CN109734965A - A kind of sisal hemp base CH/APP LBL self-assembly fire proofing and preparation method thereof - Google Patents
A kind of sisal hemp base CH/APP LBL self-assembly fire proofing and preparation method thereof Download PDFInfo
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- CN109734965A CN109734965A CN201811538423.3A CN201811538423A CN109734965A CN 109734965 A CN109734965 A CN 109734965A CN 201811538423 A CN201811538423 A CN 201811538423A CN 109734965 A CN109734965 A CN 109734965A
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Abstract
The invention discloses a kind of sisal hemp base CH/APP LBL self-assembly fire proofings and preparation method thereof.The sisal hemp base CH/APP LBL self-assembly fire proofing is made of substrate and decorative layer, the substrate is sisal fiber, the decorative layer is polycation electrolyte chitosan (CH) and polyanion electrolyte ammonium polyphosphate (APP), and polycation electrolyte chitosan (CH) and polyanion electrolyte ammonium polyphosphate (APP) pass through electrostatic LBL self-assembly alternating sorbent on sisal hemp surface.The excellent fireproof performance of sisal hemp base CH/APP LBL self-assembly fire proofing produced by the present invention, hot property significantly improves, and preparation method is simple.
Description
Technical field
The present invention relates to a kind of sisal hemp base CH/APP LBL self-assembly fire proofings and preparation method thereof, belong to novel from group
It fills flame retardant coating and modifies sisal fiber technical field.
Background technique
Sisal hemp is a kind of perennial hard fibre crop, originates in Central America, grows and be distributed part in south China
Area, ABUNDANT NATUREAL RESOURSES belong to natural agricultural crops renewable resource.Sisal fiber not only has good tensile property,
Also acid and alkali-resistance, it is corrosion-resistant, it is easy to obtain, a variety of advantages such as biodegradable, is a kind of environmentally protective natural macromolecular material,
Because its is light, the excellent mechanical property such as wear-resistant tensile has good compatibility with polymeric matrix, can be used as reinforcing material
To improve the performance of polymeric matrix.However sisal fiber is a kind of substance for being easy to burning again, this is just significantly limited
It is applied.
LBL self-assembly is as a kind of simple, multi-functional surface modification method, and earlier than 1966, Iler was reported for the first time
By the colloidal particle alternating deposit with opposite charges in glass sheet surface, it is successfully prepared the controllable plural layers of thickness.So
And up to 1991, Decher etc. passes through electrostatic layer by layer from group using the polyelectrolyte of the oppositely charged of linear structure for the first time
After dress technology is successfully prepared MULTILAYER COMPOSITE plate membrane, just widely people receive LBL self-assembly, and obtain within this decades
Quick development.Layer-by-layer refers to the method using layer-by-layer alternating deposit, by each layer molecular weak interaction
(electrostatic force, hydrogen bond etc.) is driving force, make between layers can spontaneous association to form structural integrity, performance stable, simultaneously
The process of molecule aggregate and supramolecular structure with certain specific function.Compared with traditional film build method, self assembly
Technology has several advantages that assembling process is relatively simple with a variety of film forming driving forces, reproducibility is high, to film substrate
Limitation is few, and the component and film thickness of film are controllable, and mechanical, chemical stability height.
Summary of the invention
The object of the present invention is to provide a kind of sisal hemp base CH/APP LBL self-assembly fire proofings and preparation method thereof.
Sisal hemp base CH/APP LBL self-assembly fire proofing of the invention is made of substrate and decorative layer, and the substrate is sword
Flaxen fiber, the decorative layer are polycation electrolyte chitosan (CH) and polyanion electrolyte ammonium polyphosphate (APP), gather sun
Ionic electrolytes chitosan (CH) and polyanion electrolyte ammonium polyphosphate (APP) are existed by electrostatic LBL self-assembly alternating sorbent
Sisal hemp surface.
