CN109942730A - A kind of Heterogeneous oxidation prepares brominated styrene-butadiene copolymer method - Google Patents
A kind of Heterogeneous oxidation prepares brominated styrene-butadiene copolymer method Download PDFInfo
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Abstract
The present invention provides a kind of Heterogeneous oxidation and prepares brominated styrene-butadiene copolymer method, including following key step: (1) dissolving SBS with organic solvent, organic bromine ammonium salt aqueous solution, methyl bromide inhibitor is added, a small amount of acidic catalyst is added dropwise and adjusts pH value, metal onidiges, stratification after isothermal reaction is added；(2) organic phase of lower layer after above-mentioned layering is washed into drying；(3) solid acid catalyst, organic solution containing NBS are added in the organic phase after above-mentioned drying, it is warming up to 90-100 DEG C of reflux 1-2 hours, with in alkaline matter and free bromine after cooling, is precipitated under precipitating reagent effect, filtered, be dried to obtain bromination SBS product.The production energy consumption of the method for the present invention is low, greatly reduces three waste discharge, products obtained therefrom bromine content height, high income, thermal stability are good, suitable for the fire-retardant of the foaming rubber plastics product such as polyethylene foamed, polypropylene, polystyrene.
Description
Technical field
The invention belongs to bromide fire retardant synthesis technical fields, and in particular to a kind of Heterogeneous oxidation preparation bromination benzene second
Alkene-butadiene copolymer method.
Background technique
Bromide fire retardant due to fire-retardant high efficiency, it is heat-resist, be able to satisfy the fire-retardant of various high molecular materials and want
Ask, in addition sufficient raw, cheap, the not many physical mechanical property for deteriorating substrate, be other fire retardants can not
Enemy's, all the time deep favor by people, it is that yield is maximum currently on the market, one of most widely used fire retardant.And
In current all fire retardants applied to polystyrene (PS) material, the compatibility of hexabromocyclododecane (HBCD) and PS resin
Preferably, and under lower additive amount it can make PS material that there is preferable flame retardant property, PS material can be kept to the maximum extent
The heat-insulating property of material and other physical properties, therefore and be more widely applied.
But largely research and investigation showed that bioaccumulation toxicity was very in the organism of hexabromocyclododecane in recent years
By force, have now been found that HBCD can be diffused into environment by production, use and its Waste disposal process, and as food chain
The mankind of terminal can absorb the substance from environment, cause the internal organs such as liver and thyroid gland or nerve aspect disease.And it is directed to it
Cumulative bad and toxicity in vivo, in " Convention of Stockholm about persistence organic pollutant " held in 2013
The substance is put into control register, and China also added hexabromocyclododecane to " the stringent limit of China in 2014 as signatories to a treaty
Make the toxic chemical catalogue of inlet and outlet " and at present in newly organized national standard " green product assessment technical requirements heat-insulating material "
To it as fire retardant it is also proposed that disabling requires, this just needs to find a kind of substitute for hexabromocyclododecane, is both able to satisfy ring
The requirement of guarantor will also meet the flame retardant property of product.
For above situation, currently a solution is positive research halogen-free flame retardants in the world, but halogen-free flameproof
Agent flame retarding efficiency is low, additive amount is high, price, at high cost, is commonly used in the product that toy, clothing etc. are in close contact with human body,
And building material product is difficult to receive to the influence on its high price workinprocess cost, and halogen-free flame retardants flame retardant effect is bad,
Requirement of the building material product to flame retardant property is not achieved.And compared to halogen-free flame retardants is used, by improving molecular weight, improving molecule knot
Structure is a kind of more real solution come the macromolecular bromide fire retardant for developing low toxicity, good, the weather-proof resistance to migration of thermal stability.
Since polymer base compatibility is good, it is thus possible to keep the original physical mechanical property of high polymer material, and non-migratory, hot
Stability is good, easy to process and more persistence.
