CN113185873A - Preparation method of bio-based flame-retardant and anti-photoaging PVA composite material - Google Patents
Preparation method of bio-based flame-retardant and anti-photoaging PVA composite material Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 76
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 206010051246 Photodermatosis Diseases 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 112
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 112
- 239000000843 powder Substances 0.000 claims abstract description 45
- 229920001661 Chitosan Polymers 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 15
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940068041 phytic acid Drugs 0.000 claims abstract description 15
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 15
- 239000000467 phytic acid Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 229960000583 acetic acid Drugs 0.000 claims abstract description 6
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 6
- 238000012546 transfer Methods 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
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- 230000005284 excitation Effects 0.000 claims description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
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- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 16
- 229920000867 polyelectrolyte Polymers 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
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- 238000002485 combustion reaction Methods 0.000 description 8
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- 239000003610 charcoal Substances 0.000 description 2
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- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910016653 EuF3 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
本发明公开了一种生物基阻燃及抗光老化PVA复合材料的制备方法，聚乙烯醇分散于去离子水中，升温搅拌，冷却，得PVA分散液；加入冰醋酸和壳聚糖粉末，室温下搅拌至壳聚糖粉末完全溶解；加入植酸，搅拌，超声，得生物基阻燃PVA溶液；加入荧光粉，室温下搅拌，超声，得混合溶液；将混合溶液转移至模具中干燥，脱模，得到生物基阻燃及抗光老化PVA复合材料。该制备方法制备的复合材料具有优良的阻燃性能、力学性能和吸收紫外性能等，能减少PVA受紫外的影响，提高寿命以及抗光老化性能。
The invention discloses a preparation method of a bio-based flame-retardant and anti-photoaging PVA composite material. Polyvinyl alcohol is dispersed in deionized water, heated, stirred, and cooled to obtain a PVA dispersion; glacial acetic acid and chitosan powder are added, and the temperature is room temperature. Stir until the chitosan powder is completely dissolved; add phytic acid, stir, and sonicate to obtain a bio-based flame retardant PVA solution; add fluorescent powder, stir at room temperature, and sonicate to obtain a mixed solution; transfer the mixed solution to a mold to dry, remove A bio-based flame retardant and anti-photoaging PVA composite material was obtained. The composite material prepared by the preparation method has excellent flame retardant properties, mechanical properties and ultraviolet absorption properties, etc., can reduce the influence of PVA by ultraviolet rays, and improve the lifespan and the anti-photoaging properties.
Description
Technical Field
The invention belongs to the technical field of composite materials, relates to a flame-retardant composite material, and particularly relates to a preparation method of a bio-based flame-retardant and anti-photoaging PVA composite material.
Background
Resin-based composite materials such as polyvinyl alcohol (PVA) have the characteristics of high specific strength, low density, fatigue resistance, shock absorption, chemical corrosion resistance and the like, and are widely applied to various industries and daily life of people. However, the potential hazard of fire caused by the inflammability of the fire threatens the life safety of people at all times. For this reason, a flame retardant is usually added to reduce the flammability of PVA and improve the safety of PVA. However, the addition of a large amount of flame retardant has a great influence on the mechanical properties of the material and the inherent excellent properties of the material. On the other hand, when the PVA is used outdoors, it is exposed to various environmental factors, and particularly, it is easily photooxidized by ultraviolet light, which causes the PVA to lose its gloss, change its color, crack, and embrittle, thereby deteriorating its performance. The ultraviolet absorbent is added to inhibit the photoaging of PVA, prolong the service life, save resources, reduce the cost and reduce the pollution to the environment. Common UV absorbers, e.g. TiO2And ZnS and the like can generate holes with strong oxidizing property and photo-generated electrons with strong reducing property after absorbing ultraviolet rays, and the holes and the electrons can react with oxygen, water and other substances to generate free radicals with high chemical activity and capable of reacting with PVA, so that the performance of the high polymer material is reduced, and finally the high polymer material is decomposed.
