CN102807682B - Method for preparing modified single hydrophobic polyvinyl alcohol film - Google Patents
Method for preparing modified single hydrophobic polyvinyl alcohol film Download PDFInfo
- Publication number
- CN102807682B CN102807682B CN201210305044.6A CN201210305044A CN102807682B CN 102807682 B CN102807682 B CN 102807682B CN 201210305044 A CN201210305044 A CN 201210305044A CN 102807682 B CN102807682 B CN 102807682B
- Authority
- CN
- China
- Prior art keywords
- pvoh
- film
- pva
- polyvinyl alcohol
- hydrophobically modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a method for preparing a modified single hydrophobic polyvinyl alcohol film, and relates to a method for preparing a polyvinyl alcohol film. The invention aims to solve the problem that the polyvinyl alcohol film prepared by the existing method is lack of waterproof performance. The preparation method comprises the following steps of: 1, preparing polyvinyl alcohol into film solution, and preparing the polyvinyl alcohol film on a glass plate by a curtain coating film-forming method; 2, spraying silane coupling agent acetone solution on the surface of the polyvinyl alcohol film by a high-pressure spray gun for surface modification; 3, spraying di-isocyanate acetone solution on the surface of the polyvinyl alcohol film which is processed by the step 2 by the high-pressure spray gun for graft reaction; and 4, spraying fatty alcohol acetone solution on the surface of the polyvinyl alcohol film which is processed by the step 3 by the high-pressure spray gun, and then naturally air drying for 5-20 minutes to obtain the modified single hydrophobic polyvinyl alcohol film. The polyvinyl alcohol film prepared by the method has waterproof performance. The polyvinyl alcohol film is suitable for the field of the waterproof package material.
Description
Technical field
The present invention relates to a kind of preparation method of PVA (PVOH) FILM.
Background technology
Polyvinyl alcohol is a kind of low toxicity, stable chemical nature, is easy to process the vinyl water-soluble polymer that film forming, stable chemical nature and biological degradability are good, and its good film-forming properties is applied in the fields such as packing, membrane sepn, book-binding.PVA (PVOH) FILM prepared by existing method, due to poly-hydroxy, the strong hydrogen bonding constructional feature of polyvinyl alcohol, makes it after film forming, to have strongly hydrophilic and water-soluble, and therefore, existing PVA (PVOH) FILM lacks water-repellancy, and its application aspect packing is restricted.
Summary of the invention
The present invention will solve the problem that PVA (PVOH) FILM prepared by existing method lacks water-repellancy, and a kind of preparation method of one side hydrophobically modified PVA (PVOH) FILM is provided.
The preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM of the present invention carries out according to the following steps:
One, polyvinyl alcohol solid is mixed with deionized water, under the water bath condition of 80～95 ℃, stir after 2～5h, with ultrasonoscope, in frequency, be that 28～100Hz power is under 40～100W condition, to carry out the supersound process of 8～20min, then with vacuum pump, carry out the vacuum defoamation of 5～20min, obtain massfraction and be 2%～8% polyvinyl alcohol film forming liquid, then adopt casting filming therapy on sheet glass, to prepare PVA (PVOH) FILM;
Two, silane coupling agent is dissolved in in organic solvent, to be prepared into silane coupling agent massfraction be 0.5%～2% organic solution, with high-pressure spray gun, on PVA (PVOH) FILM surface, sprays silane coupling agent organic solution 1～2min, natural air drying 5～20min;
Three, isocyanic ester is dissolved in in organic solvent, to be prepared into isocyanic ester massfraction be 0.5%～3% organic solution, with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling isocyanates organic solution 1～2min processing through step 2, natural air drying 5～20min;
Four, fatty alcohol is dissolved in in organic solvent, to be prepared into fatty alcohol massfraction be 0.2%～2% organic solution, with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling fatty alcohol organic solution 1～2min processing through step 3, natural air drying 5～20min, obtains one side hydrophobically modified PVA (PVOH) FILM; Wherein, the silane coupling agent adopting in step 2 is KH550, KH560, KH570 or KH792; The isocyanic ester that step 3 adopts is TDI, HDI, MDI or PAPI; The fatty alcohol that step 4 adopts is amylalcohol, octanol, hexadecanol or stearyl alcohol; The organic solvent adopting in step 2 and step 3 is acetone, ethanol, methyl alcohol or butanone.