Summary of the invention
For situation the technical issues of mentioning in background technique, the technical solution of the invention provides a kind of Heterogeneous oxidation system
The method of standby brominated styrene-butadiene copolymer, this method production energy consumption is low, greatly reduces three waste discharge, products obtained therefrom
Bromine content height, high income, thermal stability are good, the resistance suitable for the foaming rubber plastics product such as polyethylene foamed, polypropylene, polystyrene
Combustion.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of Heterogeneous oxidation prepares brominated styrene-butadiene copolymer method, including following key step:
(1) SBS is dissolved with organic solvent, organic bromine ammonium salt aqueous solution is added, be warming up to 20 DEG C -30 DEG C, methyl is added
Bromination inhibitor is added dropwise a small amount of acidic catalyst and adjusts pH value, metal onidiges, isothermal reaction 3-5 after addition is added
Hour, stratification；
(2) diluted alkaline of certain volume is added under the conditions of 20 DEG C -30 DEG C of constant temperature in the organic phase of lower layer after above-mentioned layering
Solution washs 2-4 times, and each wash time is that 0.5-1h removes impurity, then is washed organic phase several times with distilled water, and use is anhydrous
Calcium chloride solid is dry；
(3) solid acid catalyst is added in the organic phase after above-mentioned drying, is added and contains under the conditions of 15 DEG C -25 DEG C of temperature
NBS organic solution, is warming up to 90-100 DEG C of reflux 1-2 hours, it is cooling after in alkaline matter and free bromine, acted in precipitating reagent
Lower precipitating is filtered, is dried to obtain bromination SBS product.
Wherein, the organic solvent that SBS is dissolved in the step (1) is any one of chloroform, tetrahydrofuran, methylene chloride
Or it is a variety of, the organic solvent of the dissolution SBS and the mass ratio of the SBS are 10-25:1.
Wherein, the organic bromine ammonium salt in the step (1) is tetraethylammonium bromide, tetrabutylammonium bromide, benzyl trimethyl
The combination of one or more of ammonium bromide, benzyl triethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, it is described organic
The molar ratio of bromine ammonium salt and metal onidiges is 1.25-2:1, and the mass ratio of the organic bromine ammonium salt and the SBS are 3-11:1.
Wherein, the metal onidiges in the step (1) are ammonium ceric nitrate, any one or two kinds in ammonium phosphomolybdate,
The mass ratio of the metal onidiges and the SBS are 5.5-18:1.
Wherein, the methyl bromide inhibitor in the step (1) be tin tetrachloride, in titanium tetrachloride any one or
Two kinds, the dosage of the methyl bromide inhibitor is the 1wt%-5wt% of the SBS.
Wherein, the acidic catalyst in the step (1) be citric acid, oxalic acid, acetic acid, silicic acid any one or it is more
Kind, the dosage of the acidic catalyst is the 1wt%-10wt% of the metal onidiges.
Wherein, the dilute alkaline soln in the step (2) is any one of sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate
Or a variety of mass fractions is the aqueous solution of 5%-10%, the volume of the dilute alkaline soln is washed organic phase volume ratio with described
For 1/3-1:1.
Wherein, solid acid catalyst is made of metal solid phase carrier with Bronsted acid in the step (3), the metal solid phase
Carrier is Zr (OH)4、Co(OH)2In any one or two kinds, the dosage of the metal solid phase carrier is the SBS's
8wt%-15wt%, the Bronsted acid be sulfuric acid, hydrochloric acid, in phosphoric acid any one or it is a variety of, the Bronsted acid dosage is
The metal solid phase carrier 10wt%-20wt%.
Wherein, organic solvent used in organic solution containing NBS described in step (3) is carbon tetrachloride, dimethyl sulfoxide
In any one or two kinds, the mass ratio of organic solvent and NBS are 8-12:1, the NBS in the organic solution containing NBS
Quality and SBS mass ratio be 1-1.5:1.
Wherein, the alkaline matter in the step (3) is sodium thiosulfate, sodium hydroxide, sodium methoxide, sodium ethoxide, three second
Any one or more of hydramine, sodium sulfite, hydrazine hydrate, ammonium hydroxide.
Wherein, the precipitating reagent in the step (3) be methanol, ethyl alcohol, in isopropanol any one or it is a variety of.
