CN109776438A - A kind of heat-staple TBC method for synthesizing flame retardant - Google Patents
A kind of heat-staple TBC method for synthesizing flame retardant Download PDFInfo
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Abstract
The present invention relates to a kind of heat-staple TBC method for synthesizing flame retardant, solve perishable, discoloration, reduction electrical property etc. when there is more brominated impurity, processing of prior art synthesis TBC fire retardant, thermal stability is poor, product post-processing approach is complicated, technical problem inconvenient for use.The present invention provides a kind of heat-staple TBC method for synthesizing flame retardant, comprises the following steps that and 1) triallyl isocyanurate and organic solvent are added in reaction kettle, the organic solvent reaction system of TAIC is made;Organic solvent and quaternary ammonium salt are added in reactor, bromine Br is added dropwise2, bromating agent is made;2) bromating agent prepared in step 1) is added dropwise in the organic solvent reaction system of TAIC, heat preservation to fully reacting;3) liquid separation of washing standing goes out organic layer;4) crystal seed is added in solvent separating still, under 60~65 DEG C of vacuum conditions, filters, it is dry, obtain TBC flame retardant products.The present invention is widely used in fire-retardant FRW technical field.
Description
Technical field
The invention belongs to fire-retardant FRW technical fields, and in particular to a kind of heat-staple TBC method for synthesizing flame retardant.
Background technique
TBC fire retardant scientific name is three (2,3- dibromopropyl) fulminuric acid esters, English name Tri (2,3-
Dibromopropyl) isocyanurate (abbreviation TBC) is a kind of addition type bromide fire retardant with triazine ring, is a kind of new
Type, efficient, addition type bromide fire retardant has excellent anti-flammability, very low volatility and good compatibility, and
The characteristics such as durable, fast light, water-fast and nontoxic.It can be widely used for polyolefin, PVC, foamed polyurethane, polyphenyl alkene, ABS, unsaturation
Fire retardant in the products such as polyester, various synthetic rubber and synthetic fibers.
Three (2,3- dibromopropyl) fulminuric acid rouge (TBC) are usually by triallyl isocyanuric acid rouge (TAIC) and bromine
Plain Br2Electrophilic addition reaction is prepared.At present in industrialization product, contain a small amount of unstable bromide and free bromine etc.
The decomposition temperature of impurity, these impurity is lower, is easy to release the sour gas such as hydrogen bromide, to cause mold rotten when processing
Erosion, reduces many adverse consequences such as electrical property at product discoloration;The TBC product that addition reaction simultaneously generates is highly viscous shape, to be made
For product sale, the separation method of post-processing is complicated, environment easy to pollute, inferior separating effect and inconvenient for use.How to avoid brominated
The generation of impurity, improving the thermal stability of product and developing the post-processing approach that a kind of technique is simple and direct, environmental-friendly is mesh
Preceding urgent problem.
Summary of the invention
The object of the invention is to simple, the yields that in order to overcome the above-mentioned deficiencies of the prior art, provides a kind of response path
Xiang Gao, impurity content is few, product post-processing approach is simple and easy, and properties of product significantly improve, thermal stability is high, product uses
The heat-staple TBC method for synthesizing flame retardant of convenient environmental protection.
The technical proposal for solving the technical problem of the invention is:
A kind of heat-staple TBC method for synthesizing flame retardant, comprises the following steps that
1) triallyl isocyanurate (TAIC) and organic solvent I are added in reaction kettle according to the ratio, stirring to whole
Dissolution, is made the organic solvent reaction system of TAIC;
Organic solvent II and quaternary ammonium salt are added in reactor according to the ratio, bromine Br2 is added dropwise, it is dissolved all, is made
Bromating agent;
2) bromating agent prepared in step 1) is added dropwise in the organic solvent reaction system of TAIC, it is anti-is warming up to bromination
Answer temperature, heat preservation a period of time, until fully reacting;
3) solution after the reaction of first wash step 2), after removing water layer, the organic layer into the reaction solution in step 2)
Middle addition solution of sodium bisulfite, until the reddish brown decoloration of reaction system;Appropriate alkaline liquor is added, adjusts organic layer pH value into
Property, then second wash is carried out, it stands liquid separation and goes out organic layer;
4) suitable quantity of water is added in solvent separating still, is warming up to water temperature in the solvent separating still and is maintained at 60~65
DEG C, suitable high-purity finished product TBC finished product is added as crystal seed, under vacuum conditions, organic layer is slowly added dropwise while stirring, drips
After the completion of adding, it is stirred for a period of time, product is precipitated in the form of a powder, product is filtered out after precipitation, through being dried to obtain heat
Stable TBC flame retardant products.
