CN102228805B - Method for preparing ethylene-trifluorochlor oethylene copolymer porous membrane - Google Patents
Method for preparing ethylene-trifluorochlor oethylene copolymer porous membrane Download PDFInfo
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Abstract
The invention discloses a method for preparing an ethylene-trifluorochlor oethylene copolymer porous membrane, and belongs to the fields of high polymer material science and technology. In the method, a proper solvent, namely diethyl phthalate is provided, and the ethylene-trifluorochlor oethylene copolymer porous membrane is prepared by initiating phase separation by reducing the temperature of an ethylene-trifluorochlor oethylene copolymer/diethyl phthalate system. When the polymer concentration is lower than 60 weight percent, the section of the ethylene-trifluorochlor oethylene copolymer porous membrane has a uniform spongeous structure. By controlling the conditions such as the concentration of the ethylene-trifluorochlor oethylene copolymer, cooling rate and the like, the microstructure of the membrane can be controlled.
Description
Technical field
The present invention relates to a kind of method for preparing the ethylene-chlorotrifluoro-ethylene copolymer perforated membrane, particularly adopting diethyl phthalate is main diluent, utilize thermally induced phase separation to prepare the method for ethylene-chlorotrifluoro-ethylene copolymer perforated membrane, belong to polymer material science and technical field.
Background technology
Ethylene-chlorotrifluoro-ethylene copolymer is the alternate copolymer that CTFE and ethene were close to 1: 1.Due to ethene and CTFE alternately to form chain link at 1: 1, therefore greatly improved the thermoplasticity processing characteristics, and can keep the original premium properties of polychlorotrifluoroehomopolymer homopolymer, particularly heat-resisting (350 ℃ of decomposition temperatures), chemical-resistant and weatherability.Ethylene-chlorotrifluoro-ethylene copolymer chemical-resistant reagent corrosive nature and polytetrafluoroethylene (PTFE) are suitable, be better than Kynoar, all can not be in temperature in existing solvent lower than 120 ℃ of lower dissolve ethylene-chlorotrifluoroethylenes or make its that stress cracking occur, only have to contact with chlorinated solvent just to cause slight swelling.Because ethylene-chlorotrifluoro-ethylene copolymer has good decay resistance, extremely low permeability, surperficial is extremely smooth, possess outstanding shock resistance and quite tough and tensile mechanical strength, this polymer is widely used in draining, washing, the sewage disposal system of chemical industry, oil, and the chemical cleaning system of device, the aspects such as the distribution system of chemicals.The isolating environment that it is applicable to high temperature and high corrosion has broad application prospects at separation field, is potential desirable membrane material.Owing to not being fit to the solvent of ethylene-chlorotrifluoro-ethylene copolymer under normal temperature, (TIPS) method is considered to prepare the most suitable method of ethylene-chlorotrifluoro-ethylene copolymer microporous barrier so thermic is separated.
At present existing a small amount of document begins report and utilizes the standby ethylene-chlorotrifluoro-ethylene copolymer microporous barrier of TIPS legal system.U.S.pat.No.4623670 and 4702836 at high temperature is dissolved in ethylene-chlorotrifluoro-ethylene copolymer in chlorotrifluoroethylene, add silica, melt extrude into rear quenching film forming, use trichloroethanes extraction chlorotrifluoroethylene, hot NaOH is removed silica, obtains the ethylene-chlorotrifluoro-ethylene copolymer perforated membrane, this process diluent chlorotrifluoroethylene is expensive, extractant trichloroethanes toxicity is larger, and complex process, and membrane aperture is wayward.U.S.pat.No.7247238, in order not use the larger trichloroethanes of toxicity, reduce the cost of diluent, filter out ETHYL CTTRATE or triacetyl glycerine as diluent, blending silica, by the standby ethylene-chlorotrifluoro-ethylene copolymer perforated membrane of TIPS legal system, this preparation process is still complicated, and wayward pore structure.Ramaswamy etc. as diluent, in the situation that do not add additive, obtain different pore structures by controlling the quenching temperature with dibutyl phthalate (DBP).The method technique is simple, is easy to control, but the spore pore structure that the film for preparing is all, this structure porosity is low, and mechanical property is relatively poor.
Summary of the invention
The objective of the invention is to propose a kind of method for preparing the ethylene-chlorotrifluoro-ethylene copolymer perforated membrane, the method does not need to add any inorganic particulate or nucleator, can prepare the ethylene-chlorotrifluoro-ethylene copolymer perforated membrane with high porosity, high-intensity spongelike structure.
The preparation method of ethylene-chlorotrifluoro-ethylene copolymer perforated membrane of the present invention carries out in accordance with the following steps:
1) ethylene-chlorotrifluoro-ethylene copolymer is mixed mutually with diluent; The mass percent of therein ethylene-chlorotrifluoroethylene is 10wt%～60wt%, and the diluent mass percent is 90wt%～40wt%;
2) with step 1) in mixture add in stirred tank, be warming up to 240 ℃～270 ℃, form homogeneous phase solution, standing and defoaming;
3) with step 2) in the homogeneous phase solution of polymer directly hang and be coated in the casting solution that forms tabular on supporting network or be spun into hollow fiber by spinning head, then casting solution is immersed in cooling fluid cooling, casting solution is separated, the final curing film forming;
4) remove step 3 with extractant) diluent in the gained film, obtain ethylene-chlorotrifluoro-ethylene copolymer flat sheet membrane or ethylene-chlorotrifluoro-ethylene copolymer hollow-fibre membrane.
Step 1) the described diluent high-temperature solvent that is ethylene-chlorotrifluoro-ethylene copolymer, be perhaps the mixture of ethylene-chlorotrifluoro-ethylene copolymer high-temperature solvent and ethylene-chlorotrifluoro-ethylene copolymer non-solvent.Wherein: in mixture, Copolymer solvent quality percentage is 70wt%～100wt%, and copolymer non-solvent mass percent is 30wt%～0wt%.
The high-temperature solvent of above-mentioned ethylene-chlorotrifluoro-ethylene copolymer be diethyl phthalate or diethyl phthalate with dicyclohexyl phthalate, Ergol, dioctyl adipate, dioctylphosphoric acid ester and ATBC in one or more above double solvents that mix; Wherein, in double solvents, the mass percent of diethyl phthalate is 20wt%～90wt%; The non-solvent of described ethylene-chlorotrifluoro-ethylene copolymer is one or more the above mixtures in triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, trioctyl phosphate, tributyl phosphate, phenyl salicytate, sweet mellow wine, benzophenone, oleic acid and hexadecanol.
Step 3) described cooling fluid is one or more the above mixtures in glycerine, water, dimethicone, 1,2-PD, isobutanol, ethylene glycol and phenmethylol, and described cooling fluid chilling temperature is 0 ℃-160 ℃.
Step 4) described extractant is ethanol, n-butanol, isobutanol, isopropyl alcohol, ether, butyl ether, divinyl ether, butyl oxide, isopropyl ether, acetone or n-hexane.
The present invention compared with prior art has following outstanding effect and progressive significantly:
The present invention adopts new high-temperature solvent---diethyl phthalate, by the standby ethylene-chlorotrifluoro-ethylene copolymer perforated membrane of TIPS legal system.Adopt method of the present invention, under the condition of not adding any inorganic particulate, prepare the ethylene-chlorotrifluoro-ethylene copolymer perforated membrane, prepared perforated membrane section is the spongelike structure that homogeneous connects, and voidage is high, connectivity good, and mechanical strength is high; The diluent that the present invention adopts and ethylene-chlorotrifluoro-ethylene copolymer composition system---ethylene-chlorotrifluoro-ethylene copolymer/diethyl phthalate system liquid liquid phase separation district is wide, in polymer quality concentration during less than 60wt%, the microporous barrier for preparing by the method all has spongy membrane pore structure, has widened casting solution polymer concentration range of choice; Utilize the cheap high-temperature solvent of diethyl phthalate and other and non-solvent to mix mutually, can obtain equally the spongy membrane pore structure of desirable homogeneous, in the water flux and intensity that ensure film, reduced production cost, enlarged the range of choice of diluent.
Description of drawings
Fig. 1 is film section structure in the embodiment of the present invention 1.
Fig. 2 is film section structure in the embodiment of the present invention 2.
Fig. 3 is film section structure in the embodiment of the present invention 3.
Fig. 4 is film section structure in the embodiment of the present invention 4.
Fig. 5 is film section structure in the embodiment of the present invention 5.
Fig. 6 is film section structure in the embodiment of the present invention 6.
Fig. 7 is film section structure in the embodiment of the present invention 7.
Fig. 8 is film section structure in the embodiment of the present invention 8.
Fig. 9, Figure 10 are film section structure in the embodiment of the present invention 9.
The specific embodiment
The preparation method of ethylene-chlorotrifluoro-ethylene copolymer perforated membrane provided by the invention, carry out in accordance with the following steps:
1) ethylene-chlorotrifluoro-ethylene copolymer is mixed mutually with diluent; The mass percent of therein ethylene-chlorotrifluoroethylene is 10wt%～60wt%, and the diluent mass percent is 90wt%～40wt%;
2) with step 1) in mixture add in stirred tank, be warming up to 240 ℃～270 ℃, form homogeneous phase solution, standing and defoaming;
3) with step 2) in the homogeneous phase solution of polymer directly hang and be coated in the casting solution that forms tabular on supporting network or be spun into hollow fiber by spinning head, then casting solution is immersed in cooling fluid cooling, casting solution is separated, the final curing film forming;
4) remove step 3 with extractant) diluent in the gained film, obtain ethylene-chlorotrifluoro-ethylene copolymer flat sheet membrane or ethylene-chlorotrifluoro-ethylene copolymer hollow-fibre membrane.
Step 1) the described diluent high-temperature solvent that is ethylene-chlorotrifluoro-ethylene copolymer, it is perhaps the mixture of ethylene-chlorotrifluoro-ethylene copolymer high-temperature solvent and ethylene-chlorotrifluoro-ethylene copolymer non-solvent, wherein: in mixture, Copolymer solvent quality percentage is 70wt%～100wt%, and copolymer non-solvent mass percent is 30wt%～0wt%.
The high-temperature solvent of above-mentioned ethylene-chlorotrifluoro-ethylene copolymer be diethyl phthalate or diethyl phthalate with dicyclohexyl phthalate, Ergol, dioctyl adipate, dioctylphosphoric acid ester and ATBC in one or more above double solvents that mix; Wherein, in double solvents, the mass percent of diethyl phthalate is 20wt%～90wt%; The non-solvent of described ethylene-chlorotrifluoro-ethylene copolymer is one or more the above mixtures in triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, trioctyl phosphate, tributyl phosphate, phenyl salicytate, sweet mellow wine, benzophenone, oleic acid and hexadecanol.
Step 3) described cooling fluid is one or more the above mixtures in glycerine, water, dimethicone, 1,2-PD, isobutanol, ethylene glycol and phenmethylol, and described cooling fluid chilling temperature is 0 ℃-160 ℃.
Step 4) described extractant is ethanol, n-butanol, isobutanol, isopropyl alcohol, ether, butyl ether, divinyl ether, butyl oxide, isopropyl ether, acetone or n-hexane.
Below in conjunction with embodiment, technical scheme of the present invention is described further, but described embodiment is not construed as limiting the invention for example.In the present invention, solvent is the material of most critical, in actual production, can also according to using needs, add a certain amount of wetting agent, antioxidant or other films and mould additive.
Embodiment 1
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 10wt%, diethyl phthalate quality percentage composition is 90wt%, put into the high-temperature stirring still and be heated to 240 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is directly hung and be coated in supporting network and form flat sheet membrane, film thickness is 200 μ m, and enters into the cooling bath of liquid of 30 ℃ and make solution phase-splitting film-forming, and cooling fluid is water-bath.Flat sheet membrane after curing is dry after ethanol extraction.
The film section is the spongelike structure of homogeneous, and porosity is 84%, fracture strength 3.25MPa.
Embodiment 2
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 28wt%, diethyl phthalate quality percentage composition is 72wt%, put into the high-temperature stirring still and be heated to 240 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is directly hung and be coated in supporting network and form flat sheet membrane, film thickness is 200 μ m, and enters into the cooling bath of liquid of 30 ℃ and make solution phase-splitting film-forming, and cooling fluid is that glycerine is bathed.Flat sheet membrane after curing is dry after ethanol extraction.
The film section is the spongelike structure of homogeneous, and porosity is 71%, fracture strength 10.58MPa.
Embodiment 3
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 60wt%, diethyl phthalate quality percentage composition is 40wt%, put into the high-temperature stirring still and be heated to 250 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is directly hung and be coated in supporting network and form flat sheet membrane, film thickness is 200 μ m, and enters into the cooling bath of liquid of 30 ℃ and make solution phase-splitting film-forming, and cooling fluid is water-bath.Flat sheet membrane after curing is dry after ethanol extraction.
The film section is the spongelike structure of homogeneous, and porosity is 31%, fracture strength 14.59MPa.
Embodiment 4
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate and hexadecanol, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 30wt%, diethyl phthalate quality percentage composition is 55wt%, the quality percentage composition of hexadecanol is 15wt%, put into the high-temperature stirring still and be heated to 250 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is directly hung and be coated in supporting network and form flat sheet membrane, film thickness is 200 μ m, and enters into the cooling bath of liquid of 160 ℃ and make solution phase-splitting film-forming, and cooling fluid is silicone oil bath.Flat sheet membrane after curing is dry after ethanol extraction.
The film section is the spongelike structure of homogeneous, and porosity is 76%, fracture strength 8.26MPa.
Embodiment 5
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate and phenyl salicytate, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 30wt%, diethyl phthalate quality percentage composition is 49wt%, phenyl salicytate quality percentage composition is 21wt%, put into the high-temperature stirring still and be heated to 250 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is directly hung and be coated in supporting network and form flat sheet membrane, film thickness is 200 μ m, and enters into the cooling bath of liquid of 135 ℃ and make solution phase-splitting film-forming, and cooling fluid is that glycerine is bathed.Flat sheet membrane after curing is dry after acetone extract.
The film section is the spongelike structure of homogeneous, and porosity is 73%, fracture strength 9.68MPa.
Embodiment 6
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate, dicyclohexyl phthalate and phenyl salicytate, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 35wt%, diethyl phthalate quality percentage composition is 40.95wt%, dicyclohexyl phthalate quality percentage composition is 4.55wt%, phenyl salicytate quality percentage composition is 19.5wt%, put into the high-temperature stirring still and be heated to 250 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is directly hung and be coated in supporting network and form flat sheet membrane, film thickness is 200 μ m, and enters into the cooling bath of liquid of 0 ℃ and make solution phase-splitting film-forming, and cooling fluid is water-bath.Flat sheet membrane after curing is dry after extracted with diethyl ether.
The film section is the spongelike structure of homogeneous, and porosity is 64%, fracture strength 11.63MPa.
Embodiment 7
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate and Ergol, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 35wt%, diethyl phthalate quality percentage composition is 32.5wt%, Ergol quality percentage composition is 32.5wt%, put into the high-temperature stirring still and be heated to 260 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is directly hung and be coated in supporting network and form flat sheet membrane, film thickness is 200 μ m, and enters into the cooling bath of liquid of 60 ℃ and make solution phase-splitting film-forming, and cooling fluid is water-bath.Flat sheet membrane after curing is dry after ethanol extraction.
The film section is the spongelike structure of homogeneous, and porosity is 69%, fracture strength 10.02MPa.
Embodiment 8
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate and ATBC, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 40wt%, diethyl phthalate quality percentage composition is 12wt%, ATBC quality percentage composition is 48wt%, put into the high-temperature stirring still and be heated to 270 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is directly hung and be coated in supporting network and form flat sheet membrane, film thickness is 200 μ m, and enters into the cooling bath of liquid of 40 ℃ and make solution phase-splitting film-forming, and cooling fluid is water-bath.Flat sheet membrane after curing is dry after ethanol extraction.
The film section is the spongelike structure of homogeneous, and porosity is 53%, fracture strength 11.89MPa.
Embodiment 9
With ethylene-chlorotrifluoro-ethylene copolymer and diethyl phthalate and ATBC, its component is that ethylene-chlorotrifluoro-ethylene copolymer quality percentage composition is 40wt%, diethyl phthalate quality percentage composition is 54wt%, ATBC quality percentage composition is 6wt%, put into the high-temperature stirring still and be heated to 270 degrees centigrade, mix and form polymer homogeneous phase solution, standing 24 hours.Then the polymer homogeneous phase solution is extruded by spinning head, after being the doughnut shape, the cooling bath of liquid that enters into 30 ℃ makes solution phase-splitting film-forming, and cooling fluid is water-bath.Hollow-fibre membrane after curing is dry after ethanol extraction.The hollow-fibre membrane external diameter is 0.8mm, and internal diameter is 0.63mm.
The film section is spongelike structure, and porosity is 56%, fracture strength 12.36MPa.
Claims (3)
1. the preparation method of an ethylene-chlorotrifluoro-ethylene copolymer perforated membrane is characterized in that the method carries out as follows:
1) ethylene-chlorotrifluoro-ethylene copolymer is mixed mutually with diluent; The mass percent of therein ethylene-chlorotrifluoroethylene is 10wt%～60wt%, and the diluent mass percent is 90wt%～40wt%; Described diluent is the high-temperature solvent of ethylene-chlorotrifluoro-ethylene copolymer, it is perhaps the mixture of ethylene-chlorotrifluoro-ethylene copolymer high-temperature solvent and ethylene-chlorotrifluoro-ethylene copolymer non-solvent, wherein: in mixture, the mass percent of Copolymer solvent is 70wt%～100wt%, and the mass percent of copolymer non-solvent is 30wt%～0wt%; The high-temperature solvent of described ethylene-chlorotrifluoro-ethylene copolymer is diethyl phthalate, or one or more double solvents that mix in diethyl phthalate and dicyclohexyl phthalate, Ergol, dioctyl adipate, dioctylphosphoric acid ester and ATBC; Wherein, in double solvents, the mass percent of diethyl phthalate is 20wt%～90wt%; The non-solvent of described ethylene-chlorotrifluoro-ethylene copolymer is one or more the above mixtures in triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, trioctyl phosphate, tributyl phosphate, phenyl salicytate, sweet mellow wine, benzophenone, oleic acid and hexadecanol;
2) mixture in step 1) is added in stirred tank, be warming up to 240 ℃～270 ℃, form homogeneous phase solution, standing and defoaming;
3) with step 2) in the homogeneous phase solution that obtains directly hang and be coated on supporting network, form tabular or be spun into the casting solution of hollow fiber by spinning head, then casting solution is immersed in cooling fluid coolingly, casting solution is separated, the final curing film forming;
4) remove the diluent in the gained film in step 3) with extractant, obtain ethylene-chlorotrifluoro-ethylene copolymer flat sheet membrane or ethylene-chlorotrifluoro-ethylene copolymer hollow-fibre membrane.
2. the preparation method of a kind of ethylene-chlorotrifluoro-ethylene copolymer perforated membrane according to claim 1, it is characterized in that: described cooling fluid is glycerine, water, dimethicone, 1, the mixture that one or more in 2-propane diols, isobutanol, ethylene glycol and phenmethylol are above, described cooling fluid chilling temperature is 0 ℃-160 ℃.
3. the preparation method of a kind of ethylene-chlorotrifluoro-ethylene copolymer perforated membrane according to claim 1, is characterized in that: described extractant employing ethanol, n-butanol, isobutanol, isopropyl alcohol, ether, butyl ether, divinyl ether, butyl oxide, isopropyl ether, acetone or n-hexane.
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| CN102626594A (en) * | 2012-04-19 | 2012-08-08 | 天津大学 | Method for preparing polyvinylidene fluoride micro-porous film with thermal induced phase separation method |
| CN105297167A (en) * | 2015-11-24 | 2016-02-03 | 马海燕 | Large-diameter copolymerization polyamide monofilament and production method thereof |
| CN109420434A (en) * | 2017-09-01 | 2019-03-05 | 浙江省化工研究院有限公司 | A method of preparing ethylene-chlorotrifluoro-ethylene copolymer hollow fiber microporous membrane |
| JP6839766B2 (en) * | 2017-09-07 | 2021-03-10 | 旭化成株式会社 | Filtration method using a porous membrane |
| CN109758927A (en) * | 2017-11-09 | 2019-05-17 | 浙江省化工研究院有限公司 | A kind of preparation method of polyethylene-chlorotrifluoroethylene solvent resistant seperation film |
| CN108057346B (en) * | 2017-12-08 | 2020-12-25 | 南京工业大学 | High-flux polymer separation membrane, preparation method, diluent composition and application |
| CN108479414B (en) * | 2018-04-12 | 2020-12-25 | 南京工业大学 | Hollow fiber polymer membrane, preparation method and application thereof in brine refining |
| CN108854568B (en) * | 2018-07-03 | 2019-06-14 | 博天环境集团股份有限公司 | A kind of preparation method of the ECTFE hollow fiber porous film for membrane chemical reactor process |
| CN110141979A (en) * | 2019-05-28 | 2019-08-20 | 迈博瑞生物膜技术（南通）有限公司 | A kind of preparation method of ethylene-chlorotrifluoro-ethylene copolymer hollow fiber porous film |
| CN111842072B (en) * | 2020-07-31 | 2023-01-06 | 中国人民解放军国防科技大学 | Application of hydrophobic heat-insulating and cooling film |
| CN114887486B (en) * | 2022-05-09 | 2023-04-18 | 中国海洋大学 | Mannitol-based polyester loose composite nanofiltration membrane and preparation method and application thereof |
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| CN101569837A (en) * | 2009-05-26 | 2009-11-04 | 清华大学 | Polyvinylidene fluoride microporous film preparation method |
| WO2010071764A1 (en) * | 2008-12-19 | 2010-06-24 | 3M Innovative Properties Company | Microporous material from ethylene-chlorotrifluoroethylene copolymer and method for making same |
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| WO2010071764A1 (en) * | 2008-12-19 | 2010-06-24 | 3M Innovative Properties Company | Microporous material from ethylene-chlorotrifluoroethylene copolymer and method for making same |
| CN101569837A (en) * | 2009-05-26 | 2009-11-04 | 清华大学 | Polyvinylidene fluoride microporous film preparation method |
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