CN103772434A - Preparation method for reaction type halogen-free flame retardant - Google Patents
Preparation method for reaction type halogen-free flame retardant Download PDFInfo
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Abstract
The invention discloses a preparation method for a reaction type halogen-free flame retardant. A DOPO derivative grafted by itaconic acid is prepared through two steps, firstly, the reactant DOPO and the itaconic acid are dissolved in xylene, and reaction is performed below the boiling point of the xylene; tetrahydrofuran is added for reflux reaction until white solid is separated out, so that the reaction type halogen-free flame retardant is obtained. The preparation method provided by the invention is carried out at a relatively low temperature, so that energy consumption is reduced effectively, the reaction time is shortened, the product yield is improved, and the subsequent purification work is facilitated.
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant, relate in particular to a kind of preparation method of response type halogen-free flame retardants, adopt Itaconic Acid Grafted 9, the method for the assorted phenanthrene-10-oxide compound (DOPO) of mix-10-phosphine of 10-dihydro-9-oxy.
Background technology
Fire retardant (fire retardants) is that a class can be checked inflammable material and ignited or suppress the additive that flare spreads, can be divided into additive flame retardant and reactive flame retardant, also can be divided into organic fire-retardant and inorganic combustion inhibitor, and halogen-containing flame retardant and non-halogen flame retardant etc.
Because the smoke density that the product (as: flame-retarded resin) of interpolation halogen-containing flame retardant burns is excessive, the countries such as European Union have started content of halogen in material to propose strict requirement.Non-halogen flame retardant, take 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO, CAS:35948-25-5) and derivative as main, can solve preferably the above-mentioned defect of halogen-containing flame retardant, and acquisition has the product of low cigarette and low toxicity characteristic and adopted in a large number.
Be conventional at present a kind of non-halogen flame retardant by the DOPO derivative of Itaconic Acid Grafted DOPO gained, generally adopting dimethylbenzene is synthetic (research [D] of unsaturated polyester resin, Guangzhou: South China Science & Engineering University, 2010 of solvent single stage method; Synthetic and sign [N], Wuhan University Of Science and Engineering's journal, 2007,20 (1), the 5-7 of new phosphorus-containing flame retardant DOPO-ITA).This single stage method all take mol ratio as the DOPO of 1: 1 and methylene-succinic acid as reactant, gradation adds methylene-succinic acid in 3 hours, makes in high temperature (being greater than 150 ℃) lower long-time (being greater than 8 hours) reaction, product yield is 82.8%.The boiling point of dimethylbenzene is 137 ℃-140 ℃, and reaction has belonged to vigorous reaction at 150 ℃ and 160 ℃, and not only energy consumption of reaction is high, and the time is longer, and security is low, and products therefrom also easily lumps, aftertreatment difficulty, and productive rate is also lower.
Liu Ji equality people (preparation [R] of DOPO derivative, china academia annual meeting in 2010,2010,154-157) take toluene as solvent, take mol ratio as the DOPO of 1: 1 and methylene-succinic acid as reactant, obtain DOPO-ITA in 20 hours single stage method of 110 ℃ of reactions, product yield is 85%.This Techniques For Reducing temperature of reaction, but the reaction times truly have prolongation, fail effectively to solve long reaction time, the high and lower problem of productive rate of energy consumption.
Chinese invention patent application 200610099076.X discloses a kind of 9, the preparation method of the assorted phenanthrene-10-oxide compound of mix-10-phosphine of 10-dihydro-9-oxy and derivative thereof, the methylene-succinic acid of DOPO and equimolar amount added in the enamel reaction still that is connected with nitrogen and be warming up to 150 ℃, react and within 4 hours, make DOPO-methylene-succinic acid, yield 99%.DOPO and methylene-succinic acid are all solid matter, adopt solventless method to implement DOPO and methylene-succinic acid reaction in this technology, will make reaction process be difficult to stir and fully reaction.Because the reaction of DOPO and methylene-succinic acid is thermopositive reaction, at 150 ℃ of temperature, DOPO and methylene-succinic acid be disposable all to add and not only causes local superheating and the generation of the situation such as reaction is violent, and then cause methylene-succinic acid to cross the problem such as thermolysis and products therefrom blackout, also cause enamel reaction still internal pressure excessive, have potential safety hazard.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of response type halogen-free flame retardants, effectively to reduce energy consumption of reaction, Reaction time shorten, improve product yield and simplify subsequent purification step.