The bio-based flame retardant has the advantages of environmental protection, no pollution, high efficiency, wide raw material source and the like, and is a hotspot of the research of the flame retardant at present. Wherein PA and CH are the flame retardants commonly used in bio-based flame retardants, and the surface charges of the PA and CH are different, so that the PA and CH have the possibility of combination. Therefore, the PA and the CH react at a specific pH value to synthesize an environment-friendly bio-based polyelectrolyte compound, and the compound is compounded with the PVA to prepare the flame-retardant composite material which not only has excellent flame-retardant property, but also can improve the mechanical property. On the basis, the fluorescent powder with the ultraviolet absorption function is added into the system, so that the light aging of PVA can be inhibited, the service life of the PVA can be prolonged, and the possibility is provided for preparing the multifunctional flame-retardant composite material.
Disclosure of Invention
The invention aims to provide a preparation method of a bio-based flame-retardant and anti-photoaging PVA composite material, which can be used for preparing the PVA composite material with excellent flame-retardant property, excellent mechanical property and stronger photoaging resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a bio-based flame-retardant and anti-photoaging PVA composite material specifically comprises the following steps:
step 1: dispersing 2-5 g of polyvinyl alcohol (PVA) in 100-250 mL of deionized water, heating to 80-95 ℃, stirring for 1-3 h, and naturally cooling to room temperature to obtain a PVA dispersion liquid;
the polymerization degree of polyvinyl alcohol was 1750.
Step 2: adding 0.5-2 mL of glacial acetic acid and 0.1-1 g of chitosan powder into 100-250 mL of PVA dispersion liquid, and stirring for 2-4 h at room temperature until the chitosan powder is completely dissolved to obtain a mixed solution; adding 0.25-8 g of phytic acid into the mixed solution, stirring for 1-2 h at room temperature, and performing ultrasonic treatment for 1-4 h to obtain a bio-based flame-retardant PVA solution;
the bio-based flame retardant is a polyelectrolyte complex flame retardant obtained by reacting Phytic Acid (PA) and Chitosan (CH) at a pH value of 1-5, but in order to enable the reaction to be more sufficient and effective and enable particles generated by the reaction to be smaller, the pH value is set to be about 2 in the preparation method.
And step 3: adding fluorescent powder into the bio-based flame-retardant PVA solution obtained in the step 2, wherein the mass of the added fluorescent powder is 3-5% of the total mass of the bio-based flame-retardant PVA solution and the added fluorescent powder, stirring for 4-6 h at room temperature, and performing ultrasonic treatment for 1-2 h to obtain a mixed solution;
the fluorescent powder is excited in the wave band of 200 nm-400 nm.
Preferred phosphors are prepared by:
A. according to chemical expression Sr1.7Ba0.3Si4.7Al0.3N7.7O0.3:0.05Eu2+The stoichiometric ratio of the chemical compositions is Sr3N2、Ba3N2、Si3N4、AlN、Al2O3And EuF3Then, the cosolvent (Li) is weighed with the mass fraction of 1wt percent respectively3N) and an impurity-removing agent (C)Carbon powder), grinding the raw materials into powder, and uniformly mixing to obtain raw material powder;
B. placing the raw material powder in a closed environment with protective atmosphere, heating to 1500 ℃ at the heating rate of 5 ℃/min, roasting for 4h, and cooling to room temperature to obtain a calcined substance;
C. grinding the calcined product to obtain Sr1.7Ba0.3Si4.7Al0.3N7.7O0.3:0.05Eu2+And (3) fluorescent powder.
And 4, step 4: and transferring the mixed solution into a mold, drying for 6 hours in a drying oven at 60 ℃, and demolding to obtain the bio-based flame-retardant and anti-photoaging PVA composite material.
The composite material prepared by the preparation method is formed by combining a resin matrix, a flame-retardant additive and fluorescent powder. The flame retardant additive is chitosan and phytic acid. The resin is polyvinyl alcohol resin. The mass of the flame retardant additive accounts for 5-20% of the total mass of the composite material. The fluorescent powder accounts for 3-5% of the total mass of the composite material.
