CN108485140B - Barrier flame-retardant polyvinyl alcohol composite material and preparation method thereof - Google Patents
Barrier flame-retardant polyvinyl alcohol composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant barrier polyvinyl alcohol composite material which is prepared from raw material components of polyvinyl alcohol, graphene oxide, alpha-zirconium phosphate and sulfonated polyphosphazene microspheres by an intercalation-solution compounding method. The preparation method comprises the following specific steps: s1, ultrasonically dispersing graphene oxide, alpha-zirconium phosphate and sulfonated polyphosphazene microspheres in water to obtain a mixed solution system; s2, dissolving polyvinyl alcohol in hot water to obtain a polyvinyl alcohol aqueous solution; adding the mixed solution system prepared by the step S1 into a polyvinyl alcohol aqueous solution, and stirring for 5-10 hours to prepare a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution; and S3, pouring the mixed solution obtained in the step S2 into a glass mold, and carrying out non-isothermal drying to obtain the polyvinyl alcohol composite material. According to the polyvinyl alcohol composite material, sulfonated polyphosphazene microspheres with different structural characteristics, graphene oxide and alpha-zirconium phosphate are introduced, so that the polyvinyl alcohol material has good barrier property and flame retardance, and the comprehensive performance is improved.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a barrier flame-retardant polyvinyl alcohol composite material and a preparation method thereof.
Background
Polyvinyl alcohol (PVA) is a hydrolysis product of polyvinyl acetate, is a tasteless and nontoxic synthetic macromolecule, has three forms of flaky, flocculent or powdery solid, has a more regular molecular structure, and is a semi-crystalline polymer. The PVA has diversified properties according to different structures, alcoholysis degrees and polymerization degrees. Such as good barrier property, film forming property, biodegradability, solubility and the like, and is widely applied to food packaging, washing packaging and chemical packaging.
However, the polyvinyl alcohol material also has the general property of plastic materials, namely, the polyvinyl alcohol material is easy to burn, and the polyvinyl alcohol material for the film has extremely high requirements on gas barrier performance, and pure polyvinyl alcohol can not meet the performance requirements, so that the use and development of the material in the field of packaging materials are greatly limited. In recent years, with the rise of nano materials, people try to solve the problems of gas barrier property and flame retardance by compounding and modifying PVA and inorganic nano particles, and the required performance is realized by regulating and controlling the performance of the introduced nano particles by the following methods: the layered nanoparticles can be regarded as a gas impermeable phase due to compact and regular structure, and the layered nanoparticles with larger length-diameter ratio, high dispersion and high orientation degree can form a complex structure in a polymer matrix, so that gas permeates along a more twisted path when passing through the complex structure. Meanwhile, the added layered nano particles limit the movement of polymer molecular chains, and the free volume is reduced, so that the gas barrier property of the polymer is improved. In addition, by adding the nano particles with specific properties, after the nano particles reach a certain content, the polymer can have the properties, and the morphology of the added nano particles is regulated to ensure that the polymer has multiple properties. However, the technical research of compounding the PVA with inorganic nanoparticles is not mature enough at present, the barrier property of the obtained polyvinyl alcohol composite material needs to be further improved, and the polyvinyl alcohol composite material also has the flammability of plastic materials, so that the practical application of the polyethylene material is limited.
Disclosure of Invention
The invention aims to solve the technical problems of poor barrier property and poor flame retardance of the existing polyvinyl alcohol composite material.
In order to achieve the purpose, the invention provides a flame-retardant barrier polyvinyl alcohol composite material which is prepared from raw material components of polyvinyl alcohol, graphene oxide, alpha-zirconium phosphate and sulfonated polyphosphazene microspheres by an intercalation-solution compounding method.
Preferably, the polyvinyl alcohol composite material is prepared from the following raw materials in parts by weight by an intercalation-solution compounding method: 60-94 parts of polyvinyl alcohol, 0.5-5 parts of graphene oxide, 0.5-5 parts of alpha-zirconium phosphate and 5-30 parts of sulfonated polyphosphazene microspheres.