Preferably, in step 1), organic solvent I is methylene chloride, dichloroethanes, chloroform, carbon tetrachloride are wherein appointed
What is a kind of, and additional amount is 2~5 times that triallyl isocyanurate weight is added;Organic solvent II is phase with organic solvent I
Same organic solvent, the additional amount of organic solvent II are 2 times of I additional amount of organic solvent.
Preferably, in step 1), quaternary ammonium salt is tetraethylammonium bromide, tetrabutylammonium bromide, cetyl trimethyl bromination
Ammonium, benzyltriethylammoinium chloride are one of or several;Quaternary ammonium salt and the dropwise addition bromine Br2Mass ratio is 1~2:1.
Preferably, in step 2), in bromating agent in the organic solvent reaction system of bromine Br2 and TAIC TAIC molar ratio
For 3~3.3:1.
Preferably, in step 4), content >=98.5% of high-purity finished product TBC finished product, additional amount is to add in step 4)
Enter the 1%~3% of water;TAIC content >=99.0% in step 1).
It preferably, further include that heat stabilizer is added into heat-staple TBC flame retardant products made from step 4) in step 5),
After mixing, the TBC flame retardant products of high thermal stability are obtained.
Preferably, in step 5), heat stabilizer is organic tin stabilizer, and organic tin stabilizer is two fourth of tin dilaurate
One or more of Ji Xi, the positive Xin Jixi of tin dilaurate two, dibutyitin maleate, maleic acid dioctyltin;It is added
Amount is the 0.3~1% of the TBC flame retardant products weight being added in step 5).
Preferably, in step 3), the quality of solution of sodium bisulfite is added in the organic layer into the reaction solution in step 2)
Percent concentration is 20%.
Preferably, in step 3), after the reaction of first wash step 2) after solution, water layer, i.e. recycling step 2 are recycled) it is anti-
Quaternary ammonium salt after answering in solution, prepares raw material as bromating agent and applies
Preferably, in step 2), bromination reaction temperature is 40~80 DEG C.
Beneficial effects of the present invention:
(1) synthetic method of a kind of high thermal stability TBC fire retardant of the invention, response path is simple, good product quality,
And yield is mutually high, impurity content is few, product post-processing approach is simple and easy, and properties of product significantly improve, thermal stability is high, easily
In storage the advantages of, product environmental protection and energy saving easy to use, be suitble to industrialized production.
(2) synthetic method of a kind of high thermal stability TBC fire retardant of the invention, the mild bromating agent of the self-control used,
Significantly improve the thermal stability of product and the comprehensive utilization ratio height to bromine;By the use of heat stabilizer, production is substantially increased
The thermal stability of product is suitble to industrialized production.
(3) synthetic method of a kind of high thermal stability TBC fire retardant of the invention, preparation method have to environmental hazard
Small, product yield is high, good product quality.
Specific embodiment
The present invention is further explained in the light of specific embodiments, to help the contents of the present invention are understood.The present invention
Used in method unless otherwise required, be conventional production method;Used raw material is unless otherwise required
Conventional commercial product.
Embodiment one
A kind of method for synthesizing high thermal stability TBC fire retardant, comprising the following steps:
1) by I methylene chloride of triallyl isocyanurate (TAIC) and 100g organic solvent of 50g content >=99.0%
It is added in 1000ml reaction kettle according to the ratio, stirs to whole dissolutions, the organic solvent reaction system of TAIC is made;
II methylene chloride of 200g organic solvent and 139g tetraethylammonium bromide are added according to the ratio in 500ml reactor, dripped
Add 106g bromine Br2, dissolve it all, bromating agent be made.