The present invention prepares one side hydrophobically modified PVA (PVOH) FILM under the prerequisite that does not change the mechanical property that PVA (PVOH) FILM is good, and method is simple, easily suitability for industrialized production.The one side of one side hydrophobically modified PVA (PVOH) FILM can continue to keep PVA (PVOH) FILM hydrophilicity, and the hydrophobic contact angle of another side is up to 135 °, and its hydrophobic performance has waterproof effect, can be widely used in waterproof packing Material Field.
Accompanying drawing explanation
Fig. 1 is the test 1 hydrophobically modified PVA (PVOH) FILM hydrophilic surface contact angle obtaining;
Fig. 2 is the test 1 hydrophobically modified PVA (PVOH) FILM hydrophobic surface contact angle obtaining;
Fig. 3 is the environmental scanning electron microscope figure of the test 1 hydrophobically modified PVA (PVOH) FILM obtaining;
Fig. 4 is the test 1 infrared figure of hydrophobically modified PVA (PVOH) FILM Fourier obtaining.
Embodiment
Embodiment one: a kind of preparation method of one side hydrophobically modified PVA (PVOH) FILM, described preparation method carries out in such a way: one, polyvinyl alcohol solid is mixed with deionized water, under the water bath condition of 80～95 ℃, stir after 2～5h, with ultrasonic washing instrument, in frequency, be that 28～100Hz power is under the condition of 40～100W, to carry out the supersound process of 8～20min, then with vacuum pump, carry out the vacuum defoamation of 5～20min, obtain massfraction and be 2%～8% polyvinyl alcohol film forming liquid, then adopt casting filming therapy on sheet glass, to prepare PVA (PVOH) FILM,
Two, silane coupling agent is dissolved in in organic solvent, to be prepared into silane coupling agent massfraction be 0.5%～2% organic solution, with high-pressure spray gun to spraying silane coupling agent organic solution 1～2min, natural air drying 5～20min on PVA (PVOH) FILM surface;
Three, isocyanic ester is dissolved in in organic solvent, to be prepared into isocyanic ester massfraction be 0.5%～3% organic solution, with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling isocyanic ester organic solution 1～2min processing through step 2, natural air drying 5～20min;
Four, fatty alcohol is dissolved in in organic solvent, to be prepared into fatty alcohol massfraction be 0.2%～2% organic solution, with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling fatty alcohol organic solution 1～2min processing through step 3, natural air drying 5～20min, obtains one side hydrophobically modified PVA (PVOH) FILM; Wherein, the silane coupling agent adopting in step 2 is KH550 (γ-aminopropyl triethoxysilane), KH560 (γ-glycidyl ether oxygen propyl trimethoxy silicane), KH570 (gamma-methyl allyl acyloxypropyl trimethoxysilane) or KH792 (γ-quadrol base propyl-triethoxysilicane); The isocyanic ester that step 3 adopts is TDI (tolylene diisocyanate), HDI (hexamethylene diisocyanate), MDI (diphenylmethanediisocyanate) or PAPI (polyphenyl polymethylene polyisocyanates); The fatty alcohol that step 4 adopts is amylalcohol, octanol, hexadecanol or stearyl alcohol; The organic solvent adopting in step 2 and step 3 is acetone, ethanol, methyl alcohol or butanone.
Present embodiment is prepared one side hydrophobically modified PVA (PVOH) FILM under the prerequisite that does not change the mechanical property that PVA (PVOH) FILM is good, and method is simple, easily suitability for industrialized production.The one side of one side hydrophobically modified PVA (PVOH) FILM can continue to keep PVA (PVOH) FILM hydrophilicity, and the hydrophobic contact angle of another side is up to 135 °, and its hydrophobic performance has waterproof effect, can be widely used in waterproof packing Material Field.
