CN101724170A - Method for preparing polyolefin microporous membrane with symmetrical upper and lower surface structures - Google Patents
Method for preparing polyolefin microporous membrane with symmetrical upper and lower surface structures Download PDFInfo
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- CN101724170A CN101724170A CN200910109637A CN200910109637A CN101724170A CN 101724170 A CN101724170 A CN 101724170A CN 200910109637 A CN200910109637 A CN 200910109637A CN 200910109637 A CN200910109637 A CN 200910109637A CN 101724170 A CN101724170 A CN 101724170A
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/917—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means by applying pressurised gas to the surface of the flat article
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/18—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets by squeezing between surfaces, e.g. rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/755—Membranes, diaphragms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
Abstract
The invention provides a method for preparing a polyolefin microporous membrane with symmetrical upper and lower surface structures. The method comprises the following steps of: 1) mixing polyolefin resin with a diluting agent in a weight ratio of 1-6:4-9; 2) extruding the mixture by a neck ring mold in an extrusion flow-casting mode and performing cold rolling and strip casting to obtain a thick sheet; 3) preheating the thick sheet and stretching the preheated thick sheet longitudinally and transversely; 4) shaping the stretched thick sheet; 5) extracting the diluting agent and drying the thick sheet; 6) stretching the thick sheet transversely and shaping the stretched thick sheet; and 7) winding the shaped thick sheet. For the polyolefin microporous membrane prepared by the process steps, the upper and lower two surfaces of the thick sheet are particularly provided with a set of rollers with the same diameter respectively, or one side of an air knife is provided with a set of the rollers on a conventional cold roller and an air knife auxiliary patch device to obtain the thick sheet in an auxiliary cooling mode, and then, the thick sheet is stretched and extracted to finally obtain a product with symmetrical and uniform upper and lower surface microporous structures and good ventilation property. Furthermore, warping deformation phenomenon is prevented.
Description
Technical field
The present invention relates to a kind of preparation method of microporous polyolefin film, relate in particular to the preparation of the symmetric microporous polyolefin film of a kind of upper and lower surface structures.
Background technology
Microporous polyolefin film is to have countless intercommunication micropores, and the plastics film of aperture in 0.01～10 mu m range has been widely used in lithium ion battery at present with in the barrier film.The method of this kind of suitability for industrialized production microporous membrane mainly contains fusion drawn method and thermally induced phase separation both at home and abroad.
Fusion drawn method (being dry method) is earlier with crystalline polymer (as polypropylene) extrusion molding film forming under the condition that improves molten polymer stress, make film under no tension force or low-tension, obtain the necessary crystallization structure then through annealing, after carry out the reticulated structure that longitudinal stretching produces a kind of slit-shaped space.There are shortcomings such as aperture and the difficult control of porosity in this method, and owing to only carry out longitudinal stretching, the film transverse strength is relatively poor.Specifically describe visible U.S.Patent 3558764 (1971), 5385777 (1995).Industrialization product is provided by U.S. Celgard and Japanese Ube company.
Thermally induced phase separation (TIPS, be wet method) be at high temperature polymkeric substance (as HDPE) to be dissolved in high boiling point as in the twin screw extruder, solvent (the thinner of low volatility, as mineral oil), form uniform solution, back through port mould extrusion moulding sheet, quenching cooling on chill roll, causing solution to produce is separated, obtain having the sheet of phase separation structure, the back adopts two-way stretch equipment while or proceed step by step in length and breadth to stretching, acquisition has the film of phase separation structure, wherein adopts volatile organic solvent (extraction agent) that thinner is extracted before or after two-way stretch, thereby obtains the high molecule micropore of certain structural shape.Asahi-Kasei, the Mitsui Chemical of Japan and relevant patent JP 2004323820 (2004), the U.S.Patent 6245272 (2001) of Tonen company have reported this method.Also introduced flow process and the prescription of producing microporous membrane according to thermally induced phase separation in the patent documentations such as Patent Office of the People's Republic of China disclosed 200410051437.4,200510035680.1.Industrialization product is abroad provided by companies such as Asahi, Tonen, Entek, and domestic mainly by Foshan gold brightness in volume production.
