CN104356242A - 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
CN104356242A
CN104356242A CN201410552651.1A CN201410552651A CN104356242A CN 104356242 A CN104356242 A CN 104356242A CN 201410552651 A CN201410552651 A CN 201410552651A CN 104356242 A CN104356242 A CN 104356242A
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cellulose
flame retardant
halogen
phosphorus flame
phosphorus
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CN104356242B (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
Mierocrystalline cellulose is a kind of natural reproducible macromolecular material, and grow and be present in a large amount of abundant green plantss, its growing amount, every year up to 1,000 hundred million tons, is renewable resources exhausted never.Compared with synthetic compound, cellulose based compound has many advantages: one, and cellulose macromolecule chain has many hydroxyls, and have stronger reactivity worth and interaction performance, cost is low; Its two, cellulose materials itself is nontoxic; Therefore, Mierocrystalline cellulose is that the potential use range of substrate material will widely.Based on the focus that cellulosic investigation of materials is recent years abroad research and development.And although the grafting of common Mierocrystalline cellulose and petroleum-based compounds or copolymerization can develop the cellulose-based materials such as fabric finishing agent, building coating, aqueous adhesive, drug carrier material, but so far there are no, and preparation contains the flame retardant compound of cellulose base, have excellent flame retardant properties and nontoxic, degradable, the environment amenable feature that have natural polymer concurrently.
China in recent years fire disaster is continuous, very important to the Development and Production of flame retardant building material, and along with China's material of construction is to the further raising of energy-saving heat preserving and flame retardant properties index request, fire-retardantly will increase further with the demand of fire-retardant material.The most simple and efficient method of fire retardant material adopts fire retardant blended exactly, the total consumption of current global fire retardant has reached 1,200,000 tons/year, a few years from now on will with the speed sustainable growth of average annual 4 ~ 5%, but current fire retardant is not still popularized in the use of China, domestic flame retardant plastics accounts for the ratio of plastics less than 2%, wherein main based on halogen flame, but because halogenated flame retardant produces more cigarette and corrosive gases in thermo-cracking or when burning, and be subject to the puzzlement of dioxin problem, the use of halogenated flame retardant has been subjected to increasing restriction, in the long run, fire retardant is non-halogen is the ultimate aim that fire retardant develops.And phosphorus-nitrogen containing flame retardant only uses as additive flame retardant, general volatility is large, resistance toheat is not enough, the phosphorous nitrogen quantity of fire retardant is directly proportional substantially to flame retardant effect, therefore, the solid type phosphorus-nitrogen containing flame retardant that design and synthesis good heat resistance, consistency are 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 had had again recyclability and abundant content and nontoxic, degradable, environment amenable feature.The present invention for cellulose base phosphonium flame retardant prepared by raw material, provides good theory and technology basis to BACN exploitation and biomass economy with cellulose powder or Microcrystalline Cellulose.
Summary of the invention
the technical problem solved:the 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, be under the stirring state of 100 ~ 1000 revs/min in speed, water ratio is less than the Mierocrystalline cellulose of 1wt.% or Microcrystalline Cellulose dispersion suspension in solvent, adds small molecule amine compounds as acid binding agent and pass into nitrogen; Second step, is added drop-wise to phosphorus oxychloride in above-mentioned suspension, and maintenance temperature of reaction is 25-100 DEG C, Keep agitation 1 ~ 10 hour; 3rd step, be washed in mixture and exist without chlorion, filtering drying obtains Halogen cellulose base phosphorus flame retardant, and bake out temperature is 40 ~ 100 DEG C.
Described Mierocrystalline cellulose or Microcrystalline Cellulose are particle diameter is 100 ~ 800 orders.
Described solvent is the one in methylene dichloride, trichloromethane or tetrahydrofuran (THF), and usage quantity is 200 ~ 1000% of Mierocrystalline cellulose or Microcrystalline Cellulose weight.
Described acid binding agent is the one in triethylamine, pyridine, DMAP, and usage quantity is 1 ~ 20% of Mierocrystalline cellulose or Microcrystalline Cellulose weight.
Described phosphorus oxychloride usage quantity is 50 ~ 300% of Mierocrystalline cellulose or Microcrystalline Cellulose weight.
The Halogen cellulose base phosphorus flame retardant that above-mentioned preparation method obtains.
beneficial effect:the present invention for raw material, synthesizes the cellulose base phosphor-containing halogen-free fire retardant of a kind of environmental friendliness, excellent flame retardancy with resourceful cellulose powder or Microcrystalline Cellulose.The present invention first by cellulose powder or Microcrystalline Cellulose dispersion suspension in organic phase, add phosphorus oxychloride under stirring and generate cellulose base phosphoric acid acyl chlorides, then hydrolysis forms 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, sizing agent, coating.
Concrete advantage is as follows:
1, adopt cellulose powder or Microcrystalline Cellulose to be initiator, there is the more extensive and environment amenable advantage in source;
2, cellulose powder or Microcrystalline Cellulose are rich in hydroxyl, thus can prepare the higher halogen-free flame retardants of phosphorus content;
3, the cellulose base phosphorus flame retardant molecular weight obtained is comparatively large, does not possess small-molecular-weight fire retardant and easily separates out and decompose thus degradation shortcoming under causing flame retardant properties, and excellent flame retardancy, there is wider application prospect.
4, prepare cellulose base phosphor-containing halogen-free fire retardant, be intended to change current domestic fire retardant still based on the present situation of the large halogen containing flame-retardant of toxicity and promote agreeing with and the development of industry of biomass-based material and fire retardant material.
Embodiment
A kind of preparation method of Halogen cellulose base phosphorus flame retardant:
The first step is under the stirring state of 100 ~ 1000 revs/min in speed, water ratio is less than the cellulose powder of 1wt.% or Microcrystalline Cellulose dispersion suspension in a solvent, adds small molecule amine compounds as acid binding agent and passes into nitrogen protection;
Second step, to be added drop-wise to phosphorus oxychloride in said mixture and to keep temperature of reaction to be 25-100 DEG C and Keep agitation 1 ~ 10 hour;
3rd step, be washed in mixture and exist without chlorion, filtering drying obtains Halogen cellulose base phosphorus flame retardant, and bake out temperature is 40 ~ 100 DEG C.
Above-mentioned solvent usage quantity is 200 ~ 1000% of cellulose powder or Microcrystalline Cellulose weight; Acid binding agent usage quantity is 1 ~ 20% of cellulose powder or Microcrystalline Cellulose weight; Phosphorus oxychloride usage quantity is 50 ~ 300% of cellulose powder or Microcrystalline Cellulose weight.
In the present embodiment, can select:
Solvent usage quantity is 200%, 300%, 500%, 800% or 1000% of cellulose powder or Microcrystalline Cellulose weight, wherein preferably 200%, 300% or 500%; Cellulose powder order number is 100 orders, 200 orders, 400 orders, 600 orders or 800 orders, wherein preferably 200 orders, 400 orders, 600 orders or 800 orders; Acid binding agent usage quantity is 1%, 5%, 10%, 15% or 20% of cellulose powder or Microcrystalline Cellulose weight, wherein preferably 1%, 5% or 10%; Phosphorus oxychloride usage quantity is 50%, 80%, 120%, 150%, 200% or 300% of cellulose powder or Microcrystalline Cellulose weight, wherein preferably 80%, 120%, 150% or 200%.
Above-mentioned solvent is the one of methylene dichloride, trichloromethane or tetrahydrofuran (THF); Above-mentioned acid binding agent is the one in triethylamine, pyridine, DMAP.
In the present embodiment, can select:
The first step stirring velocity is 100,200,300,500 or 800 revs/min, wherein preferably 200,300 or 500 revs/min; Second step temperature of reaction is 40 DEG C, 60 DEG C, 80 DEG C or 100 DEG C, and wherein preferably 40 DEG C, 60 DEG C or 80 DEG C, churning time is 2,4,6 or 8 hours, wherein preferably 2,4 or 6 hours; 3rd step bake out temperature is 50 DEG C, 75 DEG C, 90 DEG C or 100 DEG C, wherein preferably 75 DEG C, 90 DEG C or 100 DEG C.
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1:
Be under the stirring state of 200 revs/min in speed, 100g water ratio be less than 1wt.% Microcrystalline Cellulose and be distributed in 500g trichloromethane, add 10g triethylamine as acid binding agent and pass into nitrogen; After being warming up to 40 DEG C, 80g phosphorus oxychloride to be added drop-wise in above-mentioned mixed solution and Keep agitation 6 hours; Adding a large amount of water rinses extremely without chlorion existence (differentiating with the silver nitrate aqueous solution of 0.1mol/L), filters and dry at 75 DEG C to obtain Halogen cellulose base phosphorus flame retardant.The flame retardant performance prepared the results are shown in subordinate list.
 
Embodiment 2:
Be under the stirring state of 300 revs/min in speed, the cellulose powder that 100g 800 order water ratio is less than 1wt.% is distributed in 300g methylene dichloride, add 10g pyridine as acid binding agent and pass into nitrogen; After being warming up to 80 DEG C, 200g phosphorus oxychloride to be added drop-wise in above-mentioned mixed solution and Keep agitation 6 hours; Adding a large amount of water rinses extremely without chlorion existence (differentiating with the silver nitrate aqueous solution of 0.1mol/L), filters and dry at 90 DEG C to obtain Halogen cellulose base phosphorus flame retardant.The flame retardant performance prepared the results are shown in subordinate list.
 
Embodiment 3:
Be under the stirring state of 500 revs/min in speed, the cellulose powder that 100g 400 order water ratio is less than 1wt.% is distributed in 500g tetrahydrofuran (THF), add 5g4-Dimethylamino pyridine as acid binding agent and pass into nitrogen; After being warming up to 80 DEG C, 120g phosphorus oxychloride to be added drop-wise in above-mentioned mixed solution and Keep agitation 6 hours; Adding a large amount of water rinses extremely without chlorion existence (differentiating with the silver nitrate aqueous solution of 0.1mol/L), filters and dry at 100 DEG C to obtain Halogen cellulose base phosphorus flame retardant.The flame retardant performance prepared the results are shown in subordinate list.
 
Embodiment 4:
Be under the stirring state of 300 revs/min in speed, the cellulose powder that 100g 600 order water ratio is less than 1wt.% is distributed in 200g tetrahydrofuran (THF), add 10g DMAP as acid binding agent and pass into nitrogen; After being warming up to 60 DEG C, 150g phosphorus oxychloride to be added drop-wise in above-mentioned mixed solution and Keep agitation 4 hours; Adding a large amount of water rinses extremely without chlorion existence (differentiating with the silver nitrate aqueous solution of 0.1mol/L), filters and dry at 100 DEG C to obtain Halogen cellulose base phosphorus flame retardant.The flame retardant performance prepared the results are shown in subordinate list.
 
Comparative example 1:
Temperature of reaction is 80 DEG C, other formula and technique identical with embodiment 1, the flame retardant performance prepared the results are shown in subordinate list.
 
Comparative example 2:
Cellulose powder order number is 200 orders, and pyridine add-on is 1g, other formula and technique identical with embodiment 2, the flame retardant performance prepared the results are shown in subordinate list.
 
Comparative example 3:
The Keep agitation time is 2 hours, other formula and technique identical with embodiment 3, the flame retardant performance prepared the results are shown in subordinate list.
 
Comparative example 4:
Cellulose powder order number is 200 orders, other formula and technique identical with embodiment 4, the flame retardant performance prepared the results are shown in subordinate 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 and temperature of reaction, reaction times, phosphorus oxychloride usage quantity, Mierocrystalline cellulose order number and acid binding agent consumption etc. have direct relation.

Claims (6)

1. the preparation method of Halogen cellulose base phosphorus flame retardant, is characterized in that step is:
The first step is under the stirring state of 100 ~ 1000 revs/min in speed, water ratio is less than the Mierocrystalline cellulose of 1wt.% or Microcrystalline Cellulose dispersion suspension in solvent, adds small molecule amine compounds as acid binding agent and passes into nitrogen;
Second step, is added drop-wise to phosphorus oxychloride in above-mentioned suspension, and maintenance temperature of reaction is 25-100 DEG C, Keep agitation 1 ~ 10 hour;
3rd step, be washed in mixture and exist without chlorion, filtering drying obtains Halogen cellulose base phosphorus flame retardant, and bake out temperature is 40 ~ 100 DEG C.
2. the preparation method of Halogen cellulose base phosphorus flame retardant according to claim 1, is characterized in that described Mierocrystalline cellulose or Microcrystalline Cellulose be particle diameter are 100 ~ 800 orders.
3. the preparation method of Halogen cellulose base phosphorus flame retardant according to claim 1, it is characterized in that described solvent is the one in methylene dichloride, trichloromethane or tetrahydrofuran (THF), usage quantity is 200 ~ 1000% of Mierocrystalline cellulose or Microcrystalline Cellulose weight.
4. the preparation method of Halogen cellulose base phosphorus flame retardant according to claim 1, it is characterized in that described acid binding agent is the one in triethylamine, pyridine, DMAP, usage quantity is 1 ~ 20% of Mierocrystalline cellulose or Microcrystalline Cellulose weight.
5. the preparation method of Halogen cellulose base phosphorus flame retardant according to claim 1, is characterized in that described phosphorus oxychloride usage quantity is 50 ~ 300% of Mierocrystalline cellulose or Microcrystalline Cellulose weight.
6. the Halogen cellulose base phosphorus flame retardant of the arbitrary described preparation method's acquisition of claim 1 ~ 5.
CN201410552651.1A 2014-10-17 2014-10-17 Halogen-free cellulose based phosphorus flame retardant and preparation method thereof Active CN104356242B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105696100A (en) * 2016-02-25 2016-06-22 东华大学 Green carbon source copolymerized anti-flaming 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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105696100A (en) * 2016-02-25 2016-06-22 东华大学 Green carbon source copolymerized anti-flaming 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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