Embodiment two: present embodiment is different from embodiment one: in step 1, the massfraction of polyvinyl alcohol film forming liquid is 4%.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: stir under the water bath condition of 85 ℃ in step 1.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: in step 2, silane coupling agent is dissolved in to be prepared into silane coupling agent massfraction in organic solvent be 2% organic solution.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: in step 2 with high-pressure spray gun to spraying silane coupling agent organic solution 1min, natural air drying 10min on PVA (PVOH) FILM surface.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: step 3 is dissolved in isocyanic ester that to be prepared into isocyanic ester massfraction in organic solvent be 2% organic solution.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: in step 3 with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling isocyanic ester organic solution 1min processing through step 2, natural air drying 10min.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: fatty alcohol is dissolved in to be prepared into fatty alcohol massfraction in organic solvent be 2% organic solution.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: use high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling fatty alcohol organic solution 1min processing through step 3, natural air drying 10min in step 4.Other is identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: the spraying condition of the high-pressure spray gun in step 2, step 3 and step 4 is: absorbed air pressure is 0.05～1MPa, it is 75L/min that air passes into speed, discharging bore Φ is 1.0mm, and spray rate is 95mL/min.Other is identical with one of embodiment one to nine.
With following verification experimental verification beneficial effect of the present invention:
Test 1
This preparation method who tests a kind of one side hydrophobically modified PVA (PVOH) FILM carries out according to the following steps:
One, polyvinyl alcohol solid is mixed with deionized water, stir 2 under the water bath condition of 85 ℃ after, with ultrasonoscope, in frequency, be that 100Hz power is under 90W condition, to carry out the supersound process of 10min, then with vacuum pump, carry out the vacuum defoamation of 10min, obtain massfraction and be 4% polyvinyl alcohol film forming liquid, then adopt casting filming therapy on sheet glass, to prepare PVA (PVOH) FILM;
Two, KH550 is dissolved in in acetone, to prepare KH550 massfraction be 2% KH550 acetone soln, with high-pressure spray gun, on PVA (PVOH) FILM surface, sprays KH550 acetone soln 1min, natural air drying 10min;
Three, tolylene diisocyanate is dissolved in in acetone, to prepare tolylene diisocyanate massfraction be 2% tolylene diisocyanate acetone soln, with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling tolylene diisocyanate acetone soln of processing through step 2,1min, natural air drying 10min;
Four, stearyl alcohol is dissolved in in acetone, to prepare stearyl alcohol massfraction be 2% stearyl alcohol acetone soln, with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling stearyl alcohol acetone soln 1min processing through step 3, natural air drying 10min, obtains one side hydrophobically modified PVA (PVOH) FILM; Wherein the spraying condition of the high-pressure spray gun in step 2, step 3 and step 4 is: absorbed air pressure is 0.1MPa, and it is 75L/min that air passes into speed, and discharging bore Φ is 1.0mm, and spray rate is 15mL/min.
The hydrophilic angle of the one side hydrophobically modified PVA (PVOH) FILM of this test preparation and hydrophobic angle as depicted in figs. 1 and 2, can find out that from Fig. 1 and Fig. 2 the one side hydrophobically modified PVA (PVOH) FILM of this test preparation has simultaneously hydrophilic, and contact angle is 23 °; And one side is hydrophobic, contact angle is 129 °.
The environmental scanning electron microscope of the one side hydrophobically modified PVA (PVOH) FILM of this test preparation as shown in Figure 2, as can be seen from Figure 2, one side hydrophobically modified PVA (PVOH) FILM thickness, in 40 μ m left and right, can be seen surface of fracture and the hydrophobic surface of film by oblique view, hydrophobic surface is slightly coarse.
The one side hydrophobically modified PVA (PVOH) FILM that the PVA (PVOH) FILM of this testing sequence one preparation, the film of processing through step 2, the film of processing through step 3 and step 4 are obtained is carried out Fourier's examination of infrared spectrum, obtain Fourier's infrared spectrogram separately, as shown in Figure 4, Fourier's infrared spectra that wherein a is PVA (PVOH) FILM, b is the Fourier's infrared spectra through the film of step 2 processing, c is that d is Fourier's infrared spectra of one side hydrophobically modified PVA (PVOH) FILM through Fourier's infrared spectra of the film of step 3 processing; Result shows still to have through parent/hydrophobic polyethylene alcohol film after each step hydrophobically modified the basic chemical structure of polyvinyl alcohol as can be seen from Figure 4.
The one side hydrophobically modified PVA (PVOH) FILM that PVA (PVOH) FILM prepared by this testing sequence one and step 4 obtain is carried out tensile strength and elongation at break analysis, show that data are as shown in table 1 separately; As known from Table 1, the film stretching intensity after modification significantly increases, and elongation at break has obvious reduction.