Producing in the microporous membrane process at the foundation thermally induced phase separation, at first is to extrude sheet by forcing machine, produces in the process at sheet usually, the sheet one side contacts with cold roller, another side contacts with air, and in order to make sheet material paste roller better, adopts air knife auxiliary at another side.To cause the sheet upper and lower surface to be heated asymmetric for the casting sheet mode like this, in the sepn process of cooling induction phase, and the degree that is separated difference, asymmetric in the micropore size that follow-up extraction back forms, microporous membrane structure is inhomogeneous, and ventilation property is not good.And, cause microporous membrane generation buckling deformation because two its surface compressed are asymmetric up and down.Microporous membrane after the making is when being used for the lithium ion battery barrier film, and ventilation property is poor, and it is low that lithium ion passes ability, and battery performance is poor.
Summary of the invention
The purpose of the embodiment of the invention is to provide that a kind of investment is little, easy to control, the big or small symmetry of micropore, and microporous membrane structure is even, the method for preparing polyolefin microporous membrane of good permeability.
The embodiment of the invention is achieved in that the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures, comprises the steps:
1), with polyolefin resin and mixing diluents, described polyolefin resin and thinner weight ratio are 1-6:4-9.Amount of diluent is too little, and the film porosity that obtains is not enough, and content is too many, one side forming process difficulty, and film bubble homogeneity and stability are not enough, and film strength is not enough on the other hand.
2), the polymkeric substance and the diluent solution that mix are cast sheet via the extruding dies postcooling.
3), cooled sheet is carried out preheating again, adopt two-way stretch equipment while or proceed step by step in length and breadth to stretching after the preheating, with film at softening temperature to a certain temperature condition between the melt temperature, longitudinally or/and horizontal direction is stretched to several times of raw footage.
4), under tension force, be lower than being higher than its draft temperature in the temperature range of fusing point and keep several seconds under certain suitable temperature, be cooled to room temperature at last, promptly handle and make Stretched Film through heat setting type.
5), thinner and carry out drying treatment in the spe membrane.
6), the cross directional stretch typing is handled.
7), rolling.In the technical scheme of the invention described above, described polyolefin resin can be selected high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), linear low density polyethylene, ultrahigh molecular weight polyethylene(UHMWPE), polypropylene, ethene, propylene for use, or be a kind of in butylene, octene, the hexene copolymer, or the mixture of above-mentioned substance.Preferred high density polyethylene(HDPE) of said polyolefins resin (HDPE) and ultrahigh molecular weight polyethylene(UHMWPE), this is a kind of degree of crystallinity height, nonpolar thermoplastic resin, and is non-hygroscopic and have good steam-preventing, and has good electrical property.
Thinner of the present invention is selected for use at high temperature has the high boiling point of excellent compatibility, difficult evaporable solvent with polyolefin resin, can be hydrocarbon polymer: nonane, how alkane, whiteruss, solid paraffin; Or be ester compound: dioctyl phthalate (DOP), dibutyl phthalate, stearate; Or the mixture of above-claimed cpd.Preferred liquid paraffin in the above-mentioned thinner, between the viscosity 70～120cst of whiteruss, viscosity is too high, is difficult for being extracted the agent extraction, and viscosity is too low, and casting sheet thickness stability is not enough.
Particularly, in the described step 1), need when adopting multiple polyolefin resin mix by high mixer earlier, or in Banbury mixer or forcing machine, carry out, the preferred twin screw extruder of forcing machine, further carry out with being blended in pyroreaction still or the forcing machine of thinner afterwards, the mixing temperature of described polyolefin resin and thinner is 180～240 ℃.
