CN104356242B - Halogen-free cellulose based phosphorus flame retardant and preparation method thereof - Google Patents

Halogen-free cellulose based phosphorus flame retardant and preparation method thereof Download PDF

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Publication number
CN104356242B
CN104356242B CN201410552651.1A CN201410552651A CN104356242B CN 104356242 B CN104356242 B CN 104356242B CN 201410552651 A CN201410552651 A CN 201410552651A CN 104356242 B CN104356242 B CN 104356242B
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flame retardant
cellulose
halogen
phosphorus
phosphorus flame
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CN104356242A (en
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陈日清
刘娟
李双
王春鹏
储富祥
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Institute of Chemical Industry of Forest Products of CAF
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Institute of Chemical Industry of Forest Products of CAF
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Abstract

The invention discloses a halogen-free cellulose based phosphorus flame retardant and a preparation method thereof. The preparation method of the halogen-free cellulose based phosphorus flame retardant comprises the following steps: step 1, dispersing and suspending cellulose or microcrystalline cellulose with a moisture content lower than 1% by weight into a solvent under a stirring situation that the stirring speed is 100-1,000 revolutions per minute, adding a micromolecular amine compound as an acid-binding agent, and introducing nitrogen; step 2, dripping phosphorus oxychloride in the suspension liquid, keeping the reaction temperature at 25-100 DEG C, and continuously stirring for 1-10 hours; step 3, washing with water until the mixture is free of chloride ions, filtering and drying the mixture to obtain the halogen-free cellulose based phosphorus flame retardant at the drying temperature of 40-100 DEG C. The halogen-free cellulose based phosphorus flame retardant obtained by the invention is excellent in flame retardant property, high in phosphorus content and environmental-friendly, and can be applied to various fields such as plastics, adhesives and coatings.

