CN106139930A - A kind of polypropylene/ethylene vinyl acetate is blended hydrophobic microporous membrane preparation method - Google Patents
A kind of polypropylene/ethylene vinyl acetate is blended hydrophobic microporous membrane preparation method Download PDFInfo
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- CN106139930A CN106139930A CN201510196837.2A CN201510196837A CN106139930A CN 106139930 A CN106139930 A CN 106139930A CN 201510196837 A CN201510196837 A CN 201510196837A CN 106139930 A CN106139930 A CN 106139930A
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Abstract
The invention discloses a kind of polypropylene/ethylene vinyl acetate and hydrophobic microporous membrane preparation method be blended, it is characterised in that component by weight: polypropylene 20～40 parts, ethylene-vinyl acetate 1～20 parts, diluent 60～80 parts, nucleator 0～1 part.The preparation of this blend film uses Thermal inactive method.The blend film of the present invention is not under conditions of changing polypropylene excellent chemical performance and higher-strength, and modified effect is notable: the mechanical performance of product film has a distinct increment, and has more preferable pliability, higher elongation at break, and service life is longer；The addition of ethylene-vinyl acetate makes membrane aperture distribution narrower, evenly, and aperture and porosity are more easily controlled, aperture 0.1 μm～1 μm, and porosity is higher than 68%；The heat conductivity of product film reduces, and is applied to Membrane Materials process, makes the temperature difference of film both sides, steam pressure difference increase, decrease thermal loss, improve the thermal efficiency.
Description
Technical field
The invention belongs to technical field of membrane separation, be specifically related to a kind of polypropylene/ethylene vinyl acetate and dewatering microporous film and system thereof are blended
Preparation Method.
Background technology
Dewatering microporous film can be applied to various new membrane separating process as the Transfer Medium of membrane contactor, including Membrane Materials, film
Extraction, film absorption, film stripping and film absorption etc..Membrane Materials (membrane distillation, MD) is compared to other membrance separation
Technology, the advantage of technology is can effectively utilize the cheap energy (such as solar energy, industrial waste heat, remaining to operate under low-temperature atmosphere-pressure
Heat) at the society of energy growing tension, there is the biggest competitiveness.MD has the biggest at the saline solution concentrating high concentration
Advantage, in reverse osmosis process, certain concentration can only be concentrated to, and MD process is concentrated to supersaturated solution, separately
Outward, Membrane Materials process also has incomparable advantage at concentrated fruit juice and traditional Chinese drug inspissation.But, MD technology large-scale industry
The core of change application and a difficult problem are selection and the utilization rates of the energy of membrane material.
At present, the hydrophobic membrane material that Membrane Materials is conventional is mainly politef, Kynoar and polypropylene, wherein polypropylene
(PP) be a kind of non-polar plastic having higher crystallinity, have good chemical stability, resistance to acids and bases, high hydrophobicity and
Heat-flash stability, the most cheap, at home and abroad have and study widely.But polypropylene film forming mechanical performance is not enough, toughness
Difference film forming is easily split, and service life is short.For widening the selection of membrane material, wide variety of polymer modification process has surface grafting,
Surface-coated, plasma method, it is blended and filling etc..Wherein polymer be blended have simple to operate, production efficiency advantages of higher,
For improving the mechanical performance of film, widening membrane material and select and the regulation and control of membrane structure have good effect.
Ethylene-vinyl acetate (ethylene vinyl acetate, EVA) hydrophobic performance is good, strong corrosion resistant (sea water resistance, acid and alkali-resistance),
Safety height contact non-hazardous.EVA is owing to introducing VAM in strand, thus reduces degree of crystallinity, toughness,
Elastic high with tension stress, heat preservation and insulation is excellent, and good permeability is applied and had good prospect at Membrane Materials.So in order to change
Kind microporous polypropylene membrane performance during MD, the present invention has selected ethylene-vinyl acetate to be blended therewith.The present invention is blended
Film has preferable toughness, is embodied in elongation at break and is much improved；And being decreased obviously do not occur in the rigidity of membrane material and intensity,
It is embodied in hot strength and changes little.Owing to after the low-crystallinity of EVA and the effect of viscosity, with polypropylene homogeneous blend, film forming is more
Adding uniformly, pore-size distribution is narrow, improves the separating property of film.In terms of the hydrophobicity of film, the hydrophobicity of EVA and PP is close,
The blend film water contact angle of preparation is stable decreases fouling membrane at 120 °～130 °, provides a kind of hydrophobic performance for MD excellent
Good separation material.So, the service life of blend film is significantly increased, and reduces running cost and the operating cost of MD process.
