CN102558605B - Fire retardant, preparation method and applications thereof - Google Patents
Fire retardant, preparation method and applications thereof Download PDFInfo
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- CN102558605B CN102558605B CN2011103986502A CN201110398650A CN102558605B CN 102558605 B CN102558605 B CN 102558605B CN 2011103986502 A CN2011103986502 A CN 2011103986502A CN 201110398650 A CN201110398650 A CN 201110398650A CN 102558605 B CN102558605 B CN 102558605B
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Abstract
The invention is suitable for the technical field of inflaming retarding and provides a fire retardant, a preparation method and application of the fire retardant. The fire retardant has a structural formula as follows. The fire retardant effectively plays a role of inflaming retarding through a fluorine element, simultaneously has high flame retardant rating and mechanical properties through oxazole heterocyclic rings, has no carcinogenicity and cannot pollute the environment. The preparation method of the fire retardant is simple in operation, low in cost and extremely suitable for industrial production.
Description
Technical field
The invention belongs to the flame-retarded technology field, relate in particular to a kind of fire retardant, its preparation method and application.
Background technology
Thermoplastic engineering plastic is applied to the every aspect of people's lives, because compare with materials such as metal, potteries, thermoplastic engineering plastic has a lot of significantly advantages, as strong as the resistance to corrosion of most of plastics, with most acid, alkali, does not react; Light weight; Waterproof durable; Tooling cost is low; It is good insulating body; Can be processed into different shapes; Recyclable recycling, environmental protection.But thermoplastic engineering plastic has inflammable shortcoming, limited its further widespread use
Press the burning grade of UL94 criteria thermoplastic engineering plastic, only have minimum HB level before modification, by the burning grade that improves plastics, arrive the V0 level, can improve on a large scale the Application Areas of plastics.Plastics often are accompanied by the molten drop phenomenon in combustion processes, in order to improve this problem, need to improve the consumption of conventional flame retardants (bromine system and antimonous oxide) in flame-retardant modified process, not only increased cost, reduced the mechanical property of material, returned environment and brought serious pollution.
Molten drop occurring when fluoropolymer can effectively prevent Plastics Combustion as fire retardant, because fluorochemicals adds in the polymkeric substance body, can improve melt strength, avoided melting vertical, helps plastics to reach higher fire-retardant rank.At present, fluorine-containing fire retardant general on market mostly is surface-treated ptfe micropowder, and tetrafluoroethylene polarity is low, in the resin that much polarity is stronger, consistency is poor, easily agglomerating, in addition, one of raw material of production tetrafluoroethylene ammonium perfluorocaprylate (PFOA) has carcinogenic possibility.
Summary of the invention
The object of the present invention is to provide a kind of fire retardant, solve in prior art fluorine-containing fire retardant and the plastic polymer compatibility performance is poor, the technical problem of contaminate environment; And, this fire retardant preparation method and application.
The present invention is achieved in that
A kind of fire retardant has following structural formula I:
Wherein, X is halogens.
And,
Above-mentioned fire retardant preparation method, comprise the steps:
Provide respectively structural formula to be
Compd A and structural formula be
Compd B;
The compd A that is 2.05～2.1: 1 by mol ratio and compd B are added in the PPA solvent, at oxygen free condition and temperature, are to react 9 hours～12 hours under 185 ℃～195 ℃ conditions, obtain the fire retardant of structural formula I, and structural formula I is:
The present invention further provides the application of above-mentioned fire retardant in engineering plastics.
Fire retardant of the present invention, by fluorine element, effectively play fire retardation; Tong Guo oxazole heterocycle makes it have higher flame retardant rating and mechanical property simultaneously, and this fire retardant does not have carinogenicity, free from environmental pollution.Fire retardant preparation method of the present invention, simple to operate, with low cost, be very suitable for suitability for industrialized production.
The accompanying drawing explanation
Fig. 1 is the fire retardant infrared spectrogram of the embodiment of the present invention one preparation;
Fig. 2 is the fire retardant nuclear magnetic spectrogram of the embodiment of the present invention one preparation.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of fire retardant, has following structural formula I:
Wherein, X is halogens, for example, and fluorine, chlorine, bromine or iodine.
In this fire retardant, contain fluorine element or/and other halogenss, wherein fluorine element content is high, can play very excellent flame retardant properties; Further, go back Bao Kuo You oxazole heterocycle in this fire retardant, nitrogen element wherein not only has anti-flaming function, also can and polymeric system (be applied to engineering plastics after polymkeric substance) in hydrogen atom to form hydrogen bond crosslinked, and then improved the consistency of fire retardant and polymkeric substance, make the engineering plastics containing this fire retardant of preparation there is higher flame retardant rating and mechanical property simultaneously.
The embodiment of the present invention further provides the preparation method of above-mentioned fire retardant, comprises the steps:
Step S01, supply raw materials:
Provide respectively structural formula to be
Compd A and structural formula be
Compd B;
Step S02, dehydration reaction:
The compd A that is 2.05～2.1: 1 by mol ratio and compd B are added in the PPA solvent, at oxygen free condition and temperature, are to react 9～12 hours under 185～195 ℃ of conditions, obtain the fire retardant of structural formula I, and structural formula I is:
Particularly, in step S01, the name of compd A is called 4 '-halogenated benzoic acid (4-XBA), for example, fluorinated acid, Chlorobenzoic Acid, bromobenzoic acid or iodobenzoic acid, compd A can be from buying and obtain on the market.The name of compd B is called two (3-amino-4-hydroxyphenyl) HFC-236fa (6F-BAHP), and compd B can be from buying and obtain on the market.
Particularly, in step S02, the mol ratio of this compd A and compd B is 2.05～2.1: 1, is preferably 2: 1.
Particularly, this PPA solvent refers to poly phosphoric acid solution, and in this poly phosphoric acid solution, the weight percentage of Vanadium Pentoxide in FLAKES is 85%～90%.The concentration of the available poly phosphoric acid solution of purchasing is less than above-mentioned concentration on the market, above-mentioned weight percentage is by adding the Vanadium Pentoxide in FLAKES solid in poly phosphoric acid solution, be heated to again thickly by oil bath etc., make Vanadium Pentoxide in FLAKES fully be dissolved in poly phosphoric acid solution and obtain.
Particularly, in step S02, the reaction of compd A and compd B is carried out under oxygen free condition, and this oxygen free condition is restriction not, for example, by reactor, passing into nitrogen, makes reactor keep oxygen-free environment.In this step, temperature of reaction is 185 ℃～195 ℃, and for example, 190 ℃, the reaction times is 9 hours～12 hours, for example 10 hours.The reaction formula of step S02 is expressed as:
Further, after reaction finishes, liquid cooling after reacting, stopped reaction.Deionized water is injected in reactor to the solid product that obtains grey black, hot-water soak, flushing are until leacheate is neutrality.Obtain white product after activated carbon decolorizing, recrystallization, vacuum-drying, i.e. the fire retardant of structural formula I.
Embodiment of the present invention fire retardant preparation method, by dehydration reaction, reacted compd A and compd B, obtains the fire retardant of structural formula I, realized this fire retardant grade and mechanical property, and this fire retardant does not have carinogenicity, free from environmental pollution.Fire retardant preparation method of the present invention, simple to operate, with low cost, be very suitable for suitability for industrialized production.
The embodiment of the present invention further provides the application of above-mentioned fire retardant in engineering plastics.For example, this fire retardant is applied in polycarbonate engineering plastic, obtains the polycarbonate engineering plastic that contains this fire retardant.
Below in conjunction with specific embodiment, above-mentioned fire retardant preparation method is described in detail.
Embodiment mono-
The embodiment of the present invention one fire retardant preparation method, comprise the steps:
Provide respectively structural formula to be
Compd A and structural formula be
Compd B;
To the PPA and the 21g P that add 62.7g80% in the 250ml reactor that mechanical stirring, nitrogen inlet/outlet are housed
2O
5As the mixed solvent of reaction, P in mixed solvent
2O
5Solid content be 85%, reactor is placed in to the oil bath of 170 ℃, start stirring, make solid P
2O
5Well be dissolved in PPA and obtain the very solvent system of thickness, cool to room temperature, 2.8g (20.0mmol) 4-FBA and 3.7g (10mmol) 6F-BAHP are joined in reactor, at room temperature rouse nitrogen 15min to get rid of the air in flask, temperature is adjusted to 190 ℃ afterwards, lower reaction 10 hours, cooling, stopped reaction.Deionized water is injected in reaction flask to the solid product that obtains grey black, hot-water soak, flushing are until leacheate is neutrality.Obtain white product after activated carbon decolorizing, recrystallizing methanol, vacuum-drying, i.e. the fire retardant of structural formula I.Productive rate 96%.
Products therefrom has been carried out to structural characterization, has comprised infrared spectra,
1H nuclear-magnetism spectrum, prove and successfully synthesize the purpose product.
Please refer to Fig. 1, Fig. 1 shows the infrared spectrogram of the material that the embodiment of the present invention one is prepared, as can be seen from Figure 1, and in Fig. 1 1566 and 964cm
-1The place the other Dui Ying of absorption peak Fen Yu oxazole ring on-C=N and-the C-O absorption peak.
Please refer to Fig. 2, Fig. 2 shows the nmr spectrum of the material that the embodiment of the present invention one is prepared, and as can be seen from Figure 2, this compound has 5 kinds of different hydrogen protons, due to the impact of fluorine atom, comparatively complicated split minute appearred in the hydrogen proton (H1) that is adjacent.Concrete ownership shows in diagram that.
1H?NMR(CDCl
3)：8.27-8.22(m，4H)，7.92(s，2H)，7.58-7.50(d，2H)，7.42-7.35(d，2H)，7.25-7.20(m，4H)。
Can show that from Fig. 1 and Fig. 2 embodiment of the present invention fire retardant preparation method has prepared the fire retardant of structural formula I.
Embodiment bis-
The embodiment of the present invention two fire retardant preparation methods, comprise the steps:
Provide respectively structural formula to be
Compd A and structural formula be
Compd B;
To the PPA and the 30g P that add 61g 80% in the 400ml reactor that mechanical stirring, nitrogen inlet/outlet are housed
2O
5As the mixed solvent of reaction, P in mixed solvent
2O
5Solid content be 86%, reactor is placed in to the oil bath of 170 ℃, start stirring, make solid P
2O
5Well be dissolved in PPA and obtain the very solvent system of thickness, cool to room temperature, 3.1g (20.0mmol) 4-ClBA and 3.7g (10mmol) 6F-BAHP are joined in reactor, at room temperature rouse nitrogen 15min to get rid of the air in flask, afterwards, temperature is adjusted under 190 ℃, reacts 10 hours, cooling, stopped reaction.
Deionized water is injected in reaction flask to the solid product that obtains grey black, hot-water soak, flushing are until leacheate is neutrality.Obtain white product after activated carbon decolorizing, ethyl alcohol recrystallization, vacuum-drying, productive rate 96%.Products therefrom has been carried out to structural characterization, has comprised infrared spectra,
1H nuclear-magnetism spectrum, prove and successfully synthesize the purpose product.
The infrared spectra of the material that the embodiment of the present invention two is prepared is similar with embodiment mono-with nmr spectrum, at this, does not repeat to set forth.
Embodiment tri-
The embodiment of the present invention three fire retardant preparation methods, comprise the steps:
Provide respectively structural formula to be
Compd A and structural formula be
Compd B;
To the PPA and the 60g P that add 80g80% in the 500ml reactor that mechanical stirring, nitrogen inlet/outlet are housed
2O
5As the mixed solvent of reaction, P in mixed solvent
2O
5Solid content be about 89%, reactor is placed in to the oil bath of 170 ℃, start stirring, make solid P
2O
5Well be dissolved in PPA and obtain the very solvent system of thickness, cool to room temperature, 16.0g (80.0mmol) 4-BrBA and 14.8g (40mmol) 6F-BAHP are joined in reactor, at room temperature rouse nitrogen 15min to get rid of the air in flask, afterwards, temperature is adjusted under 190 ℃ and reacts 10 hours, cooling, stopped reaction.
Deionized water is injected in reaction flask to the solid product that obtains grey black, hot-water soak, flushing are until leacheate is neutrality.Obtain white product after activated carbon decolorizing, propyl alcohol recrystallization, vacuum-drying, productive rate 96%.
The infrared spectra of the material that the embodiment of the present invention three is prepared is similar with embodiment mono-with nmr spectrum, at this, does not repeat to set forth.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. a fire retardant has following structural formula I:
Wherein, X is halogens.
2. fire retardant as claimed in claim 1, is characterized in that, described halogens is selected from fluorine, chlorine, bromine or iodine.
3. the preparation method of fire retardant as claimed in claim 1, comprise the steps:
Provide respectively structural formula to be
Compd A and structural formula be
Compd B;
The compd A that is 2.05～2.1:1 by mol ratio and compd B are added in the PPA solvent, at oxygen free condition and temperature, are to react 9 hours～12 hours under 185 ℃～195 ℃ conditions, obtain the fire retardant of structural formula I, and the structural formula I is
Wherein, X is halogens, and described PPA solvent is poly phosphoric acid solution, and in described poly phosphoric acid solution, the weight percentage of Vanadium Pentoxide in FLAKES is 85%～90%.
4. fire retardant preparation method as claimed in claim 3, is characterized in that, described halogens is selected from fluorine, chlorine, bromine or iodine.
5. fire retardant preparation method as described as claim 3 or 4, is characterized in that, P in described PPA solvent
2O
5The quality percentage composition be 85%～90%.
6. fire retardant preparation method as claimed in claim 5, is characterized in that, also comprises the recrystallization purifying step, and in described recrystallization purifying step, recrystallization reagent is methyl alcohol, ethanol, propyl alcohol, butanols or its mixing solutions.
7. the application of fire retardant as claimed in claim 1 or 2 in engineering plastics.
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| CN102558605B true CN102558605B (en) | 2013-12-04 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323664A (en) * | 2008-07-24 | 2008-12-17 | 上海交通大学 | Preparation of polybenzoxazole |
| CN101333335A (en) * | 2008-03-28 | 2008-12-31 | 华德塑料制品有限公司 | Nylon composite material modified by poly(p-phenylenebenzobisoxazole) and method for preparing same |
| CN101389684A (en) * | 2006-03-28 | 2009-03-18 | 株式会社艾迪科 | Curable epoxy resin composition |
| CN102250117A (en) * | 2011-05-11 | 2011-11-23 | 华东理工大学 | Dibenzoxazine containing oxazole ring and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101389684A (en) * | 2006-03-28 | 2009-03-18 | 株式会社艾迪科 | Curable epoxy resin composition |
| CN101333335A (en) * | 2008-03-28 | 2008-12-31 | 华德塑料制品有限公司 | Nylon composite material modified by poly(p-phenylenebenzobisoxazole) and method for preparing same |
| CN101323664A (en) * | 2008-07-24 | 2008-12-17 | 上海交通大学 | Preparation of polybenzoxazole |
| CN102250117A (en) * | 2011-05-11 | 2011-11-23 | 华东理工大学 | Dibenzoxazine containing oxazole ring and preparation method thereof |
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Effective date of registration: 20171228 Address after: 241000 Anhui city of Wuhu Province Economic and Technological Development Zone Dong Liang Road No. 9 Patentee after: Polymer Science (Anhui) New Material Co., Ltd. Address before: Two, C2, A19, 518103 Bridge Fu Qiao third industrial zone, Fuyong street, Baoan District, Guangdong, Shenzhen, China Patentee before: Shenzhen Keju New Material Co., Ltd. |
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