CN107129599B - A kind of method that nano-crystalline cellulose template prepares expansion type flame retardant - Google Patents
A kind of method that nano-crystalline cellulose template prepares expansion type flame retardant Download PDFInfo
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- CN107129599B CN107129599B CN201710491513.0A CN201710491513A CN107129599B CN 107129599 B CN107129599 B CN 107129599B CN 201710491513 A CN201710491513 A CN 201710491513A CN 107129599 B CN107129599 B CN 107129599B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention discloses a kind of method that nano-crystalline cellulose template prepares expansion type flame retardant.By nano-cellulose stock dispersion into deionized water, ultrasonic disperse to uniform, adjusting nano-cellulose gel pH to neutrality.Nitrogenous compound ethylenediamine, urea are added in nano-cellulose colloid, is sufficiently stirred, phosphorus-containing compound diethyl phosphate, ammonium dihydrogen phosphate is then added, is sufficiently stirred, phosphorous nitrogenous expansion type flame retardant is prepared.Expansion type flame retardant carbon-collecting source prepared by the present invention, acid source, gas source have good flame retardant property in one.Limit oxygen index improves 25~42% after handling wood plastic composite.Synthesis process Green is environmentally friendly, easy to operate.
Description
Technical field
The present invention relates to fire-retardant FRW fields, and in particular to a kind of to prepare expansion type flame retardant by nano-cellulose
Method.
Background technique
Intumescent Retardant System is one using carbon, nitrogen, phosphorus as the flame-retardant system of core component, mainly by acid source, charcoal source, gas source
Three parts composition.Acid source is also known as dehydrating agent or charing promotor, the chemical combination of energy in-situ preparation acid usually in inorganic acid or burning
Object, such as phosphoric acid, boric acid, sulfuric acid and phosphate；Carbon forming agent is also in charcoal source, it is the basis to form foam charring layer, mainly
The high polyol of some phosphorus content, such as starch, sucrose, dextrin, pentaerythrite, ethylene glycol, phenolic resin；Gas source
Foaming source is cried, is nitrogenous compound, such as urea, melamine, polyamide.Wherein acid source generates acid in burning, as de-
Aqua is reacted with charcoal source generates layer of charcoal, and gas source release gas expands layer of charcoal, so that trap heat transmitting and starvation, are realized
Fire-retardant purpose.In existing Intumscent Flame Retardant System, compounded mostly by acid source, gas source, carbon source, such as polyphosphoric acid
Ammonium/melamine/pentaerythrite compounded combination forms Intumscent Flame Retardant System.Simple compounding causes the synergistic effect of three elements
Decreased effectiveness promotes its flame retarding efficiency unobvious.
Nano-cellulose (nanocellulose) be diameter be 1~100nm, length be tens nanometers to several microns surpass
The general designation of microfibre is the minimal physical structural unit of cellulose.Compared with general fibre element, nano-cellulose has high-purity
Degree, high-crystallinity, high-specific surface area, high Young's modulus, high intensity characteristic, while there is multi-stage artery structure, its surface to contain
There are multiple reactive hydroxyls, be easy to be grafted siloxy, amino, absorption electronics etc., therefore illustrates on materials synthesis excellent
Different template effect.In recent years, it gradually attracts attention using nano-cellulose as templated synthesis fire retardant.Open patent of invention
104830022 B of CN reports a kind of expansion type flame retardant and the preparation method and application thereof of electrostatic bunching preparation, with acid source
Ammonium polyphosphate is kernel, and the surface of kernel is coated with one layer of dicyandiamide formaldehyde resin as gas source, dicyandiamide formaldehyde resin outer layer
One layer of nano-cellulose is adsorbed as charcoal source.Open 105034108 B of patent of invention CN uses crystalline state nanometer cellulose to divide
Dephasing prepares polymolecularity ammonium polyphosphate colloid.With individually using ammonium polyphosphate compared with, modified ammonium polyphosphate dispersibility improves,
But it can not solve the problems, such as strong colloid hygroscopicity, thermal stability decline and flame retarding efficiency decline.Open patent of invention CN
106003887 A use layer-by-layer, prepare intumescent composite flame-retardant film by matrix of crystalline state nanometer cellulose.So
And the effect of expansion type flame-retarding film is often built upon on the basis of high mass content, further increases flame retarding efficiency, reduces matter
Content is measured, improving with the compatibility of basis material is the target pursued.
Summary of the invention
The purpose of the present invention: a kind of method for preparing expansion type flame retardant using nano-cellulose for template is provided.
Technical solution of the invention: by nano-cellulose stock dispersion into deionized water, ultrasonic disperse to uniform,
Nano-cellulose gel pH is adjusted to 7.Nitrogenous compound ethylenediamine, urea are added in nano-cellulose colloid, sufficiently stirs
It mixes, phosphorus-containing compound diethyl phosphate, ammonium dihydrogen phosphate is then added, is sufficiently stirred, expansion type flame retardant is prepared.
A kind of nano-crystalline cellulose template prepare the specific of expansion type flame retardant the preparation method is as follows:
(1) in mass ratio (1~5): 100 weigh nano-cellulose, deionized water, and ultrasonic disperse is carried out in ice-water bath,
Power is 800~1000w, and the time is 10~30min, obtains nano-cellulose colloid, adjusts the pH value of nano-cellulose colloid
To 7；
(2) nitrogenous compound is added in the nano-cellulose colloid made from step (1), so that nitrogenous compound: nanometer
The mass ratio of cellulose is (1.8~5.5): 1, it is warming up to 50~70 DEG C under nitrogen protection, 4~6h is sufficiently stirred, is contained
Nitrogen nano fiber element colloid；
(3) phosphorus-containing compound is added in the nitrogenous nano-cellulose colloid made from step (2), so that phosphorus-containing compound:
The mass ratio of nano-cellulose is (2~5): 1, it is warming up to 50~70 DEG C under nitrogen protection, 3~5h is sufficiently stirred, obtains swollen
Swollen type fire retardant.
Advantages of the present invention:
(1) present invention utilizes the high-specific surface area of nano-cellulose, is introduced into flame-retardant system as charcoal source.
(2) present invention utilizes polymolecularity, the high reaction activity of nano-cellulose, promotes nitrogen, dividing equally for phosphorus to disperse, simultaneously
Overcome the deficiency of flame retarding efficiency when Intumscent Flame Retardant System simply compounds.
(3) expansion type flame retardant carbon-collecting source prepared by the present invention, acid source, gas source have good flame retardant property in one.
Performance test shows: being handled with the expansion type flame retardant that nano-crystalline cellulose template is prepared wood plastic composite, wood
The oxygen index (OI) of plastic composite materials improves 25~42%.
(4) synthesis process Green is environmentally friendly, easy to operate, can be used for industrialized mass production.
Specific embodiment
Embodiment 1,
(1) in mass ratio 1: 100 nano-cellulose, deionized water are weighed, ultrasonic disperse, ultrasonic function is carried out in ice-water bath
Rate 800w, ultrasonic time 10min, obtain 1% nano-cellulose colloid, adjust the pH value of nano-cellulose colloid to 7；
(2) urea is added in the nano-cellulose colloid made from step (1), so that urea: the quality of nano-cellulose
Than being 1.8: 1, it is warming up to 50~70 DEG C under nitrogen protection, 4~6h is sufficiently stirred, obtains nitrogenous nano-cellulose colloid；
(3) diethyl phosphate is added in the nitrogenous nano-cellulose colloid made from step (2), so that diethyl phosphate:
The mass ratio of nano-cellulose is 2: 1, is warming up to 50~70 DEG C under nitrogen protection, 3~5h is sufficiently stirred, and obtains intumescent resistance
Fire agent.
Wood plastic composite is handled with the expansion type flame retardant that nano-crystalline cellulose template is prepared, after tested,
The oxygen index (OI) of wood plastic composite improves 25%.
Embodiment 2,
(1) in mass ratio 3: 100 nano-cellulose, deionized water are weighed, ultrasonic disperse, ultrasonic function is carried out in ice-water bath
Rate 1000w, ultrasonic time 30min, obtain 3% nano-cellulose colloid, adjust the pH value of nano-cellulose colloid to 7；
(2) urea is added in the nano-cellulose colloid made from step (1), so that urea: the quality of nano-cellulose
Than being 3.5: 1, it is warming up to 50~70 DEG C under nitrogen protection, 4~6h is sufficiently stirred, obtains nitrogenous nano-cellulose colloid；
(3) ammonium dihydrogen phosphate is added in the nitrogenous nano-cellulose colloid made from step (2), so that ammonium dihydrogen phosphate:
The mass ratio of nano-cellulose is 3: 1, is warming up to 50~70 DEG C under nitrogen protection, 3~5h is sufficiently stirred, and obtains intumescent resistance
Fire agent.
Wood plastic composite is handled with the expansion type flame retardant that nano-crystalline cellulose template is prepared, after tested,
The oxygen index (OI) of wood plastic composite improves 37%.
Embodiment 3,
(1) in mass ratio 5: 100 nano-cellulose, deionized water are weighed, ultrasonic disperse, ultrasonic function is carried out in ice-water bath
Rate 800w, ultrasonic time 10min, obtain 5% nano-cellulose colloid, adjust the pH value of nano-cellulose colloid to 7；
(2) ethylenediamine is added in the nano-cellulose colloid made from step (1), so that ethylenediamine: nano-cellulose
Mass ratio is 2.5: 1, is warming up to 50~70 DEG C under nitrogen protection, 4~6h is sufficiently stirred, and obtains nitrogenous nano-cellulose glue
Body；
(3) diethyl phosphate is added in the nitrogenous nano-cellulose colloid made from step (2), so that diethyl phosphate:
The mass ratio of nano-cellulose is 5: 1, is warming up to 50~70 DEG C under nitrogen protection, 3~5h is sufficiently stirred, and obtains intumescent resistance
Fire agent.
Wood plastic composite is handled with the expansion type flame retardant that nano-crystalline cellulose template is prepared, after tested,
The oxygen index (OI) of wood plastic composite improves 42%.
Embodiment 4,
(1) in mass ratio 3: 100 nano-cellulose, deionized water are weighed, ultrasonic disperse, ultrasonic function is carried out in ice-water bath
Rate 1000w, ultrasonic time 30min, obtain 3% nano-cellulose colloid, adjust the pH value of nano-cellulose colloid to 7；
(2) ethylenediamine is added in the nano-cellulose colloid made from step (1), so that ethylenediamine: nano-cellulose
Mass ratio is 5.5: 1, is warming up to 50~70 DEG C under nitrogen protection, 4~6h is sufficiently stirred, and obtains nitrogenous nano-cellulose glue
Body；
(3) ammonium dihydrogen phosphate is added in the nitrogenous nano-cellulose colloid made from step (2), so that ammonium dihydrogen phosphate:
The mass ratio of nano-cellulose is 4: 1, is warming up to 50~70 DEG C under nitrogen protection, 3~5h is sufficiently stirred, and obtains intumescent resistance
Fire agent.
Wood plastic composite is handled with the expansion type flame retardant that nano-crystalline cellulose template is prepared, after tested,
The oxygen index (OI) of wood plastic composite improves 31%.
Claims (3)
1. a kind of method that nano-crystalline cellulose template prepares expansion type flame retardant, it is characterised in that sequentially include the following steps:
(1) in mass ratio (1~5): 100 weigh nano-cellulose, deionized water, carry out ultrasonic disperse, and power is 800~
1000w, time are 10~30min, obtain nano-cellulose colloid, adjust the pH value of nano-cellulose colloid to 7；
(2) nitrogenous compound is added in the nano-cellulose colloid made from step (1), so that nitrogenous compound: nanofiber
The mass ratio of element is (1.8~5.5): 1, it is warming up to 50~70 DEG C under nitrogen protection, 4~6h is sufficiently stirred, obtains nitrogenous receive
Rice cellulose colloid；
(3) phosphorus-containing compound is added in the nitrogenous nano-cellulose colloid made from step (2), so that phosphorus-containing compound: nanometer
The mass ratio of cellulose is (2~5): 1, it is warming up to 50~70 DEG C under nitrogen protection, 3~5h is sufficiently stirred, obtains intumescent
Fire retardant；
The nitrogenous compound is ethylenediamine, urea, and the phosphorus-containing compound is diethyl phosphate, ammonium dihydrogen phosphate.
2. the method that a kind of nano-crystalline cellulose template according to claim 1 prepares expansion type flame retardant, it is characterised in that
Nano-cellulose is nano cellulose crystal, nano-cellulose whisker, nano-cellulose fibril.
3. the method that a kind of nano-crystalline cellulose template according to claim 1 prepares expansion type flame retardant, it is characterised in that
Ultrasonic disperse carries out in ice-water bath.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804218A (en) * | 2015-04-28 | 2015-07-29 | 中科院广州化学有限公司南雄材料生产基地 | Nanocellulose surface-modified core-shell structure fire retardant, and preparation method and application of fire retardant |
| CN104816365A (en) * | 2015-04-04 | 2015-08-05 | 北京化工大学 | Water-soluble expanded wood fire retardation agent and preparation method thereof |
| CN105924679A (en) * | 2016-05-11 | 2016-09-07 | 南京林业大学 | Nano-composite intumescent flame retardant and preparing method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104816365A (en) * | 2015-04-04 | 2015-08-05 | 北京化工大学 | Water-soluble expanded wood fire retardation agent and preparation method thereof |
| CN104804218A (en) * | 2015-04-28 | 2015-07-29 | 中科院广州化学有限公司南雄材料生产基地 | Nanocellulose surface-modified core-shell structure fire retardant, and preparation method and application of fire retardant |
| CN105924679A (en) * | 2016-05-11 | 2016-09-07 | 南京林业大学 | Nano-composite intumescent flame retardant and preparing method thereof |
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Application publication date: 20170905 Assignee: Guangxi Prince Wood Industry Co., Ltd Assignor: NANJING FORESTRY University Contract record no.: X2020980002822 Denomination of invention: Method for preparing intumescent flame retardant by using nano-cellulose template Granted publication date: 20190910 License type: Common License Record date: 20200605 |