And the heat conductivity of EVA is low, there is preferable heat-insulating property, improve the thermal efficiency during MD, effectively reduce MD
The energy consumption of process.
Due to polypropylene, ethylene-vinyl acetate at normal temperatures insoluble in any solvent, therefore the present invention uses thermally induced phase separation to prepare
Polypropylene/ethylene vinyl acetate blend film.Thermally induced phase separation is that A.J.Castro is in United States Patent (USP) US4247498 (1980)
The film-forming method of a kind of simple novelty proposed, is, the principle of low temperature split-phase compatible based on macromolecular solution high temperature and forms micropore,
Can be applicable to many can not be with the crystalline polymer of common solwution method masking due to normal-temperature dissolution degree difference.Thermally induced phase separation
The microporous membrane of preparation, higher than film-strength prepared by phase separation method, and aperture higher than membrane porosity prepared by fusion drawn
It is more evenly distributed.
Chinese patent CN101649088A, CN200510041012.X, CN201010191837.0, CN01144479.7 are public
Open thermally induced phase separation and prepared hydrophobic polypropylene microporous membrane, used Thermal inactive method, by changing polymer and diluent
Proportioning regulation and control product microporous polypropylene membrane pore-size distribution and porosity.But polypropylene screen toughness is not enough, frangible, it is applied to film
Hydrophiling easily occurs in still-process, and service life is short, and above patent does not solve that polypropylene mechanical strength is low, toughness is not enough
Problem, does not proposes solution yet.Polypropylene/ethylene vinyl acetate prepared by the present invention is blended dewatering microporous film, and microcellular structure is equal
Even, porosity is high, be difficult to hydrophiling, and have more preferable mechanical performance with maintain MD process run steadily in the long term.Both at home and abroad
Not yet it is related to polypropylene/ethylene vinyl acetate and the report of dewatering microporous film is blended.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of polypropylene/ethylene vinyl acetate and dewatering microporous film is blended
Preparation method.Polypropylene/ethylene vinyl acetate prepared by the present invention is blended dewatering microporous film and is not changing polypropylene good chemical product
Under the conditions of property, higher-strength, modified effect is particularly significant: first improve the mechanical performance of film, have more preferable pliability,
Higher elongation at break, service life is longer；Secondly, the addition of ethylene-vinyl acetate reduces polyacrylic degree of crystallinity, makes
Membrane aperture distribution is narrower, and evenly, aperture and porosity are more easily controlled, and aperture 0.1 μm～1 μm, porosity reaches 68%
Above；Again reduce the heat conductivity of film, be especially applicable to MD process, make the temperature difference of film both sides, steam pressure difference increase
Greatly, decrease thermal loss, improve the thermal efficiency.
Meanwhile, the invention provides above-mentioned polypropylene/ethylene vinyl acetate and the preparation method of dewatering microporous film be blended, simple to operate,
Convenient, comprise the steps:
(1) will weigh by weight: polypropylene 20～40 parts, ethylene-vinyl acetate 1～20 parts, diluent 60～80 parts,
Nucleator 0～1 part；
(2) mixing raw material step (1) weighed adds stirring in reactor, is passed through nitrogen protection, is heated to 180 DEG C～220 DEG C,
Stop after stirring more than 4 hours, stand deaeration in more than 2 hours, obtain homogeneous casting solution；
(3) (2) gained casting solution is coated on polyester non-woven fabric surface and spreads to tabular；Or extruded by double screw extruder,
Temperature is 180 DEG C～200 DEG C, is spun into hollow fiber through spinning head；Cool and solidify subsequently in 0 DEG C～50 DEG C of tanks.
(4) by the film immersion extract of step (3) molding more than 24 hours, 30 DEG C～60 DEG C of vacuum after having extracted, are put into
Being dried in baking oven, the polypropylene/ethylene vinyl acetate obtaining the present invention is blended dewatering microporous film.
Above-mentioned diluent is dimethyl phthalate, diethyl phthalate, dibutyl phthalate, O-phthalic
One or several in dioctyl phthalate, Oleum Glycines and other plant oil.
Above-mentioned nucleator is the one in adipic acid, suberic acid, dibenzylidene sorbitol.
Above-mentioned extractant is one or several combinations in methanol, ethanol, propanol, the third triketone, normal hexane.