The present invention the beneficial effects are as follows:
(1) a kind of synthetic method of high-heat stability bromized SBS disclosed in patent document CN201710655808,
In, using this strong acid of hydrobromic acid as bromide, which is the reagent of strong corrosive, strong volatility and easily sucking intoxicating, this
For the bromide used in scheme for organic bromine ammonium salt, the bromide is stable, safe and nontoxic, and then the production security in this programme, behaviour
The property made is more preferable；And metal ion can recycle in water phase, that is, the cost of product preparation can be reduced by reducing environmental pollution again；
(2) compared with bromine makees bromating agent, with organic bromine ammonium salt it is that bromating agent reaction condition is mild, easily controllable, and gold
Belong to the coordination of ion so that the bromine addition of double bond is more accurate, make product bromine content high, high income, thermal stability is more preferable
(3) PH acidic value is regulated and controled using acidic catalyst, improves the oxidisability of metal ion, it is ensured that bromide ion is formed
Rate ensure that the yield and quality of product；
(4) catalyst is done using solid proton acid, quantitative bromine is oriented on styrene-butadiene main chain carbon and is taken
In generation, ensure that all bromo elements are bonded on the main chain of styrene-butadiene copolymer, and thermal stability is substituted in benzene than bromine
It to get well on ring, so that product is good with polystyrene material compatibility, the mechanical performance of the material after addition will not be generated negative
It influences；
(5) it is precipitated using precipitating reagent, so that the crystallization degree of product is high, thermal stability is high, and product dispersibility is more preferable
It is more stable.
Detailed description of the invention
Fig. 1 is process principle figure of the invention, and the present invention is that raw material progress is double with styrene-butadiene copolymer (SBS)
The addition of key bromine and benzyl position bromine replace two kinds of reactions, wherein the first step is reacted under acidic catalysis conditions, and the oxygen of metal ion is utilized
The property changed obtains bromide, while bromide cracks out bromine free radical orientation and double bond addition reaction in SBS in organic phase；Second
For step using N- bromo-succinimide (NBS) as bromating agent, the orientation that aliphatic chain benzyl position is carried out under solid acid catalysis quantifies bromine
Change, improves bromine conversion ratio.
Fig. 2 SBS and bromination SBS infrared spectrum comparative analysis figure；Wherein, (A) SBS infrared spectrum；(B) bromination SBS is infrared
Spectrogram；(A) SBS FTIR: styrene characteristic peak (698cm-1And 756cm-1), 1,2- vinyl characteristic peak: 910cm-1It is anti-with Isosorbide-5-Nitrae
Formula characteristic peak: 966cm-1；(B) bromination SBS FTIR: styrene characteristic peak (698cm-1And 756cm-1), 1,2- vinyl feature
Peak: 908cm-1With the trans- characteristic peak of Isosorbide-5-Nitrae: 966cm-1, carbon-bromine key characteristic peak: 547cm-1；Carbon-bromine key characteristic peak: 547cm-1For
Fatty carbon connects the infrared region of bromine, it was demonstrated that bromo element addition, substitution feasibility on main chain.
Fig. 3 SBS and bromination SBS nmr spectrum comparative analysis figure；Wherein, (A) SBS nmr spectrum；(B) bromination
SBS nmr spectrum；(A)SBS(CDCl3)1HNMR: aromatic series hydrogen (6.3-7.3ppm), alkene race hydrogen (1,2- vinyl: 4.9-
5.1ppm；Isosorbide-5-Nitrae-is trans- and Isosorbide-5-Nitrae-is cis-: 5.3-5.5ppm), aliphatic hydrogen (0.5-2.5ppm)；(B) bromination SBS (CDCl3)1HNMR: aromatic series hydrogen (6.3-7.3ppm), bromo hydrogen (3.7-4.3ppm) aliphatic hydrogen (0.5-2.5ppm)；SBS fourth in raw material
The chemical displacement value of carbon-carbon double bond on diene segment are as follows: 1,2- vinyl: 4.9-5.1ppm；Isosorbide-5-Nitrae-is trans- and Isosorbide-5-Nitrae-is cis-:
5.3-5.5ppm；The chemical displacement value of carbon-carbon double bond disappears after product bromine addition, illustrates double bond addition, and in 3.7-4.3ppm
There is new chemical displacement value, is compared through standard spectrogram, the hydrogen atom being determined as on carbon-bromine key, while product fatty race hydrogen
Peak value is substantially reduced compared to the peak value of SBS aliphatic hydrogen, illustrates that NBS is extremely successful to the substitution of main chain aliphatic hydrogen.