2) bromating agent prepared in step 1) is added dropwise in the organic solvent reaction system of TAIC, bromine in bromating agent
Br2Molar ratio with TAIC in the organic solvent reaction system of TAIC is 3.3:1, and being warming up to bromination reaction temperature is 40 DEG C, is protected
Temperature 20 hours, until fully reacting.
3) solution after first wash step 2) is reacted is carried out, after removing water layer, to the organic of the reaction solution in step 2)
The solution of sodium bisulfite that mass percent concentration is 20% is added in layer, until the reddish brown decoloration of reaction system;It is added appropriate
Lye, adjusting organic layer pH value to neutrality, then second wash is carried out, 200ml water is added in reaction system, liquid separation is stood and goes out
Organic layer;After the reaction of first wash step 2) after solution, water layer, washing recycling tetraethylammonium bromide, i.e. recycling step are recycled
2) quaternary ammonium salt after reacting in solution, prepares raw material as bromating agent and applies, and the rate of recovery is 90%~98%.
4) 1000ml water is added in the solvent separating still of 2000ml, is warming up to water temperature in solvent separating still and is maintained at 60
DEG C, the high-purity finished product TBC finished product of suitable 10g content >=98.5% is added as crystal seed;Under vacuum conditions, vacuum degree control
System -0.9Mpa, is slowly added dropwise organic layer while stirring, after being added dropwise to complete, is stirred for 5 hours, analyses product in the form of a powder
Out, product is filtered out after precipitation, through drying, obtains heat-staple TBC flame retardant products 144.8g, utilize halogenated alkane dichloromethane
Alkane azeotrope with water but immiscible principle are aided with negative pressure, realize the product Crystallization Separation under lower temperature, yield 98.9%, bromine
Content 65.6%, 107~110 DEG C of fusing point.
5) 0.3% tin dilaurate of heat stabilizer, two fourth is added into heat-staple TBC flame retardant products made from step 4)
Ji Xi obtains the TBC flame retardant products of high thermal stability after mixing.Thermal stability test is carried out, 5%WLT is up to 280
℃。
Embodiment 2
A kind of fire-retardant agent method of high thermal stability TBC is synthesized, is comprised the following steps that
1) by I carbon tetrachloride of triallyl isocyanurate (TAIC) and 250g organic solvent of 50g content >=99.0%
It is added in 1000ml reaction kettle according to the ratio, stirs to whole dissolutions, the organic solvent reaction system of TAIC is made;
It is anti-that 500ml is added in II carbon tetrachloride of 200g organic solvent and quaternary ammonium salt 192g benzyltriethylammoinium chloride according to the ratio
It answers in device, 96g bromine Br is added dropwise2, dissolve it all, bromating agent be made.
2) bromating agent prepared in step 1) is added dropwise in the organic solvent reaction system of TAIC, it is anti-is warming up to bromination
Answering temperature is 80 DEG C, 20 hours a period of times of heat preservation, until fully reacting;The organic solvent of bromine Br2 and TAIC are anti-in bromating agent
The molar ratio for answering TAIC in system is 3:1.
3) solution after first wash step 2) is reacted, after removing water layer, having into the reaction solution in step 2) are carried out
The solution of sodium bisulfite that mass percent concentration is 20% is added in machine layer, until the reddish brown decoloration of reaction system;It is added suitable
Lye, adjusting organic layer pH value to neutrality are measured, then carries out second wash, 200ml water is added in reaction system, stands liquid separation
Organic layer out;After the reaction of first wash step 2) after solution, water layer is recycled, washing recycling benzyltriethylammoinium chloride returns
The quaternary ammonium salt benzyltriethylammoinium chloride after step 2) is reacted in solution is received, raw material is prepared as bromating agent and applies, the rate of recovery is
90%~98%.
4) 1000ml water is added in the solvent separating still of 2000ml, is warming up to water temperature in the solvent separating still and keeps
At 65 DEG C, the high-purity finished product TBC finished product of suitable 30g content >=98.5% is added as crystal seed;Under vacuum conditions, vacuum
Control -0.9Mpa is spent, organic layer is slowly added dropwise while stirring, after being added dropwise to complete, is stirred for 5 hours, makes product with the shape of powder
Formula is precipitated, and product is filtered out after precipitation, through drying, heat-staple TBC flame retardant products 144.8g is obtained, utilizes halogenated alkane four
Chlorination carbon azeotrope with water but immiscible principle are aided with negative pressure, realize the product Crystallization Separation under lower temperature, yield
99.2%, bromine content 65.3%, 107~110 DEG C of fusing point.