Compared with prior art, the present invention being blended by polypropylene and ethylene-vinyl acetate, the film of preparation has polypropylene material
Outstanding chemical-resistance and the characteristic of the advantage such as rigidity, be provided simultaneously with the good hydrophobicity of ethylene vinyl acetate material, pliability,
The characteristic such as low-crystallinity and heat-insulating property；Blend film has two kinds of polymer premium properties concurrently, learns from other's strong points to offset one's weaknesses.Preparation process is the highest
Effect, membrane material is with low cost, and membrane pore structure is prone to regulation and control, uniform narrow pore-size distribution；The polypropylene/ethylene vinyl acetate of preparation is altogether
Mixed hydrophobic microporous membrane flux is high, contamination resistance is strong, mechanical strength is high, rejection is high, currently mainly tests vacuum membrane distillation
Process, and this blend film should be able to more preferably in the application effect of direct contact membrane distillation, concrete effect needs to be put into practice further to test
Card.The film-forming method of the present invention is simple, it is easy to operation, raw material polypropylene and ethylene-vinyl acetate progression cheap and easy to get, safe reach
To food stage (nontoxic, harmless, pollution-free), diluent environmental protection used.
Accompanying drawing explanation
Fig. 1 is the film section SEM figure of embodiment 1.
Fig. 2 is the film section SEM figure of embodiment 2.
Fig. 3 is the film section SEM figure of embodiment 3.
Detailed description of the invention
Embodiment 1
(1) weigh by weight: 70 parts of diluent Oleum Glycines, totally 30 parts (isotactic polypropylene/ethylene vinyl acetate second of other materials
Alkene/nucleator adipic acid, mass ratio is 27.13/2.71/0.15；
(2) mixing raw material step (1) weighed adds in reactor, is passed through nitrogen protection, is heated to 180 DEG C～220 DEG C,
Stop stirring after more than 4 hours, stand deaeration in more than 2 hours, obtain homogeneous casting solution；
(3) (2) gained casting solution being coated on polyester non-woven fabric surface and spread to tabular, scraping film temperature is 180 DEG C, then
Enter in 20 DEG C of tanks and cool and solidify
(4) the n-hexane extraction agent ultrasonic extraction of the film purity 95% step (3) prepared 24 hours, puts after having extracted
Enter in 30 DEG C～60 DEG C of vacuum drying ovens and be dried, i.e. obtain a kind of polypropylene/ethylene vinyl acetate and dewatering microporous film is blended.
Film section is sheet and finger-like pore interphase structure, products obtained therefrom membrane porosity 69.8%, aperture 0.5 μm～1 μm, water
Contact angle 124.6 °, hot strength 16.7MPa, elongation at break 15.4%.It is applied to 0.5mol L-1NaCl aqueous solution true
Empty Membrane Materials process, when feed rate is 30L h-1, when feeding temperature is 80 DEG C, membrane flux 16.8kg m-2·h-1, rejection
Higher than 99.99%.
Embodiment 2
(1) weigh by weight: 70 parts of diluent Oleum Glycines, totally 30 parts (isotactic polypropylene/ethylene vinyl acetate second of other materials
Alkene/nucleator adipic acid, mass ratio is 25.59/4.26/0.15；
(2) mixing raw material step (1) weighed adds stirring in reactor, is passed through nitrogen protection, is heated to 180～220 DEG C,
Stop stirring after more than 4 hours, stand deaeration in more than 2 hours, obtain homogeneous casting solution；
(3) (2) gained casting solution being coated on polyester non-woven fabric surface and spread to tabular, scraping film temperature is 180 DEG C, then
Enter in 20 DEG C of tanks and cool and solidify
(4) the n-hexane extraction agent ultrasonic extraction of the film purity 95% step (3) prepared 24 hours, puts after having extracted
Enter in 30 DEG C～60 DEG C of vacuum drying ovens and be dried, i.e. obtain a kind of polypropylene/ethylene vinyl acetate and dewatering microporous film is blended.
Film section is sheet and finger dress hole interphase structure, products obtained therefrom membrane porosity 68.8%, aperture 0.2 μm～0.4 μm,
Water contact angle 126.6 °, hot strength 15.2MPa, elongation at break 19.8%.It is applied to 0.5mol L-1NaCl aqueous solution
Vacuum membrane distillation process, when feed rate is 30L h-1, when feeding temperature is 80 DEG C, membrane flux 18.2kg m-2·h-1, retain
Rate is higher than 99.99%.