Fig. 4 SBS, bromine are the product of bromide synthesis, by method in patent document CN201710655808 are with hydrobromic acid
Product, the organic bromine ammonium salt of bromide synthesis are the thermogravimetric curve comparative analysis figure of the product of bromide synthesis；Wherein, the heat of (A) SBS
Weight curve: starting weightless temperature is 377 DEG C；(B) thermogravimetric curve of bromide synthetic bromide SBS is done in comparative example 4 with bromine: starting
Weightless temperature is 177 DEG C；(C) it is synthesized by method in documents CN201710655808 by bromide of hydrobromic acid in comparative example 2
Bromination SBS thermogravimetric curve: starting weightless temperature be 201 DEG C；(D) it is synthesized using organic bromine ammonium salt as bromide in embodiment 1
The thermogravimetric curve of bromination SBS: starting weightless temperature is 233 DEG C.The starting weightless temperature for comparing raw material SBS, SBS after bromination its
Starting weightless temperature value is substantially reduced.It but is the bromination SBS of bromide synthesis, reaction condition milder, and gold with organic bromine ammonium salt
The oxidisability and solid proton acid for belonging to ion make catalyst and make bromine addition and substitution more accurate, than making of hydrobromic acid and bromine
The bromination SBS of bromide synthesis, it is smaller to the destruction of macromolecular chain, products therefrom molecular structure is more orderly, therefore with organic bromine ammonium
Salt is that bromide is higher than the bromination SBS starting weightless temperature for making bromide synthesis of other reagents, thermal stability is more preferable.In XPS plate
In the production technology of material, it is comparatively bromide with organic bromine ammonium salt, through gold that production temperature range, which is generally 170 DEG C -210 DEG C,
It is stronger to belong to the bromination SBS applicability that ionic oxide formation is catalyzed.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
In addition to being defined, technical term used in following embodiment has and the invention one of ordinary skill in the art
The identical meanings being commonly understood by.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；
The experimental method is unless otherwise specified conventional method.
Embodiment 1
(1) 10g SBS 70ml organic solvents, chloroform is dissolved, 45% tetraethylammonium bromide aqueous solution of 180g is added, risen
0.3g tin tetrachloride is added to 25 DEG C in temperature, and 50% aqueous citric acid solution of 4.8g is added dropwise and makees catalyst, 154g ammonium ceric nitrate is added,
Isothermal reaction 3-5 hours after addition, stratification；
(2) organic phase of lower layer after above-mentioned layering is washed under the conditions of 25 DEG C of constant temperature with each 50ml 5%NaOH solution
It washs 2-4 times, each wash time is that 0.5-1h removes impurity, then is washed organic phase several times with 50ml distilled water, and lower layer is organic
It is mutually dry with anhydrous calcium chloride solid；
(3) organic after above-mentioned drying is added to 1g Zr (OH)4With 0.2g phosphoric acid, in 15 DEG C of -25 DEG C of conditions of temperature
Under, the 80ml dimethyl sulphoxide solution of the NBS containing 10g is added, is warming up to 90-100 DEG C of reflux 1-2 hours, uses hydroxide after cooling
With excessive bromine in sodium, is precipitated under the action of ethyl alcohol, filtered, be dried to obtain 33.75g bromination SBS product.
Embodiment 2
(1) 10gSBS 70ml organic solvents, chloroform is dissolved, 45% tetraethylammonium bromide aqueous solution of 180g is added, risen
0.3g tin tetrachloride is added to 25 DEG C in temperature, and 154g ammonium ceric nitrate is added, and isothermal reaction 3-5 hours after addition, stands and divides
Layer；
(2) organic phase of lower layer after above-mentioned layering is washed under the conditions of 25 DEG C of constant temperature with each 50ml 5%NaOH solution
It washs 2-4 times, each wash time is that 0.5-1h removes impurity, then is washed organic phase several times with 50ml distilled water, and lower layer is organic
It is mutually dry with anhydrous calcium chloride solid；
(3) organic after above-mentioned drying is added to 1g Zr (OH)4With 0.2g phosphoric acid, in 15 DEG C of -25 DEG C of conditions of temperature
Under, the 80ml dimethyl sulphoxide solution of the NBS containing 10g is added, is warming up to 90-100 DEG C of reflux 1-2 hours, uses hydroxide after cooling
With excessive bromine in sodium, is precipitated under the action of ethyl alcohol, filtered, be dried to obtain 17.58g bromination SBS product.