Particularly, described step 2) in, the polymkeric substance and the diluent solution that mix are cast sheet via the extruding dies postcooling, described mouthful of mould is T-type or rack-style, and die temperature is 180～240 ℃, and the described type of cooling adopts at the casting sheet and two surfaces is installed by the identical roller of one cover diameter respectively up and down, or on big cold roller and the auxiliary paster apparatus of air knife, the auxiliary cooling of one cover roller simultaneously is installed and obtains sheet, described roller diameter 200～1000mm, 15～50 ℃ of roller temperatures at its air knife.Like this, can make the casting sheet in the process that forms sheet, upper and lower surface is shunk consistent, and in the sepn process of cooling induction phase, the degree that is separated is identical, the micropore size symmetry that follow-up extraction back is formed, and microporous membrane structure is even, can not produce the buckling deformation phenomenon.Particularly, in the described step 3), earlier sheet is placed the baking oven preheating, or carries out preheating by roller, 100～150 ℃ of preheating temperatures, warm up time 1～100s; Carry out two-way stretch afterwards, or the horizontal step drawing in earlier vertical back, or synchro-draw, its longitudinal stretching is than 3～7 times, and cross directional stretch is than 3～9 times, 100～150 ℃ of draft temperatures.
Particularly, in the described step 4), the film after stretched is done typing and is handled, 100～150 ℃ of treatment temps, treatment time 1～100s.Particularly, extraction agent in the described step 5) is selected for use with thinner has good consistency, and and a kind of in inconsistent hydro carbons, hydrochloric ether, fluorinated hydrocarbons or the ketones solvent between the polyolefin resin, or adopt non-inflammable and explosive and not halogen-containing organic solvent with height Environmental Safety.Wherein, described varsol is pentane, hexane, heptane, decane, hydrochloric ether is trichloromethane or tetracol phenixin, and ketones solvent is acetone or butanone, and described organic solvent is diethylene glycol dimethyl ether, dihydroxy ethyl butyl ether, diethylene glycol monoethyl ether or diethylene glycol diethyl ether.At first extract microporous polyolefin film during extraction and produce raw materials used high boiling point thinner, after adopt again that volatile and non-inflammable and explosive solvent cleans film under the normal temperature, this kind solvent down after the volatilization, stays microvoid structure in normal temperature or heated condition in film.
For further improving microvoid structure in the film, carry out secondary heat setting type after the cross directional stretch typing of described step 6) is handled and handle 100～150 ℃ of wherein heat setting type treatment temps, 1～100 second treatment time, 1～1.5 times of stretching ratio.
As of the present invention further, in the described step 1), also can be added with and to improve wear resistance, improve the filler of the follow-up use properties of microporous membrane, described filler proportion is 5～15% of a gross weight, described filler can be selected a kind of in silicon-dioxide, titanium dioxide, the lime carbonate or their mixture, the excellent silicon-dioxide of preferred surface treated dispersiveness for use.
As further of the present invention, in the described step 1), also nucleator can be added or/and oxidation inhibitor, described nucleator proportion is 1～5% of a gross weight, described oxidation inhibitor proportion be gross weight 0.1～0.5%), described nucleator is selected a kind of or mixture in aliphatic carboxylic acid metal compound, sorbyl alcohol benzal derivative, aromatic carboxylic acid metallic compound, organophosphate and xylonic acid and derivatives class, Sodium Benzoate and two (p-tert-butyl benzoic acid) carboxyl aluminium etc. for use, and oxidation inhibitor selects for use in the polyolefine commonly used 1010 or 1076 and 168 to be used.Wherein said nucleator can promote the crystallisation process of molecule and accelerate crystallization velocity, improve crystallinity of polymer, thereby improve hardness, Young's modulus, tensile strength, the yield strength of plastics, also can prevent plastics post crystallization phenomenon, thereby improve the dimensional stability of goods.Described oxidation inhibitor can suppress or delay the oxidative degradation of plastics and prolong its work-ing life, can improve the plastics film quality.