Prepare the specific steps of sisal hemp base CH/APP LBL self-assembly fire proofing are as follows:
(1) it pre-processes
The sisal hemp of strip is impregnated 1-5 days in the sodium hydroxide solution of 2-10% concentration, removes the small molecule on sisal fiber surface
Substance, the small-molecule substance include lignin, pectin and waxy substance.
(2) on-line treatment
Pretreated sisal hemp is put into the sulfuric acid solution that mass concentration is 30-60%, impregnating 1-5 minutes at 30-60 DEG C makes
Sisal hemp takes negative electricity, and distilled water cleans 1-3 times, and filtering is spare.
(3) preparation of self assembly solution
The preparation of chitosan solution: chitosan is dissolved with acetic acid solution, and sodium chloride is added, stirs 8-15 hours, makes at room temperature
It is completely dissolved, and the chitosan solution that mass concentration is 0.1-2% is made.
The preparation of ammonium polyphosphate solution: ammonium polyphosphate is dissolved in distilled water, is stirred 8-15 hours at room temperature, is made it
It is completely dissolved, the ammonium polyphosphate solution that concentration is 1-5 mg/mL is made.
(4) preparation of sisal hemp base CH/APP LBL self-assembly fire proofing
Treated, sisal hemp is shredded, and is well dispersed in chitosan solution, magnetic agitation 1-3 hours, after stirring, then is used
Acetic acid solution washing filters 1-3 times；The sisal fiber drained is dipped into ammonium polyphosphate solution, after magnetic agitation 1-3 hours,
It is washed with distilled water suction filtration again 1-3 times, completes the adsorption process of a chitosan coat, ammonium polyphosphate coating；Repeat above-mentioned mistake
Journey 5-20 times obtains 5-20 layers of alternating sorbent in the composite material of sisal hemp substrate surface, i.e. sisal hemp base CH/APP LBL self-assembly
Fire proofing.
The volume fraction of the acetic acid solution is 0.5-2% v/v.
Advantages of the present invention: the present invention using electrostatic layer-by-layer successfully by polycation electrolyte chitosan and
Polyanion electrolyte ammonium polyphosphate alternating sorbent can prepare the sisal hemp system composite wood of the required number of plies on sisal fiber surface
Material.This composite material is significantly improved in terms of hot property, is expected in the stable cellulose of hot property as enhanced composite wood
Utilization in material field.Meanwhile the SF (CH/APP) prepared by layer-by-layernThe composite material of system, is formed
Multilayer membrane stability it is preferable.And material used in the composite material is all renewable degradable green material, institute's structure
The flame retardant coating built is halogen-free, and meets environmentally protective fire-retardant theory.
Detailed description of the invention
Fig. 1 is the schematic diagram of sisal fiber LBL self-assembly chitosan (CH) and ammonium polyphosphate (CH).
Fig. 2 is SF, SF (CH/APP)5With SF (CH/APP)10The thermogravimetric curve of sample.It can be seen that as CH/APP is applied
The number of plies increases, and initial decomposition temperature (decompose 5% temperature) gradually decreases, by pure SF 261.64 DEG C of temperature of initial decomposition gradually
It is reduced to SF (CH/APP)10258.97 DEG C.Three kinds of materials are also very regular in 800 DEG C of carbon yield, SF, SF (CH/
APP)5With SF (CH/APP)10Carbon yield be respectively 6.658%, 18.09%, 21.60%.The sample of 10 layers of 5 layers of assembling and assembling
The carbon yield than pure SF improves 11.432% and 14.942% respectively.Illustrate that CH/APP coating has the hot property of SF obviously to change
Kind, Residual carbon significantly improves.
Fig. 3 is using testing vertical flammability machine to SF, SF (CH/APP)5With SF (CH/APP)10These three samples are fired
Burn test.It can be seen from the figure that after assembling CH/APP coating, sisal fiber no longer occur it is remaining burn, and with assembling
The increase of the number of plies, after flame time is reduced, carbon yield increases.Illustrate that constructing flame retardant coating by alternating sorbent CH and APP can mention
The flame retardant property of high sisal fiber.