Embodiment 3
(1) 10g SBS 70ml organic solvents, chloroform is dissolved, 45% tetraethylammonium bromide aqueous solution of 180g is added, risen
0.3g tin tetrachloride is added to 25 DEG C in temperature, and 50% aqueous sodium carbonate of 4.8g is added dropwise and makees catalyst, 154g ammonium ceric nitrate is added,
Isothermal reaction 3-5 hours after addition, stratification；
(2) organic phase of lower layer after above-mentioned layering is washed under the conditions of 25 DEG C of constant temperature with each 50ml 5%NaOH solution
It washs 2-4 times, each wash time is that 0.5-1h removes impurity, then is washed organic phase several times with 50ml distilled water, and lower layer is organic
It is mutually dry with anhydrous calcium chloride solid；
(3) organic after above-mentioned drying is added to 1g Zr (OH)4With 0.2g phosphoric acid, in 15 DEG C of -25 DEG C of conditions of temperature
Under, the 80ml carbon tetrachloride solution of the NBS containing 10g is added, is warming up to 90-100 DEG C of reflux 1-2 hours, uses sodium hydroxide after cooling
Excessive bromine is neutralized, is precipitated under the action of ethyl alcohol, filtered, be dried to obtain 15.92g bromination SBS product.
Embodiment 4
(1) 10g SBS 70ml organic solvents, chloroform is dissolved, 45% tetraethylammonium bromide aqueous solution of 180g is added, risen
0.3g tin tetrachloride is added to 25 DEG C in temperature, and 50% aqueous citric acid solution of 4.8g is added dropwise and makees catalyst, 154g ammonium ceric nitrate is added,
Isothermal reaction 3-5 hours after addition, stratification；
(2) organic phase of lower layer after above-mentioned layering is washed under the conditions of 25 DEG C of constant temperature with each 50ml 5%NaOH solution
It washs 2-4 times, each wash time is that 0.5-1h removes impurity, then is washed organic phase several times with 50ml distilled water, and lower layer is organic
It is mutually dry with anhydrous calcium chloride solid；
(3) under the conditions of 15 DEG C of -25 DEG C of temperature, by organic 80ml diformazan for being added to the NBS containing 10g after above-mentioned drying
Base sulfoxide solution, is warming up to 90-100 DEG C of reflux 1-2 hours, it is cooling after in sodium hydroxide and excessive bromine, in the work of ethyl alcohol
With lower precipitating, is filtered, is dried to obtain 22.37g bromination SBS product.
Embodiment 5
(1) 15gSBS 210ml organic solvent tetrahydrofuran is dissolved, 45% benzyltrimethylammonium bromide of 130g is added
Aqueous solution is warming up to 25 DEG C, and 0.15g titanium tetrachloride is added, and 50% oxalic acid aqueous solution of 5.9g is added dropwise as catalyst, is added
260g ammonium phosphomolybdate, isothermal reaction 3-5 hours after addition, stratification；
(2) by the organic phase of lower layer after above-mentioned layering, under the conditions of 25 DEG C of constant temperature, with each 10% ammonia scrubbing of 70ml
2-4 times, each wash time is that 0.5-1h removes impurity, then is washed organic phase several times with 50ml distilled water, lower layer's organic phase
It is dry with anhydrous calcium chloride solid；
(3) organic after above-mentioned drying is added to 1.5g Zr (OH)4With 0.15g hydrochloric acid, in 15 DEG C of -25 DEG C of items of temperature
Under part, the 135ml dimethyl sulphoxide solution of the NBS containing 15g is added, 90-100 DEG C of reflux 1-2 hours is warming up to, with three after cooling
With excessive bromine in ethanol amine, is precipitated under the action of methanol, filtered, be dried to obtain 51.45g bromination SBS product.
Embodiment 6
(1) 20gSBS 300ml organic solvent dichloromethane is dissolved, 45% benzyl triethyl ammonium bromide of 380g is added
Aqueous solution is warming up to 25 DEG C, and 0.6g tin tetrachloride is added, and 38% aqueous acetic acid of 21g is added dropwise as catalyst, 260g is added
Ammonium ceric nitrate, isothermal reaction 3-5 hours after addition, stratification；
(2) molten with each 10% sodium carbonate of 100ml under the conditions of 25 DEG C of constant temperature by the organic phase of lower layer after above-mentioned layering
Liquid washs 2-4 times, and each wash time is that 0.5-1h removes impurity, then is washed organic phase several times with 100ml distilled water, lower layer
Organic phase is dry with anhydrous calcium chloride solid；
(3) 2g Co (OH) is added in the organic layer after above-mentioned drying2With 0.4g sulfuric acid, in 15 DEG C of -25 DEG C of conditions of temperature
Under, the 140ml carbon tetrachloride solution of the NBS containing 20g is added, 90-100 DEG C of reflux 1-2 hours is warming up to, with three ethyl alcohol after cooling
With excessive bromine in amine, is precipitated under the action of ethyl alcohol, filtered, be dried to obtain 63.74g bromination SBS product.
Embodiment 1,2,3 is to do comparative test to the selection of catalyst in first step double bond addition reaction, selects acid respectively
Property catalysis, without catalysis, base catalysis, in the identical situation of other reaction conditions, compare 3 embodiments yield find in acid
Property be catalyzed lower yield highest, take second place without catalysis, base catalysis it is minimum, illustrate that the oxidisability of metal ion in acid condition obtains
Maximum plays, and ensure that the formation rate of bromide ion, while being more advantageous to double bond bromine under acid condition and being unfolded into electron deficient shape
State is more conducive to the nucleophilic addition that bromine anion is close and completion is in double bond.Opposite base catalysis has inhibition gold instead
The effect for belonging to ionic oxide formation is also unfavorable for double bond and opens completion nucleophilic addition while being unfavorable for the formation of bromide ion；It is real
Example 4 is applied compared with Example 1 in addition to not having that bromine substitution reaction of the solid acid catalyst to assist NBS, other conditions all one are added
Sample, solid acid there are one to be a carrier as Bromonium ion, it is ensured that Bromonium ion stability namely guarantees to join
Come with the Bromonium ion concentration reacted, two so that benzyl position hydrogen is more vivaciously also beneficial to the parental materials of Bromonium ion.Embodiment 5,6
Compared with Example 1, under SBS, organic bromine ammonium salt, metal onidiges, NBS bromo agent investment ratio same case, investment is selected
Under the conditions of amount gradient is increased, yield is also scaling up substantially, it was demonstrated that repeatable and each raw material, the catalyst of embodiment
Between feed ratio correctness.
Comparative example 1
(1) 10g SBS 100g organic solvent dichloroethanes is dissolved, is added in the hydrogen peroxide solution of 10g 50%, adds
Enter 0.2g tetrabutylammonium bromide and 0.1g tin tetrachloride as catalyst, is warming up to 35-60 DEG C, the hydrobromic acid of 30g 50% is added dropwise
Aqueous solution is added dropwise 50 DEG C of maintaining reaction temperature, reacts 5h, is cooled to room temperature, stratification；
(2) 0.2g hydrogen peroxide and 0.2g sodium methoxide is added in the lower organic layer after above-mentioned layering, is warming up to 60 DEG C of heat preservations
2h removes impurity, and 100g water is added, and washing is then allowed to stand layering, and lower organic layer is dry with calcium chloride solid；
(3) organic after above-mentioned drying is added to 1g Zr (OH)4With 0.2g phosphoric acid, in 15 DEG C of -25 DEG C of conditions of temperature
Under, the 80ml dimethyl sulphoxide solution of the NBS containing 10g is added, is warming up to 90-100 DEG C of reflux 1-2 hours, uses hydroxide after cooling
With excessive bromine in sodium, is precipitated under the action of ethyl alcohol, filtered, be dried to obtain 26.32g bromination SBS product.
Comparative example 2
(1) 10g SBS 100g organic solvent dichloroethanes is dissolved, is added in the hydrogen peroxide solution of 10g 50%, adds
Enter 0.2g tetrabutylammonium bromide and 0.1g tin tetrachloride as catalyst, is warming up to 35-60 DEG C, the hydrobromic acid of 30g 50% is added dropwise
Aqueous solution is added dropwise 50 DEG C of maintaining reaction temperature, reacts 5h, is cooled to room temperature, stratification；
(2) 0.2g hydrogen peroxide and 0.2g sodium methoxide is added in the lower organic layer after above-mentioned layering, is warming up to 60 DEG C of heat preservations
2h removes impurity, and 100g water is added, and washing is then allowed to stand layering, and lower organic layer is dry with calcium chloride solid；
(3) composite catalyst 0.3g ferric trichloride and 0.1g iodine, control reaction will be added in the organic layer after above-mentioned drying
5-8 DEG C of temperature, the dichloroethane solution containing bromine chloride 24g is added dropwise, then in ammonium hydroxide and excessive bromine, in water and 2wt%
Poly-vinyl alcohol solution under the action of be warming up to 100 DEG C, solvent is distilled off, filtered, be dried to obtain 24.85g bromination SBS production
Product.
