CN102653593A - Preparation method of nitrogen-phosphorus composite flame retardant - Google Patents
Preparation method of nitrogen-phosphorus composite flame retardant Download PDFInfo
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- CN102653593A CN102653593A CN2012101210065A CN201210121006A CN102653593A CN 102653593 A CN102653593 A CN 102653593A CN 2012101210065 A CN2012101210065 A CN 2012101210065A CN 201210121006 A CN201210121006 A CN 201210121006A CN 102653593 A CN102653593 A CN 102653593A
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- tetramethylolmethane
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Abstract
The invention relates to a preparation method of a nitrogen-phosphorus composite flame retardant, and the preparation method comprises the following steps of: after phosphoric acid is preheated, slowly adding pentaerythritol into the preheated phosphoric acid, carrying out reaction at high temperature for a while, then adding a water solution into the product of the reaction, slowly adding aniline into the mixed solution, and continuously carrying out reaction at high temperature; then cooling to the room temperature, filtering, removing filtrate, so as to obtain a leached solid matter; cleaning the obtained leached solid matter by use of alcohol so as to remove excess aniline and pentaerythritol; and leaching again, and drying, so as to obtain the nitrogen-phosphorus composite flame retardant. The nitrogen-phosphorus composite flame retardant is good in flame retardant property and free from halogen, can be used for producing a wood-plastic composite material and manufacturing products of the wood-plastic composite material, and belongs to the technical field of halogen-free flame retardant.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen phosphorus compound flame retardant, this fire retardant mainly is used in the manufacturing of production and goods thereof of Wood-plastic material, belongs to the halogen-free flame retardants technical field.
Technical background
Wood plastic composite is to be main raw material with wood chip, rice chaff and waste or used plastics etc., handles a kind of basic material of post-treatment moulding through special process, and its product is mainly as the substitute of timber.The pressure that the exploitation Wood-plastic material was becoming tight for comprehensive utilization of waste materials, environment protection and alleviation natural timber day all has crucial meaning, thereby has received global extensive attention.But even so, main raw material plant fiber powder in the wood plastic composite and plastics all are inflammable materials, so wood plastic composite do not possess flame retardant resistance, have security against fire hidden danger.Need the application scenario of fire-retardant fireproof for some, common wood plastic composite is also inapplicable.Thereby in recent years, the flame retardant resistance of wood plastic composite more and more receives people's attention.The invention BACN, it is very necessary to improve the wood plastic composite flame retardant properties, becomes inexorable trend of current wood plastic composite research field.
The fire retardant kind is numerous; Wherein a kind of important fire retardant is halogen-containing compound; This based flame retardant has good flame-retardant effect when material combustion, but can produce a large amount of smog and toxic gas, and it is applied in many occasions and is restricted: and halogen-free flame retardants can overcome above-mentioned deficiency.In halogen-free flame retardants commonly used, it is better to the plastics flame retardant effect to contain MOX such as Mg, Al or oxyhydroxide, but usage quantity is generally bigger; For wood plastic composite,, thereby be not easy to add again MOX or oxyhydroxide fire retardants such as a large amount of Mg, Al because the content of plant fiber powder wherein and other fillers is higher; If a large amount of the use; Both increased technology difficulty, especially the bending property negative impact is bigger to material mechanical performance simultaneously, so seldom adopt.
Summary of the invention
The objective of the invention is provides a kind of nitrogen phosphorus compound flame retardant and preparation method thereof to above-mentioned weak point: select phosphoric acid, tetramethylolmethane and aniline monomer generation copolyreaction for use; Select the unnecessary monomer of solvent flush away with low cost for use, preparation has good flame-retardance ability, Halogen, is specially adapted to the fire retardant of flame-retardant wood-plastic composite material.
For realizing that the technical scheme that the object of the invention adopts is: utilize not halogen-containing phosphoric acid, tetramethylolmethane and aniline monomer; Make its polymerization reaction take place under suitable condition; Select the unnecessary monomer of solvent flush away with low cost for use, thus prepare have good flame-retardance can, the fire retardant of composite, the Halogen of nitrogen phosphorus.
A kind of preparation method of nitrogen phosphorus compound flame retardant takes following scheme to realize:
In the 250ml there-necked flask, add 15～25g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 10～20min, slowly add 13～16g tetramethylolmethane; 100 ℃ are reacted 2～3h down, add the aqueous solution of 20～40mL, slowly add 7～11g aniline again; Continue reaction 3～5h down at 100 ℃, be cooled to room temperature then, filter; Remove filtrating, obtain solid and leach thing, divide 2～4 cleaning solids to leach thing with 50～100mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment
Following embodiment is to further specify of the present invention, rather than limits scope of the present invention.