Embodiment 3
(1) will weigh by weight: diluent 75 parts (Oleum Glycines/dibutyl phthalate, mass ratio is 35.5/35.5),
(isotactic polypropylene/ethylene-vinyl acetate/nucleator adipic acid, mass ratio is 22.61/2.26/0.125 to other materials totally 25 parts；
(2) mixing raw material step (1) weighed adds stirring in reactor, is passed through nitrogen protection, is heated to 180 DEG C～220 DEG C,
Stop stirring after more than 4 hours, stand deaeration in more than 2 hours, obtain homogeneous casting solution；
(3) (2) gained casting solution being coated on polyester non-woven fabric surface and spread to tabular, scraping film temperature is 180 DEG C, then
Enter in 20 DEG C of tanks and cool and solidify
(4) the n-hexane extraction agent ultrasonic extraction of the film purity 95% step (3) prepared 24 hours, puts after having extracted
Enter in 30 DEG C～60 DEG C of vacuum drying ovens and be dried, i.e. obtain a kind of polypropylene/ethylene vinyl acetate and dewatering microporous film is blended.
Film section is sheet and finger dress hole interphase structure, products obtained therefrom membrane porosity 73.6%, aperture 0.25 μm～0.45 μm,
Water contact angle 115.8 °, hot strength 14.8MPa, elongation at break 19.7%.It is applied to 05mol L-1NaCl aqueous solution
Vacuum membrane distillation process, when feed rate is 30L h-1, when feeding temperature is 80 DEG C, membrane flux 14.5kg m-2·h-1, retain
Rate is higher than 99.99%.
Comparative example 1
(1) will weigh by weight: 70 parts of diluent Oleum Glycines, (isotactic polypropylene/nucleator is own for other materials totally 30 parts
Diacid, mass ratio is 29.95/0.15；
(2) mixing raw material step (1) weighed adds stirring in reactor, is passed through nitrogen protection, is heated to 180 DEG C～220 DEG C,
Stop stirring after more than 4 hours, stand deaeration in more than 2 hours, obtain homogeneous casting solution；
(3) (2) gained casting solution being coated on polyester non-woven fabric surface and spread to tabular, scraping film temperature is 180 DEG C, then
Enter in 20 DEG C of tanks and cool and solidify
(4) the n-hexane extraction agent ultrasonic extraction of the film purity 95% step (3) prepared 24 hours, puts after having extracted
Enter in 30 DEG C～60 DEG C of vacuum drying ovens and be dried, i.e. obtain a kind of polypropylene/ethylene vinyl acetate and dewatering microporous film is blended.
Film section is finger dress pore structure, products obtained therefrom membrane porosity 68.8%, water contact angle 116 °, hot strength 16.6MPa,
Elongation at break 12.2%.It is applied to 0.5mol L-1The vacuum membrane distillation process of NaCl aqueous solution, when feed rate is 30L h-1,
When feeding temperature is 80 DEG C, membrane flux 14.0kg m-2·h-1, rejection is higher than 99.99%.
By comparative example: the hydrophobic polypropylene microporous membrane of polymer content such as compare, polypropylene/ethylene vinyl acetate is blended to be dredged
The mechanical performance of water microporous membrane is higher, and pliability is good, elongation at break is high, and the service life of film is longer；Secondly, ethylene vinyl acetate
The addition of ethylene reduces polyacrylic degree of crystallinity, makes the pore-size distribution of hydrophobic membrane evenly, and aperture and porosity are easily controllable,
Aperture is in 0.1 μm～1 μm, and porosity reaches more than 68%；The raising of film heat-insulating property again, particularly application and Membrane Materials mistake
Journey, the heat-insulating property of film makes the temperature difference of film both sides, steam pressure difference increase, decreases thermal loss, improves the thermal efficiency, make
Rejection and flux all raise.Utilize blended its membrane property of dewatering microporous film of the inventive method preparation to be significantly better than single polypropylene to dredge
Water microporous membrane, particularly in terms of the service life of film and the thermal efficiency of Membrane Materials.
Examples detailed above is only present pre-ferred embodiments, and should in no way limit the present invention.Every basis is in the equivalent of the present invention
Change or equivalents, within the scope of being all contained in rights protection of the present invention.
Claims (8)
1. a polypropylene/ethylene vinyl acetate is blended dewatering microporous film, it is characterised in that component by weight: polypropylene 20～40 parts, ethylene-vinyl acetate 1～20 parts, diluent 60～80 parts, nucleator 0～1 part.