Comparative example 3
(1) 10g SBS 70ml organic solvents, chloroform is dissolved, 45% tetraethylammonium bromide aqueous solution of 180g is added, risen
0.3g tin tetrachloride is added to 25 DEG C in temperature, and 50% aqueous citric acid solution of 4.8g is added dropwise and makees catalyst, 154g ammonium ceric nitrate is added,
Isothermal reaction 3-5 hours after addition, stratification；
(2) organic phase of lower layer after above-mentioned layering is washed under the conditions of 25 DEG C of constant temperature with each 50ml 5%NaOH solution
It washs 2-4 times, each wash time is that 0.5-1h removes impurity, then is washed organic phase several times with 50ml distilled water, and lower layer is organic
It is mutually dry with anhydrous calcium chloride solid；
(3) composite catalyst 0.3g ferric trichloride and 0.1g iodine, control reaction will be added in the organic layer after above-mentioned drying
5-8 DEG C of temperature, the dichloroethane solution containing bromine chloride 24g is added dropwise, then in ammonium hydroxide and excessive bromine, in water and 2wt%
Poly-vinyl alcohol solution under the action of be warming up to 100 DEG C, solvent is distilled off, filtered, be dried to obtain 28.71g bromination SBS production
Product.
Comparative example 4
(1) 10g SBS 70ml organic solvents, chloroform is dissolved, it, will while being stirred under the conditions of 0 DEG C of ice-water bath
The bromine of 30.8ml is slowly dropped in solution with the speed of 1d/2s；
2h is reacted under the conditions of (2) 0 DEG C, is warming up to 25 DEG C of reaction 1h, is warming up to 50 DEG C of reaction 1h, is warming up to 75 DEG C of reaction 2h
Afterwards, it is down to incubation at room temperature 20min naturally；It is precipitated using methanol as anti-solvent, is filtered, is dried to obtain 35.25g bromination
SBS product.
The method that comparative example 1 distinguishes the double bond bromine addition for being comparative example 1 compared with Example 1 is different, and comparative example 1 uses
Hydrogen peroxide make oxidant, hydrobromic acid provides bromide, hydrobromic acid strong corrosive for the organic bromine ammonium salt that compares, strong volatility and
Easily sucking intoxicating, i.e., it is unstable to be unfavorable for that reaction, intoxicating all has the mankind and environment and endangers again, so compared with Example 1
Its low yield.Embodiment 2 then goes to implement fully according to the method for patent document CN201710655808, find its yield compared to pair
It also wants low for ratio 1, illustrates to do the relationship that brominated reagent can be easier input and output with NBS, bromine band reacts more
Precisely.The method that the addition of double bond bromine uses present case compared with comparative example 1 of comparative example 3, but bromine replaces using patent text
The method of part CN201710655808 goes to implement, it can be seen that although yield is lower than embodiment 1, but than comparative example 1
Height, and its yield highest in comparative example 1,2,3, illustrate the ratio that bromine addition reaction accounts in the bromine ingredient of product in whole process
Example is heavier, and it is identical that this, which selects polybutadiene ingredient accounting 70% in SBS with us, and there are two bromines simultaneously for double bond addition
It is added to main chain and bromine substitution is to replace one by one, addition reaction proportion is more, so there can be the production of comparative example 1,2,3
The comparing result of product yield.Bromine is selected to do bromide in comparative example 4, yield is more slightly higher than embodiment 1, but due to bromine pair
The bromination non-selectivity of SBS, part hydrogen may be substituted on phenyl ring in product, and the structure of product and order is caused to be broken
The bad thermostabilization to influence fire retardant leads to its thermostabilization reduction, is unfavorable for adding in the production of the foam process such as XPS
It uses.
One embodiment of the present invention has been described in detail above, but the content is only preferable implementation of the invention
Example, should not be considered as limiting the scope of the invention.It is all according to all the changes and improvements made by the present patent application range
Deng should still be within the scope of the patent of the present invention.
Claims (10)
1. a kind of Heterogeneous oxidation prepares brominated styrene-butadiene copolymer method, which is characterized in that including following main
Step:
(1) SBS is dissolved with organic solvent, organic bromine ammonium salt aqueous solution is added, be warming up to 20 DEG C -30 DEG C, methyl bromide is added
Inhibitor is added dropwise a small amount of acidic catalyst and adjusts pH value, metal onidiges are added, isothermal reaction 3-5 hours after addition,
Stratification；
(2) dilute alkaline soln of certain volume is added under the conditions of 20 DEG C -30 DEG C of constant temperature in the organic phase of lower layer after above-mentioned layering
Washing 2-4 times, each wash time are that 0.5-1h removes impurity, then is washed organic phase several times, with anhydrous chlorination with distilled water
Calcium solid is dry；
(3) solid acid catalyst is added in the organic phase after above-mentioned drying, is added under the conditions of 15 DEG C -30 DEG C of temperature and contains NBS
Organic solution, is warming up to 90-100 DEG C of reflux 1-2 hours, it is cooling after in alkaline matter and free bromine, under precipitating reagent effect
Precipitating, is filtered, is dried to obtain bromination SBS product.
2. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method, special
Sign is, in the step (1) organic solvent of dissolution SBS be chloroform, tetrahydrofuran, methylene chloride any one or it is more
Kind, the organic solvent of the dissolution SBS and the mass ratio of the SBS are 10-25:1.
3. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method, special
Sign is, the organic bromine ammonium salt in the step (1) be tetraethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium bromide,
The combination of one or more of benzyl triethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, the organic bromine ammonium salt
It is 1.25-2:1 with the molar ratios of metal onidiges, the mass ratio of the organic bromine ammonium salt and the SBS are 3-11:1.
4. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method, special
Sign is, the metal onidiges in the step (1) are ammonium ceric nitrate, any one or two kinds in ammonium phosphomolybdate, the gold
The mass ratio for belonging to oxidant and the SBS is 5.5-18:1.
5. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method, special
Sign is, the methyl bromide inhibitor in the step (1) is tin tetrachloride, any one or two kinds in titanium tetrachloride,
The dosage of the methyl bromide inhibitor is the 1wt%-5wt% of the SBS.
6. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method, special
Sign is that the acidic catalyst in the step (1) is any one or more of citric acid, oxalic acid, acetic acid, silicic acid, described
The dosage of acidic catalyst is the 1wt%-10wt% of the metal onidiges.
7. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method, special
Sign is that the dilute alkaline soln in the step (2) is any one or more of sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate
Mass fraction be 5%-10% aqueous solution, the volume of the dilute alkaline soln and it is described be washed organic phase volume ratio be 1/3-
1:1。
8. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method, special
Sign is that solid acid catalyst is made of metal solid phase carrier with Bronsted acid in the step (3), and the metal solid phase carrier is
Zr(OH)4、Co(OH)2In any one or two kinds, the dosage of the metal solid phase carrier is the 8wt%- of the SBS
15wt%, the Bronsted acid be sulfuric acid, hydrochloric acid, in phosphoric acid any one or it is a variety of, the Bronsted acid dosage is the gold
Belong to solid phase carrier 10wt%-20wt%.
9. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method, special
Sign is, organic solvent used in organic solution containing NBS described in step (3) is carbon tetrachloride, appointing in dimethyl sulfoxide
It anticipates one or two kinds of, the mass ratio of organic solvent and NBS are 8-12:1, the quality of the NBS in the organic solution containing NBS
Mass ratio with SBS is 1-1.5:1.
10. a kind of Heterogeneous oxidation according to claim 1 prepares brominated styrene-butadiene copolymer method,
Be characterized in that, the alkaline matter in the step (3) be sodium thiosulfate, sodium hydroxide, sodium methoxide, sodium ethoxide, triethanolamine,
Any one or more of sodium sulfite, hydrazine hydrate, ammonium hydroxide.
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| CN111269370A (en) * | 2020-03-18 | 2020-06-12 | 山东润科化工股份有限公司 | Synthesis method of brominated butadiene-styrene block copolymer |
| CN114605731A (en) * | 2022-03-31 | 2022-06-10 | 淄博市临淄六顺新材料有限公司 | Flame-retardant polyolefin ionic polymer alloy material for rotational molding and production process thereof |
| CN116535553A (en) * | 2023-07-04 | 2023-08-04 | 潍坊双丰化工有限公司 | Preparation method of high-thermal-stability brominated polystyrene |
| CN117362522A (en) * | 2023-10-10 | 2024-01-09 | 山东敏德化工有限公司 | Preparation method of brominated styrene/butadiene copolymer |
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