 | 2017-07-04 | 合肥工业大学 | A kind of environmentally friendly low cigarette expansion type flame retardant and preparation method thereof |
| CN108912065B (en) * | 2018-08-29 | 2022-03-11 | 潍坊玉成化工有限公司 | Preparation method of tri (pentabromophenoxy) isocyanurate |
| CN114940690A (en) * | 2022-07-07 | 2022-08-26 | 昆明理工大学 | Tetrapropyl phosphonium hydroxide and preparation method and application thereof |
| CN116478420B (en) * | 2023-05-04 | 2023-11-28 | 西南林业大学 | Covalent triazine framework material and preparation method and application thereof |
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