CN103157391A - Preparation method of polyvinylidene fluoride porous film - Google Patents
Preparation method of polyvinylidene fluoride porous film Download PDFInfo
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- CN103157391A CN103157391A CN2012103471089A CN201210347108A CN103157391A CN 103157391 A CN103157391 A CN 103157391A CN 2012103471089 A CN2012103471089 A CN 2012103471089A CN 201210347108 A CN201210347108 A CN 201210347108A CN 103157391 A CN103157391 A CN 103157391A
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Abstract
The invention discloses a preparation method of a polyvinylidene fluoride porous film. The preparation method includes the steps of preparation of casting film liquid, core liquid and outer gel bath, spinning of a hollow fibrous film, and the like. The preparation method is simple in process, can achieve industrialized production, and is stable in quality of products; and due to the fact that nonsolvent-induced phase-change solidification technology is adopted, porosity of the prepared film reaches 80%, flux reaches 21 kg*m-3h-1 under the low operating temperature of 65 DEG C, the retention rate can reach over 99%, and the preparation method is quite suitable for being applied to film distillation separation technology.
Description
Technical field
The present invention relates to a kind of preparation method of polyvinylidene fluoride porous film.
Background technology
Kynoar has good physical and chemical performance and chemical property as a kind of semicrystalline polymeric, has become in recent years the material that the hydrophobic porous diffusion barrier of preparation is favored.Kynoar is the highest (500kg/cm of hot strength in fluoroplastics
2), the kind that impact strength and anti-wear performance are good, and it can use at-40-150 ℃ long-term, be difficult for by corrosion such as strong acid, highly basic, strong oxidizer and halogens, only can be dissolved in the organic solvent of the strong polarity such as 1-METHYLPYRROLIDONE (NMP), dimethyl acetyl (DMAC), dimethyl formamide (DMF).Based on above characteristics, Kynoar is very excellent material of preparation diffusion barrier.
In film separated science and technology field, required film should have high flux, the characteristics of high thermal efficiency and long life, and these advantages all depend on the high porosity that film itself has, best pore size and pore-size distribution, and the characteristics such as hydrophobicity and mechanical performance.Yet the existing film that is applied on film distillation technology is mostly generally to be used for the business dewatering microporous film of micro-filtration and ultra-filtration and separation process, and its material is mainly polypropylene (PP), polyethylene (PE) and polytetrafluoroethylene (PTFE) etc.What the masking mode of these commercial membranes adopted is sintering process, pulling method, melt spinning-cooling pulling method and the thermally induced phase separation etc. of complex process, and the surface apertures heterogeneity of prepared film, porosity are 40-60%, and flux is lower than 10kgm in the film still-process
-3h
-1, rejection is 90～95%, does not reach the requirement of film distillation technology.
Summary of the invention:
The purpose of this invention is to provide a kind of the preparation for commercial membranes flux and the lower present situation of rejection, by add in casting solution add and adopt mix outside the method for gel, prepared high flux, high rejection and be applicable to the method for the polyvinylidene fluoride porous film of film distillation technology.
In order to achieve the above object, technical scheme of the present invention comprises:
1. the preparation of casting solution, core liquid and outer coagulation bath:
Casting solution adopts polyvinylidene fluoride polymer, polar solvent and additive three kinds of substances in percentage by weight 12-18 %, 70-88%, and 0.1-10% mixes at 60-70 ℃; Wherein polar solvent is 1-METHYLPYRROLIDONE; It is in glycerine, ethylene glycol and polyvinylpyrrolidone a kind of that additive forms;
The mixed liquor that consists of water or organic reagent 1-METHYLPYRROLIDONE and water of core liquid, wherein the mass ratio of organic reagent and water is 10-50 %;
Outer coagulation bath is the mixed liquor of water or another organic reagent and water, and wherein another organic reagent is a kind of in methyl alcohol, ethanol, isopropyl alcohol and 1-METHYLPYRROLIDONE, and the mass ratio of another organic reagent and water is 10-50 %;
2. the spinning of hollow-fibre membrane:
Casting solution orifice flow outside spinning head is gone out, core liquid is flowed out from the spinning head endoporus, and both flow velocity is 3-10ml/min; The film silk that forms is through after the air gap height of 2-16cm, collects after entering outer coagulation bath phase transformation moulding with the wire winding speed of 3-10m/min, and 25-50 ℃ of the casting solution temperature in said process, 25-50 ℃ of core liquid temp, the coagulation bath temperature is 25-50 ℃;
As improvement, described outer coagulation bath is divided into different two groups; The casting solution that flows out from spinning head in the spinning process of hollow-fibre membrane and core liquid are successively by coagulation bath outside different two groups.
As further improvement, also comprise the hollow-fibre membrane post-processing step after the spinning step of hollow-fibre membrane, at first the film silk of collecting is put into water soaked 48-64 hour, remove remaining polar solvent, then soak 2-3 hour except the contained aqueous solution in the striping silk at methyl alcohol, put at last n-hexane and soaked 2-3 hour, carry out drying after sloughing methanol solution.
Beneficial effect of the present invention is:
1, technique is simple, can realize suitability for industrialized production, constant product quality;
2, adopted non-solvent to cause the phase transformation curing technology, prepared membrane porosity reaches 80%, reaches 21kgm at 65 ℃ of lower flux of lower operating temperature
-3h
-1, rejection can reach more than 99%, is well suited for being applied to film separated technology.
The specific embodiment
Embodiment one:
1. the preparation of casting solution, core liquid and outer coagulation bath:
Casting solution adopts polyvinylidene fluoride polymer, solvent 1-METHYLPYRROLIDONE and three kinds of substances in percentage by weight 15% of additive ethylene glycol, 83.9%, 0.1% to mix at 60 ℃; Core liquid consist of water; Coagulation bath consist of water.
2. the spinning of hollow-fibre membrane:
Casting solution orifice flow outside spinning head is gone out, core liquid is flowed out from the spinning head endoporus, and the casting solution flow velocity is 3 ml/min, the core flow velocity is 10ml/min; The film silk that forms is through after the air gap height of 2cm, collects after entering outer coagulation bath phase transformation moulding with the wire winding speed of 10m/min, and the casting solution temperature 50 C in said process, 50 ℃ of core liquid temps, the coagulation bath temperature is 25 ℃.
The film silk of making is by the test of film separated, and its membrane flux is 4.12 kgm
-3h
-1With rejection 99.9%.
Embodiment two:
1. the preparation of casting solution, core liquid and outer coagulation bath:
Casting solution adopts polyvinylidene fluoride polymer, solvent 1-METHYLPYRROLIDONE and three kinds of substances in percentage by weight 12% of additive glycerine, 78%, 10% to mix at 60 ℃; Core liquid consist of water; Coagulation bath is divided into the two groups of different outer coagulation baths of the aqueous solution and water that contain ethanol 50wt%;
2. the spinning of hollow-fibre membrane:
Casting solution orifice flow outside spinning head is gone out, core liquid is flowed out from the spinning head endoporus, and the casting solution flow velocity is 4 ml/min, the core flow velocity is 3ml/min; The film silk that forms is through after the air gap height of 8cm, with the wire winding speed of 10m/min successively by collecting after aforementioned two groups of different outer coagulation bath phase transformation moulding, 25 ℃ of the casting solution temperature in said process, 25 ℃ of core liquid temps, the coagulation bath temperature is 25 ℃.
3. hollow-fibre membrane post processing:
At first the film silk of collecting is put into water soaked 48 hours, remove remaining polar solvent, then soak 2 hours except the contained aqueous solution in the striping silk in methyl alcohol, put at last n-hexane and soaked 2 hours, carry out drying after sloughing methanol solution.
The film silk of making is by the test of film separated, and its membrane flux is 21.1 kgm
-3h
-1With rejection 99.9%.
Embodiment three:
1. the preparation of casting solution, core liquid and outer coagulation bath:
Casting solution adopts polyvinylidene fluoride polymer, solvent 1-METHYLPYRROLIDONE and three kinds of substances in percentage by weight 18% of additive glycerine, 77%, 5% to mix at 60 ℃; Core liquid consist of water; Coagulation bath is divided into the two groups of different outer coagulation baths of the aqueous solution and water that contain ethanol 10 wt%.
2. the spinning of hollow-fibre membrane:
Casting solution orifice flow outside spinning head is gone out, core liquid is flowed out from the spinning head endoporus, and the casting solution flow velocity is 4 ml/min, the core flow velocity is 3ml/min; The film silk that forms is through after the air gap height of 8cm, with the wire winding speed of 3m/min successively by collecting after aforementioned two groups of different outer coagulation bath phase transformation moulding, 25 ℃ of the casting solution temperature in said process, 25 ℃ of core liquid temps, the coagulation bath temperature is 25 ℃.
3. hollow-fibre membrane post processing:
At first the film silk of collecting is put into water soaked 72 hours, remove remaining polar solvent, then soak 3 hours except the contained aqueous solution in the striping silk in methyl alcohol, put at last n-hexane and soaked 3 hours, carry out drying after sloughing methanol solution.
The film silk of making is by the test of film separated, and its membrane flux is 9.93 kgm
-3h
-1With rejection 99.9%
Embodiment four:
1. the preparation of casting solution, core liquid and outer coagulation bath:
Casting solution adopts polyvinylidene fluoride polymer, solvent 1-METHYLPYRROLIDONE and three kinds of substances in percentage by weight 15% of additive polyvinylpyrrolidone, 83.9%, 0.1% to mix at 60 ℃; Core liquid is the aqueous solution that contains 1-METHYLPYRROLIDONE 50 wt%; Coagulation bath is divided into the two groups of different outer coagulation baths of the aqueous solution and water that contain 1-METHYLPYRROLIDONE 50 wt%.
2. the spinning of hollow-fibre membrane:
Casting solution orifice flow outside spinning head is gone out, core liquid is flowed out from the spinning head endoporus, and the casting solution flow velocity is 4 ml/min, the core flow velocity is 3ml/min; The film silk that forms is through after the air gap height of 16cm, with the wire winding speed of 6m/min successively by collecting after aforementioned two groups of different outer coagulation bath phase transformation moulding, 25 ℃ of the casting solution temperature in said process, 25 ℃ of core liquid temps, the coagulation bath temperature is 25 ℃.
3. hollow-fibre membrane post processing:
At first the film silk of collecting is put into water soaked 72 hours, remove remaining polar solvent, then soak 3 hours except the contained aqueous solution in the striping silk in methyl alcohol, put at last n-hexane and soaked 3 hours, carry out drying after sloughing methanol solution.
The film silk of making is by the test of film separated, and its membrane flux is 15.4kgm
-3h
-1With rejection 99.9%.
Claims (3)
1. the preparation method of a polyvinylidene fluoride porous film, is characterized in that, comprises the following steps:
1. the preparation of casting solution, core liquid and outer coagulation bath:
Casting solution adopts polyvinylidene fluoride polymer, polar solvent and additive three kinds of substances in percentage by weight 12-18%, 70-88%, and 0.-10% mixes at 60-70 ℃; Wherein polar solvent is 1-METHYLPYRROLIDONE; It is in glycerine, ethylene glycol and polyvinylpyrrolidone a kind of that additive forms;
The mixed liquor that consists of water or organic reagent 1-METHYLPYRROLIDONE and water of core liquid, wherein the mass ratio of organic reagent and water is 10-50%;
Outer coagulation bath is the mixed liquor of water or another organic reagent and water, and wherein another organic reagent is a kind of in methyl alcohol, ethanol, isopropyl alcohol and 1-METHYLPYRROLIDONE, and the mass ratio of another organic reagent and water is 10-50%;
2. the spinning of hollow-fibre membrane:
Casting solution orifice flow outside spinning head is gone out, core liquid is flowed out from the spinning head endoporus, and both flow velocity is 3-10ml/min; The film silk that forms is through after the air gap height of 2-16cm, collects after entering outer coagulation bath phase transformation moulding with the wire winding speed of 3-10m/min, and 25-50 ℃ of the casting solution temperature in said process, 25-50 ℃ of core liquid temp, the coagulation bath temperature is 25-50 ℃.
2. according to claim 1 a kind of preparation method of polyvinylidene fluoride porous film, is characterized in that, described outer coagulation bath is divided into different two groups; The casting solution that flows out from spinning head in the spinning process of hollow-fibre membrane and core liquid are successively by coagulation bath outside different two groups.
3. according to claim 1 a kind of preparation method of polyvinylidene fluoride porous film, it is characterized in that, also comprise the hollow-fibre membrane post-processing step after the spinning step of hollow-fibre membrane, at first the film silk of collecting is put into water soaked 48-64 hour, remove remaining polar solvent, then soak 2-3 hour except the contained aqueous solution in the striping silk at methyl alcohol, put at last n-hexane and soaked 2-3 hour, carry out drying after sloughing methanol solution.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432915A (en) * | 2013-08-23 | 2013-12-11 | 长沙奕景环保科技有限公司 | Method for preparing polyvinylidene-fluoride bilayer hollow fiber membrane |
| CN105214527A (en) * | 2015-10-12 | 2016-01-06 | 中南大学 | A kind of preparation technology of ultra-hydrophobic polyvinylidene fluoride hexafluoropropene perforated membrane |
| CN107174964A (en) * | 2017-07-24 | 2017-09-19 | 上海应用技术大学 | A kind of use isopropanol coagulation bath regulates and controls the method that hydrophilic F127 PVDF are modified membrane structure |
| WO2018080398A1 (en) * | 2016-10-26 | 2018-05-03 | National University Of Singapore | A hollow fiber membrane |
| CN108079795A (en) * | 2017-12-13 | 2018-05-29 | 浙江长兴求是膜技术有限公司 | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method |
| CN108192129A (en) * | 2017-11-30 | 2018-06-22 | 南京工业大学 | Super-hydrophobic polyvinylidene fluoride aerogel material and preparation method thereof |
| CN108993173A (en) * | 2017-12-27 | 2018-12-14 | 中南大学 | It is a kind of for the PVDF hollow-fibre membrane of membrane distillation and its preparation and application |
| CN109316971A (en) * | 2018-10-19 | 2019-02-12 | 武汉大学深圳研究院 | A kind of hollow-fibre membrane crushing resistance and water flux Enhancement Method |
| CN113244784A (en) * | 2021-04-27 | 2021-08-13 | 陕西禹慧智通环保科技有限公司 | Porous hydrophobic microporous membrane and preparation method and application thereof |
| CN113578073A (en) * | 2021-06-03 | 2021-11-02 | 徐州禹慧环境科技研究院有限公司 | Preparation method of modified hollow fiber hydrophobic microporous membrane for membrane distillation |
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| CN101733023A (en) * | 2010-02-02 | 2010-06-16 | 顾涌 | Method for manufacturing polyvinylidene fluoride hollow fiber membrane |
| CN102068923A (en) * | 2010-12-31 | 2011-05-25 | 河北诺恩水净化设备有限公司 | Method for preparing polyvinylidene fluoride hollow fiber membrane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733023A (en) * | 2010-02-02 | 2010-06-16 | 顾涌 | Method for manufacturing polyvinylidene fluoride hollow fiber membrane |
| CN102068923A (en) * | 2010-12-31 | 2011-05-25 | 河北诺恩水净化设备有限公司 | Method for preparing polyvinylidene fluoride hollow fiber membrane |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432915A (en) * | 2013-08-23 | 2013-12-11 | 长沙奕景环保科技有限公司 | Method for preparing polyvinylidene-fluoride bilayer hollow fiber membrane |
| CN105214527A (en) * | 2015-10-12 | 2016-01-06 | 中南大学 | A kind of preparation technology of ultra-hydrophobic polyvinylidene fluoride hexafluoropropene perforated membrane |
| US20190247802A1 (en) * | 2016-10-26 | 2019-08-15 | National University Of Singapore | A hollow fiber membrane |
| WO2018080398A1 (en) * | 2016-10-26 | 2018-05-03 | National University Of Singapore | A hollow fiber membrane |
| CN109906112A (en) * | 2016-10-26 | 2019-06-18 | 新加坡国立大学 | Hollow-fibre membrane |
| US10967331B2 (en) | 2016-10-26 | 2021-04-06 | National University Of Singapore | Hollow fiber membrane |
| CN107174964A (en) * | 2017-07-24 | 2017-09-19 | 上海应用技术大学 | A kind of use isopropanol coagulation bath regulates and controls the method that hydrophilic F127 PVDF are modified membrane structure |
| CN108192129A (en) * | 2017-11-30 | 2018-06-22 | 南京工业大学 | Super-hydrophobic polyvinylidene fluoride aerogel material and preparation method thereof |
| CN108079795A (en) * | 2017-12-13 | 2018-05-29 | 浙江长兴求是膜技术有限公司 | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method |
| CN108993173A (en) * | 2017-12-27 | 2018-12-14 | 中南大学 | It is a kind of for the PVDF hollow-fibre membrane of membrane distillation and its preparation and application |
| CN109316971A (en) * | 2018-10-19 | 2019-02-12 | 武汉大学深圳研究院 | A kind of hollow-fibre membrane crushing resistance and water flux Enhancement Method |
| CN113244784A (en) * | 2021-04-27 | 2021-08-13 | 陕西禹慧智通环保科技有限公司 | Porous hydrophobic microporous membrane and preparation method and application thereof |
| CN113578073A (en) * | 2021-06-03 | 2021-11-02 | 徐州禹慧环境科技研究院有限公司 | Preparation method of modified hollow fiber hydrophobic microporous membrane for membrane distillation |
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Application publication date: 20130619 |