For achieving the above object, the preparation method of response type halogen-free flame retardants of the present invention, adopts two-step approach to make the DOPO derivative of Itaconic Acid Grafted.Reactant DOPO and methylene-succinic acid are dissolved in dimethylbenzene by the first step, in 120 ℃ of-130 ℃ of reactions, with the quick generation of induced product; Second step adds tetrahydrofuran (THF), in 96 ℃ of-106 ℃ of back flow reaction, separates out to white solid.Reaction formula is as follows:
Reactant DOPO and methylene-succinic acid are dissolved in hot dimethylbenzene above entirely at 65 ℃, and product (methylene-succinic acid-DOPO) is insoluble to hot dimethylbenzene.DOPO and methylene-succinic acid are to react in 120 ℃ of-130 ℃ of xylene solutions in temperature, and solution becomes muddy by clarifying, and shows to have product to generate.
Empirical tests, reaction second step adds after tetrahydrofuran (THF), and product solubleness in hot dimethylbenzene and tetrahydrofuran (THF) mixed solvent increases, and dispersed solvent and the combination thereof that is also better than other.Therefore, after second step adds tetrahydrofuran (THF), reaction system (dissolving the dimethylbenzene system of respond thing and product) becomes clarification by muddiness, but along with reaction is carried out and the increasing of product, product is separated out after reaching capacity in mixed solvent, make reaction system become gradually again muddy, until produce a large amount of white solid product, the reaction times is longer, and the product of separating out is more.According to the result of test of many times, the 2-3 after mixed solvent muddiness hour the product that generates more, the time extends again, product slowly increases.
The preparation method of response type halogen-free flame retardants of the present invention, in its first step reaction, adopts the excessive method of reactant methylene-succinic acid, reaction is carried out more complete, thereby is conducive to improve productive rate.Through experimental verification, DOPO: methylene-succinic acid < 1: 1.02 o'clock, methylene-succinic acid is very little excessive, and productive rate is on the low side; DOPO: methylene-succinic acid > 1: 1.1 o'clock, along with the excessive number of methylene-succinic acid increases, productive rate no longer significantly increases.Therefore, the consumption of reactant DOPO and methylene-succinic acid is preferential selects 1: 1.02-1: 1.1, and mol ratio, as: but be not limited only to 1: 1.02,1: 1.03,1: 1.04,1: 1.05,1: 1.06,1: 1.07,1: 1.08,1: 1.09 and 1: 1.1.
The preparation method of response type halogen-free flame retardants of the present invention, in second step reaction, adding of tetrahydrofuran (THF) can be used the factors such as total consumption, reactant cumulative volume and dimethylbenzene consumption to adjust according to it, fully mix with reaction system (dissolving the dimethylbenzene system of respond thing and product) with the favourable tetrahydrofuran (THF) that is better than, as: when the less or/and total consumption of tetrahydrofuran (THF) of reactant cumulative volume hour, can select the mode once adding rapidly; Modes such as can selecting once slowly to add, once at the uniform velocity add or repeatedly add in the time of the large or/and total large usage quantity of tetrahydrofuran (THF) of reactant cumulative volume, also can adopt the mode once adding rapidly.The boiling point of dimethylbenzene is 137 ℃-140 ℃, and the boiling point of tetrahydrofuran (THF) is 65.4 ℃.Dimethylbenzene: the weight ratio < of tetrahydrofuran (THF) 1.2: 1 o'clock, the amount of tetrahydrofuran (THF) increases, and mixed solvent is just refluxing below lower than 98 ℃, but causes temperature of reaction on the low side, and speed of response declines; Dimethylbenzene: the weight ratio > of tetrahydrofuran (THF) 2: 1, the amount of tetrahydrofuran (THF) reduces, the boiling point of mixed solvent is higher, cause temperature of reaction higher, speed of response is too fast, the dispersiveness of product in the few mixed solvent of tetrahydrofuran (THF) amount reduces, and easily produces the phenomenons such as caking, is difficult for purifying.Therefore, the weight ratio of the present invention's dimethylbenzene used and tetrahydrofuran (THF) used is 1.2: 1-2: 1, as: but be not limited only to 1.2: 1,1.3: 1,1.4: 1,1.5: 1,1.6: 1,1.7: 1,1.8: 1,1.9: 1 and 2: 1.
The preparation method of response type halogen-free flame retardants of the present invention, the solvent temperature of preferential selective reaction thing DOPO in dimethylbenzene is 65 ℃-90 ℃, the solvent temperature of reactant methylene-succinic acid in the xylene solution of DOPO is 65 ℃-90 ℃.The method can make fully mixing of reactant DOPO and methylene-succinic acid, is easy to stir, and reduces reactant concn, the partial concn of avoiding solid to feed intake causing is too high, has reduced reactive behavior, has solved that solid feeds intake the violent heat-dissipating of reaction and the potential safety hazard that produces.
The preparation method of the above-mentioned various response type halogen-free flame retardantss of the present invention, products therefrom is crude product, also needs just can obtain exquisite product through a follow-up step or some step purifying.A kind of concrete purification process, as: after reaction terminating, shift out immediately product, after cooling and standing, be divided into two-layer, upper strata is the mixed solvent of dimethylbenzene and tetrahydrofuran (THF), lower floor is the thick product of product, thick product process solvent (as: acetone, ethanol or its mixing) washs and is dried and obtains smart product, and gained dimethylbenzene and tetrahydrofuran (THF) mixed solvent also can reuse.In addition, also can reuse after distillation for the solvent (as: acetone, ethanol or its mixing) washing, distill remaining unreacted DOPO and methylene-succinic acid and can reuse equally.These methods are grasped also conventional use by those skilled in the art, or can change according to actual needs, combine or improve.
The product that the preparation method of the above-mentioned various response type halogen-free flame retardantss of the present invention makes, purified after, the structure of gained compound is as follows:
The beneficial effect that technical solution of the present invention realizes:
The preparation method of response type halogen-free flame retardants provided by the invention, adopts the two-step approach of carrying out under different solvents and differing temps to make the DOPO derivative of Itaconic Acid Grafted.The first step reaction is carried out at higher temperature, is beneficial to the quick generation of product, adopts that disposable to add slightly excessive methylene-succinic acid be reactant simultaneously, not only makes reaction carry out more complete, is conducive to improve productive rate, has also greatly shortened the reaction times.Second step adds another kind of solvent---tetrahydrofuran (THF), form mixed solvent with dimethylbenzene, improve the dispersiveness of product, and at lower temperature back flow reaction, mode by cooling not only makes product can be uniformly dispersed in mixed solvent, also avoid the product caking acutely causing because reacting, be unfavorable for the problem of subsequent step processing.
The whole bag of tricks provided by the invention, has not only realized the object of effective reduction energy consumption of reaction and Reaction time shorten, has also improved product yield (more than 95%), and subsequent purification and refining work are more simplified.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the present invention is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in claim scope of the present invention.
If the present invention's reagent used does not clearly indicate, all purchased from Sigma-aldrich (Sigma-Aldrich).
