CN105153468B - A kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems and preparation method thereof - Google Patents

A kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems and preparation method thereof Download PDF

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CN105153468B
CN105153468B CN201510654283.6A CN201510654283A CN105153468B CN 105153468 B CN105153468 B CN 105153468B CN 201510654283 A CN201510654283 A CN 201510654283A CN 105153468 B CN105153468 B CN 105153468B
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montmorillonite
silicon systems
flame
nitrogen silicon
phosphorus nitrogen
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CN105153468A (en
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黄国波
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Taizhou University
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Abstract

The present invention relates to a kind of fire retardant, more particularly to a kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems and preparation method thereof.A kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems, the phosphorus nitrogen silicon systems compound and montmorillonite powder particle that the fire retardant is made of silane coupling agent, the phosphorous chloride compounds of amino-contained are made by solid state shear pulrerizing, and phosphorus nitrogen silicon systems compound is grafted by chemical bond in montmorillonite.In the preparation process of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems of the present invention, the amino of silane coupling agent is reacted with phosphoryl chloride phosphorus oxychloride generates byproduct hydrogen chloride gas, part takes reaction system out of by nitrogen, catalyst of the part as silane coupling agent and montmorillonite surface hydroxyl condensation reaction, so that silane coupling agent is passed through solid phase reaction and is grafted to montmorillonite surface, be conducive to the raising that solid phase connects reaction rate, shorten the reaction time.