Description

Halogen cellulose base phosphorus flame retardant and preparation method thereof
Technical field
The invention belongs to technical field of flame retardant, be specifically related to a kind of Halogen cellulose base phosphorus flame retardant and preparation method thereof.
Background technology
Cellulose is a kind of natural reproducible macromolecular material, grows and is present in substantial amounts of abundant green plants, and its growing amount up to 100,000,000,000 tons every year, is Renewable resource exhausted never.Compared with synthesis compound, cellulose based compound has many advantages: one, cellulose macromolecule chain has many hydroxyls, has stronger reactivity worth and interaction performance, low cost;Its two, cellulosic material itself is nontoxic;Therefore, cellulose is that the potential range of host material will widely.Investigation of materials based on cellulose is the focus of recent years abroad research and development.And although common cellulose and the grafting of petroleum-based compounds or copolymerization can develop the cellulosic-based materials such as fabric finishing agent, building coating, aqueous adhesive, drug carrier material, but so far there are no the preparation flame retardant compound containing cellulose base, nontoxic, degradable, the environment amenable feature having excellent fire resistance concurrently with having natural polymer.
China's fire disaster in recent years is continuous, the most particularly significant to the Development and Production of flame retardant building material, and along with China's construction material is to energy-saving heat preserving and the further raising of fire resistance index request, the fire-retardant demand with fire proofing material will increase further.The most simple and efficient method of fire proofing uses fire retardant to be blended exactly, the whole world total consumption of fire retardant has reached 1,200,000 tons/year at present, a few years from now on will be with average annual 4~the speed sustainable growth of 5%, but current fire retardant is not popularized in the use of China, domestic flame retardant plastics accounts for the ratio of plastic less than 2%, wherein main based on halogen flame, but owing to halogenated flame retardant produces more cigarette and corrosive gas when thermal cracking or burning, and perplexed by two English problems, the use of halogenated flame retardant has been subjected to more and more limit, in the long run, fire retardant is non-halogen be fire retardant development final goal.And phosphorus-nitrogen containing flame retardant is only used as additive flame retardant and uses, general volatility is big, heat resistance is not enough, the phosphorous nitrogen quantity of fire retardant and flame retardant effect generally direct ratio, therefore, the solid type phosphorus-nitrogen containing flame retardant that design synthesis is heat-resist, the compatibility good, flame retardant effect is excellent, is the Main way of research at present.And biomass-based Nitrogen-and Phosphorus-containing fire retardant had both had flame retardant effect, its raw material sources have again recyclability and abundant content and nontoxic, degradable, environment amenable feature.The present invention prepares cellulose base phosphonium flame retardant with cellulose powder or microcrystalline Cellulose for raw material, provides good theory and technology basis to BACN exploitation and biomass economy.
Summary of the invention
Solve the technical problem that:The present invention provides a kind of environmentally friendly and simple and easy to do Halogen cellulose base phosphorus flame retardant and preparation method thereof.
Technical scheme:
The preparation method of Halogen cellulose base phosphorus flame retardant, step is: the first step, under the stirring state that speed is 100~1000 revs/min, cellulose or microcrystalline Cellulose dispersion that moisture content is less than 1wt.% are suspended in solvent, add small molecule amine compounds and as acid binding agent and are passed through nitrogen;Second step, is added drop-wise to phosphorus oxychloride in above-mentioned suspension, keeps reaction temperature to be 25-100 DEG C, continuously stirred 1 ~ 10 hour;3rd step, is washed in mixture exist without chloride ion, and filtering drying obtains Halogen cellulose base phosphorus flame retardant, and drying temperature is 40 ~ 100 DEG C.
Described cellulose or microcrystalline Cellulose be particle diameter be 100~800 mesh.
Described solvent is the one in dichloromethane, chloroform or oxolane, and usage amount is cellulose or the 200 of microcrystalline Cellulose weight~1000%.
Described acid binding agent is the one in triethylamine, pyridine, DMAP, and usage amount is cellulose or the 1 of microcrystalline Cellulose weight~20%.
Described phosphorus oxychloride usage amount is cellulose or the 50 of microcrystalline Cellulose weight~300%.
The Halogen cellulose base phosphorus flame retardant that above-mentioned preparation method obtains.