Embodiment 1
In tri-mouthfuls of round-bottomed flasks of 1000ml that stirrer, thermopair and prolong are housed, add 216g DOPO(1.0mol) and 220g dimethylbenzene, in 65 ℃ of insulations until DOPO dissolving, the disposable 140g methylene-succinic acid (1.08mol) that adds wherein again, to methylene-succinic acid after 70 ℃ of dissolvings, temperature of reaction is risen to 120 ℃-130 ℃, react approximately 30 minutes, become after muddiness by clarification gradually until solution; After adding wherein 132g tetrahydrofuran (THF), solution becomes clarification again, temperature is dropped to simultaneously 100 ℃ of-102 ℃ of back flow reaction after approximately 2 hours solution become gradually muddy, again after 2 hours, separate out a large amount of white solid product and obtain the DOPO derivative crude product of Itaconic Acid Grafted.
Shift out while hot product, layering after cooling leaving standstill, upper strata is the mixed solvent of dimethylbenzene and tetrahydrofuran (THF), lower floor is thick product, solvent xylene and tetrahydrofuran (THF) recycling; Thick product is through acetone, washing with alcohol and the dry DOPO derivative essence product that obtains 332.4g Itaconic Acid Grafted.
After testing, (DSC records fusing point to the DOPO derivative that product is Itaconic Acid Grafted: 192 ℃; Results of elemental analyses: C:59.21%; H:4.35%; Theoretical value: C:58.97%, H:4.37%), productive rate is that 96.1%(refers to table 1).
Embodiment 2
In tri-mouthfuls of round-bottomed flasks of 2000ml that stirrer, thermopair and prolong are housed, add 432g DOPO(2.0mol) and 500g dimethylbenzene, in 70 ℃ of insulations until DOPO dissolving, the disposable 278g methylene-succinic acid (2.14mol) that adds wherein again, to methylene-succinic acid after 70 ℃ of dissolvings, temperature of reaction is risen to 120 ℃-130 ℃, react approximately 40 minutes, become after muddiness by clarification gradually until solution; After adding wherein 260g tetrahydrofuran (THF), solution becomes clarification again, temperature is dropped to simultaneously 103 ℃ of-105 ℃ of back flow reaction after approximately 2 hours solution become gradually muddy, again after 2.5 hours, separate out a large amount of white solid product and obtain the DOPO derivative crude product of Itaconic Acid Grafted.
Shift out while hot product, layering after cooling leaving standstill, upper strata is the mixed solvent of dimethylbenzene and tetrahydrofuran (THF), lower floor is thick product, solvent xylene and tetrahydrofuran (THF) recycling; Thick product is through acetone, washing with alcohol and the dry DOPO derivative essence product that obtains 680.7g Itaconic Acid Grafted.
After testing, (DSC records fusing point to the DOPO derivative that product is Itaconic Acid Grafted: 191 ℃; Results of elemental analyses: C:59.21%; H:4.35%; Theoretical value: C:58.97%, H:4.37%), productive rate is that 98.4%(refers to table 1).
Embodiment 3
In tri-mouthfuls of round-bottomed flasks of 1000ml that stirrer, thermopair and prolong are housed, add 216g DOPO(1.0mol) and 300g dimethylbenzene, in 80 ℃ of insulations until DOPO dissolving, the disposable 143g methylene-succinic acid (1.1mol) that adds wherein again, to methylene-succinic acid after 80 ℃ of dissolvings, temperature of reaction is risen to 120 ℃-130 ℃, react approximately 25 minutes, become after muddiness by clarification gradually until solution; After adding wherein 200g tetrahydrofuran (THF), solution becomes clarification again, temperature is dropped to simultaneously 98 ℃ of-101 ℃ of back flow reaction after approximately 2.5 hours solution become gradually muddy, again after 1.5 hours, separate out a large amount of white solid product and obtain the DOPO derivative crude product of Itaconic Acid Grafted.
Shift out while hot product, layering after cooling leaving standstill, upper strata is the mixed solvent of dimethylbenzene and tetrahydrofuran (THF), lower floor is thick product, solvent xylene and tetrahydrofuran (THF) recycling; Thick product is through acetone, washing with alcohol and the dry DOPO derivative essence product that obtains 337.4g Itaconic Acid Grafted.