Table 1
Note: number 1 for PVA (PVOH) FILM, number 2 one side hydrophobically modified PVA (PVOH) FILM for obtaining
Claims (9)
1. a preparation method for one side hydrophobically modified PVA (PVOH) FILM, is characterized in that the preparation method of one side hydrophobically modified PVA (PVOH) FILM realizes by following steps:
One, polyvinyl alcohol solid is mixed with deionized water, under the water bath condition of 80～95 ℃, stir after 2～5h, with ultrasonoscope, in frequency, be under 28～100Hz, the power condition that is 40～100W, to carry out the supersound process of 8～20min, then with vacuum pump, carry out the vacuum defoamation of 5～20min, obtain massfraction and be 2%～8% polyvinyl alcohol film forming liquid, then adopt casting filming therapy on sheet glass, to prepare PVA (PVOH) FILM;
Two, silane coupling agent is dissolved in in organic solvent, to be prepared into silane coupling agent massfraction be 0.5%～2% organic solution, with high-pressure spray gun, on PVA (PVOH) FILM surface, sprays silane coupling agent organic solution 1～2min, natural air drying 5～20min;
Three, isocyanic ester is dissolved in in organic solvent, to be prepared into isocyanic ester massfraction be 1.0%～3.0% organic solution, with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling isocyanic ester organic solution 1～2min processing through step 2, natural air drying 5～20min;
Four, fatty alcohol is dissolved in in organic solvent, to be prepared into fatty alcohol massfraction be 0.2%～2% organic solution, with high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling fatty alcohol organic solution 1～2min processing through step 3, natural air drying 5～20min, obtains one side hydrophobically modified PVA (PVOH) FILM; Wherein, the silane coupling agent adopting in step 2 is KH550, KH560, KH570 or KH792; The isocyanic ester that step 3 adopts is TDI, HDI, MDI or PAPI; The fatty alcohol that step 4 adopts is amylalcohol, octanol, hexadecanol or stearyl alcohol; The organic solvent adopting in step 2 and step 3 is acetone, ethanol, methyl alcohol or butanone; The spraying condition of the high-pressure spray gun in step 2, step 3 and step 4 is: absorbed air pressure is 0.05～1MPa, and it is 75L/min that air passes into speed, and discharging bore Φ is 1.0mm, and spray rate is 95mL/min.
2. the preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM according to claim 1, the massfraction that it is characterized in that polyvinyl alcohol film forming liquid in step 1 is 4%.
3. the preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM according to claim 1 and 2, is characterized in that under the water bath condition of 85 ℃, stirring in step 1.
4. the preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM according to claim 3, is characterized in that in step 2, silane coupling agent being dissolved in that in organic solvent, to be prepared into silane coupling agent massfraction be 2% organic solution.
5. the preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM according to claim 4, is characterized in that in step 2 with high-pressure spray gun spraying silane coupling agent organic solution 1min, natural air drying 10min on PVA (PVOH) FILM surface.
6. the preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM according to claim 5, is characterized in that step 3 is dissolved in isocyanic ester that in organic solvent, to be prepared into isocyanic ester massfraction be 2% organic solution.
7. the preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM according to claim 6, it is characterized in that using high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling isocyanic ester organic solution 1min processing through step 2, natural air drying 10min in step 3.
8. the preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM according to claim 7, is characterized in that in step 4, fatty alcohol being dissolved in that in organic solvent, to prepare fatty alcohol massfraction be 2% organic solution.
