CN105080814B - LBL self assembly polyelectrolyte nano flame retardant coating and preparation method thereof - Google Patents
LBL self assembly polyelectrolyte nano flame retardant coating and preparation method thereof Download PDFInfo
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- CN105080814B CN105080814B CN201410162821.5A CN201410162821A CN105080814B CN 105080814 B CN105080814 B CN 105080814B CN 201410162821 A CN201410162821 A CN 201410162821A CN 105080814 B CN105080814 B CN 105080814B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
Abstract
The invention discloses a kind of LBL self assembly polyelectrolyte nano flame retardant coating and preparation method thereof, comprise the following steps：1) pre-process：Matrix material is put into acid solution and soaked, is dried after being cleaned with water；2) self assembly：The matrix material of pretreatment is put into cationic polyelectrolyte solution and soaked, after forming one layer of cationic membrane, taking-up is dried after being cleaned with water, is then placed in anionic polyelectrolyte solution and is soaked, and is dried after being cleaned after one layer of anionic membrane of formation with water；It is multiple to be repeated in above-mentioned self assembling process, i.e., LBL self assembly polyelectrolyte nano flame retardant coating is made in substrate material surface.The present invention prepares polyelectrolyte nano flame retardant coating using LBL self assembly technology, it is green, and preparation method is simple and easy, does not destroy the internal structure of matrix material, there is higher flame retarding efficiency simultaneously, suitable for forming flame retardant coating on fabric, timber, foam, plastic or other material surface.
Description
Technical field
The invention belongs to flame retardant coating preparation field, more particularly to the system of LBL self assembly polyelectrolyte nano flame retardant coating
Preparation Method and thus obtained flame retardant coating.
Background technology
LBL self assembly (Layer-by-layer assembly, L-b-L) technology is to develop the early 1990s in last century
A kind of process for modifying surface come, the composition, thickness, structural form on colloidal particle surface etc. can be carried out on nanoscale accurate
Really control.This package technique alternately immerses the polyelectrolyte solution with opposite charges using the particle of ionization as template
In, the regular hour is soaked, taking-up is rinsed well, and circulation above procedure can be obtained by Multilayer system.LBL self assembly skill
Art has the advantages that applied widely, generation microballoon property is controllable, environment-friendly, simple and reproducible, thus in biology
The field such as sensor, drug delivery system, electronics and optics, seperation film and catalysis all shows wide application prospect.
In recent years, L-b-L technologies are applied to fire proofing field, by LBL self assembly nano flame retardant coating to improve
The fire protecting performance of material.Compared with traditional flame resistant method, such as flame-retardant additive is added in the material, prepared by L-b-L technologies
Nano flame retardant coating have and do not deteriorate the self property of matrix material, flame retarding efficiency is high, and operating process is easy, environmentally friendly
Etc. advantage.
But the most of polyelectrolyte used at present all be ionization nano-particle, for example, montmorillonite, graphene,
On the one hand CNT etc., the coating of these nano-particles can change the color of matrix material, another aspect flame retarding efficiency needs
Improved in further.Therefore, need badly and develop a kind of green, flame retarding efficiency is high, applied widely and do not destroy matrix material
Expect the polyelectrolyte nano flame retardant coating of internal structure.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：Matrix material is put into acid molten
Immersion is pre-processed in liquid, and then pretreated matrix material is put into cationic polyelectrolyte solution and soaked, and is taken out
Cleaned and dried with water, be then placed in anionic polyelectrolyte solution and soak, taking-up is cleaned and dried with water, passes through alternately weight
It is put into cationic polyelectrolyte solution with anionic polyelectrolyte solution, i.e., is made in substrate material surface successively from group again
Polyelectrolyte nano flame retardant coating is filled, so as to complete the present invention.