After testing, (DSC records fusing point to the DOPO derivative that product is Itaconic Acid Grafted: 192 ℃; Results of elemental analyses: C:59.21%, H:4.35%; Theoretical value: C:58.97%, H:4.37%), productive rate is that 97.5%(refers to table 1).
Embodiment 4
In tri-mouthfuls of round-bottomed flasks of 2000ml that stirrer, thermopair and prolong are housed, add 432g DOPO(2.0mol) and 600g dimethylbenzene, in 70 ℃ of insulations until DOPO dissolving, the disposable 286g methylene-succinic acid (2.2mol) that adds wherein again, to methylene-succinic acid after 70 ℃ of dissolvings, temperature of reaction is risen to 120 ℃-130 ℃, react approximately 40 minutes, become after muddiness by clarification gradually until solution; After adding wherein 300g tetrahydrofuran (THF), solution becomes clarification again, temperature is dropped to simultaneously 104 ℃ of-106 ℃ of back flow reaction after approximately 2 hours solution become gradually muddy, again after 2.5 hours, separate out a large amount of white solid product and obtain the DOPO derivative crude product of Itaconic Acid Grafted.
Shift out while hot product, layering after cooling leaving standstill, upper strata is the mixed solvent of dimethylbenzene and tetrahydrofuran (THF), lower floor is thick product, solvent xylene and tetrahydrofuran (THF) recycling; Thick product is through acetone, washing with alcohol and the dry DOPO derivative essence product that obtains 678.2g Itaconic Acid Grafted.
After testing, (DSC records fusing point to the DOPO derivative that product is Itaconic Acid Grafted: 194 ℃; Results of elemental analyses: C:59.21%, H:4.35%; Theoretical value: C:58.97%, H:4.37%), productive rate is that 98.0%(refers to table 1).
Embodiment 5
In tri-mouthfuls of round-bottomed flasks of 1000ml that stirrer, thermopair and prolong are housed, add 216g DOPO(1.0mol) and 400g dimethylbenzene, in 65 ℃ of insulations until DOPO dissolving, the disposable 134g methylene-succinic acid (1.03mol) that adds wherein again, to methylene-succinic acid after 65 ℃ of dissolvings, temperature of reaction is risen to 120 ℃-130 ℃, react approximately 1 hour, become after muddiness by clarification gradually until solution; After adding wherein 220g tetrahydrofuran (THF), solution becomes clarification again, temperature is dropped to simultaneously 101 ℃ of-104 ℃ of back flow reaction after approximately 2 hours solution become gradually muddy, again after 3 hours, separate out a large amount of white solid product and obtain the DOPO derivative crude product of Itaconic Acid Grafted.
Shift out while hot product, layering after cooling leaving standstill, upper strata is the mixed solvent of dimethylbenzene and tetrahydrofuran (THF), lower floor is thick product, solvent xylene and tetrahydrofuran (THF) recycling; Thick product is through acetone, washing with alcohol and the dry DOPO derivative essence product that obtains 330.2g Itaconic Acid Grafted.
After testing, (DSC records fusing point to the DOPO derivative that product is Itaconic Acid Grafted: 192 ℃; Results of elemental analyses: C:59.21%, H:4.35%; Theoretical value: C:58.97%, H:4.37%), productive rate is that 95.4%(refers to table 1).
Embodiment 6
In tri-mouthfuls of round-bottomed flasks of 2000ml that stirrer, thermopair and prolong are housed, add 432g DOPO(2.0mol) and 500g dimethylbenzene, in 70 ℃ of insulations until DOPO dissolving, the disposable 265g methylene-succinic acid (2.04mol) that adds wherein again, to methylene-succinic acid after 70 ℃ of dissolvings, temperature of reaction is risen to 120 ℃-130 ℃, react approximately 1.5 hours, become after muddiness by clarification gradually until solution; After adding wherein 380g tetrahydrofuran (THF), solution becomes clarification again, temperature is dropped to simultaneously 96 ℃ of-100 ℃ of back flow reaction after approximately 2.5 hours solution become gradually muddy, again after 2 hours, separate out a large amount of white solid product and obtain the DOPO derivative crude product of Itaconic Acid Grafted.