The bio-based polyelectrolyte composite flame retardant can obviously improve the mechanical property of the PVA composite material. The reasons can be summarized as the following three points: first, since the composite material contains CH, the CH has a large molecular weight and the carbon skeleton is more stable and rigid than PVA. Secondly, the interaction between pure PVA molecules is mainly through hydrogen bonds, which belongs to a weak interaction force, and the bio-based polyelectrolyte composite flame retardant and PVA can form phosphonate ester bonds (strong interaction force) under the action of ultrasound to replace partial hydrogen bonds, which is beneficial to improving the mechanical property. Finally, the polyelectrolyte compound formed by the reaction of phytic acid and chitosan is dispersed into the PVA molecular chain, so that the movement of the PVA molecular chain is hindered, and the PVA molecular chain can move to generate fracture by a larger force in the stretching process. Therefore, the multifunctional flame-retardant PVA composite material prepared by the invention has excellent mechanical properties.
The phosphorus-containing compound generated in the decomposition process of the bio-based polyelectrolyte composite flame retardant can catalyze the dehydration of the matrix into charcoal, and is beneficial to blocking heat transfer and volatilization of inflammable matters. In the gas phase, phosphorus-containing compounds generate phosphorus-containing groups (PO., HPO.) during the combustion reaction, and the phosphorus-containing groups can effectively capture free radicals generated during the combustion reaction, thereby cutting off the combustion reaction. In addition, the nitrogen-containing compound also releases a flame-retardant gas (such as ammonia gas, nitrogen gas, water vapor and the like) during combustion, thereby diluting the combustible gas and oxygen and carrying away heat. Therefore, the bio-based flame-retardant PVA composite material prepared by the preparation method has excellent flame-retardant performance.
TiO2And ZnS and the like can generate holes with strong oxidizing property and photo-generated electrons with strong reducing property after absorbing ultraviolet rays, and the holes and the electrons can react with oxygen, water and other substances to generate free radicals with high chemical activity and capable of reacting with PVA, so that the performance of the high polymer material is reduced, and finally the high polymer material is decomposed. The holes and electrons generated after the fluorescent powder added in the preparation method absorbs ultraviolet rays are recombined and consumed within the time of nanosecond to microsecond level, and do not participate in the reaction with oxygen and water.
The preparation method of the invention has the following advantages:
1) the prepared composite material is added with the bio-based polyelectrolyte composite flame retardant, and has the advantages of small addition amount, wide raw material source and low cost.
2) The bio-based polyelectrolyte composite flame retardant belongs to a bio-based flame retardant, has the characteristics of no halogen, environmental protection, no toxicity, no corrosiveness and the like, does not generate toxic waste during preparation and use, and is an environment-friendly flame retardant.
3) Besides excellent flame retardant property, the prepared PVA composite material is added with the fluorescent powder, so that the ultraviolet absorption effect of the fluorescent powder is benefited, the influence of ultraviolet on PVA is reduced, the service life of the PVA composite material is prolonged, and the light aging resistance of the PVA composite material is improved.
4) The matrix of the prepared composite material is PVA, so the composite material has wide application range and can be used in the field of coatings such as building coatings.
5) The prepared composite material has excellent flame retardant property, mechanical property, ultraviolet absorption property and the like.
Drawings
FIG. 1 is a graph showing the results of UL-94 test of PVA composite prepared in example 3, wherein a is a picture of appearance before the test and b is a picture of appearance after the test.
FIG. 2 is a graph showing the LOI test results of the PVA composite prepared in example 3, wherein the a-graph is a picture of the appearance before the test and the b-graph is a picture of the appearance after the test.
FIG. 3 is an XRD pattern of the phosphor in the preparation method of the present invention.
FIG. 4 is a DRS graph of PVA composites made in example 3 and polyvinyl alcohol samples made in comparative example.
FIG. 5 is an excitation spectrum of the phosphor in the preparation method of the present invention.