Fig. 4 is to carry out observation to sisal fiber assembling front and back using petrographic microscope to take pictures, and (a) figure and (b) figure are respectively
SF and SF (CH/APP) under 50*10 times of transmitted light of petrographic microscope10Surface topography, and (c) figure and (d) figure are respectively 10*10
SF carbon residue and SF (CH/APP) after combustion testing under times reflected light10The surface topography of carbon residue.From the comparison of figure (a) and figure (b), though
It is so unobvious, but can be seen that SF (CH/APP)10Surface ratio SF surface it is more smooth, it is also deep not as SF
Gully.And it can be seen that SF (CH/APP) from the comparison of figure (c) and figure (d)10The size of the size ratio SF carbon residue of carbon residue is wanted
Greatly, SF (CH/APP)10Carbon residue is also able to maintain the pattern of sisal fiber substantially, and SF carbon residue is shunk at apparent helical form.
It can be seen that the CH/APP coating constructed is at high temperature, a degree of protection is carried out to sisal fiber, has improved sword
The flame retardant property of flaxen fiber.Wherein, SF is pure sisal fiber；SF(CH/APP)5Alternately to have coated 5 strata cationic polyelectrolytes
The sisal fiber of chitosan and polyanion electrolyte ammonium polyphosphate coating；SF(CH/APP)10Alternately to have coated 10 stratas sun
The sisal fiber of ionic electrolytes chitosan and polyanion electrolyte ammonium polyphosphate coating.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within claims appended by the application and limited
Range.
Embodiment 1:
(1) it pre-processes
The sisal hemp of 15 g strips is impregnated two days in the NaOH solution of 5% concentration, removes lignin, the fruit on sisal fiber surface
The small-molecule substances such as glue, waxy substance.
(2) on-line treatment
Pretreated sisal hemp is put into the sulfuric acid solution that mass concentration is 45%, it is negative that 50 DEG C of immersions take sisal hemp in 2 minutes
Electricity, distilled water clean 2 times, filtering.
(3) preparation of self assembly solution
The preparation of chitosan solution (0.2% wt): dissolving 2 g chitosans with the acetic acid solution that 1000 mL volume fractions are 1%, and
5.8 g sodium chloride are added, stirs 12 h at room temperature, makes it completely dissolved.
The preparation of (1 mg/mL) ammonium polyphosphate solution: weighing 1 g ammonium polyphosphate, is dissolved in 1000 ml distilled water, room
Temperature is lower to stir 12 h, makes it completely dissolved.Slurry is 1% v/v acetic acid solution and distilled water.
(4) preparation of coating
Treated, sisal hemp is shredded, and sisal hemp is well dispersed in 1000 mL 0.1M NaCl, the shell that mass concentration is 0.2% is poly-
In sugared (CH) solution (containing 1% v/v acetic acid), one hour of magnetic agitation after stirring, filters recycling chitosan (CH) solution
(assembles concentration that general recovered liquid can be renewed again with 2 to 3 times), then suction filtration is washed 2 times with 1% v/v acetic acid.By the sisal hemp drained fibre
Dimension is dipped into 1000 mL, and concentration is after magnetic agitation 1 hour, to filter in 1mg/mL ammonium polyphosphate (APP) solution and recycle poly- phosphorus
Sour ammonium (APP) solution, then it is washed with distilled water suction filtration 2 times, this completes the adsorption process of one layer of CH/APP coating, repeat to grasp
Make above step 5 times, can be prepared by SF (CH/APP)5Composite material.
Embodiment 2:
(1) it pre-processes
The sisal hemp of 15 g strips is impregnated two days in the NaOH solution of 5% concentration, removes lignin, the fruit on sisal fiber surface
The small-molecule substances such as glue, waxy substance.