5) 1% maleic acid di-n-octyl of heat stabilizer is added into heat-staple TBC flame retardant products made from step 4)
Tin obtains the TBC flame retardant products of high thermal stability after mixing.Thermal stability test is carried out, 5%WLT is up to 280 DEG C.
Embodiment 3
A kind of fire-retardant agent method of heat-staple TBC is synthesized, is comprised the following steps that
1) by I dichloroethanes of triallyl isocyanurate (TAIC) and 120g organic solvent of 50g content >=99.0%
It is added in 1000ml reaction kettle according to the ratio, stirs to whole dissolutions, the organic solvent reaction system of TAIC is made;
500ml reactor is added in II dichloroethanes of 200g organic solvent and quaternary ammonium salt 151g tetrabutylammonium bromide according to the ratio
In, 101g bromine Br is added dropwise2, dissolve it all, bromating agent be made;
2) bromating agent prepared in step 1) is added dropwise in the organic solvent reaction system of TAIC, it is anti-is warming up to bromination
Answering temperature is 50 DEG C, 20 hours is kept the temperature, until fully reacting;Bromine Br in bromating agent2In the organic solvent reaction system of TAIC
The molar ratio of TAIC is 3.2:1.
3) solution after first wash step 2) is reacted, after removing water layer, having into the reaction solution in step 2) are carried out
The solution of sodium bisulfite that mass percent concentration is 20% is added in machine layer, until the reddish brown decoloration of reaction system;It is added suitable
Lye, adjusting organic layer pH value to neutrality are measured, then carries out second wash, 200ml water is added in reaction system, stands liquid separation
Organic layer out;After the reaction of first wash step 2) after solution, water layer, washing recycling tetrabutylammonium bromide, i.e. recycling step are recycled
It is rapid 2) react after quaternary ammonium salt tetrabutylammonium bromide in solution, prepare raw material as bromating agent and apply, the rate of recovery is 90%~
98%.
4) 1000ml water is added in the solvent separating still of 2000ml, is warming up to water temperature in solvent separating still and is maintained at 62
DEG C, the high-purity finished product TBC finished product of suitable 20g content >=98.5% is added as crystal seed;Under vacuum conditions, vacuum degree control
System -0.9Mpa, is slowly added dropwise organic layer while stirring, after being added dropwise to complete, is stirred for 5 hours, analyses product in the form of a powder
Out, product is filtered out after precipitation, through drying, obtains heat-staple TBC flame retardant products 144.8g, utilizes two chloroethene of halogenated alkane
Alkane azeotrope with water but immiscible principle are aided with negative pressure, realize the product Crystallization Separation under lower temperature, yield 99.3%, bromine
Content 65.4%, 107~110 DEG C of fusing point.
5) 0.5% maleic acid dibutyl of heat stabilizer is added into heat-staple TBC flame retardant products made from step 4)
Tin obtains the TBC flame retardant products of high thermal stability after mixing.Thermal stability test is carried out, 5%WLT is up to 280 DEG C.
Embodiment 4
A kind of fire-retardant agent method of heat-staple TBC is synthesized, is comprised the following steps that
1) by I chloroform of triallyl isocyanurate (TAIC) and 200g organic solvent of 50g content >=99.0%
It is added in 1000ml reaction kettle according to the ratio, stirs to whole dissolutions, the organic solvent reaction system of TAIC is made;
II chloroform of 200g organic solvent and quaternary ammonium salt 159g cetyl trimethylammonium bromide are added according to the ratio
In 500ml reactor, 106g bromine Br is added dropwise2, dissolve it all, bromating agent be made;
2) bromating agent prepared in step 1) is added dropwise in the organic solvent reaction system of TAIC, it is anti-is warming up to bromination
Answering temperature is 60 DEG C, 20 hours is kept the temperature, until fully reacting;Bromine Br in bromating agent2In the organic solvent reaction system of TAIC
The molar ratio of TAIC is 3.3:1.