FIG. 6 is a bar graph showing the tensile strength of PVA composite materials prepared in examples 1 to 3 and polyvinyl alcohol samples prepared in comparative examples.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
Dispersing 2g of polyvinyl alcohol with the polymerization degree of 1750 in 100mL of deionized water, heating to 80 ℃, stirring for 1h, and naturally cooling to room temperature to obtain PVA dispersion liquid; adding 0.5mL of glacial acetic acid and 0.1g of chitosan powder into 100mL of PVA dispersion liquid, and stirring for 2h at room temperature until the chitosan powder is completely dissolved to obtain a mixed solution; adding 0.25g of phytic acid into the mixed solution, stirring for 1h at room temperature, and then performing ultrasonic treatment for 1h to obtain a bio-based flame-retardant PVA solution; adding fluorescent powder excited in a wave band of 200-400 nm into the bio-based flame-retardant PVA solution, wherein the mass of the added fluorescent powder is 3% of that of the bio-based flame-retardant PVA solution and the fluorescent powder, stirring for 4 hours at room temperature, and then carrying out ultrasonic treatment for 1 hour to obtain a mixed solution; and transferring the mixed solution into a mold, drying for 6 hours in a drying oven at 60 ℃, and demolding to obtain the bio-based flame-retardant and anti-photoaging PVA composite material.
Example 2
Dispersing 5g of polyvinyl alcohol with the polymerization degree of 1750 in 250mL of deionized water, heating to 95 ℃, stirring for 3 hours, and naturally cooling to room temperature to obtain PVA dispersion liquid; adding 2mL of glacial acetic acid and 1g of chitosan powder into 250mL of PVA dispersion liquid, and stirring for 4h at room temperature until the chitosan powder is completely dissolved to obtain a mixed solution; adding 8g of phytic acid into the mixed solution, stirring for 2 hours at room temperature, and then carrying out ultrasonic treatment for 4 hours to obtain a bio-based flame-retardant PVA solution; adding fluorescent powder excited in a wave band of 200-400 nm into the bio-based flame-retardant PVA solution, wherein the mass of the added fluorescent powder is 5% of the total mass of the bio-based flame-retardant PVA solution and the fluorescent powder, stirring for 6 hours at room temperature, and performing ultrasonic treatment for 2 hours to obtain a mixed solution; and transferring the mixed solution into a mold, drying for 6 hours in a drying oven at 60 ℃, and demolding to obtain the bio-based flame-retardant and anti-photoaging PVA composite material.
Example 3
Dispersing 3.5g of polyvinyl alcohol with the polymerization degree of 1750 in 175mL of deionized water, heating to 87.5 ℃, stirring for 2 hours, and naturally cooling to room temperature to obtain PVA dispersion; adding 1.25mL of glacial acetic acid and 0.55g of chitosan powder into 175mL of PVA dispersion liquid, and stirring for 3 hours at room temperature until the chitosan powder is completely dissolved to obtain mixed liquid; adding 4.125g of phytic acid into the mixed solution, stirring for 1.5h at room temperature, and then carrying out ultrasonic treatment for 2.5h to obtain a bio-based flame-retardant PVA solution; adding fluorescent powder excited in a wave band of 200-400 nm into the bio-based flame-retardant PVA solution, wherein the mass of the added fluorescent powder is 4% of the total mass of the bio-based flame-retardant PVA and the fluorescent powder, stirring for 5 hours at room temperature, and then carrying out ultrasonic treatment for 1.5 hours to obtain a mixed solution; and transferring the mixed solution into a mold, drying for 6 hours in a drying oven at 60 ℃, and demolding to obtain the bio-based flame-retardant and anti-photoaging PVA composite material.
Comparative example
Dispersing 5g of polyvinyl alcohol (PVA) with the polymerization degree of 1750 in 250mL of deionized water, heating to 95 ℃, stirring for 3h, and naturally cooling to room temperature to obtain PVA dispersion liquid; and drying the mixture in a drying oven at the temperature of 60 ℃ for 6 hours to obtain a polyvinyl alcohol sample.