(2) on-line treatment
Pretreated sisal hemp is put into the sulfuric acid solution that mass concentration is 45%, it is negative that 50 DEG C of immersions take sisal hemp in 2 minutes
Electricity, distilled water clean 2 times, filtering.
(3) preparation of self assembly solution
The preparation of chitosan solution (0.2% wt): dissolving 2 g chitosans with the acetic acid solution that 1000 mL volume fractions are 1%, and
5.8 g sodium chloride are added, stirs 12 h at room temperature, makes it completely dissolved.
The preparation of (1 mg/mL) ammonium polyphosphate solution: weighing 1 g ammonium polyphosphate, is dissolved in 1000 mL distilled water, room
Temperature is lower to stir 12 h, makes it completely dissolved.Slurry is 1% v/v acetic acid solution and distilled water.
(4) preparation of coating
Treated, sisal hemp is shredded, and sisal hemp is well dispersed in 1000 mL, 0.1 M NaCl, the shell that mass concentration is 0.2%
In glycan (CH) solution (containing 1% v/v acetic acid), one hour of magnetic agitation, after stirring, it is molten to filter recycling chitosan (CH)
Liquid (assembles concentration that general recovered liquid can be renewed again with 2 to 3 times), then suction filtration is washed 2 times with 1% v/v acetic acid.The sisal hemp that will be drained
Fiber is dipped into 1000 mL, and concentration is that after magnetic agitation one hour, it is poly- to filter recycling in 1mg/mL ammonium polyphosphate (APP) solution
Ammonium phosphate (APP) solution, then it is washed with distilled water suction filtration 2 times, this completes the adsorption processes of one layer of CH/APP coating, repeat
Operation above step 10 times, can be prepared by SF (CH/APP)10Composite material.
Embodiment 3:
(1) it pre-processes
The sisal hemp of 15 g strips is impregnated two days in the NaOH solution of 5% concentration, removes lignin, the fruit on sisal fiber surface
The small-molecule substances such as glue, waxy substance.
(2) on-line treatment
Pretreated sisal hemp is put into the sulfuric acid solution that mass concentration is 45%, it is negative that 50 DEG C of immersions take sisal hemp in 2 minutes
Electricity, distilled water clean 2 times, filtering.
(3) preparation of self assembly solution
The preparation of chitosan solution (0.2% wt): dissolving 2 g chitosans with the acetic acid solution that 1000 mL volume fractions are 1%, and
5.8 g sodium chloride are added, stirs 12 h at room temperature, makes it completely dissolved.
The preparation of (1 mg/mL) ammonium polyphosphate solution: weighing 1 g ammonium polyphosphate, is dissolved in 1000 mL distilled water, room
Temperature is lower to stir 12 h, makes it completely dissolved.Slurry is 1% v/v acetic acid solution and distilled water.
(4) preparation of coating
Treated, sisal hemp is shredded, and sisal hemp is well dispersed in 1000 mL, 0.1 M NaCl, the shell that mass concentration is 0.2%
In glycan (CH) solution (containing 1% v/v acetic acid), one hour of magnetic agitation, after stirring, it is molten to filter recycling chitosan (CH)
Liquid (assembles concentration that general recovered liquid can be renewed again with 2 to 3 times), then suction filtration is washed 2 times with 1% v/v acetic acid.The sisal hemp that will be drained
Fiber is dipped into 1000 mL, and concentration is that after magnetic agitation 1 hour, it is poly- to filter recycling in 1 mg/mL ammonium polyphosphate (APP) solution
Ammonium phosphate (APP) solution, then it is washed with distilled water suction filtration 2 times, this completes the adsorption processes of one layer of CH/APP coating, repeat
Operation above step 20 times, can be prepared by SF (CH/APP)20Composite material.