Preferably, the aspect ratio of the graphene oxide is 500-5000.
Preferably, the aspect ratio of the alpha-zirconium phosphate is 100-1500.
Preferably, the particle size of the sulfonated polyphosphazene microspheres is 0.01-5.0 μm.
Preferably, the mass of the sulfonic group in the sulfonated polyphosphazene microsphere accounts for 0.5-9.0% of the total mass of the microsphere.
The preparation method of the barrier flame-retardant polyvinyl alcohol composite material comprises the following steps:
s1, ultrasonically dispersing 0.5-5 parts by weight of graphene oxide, 0.5-5 parts by weight of alpha-zirconium phosphate and 5-30 parts by weight of sulfonated polyphosphazene microspheres in 5-50 parts by weight of water to obtain a graphene oxide/alpha-zirconium phosphate/sulfonated polyphosphazene microsphere mixed solution system;
s2, dissolving 60-94 parts by weight of polyvinyl alcohol in 70-100 parts by weight of water at the temperature of 80-95 ℃ to obtain a polyvinyl alcohol aqueous solution; adding the mixed solution system prepared in the step S1 into a polyvinyl alcohol aqueous solution, and stirring for 5-10 hours to prepare a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution;
and S3, pouring the mixed solution obtained in the step S2 into a glass mold, and removing the dispersion medium by non-isothermal drying to obtain a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide composite membrane (PVA/sPSZ/alpha-ZrP/GO), namely the flame-retardant barrier polyvinyl alcohol composite material.
Preferably, in the step S3, the mixed solution obtained in the step S2 is poured into a glass mold by a casting film forming method.
Preferably, the non-isothermal drying is divided into two stages, the first stage is drying at 20-30 ℃ for 2-3 days, and the second stage is drying at 35-45 ℃ for 3-5 days.
Preferably, in the step S2, 60 to 94 parts by weight of polyvinyl alcohol is added to 70 to 100 parts by weight of hot water with a temperature of 80 to 95 ℃, and stirred and dissolved for 5 to 10 hours to obtain a polyvinyl alcohol aqueous solution.
The invention has the advantages that:
(1) the polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide composite material (PVA/sPSZ/alpha-ZrP/GO) prepared by the invention adopts alpha-zirconium phosphate with a nano-level dispersed lamellar structure and graphene oxide with a micron-level dispersed monolithic layer thickness, has a larger length-diameter ratio, can be uniformly dispersed in an aqueous solution, and carries out oxygen barrier modification on polyvinyl alcohol dissolved in water by an intercalation-solution compounding method; meanwhile, the introduced sulfonated polyphosphazene microspheres with a cross-linking structure, the graphene oxide and the alpha-zirconium phosphate form a multi-dimensional gas permeation structure, so that the oxygen barrier property is further improved.
(2) Because the sulfonated polyphosphazene contains a large amount of N, P elements in the molecular structure and a certain content of P elements in the alpha-zirconium phosphate molecular structure, the polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide material has barrier flame retardant property; the problem that the oxygen barrier property of the polyvinyl alcohol material prepared by the prior art is poor is solved, and the problem that the plastic material is flammable is also solved.
(3) The comprehensive properties of the polyvinyl alcohol composite material, such as mechanical property, thermal property and the like, are further improved.
(4) The dispersion medium in the preparation process of the polyvinyl alcohol composite material is water, so that the polyvinyl alcohol composite material is non-toxic, pollution-free, ecological and environment-friendly, and conforms to the current development trend of environment-friendly materials; the preparation process is simple, the cost is low, and the industrial production is easy to realize; has great practical value and popularization value.
Drawings
FIG. 1 is a graph of the oxygen permeability coefficient of the polyvinyl alcohol composite prepared in example 1 and the pure polyvinyl alcohol material of comparative example 1.
Figure 2 is a graph of the Heat Release Rate (HRR) of the polyvinyl alcohol composite prepared in example 1 versus the neat polyvinyl alcohol material of comparative example 1.