Embodiment 1:
In the 250ml there-necked flask, add 15g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 10min, slowly add the 13g tetramethylolmethane, 100 ℃ are reacted 2h down; Add the aqueous solution of 20mL, slowly add 7g aniline again, continue reaction 3h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 2 cleaning solids to leach thing with 50mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment 2:
In the 250ml there-necked flask, add 25g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 20min, slowly add the 16g tetramethylolmethane, 100 ℃ are reacted 3h down; Add the aqueous solution of 40mL, slowly add 11g aniline again, continue reaction 5h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 4 cleaning solids to leach thing with 100mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment 3:
In the 250ml there-necked flask, add 20g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 15min, slowly add the 14.5g tetramethylolmethane, 100 ℃ are reacted 2.5h down; Add the aqueous solution of 30mL, slowly add 9g aniline again, continue reaction 4h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 3 cleaning solids to leach thing with 75mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment 4:
In the 250ml there-necked flask, add 15g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 15min, slowly add the 16g tetramethylolmethane, 100 ℃ are reacted 2h down; Add the aqueous solution of 30mL, slowly add 11g aniline again, continue reaction 3h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 4 cleaning solids to leach thing with 75mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment 5:
In the 250ml there-necked flask, add 20g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 20min, slowly add the 13g tetramethylolmethane, 100 ℃ are reacted 2.5h down; Add the aqueous solution of 40mL, slowly add 7g aniline again, continue reaction 4h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 2 cleaning solids to leach thing with 100mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment 6:
In the 250ml there-necked flask, add 25g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 10min, slowly add the 14.5g tetramethylolmethane, 100 ℃ are reacted 3h down; Add the aqueous solution of 20mL, slowly add 9g aniline again, continue reaction 4.5h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 3 cleaning solids to leach thing with 50mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment 7:
In the 250ml there-necked flask, add 15g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 10min, slowly add the 13g tetramethylolmethane, 100 ℃ are reacted 3h down; Add the aqueous solution of 40mL, slowly add 11g aniline again, continue reaction 5h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 4 cleaning solids to leach thing with 50mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment 8:
In the 250ml there-necked flask, add 25g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 20min, slowly add the 16g tetramethylolmethane, 100 ℃ are reacted 2h down; Add the aqueous solution of 20mL, slowly add 7g aniline again, continue reaction 4h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 3 cleaning solids to leach thing with 75mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Embodiment 9:
In the 250ml there-necked flask, add 18g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 16min, slowly add the 15g tetramethylolmethane, 100 ℃ are reacted 2.6h down; Add the aqueous solution of 35mL, slowly add 10g aniline again, continue reaction 4.5h down, be cooled to room temperature then at 100 ℃; Filter, remove filtrating, obtain solid and leach thing, divide 2 cleaning solids to leach thing with 80mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
Below detect the effect of the proof embodiment of the invention 1 through test, its detected result is following:
Get 50g exsiccant wood powder, 40g high density polyethylene(HDPE), 10g maleic anhydride grafted polyethylene and 20g nitrogen phosphorus compound flame retardant; Behind the calendering mixing; Be molded into sheet material, detect its MOR and flame retardant effect, MOR: 34.56MPa; Limiting oxygen index(LOI): 28.2 (%), testing vertical flammability reaches the FV-0 level.
Above result shows that nitrogen phosphorus compound flame retardant of the present invention has tangible flame retardant properties to wood plastic composite, and the MOR of gained wood plastic composite obviously surpasses the requirement of the forestry industry standard LY/T 1613-2004 of the People's Republic of China.
Claims (1)
1. the preparation method of a nitrogen phosphorus compound flame retardant is characterized in that:
In the 250ml there-necked flask, add 15～25g phosphoric acid (mass concentration 80%), behind 100 ℃ of following preheating 10～20min, slowly add 13～16g tetramethylolmethane; 100 ℃ are reacted 2～3h down, add the aqueous solution of 20～40mL, slowly add 7～11g aniline again; Continue reaction 3～5h down at 100 ℃, be cooled to room temperature then, filter; Remove filtrating, obtain solid and leach thing, divide 2～4 cleaning solids to leach thing with 50～100mL ethanol; Aniline that flush away is wherein unnecessary and tetramethylolmethane, suction filtration, drying obtain a kind of nitrogen phosphorus compound flame retardant once more.
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| CN2012101210065A CN102653593B (en) | 2012-04-24 | 2012-04-24 | Preparation method of nitrogen-phosphorus composite flame retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101575351A (en) * | 2009-05-30 | 2009-11-11 | 山东天一化学有限公司 | Method for preparing phosphorus-nitrogen expanding fire retardant |
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| CN101575351A (en) * | 2009-05-30 | 2009-11-11 | 山东天一化学有限公司 | Method for preparing phosphorus-nitrogen expanding fire retardant |
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Effective date of registration: 20160106 Address after: 510000 longan cave, Tianhe District, Guangdong, Guangzhou, Shahe Patentee after: Guangdong forestry science and Technology Development Co.,Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Patentee before: Nanjing Forestry University |
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Granted publication date: 20130925 |