Claims (2)
1. a kind of sisal hemp base CH/APP LBL self-assembly fire proofing, it is characterised in that the fire proofing is by substrate and decorative layer group
At the substrate is sisal fiber, and the decorative layer is polycation electrolyte chitosan and polyanion electrolyte polyphosphoric acid
Ammonium, polycation electrolyte chitosan and polyanion electrolyte ammonium polyphosphate are by electrostatic LBL self-assembly alternating sorbent in sword
Numb surface.
2. a kind of preparation method of sisal hemp base CH/APP LBL self-assembly fire proofing as described in claim 1, it is characterised in that
Specific steps are as follows:
(1) it pre-processes
The sisal hemp of strip is impregnated 1-5 days in the sodium hydroxide solution of 2-10% concentration, removes the small molecule on sisal fiber surface
Substance, the small-molecule substance include lignin, pectin and waxy substance；
(2) on-line treatment
Pretreated sisal hemp is put into the sulfuric acid solution that mass concentration is 30-60%, impregnating 1-5 minutes at 30-60 DEG C makes
Sisal hemp takes negative electricity, and distilled water cleans 1-3 times, and filtering is spare；
(3) preparation of self assembly solution
The preparation of chitosan solution: chitosan is dissolved with acetic acid solution, and sodium chloride is added, stirs 8-15 hours, makes at room temperature
It is completely dissolved, and the chitosan solution that mass concentration is 0.1-2% is made；
The preparation of ammonium polyphosphate solution: ammonium polyphosphate is dissolved in distilled water, is stirred 8-15 hours at room temperature, makes it completely
The ammonium polyphosphate solution that concentration is 1-5 mg/mL is made in dissolution；
(4) preparation of sisal hemp base CH/APP LBL self-assembly fire proofing
Treated, sisal hemp is shredded, and is well dispersed in chitosan solution, magnetic agitation 1-3 hours, after stirring, then is used
Acetic acid solution washing filters 1-3 times；The sisal fiber drained is dipped into ammonium polyphosphate solution, after magnetic agitation 1-3 hours,
It is washed with distilled water suction filtration again 1-3 times, completes the adsorption process of a chitosan coat, ammonium polyphosphate coating；Repeat above-mentioned mistake
Journey 5-20 times obtains 5-20 layers of alternating sorbent in the composite material of sisal hemp substrate surface, i.e. sisal hemp base CH/APP LBL self-assembly
Fire proofing；
The volume fraction of the acetic acid solution is 0.5-2% v/v.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115198527A (en) * | 2022-07-04 | 2022-10-18 | 同济大学 | Layer-by-layer self-assembly flame-retardant fabric based on full-biomass flame-retardant system and preparation method thereof |
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| CN103408789A (en) * | 2013-05-13 | 2013-11-27 | 四川大学 | High-efficiency flame-retardant modified melamino-formaldehyde foams and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408789A (en) * | 2013-05-13 | 2013-11-27 | 四川大学 | High-efficiency flame-retardant modified melamino-formaldehyde foams and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| FEI FANG等: ""Intumescent flame retardant coatings on cotton fabric of chitosan and ammonium polyphosphate via layer-by-layer assembly"", 《SURFACE & COATINGS TECHNOLOGY》 * |
| 唐见茂: "《绿色复合材料》", 31 December 2016, 中国铁道出版社 * |
| 曾思华等: ""剑麻纤维素微晶(壳聚糖/聚对苯乙烯磺酸钠)层层自组装及其复合材料的热性能和阻燃性能"", 《高分子材料科学与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115198527A (en) * | 2022-07-04 | 2022-10-18 | 同济大学 | Layer-by-layer self-assembly flame-retardant fabric based on full-biomass flame-retardant system and preparation method thereof |
| CN115198527B (en) * | 2022-07-04 | 2023-09-26 | 同济大学 | Layer-by-layer self-assembled flame-retardant fabric based on full biomass flame-retardant system and preparation method thereof |
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