The results of the limited oxygen index test and the vertical combustion test on the bio-based flame-retardant and photoaging-resistant PVA composite materials prepared in examples 1-3 and the polyvinyl alcohol samples prepared in the comparative example are shown in Table 1.
TABLE 1 results of testing the vertical burning, limiting oxygen index of the composite materials prepared in examples 1-3 and the polyvinyl alcohol samples prepared in comparative examples
As can be seen from Table 1, the limiting oxygen index of the PVA composite materials prepared in examples 1-3 is obviously improved along with the increase of the addition amount of the flame retardant, and the flame retardant property of the PVA composite material prepared by the preparation method is obviously improved compared with that of pure polyvinyl alcohol. In example 2, after the addition amount of the flame retardant reaches 10%, the limit oxygen index can reach 30%, and the oxygen index of the composite material can reach a higher value only by adding 10%. When the addition amount reaches 20%, the vertical burning grade reaches V-0 grade. The bio-based flame retardant prepared by the preparation method provided by the invention is proved to have excellent flame retardant efficiency.
The UL-94 test result of the PVA composite prepared in example 3 is shown in FIG. 1, in which a is a picture of the appearance before the test and b is a picture of the appearance after the test. The LOI test result of the PVA composite prepared in example 3 is shown in fig. 2, in which a of fig. 2 is an appearance picture before the test, and b of fig. 2 is an appearance picture after the test. As can be seen from fig. 1 and 2, the sample substantially retained its original shape after combustion and self-extinguished without dripping. The flame retardant is mainly due to the flame retardant effect of the flame retardant in gas phase and condensed phase, and phosphorus-containing compounds generated in the decomposition process of the bio-based polyelectrolyte composite flame retardant can catalyze the dehydration of a substrate into charcoal, thereby being beneficial to hindering heat transfer and volatilizing inflammable matters. In the gas phase, phosphorus-containing compounds generate phosphorus radicals (PO.., HPO.) during the combustion reaction, and these radicals can capture the radicals circulating in the gas phase during combustion, and in addition, release the difficult-to-combust gases to dilute the combustible gases, oxygen and heat. Thereby leading the composite material to obtain excellent flame retardant property.
Fig. 3 is an XRD pattern of the phosphor used in the examples, and it can be seen that sample XRD is consistent with PDF card, demonstrating that it is free of impurities. FIG. 4 is a DRS diagram of the PVA composite material prepared in example 3 and the PVA sample prepared in the comparative example, and it can be observed that, compared with a pure PVA sample, the composite film transmits less light in a wavelength band of 200-400 nm, which illustrates that the composite flame retardant material added with the fluorescent powder absorbs most of ultraviolet rays in the wavelength band, reduces the influence of the ultraviolet rays on the service life of the PVA, and thus achieves the anti-photoaging performance. FIG. 5 is an excitation spectrum of the phosphor used in the example, and it can be seen that the phosphor shows broadband excitation of 250-550 nm under 606nm monitoring, which illustrates that the phosphor can effectively absorb near-ultraviolet wavelength of 250-550 nm, and is consistent with the ultraviolet absorption result of FIG. 4.
The mechanical property test results of the PVA composite materials prepared in the embodiments 1-3 and the polyvinyl alcohol samples prepared in the comparative examples are shown in FIG. 6, and it can be seen that the tensile strength of the prepared PVA composite materials is obviously improved, because the PVA composite materials contain CH, the CH has large molecular weight, and the carbon skeleton is more stable and rigid compared with pure PVA. Secondly, the interaction between pure PVA molecules is mainly through hydrogen bonds, which belongs to a weak interaction force, and the bio-based polyelectrolyte composite flame retardant and PVA can form phosphonate ester bonds (strong interaction force) under the action of ultrasound to replace partial hydrogen bonds, which is beneficial to improving the mechanical property. Finally, polyelectrolyte complexes formed by the reaction of phytic acid and chitosan are dispersed in the molecular chain of PVA, thus hindering the movement of the molecular chain of PVA. Therefore, the prepared multifunctional flame-retardant PVA composite material has excellent mechanical properties.
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