An object of the present invention is to provide a kind of preparation method of LBL self assembly polyelectrolyte nano flame retardant coating,
It is characterised in that it includes following steps：
(1) pre-process：Matrix material is put into acid solution and soaked, is dried after then being cleaned with water；
(2) self assembly：The matrix material of pretreatment in step (1) is put into cationic polyelectrolyte solution and soaked,
After substrate material surface forms one layer of cationic memebrane, dry, be then placed in anionic polyelectrolyte solution after being cleaned with water
Immersion, and after one layer of anionic membrane of surface formation, dried after being cleaned with water；
It is multiple to be repeated in above-mentioned self assembling process, i.e., LBL self assembly polyelectrolyte nanometer is made in substrate material surface
Flame retardant coating.
It is a kind of poly- electric in substrate material surface LBL self assembly according to the above method another object of the present invention is to provide
Prepared by solving matter nano flame retardant coating.
A further object of the present invention is the purposes of above-mentioned LBL self assembly polyelectrolyte nano flame retardant coating, that is, is used as knitting
The flame retardant coating of the substrate material surfaces such as thing, timber, foam or plastics.
It is provided by the invention successively to assemble polyelectrolyte nano flame retardant coating, wherein, used polyelectrolyte green ring
Protect, wide material sources, therefore preparation method is simple and easy, cost is cheap, and compared with traditional flame resistant method, use is provided by the present invention
Nano flame retardant coating has more preferable flame retarding efficiency, suitable for the flameproof protection of different matrix material.
Brief description of the drawings
Fig. 1 shows the electron scanning micrograph of the polyelectrolyte nano flame retardant coating by the gained of embodiment 1；
Fig. 2 shows the electron scanning micrograph of the polyelectrolyte nano flame retardant coating by the gained of embodiment 2；
Fig. 3 shows the electron scanning micrograph on the surface by the uncoated polyurethane foam of comparative example 1；
Fig. 4 is shown by the heat release rate curve of gained polyurethane foam in embodiment 1, embodiment 2 and comparative example 1；
Fig. 5 shows the polyurethane by being burned after the test of the polyurethane foam progress HRR of the gained of embodiment 1
The electron scanning micrograph of foam；
Fig. 6 shows the polyurethane by being burned after the test of the polyurethane foam progress HRR of the gained of embodiment 2
The electron scanning micrograph of foam；
Fig. 7 shows the polyurethane foam by being burned after the test of the polyurethane foam progress HRR of comparative example 1
Electron scanning micrograph；
Fig. 8 a show that the terylene in comparative example 2 carries out the photo of vertical burn test；
Fig. 8 b show that the terylene of gained in embodiment 3 carries out the photo of vertical burn test；
Fig. 9 a show that the polyurethane foam of gained in embodiment 1 carries out the snapshot of horizontal firing test；
Fig. 9 b show that the polyurethane foam of gained in embodiment 2 carries out the snapshot of horizontal firing test；
Fig. 9 c show that the polyurethane foam in comparative example 3 carries out the snapshot of horizontal firing test.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
To be clear, clear and definite.
According to an aspect of the present invention, there is provided a kind of preparation side of LBL self assembly polyelectrolyte nano flame retardant coating
Method, comprise the following steps：
Step 1, it is pre-treatment step：Matrix material is put into acid solution and soaked, is dried after then being cleaned with water.
According to the present invention, described matrix material is fabric, timber, foam or plastics, the preferably fabric such as terylene, polyurethane etc.
Foamed material.In order to be soaked, matrix material can be processed into suitable shape such as cuboid, and appropriate yardstick, such as
Centimetre, decimeter even rice magnitude.
Described matrix material is first put into immersion in acid solution to be pre-processed, this pretreatment is favorably improved matrix
The adsorptivity of material surface, so as to contribute to some compounds in the deposition of substrate material surface.
According to the present invention, soak 5 seconds to 30 minutes, then cleaned with water, especially, from deionization in an acidic solution
Water clean, after cleaning can naturally dry, can also heating, drying, such as dried in an oven at a certain temperature.If leaching
The time is steeped less than 5 seconds, because the time is too short, with substrate material surface electrostatic adsorption can not occur for acidic materials well,
The absorption affinity with matrix material is then substantially reduced, so as to influence the adhesive force of substrate material surface, as time went on, matrix
The acidic materials of material surface absorption tend to reach saturation, that is, can reach saturation after soaking 30 minutes, if extending the time again,
Unnecessary waste can be caused, also influences whether operating efficiency.Found by research, soak time preferably 7 seconds to 15 minutes, more
Preferably 10 seconds to 5 minutes, it may be such that adsorption effect and efficiency are optimal.