Description

A kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems and preparation method thereof
Technical field
The present invention relates to a kind of fire retardant, more particularly to the compound loaded montmorillonite flame-retardant agent of a kind of phosphorus nitrogen silicon systems and its system Preparation Method.
Background technology
Montmorillonite has that flame retarding efficiency is high, additive amount is low, Halogen is less toxic, environmental-friendly etc. as a kind of flame-retardant additive Advantage is modified field in flame retardance of polymer and has broad application prospects.With deepening continuously for composite technology research, more Carry out more polymer-montmorillonoid composite materials as high-performance, multi-functional fire proofing, electronic apparatus, aerospace, There is more and more extensive purposes in building, automobile and other industries.Halogen-free flame retardants --- organic phosphorus-nitrogen compound has few cigarette, low The advantages such as poison, hydrolysis, stability is good, montmorillonite/polymer composites are the fire proofings of a kind of " environmentally protective ", with biography System filled polymer is compared, and has many advantages, such as that dosage is few, at low cost, flame-retarded efficiency is high, smoke amount is few.In conjunction with the advantage of the two, Can realize the organophosphor nitrogen silicon systems compound of organ-mmt by MOLECULE DESIGN and synthesizing, the compound and montmorillonite into Line unit connection reaction, obtains NEW TYPE OF COMPOSITE fire retardant --- the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems.
Organic modification is carried out to montmorillonite using phosphorus nitrogen silicon systems compound, improve montmorillonite and is enriched with the swollen of its surface Swollen type fire retardant reduces the migration for the fire retardant small molecule for being anchored at montmorillonite surface in the dispersibility of polymeric matrix, So that montmorillonite and fire retardant is preferably played synergistic effect, is conducive to realize high molecular fire retardant material under the premise of few additive High performance etc..However, in the preparation of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems, since montmorillonite is inorganic chemical Object, disperses very poor in organic solvent, and a large amount of organic solvent need to be added and just can guarantee being smoothed out for reaction, is needed after reaction pair Organic solvent is distilled to recover, and energy consumption is very big, of high cost, is unfavorable for industrialized production.Phosphorus is synthesized using solid state shear pulrerizing The compound loaded montmorillonite flame-retardant agent of nitrogen silicon systems not only enormously simplifies synthesis technology, but also the low, energy consumption with reaction cost The advantages such as small, solvent-free provide a kind of new approach to solve the problems, such as that above-mentioned fire retardant preparation exists.
Invention content
The purpose of the present invention is to provide a kind of a kind of compound loaded cover of phosphorus nitrogen silicon systems with excellent flame retardant performance to take off Native fire retardant.
The present invention also provides the preparation methods of the compound loaded montmorillonite flame-retardant agent of the phosphorus nitrogen silicon systems.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems, the fire retardant be by amino-contained silane coupling agent, contain The phosphorus nitrogen silicon systems compound of phosphinylidyne chlorine compound composition is made with montmorillonite powder particle by solid state shear pulrerizing, phosphorus nitrogen silicon systems Compound is grafted by chemical bond in montmorillonite.
A kind of preparation method of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems, by the silane coupled of amino-contained The compound loaded montmorillonite of phosphorus nitrogen silicon systems is made by solid state shear pulrerizing in agent, phosphorous chloride compounds and montmorillonite powder particle Fire retardant.Further, the silane coupling agent of amino-contained and phosphorous chloride compounds, montmorillonite are added in ball mill, It is ground 20~150 minutes under conditions of logical nitrogen, the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems is made.
Preferably, the mass ratio that feeds intake of the silane coupling agent of the montmorillonite and amino-contained is 1.0:0.02~ 0.38, the amount ratio of the substance that feeds intake of the silane coupling agent of the amino-contained and phosphorous chloride compounds is 1.0:1.0~2.5.
Preferably, the silane coupling agent of the amino-contained is selected from one of the following:N- aminoethyls-γ-aminopropyl front three Oxysilane, 3- (2- aminoethyls base) propyl-triethoxysilicane, 3- aminopropyl trimethoxysilanes, three ethoxy of 3- aminopropyls Base silane.
Preferably, the phosphorous chloride compounds are selected from one of the following:Solutions of dimethyl phosphoryl chlorine, diethylchlorophosphate, Diphenyl phosphoryl chlorine.
Preferably, in the preparation process condition, 21.7~38 revs/min of balling drum rotating speed is passed through nitrogen Flow velocity rate is 0.1~20 cubic meters per minute.
Application of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems in terms of preparing flame retardant composite material a kind of described in, It is in terms of 100% by the weight of thermoplastic, the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems is in thermoplastic Additive amount is 5%~30%.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects:
1, in the preparation process of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems of the present invention, silane coupling agent Amino is reacted with phosphoryl chloride phosphorus oxychloride generates byproduct hydrogen chloride gas, partly takes reaction system out of by nitrogen, is partly used as silane even The catalyst for joining agent and montmorillonite surface hydroxyl condensation reaction, makes silane coupling agent pass through solid phase reaction and is grafted to montmorillonite table Face is conducive to the raising that solid phase connects reaction rate, shortens the reaction time;
2, the preparation method of fire retardant of the present invention uses solid-phase sequencing reaction, not only simplifies synthesis technology Route, and the discharge for reducing reaction cost, reducing energy consumption and pollutant;
3, the preparation method of fire retardant of the present invention utilizes solid state shear pulrerizing, and it is negative to be conducive to phosphorus nitrogen silicon systems compound It is loaded in montmorillonite surface, while improving its dispersibility, flame retardant effect of the fire retardant to high molecular material is enhanced, reduces fire-retardant Agent reduces the manufacturing cost of fire proofing in the usage amount of high molecular material;
4, fire retardant preparation process of the present invention is easy to operate, and process route is simple, manufacturing cost is cheap, green ring It protects and low energy consumption, products therefrom is easy to industrialized production without separation.
Specific implementation mode
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.It should be appreciated that this hair Bright implementation is not limited to the following examples, and the accommodation in any form made to the present invention and/or changed will all be fallen Enter the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc. It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field Rule method.
Embodiment 1
1500 kilograms of montmorillonites are added in the ball mill for being connected with nitrogen access tube, ball mill specification be Ф 900 × 1800, ball load is 1.5 tons, under conditions of 38 revs/min of balling drum rotating speed, is separately added into 150 kilograms of 3- aminopropyls Trimethoxy silane and 175 kilograms of diphenyl phosphoryl chlorine are ground under the conditions of being passed through nitrogen stream rate and being 0.5 cubic meters per minute Mill reaction 40 minutes, is made the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems, yield 97.9%.
Embodiment 2
With embodiment 1, raw material is the synthetic operation of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems:Montmorillonite, N- ammonia Ethyl-γ-aminopropyltrimethoxysilane, solutions of dimethyl phosphoryl chlorine.The addition of montmorillonite is 38000 kilograms, montmorillonite and N- The mass ratio that feeds intake of aminoethyl-γ-aminopropyltrimethoxysilane is 1.0:0.02, N- aminoethyl-γ-aminopropyl trimethoxy The amount ratio of silane and the substance that feeds intake of solutions of dimethyl phosphoryl chlorine is 1.0:2.5, ball mill specification is Ф 2200 × 7500, and ball load is 35 tons, 21.7 revs/min of drum rotation speed, milling time is 20 minutes, and it is 0.1 cubic meters per minute, yield to be passed through nitrogen stream rate It is 99.1%.
Embodiment 3
With embodiment 1, raw material is the synthetic operation of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems:Montmorillonite, 3- (2- Aminoethyl base) propyl-triethoxysilicane, diethylchlorophosphate.The addition of montmorillonite is 4500 kilograms, montmorillonite and 3- The mass ratio that feeds intake of (2- aminoethyls base) propyl-triethoxysilicane is 1.0:0.38,3- (2- aminoethyls base) propyl, three second The amount ratio of the substance that feeds intake of oxysilane and diethylchlorophosphate is 1.0:2.2, ball mill specification is Ф 1500 × 3000, fills ball Amount is 7.5 tons, and 29.7 revs/min of drum rotation speed, milling time is 150 minutes, and it is 20 cubes ms/min to be passed through nitrogen stream rate Clock, yield 97.3%.
Embodiment 4
With embodiment 1, raw material is the synthetic operation of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems:Montmorillonite, N- ammonia Ethyl-γ-aminopropyltrimethoxysilane, diphenyl phosphoryl chlorine.The addition of montmorillonite is 4500 kilograms, montmorillonite and N- The mass ratio that feeds intake of aminoethyl-γ-aminopropyltrimethoxysilane is 1.0:0.14, N- aminoethyl-γ-aminopropyl trimethoxy The amount ratio of silane and the substance that feeds intake of diphenyl phosphoryl chlorine is 1.0:2.3, ball mill specification is Ф 1500 × 3000, ball load It it is 7.5 tons, 29.7 revs/min of drum rotation speed, milling time is 60 minutes, and it is 12 cubic meters per minutes to be passed through nitrogen stream rate, is received Rate is 98.3%.
Embodiment 5
With embodiment 1, raw material is the synthetic operation of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems:Montmorillonite, 3- ammonia Propyl-triethoxysilicane, diethylchlorophosphate.The addition of montmorillonite is 1200 kilograms, montmorillonite and three ethoxy of 3- aminopropyls The mass ratio that feeds intake of base silane is 1.0:The amount of the substance that feeds intake of 0.22,3- aminopropyl triethoxysilane and diethylchlorophosphate Than being 1.0:1.25, ball mill specification is Ф 900 × 1800, and ball load is 1.5 tons, 36 revs/min of drum rotation speed, milling time It it is 45 minutes, it is 6.7 cubic meters per minutes, yield 98.6% to be passed through nitrogen stream rate.
Embodiment 6:The application of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems
The preparation manipulation of the compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems is the same as embodiment 1.120 kg polypropylene is (molten Melt index be 2.3 grams/10 minutes, producer be Yangtze petrochemical industry) and 15 kilograms of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems put Enter dispersion machine to stir 20 minutes, by said mixture after taking-up, by screw extruder (processing temperature ranging from 180~210 DEG C) extruding pelletization, the compound loaded montmorillonite flame-retardant agent composite material of polypropylene/phosphorus nitrogen silicon systems is obtained, cone calorimetry measures The results are shown in Table 1 for the fire-retardant performance of the composite material.
Table 1
Note:Polypropylene/organic montmorillonite fire-retardant composite material:Organo montmorillonite is 8 with polyacrylic mass ratio:1, have Machine montmorillonite is the montmorillonite of cetyl trimethylammonium bromide organic-treating, cetyl trimethylammonium bromide and montmorillonite Mass ratio is 25:3;The compound loaded montmorillonite flame-retardant agent composite material of polypropylene/phosphorus nitrogen silicon systems:Phosphorus nitrogen silicon systems are compound loaded Montmorillonite flame-retardant agent is 8 with polyacrylic mass ratio:1, phosphorus nitrogen silicon systems compound is 25 with montmorillonite mass ratio:3.
By table 1 it is found that compared with pure polypropylene, be added to the polypropylene of the compound loaded montmorillonite of phosphorus nitrogen silicon systems/ The heat release rate peak value of the compound loaded montmorillonite flame-retardant agent composite material of phosphorus nitrogen silicon systems reduces 56%, and burning time extends About 7 seconds, hot total volume, specific extinction area average, mass loss Mean Speed had different degrees of decline, show phosphorus nitrogen The compound loaded montmorillonite of silicon systems can effectively improve polyacrylic flame retardant property, and its to polyacrylic fire retardation better than similar Flame retardant products organo montmorillonite.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form Limitation, on the premise of not exceeding the technical scheme recorded in the claims also other variations and modifications.