Polypropylene/ethylene vinyl acetate the most according to claim 1 is blended dewatering microporous film, it is characterized in that, described ethylene-vinyl acetate, includes without being confined to vinyl acetate (VA) mass content and is respectively the ethylene-vinyl acetate (EVA) of 8w%, 18w%, 40w%.
Polypropylene/ethylene vinyl acetate the most according to claim 1 is blended dewatering microporous film, it is characterized in that, described polypropylene includes the one in isotactic polypropylene (isotactic polyprolene), random polypropylene (atactic polypropylene), syndiotactic polypropylene (syndiotactic polypropylene).
Polypropylene/ethylene vinyl acetate the most according to claim 1 is blended dewatering microporous film, it is characterized in that, described diluent is one or several the combination in Oleum Glycines, salad oil, dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl ether, liquid paraffin, calcium stearate.
Polypropylene/ethylene vinyl acetate the most according to claim 1 is blended dewatering microporous film, it is characterised in that described nucleator agent is the one in adipic acid, suberic acid, dibenzylidene sorbitol or benzoic acid.
6. the polypropylene/ethylene vinyl acetate described in claim 1 is blended a preparation method for dewatering microporous film, and it comprises the steps:
(1) weigh by weight: polypropylene 20～40 parts, ethylene-vinyl acetate 1～20 parts, diluent 60～80 parts, nucleator 0～1 part.
(2) mixing raw material step (1) weighed adds stirring in reactor, is passed through nitrogen protection, is heated to 180 DEG C～220 DEG C, stops, standing deaeration in more than 2 hours, obtain homogeneous casting solution after stirring more than 4 hours.
(3) (2) gained casting solution is coated on polyester non-woven fabric surface and spreads to tabular；Or extruded by double screw extruder, temperature is 180 DEG C～200 DEG C, is spun into hollow fiber through spinning head；Occur to be separated subsequently into 0 DEG C～50 DEG C of coagulating baths.
(4) by the film immersion extract of step (3) molding more than 24 hours, having extracted to be placed in 30 DEG C～60 DEG C of vacuum drying ovens and be dried, the to be extracted dose of polypropylene/ethylene vinyl acetate i.e. obtaining the present invention completely after evaporation is blended dewatering microporous film.
Method the most according to claim 6, it is characterised in that described non-woven fabrics includes without being confined to polyethylene terephthalate (PET) material.
Method the most according to claim 6, it is characterised in that the combination of one or more in described extractant methanol, ethanol, acetone, normal hexane.
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| CN201510196837.2A CN106139930A (en) | 2015-04-21 | 2015-04-21 | A kind of polypropylene/ethylene vinyl acetate is blended hydrophobic microporous membrane preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109304104A (en) * | 2017-07-26 | 2019-02-05 | 天津科技大学 | A kind of polypropylene/ethylene octene copolymer blending hydrophobic microporous membrane preparation method |
| CN115105633A (en) * | 2022-07-27 | 2022-09-27 | 四川大学 | Chemical etching open-pore porous polypropylene pipe and preparation method thereof |
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| CN1597073A (en) * | 2004-08-06 | 2005-03-23 | 天津科技大学 | Method of preparing polypropylene plate micropore membrane using thermo phase separation |
| CN102228804A (en) * | 2011-04-15 | 2011-11-02 | 天津科技大学 | Method for preparing hydrophobic microporous membrane and membrane prepared by method |
| CN102492223A (en) * | 2011-12-08 | 2012-06-13 | 大连工业大学 | Novel EVA (Ethylene Vinylacetate) dynamic vulcanized, toughened and modified polypropylene material and preparation method thereof |
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2015
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| CN1597073A (en) * | 2004-08-06 | 2005-03-23 | 天津科技大学 | Method of preparing polypropylene plate micropore membrane using thermo phase separation |
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| CN102492223A (en) * | 2011-12-08 | 2012-06-13 | 大连工业大学 | Novel EVA (Ethylene Vinylacetate) dynamic vulcanized, toughened and modified polypropylene material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109304104A (en) * | 2017-07-26 | 2019-02-05 | 天津科技大学 | A kind of polypropylene/ethylene octene copolymer blending hydrophobic microporous membrane preparation method |
| CN115105633A (en) * | 2022-07-27 | 2022-09-27 | 四川大学 | Chemical etching open-pore porous polypropylene pipe and preparation method thereof |
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Application publication date: 20161123 |