Beneficial effect:The present invention, with resourceful cellulose powder or microcrystalline Cellulose as raw material, synthesizes the cellulose base phosphor-containing halogen-free fire retardant of a kind of environmental friendliness, excellent flame retardancy.First cellulose powder or microcrystalline Cellulose are disperseed to be suspended in organic facies by the present invention, and stirring is lower adds phosphorus oxychloride generation cellulose base phosphoric acid acyl chlorides, then hydrolyzes to form cellulose base phosphoric acid, i.e. cellulose base phosphor-containing halogen-free fire retardant.The cellulose base phosphor-containing halogen-free fire retardant that the present invention obtains has the features such as excellent flame retardancy, phosphorus content be high, environmentally friendly, can be applicable to the every field such as plastics, adhesive, coating.
Concrete advantage is as follows:
1, using cellulose powder or microcrystalline Cellulose is starting material, has the wide and environment amenable advantage in source;
2, cellulose powder or microcrystalline Cellulose are rich in hydroxyl, such that it is able to prepare the halogen-free flame retardants that phosphorus content is higher;
3, the cellulose base phosphorus flame retardant molecular weight obtained is relatively big, does not possess small-molecular-weight fire retardant and easily separates out and decompose thus cause degradation shortcoming under fire resistance, and excellent flame retardancy, has wider application prospect.
4, cellulose base phosphor-containing halogen-free fire retardant is prepared, it is intended to change current domestic fire retardant still based on the present situation of the big halogen containing flame-retardant of toxicity and promote agreeing with and the development of industry of biomass-based material and fire proofing.
Detailed description of the invention
A kind of preparation method of Halogen cellulose base phosphorus flame retardant:
The first step, under the stirring state that speed is 100~1000 revs/min, suspends moisture content in a solvent less than the cellulose powder of 1wt.% or microcrystalline Cellulose dispersion, adds small molecule amine compounds and as acid binding agent and is passed through nitrogen and protects;
Second step, phosphorus oxychloride being added drop-wise in said mixture and keeping reaction temperature is 25-100 DEG C and continuously stirred 1 ~ 10 hour;
3rd step, is washed in mixture exist without chloride ion, and filtering drying obtains Halogen cellulose base phosphorus flame retardant, and drying temperature is 40 ~ 100 DEG C.
Above-mentioned solvent usage amount is cellulose powder or the 200 of microcrystalline Cellulose weight~1000%;Acid binding agent usage amount is cellulose powder or the 1 of microcrystalline Cellulose weight~20%;Phosphorus oxychloride usage amount is cellulose powder or the 50 of microcrystalline Cellulose weight~300%.
In the present embodiment, optional:
Solvent usage amount is cellulose powder or the 200% of microcrystalline Cellulose weight, 300%, 500%, 800% or 1000%, the most preferably 200%, 300% or 500%;Cellulose powder mesh number is 100 mesh, 200 mesh, 400 mesh, 600 mesh or 800 mesh, the most preferably 200 mesh, 400 mesh, 600 mesh or 800 mesh;Acid binding agent usage amount is cellulose powder or the 1% of microcrystalline Cellulose weight, 5%, 10%, 15% or 20%, the most preferably 1%, 5% or 10%;Phosphorus oxychloride usage amount is cellulose powder or the 50% of microcrystalline Cellulose weight, 80%, 120%, 150%, 200% or 300%, the most preferably 80%, 120%, 150% or 200%.
Above-mentioned solvent is the one of dichloromethane, chloroform or oxolane;Above-mentioned acid binding agent is the one in triethylamine, pyridine, DMAP.
In the present embodiment, optional:
First step mixing speed is 100,200,300,500 or 800 revs/min, the most preferably 200,300 or 500 revs/min;Second step reaction temperature is 40 DEG C, 60 DEG C, 80 DEG C or 100 DEG C, the most preferably 40 DEG C, 60 DEG C or 80 DEG C, and mixing time is 2,4,6 or 8 hours, the most preferably 2,4 or 6 hours;It is 50 DEG C, 75 DEG C, 90 DEG C or 100 DEG C that 3rd step dries temperature, the most preferably 75 DEG C, 90 DEG C or 100 DEG C.
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1:
Under the stirring state that speed is 200 revs/min, 100g moisture content is distributed in 500g chloroform less than 1wt.% microcrystalline Cellulose, adds 10g triethylamine and as acid binding agent and be passed through nitrogen;80g phosphorus oxychloride is added drop-wise in above-mentioned mixed liquor and continuously stirred 6 hours after being warming up to 40 DEG C;Add substantial amounts of water to rinse to without chloride ion existence (differentiating with the silver nitrate aqueous solution of 0.1mol/L), filter and drying obtains Halogen cellulose base phosphorus flame retardant at 75 DEG C.The flame retardant performance result prepared sees attached list.
Embodiment 2:
Under the stirring state that speed is 300 revs/min, the 100g 800 mesh moisture content cellulose powder less than 1wt.% is distributed in 300g dichloromethane, adds 10g pyridine and as acid binding agent and be passed through nitrogen;200g phosphorus oxychloride is added drop-wise in above-mentioned mixed liquor and continuously stirred 6 hours after being warming up to 80 DEG C;Add substantial amounts of water to rinse to without chloride ion existence (differentiating with the silver nitrate aqueous solution of 0.1mol/L), filter and drying obtains Halogen cellulose base phosphorus flame retardant at 90 DEG C.The flame retardant performance result prepared sees attached list.
Embodiment 3:
Under the stirring state that speed is 500 revs/min, the 100g 400 mesh moisture content cellulose powder less than 1wt.% is distributed in 500g oxolane, adds 5g4-dimethylamino naphthyridine and as acid binding agent and be passed through nitrogen;120g phosphorus oxychloride is added drop-wise in above-mentioned mixed liquor and continuously stirred 6 hours after being warming up to 80 DEG C;Add substantial amounts of water to rinse to without chloride ion existence (differentiating with the silver nitrate aqueous solution of 0.1mol/L), filter and drying obtains Halogen cellulose base phosphorus flame retardant at 100 DEG C.The flame retardant performance result prepared sees attached list.
Embodiment 4:
Under the stirring state that speed is 300 revs/min, the 100g 600 mesh moisture content cellulose powder less than 1wt.% is distributed in 200g oxolane, adds 10g DMAP and as acid binding agent and be passed through nitrogen;150g phosphorus oxychloride is added drop-wise in above-mentioned mixed liquor and continuously stirred 4 hours after being warming up to 60 DEG C;Add substantial amounts of water to rinse to without chloride ion existence (differentiating with the silver nitrate aqueous solution of 0.1mol/L), filter and drying obtains Halogen cellulose base phosphorus flame retardant at 100 DEG C.The flame retardant performance result prepared sees attached list.
Comparative example 1:
Reaction temperature is 80 DEG C, and other formula and technique are same as in Example 1, and the flame retardant performance result prepared sees attached list.
Comparative example 2:
Cellulose powder mesh number is 200 mesh, and pyridine addition is 1g, and other formula and technique are same as in Example 2, and the flame retardant performance result prepared sees attached list.
Comparative example 3:
The continuously stirred time is 2 hours, and other formula and technique are same as in Example 3, and the flame retardant performance result prepared sees attached list.
Comparative example 4:
Cellulose powder mesh number is 200 mesh, and other formula and technique are the same as in Example 4, and the flame retardant performance result prepared sees attached list.
Subordinate list: Halogen cellulose base phosphorus flame retardant the performance test results *
Outward appearance Phosphorus content (%) 500 DEG C of carbon yields (%) 5% decomposition temperature (DEG C)
Embodiment 1 White powder 8.5 16.2 220
Embodiment 2 Yellow powder 18.8 45.8 330
Embodiment 3 Pale yellow powder 13.9 30.7 300
Embodiment 4 Yellow powder 17.0 42.6 315
Comparative example 1 White powder 10.4 20.3 264
Comparative example 2 Yellow powder 14.0 35.4 296
Comparative example 3 White powder 10.6 22.0 271
Comparative example 4 Yellow powder 14.8 36.5 306
* unreacted cellulose powder 5% decomposition temperature is 167 DEG C, and 500 DEG C of carbon yields are 0%;
Along with the rising of phosphorus content, carbon yield during fire retardant 500 DEG C increases, and 5% decomposition temperature of fire retardant also increases;The phosphorus content of halogen-free flame retardants has direct relation with reaction temperature, response time, phosphorus oxychloride usage amount, cellulose mesh number and acid binding agent consumption etc..

Claims (1)

1. the preparation method of Halogen cellulose base phosphorus flame retardant, it is characterized in that step is: under the stirring state that speed is 300 revs/min, the 100g 800 mesh moisture content cellulose powder less than 1wt.% is distributed in 300g dichloromethane, adds 10g pyridine and as acid binding agent and be passed through nitrogen;200g phosphorus oxychloride is added drop-wise in above-mentioned mixed liquor and continuously stirred 6 hours after being warming up to 80 DEG C;Add substantial amounts of water to rinse to without chloride ion existence, differentiate with the silver nitrate aqueous solution of 0.1mol/L, filter and drying obtains Halogen cellulose base phosphorus flame retardant at 90 DEG C.
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CN105696100B (en) * 2016-02-25 2017-10-24 东华大学 A kind of green charcoal source copolymerization flame-proof polylactic acid fiber and preparation method thereof
CN106674356A (en) * 2016-11-28 2017-05-17 宣城市聚源精细化工有限公司 Preparation method of fire retardants containing fiber-based phosphatidic acid
CN108148273A (en) * 2017-12-20 2018-06-12 阮小军 Household electrical appliances special-purpose anti-flaming plastics and its production technology

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