FIG. 3 is a graph of the smoke generation rate (SPR) of the polyvinyl alcohol composite prepared in example 1 versus the pure polyvinyl alcohol material of comparative example 1.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
A preparation method of a barrier flame-retardant polyvinyl alcohol composite material comprises the following steps:
step S1, adding 0.7 part by weight of graphene oxide with the length-diameter ratio of 500, 0.5 part by weight of alpha-zirconium phosphate with the length-diameter ratio of 200 and 5 parts by weight of sulfonated polyphosphazene microspheres with the particle size of 1 mu m and the sulfonation degree of 5% into 10 parts by weight of water, and performing ultrasonic dispersion at 100 kilohertz for 60min to obtain a sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution system; wherein, the sulfonation degree of 5 percent means that the mass of sulfonic groups in the sulfonated polyphosphazene microspheres accounts for 5 percent of the total mass of the microspheres;
step S2, adding 94 parts by weight of polyvinyl alcohol into 75 parts by weight of deionized water with the temperature of 95 ℃, stirring and dissolving for 5 hours to obtain a polyvinyl alcohol aqueous solution; then adding the sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution system prepared in the step S1 into a polyvinyl alcohol aqueous solution, and magnetically stirring for 5 hours at 1000rpm to prepare a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution;
step S3, pouring the mixed solution of polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide prepared in the step S2 into a glass mold, drying the mixed solution at 25 ℃ for 2 days, and then drying the dried mixed solution at 35 ℃ for 5 days to remove moisture, so as to obtain the polyvinyl alcohol composite material (PVA/sPSZ/alpha-ZrP/GO) with the flame retardant barrier property.
Example 2
A preparation method of a barrier flame-retardant polyvinyl alcohol composite material comprises the following steps:
step S1, adding 1 part by weight of graphene oxide with the length-diameter ratio of 2000, 1 part by weight of alpha-zirconium phosphate with the length-diameter ratio of 500 and 10 parts by weight of sulfonated polyphosphazene microspheres with the particle size of 0.5 mu m and the sulfonation degree of 3 percent into 20 parts by weight of water, and ultrasonically dispersing at 100 kilohertz for 30min to obtain a sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution system; wherein, the sulfonation degree of 3 percent means that the mass of sulfonic groups in the sulfonated polyphosphazene microspheres accounts for 3 percent of the total mass of the microspheres;
step S2, adding 88 parts by weight of polyvinyl alcohol into 75 parts by weight of deionized water with the temperature of 85 ℃, stirring and dissolving for 6 hours to obtain a polyvinyl alcohol aqueous solution; then adding the sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution system prepared in the step S1 into a polyvinyl alcohol aqueous solution, and magnetically stirring at 8000rpm for 7 hours to prepare a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution;
step S3, pouring the mixed solution of polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide prepared in the step S2 into a glass mold through a tape casting film forming method, drying the mixed solution at 35 ℃ for 3 days, and then drying the dried mixed solution at 40 ℃ for 5 days to remove moisture, so as to obtain the polyvinyl alcohol composite material (PVA/sPSZ/alpha-ZrP/GO) with the flame retardant and barrier properties.
Example 3
And step S1, adding 2 parts by weight of graphene oxide with the length-diameter ratio of 3000, 3 parts by weight of alpha-zirconium phosphate with the length-diameter ratio of 1000 and 15 parts by weight of sulfonated polyphosphazene microspheres with the particle size of 2 mu m and the sulfonation degree of 9% into 25 parts by weight of water, and ultrasonically dispersing at 100 kilohertz for 60min to obtain a sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution system.
Step S2, adding 60 parts by weight of polyvinyl alcohol into 90 parts by weight of deionized water with the temperature of 80 ℃, stirring and dissolving for 6 hours to obtain a polyvinyl alcohol aqueous solution; then adding the sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution system prepared in the step S1 into a polyvinyl alcohol aqueous solution, and magnetically stirring at 500rpm for 8 hours to prepare a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution;
step S3, pouring the mixed solution of polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide prepared in the step S2 into a glass mold through a tape casting film forming method, drying the mixed solution at 30 ℃ for 2 days, and then drying the dried mixed solution at 40 ℃ for 5 days to remove moisture, thereby obtaining the polyvinyl alcohol composite material (PVA/sPSZ/alpha-ZrP/GO) with the flame retardant barrier property.