3) solution after first wash step 2) is reacted, after removing water layer, having into the reaction solution in step 2) are carried out
The solution of sodium bisulfite that mass percent concentration is 20% is added in machine layer, until the reddish brown decoloration of reaction system;It is added suitable
Lye, adjusting organic layer pH value to neutrality are measured, then carries out second wash, 200ml water is added in reaction system, stands liquid separation
Organic layer out;After the reaction of first wash step 2) after solution, water layer is recycled, cetyl trimethylammonium bromide is recycled in washing,
That is recycling step 2) quaternary ammonium salt cetyl trimethylammonium bromide after reaction in solution, raw material, which is prepared, as bromating agent applies,
The rate of recovery is 90%~98%.
4) 1000ml water is added in the solvent separating still of 2000ml, is warming up to water temperature in solvent separating still and is maintained at 65
DEG C, the high-purity finished product TBC finished product of suitable 25g content >=98.5% is added as crystal seed;Under vacuum conditions, vacuum degree control
System -0.9Mpa, is slowly added dropwise organic layer while stirring, after being added dropwise to complete, is stirred for 5 hours, analyses product in the form of a powder
Out, product is filtered out after precipitation, through drying, obtains heat-staple TBC flame retardant products 144.8g, utilizes three chloromethane of halogenated alkane
Alkane azeotrope with water but immiscible principle are aided with negative pressure, realize the product Crystallization Separation under lower temperature, yield 99.1%, bromine
Content 65.8%, 107~110 DEG C of fusing point.
5) 0.8% tin dilaurate two of heat stabilizer is being added just into heat-staple TBC flame retardant products made from step 4)
Xin Jixi obtains the TBC flame retardant products of high thermal stability after mixing.Thermal stability test is carried out, 5%WLT reaches
280℃。
Embodiment 5
A kind of fire-retardant agent method of heat-staple TBC is synthesized, is comprised the following steps that
1) by I methylene chloride of triallyl isocyanurate (TAIC) and 150g organic solvent of 50g content >=99.0%
It is added in 1000ml reaction kettle according to the ratio, stirs to whole dissolutions, the organic solvent reaction system of TAIC is made;
500ml reactor is added in II methylene chloride of 200g organic solvent and quaternary ammonium salt 139g tetraethylammonium bromide according to the ratio
In, 106g bromine Br is added dropwise2, dissolve it all, bromating agent be made;
2) bromating agent prepared in step 1) is added dropwise in the organic solvent reaction system of TAIC, it is anti-is warming up to bromination
Answering temperature is 60 DEG C, 20 hours is kept the temperature, until fully reacting;Bromine Br in bromating agent2In the organic solvent reaction system of TAIC
The molar ratio of TAIC is 3.3:1.
3) solution after first wash step 2) is reacted, after removing water layer, having into the reaction solution in step 2) are carried out
The solution of sodium bisulfite that mass percent concentration is 20% is added in machine layer, until the reddish brown decoloration of reaction system;It is added suitable
Lye, adjusting organic layer pH value to neutrality are measured, then carries out second wash, 200ml water is added in reaction system, stands liquid separation
Organic layer out;After the reaction of first wash step 2) after solution, water layer, washing recycling tetraethylammonium bromide, i.e. recycling step are recycled
Quaternary ammonium salt after rapid 2) reaction in solution, prepares raw material as bromating agent and applies, and the rate of recovery is 90%~98%.
4) 1000ml water is added in the solvent separating still of 2000ml, is warming up to water temperature in solvent separating still and is maintained at 62
DEG C, the high-purity finished product TBC finished product of suitable 20g content >=98.5% is added as crystal seed;Under vacuum conditions, vacuum degree control
System -0.9Mpa, is slowly added dropwise organic layer while stirring, after being added dropwise to complete, is stirred for 5 hours, analyses product in the form of a powder
Out, product is filtered out after precipitation, through drying, obtains heat-staple TBC flame retardant products 144.8g, utilize halogenated alkane dichloromethane
Alkane azeotrope with water but immiscible principle are aided with negative pressure, realize the product Crystallization Separation under lower temperature, yield 99.5%, bromine
Content 65.6%, 107~110 DEG C of fusing point.
5) 0.5% maleic acid dibutyl of heat stabilizer is added into heat-staple TBC flame retardant products made from step 4)
Tin obtains the TBC flame retardant products of high thermal stability after mixing.Thermal stability test is carried out, 5%WLT is up to 280 DEG C.
The experimental data of above embodiments 1- embodiment 5 is further analysed below and is summarized as follows:
Heat-staple TBC method for synthesizing flame retardant provided by the invention, the process employs the conjunctions before being totally different from
At method, the self-control bromating agent that the present invention uses improves the thermal stability of product, high to the comprehensive utilization ratio of bromine;Its preparation side
Method has small to environmental hazard, and product yield is high, and good product quality substantially increases product by the use of heat stabilizer
Thermal stability is suitble to industrialized production.
Good homogeneous reaction system is to realize complete bromination, the primary condition of rapid bromination, and TAIC is relatively soluble in halogenated
In alkanes organic solvent, in a kind of heat-staple TBC method for synthesizing flame retardant of the invention, subsequent handling can also be by washing
And etc., so choosing a kind of and immiscible organic solvent of water is extremely beneficial for subsequent product treatment.As excellent
Choosing, in implementation of the invention, reaction dissolvent be one of methylene chloride, dichloroethanes, chloroform, carbon tetrachloride,
Dosage is 2~5 times of triallyl isocyanurate weight.
The function base of TAIC is three allyls.Room temperature, without catalyst agent under conditions of, double bond and bromine on allyl
Plain Br2It can produce electrophilic addition reaction, but due to bromine Br2For stronger bromide reagent, as bromine Br2The more situation of amount
Under, it will lead to product colour jaundice, acid value increase, thermal stability variation, as bromine Br2It measures in insufficient situation, product will be made
Yield decline, and crystallize difficult.In the synthetic method of the TBC flame retardant products of high thermal stability of the invention, according to should need
It asks and prepares a kind of special mild brominated systems, not only can guarantee the abundant reaction of raw material, but also the generation of by-product can be inhibited,
Guarantee that product has excellent thermal stability.Quaternary ammonium salt can be combined into mild bromide reagent with bromine, bromine is transferred to double
After key realizes addition reaction, quaternary ammonium salt is formed again, itself is not involved in the progress of main reaction, as just the medium transfer of bromine,
Extremely beneficial effect is achieved in the present invention, remarkably promotes the thermal stability and yield for improving product, and is crystallized simple easy
Row.Preferably, quaternary ammonium salt is tetraethylammonium bromide, tetrabutylammonium bromide, cetyl trimethylammonium bromide, benzyl triethyl ammonium chlorine
Change one or more of ammonium.
On the one hand, the present invention chemically set out by dynamic (dynamical) angle, the instrumentality of quaternary ammonium salt is comprehensively considered, to avoid
In reaction process, bromine Br2In conjunction with directly carrying out bromination with double bond, to quaternary ammonium salt and bromine Br2Ratio choosing is optimized
It selects.Preferably, quaternary ammonium salt and bromine Br2 mass ratio are 1~2:1.
On the other hand, mild brominated systems avoid bromine Br2The jaundice of product color caused by excess, brominated impurity
The problem of.It is known, it is suitable for the abundant reaction that excessive bromating agent can guarantee TAIC raw material.Preferably, bromating agent and TAIC
Molar ratio is 3~3.3:1.
There are also one side, in the prior art with bromine Br2When preparing TBC product for raw material, because of bromine Br2Activity it is higher,
Usually all it is aided with refrigeration facility, control system reaction temperature is between -5 DEG C~10 DEG C.And the present invention is in the specific implementation process
Bromination reaction is carried out with more mild bromide reagent, chemically thermodynamics are analyzed, and appropriate heating helps speed up instead
Answer process.Preferably, bromination reaction temperature is 40~80 DEG C, keeps reaction condition mild, and easy reaction saves cost.