To sum up, the present invention is according to the thermal induction mechanism that is separated, in the technological process of making microporous polyolefin film, employing is installed the identical roller of a cover diameter respectively in two surfaces up and down at sheet, or on the cold roller and the auxiliary paster apparatus of air knife of routine, at air knife the auxiliary refrigerative mode of one cover roller is installed simultaneously and obtains sheet, after adopting conventional stretching and extraction at sheet then, finally can obtain the upper and lower surface microvoid structure symmetrically and evenly, the microporous polyolefin film product of good permeability, and can not produce the buckling deformation phenomenon in the course of processing.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Embodiment 1:
The high density polyethylene(HDPE) (133 ℃ of fusing points) of 10% (weight) is dropped in the twin screw extruder (diameter 78mm, L/D=50, strong mixed milling type), the whiteruss (kinematic viscosity 90cst/40 ℃) that adds 90% (weight) with volume pump by the side direction spout, melting mixing is modulated into solution under 200 ℃, 150 rev/mins condition, this solution is passed through T-pattern head (die lip opening degree 0.8mm, 180 ℃ of die head temperatures) and behind the roller of the two diameter symmetry casting sheet obtain sheet, roller diameter 200mm, 15 ℃ of roller temperatures.Will be on the sheet preheating basis stretch by two-way stretch equipment, warm up time 10S, 100 ℃ of preheating temperatures, 3 * 3 times of stretch ratios (be longitudinal stretching than 3 times, cross directional stretch is than 3 times); Do typing then and handle 100 ℃ of treatment temps, treatment time 10s; The whiteruss in the butanone extraction film is adopted in the back, and dry back is carried out the cross directional stretch typing at 100 ℃ and handled, and 1.0 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Embodiment 2:
The polypropylene (167 ℃ of fusing points) of 60% (weight) is dropped in the twin screw extruder (diameter 78mm, L/D=50, strong mixed milling type), the whiteruss (kinematic viscosity 90cst/40 ℃) that adds 40% (weight) with volume pump by the side direction spout, melting mixing is modulated into solution under 200 ℃, 150 rev/mins condition, this solution is passed through T-pattern head (die lip opening degree 0.8mm, 240 ℃ of die head temperatures) and behind the roller of the two diameter symmetry casting sheet obtain sheet, roller diameter 1000mm, 50 ℃ of roller temperatures.Will be on the sheet preheating basis stretch 150 ℃ of preheating temperatures, 5 * 9 times of stretch ratios (be longitudinal stretching than 5 times, cross directional stretch is than 9 times) by two-way stretch equipment; Do typing then and handle 150 ℃ of treatment temps, treatment time 100s; The whiteruss in the butanone extraction film is adopted in the back, and dry back is carried out the cross directional stretch typing at 150 ℃ and handled, and 1.5 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Embodiment 3:
It is in 180 ℃ the Banbury mixer that the polyethylene (133 ℃ of fusing points) of 20% (weight) input is preestablished temperature, the dioctyl phthalate (DOP) that adds 80% (weight) with volume pump by the side direction spout, melting mixing is modulated into solution under 200 ℃, 150 rev/mins condition, this solution is passed through rack-style mouth mould (die lip opening degree 0.8mm, 200 ℃ of die head temperatures) and behind the roller of the two diameter symmetry casting sheet obtain sheet, roller diameter 800mm, 15 ℃ of roller temperatures.With two-way stretch on the sheet preheating basis, 125 ℃ of preheating temperatures, 3 * 3 times of stretch ratios (be longitudinal stretching than 3 times, cross directional stretch is than 3 times); Do typing then and handle 125 ℃ of treatment temps, treatment time 10s; The dioctyl phthalate (DOP) in the butanone extraction film is adopted in the back, and dry back is carried out the cross directional stretch typing at 125 ℃ and handled, and 1.4 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Embodiment 4:
The polypropylene (167 ℃ of fusing points) of 30% (weight) is dropped in the twin screw extruder (diameter 78mm, L/D=50, strong mixed milling type), the stearate that adds 70% (weight) with volume pump by the side direction spout, melting mixing is modulated into solution under 200 ℃, 150 rev/mins condition, this solution is passed through T-pattern head (die lip opening degree 0.8mm, 200 ℃ of die head temperatures) and conventional cold roller (diameter 800mm) add air knife casting sheet mode and obtain sheet, at air knife the roller that one diameter is 300mm is installed simultaneously, 15 ℃ of two roller temperatures.With two-way stretch on the sheet preheating basis, 125 ℃ of preheating temperatures, 3 * 3 times of stretch ratios (be longitudinal stretching than 3 times, cross directional stretch is than 3 times); Do typing then and handle 125 ℃ of treatment temps, treatment time 50s; The stearate in the dichloromethane extraction film is adopted in the back, and dry back is carried out the cross directional stretch typing at 140 ℃ and handled, and 1.3 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Embodiment 5:
High density polyethylene(HDPE) and medium-density polyethylene with 30% (weight) drops into the high mixer mixing earlier, (133 ℃ of fusing points) drops into twin screw extruder (diameter 78mm then, L/D=50, strong mixed milling type) in, the whiteruss (t/40 ℃ of kinematic viscosity 90cs) that adds 70% (weight) with volume pump by the side direction spout, at 200 ℃, melting mixing is modulated into solution under 150 rev/mins the condition, this solution is passed through T-pattern head (die lip opening degree 0.8mm, 200 ℃ of die head temperatures) and behind the roller of the two diameter symmetry casting sheet obtain sheet, roller diameter 500mm, 50 ℃ of roller temperatures.With two-way stretch on the sheet preheating basis, 125 ℃ of preheating temperatures, 4 * 5 times of stretch ratios (be longitudinal stretching than 4 times, cross directional stretch is than 5 times); Do typing again and handle 140 ℃ of treatment temps, treatment time 70s; The whiteruss in the diethylene glycol dimethyl ether extraction film is adopted in the back, and dry back is carried out the cross directional stretch typing at 140 ℃ and handled, and 1.2 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Embodiment 6:
The high density polyethylene(HDPE) (133 ℃ of fusing points) of 30% (weight) is dropped into twin screw extruder (diameter 78mm, L/D=50, strong mixed milling type) in, the whiteruss (kinematic viscosity 90cst/40 ℃) that adds 65% (weight) with volume pump by the side direction spout, add 5% silica filler simultaneously, at 200 ℃, melting mixing is modulated into solution under 150 rev/mins the condition, this solution is passed through T-pattern head (die lip opening degree 0.8mm, 200 ℃ of die head temperatures) and conventional cold roller (diameter 800mm) add air knife casting sheet mode and obtain sheet, at air knife the roller that one diameter is 500mm is installed simultaneously, 30 ℃ of two roller temperatures.With two-way stretch on the sheet preheating basis, 125 ℃ of preheating temperatures, 6 * 8 times of stretch ratios (be longitudinal stretching than 6 times, cross directional stretch is than 8 times); Do typing again and handle 125 ℃ of treatment temps, treatment time 10s; The whiteruss in the butanone extraction film is adopted in the back, and dry back is carried out the cross directional stretch typing at 125 ℃ and handled, and 1.4 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Embodiment 7:
The polypropylene (167 ℃ of fusing points) of 20% (weight) is dropped into twin screw extruder (diameter 78mm, L/D=50, strong mixed milling type) in, the whiteruss (kinematic viscosity 90cst/40 ℃) that adds 70% (weight) with volume pump by the side direction spout, add 3% silicon-dioxide simultaneously, 1.8% Sodium Benzoate nucleator, 0.2% 1010/168 oxidation inhibitor, at 200 ℃, melting mixing is modulated into solution under 150 rev/mins the condition, this solution is passed through T-pattern head (die lip opening degree 0.8mm, 200 ℃ of die head temperatures) and conventional cold roller (diameter 800mm) add air knife casting sheet mode and obtain sheet, at air knife the roller that one diameter is 500mm is installed simultaneously, 30 ℃ of two roller temperatures.With two-way stretch on the sheet preheating basis, 125 ℃ of preheating temperatures, 3 * 3 times of stretch ratios (be longitudinal stretching than 3 times, cross directional stretch is than 3 times); Do typing again and handle 125 ℃ of treatment temps, treatment time 60s.The whiteruss in the butanone extraction film is adopted in the back, and dry back is 145 ℃ of processing of finalizing the design, and 1.4 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Comparative example 1:
The high density polyethylene(HDPE) (133 ℃ of fusing points) of 30% (weight) is dropped in the twin screw extruder (diameter 78mm, L/D=50, strong mixed milling type), the whiteruss (kinematic viscosity 90cst/40 ℃) that adds 70% (weight) with volume pump by the side direction spout, melting mixing is modulated into solution under 200 ℃, 150 rev/mins condition, this solution is passed through T-pattern head (die lip opening degree 0.8mm, 200 ℃ of die head temperatures) and conventional cold roller (diameter 800mm) add air knife casting sheet mode and obtain sheet, 15 ℃ of roller temperatures.With two-way stretch on the sheet preheating basis, 125 ℃ of preheating temperatures, 3 * 3 times of stretch ratios.Typing is handled, 125 ℃ of treatment temps, treatment time 10s.The whiteruss in the butanone extraction film is adopted in the back, and dry back is 125 ℃ of processing of finalizing the design, and 1.4 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Comparative example 2:
The polypropylene (167 ℃ of fusing points) of 30% (weight) is dropped in the twin screw extruder (diameter 78mm, L/D=50, strong mixed milling type), the whiteruss (kinematic viscosity 90cst/40 ℃) that adds 70% (weight) with volume pump by the side direction spout, melting mixing is modulated into solution under 200 ℃, 150 rev/mins condition, this solution is passed through T-pattern head (die lip opening degree 0.8mm, 200 ℃ of die head temperatures) and conventional cold roller (diameter 800mm) add air knife casting sheet mode and obtain sheet, 30 ℃ of roller temperatures.With two-way stretch on the sheet preheating basis, 125 ℃ of preheating temperatures, 3 * 3 times of stretch ratios.Typing is handled, 125 ℃ of treatment temps, treatment time 10s.The whiteruss in the butanone extraction film is adopted in the back, and dry back is 125 ℃ of processing of finalizing the design, and 1.4 times of stretching ratios make rolling behind the microporous polyolefin film finished product.
Embodiment and comparative example comparative result see Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | Comparative example 2 | |
| Thickness um | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 |
| Porosity % | ??45 | ??43 | ??44 | ??44 | ??42 | ??45 | ??43 | ??45 | ??42 |
| Gas permeability sec/100ml | ??380 | ??400 | ??340 | ??360 | ??420 | ??330 | ??360 | ??450 | ??480 |
The embodiment of the invention is compared as can be seen with comparative example 1,2, the microporous membrane that has adopted casting sheet mode of the present invention to obtain, it is more even to compare the microporous membrane structure that conventional casting sheet mode obtains, and ventilation property improves.The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. the symmetric method for preparing polyolefin microporous membrane of upper and lower surface structures is characterized in that, comprises the steps:
1), with polyolefin resin and mixing diluents, described polyolefin resin and thinner weight ratio are 1-6: 4-9;
2), employing is extruded and is obtained sheet after the curtain coating mode is extruded cold roller casting sheet with said mixture through port mould;
3), will carry out after the sheet preheating in length and breadth to stretching;
4), typing is handled;
5), extraction thinner and dry;
6), the cross directional stretch typing is handled;
7), rolling.
2. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 1, it is characterized in that, described polyolefin resin is a kind of in high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), linear low density polyethylene, ultrahigh molecular weight polyethylene(UHMWPE), polypropylene, ethene and propylene or butylene, octene, the hexene copolymer, or the mixture of above-mentioned substance.
3. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 1 is characterized in that, described thinner is a hydrocarbon polymer: nonane, how alkane, whiteruss, solid paraffin; Or be ester compound: dioctyl phthalate (DOP), dibutyl phthalate, stearate; Or the mixture of above-claimed cpd.
4. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 2, it is characterized in that, in the described step 1), need when adopting multiple polyolefin resin mix by high mixer earlier, or in Banbury mixer or forcing machine, carry out, further carry out with being blended in pyroreaction still or the forcing machine of thinner afterwards, the mixing temperature of described polyolefin resin and thinner is 180～240 ℃.
5. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 1, it is characterized in that, described step 2) in, is with the polymkeric substance and the diluent solution that mix in extruding casting sheet process by forcing machine curtain coating, cold roller casting sheet acquisition sheet, in casting sheet upper and lower surface the identical roller of two diameters is installed respectively, or on large roller cooling and the auxiliary paster apparatus of air knife, assist cooling and obtain sheet at the simultaneously auxiliary roller that installs additional of air knife.
6. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 5, it is characterized in that described extruding dies is selected T-type or rack-style mouth mould, 180～240 ℃ of its die temperatures for use, described roller diameter 200～1000mm, 15～50 ℃ of roller temperatures.
7. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 1 is characterized in that, in the described step 3), preheating is carried out in baking oven, or by the roller preheating, wherein preheating temperature is 100～150 ℃, warm up time 1～100s, carry out two-way stretch after the preheating, it is the horizontal step drawing in vertical earlier back, or synchro-draw, and described longitudinal stretching is than 3～7 times, cross directional stretch is than 3～9 times, 100～150 ℃ of draft temperatures.
8. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 1 is characterized in that, the shaping film treatment temp in the described step 4) after stretched is 100～150 ℃, treatment time 1～100s.
9. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 1, it is characterized in that, extraction agent in the described step 5) is a kind of in hydro carbons, hydrochloric ether, fluorinated hydrocarbons or the ketones solvent, or adopts non-inflammable and explosive and not halogen-containing organic solvent with height Environmental Safety.
10. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 9, it is characterized in that, described varsol is pentane, hexane, heptane, decane, hydrochloric ether is trichloromethane or tetracol phenixin, ketones solvent is acetone or butanone, and described organic solvent is diethylene glycol dimethyl ether, dihydroxy ethyl butyl ether, diethylene glycol monoethyl ether or diethylene glycol diethyl ether.
11. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 1, it is characterized in that, also carrying out secondary heat setting type after the cross directional stretch typing of described step 6) is handled handles, 100～150 ℃ of wherein heat setting type treatment temps, 1～100 second treatment time, 1～1.5 times of stretching ratio.
12. the symmetric method for preparing polyolefin microporous membrane of a kind of upper and lower surface structures according to claim 1, it is characterized in that, in the described step 1), also be added with 5～15% fillers, described filler is a kind of in silicon-dioxide, titanium dioxide, the lime carbonate or their mixture.
13. according to claim 1 or the symmetric method for preparing polyolefin microporous membrane of 12 described a kind of upper and lower surface structures, it is characterized in that, in the described step 1), also be added with 1～5% nucleator or/and 0.1～0.5% oxidation inhibitor, described nucleator is selected a kind of in aliphatic carboxylic acid metal compound, sorbyl alcohol benzal derivative, aromatic carboxylic acid metallic compound, organophosphate and xylonic acid and derivatives class, Sodium Benzoate and the two carboxyl aluminium etc. or their mixture for use, and described oxidation inhibitor selects for use in the polyolefine commonly used 1010 or 1076 and 168 to be used.
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| PCT/CN2010/078747 WO2011057585A1 (en) | 2009-11-16 | 2010-11-15 | Preparation method of polyolefin microporous membrane with symmetrical structure on top and bottom surfaces |
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| CN101724170B (en) | 2012-02-15 |
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