Example 4
And step S1, adding 5 parts by weight of graphene oxide with the length-diameter ratio of 5000, 5 parts by weight of alpha-zirconium phosphate with the length-diameter ratio of 1500 and 30 parts by weight of sulfonated polyphosphazene microspheres with the particle size of 5 mu m and the sulfonation degree of 0.5 percent into 50 parts by weight of water, and ultrasonically dispersing at 100 kilohertz for 60min to obtain a sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution system.
Step S2, adding 77 parts by weight of polyvinyl alcohol into 100 parts by weight of deionized water with the temperature of 95 ℃, stirring and dissolving for 5 hours to obtain a polyvinyl alcohol aqueous solution; then adding the sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution system prepared in the step S1 into a polyvinyl alcohol aqueous solution, and magnetically stirring at 600rpm for 10 hours to prepare a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution;
step S3, pouring the mixed solution of polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide prepared in the step S2 into a glass mold through a tape casting film forming method, drying for 3 days at 25 ℃, then drying for 5 days at 40 ℃ to remove moisture, and finally obtaining the polyvinyl alcohol composite material (PVA/sPSZ/alpha-ZrP/GO) with the flame retardant blocking performance.
Comparative example 1
Adding 5 parts by weight of polyvinyl alcohol into 100 parts by weight of deionized water with the temperature of 95 ℃, and stirring for dissolving for 5 hours. Pouring the polyvinyl alcohol solution into a glass mold by a tape casting film forming method, firstly drying at 25 ℃ for 2 days, and then drying at 35 ℃ for 5 days to remove water, and finally obtaining the unmodified pure polyvinyl alcohol material.
The polyvinyl alcohol composite material prepared in example 1 and the pure polyvinyl alcohol material prepared in comparative example 1 were subjected to tests of oxygen permeability coefficient, Heat Release Rate (HRR), and smoke generation rate (SPR).
Oxygen permeability coefficient test: the gas permeameter of the model VAC-A2 of the electrooptic electromechanical technology company of the Jinan Languang is adopted. The experimental temperature was 40 ℃ and the relative humidity was 0%. Preparing a sample to be tested into a wafer with the diameter of 50mm, and placing and clamping the wafer between an upper testing cavity and a lower testing cavity; filling nitrogen with a certain pressure (0.1MPa) into the test upper cavity, and ensuring that a constant pressure difference is formed at two sides of the sample; under the action of the pressure difference gradient, oxygen permeates from the high-pressure side (upper cavity) to the low-pressure side (lower cavity), so that the oxygen permeability coefficient is obtained.
CONE Calorimetry (CONE) test: testing parameters such as Heat Release Rate (HRR), smoke generation rate (SPR) and the like of a sample to be tested by adopting a CONE Calorimeter (CONE) of FTT British company according to ISO 5660 standard, wherein the radiation intensity is 35KW/m2And the sample size is 100mm × 100mm × 0.5mm, and the sample to be detected is placed on the tin foil paper.
FIG. 1 shows a polyvinyl alcohol composite prepared in example 1 and a polyvinyl alcohol composite prepared in comparative example 1And (3) an oxygen permeability coefficient graph of the prepared pure polyvinyl alcohol material. As can be seen from the figure, the pure polyvinyl alcohol material of comparative example 1 has an oxygen permeability coefficient (P)O2) Is 1.890 × 10-16cm3cmcm-2s-1Pa-1The polyvinyl alcohol composite material prepared in example 1 has an oxygen permeability coefficient (P) due to the addition of sulfonated polyphosphazene, α -zirconium phosphate and graphene oxideO2) Is 0.425 × 10-16cm3cm cm-2s-1Pa-1And the reduction is 78%. Fig. 2 and 3 are graphs of Heat Release Rate (HRR) and smoke generation rate (SPR) of the polyvinyl alcohol composite prepared in example 1 and the pure polyvinyl alcohol material prepared in comparative example 1, respectively. It can be seen that the pure PVA film of comparative example 1 rapidly burned after ignition at 463kW m-2The peak value appears, the flame-retardant barrier type polyvinyl alcohol composite material of the example 1 delays a period of time after ignition to start burning, and the peak value is 319kWm-2. For the smoke generation rate, the peak value of the SPR curve of the flame-retardant barrier type polyvinyl alcohol composite material is only 0.09m2s-1Compared with the pure polyvinyl alcohol material of comparative example 1, the material has better smoke suppression effect.