The synthetic method of the TBC flame retardant products of high thermal stability of the invention, quaternary ammonium salt as it is a kind of costly
Medium auxiliary agent uses, and any variation does not occur for rear its before the reaction, and reasonable way of recycling determines the feasibility of the technique.It can
Know, quaternary ammonium salt has biggish solubility in water, is almost insoluble state in halogenated alkane.It is preferred, therefore, that season
Ammonium salt carries out recovery by the way of washing, and the rate of recovery is 90%~98%, and environmental protection and energy saving save significantly on cost, are suitble to
The production of modern industry meets the energy-saving and environment friendly theory of today's society pursuit, is conducive to sustainable development.
The fusing point of TBC product is 105 DEG C or so, and product has high dissolubility in halogenated alkanes solvents, with
The raising of temperature, even if product can also become highly viscous state, the separation of solvent and the crystallization of product in the presence of a small amount of solvent
It is one of the difficult point of the Product industrialization.General method is that the Crystallization Separation of product is realized by the way of inverse solvent, still
The introducing of new organic solvent all causes extreme difficulties for the reasonable separation of solvent and natural environment, while in mixed solvent
In, product cannot completely crystallize precipitation, also leverage the yield of product.The TBC of high thermal stability of the invention is fire-retardant
In the synthetic method of agent product, halogenated alkane azeotrope with water but immiscible principle are made full use of, is aided with negative pressure, is realized compared with low temperature
Product Crystallization Separation under degree.Preferably, water temperature is maintained at 60~65 DEG C in solvent separating still, and environmental protection and energy saving, operation is easy, and
Significantly improve the yield and quality of product.
It is that graininess is precipitated that TBC product is not easy crystallization in water, especially the organic solvent full of saturation in kettle
In the state of steam, crystallization is particularly difficult.The present invention is by the way that suitable high-purity finished product TBC is added into crystallization kettle
Product crystallization provides crystal seed, realizes the rapid crystallization of product.
The thermal stability for improving TBC product generallys use organic solvent recrystallization or is aided with the suction of active carbon diatomite
Attached mode improves its purity, the disadvantage is that process is tedious, complicated for operation, production cost is higher, simultaneously for product thermostabilization
Property raising help it is little.The present invention uses the method that appropriate organic tin heat stabilizer is added into finished product TBC, hence it is evident that improves
The thermal stability of TBC.
The above is only the embodiment of the present invention, such as quaternary ammonium salt is tetraethylammonium bromide, tetrabutylammonium bromide, 16
One or more of alkyl trimethyl ammonium bromide, benzyltriethylammoinium chloride, may be implemented the present invention.
Only as described above, only specific embodiments of the present invention, when the model that cannot be limited the present invention with this and implement
It encloses, it is all according to equivalent changes and modifications within the scope of the patent application of the present invention, it is all covered by the present invention.
Claims (10)
1. a kind of heat-staple TBC method for synthesizing flame retardant, which is characterized in that comprise the following steps that
1) triallyl isocyanurate (TAIC) and organic solvent I are added in reaction kettle according to the ratio, stirring to whole dissolutions,
The organic solvent reaction system of TAIC is made;
Organic solvent II and quaternary ammonium salt are added in reactor according to the ratio, bromine Br2 is added dropwise, it is dissolved all, bromination is made
Agent;
2) bromating agent prepared in step 1) is added dropwise in the organic solvent reaction system of TAIC, is warming up to bromination reaction temperature
Degree, heat preservation a period of time, until fully reacting;
3) solution after the reaction of first wash step 2), after removing water layer, adds in the organic layer into the reaction solution in step 2)
Enter solution of sodium bisulfite, until the reddish brown decoloration of reaction system;Addition appropriate alkaline liquor, adjusting organic layer pH value to neutrality, then
Second wash is carried out, liquid separation is stood and goes out organic layer;
4) suitable quantity of water is added in solvent separating still, is warming up to water temperature in the solvent separating still and is maintained at 60~65 DEG C, adds
Enter suitable high-purity finished product TBC finished product as crystal seed, under vacuum conditions, organic layer is slowly added dropwise while stirring, drips
Cheng Hou is stirred for a period of time, product is precipitated in the form of a powder, product is filtered out after precipitation, through drying, obtains thermostabilization
TBC flame retardant products.
2. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 1, which is characterized in that in step 1), institute
Stating organic solvent I is methylene chloride, dichloroethanes, chloroform, carbon tetrachloride any of which, and additional amount is to be added three
2~5 times of allyl chlorinated isocyanurates weight;The organic solvent II is identical organic solvent with the organic solvent I, described
The additional amount of organic solvent II is 2 times of I additional amount of organic solvent.
3. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 1, which is characterized in that in step 1), institute
State quaternary ammonium salt be tetraethylammonium bromide, tetrabutylammonium bromide, cetyl trimethylammonium bromide, benzyltriethylammoinium chloride wherein
It is one or more of;The quaternary ammonium salt and the dropwise addition bromine Br2Mass ratio is 1~2:1.
4. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 1, which is characterized in that in step 2), institute
State bromine Br in bromating agent2Molar ratio with TAIC in the organic solvent reaction system of the TAIC is 3~3.3:1.
5. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 1, which is characterized in that in step 4), institute
Content >=98.5% of high-purity finished product TBC finished product is stated, additional amount is that the 1%~3% of water is added in step 4);Step 1)
Described in TAIC content >=99.0%.
6. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 1, which is characterized in that further include step
5) heat stabilizer is added into heat-staple TBC flame retardant products made from step 4), after mixing, obtains high thermal stability
TBC flame retardant products.
7. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 6, which is characterized in that in step 5), institute
State heat stabilizer be organic tin stabilizer, the organic tin stabilizer be dibutyl tin dilaurate, tin dilaurate two just
One or more of Xin Jixi, dibutyitin maleate, maleic acid dioctyltin;Its additional amount is to be added in step 5)
The 0.3~1% of TBC flame retardant products weight.
8. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 1, which is characterized in that in step 3), to
The mass percent concentration that solution of sodium bisulfite is added in organic layer in reaction solution in the step 2) is 20%.
9. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 1, which is characterized in that in step 3), institute
State and after solution, recycle water layer, i.e. recycling step 2 after the reaction of first wash step 2)) quaternary ammonium salt after reaction in solution, as
Bromating agent prepares raw material and applies.
10. a kind of heat-staple TBC method for synthesizing flame retardant according to claim 1, which is characterized in that in step 2),
The bromination reaction temperature is 40~80 DEG C.
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CN115947881A (en) * | 2023-03-15 | 2023-04-11 | 山东润科化工股份有限公司 | Synthesis method of brominated ethylene propylene diene monomer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102617496A (en) * | 2012-02-15 | 2012-08-01 | 中国石油大学(华东) | Synthetic method of tris (2,3-dibromopropyl) sulfone isocyanurate |
CN103288586A (en) * | 2013-05-20 | 2013-09-11 | 潍坊日兴化工有限公司 | Method for synthesizing 1,2-dibromopropane by utilizing propylene |
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 |
CN109020909A (en) * | 2018-06-28 | 2018-12-18 | 江苏科利新材料有限公司 | A kind of preparation method of three (2,3- dibromopropyl) fulminuric acid esters |
-
2019
- 2019-03-27 CN CN201910237987.1A patent/CN109776438A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102617496A (en) * | 2012-02-15 | 2012-08-01 | 中国石油大学(华东) | Synthetic method of tris (2,3-dibromopropyl) sulfone isocyanurate |
CN103288586A (en) * | 2013-05-20 | 2013-09-11 | 潍坊日兴化工有限公司 | Method for synthesizing 1,2-dibromopropane by utilizing propylene |
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 |
CN109020909A (en) * | 2018-06-28 | 2018-12-18 | 江苏科利新材料有限公司 | A kind of preparation method of three (2,3- dibromopropyl) fulminuric acid esters |
Non-Patent Citations (5)
Title |
---|
BY L. FARKAS ET AL.: "Brominations with Tetramethylammonium Bromide-Bromine Mixtures", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
姚其正 等: "《药物合成反应》", 30 September 2012, 中国医药科技出版社 * |
张国强 等: "溴化SBS合成工艺研究开发", 《山东化工》 * |
汪菊英 等: "《塑料助剂品种及选用速查手册》", 31 January 2017, 文化发展出版社 * |
沈磊 等: "相转移催化合成三溴季铵盐", 《精细化工中间体》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115947881A (en) * | 2023-03-15 | 2023-04-11 | 山东润科化工股份有限公司 | Synthesis method of brominated ethylene propylene diene monomer |
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