Claims (3)

1. a kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems, it is characterised in that:The fire retardant, which is that there are as below methods, to be made: 1500 kilograms of montmorillonites are added in the ball mill for being connected with nitrogen access tube, ball mill specification is Ф 900 × 1800, ball load It is 1.5 tons, under conditions of 38 revs/min of balling drum rotating speed, is separately added into 150 kilograms of 3- aminopropyl trimethoxysilanes With 175 kilograms of diphenyl phosphoryl chlorine, the griding reaction 40 minutes under the conditions of being passed through nitrogen stream rate and being 0.5 cubic meters per minute, The compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems is made.
2. a kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems, it is characterised in that:The fire retardant, which is that there are as below methods, to be made: Montmorillonite is added in the ball mill for being connected with nitrogen access tube, under conditions of 21.7 revs/min of balling drum rotating speed, point Not Jia Ru N- aminoethyls-γ-aminopropyltrimethoxysilane, solutions of dimethyl phosphoryl chlorine, be passed through nitrogen stream rate be 0.1 cube The compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems is made in griding reaction 20 minutes under the conditions of m/min;The addition of montmorillonite It it is 38000 kilograms, montmorillonite and the mass ratio that feeds intake of N- aminoethyls-γ-aminopropyltrimethoxysilane are 1.0:0.02, N- ammonia The amount ratio of ethyl-γ-aminopropyltrimethoxysilane and the substance that feeds intake of solutions of dimethyl phosphoryl chlorine is 1.0:2.5, ball mill specification For Ф 2200 × 7500, ball load is 35 tons.
3. a kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems, it is characterised in that:The fire retardant, which is that there are as below methods, to be made: Montmorillonite being added in the ball mill for being connected with nitrogen access tube, ball mill specification is Ф 900 × 1800, and ball load is 1.5 tons, Under conditions of 36 revs/min of balling drum rotating speed, it is separately added into 3- aminopropyl triethoxysilanes, diethylchlorophosphate, Griding reaction 45 minutes, is made the compound loaded illiteracy of phosphorus nitrogen silicon systems under the conditions of being passed through nitrogen stream rate and being 6.7 cubic meters per minute De- soil fire retardant;The addition of montmorillonite is 1200 kilograms, the mass ratio that feeds intake of montmorillonite and 3- aminopropyl triethoxysilanes It is 1.0:The amount ratio of the substance that feeds intake of 0.22,3- aminopropyl triethoxysilane and diethylchlorophosphate is 1.0:1.25.
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CN102757581A (en) * 2012-07-31 2012-10-31 华南理工大学 Intumescent flame retardant functional silicate and preparation method thereof

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CN102757581A (en) * 2012-07-31 2012-10-31 华南理工大学 Intumescent flame retardant functional silicate and preparation method thereof

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