In conclusion, the polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide material prepared by the invention has high oxygen barrier property, and simultaneously meets good flame retardant effect on the basis, so that the problem of poor oxygen barrier property of the polyvinyl alcohol material in the prior art is solved, and the problem of flammability of plastic materials is also solved. Meanwhile, in the preparation process of the composite material, the dispersion medium is water, so that the composite material is non-toxic, pollution-free, ecological and environment-friendly, and conforms to the development trend of the current environment-friendly material.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The flame-retardant barrier type polyvinyl alcohol composite material is characterized by being prepared from raw material components of polyvinyl alcohol, graphene oxide, alpha-zirconium phosphate and sulfonated polyphosphazene microspheres by an intercalation-solution compounding method, wherein the length-diameter ratio of the graphene oxide is 500-5000, the length-diameter ratio of the alpha-zirconium phosphate is 100-1500, and the particle size of the sulfonated polyphosphazene microspheres is 0.01-5.0 mu m.
2. The flame-retardant barrier polyvinyl alcohol composite material as claimed in claim 1, which is prepared by the intercalation-solution compounding method of the following raw materials in parts by weight: 60-94 parts of polyvinyl alcohol, 0.5-5 parts of graphene oxide, 0.5-5 parts of alpha-zirconium phosphate and 5-30 parts of sulfonated polyphosphazene microspheres.
3. The flame retardant barrier polyvinyl alcohol composite of claim 2 wherein the mass of sulfonic acid groups in the sulfonated polyphosphazene microspheres is 0.5-9.0% of the total mass of the microspheres.
4. The preparation method of the barrier flame retardant polyvinyl alcohol composite material according to any one of claims 1 to 3, wherein the method comprises the following steps:
s1, ultrasonically dispersing 0.5-5 parts by weight of graphene oxide, 0.5-5 parts by weight of alpha-zirconium phosphate and 5-30 parts by weight of sulfonated polyphosphazene microspheres in 5-50 parts by weight of water to obtain a graphene oxide/alpha-zirconium phosphate/sulfonated polyphosphazene microsphere mixed solution system;
s2, dissolving 60-94 parts by weight of polyvinyl alcohol in 70-100 parts by weight of water at the temperature of 80-95 ℃ to obtain a polyvinyl alcohol aqueous solution; adding the mixed solution system prepared in the step S1 into a polyvinyl alcohol aqueous solution, and stirring for 5-10 hours to prepare a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide mixed solution;
s3, pouring the mixed solution obtained in the step S2 into a glass mold, and removing a dispersion medium through non-isothermal drying to obtain a polyvinyl alcohol/sulfonated polyphosphazene/alpha-zirconium phosphate/graphene oxide composite membrane, namely the flame-retardant barrier polyvinyl alcohol composite material; the non-isothermal drying is divided into two stages, wherein the first stage is drying at 20-30 ℃ for 2-3 days, and the second stage is drying at 35-45 ℃ for 3-5 days.
5. The method of claim 4, wherein in step S3, the mixture obtained in step S2 is poured into a glass mold by a casting method.
6. The method according to claim 4, wherein in step S2, the polyvinyl alcohol is dissolved in 70-100 parts by weight of hot water at 80-95 ℃ for 5-10h under stirring to obtain the aqueous solution of polyvinyl alcohol, wherein the polyvinyl alcohol is added in 60-94 parts by weight.
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| CN105694107A (en) * | 2016-01-26 | 2016-06-22 | 同济大学 | Preparation method of nano alpha-zirconium phosphate loaded graphene oxide flame retardant |
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