In the present invention, the acid solution be polyacrylic acid, polyphosphoric acids, polymalic acid the aqueous solution in one kind or
It is a variety of.Because polyacrylic acid, polyphosphoric acids and polymalic acid are respectively provided with higher degree of ionization, and it is the material of HMW,
It is strong with the active force of matrix material, it can adsorb well in substrate material surface, while also greatly strengthen substrate material surface
Adhesive force.In addition, above-mentioned three kinds of acid is more friendly to environment.
According to the present invention, the mass percent concentration of acid solution is 0.3%~30%, if less than 0.3%, it is impossible to very well
Electrostatic adsorption occurs with matrix material, if higher than 30%, will not have better effect, acid and matrix material can be influenceed on the contrary
The active force on surface is expected, so as to be unfavorable for improving substrate material surface adhesive force.Especially, the mass percent of acid solution is dense
Degree preferably 0.5%~20%, more preferably 0.5%~10%.
Especially, described matrix material can use organic solvent, such as acetone or ethanol to carry out clearly before being pretreated
Wash, then cleaned with water, especially, cleaned from deionized water, then naturally dry or dried at a certain temperature.
Step 2, self assembly：The matrix material of pretreatment is put into cationic polyelectrolyte solution and soaked, in matrix material
After expecting that surface forms one layer of cationic memebrane, dried after being cleaned with water, be then placed in anionic polyelectrolyte solution and soak, again
After forming one layer of anionic membrane on surface, dried after being cleaned with water.
According to the present invention, soaked 5 seconds to 30 points in cationic polyelectrolyte solution by pretreated matrix material
Clock, cleaned after immersion with water, especially, from deionized water clean, clean it is one or many after dry, can naturally dry,
It can at a certain temperature dry, such as be dried in an oven, such as may be selected to dry 6~15 hours at 50~80 DEG C.Its
In, if soak time is less than 5 seconds, in a short time, can not be adsorbed well after the pre-treatment with cationic polyelectrolyte
On substrate material surface, if more than 30 minutes, due to having reached full with the cationic polyelectrolyte that substrate material surface adsorbs
With unnecessary waste can be caused by then extending the time, while can influence adsorption effect on the contrary.Especially, soak time preferably 7 seconds
By 15 minutes, more preferably 10 seconds to 5 minutes.
In a preferred embodiment, the cationic polyelectrolyte solution is chitosan, polyallylamine hydrochloride, poly- two
Methyl diallyl ammonium chloride, pR hydrochloride, polyethyleneimine the aqueous solution in one or more.From upper
State the cationic polyelectrolyte of macromolecule, on the one hand, the absorption affinity with pretreated substrate material surface can be strengthened, it is another
Aspect, because above-mentioned cationic polyelectrolyte nitrogen content is high, nitrogenous gas is easily discharged at high temperature, while be easily carbonized,
So as to reach preferable flame retardant effect.
According to the present invention, the mass percent concentration of the cationic polyelectrolyte solution is 0.3%~30%, preferably
0.5~20%, more preferably 0.5~10%.
, can be in matrix material table due to suction-operated after soaking certain time in above-mentioned cationic polyelectrolyte solution
Face forms one layer of cationic memebrane, after being then cleaned and dried, then immerses in anion electrolyte solution, due to the phase of positive and negative charge
Mutual sucking action and intermolecular interaction force so that anionic polyelectrolyte is deposited, and one is formed again in substrate material surface
Layer anionic membrane, further, since cationic polyelectrolyte is different from the molecule amount of crimp of anionic polyelectrolyte, then two
Person forms the coating of even compact in substrate material surface jointly, and layer protecting film is provided for matrix material, so as to more preferable
Heat-insulated oxygen barrier, improve the fire resistance of matrix material.
According to the present invention, the anionic polyelectrolyte solution is alginate, phosphenylic acid, cyclodextrin-butyl sulfonic acid
Sodium, polyvinyl sulfuric acid salt, poly-aspartate, phosphotidats the aqueous solution in one or more.From the poly- electricity of above-mentioned anion
Xie Zhi, on the one hand, good suction-operated can occur with cationic polyelectrolyte, on the other hand, because itself has well
Fire resistance, then substantially increase the fire resistance of coating.
Study and find through inventor, the mass percent concentration of anionic polyelectrolyte solution is 0.3%~30%, reachable
To preferable adsorption effect and flame retardant effect, in particular it is preferred to 0.5~20%, more preferably 0.5~10%.
In step 2, pretreated matrix material is used after being soaked 5 seconds to 30 minutes in anionic polyelectrolyte solution
Water cleans, and especially, is cleaned from deionized water, is then dried, can naturally dry, or dried at 50~80 DEG C
6~15 hours.Wherein, soak time preferably 7 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, it can reach optimal absorption effect
Fruit.
In the present invention, it is repeated in that above-mentioned self assembling process is multiple, depending on the desired coating layer thickness reached and/or fire-retardant
Depending on effect, such as it can be repeated 2 times to 60 times, preferably 5 times to 50 times, more preferably 10 times to 30 times, i.e., in matrix material table
Simultaneously nano flame retardant coating is finally made in face LBL self assembly polyelectrolyte, and its thickness is usually nanoscale.As needed, can also
Repeat more times, due to the difference of selected material, even up to micron order.
Therefore, another aspect of the present invention is to provide according to the above method in the poly- electrolysis of substrate material surface LBL self assembly
Prepared by matter nano flame retardant coating, coating layer thickness is usually nanoscale, such as more than ten nanometers to hundreds of nanometers, such as 15nm extremely
900nm, preferably 75nm are to 750nm, more preferably 150nm to 450nm, as needed, select polyelectrolyte solution then different, or
Repeat more times, even up to micron order.
The nano flame retardant coating being prepared according to method of the present invention, first by cationic polyelectrolyte
Positive charge in substrate material surface with after suction-operated occurs for the substrate material surface that pretreatment obtains, depositing, then matrix
Material surface is positively charged, then, when being again dipped into anionic polyelectrolyte solution, because positive and negative charge attracts each other work
With, and the interaction force between macromolecular, anionic polyelectrolyte is in the surface of matrix material deposition, substrate material surface
The positive charge of institute's band is shielded, and then, remaining negative electrical charge make it that substrate material surface is negatively charged, when being alternately repeated leaching successively
After entering in cationic polyelectrolyte solution and anionic polyelectrolyte solution, substrate material surface layer by layer deposition polyelectrolyte.
In pretreatment and self assembling process, due to being only that simple absorption is made between polyelectrolyte and matrix material and polyelectrolyte
With, therefore preparation method provided by the present invention can't destroy the structure of matrix material, so as to which matrix material sheet will not be changed
The performance of body, while the coating of the even compact formed has heat-insulated oxygen barrier effect well and prevents the outside of fuel gas
Effusion, so as to reach fire-retardant purpose.
In a preferred embodiment, the pH value of the cationic polyelectrolyte solution and anionic polyelectrolyte solution
Keep identical, pH value can be adjusted to 4~9 with hydrochloric acid or sodium hydroxide.Between pH is 4~9, the poly- electrolysis of cation may be such that
Matter and anionic polyelectrolyte carry appropriate electric charge so that post-depositional coating more even compact, it is optimal so as to reach
Flame retardant effect.If anionic polyelectrolyte carried charge is excessive, less molecule is needed to deshield cationic polyelectrolyte institute
The positive charge of band, therefore less anionic polyelectrolyte deposits, then can influence the fire resistance of coating.If anionic polyelectrolyte
Matter carried charge is very few, then needs more molecules to deshield the positive charge of cationic polyelectrolyte institute band, thus it is more it is cloudy from
Sub- polyelectrolyte deposition, then the repulsive interaction of itself can influence the even compact performance of the coating of deposition, so as to influence coating
Fire resistance.Especially, pH value is preferably 5~8, and more preferably 6.
According to the present invention, the molar concentration of hydrochloric acid mentioned above is 0.5~2mol/l, and the molar concentration of sodium hydroxide is
0.5~2mol/l, especially, the molar concentration of hydrochloric acid and sodium hydroxide is 1~1.5mol/l.
Another aspect of the invention is related to the purposes of the LBL self assembly polyelectrolyte nano flame retardant coating, i.e., by successively
Self assembly is on matrix material such as fabric (especially terylene), timber, foam (especially polyurethane) or the surface of plastics, not
On the premise of changing these matrix materials performances itself, its flame retarding efficiency is greatly improved, plays flame retardant coating effect, and this hair
Bright provided coating has wide range of applications, more friendly to environment.
Embodiment
The present invention is further described below by way of instantiation.But these examples are only exemplary, not to this
The protection domain of invention forms any restrictions.
It is related to multiple material or reagent in following embodiments and comparative example, they is not particularly limited, can uses
The commercially available commercial sources of in the market, it can also be prepared by conventional method laboratory scale or production scale.
In non-limiting manner, reagent used in following embodiments and comparative example is bought in Sigma Aldrich.
Embodiment 1
Polyurethane foam is cut to 10cm × 10cm × 3cm；
Weigh 0.5g polyacrylic acid to be added in 99.5g deionized waters, stirring is standby to being completely dissolved；
Weigh 5g chitosans to be added in 995g deionized waters, stirring is standby to being completely dissolved；
Weigh 20g sodium alginates to be added in 980g deionized waters, stirring is standby to being completely dissolved；
1) pre-process：Take the polyurethane foam cut to immerse in above-mentioned polyacrylic acid solution, after soaking 300 seconds, spend
Ionized water cleans, and then dries；
2) self assembly：The polyurethane foam of above-mentioned pretreatment is put into above-mentioned chitosan solution and soaked 60 seconds, Ran Houyong
Dried after deionized water cleaning, be then placed in after being soaked 60 seconds in above-mentioned sodium alginate soln, cleaned with deionized water, then dried
It is dry；
It is repeated in above-mentioned self assembling process 5 times, i.e., 5 double-deck self assembly polyelectrolyte is made in substrate material surface and receives
Rice flame retardant coating, its thickness is about 155nm, and its electron scanning micrograph is as shown in Figure 1.
Embodiment 2
Polyurethane foam is cut to 10cm × 10cm × 3cm；
Weigh 0.5g polyacrylic acid to be added in 99.5g deionized waters, stirring is standby to being completely dissolved；
Weigh 5g chitosans to be added in 995g deionized waters, stirring is standby to being completely dissolved；
Weigh 20g sodium alginates to be added in 980g deionized waters, stirring is standby to being completely dissolved；
1) pre-process：Take the polyurethane foam cut to immerse in above-mentioned polyacrylic acid solution, after soaking 300 seconds, spend
Ionized water cleans, and then dries；
2) self assembly：The polyurethane foam of above-mentioned pretreatment is put into above-mentioned chitosan solution and soaked 60 seconds, Ran Houyong
Dried after deionized water cleaning, be then placed in after being soaked 60 seconds in above-mentioned sodium alginate soln, cleaned with deionized water, then dried
It is dry；
It is repeated in above-mentioned self assembling process 10 times, i.e., 10 double-deck self assembly polyelectrolyte is made in substrate material surface
Nano flame retardant coating, its thickness are about 323nm, and its electron scanning micrograph is as shown in Figure 2.
Embodiment 3
Terylene is cut to 30cm × 8cm；
Weigh 5g polyacrylic acid to be added in 95g deionized waters, stirring is standby to being completely dissolved；
Weigh 5g chitosans to be added in 995g deionized waters, stirring is standby to being completely dissolved；
Weigh 40g phosphenylic acids to be added in 960g deionized waters, stirring is standby to being completely dissolved；
1) pre-process：The terylene cut is taken to immerse in above-mentioned polyacrylic acid solution, it is clear with deionized water after soaking 60 seconds
Wash, then dry；
2) self assembly：The terylene of above-mentioned pretreatment is put into above-mentioned chitosan solution and soaked 60 seconds, then uses deionization
Dried after water cleaning, be then placed in after being soaked 60 seconds in above-mentioned phosphenylic acid solution, cleaned with deionized water, then dried；
It is repeated in above-mentioned self assembling process 10 times, i.e., 10 double-deck self assembly polyelectrolyte is made in substrate material surface
Nano flame retardant coating, its thickness are about 302nm.
Embodiment 4
Polyurethane foam is cut to 10cm × 10cm × 3cm；
Weigh 0.5g polyphosphoric acids to be added in 99.5g deionized waters, stirring is standby to being completely dissolved；
Weigh 100g polypropylene amine hydrochloric acid to be added in 900g deionized waters, stirring is standby to being completely dissolved；
Weigh 60g cyclodextrin-butyl sulfonic acid sodium to be added in 940g deionized waters, stirring is standby to being completely dissolved；
1) pre-process：Take the polyurethane foam that cuts to immerse in above-mentioned poly phosphoric acid solution, after immersion 60 seconds, spend from
Sub- water cleaning, is then dried；
2) self assembly：The polyurethane foam of above-mentioned pretreatment is put into above-mentioned polypropylene amine hydrochloric acid solution and soaked 60 seconds,
Then dry, be then placed in after being soaked 60 seconds in above-mentioned cyclodextrin-butyl sulfonic acid sodium solution after being cleaned with deionized water, spend from
Sub- water cleaning, is then dried；
It is repeated in above-mentioned self assembling process 15 times, i.e., 15 double-deck self assembly polyelectrolyte is made in substrate material surface
Nano flame retardant coating, its thickness are about 495nm.
Embodiment 5
Terylene is cut to 30cm × 8cm；
Weigh 0.5g polymalic acids to be added in 99.5g deionized waters, stirring is standby to being completely dissolved；
Weigh 20g pR hydrochlorides to be added in 980g deionized waters, stirring is standby to being completely dissolved；
Weigh 5g polyvinyl sulfuric acid salt to be added in 995g deionized waters, stirring is standby to being completely dissolved；
1) pre-process：The terylene cut is taken to immerse in above-mentioned polymalic acid solution, it is clear with deionized water after soaking 60 seconds
Wash, then dry；
2) self assembly：The polyurethane foam of above-mentioned pretreatment is put into above-mentioned pR HCI solution and soaked
60 seconds, dry, be then placed in after being soaked 60 seconds in above-mentioned polyvinyl sulfuric acid salting liquid after then being cleaned with deionized water, spend from
Sub- water cleaning, is then dried；
It is repeated in above-mentioned self assembling process 20 times, i.e., 20 double-deck self assembly polyelectrolyte is made in substrate material surface
Nano flame retardant coating, its thickness are about 713nm.
Embodiment 6
Polyurethane foam is cut to 10cm × 10cm × 3cm；
Weigh 10g polyacrylic acid to be added in 90g deionized waters, stirring is standby to being completely dissolved；
Weigh 20g chitosans to be added in 980g deionized waters, stir to being completely dissolved, it is then molten with 1mol/l hydrochloric acid
The pH value of liquid regulation chitosan solution is 6, standby；
Weigh 100g phosphenylic acids to be added in 900g deionized waters, stir to being completely dissolved, then with 1mol/l salt
The pH value of acid solution regulation phosphenylic acid solution is 6, standby；
1) pre-process：Take the polyurethane foam that cuts to immerse in above-mentioned polyacrylic acid solution, after immersion 10 seconds, spend from
Sub- water cleaning, is then dried；
2) self assembly：The polyurethane foam of above-mentioned pretreatment is put into above-mentioned chitosan solution and soaked 10 seconds, Ran Houyong
Dried after deionized water cleaning, be then placed in after being soaked 10 seconds in above-mentioned phosphenylic acid solution, cleaned with deionized water, then dried
It is dry；
It is repeated in above-mentioned self assembling process 10 times, i.e., 10 double-deck self assembly polyelectrolyte is made in substrate material surface
Nano flame retardant coating, its thickness are about 287nm.
Comparative example
Comparative example 1
The polyurethane foam cut in Example 1, without any coating, its electron scanning micrograph is such as
Shown in Fig. 3.
Comparative example 2
The terylene cut in Example 3, without any coating.
Comparative example 3
Embodiment 1 is repeated, wherein, weigh 1g sodium alginates and be added in 999g deionized waters, stirring is standby to being completely dissolved
With other conditions are constant.
Test example
Test example 1：ESEM I
To the polyurethane foam coated with polyelectrolyte nano flame retardant coating being prepared in embodiment 1 and embodiment 2
With comparative example 1 uncoated polyurethane foam be scanned Electronic Speculum experiment, its result respectively as shown in Figure 1, Figure 2 and Figure 3.
Scanning electron micrograph according to Fig. 1, Fig. 2 and Fig. 3, it is in comparative example 1 it can be seen that uncoated
Natural porous structure and more smooth is presented in polyurethane foam surface, and the surface of the polyurethane foam in embodiment 1 is very thick
It is rough, it is impossible to see the structure of polyurethane foam itself, in example 2, it can be seen that the space on polyurethane foam surface is filled out
It is full, show that the surface of polyurethane foam clearly deposited thicker coating.Therefore can draw, by pretreatment and self assembly
Cheng Hou, polyelectrolyte are evenly distributed on the surface of polyurethane foam.
Test example 2：Heat release rate testing
According to ISO5660-1-2002《Reaction to fire experiment heat release, smoke-producing amount and mass loss rate-part 1：Heat is released
Put speed (Cone calorimeter)》Standard, using FTT cone calorimetries (combustion testing technology company of Britain), in radiation flux
For 35kW/m2Under the conditions of test sample parameter such as HRR when burning.
According to the above method, embodiment 1 and embodiment 2 are prepared coated with polyelectrolyte nano flame retardant coating
Polyurethane foam and the uncoated polyurethane foam of comparative example 1 carry out the test of HRR, and its result is as shown in Figure 4.
Heat release rate curve figure according to Fig. 4, it can be deduced that important parameter as shown in table 1：
Table 1
It can be drawn by the parameter in table 1, the heat release speed of the polyurethane foam by the coating of polyelectrolyte nano coating
Rate peak value significantly declines, and the intensity of a fire is decreased obviously, and the time increase for igniting required, total heat that discharges has declined, and shows
The polyurethane foam coated by polyelectrolyte can preferably suppress the intensity of a fire, and the possibility that material is ignited declines, and have good
Good fire resistance.
Test example 3：ESEM II
The polyurethane foam coated with polyelectrolyte nano flame retardant coating that is prepared in embodiment 1 and embodiment 2 and
After the uncoated polyurethane foam of comparative example 1 carries out the test of HRR, burned polyurethane foam is scanned
Electronic Speculum, its result is as shown in Fig. 5, Fig. 6 and Fig. 7.
Electron scanning micrograph according to Fig. 5, Fig. 6 and Fig. 7 can be seen that in the figure 7, and uncoated is poly-
Loose porous form is presented after urethane foam combustion, in Figure 5, the polyurethane foam after burning shows more continuous densification
Form, in figure 6, continuous fine and close form is presented in polyurethane foam after burning.Thus illustrate, coated by polyelectrolyte
Polyurethane foam afterwards can provide diaphragm for base material, and the transmission of material and heat, good so as to reach when reducing burning
Flame retardant effect.
Test example 4：Vertical burn test
According to ASTM D6413-2008《Textile combustion performance test normal beam technique》, using UL-94 fire resistance analyzers
(combustion testing technology company of Britain), determine the vertical combustion performance of terylene.
According to the above method, vertical burn test, its result such as Fig. 8 a are carried out to the terylene in embodiment 3 and comparative example 2
Shown in Fig. 8 b.
Contrast photo according to Fig. 8 a and Fig. 8 b can be seen that terylene contact burning things which may cause a fire disaster it is inflammable, propagation of flame, burning is held
Continuous 20s；And only melted after coating the terylene contact burning things which may cause a fire disaster of 10 double-deck chitosans-phosphenylic acid nano flame retardant coating, not
It was found that naked light, combustion continuation 10s.