Shift out while hot product, layering after cooling leaving standstill, upper strata is the mixed solvent of dimethylbenzene and tetrahydrofuran (THF), lower floor is thick product, solvent xylene and tetrahydrofuran (THF) recycling; Thick product is through acetone, washing with alcohol and the dry DOPO derivative essence product that obtains 657.5g Itaconic Acid Grafted.
After testing, (DSC records fusing point to the DOPO derivative that product is Itaconic Acid Grafted: 192 ℃; Results of elemental analyses: C:59.21%, H:4.35%; Theoretical value: C:58.97%, H:4.37%), productive rate is that 95.0%(refers to table 1).
Table 1
* in form, " existing method " is the research [D] according to unsaturated polyester resin, Guangzhou: South China Science & Engineering University, 2010 technical schemes of recording.
From table 1, method provided by the invention adopts that methylene-succinic acid is disposable to add, and has greatly shortened the reaction times, and each products collection efficiency of gained is also significantly increased.
Claims (5)
1. a preparation method for response type halogen-free flame retardants, comprises that step is as follows:
The first step: reactant DOPO and excessive methylene-succinic acid are dissolved in to dimethylbenzene, in 120 ℃ of-130 ℃ of reactions;
Second step: add tetrahydrofuran (THF), in 96 ℃ of-106 ℃ of back flow reaction, separate out to white solid.
2. the preparation method of response type halogen-free flame retardants according to claim 1, is characterized in that described DOPO and the consumption of methylene-succinic acid are 1: 1.02-1: 1.1, and mol ratio.
3. the preparation method of response type halogen-free flame retardants according to claim 1, is characterized in that the solvent temperature of described DOPO in described dimethylbenzene is 65 ℃-90 ℃.
4. the preparation method of response type halogen-free flame retardants according to claim 1, is characterized in that the solvent temperature of described methylene-succinic acid in described xylene solution is 65 ℃-90 ℃.
5. the preparation method of response type halogen-free flame retardants according to claim 1, the weight ratio of the dimethylbenzene described in it is characterized in that and described tetrahydrofuran (THF) is 1.2: 1-2: 1.
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| CN103980470A (en) * | 2014-06-04 | 2014-08-13 | 青岛科技大学 | Phosphorus-containing flame-retardant alkyd resin and preparation method thereof |
| CN105017514A (en) * | 2015-07-29 | 2015-11-04 | 杭州弘昇科技有限公司 | Halogen-free flame-retardant macromolecular damping spring and preparation method thereof |
| CN105175777A (en) * | 2015-07-25 | 2015-12-23 | 福建师范大学泉港石化研究院 | Phosphorus-nitrogen co-reactive flame retardant used for polyurethane, preparation method therefor and application thereof |
| CN114409842A (en) * | 2022-02-25 | 2022-04-29 | 陕西科技大学 | Acrylate coal flame-retardant dust suppressant and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103980470A (en) * | 2014-06-04 | 2014-08-13 | 青岛科技大学 | Phosphorus-containing flame-retardant alkyd resin and preparation method thereof |
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| CN105175777B (en) * | 2015-07-25 | 2017-10-31 | 福建师范大学泉港石化研究院 | It is a kind of for phosphorus nitrogen concerted reaction type fire retardant of polyurethane and its preparation method and application |
| CN105017514A (en) * | 2015-07-29 | 2015-11-04 | 杭州弘昇科技有限公司 | Halogen-free flame-retardant macromolecular damping spring and preparation method thereof |
| CN114409842A (en) * | 2022-02-25 | 2022-04-29 | 陕西科技大学 | Acrylate coal flame-retardant dust suppressant and preparation method thereof |
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Application publication date: 20140507 |