CN107129599A - 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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- CN107129599A CN107129599A CN201710491513.0A CN201710491513A CN107129599A CN 107129599 A CN107129599 A CN 107129599A CN 201710491513 A CN201710491513 A CN 201710491513A CN 107129599 A CN107129599 A CN 107129599A
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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, regulation nano-cellulose gel pH to neutrality.Nitrogen-containing compound ethylenediamine, urea are added in nano-cellulose colloid, is sufficiently stirred for, phosphorus-containing compound diethyl phosphate, ammonium dihydrogen phosphate is then added, is sufficiently stirred for, prepares phosphorous nitrogenous expansion type flame retardant.Expansion type flame retardant carbon-collecting source prepared by the present invention, acid source, source of the gas are in one, with good fire resistance.Limited oxygen index improves 25~42% after handling wood plastic composite.Building-up process Green is environmentally friendly, easy to operate.
Description
Technical field
The present invention relates to fire-retardant FRW field, and in particular to a kind of to prepare expansion type flame retardant by nano-cellulose
Method.
Background technology
Intumescent Retardant System be one using carbon, nitrogen, phosphorus as nucleus flame-retardant system, mainly by acid source, charcoal source, source of the gas
Three parts are constituted.Acid source is also known as dehydrating agent or charing accelerator, can the sour chemical combination of in-situ preparation usually in inorganic acid or burning
Thing, such as phosphoric acid, boric acid, sulfuric acid and phosphate；Carbon forming agent is also in charcoal source, and 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；Source of the gas
Foaming source is cried, is nitrogen-containing compound, such as urea, melamine, polyamide.Wherein acid source produces acid in burning, as de-
Aqua and charcoal source reaction generation layer of charcoal, source of the gas release gas expands layer of charcoal, so that trap heat transmission and starvation, are realized
Fire-retardant purpose.In existing Intumscent Flame Retardant System, formed mostly by acid source, source of the gas, carbon source compounding, such as polyphosphoric acid
Ammonium/melamine/pentaerythrite compounded combination formation Intumscent Flame Retardant System.Simple compounding causes the synergy of three elements
Decreased effectiveness, makes the lifting of its flame retarding efficiency unobvious.
Nano-cellulose (nanocellulose) is a diameter of 1~100nm, and length surpasses for tens nanometers to several microns
The general designation of microfibre, is the minimal physical construction unit of cellulose.Compared with general fibre element, nano-cellulose possesses high-purity
Degree, high-crystallinity, high-specific surface area, high Young's modulus, the characteristic of high intensity, while having multi-stage artery structure, its surface to contain
There are multiple reactive hydroxyls, it is easy to be grafted siloxy, amino, absorption electronics etc., therefore illustrate on materials synthesis excellent
Different template effect.In recent years, gradually attracted attention as templated synthesis fire retardant using nano-cellulose.Open patent of invention
The B of CN 104830022 report expansion type flame retardant prepared by a kind of electrostatic bunching and preparation method and application, and it is with acid source
APP is kernel, and the Surface coating of kernel one layer of dicyandiamide formaldehyde resin as source of the gas, dicyandiamide formaldehyde resin outer layer
One layer of nano-cellulose is adsorbed as charcoal source.The open B of patent of invention CN 105034108 use crystalline state nanometer cellulose to divide
Dephasing prepares polymolecularity APP colloid.Compared with individually using APP, modified APP dispersiveness is improved,
But, it is impossible to solve the problem of strong colloid hygroscopicity, heat endurance decline and flame retarding efficiency decline.Open patent of invention CN
106003887 A use layer-by-layer, and intumescent composite flame-retardant film is prepared 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 improves flame retarding efficiency, reduces matter
Content is measured, the compatibility improved with matrix material is the target pursued.
The content of the invention
The purpose of the present invention：It is the method that template prepares expansion type flame retardant to provide a kind of utilization nano-cellulose.
The technical solution of the present invention：By nano-cellulose stock dispersion into deionized water, ultrasonic disperse to uniform,
Nano-cellulose gel pH is adjusted to 7.Nitrogen-containing compound ethylenediamine, urea are added in nano-cellulose colloid, is fully stirred
Mix, then add phosphorus-containing compound diethyl phosphate, ammonium dihydrogen phosphate, be sufficiently stirred for, prepare expansion type flame retardant.
The specific preparation method that a kind of nano-crystalline cellulose template prepares expansion type flame retardant 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) nitrogen-containing compound is added in nano-cellulose colloid made from step (1) so that nitrogen-containing compound: nanometer
The mass ratio of cellulose is (1.8~5.5): 1,50~70 DEG C are warming up under nitrogen protection, 4~6h is sufficiently stirred for, and are contained
Nitrogen nano fiber element colloid；
(3) phosphorus-containing compound is added in nitrogenous nano-cellulose colloid made from step (2) so that phosphorus-containing compound:
The mass ratio of nano-cellulose is (2~5): 1,50~70 DEG C are warming up under nitrogen protection, 3~5h is sufficiently stirred for, and obtain swollen
Swollen type fire retardant.
Advantages of the present invention：
(1) present invention is introduced into flame-retardant system as charcoal source using the high-specific surface area of nano-cellulose.
(2) present invention promotes nitrogen, dividing equally for phosphorus to disperse, simultaneously using polymolecularity, the high reaction activity of nano-cellulose
Overcome the deficiency of flame retarding efficiency when Intumscent Flame Retardant System is simply compounded.
(3) the expansion type flame retardant carbon-collecting source of the invention prepared, acid source, source of the gas are in one, with good fire resistance.
Performance test shows：Wood plastic composite is handled with the expansion type flame retardant that nano-crystalline cellulose template is prepared, wood
The oxygen index (OI) of plastic composite materials improves 25~42%.
(4) building-up process Green is environmentally friendly, easy to operate, available for industrialized mass production.
Embodiment
Embodiment 1,
(1) in mass ratio 1: 100 nano-cellulose, deionized water are weighed, ultrasonic disperse, ultrasonic work(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 nano-cellulose colloid made from step (1) so that urea: the quality of nano-cellulose
Than for 1.8: 1,50~70 DEG C being warming up under nitrogen protection, 4~6h is sufficiently stirred for, nitrogenous nano-cellulose colloid is obtained；
(3) diethyl phosphate is added in nitrogenous nano-cellulose colloid made from step (2) so that diethyl phosphate:
The mass ratio of nano-cellulose is 2: 1, and 50~70 DEG C are warming up under nitrogen protection, 3~5h is sufficiently stirred for, 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 work(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 nano-cellulose colloid made from step (1) so that urea: the quality of nano-cellulose
Than for 3.5: 1,50~70 DEG C being warming up under nitrogen protection, 4~6h is sufficiently stirred for, nitrogenous nano-cellulose colloid is obtained；
(3) ammonium dihydrogen phosphate is added in nitrogenous nano-cellulose colloid made from step (2) so that ammonium dihydrogen phosphate:
The mass ratio of nano-cellulose is 3: 1, and 50~70 DEG C are warming up under nitrogen protection, 3~5h is sufficiently stirred for, 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 work(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 nano-cellulose colloid made from step (1) so that ethylenediamine: nano-cellulose
Mass ratio is 2.5: 1, and 50~70 DEG C are warming up under nitrogen protection, 4~6h is sufficiently stirred for, and obtains nitrogenous nano-cellulose glue
Body；
(3) diethyl phosphate is added in nitrogenous nano-cellulose colloid made from step (2) so that diethyl phosphate:
The mass ratio of nano-cellulose is 5: 1, and 50~70 DEG C are warming up under nitrogen protection, 3~5h is sufficiently stirred for, 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 work(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 nano-cellulose colloid made from step (1) so that ethylenediamine: nano-cellulose
Mass ratio is 5.5: 1, and 50~70 DEG C are warming up under nitrogen protection, 4~6h is sufficiently stirred for, and obtains nitrogenous nano-cellulose glue
Body；
(3) ammonium dihydrogen phosphate is added in nitrogenous nano-cellulose colloid made from step (2) so that ammonium dihydrogen phosphate:
The mass ratio of nano-cellulose is 4: 1, and 50~70 DEG C are warming up under nitrogen protection, 3~5h is sufficiently stirred for, 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 carry out according to the following steps：
(1) ultrasonic disperse in mass ratio (1~5): 100 weigh nano-cellulose, deionized water, is carried out, power is 800~
1000w, the time is 10~30min, obtains nano-cellulose colloid, adjusts the pH value of nano-cellulose colloid to 7；
(2) nitrogen-containing compound is added in nano-cellulose colloid made from step (1) so that nitrogen-containing compound: nanofiber
The mass ratio of element is (1.8~5.5): 1,50~70 DEG C are warming up under nitrogen protection, 4~6h is sufficiently stirred for, and obtain nitrogenous receive
Rice cellulose colloid；
(3) phosphorus-containing compound is added in nitrogenous nano-cellulose colloid made from step (2) so that phosphorus-containing compound: nanometer
The mass ratio of cellulose is (2~5): 1,50~70 DEG C are warming up under nitrogen protection, 3~5h is sufficiently stirred for, and obtain intumescent
Fire retardant；
The nitrogen-containing 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 is carried out in ice-water bath.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020109654A1 (en) * | 2018-11-30 | 2020-06-04 | Xpyro Oy | Method and aqueous composition for preventing wildfire |
| CN114990731A (en) * | 2022-04-20 | 2022-09-02 | 浙江安顺化纤有限公司 | PLA/PBAT composite flame-retardant antibacterial degradable short fiber and preparation method thereof |
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 |
-
2017
- 2017-06-20 CN CN201710491513.0A patent/CN107129599B/en active Active
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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020109654A1 (en) * | 2018-11-30 | 2020-06-04 | Xpyro Oy | Method and aqueous composition for preventing wildfire |
| CN113453768A (en) * | 2018-11-30 | 2021-09-28 | 埃克斯派洛有限公司 | Method and aqueous composition for preventing wildfires |
| CN114990731A (en) * | 2022-04-20 | 2022-09-02 | 浙江安顺化纤有限公司 | PLA/PBAT composite flame-retardant antibacterial degradable short fiber and preparation method thereof |
| CN114990731B (en) * | 2022-04-20 | 2023-11-03 | 浙江安顺化纤有限公司 | PLA/PBAT composite flame-retardant antibacterial degradable short fiber and preparation 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 |
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