Test example 5：Horizontal firing is tested
According to GB/T8332-2008《Foamed plastics combustibility test method-horizontal firing method》, it is fire-retardant using UL-94
Fabricmeter (combustion testing technology company of Britain), determine the horizontal firing performance of polyurethane foam.
According to the above method, horizontal firing is carried out to the polyurethane foam of gained in embodiment 1, embodiment 2 and comparative example 3
Test, its result is as shown in Fig. 9 a, Fig. 9 b and Fig. 9 c.
Contrast snapshot according to Fig. 9 a, Fig. 9 b and Fig. 9 c can be seen that by poly- obtained by embodiment 1 and embodiment 2
Urethane foam flame retardant effect is more preferable.
The present invention is described in detail above in association with embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
A variety of equivalencing, modification or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is determined by the appended claims.
Claims (10)
1. a kind of preparation method of LBL self assembly polyelectrolyte nano flame retardant coating, it is characterised in that comprise the following steps：
(1) pre-process：Matrix material is put into acid solution and soaked, is dried after then being cleaned with water；The acid solution is
Polyacrylic acid, polyphosphoric acids, polymalic acid the aqueous solution in one or more；It is in mass percent concentration by matrix material
Soaked 5 seconds to 30 minutes in 0.3%~30% acid solution；
(2) self assembly：The matrix material of pretreatment in step (1) is put into cationic polyelectrolyte solution and soaked, in matrix
After material surface forms one layer of cationic memebrane, dried after being cleaned with water, be then placed in anionic polyelectrolyte solution and soak,
After forming one layer of anionic membrane on surface again, dried after being cleaned with water；
It is multiple to be repeated in above-mentioned self assembling process, i.e., LBL self assembly polyelectrolyte nano flame retardant is made in substrate material surface
Coating；
The cationic polyelectrolyte solution is chitosan, polyallylamine hydrochloride, PDDA, poly-
L-arginine hydrochloride, polyethyleneimine the aqueous solution in one or more；
The anionic polyelectrolyte solution be alginate, phosphenylic acid, cyclodextrin-butyl sulfonic acid sodium, polyvinyl sulfuric acid salt,
Poly-aspartate, phosphotidats the aqueous solution in one or more；
It is with hydrochloric acid or sodium hydroxide that cationic polyelectrolyte solution and anionic polyelectrolyte is molten before step (2) is carried out
The pH value of liquid is adjusted to 4~9.
2. preparation method according to claim 1, it is characterised in that in step (1), described matrix material be fabric,
Timber, foam or plastics.
3. preparation method according to claim 1, it is characterised in that in step (1), by matrix material in quality percentage
Specific concentration is to be soaked 7 seconds to 15 minutes in 0.5%~20% acid solution.
4. preparation method according to claim 3, it is characterised in that be in mass percent concentration by matrix material
Soaked 10 seconds to 5 minutes in 0.5%~10% acid solution.
5. preparation method according to claim 1, it is characterised in that in step (2), the cationic polyelectrolyte is molten
The mass percent concentration of liquid is 0.3%~30%, and soak time is 5 seconds to 30 minutes.
6. according to the method for claim 5, it is characterised in that the mass percent of the cationic polyelectrolyte solution is dense
Spend for 0.5%~10%, soak time is 10 seconds to 5 minutes.
7. preparation method according to claim 1, it is characterised in that in step (2), the anionic polyelectrolyte is molten
The mass percent concentration of liquid is 0.3%~30%, and soak time is 5 seconds to 30 minutes.
8. preparation method according to claim 7, it is characterised in that the quality percentage of the anionic polyelectrolyte solution
Specific concentration is 0.5%~10%, and soak time is 10 seconds to 5 minutes.
9. preparation method according to claim 1, it is characterised in that before step (2) is carried out, with hydrochloric acid or hydroxide
The pH value of cationic polyelectrolyte solution and anionic polyelectrolyte solution is adjusted to 5~8 by sodium.
10. preparation method according to claim 9, it is characterised in that before step (2) is carried out, with hydrochloric acid or hydrogen-oxygen
Change sodium and the pH value of cationic polyelectrolyte solution and anionic polyelectrolyte solution is adjusted to 6.
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