9. the preparation method of a kind of one side hydrophobically modified PVA (PVOH) FILM according to claim 8, it is characterized in that using high-pressure spray gun to the PVA (PVOH) FILM surface sprinkling fatty alcohol organic solution 1min processing through step 3, natural air drying 10min in step 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210305044.6A CN102807682B (en) | 2012-08-24 | 2012-08-24 | Method for preparing modified single hydrophobic polyvinyl alcohol film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210305044.6A CN102807682B (en) | 2012-08-24 | 2012-08-24 | Method for preparing modified single hydrophobic polyvinyl alcohol film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102807682A CN102807682A (en) | 2012-12-05 |
| CN102807682B true CN102807682B (en) | 2014-02-19 |
Family
ID=47231564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210305044.6A Expired - Fee Related CN102807682B (en) | 2012-08-24 | 2012-08-24 | Method for preparing modified single hydrophobic polyvinyl alcohol film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102807682B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103744141B (en) * | 2013-12-25 | 2016-07-20 | 云南云天化股份有限公司 | A kind of preparation method of Pva Polarizing Film |
| CN105400109B (en) * | 2015-11-06 | 2018-01-05 | 芜湖市伟华泡塑有限公司 | A kind of modified polyvinylalcohol foamed plastics and preparation method thereof |
| CN106883442B (en) * | 2017-03-24 | 2019-07-26 | 怀化学院 | A kind of preparation method of fluorided-modified polyvinyl alcohol film |
| CN107082895A (en) * | 2017-04-27 | 2017-08-22 | 上海交通大学 | The preparation method of degradable nano antibacterial film |
| CN110016155A (en) * | 2019-04-18 | 2019-07-16 | 北京林业大学 | A kind of preparation method of fluorinated polyethylene alcohol-silica single side hydrophobic film |
| CN110171831B (en) * | 2019-04-29 | 2021-07-06 | 南京工业大学 | Hydrophobic two-dimensional Ti at normal temperature3C2TxPreparation method of (MXene) film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101557931A (en) * | 2006-10-27 | 2009-10-14 | 武冈真司 | Thin film-like polymer structure and method for preparing the same |
-
2012
- 2012-08-24 CN CN201210305044.6A patent/CN102807682B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101557931A (en) * | 2006-10-27 | 2009-10-14 | 武冈真司 | Thin film-like polymer structure and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102807682A (en) | 2012-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102807682B (en) | Method for preparing modified single hydrophobic polyvinyl alcohol film | |
| Zeng et al. | The bonding strength, water resistance and flame retardancy of soy protein-based adhesive by incorporating tailor-made core–shell nanohybrid compounds | |
| Wu et al. | Robust microcapsules with polyurea/silica hybrid shell for one-part self-healing anticorrosion coatings | |
| Wang et al. | Bio-inspired cellulose nanofiber-reinforced soy protein resin adhesives with dopamine-induced codeposition of “water-resistant” interphases | |
| Greco et al. | Ultra-thin conductive free-standing PEDOT/PSS nanofilms | |
| CN103952945B (en) | A kind of preparation method of anti abrasive super-hydrophobic filter paper | |
| CN107497301A (en) | A kind of dual bionical method for constructing membrane distillation super-hydrophobic film | |
| CN113667340A (en) | Corrosion inhibition material and application thereof | |
| Wang et al. | Synthesis of novel nano hyperbranched polymer resin and its corrosion resistance in coatings | |
| CN110790260A (en) | Preparation method of biomass-derived porous carbon nanosheet modified with phytic acid and KH550 | |
| Wei et al. | Electrodeposition of a biopolymeric hydrogel in track-etched micropores | |
| CN111944144A (en) | Self-supporting catecholamine film and preparation method and application thereof | |
| Yin et al. | Argon plasma-induced graft polymerization of PEGMA on chitosan membrane surface for cell adhesion improvement | |
| CN108250941B (en) | Low-surface-energy material with micro-nano groove structure and preparation method thereof | |
| CN110591159B (en) | Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof | |
| Parizi et al. | Improving mechanical properties of glass fiber reinforced polymers through silica-based surface nanoengineering | |
| CN109517473B (en) | High-strength waterproof epoxy resin coating and preparation method thereof | |
| Chen et al. | High solid and low viscosity waterborne polyurethane acrylate with excellent anti-corrosion and anti-bacterial performances | |
| Xing et al. | Biodegradable, superhydrophobic walnut wood membrane for the separation of oil/water mixtures | |
| CN102775603B (en) | Preparation method of laminar polyaniline for anticorrosive paint | |
| CN110396175B (en) | Self-emulsifying antibacterial water-based epoxy resin and application thereof in wood and bamboo protection | |
| CN107201660B (en) | A kind of hydrophobic coating material and coating production applied to pbo fiber surface | |
| Startek et al. | Oxygen barrier enhancement of polymeric foil by sol-gel-derived hybrid silica layers | |
| CN113861723B (en) | Modified ferroferric oxide particle, preparation method and application thereof, modified ferroferric oxide/epoxy composite coating and application thereof | |
| Pham et al. | Optimizing the superhydrophobicity of the composite PDMS/PUA film produced by a R2R system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140219 Termination date: 20190824 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |