CN103755985A - Preparation method of high-strength polyvinyl alcohol composite membrane - Google Patents
Preparation method of high-strength polyvinyl alcohol composite membrane Download PDFInfo
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- CN103755985A CN103755985A CN201410007519.2A CN201410007519A CN103755985A CN 103755985 A CN103755985 A CN 103755985A CN 201410007519 A CN201410007519 A CN 201410007519A CN 103755985 A CN103755985 A CN 103755985A
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- double hydroxide
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 163
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 160
- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000010992 reflux Methods 0.000 claims abstract description 20
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 9
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 153
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 147
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 141
- 238000003756 stirring Methods 0.000 claims description 68
- 239000008367 deionised water Substances 0.000 claims description 53
- 229910021641 deionized water Inorganic materials 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 238000002425 crystallisation Methods 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 23
- 238000000967 suction filtration Methods 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 30
- 239000002245 particle Substances 0.000 abstract description 18
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 34
- 238000002441 X-ray diffraction Methods 0.000 description 20
- 238000002834 transmittance Methods 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000011521 glass Substances 0.000 description 18
- 238000006136 alcoholysis reaction Methods 0.000 description 17
- 238000001704 evaporation Methods 0.000 description 17
- 230000008020 evaporation Effects 0.000 description 17
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- 230000000052 comparative effect Effects 0.000 description 7
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910003023 Mg-Al Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a high-strength polyvinyl alcohol composite membrane. The method comprises the following steps: synthesizing nanoscale layered bi-metal hydroxides by a hydrothermal method; carrying out ultrasonic and reflux treatment in water according to a certain ratio, and then adding a certain amount of polyvinyl alcohol particles for dissolving, so as to obtain a mixed solution; preparing the polyvinyl alcohol/layered bi-metal hydroxide composite membrane by pouring and volatilization methods. By adopting the low-content layered metal hydroxide-enhanced polyvinyl alcohol composite membrane prepared by the method, the tensile strength and the Young modulus are respectively improved by about 100% and 150% in comparison with a pure polyvinyl alcohol membrane, excellent mechanical property is displayed, original high transparency of the polyvinyl alcohol membrane is kept, and the preparation method provided by the invention is carried out in a water phase, and is simple in technology, friendly to environment and low in cost.
Description
Technical field
The present invention relates to the technical field of macromolecule membrane, particularly a kind of preparation method of high strength poly vinyl alcohol composite membrane.
Background technology
Layered double hydroxide (Layered Double Hydroxides) refers to that interlayer has the lamellar structure compound of commutative negatively charged ion, and composition can represent with following general formula: [M
2+ 1-xm
3+ x(OH)
2] (A
n-)
x/nmH
2o, wherein M
2+, M
3+respectively divalence and trivalent metal cation, A
n-be can stable existence in basic solution the negatively charged ion that is positioned at interlayer.Between the main body laminate of double-metal hydroxide, have strong covalent linkage, interlayer is a kind of weak interaction force, passes through the combinations such as hydrogen bond, Van der Waals force, electrostatic force between Subjective and Objective.The supramolecular structure of layered double hydroxide multielement, multikey type, makes it in various fields such as catalysis, absorption, medicine, ion-exchange, environmental engineering, industry are fire-retardant, all represent great potential and tempting prospect.
Polyvinyl alcohol is a kind of polyhydric water-soluble polymers, has biocompatibility, biodegradability, the excellent properties such as water-soluble.Polyvinyl alcohol can be used for masking, drug release and artificial medical facilities etc.But the physical strength of polyvinyl alcohol film is still not high, and this has limited its range of application.In order to improve the mechanical property of polyvinyl alcohol film, conventionally itself and organic or inorganic material can be carried out to composite modification.
Preparation method about polyvinyl alcohol/layered double hydroxide laminated film, in now studies have reported that, (the Baoguang Li such as Lee, Yuan Hu, Rui Zhang, Zuyao Chen, Weicheng Fan, Preparation of the poly (vinyl alcohol)/layered double hydroxide nanocomposite[J], Mater.Res.Bull, 2003,38:1567～1572) by leafing/recombination method, prepared intercalation polyvinyl alcohol/Mg-Al layered double hydroxide composite membrane.(the B.Ramaraj such as Ramaraj, Sanjay K.Nayak, Kuk Ro Yoon, Poly (vinyl alcohol) and layered double hydroxide composites:Thermal and mechanical properties[J], J.Appl.Polym.Sci., 2010,116:1671～1677) by solution intercalation technique, prepare polyvinyl alcohol/layered double hydroxide composite membrane, wherein layered double hydroxide is micron order, and reinforced effects is not remarkable.Yellow (the Shu Huang that waits, Xi Cen, Hong Zhu, Zhe Yang, Yang Yang, Weng Weei Tjiu, Tianxi Liu, Facile preparation of poly (vinyl alcohol) nanocomposiJes with pristine layered double hydroxides[J], Mater.Chem.and Phys., 2011, 130:890～896) by quick nucleation and slow crystallization method, synthesized the Mg-Al layered double hydroxide of nanoscale, and prepared polyvinyl alcohol/layered duplex metal hydroxide nanometer composite membrane with solution blended process, but in this process, used noxious solvent methyl alcohol.
Summary of the invention
The object of the invention is for above-mentioned existing methodical deficiency, a kind of preparation method of high strength poly vinyl alcohol composite membrane of simple possible is provided, under aqueous environment, utilizes nano-layered double hydroxides to prepare the method for enhanced polyethylene alcohol composite membrane completely.The method is when keeping polyvinyl alcohol film high transparent, and few addition can increase substantially its mechanical strength, and technique is simple, environmental friendliness.
The preparation method who the invention discloses a kind of high strength poly vinyl alcohol composite membrane, comprises the steps:
(1) solubility divalent metal salt and solubility trivalent metal salt are dissolved in to deionized water, then add alkaline matter, after being uniformly mixed, obtain reaction solution; Described reaction solution is crystallization 1～72h at 80～110 ℃, through suction filtration, dry, obtains layered double hydroxide;
(2) layered double hydroxide step (1) being obtained joins in deionized water, after ultrasonic dispersion, stirring and refluxing are processed, obtains dispersion liquid; In dispersion liquid, add granule of polyvinyl alcohol, after stirring, dissolving, obtain polyvinyl alcohol/layered double hydroxide mixed solution;
(3) polyvinyl alcohol/layered double hydroxide mixed solution that step (2) obtains obtains described high strength poly vinyl alcohol composite membrane through cast, after standing, dry.
High strength poly vinyl alcohol composite membrane prepared by the present invention is that polyvinyl alcohol/layered double hydroxide strengthens composite membrane, between composite membrane laminate double-metal hydroxide and polyvinyl alcohol, by this noncovalent interaction of hydrogen bond, mutually combines.The ultrasonication that layered double hydroxide aqueous dispersions carries out before blend, stirring and refluxing are processed, be beneficial to layered double hydroxide dispersion, peel off, and be conducive to the intercalation of follow-up polyvinyl alcohol molecule chain.In preparation technology, granule of polyvinyl alcohol is added to stirring and dissolving in scattered layered double hydroxide dispersion liquid, the layered double hydroxide of maintenance system middle and high concentration, make polyvinyl alcohol in dissolution process, molecular chain can be unfolded and is adsorbed on layered double hydroxide laminate surface or intercalation enters layered double hydroxide interlayer, make dispersion and the mixed effect of co-mixing system better, then increased substantially the over-all properties of composite membrane.
As preferably, the metal ion in described solubility divalent metal salt is Co
2+, Ni
2+, Cu
2+, Zn
2+, Mg
2+in one or both; Metal ion in described solubility trivalent metal salt is Al
3+, Cr
3+, Fe
3+, In
3+in one or both; Described solubility divalent metal salt, the negatively charged ion of trivalent metal salt are NO
3 -, Cl
-, SO
4 2-in one or both.
As preferably, described alkaline matter is sodium hydroxide, potassium hydroxide, urea or ammoniacal liquor.
As preferably, in described reaction solution, the total concn of solubility divalent metal salt and solubility trivalent metal salt is 0.06～1mol/L, the mol ratio of solubility divalent metal salt and solubility trivalent metal salt is 0.6～10:1, and the mol ratio of solubility divalent metal salt and solubility trivalent metal salt total amount and alkaline matter is 1:1～10.
The polymerization degree of described granule of polyvinyl alcohol is 1000～5000, and alcoholysis degree is 85～99%.
As preferably, the quality of layered double-metal hydroxide is 0.1～10wt% of polyvinyl alcohol quality, more preferably 0.8～1.6wt%.
As preferably, in described polyvinyl alcohol/layered double hydroxide mixed solution, the mass percentage concentration of polyvinyl alcohol is 2～20wt%, in this concentration range, and the easy film forming of polyvinyl alcohol.
As preferably, described in step (1), crystallization time is 12～24h.Crystallization time is too short, and grain growing is incomplete; Crystallization time is long, and intercrystalline is assembled serious.
As preferably, the time of described ultrasonic dispersion is 10min～8h; The described reflow treatment time is 10min～10h.Through ultrasonic dispersion agent reflux, process, can further promote the dispersion of lamella in layered double hydroxide and peel off, the intercalation that is conducive to polyvinyl alcohol molecule chain has guaranteed to realize the raising to composite membrane of polyvinyl alcohol mechanical property under lower consumption simultaneously.
Described cast, concrete steps standing, drying and forming-film are:
Pour mixed solution into glass guide channel film forming, in stink cupboard, after standing for some time, in vacuum drying oven, heat up dry, obtain layered double hydroxide enhanced polyethylene alcohol composite membrane.
Compared with prior art, tool of the present invention has the following advantages:
1, preparation method of the present invention does not use any organic solvent in whole preparation process, and dispersion process is simple, and blend mould making process is easily gone, environmental friendliness.
2, pass through mechanics property analysis, the composite membrane of polyvinyl alcohol containing a small amount of layered double hydroxide that the present invention prepares, its tensile strength and Young's modulus have improved respectively more than nearly 100% and 150% compared with polyvinyl alcohol body, have represented excellent mechanical property; And visible transmission spectroscopic analysis shows, layered double hydroxide add the transparency that does not significantly reduce polyvinyl alcohol film.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the layered double hydroxide that makes of embodiment 1;
Fig. 2 is the TEM figure of the layered double hydroxide that makes of embodiment 1;
Fig. 3 is the TEM figure of the high strength poly vinyl alcohol composite membrane that makes of embodiment 2;
Fig. 4 is the XRD figure of the high strength poly vinyl alcohol composite membrane that makes of embodiment 2;
Fig. 5 is the XRD figure of the high strength poly vinyl alcohol composite membrane that makes of comparative example 1.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
In 50mL deionized water, add 2.0g Mg (NO
3)
2with 1.31g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 0.9g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 8h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.05g is scattered in 100mL deionized water, and supersound process 30min, is transferred to there-necked flask, stirring and refluxing 40min under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
The XRD spectra of the layered double hydroxide of preparing in the present embodiment as shown in Figure 1, as can be seen from the figure, curve baseline is steady, the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, illustrate and really synthesized layered double hydroxide, and its symmetry is good, degree of crystallinity is higher.
As shown in Figure 2, as can be seen from the figure, layered double hydroxide size is below 100nm for the stereoscan photograph of the layered double hydroxide of preparing in the present embodiment.
The tensile strength of the high strength poly vinyl alcohol composite membrane of preparing in the present embodiment is that the tensile strength of the pure polyvinyl alcohol film of 80MPa(is 58MPa), Young's modulus is that the Young's modulus of the pure polyvinyl alcohol film of 1100MPa(is 700MPa), visible region average transmittance is that the transmittance of the pure polyvinyl alcohol film of 88%(is 90%).
The preparation process of pure polyvinyl alcohol film is: 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50) joins in deionized water, obtains until completely dissolved the aqueous solution.Pour the aqueous solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain pure polyvinyl alcohol film.
Embodiment 2:
In 50mL deionized water, add 3.9g Mg (NO
3)
2with 2.9g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 12h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 50min, is transferred to there-necked flask, stirring and refluxing 6h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size below 100nm, and in polyvinyl alcohol dispersed better (see figure 3).The XRD spectra of polyvinyl alcohol/layered double hydroxide composite membrane is shown in Fig. 4, and two characteristic peaks (003) and (006) of layered double hydroxide disappear substantially, shows that this bedded substance major part is the state of peeling off.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 120MPa, and Young's modulus is 1800MPa, and visible region average transmittance is 89%.
Embodiment 3:
In 50mL deionized water, add 3.9g Co (NO
3)
2with 2.9g Cr (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 1h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 10min, is transferred to there-necked flask, stirring and refluxing 1h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, but (003) and (006) two peak are so not sharp-pointed, show that synthetic layered double hydroxide crystallization is general.Layered double hydroxide size is between 100～1000nm, better dispersed in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 75MPa, and Young's modulus is 1000MPa, and visible region average transmittance is 85%.
Embodiment 4:
In 50mL deionized water, add 3.9g Co (NO
3)
2with 2.9g Cr (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 72h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 20min, is transferred to there-necked flask, stirring and refluxing 5h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is between 100～1500nm, better dispersed in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 95MPa, and Young's modulus is 1400MPa, and visible region average transmittance is 81%.
Embodiment 5:
In 50mL deionized water, add 3.9g Mg (NO
3)
2with 2.9g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 16h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 1.0g is scattered in 100mL deionized water, after supersound process 1h, is transferred to there-necked flask, stirring and refluxing 5h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is in 100nm left and right, better dispersed in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 78MPa, and Young's modulus is 1150MPa, and visible region average transmittance is 70%.
Embodiment 6:
In 50mL deionized water, add 12.0g Mg (NO
3)
2with 6.0g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 10.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 80 ℃ of baking oven crystallization 16h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.2g is scattered in 100mL deionized water, after supersound process 3h, is transferred to there-necked flask, stirring and refluxing 4h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is between 100～500nm, better dispersed in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 105MPa, and Young's modulus is 1650MPa, and visible region average transmittance is 85%.
Embodiment 7:
In 50mL deionized water, add 1.0g Mg (NO
3)
2with 0.2g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 18.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 10h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.08g is scattered in 100mL deionized water, after supersound process 30min, is transferred to there-necked flask, stirring and refluxing 2.5h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is similar to Fig. 1.Curve baseline is steady, the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, illustrate and really synthesized layered double hydroxide, and its symmetry is good, degree of crystallinity is higher, and size of particles is below 100nm, and in polyvinyl alcohol, dispersiveness is also better.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 110MPa, and Young's modulus is 1700MPa, and visible region average transmittance is 89%.
Embodiment 8:
In 50mL deionized water, add 2.0g Mg (Cl)
2with 0.2g Al (Cl)
3, stirring and dissolving; In 25mL deionized water, add 5.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 10h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 30min, is transferred to there-necked flask, stirring and refluxing 3h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is below 100nm, better dispersed in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 118MPa, and Young's modulus is 1780MPa, and visible region average transmittance is 89%.
Embodiment 9:
In 50mL deionized water, add 2.0g CuSO
4with 1.5g Fe
2(SO
4)
3, stirring and dissolving; Add 25mL ammoniacal liquor (concentration is 20%), stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 10h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 2h, is transferred to there-necked flask, stirring and refluxing 3h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is below 100nm, and dispersiveness is better in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 118MPa, and Young's modulus is 1780MPa, and visible region average transmittance is 89%.
Embodiment 10:
In 50mL deionized water, add 2.0g Ni (NO
3)
2with 1.5g In (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 3.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 16h, suction filtration, vacuum-drying, obtain layered bi-metal oxide compound.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 2h, is transferred to there-necked flask, stirring and refluxing 4h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is similar to Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is below 100nm, and dispersiveness is better in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 110MPa, and Young's modulus is 1700MPa, and visible region average transmittance is 89%.
Embodiment 11:
In 50mL deionized water, add 3.9g Zn (NO
3)
2with 2.9g Cr (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 3.0g urea, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 16h, suction filtration, vacuum-drying, obtain layered bi-metal oxide compound.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 20min, is transferred to there-necked flask, stirring and refluxing 1h under oil bath condition.Add 19g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is in 100nm left and right, better dispersed in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 85MPa, and Young's modulus is 1000MPa, and visible region average transmittance is 88%.
Embodiment 12:
In 50mL deionized water, add 3.9g Zn (NO
3)
2with 2.9g Cr (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g KOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 15h, suction filtration, vacuum-drying, obtain layered bi-metal oxide compound.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 4h, is transferred to there-necked flask, stirring and refluxing 10h under oil bath condition.Add 2g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is in 100nm left and right, better dispersed in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 85MPa, and Young's modulus is 1000MPa, and visible region average transmittance is 70%.
Embodiment 13:
In 50mL deionized water, add 3.9g Mg (NO
3)
2with 2.9g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 12h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 50min, is transferred to there-necked flask, stirring and refluxing 6h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA1788, alcoholysis degree 88%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is below 100nm, and dispersiveness is better in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is that the 98MPa(trade mark is that the pure PVA (PVOH) FILM tensile strength that PVA1788 makes is 50MPa), Young's modulus is that the 1600MPa(trade mark is that the pure PVA (PVOH) FILM Young's modulus that PVA1788 makes is 615MPa), visible region average transmittance is that the 89%(trade mark is that the transmittance of the pure PVA (PVOH) FILM that makes of PVA1788 is 91%).
Embodiment 14:
In 50mL deionized water, add 3.9g Mg (NO
3)
2with 2.9g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 12h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 100mL deionized water, after supersound process 50min, is transferred to there-necked flask, stirring and refluxing 6h under oil bath condition.Add 10g polyvinyl alcohol particle (trade mark is PVA2499, alcoholysis degree 99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In the present embodiment, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is below 100nm, and dispersiveness is better in polyvinyl alcohol.
In the present embodiment, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is that the 140MPa(trade mark is that the pure PVA (PVOH) FILM tensile strength that PVA2499 makes is 78MPa), Young's modulus is that the 2000MPa(trade mark is that the pure PVA (PVOH) FILM Young's modulus that PVA2499 makes is 880MPa), visible region average transmittance is that the 89%(trade mark is that the transmittance of the pure PVA (PVOH) FILM that makes of PVA1788 is 90%).
Comparative example 1
In 50mL deionized water, add 3.9g Mg (NO
3)
2with 2.9g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 12h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 100mL deionized water to supersound process 50min.Add 10g polyvinyl alcohol particle (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) to stir, after polyvinyl alcohol dissolves completely, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In this comparative example, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is below 100nm, and dispersiveness is better in polyvinyl alcohol.The XRD spectra of polyvinyl alcohol/layered double hydroxide composite membrane is shown in Fig. 5, has still demonstrated two characteristic peaks (003) and (006) of layered double hydroxide, shows that this bedded substance is due to without backflow, therefore fail to peel off.
In this comparative example, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 97MPa, and Young's modulus is 1400MPa, and visible region average transmittance is 85%.
Comparative example 2
In 50mL deionized water, add 3.9g Mg (NO
3)
2with 2.9g Al (NO
3)
3, stirring and dissolving; In 25mL deionized water, add 2.0g NaOH, stirring and dissolving.Both are uniformly mixed rapidly in water heating kettle, then move into 100 ℃ of baking oven crystallization 12h, suction filtration, vacuum-drying, obtain layered double hydroxide.
The above-mentioned product of 0.1g is scattered in 30mL deionized water, and supersound process 50min, is transferred to there-necked flask, and stirring and refluxing 6h under oil bath condition, obtains layered double hydroxide aqueous dispersions.10g polyvinyl alcohol (trade mark is PVA1750 ± 50, alcoholysis degree 98～99%) is dissolved in 70ml deionized water, after dissolving completely, obtains polyvinyl alcohol water solution.The two is mixed, obtain mixed aqueous solution.After pour mixed solution into glass guide channel and film, be placed in stink cupboard and spend the night after evaporation dewaters, be positioned over vacuum drying oven and progressively heat up lower dryly, obtain polyvinyl alcohol/layered double hydroxide composite membrane.
In this comparative example, the XRD spectra of prepared layered double hydroxide is identical with Fig. 1.Baseline is steady, and the characteristic peak positions of product diffraction peak position and layered double hydroxide is coincide, and (003) and (006) two peak sharp-pointed, symmetry is good, shows that synthetic layered double hydroxide perfect crystalline and degree of crystallinity are high.Layered double hydroxide size is below 100nm.XRD spectra and Fig. 5 of polyvinyl alcohol/layered double hydroxide composite membrane are basic identical, two characteristic peaks (003) and (006) of layered double hydroxide have still been demonstrated, show adding of high concentration of polyethylene alcohol, promoted on the contrary the gathering of layered double hydroxide.
In this comparative example, the tensile strength of prepared polyvinyl alcohol/layered double hydroxide composite membrane is 90MPa, and Young's modulus is 1200MPa, and visible region average transmittance is 86%.
Claims (10)
1. a preparation method for high strength poly vinyl alcohol composite membrane, is characterized in that, comprises the steps:
(1) solubility divalent metal salt and solubility trivalent metal salt are dissolved in to deionized water, then add alkaline matter, after being uniformly mixed, obtain reaction solution; Described reaction solution is crystallization 1～72h at 80～110 ℃, through suction filtration, dry, obtains layered double hydroxide;
(2) layered double hydroxide step (1) being obtained joins in deionized water, after ultrasonic dispersion, stirring and refluxing are processed, obtains dispersion liquid; In dispersion liquid, add granule of polyvinyl alcohol, after stirring, dissolving, obtain polyvinyl alcohol/layered double hydroxide mixed solution;
(3) polyvinyl alcohol/layered double hydroxide mixed solution that step (2) obtains obtains described high strength poly vinyl alcohol composite membrane through cast, after standing, dry.
2. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 1, is characterized in that, the metal ion in described solubility divalent metal salt is Co
2+, Ni
2+, Cu
2+, Zn
2+, Mg
2+in one or both;
Metal ion in described solubility trivalent metal salt is Al
3+, Cr
3+, Fe
3+, In
3+in one or both;
Described solubility divalent metal salt, the negatively charged ion of trivalent metal salt are NO
3 -, Cl
-, SO
4 2-in one or both.
3. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 1, is characterized in that, described alkaline matter is sodium hydroxide, potassium hydroxide, urea or ammoniacal liquor.
4. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 1, it is characterized in that, in described reaction solution, the total concn of solubility divalent metal salt and solubility trivalent metal salt is 0.06～1mol/L, the mol ratio of solubility divalent metal salt and solubility trivalent metal salt is 0.6～10:1, and the mol ratio of solubility divalent metal salt and solubility trivalent metal salt total amount and alkaline matter is 1:1～10.
5. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 1, is characterized in that, the quality of layered double-metal hydroxide is 0.1～10wt% of polyvinyl alcohol quality.
6. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 5, is characterized in that, the quality of layered double-metal hydroxide is 0.8～1.6wt% of polyvinyl alcohol quality.
7. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 6, is characterized in that, in described polyvinyl alcohol/layered double hydroxide mixed solution, the mass percentage concentration of polyvinyl alcohol is 2～20wt%.
8. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 7, is characterized in that, described in step (1), crystallization time is 12～24h.
9. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 8, is characterized in that, the time of ultrasonic dispersion described in step (2) is 10min～8h.
10. the preparation method of high strength poly vinyl alcohol composite membrane according to claim 9, is characterized in that, the reflow treatment time described in step (2) is 10min～10h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106012047A (en) * | 2016-05-24 | 2016-10-12 | 浙江大学 | Method using electrostatic spinning mode to manufacture shape-controllable poval composite fiber |
| CN111701460A (en) * | 2020-07-20 | 2020-09-25 | 南阳师范学院 | Preparation method of boron nitride modified layered double hydroxide/polyvinyl alcohol separation membrane |
| CN112086607A (en) * | 2019-06-12 | 2020-12-15 | 中南大学 | Composite diaphragm material of polymer @ two-dimensional material modified layered double hydroxide, and preparation method and application thereof |
-
2014
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Non-Patent Citations (1)
| Title |
|---|
| 王德龙等: "聚乙烯醇/层状双金属氢氧化物纳米复合材料的合成与性能研究", 《2004年中国阻燃学会年会》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106012047A (en) * | 2016-05-24 | 2016-10-12 | 浙江大学 | Method using electrostatic spinning mode to manufacture shape-controllable poval composite fiber |
| CN106012047B (en) * | 2016-05-24 | 2018-06-26 | 浙江大学 | The method that the polyvinyl alcohol composite fiber of morphology controllable is prepared using method of electrostatic spinning |
| CN112086607A (en) * | 2019-06-12 | 2020-12-15 | 中南大学 | Composite diaphragm material of polymer @ two-dimensional material modified layered double hydroxide, and preparation method and application thereof |
| CN112086607B (en) * | 2019-06-12 | 2021-10-15 | 中南大学 | Composite diaphragm material and preparation method and application thereof |
| CN111701460A (en) * | 2020-07-20 | 2020-09-25 | 南阳师范学院 | Preparation method of boron nitride modified layered double hydroxide/polyvinyl alcohol separation membrane |
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