CN101921429B - Ultrahigh molecular weight polypropylene/epoxy resin composite membrane and preparation method thereof - Google Patents
Ultrahigh molecular weight polypropylene/epoxy resin composite membrane and preparation method thereof Download PDFInfo
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- CN101921429B CN101921429B CN2010102555459A CN201010255545A CN101921429B CN 101921429 B CN101921429 B CN 101921429B CN 2010102555459 A CN2010102555459 A CN 2010102555459A CN 201010255545 A CN201010255545 A CN 201010255545A CN 101921429 B CN101921429 B CN 101921429B
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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
-
- 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
- B29C48/04—Particle-shaped
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses an ultrahigh molecular weight polypropylene (UHMWPP)/epoxy resin composite battery membrane and a preparation method thereof, wherein the ultrahigh molecular weight polypropylene (UHMWPP)/epoxy resin composite battery membrane comprises the following compositions of 100 parts of ultrahigh molecular weight polypropylene powder and high density polyethylene powder, 0.01-20 parts of epoxy resin, 0-10 parts of curing agent, 0.01-1 part of antioxidant and 0.01-1 part of assistant antioxidant, wherein the ratio of the ultrahigh molecular weight polypropylene powder and the high density polyethylene is 1:9-9:1. The invention has the advantages that epoxy resin as a modifier has excellent performance per se, expresses better performance in comparison with other modifiers during compounding with the UHMWPP, particularly the processability and the heat resistance, small damage on the traditional excellent performance of the UHMWPP, simpler implementation method compared with a high-energy radiation modification method, simple required equipment and can directly carry out production by a little improving the traditional production equipment of an UHMWPP membrane.
Description
Technical field
The present invention relates to ultrahigh molecular weight polypropylene/epoxy resin composite membrane and preparation method thereof, particularly the ultrahigh molecular weight polypropylene/epoxy resin composite membrane of wet method preparation.
Background technology
Microporous membrane is used for various uses, comprising: be used for dividing plate, tripping device (for example mass transfer rig and filtration unit), medical facilities (for example blood oxidation and dialysis), pressure-regulator, synthetic paper of electrochemical appliance (for example battery, fuel cell and electrical condenser) or the like.
The technology of making microporous polyolefin film can roughly be divided into dry process (or CELGARD technology) and wet processing.
CELGARD technology comprises makes the fusion of semicrystalline polyolefins resin, and melts is squeezed into film, makes film annealing, and with film directed (or stretching) to form micropore.CELGARD technology does not comprise extraction steps (being that solvent is handled), thereby itself is simpler than wet method technology.
Wet processing comprises polyolefin resin mixed with liquid hydrocarbon or some other low molecular weight substances, makes mixtinite heating and fusion, and melts is squeezed into thin slice, directed (or stretching) thin slice, and with volatile solvent liquid is extracted from thin slice.Wet processing is used to make the microporous membrane that comprises extrahigh-molecular weight polyolefins.
Wet processing generally includes a kind of in the following phase separation: (1) liquid-liquid phase separation; Or (2) solid-liquid is separated.Liquid-liquid phase separation is also claimed TIPS, is meant to form rich in polymers liquid phase matrix and the poor polymkeric substance liquid phase of dispersive, and solidifies with polymkeric substance subsequently.Solid-liquid is separated, and also claims GEL technology, is meant that polymkeric substance is by the crystallization of melting mixing body.
Can buy by filling or the microporous membrane of the UHMWPP preparation of filler particles not from the Asahi Chemical of Tokyo of the Tonen Chemical of Tokyo of the Daramic of Owensboro of KY, Japan and Japan.The film of these kinds also is disclosed in, for example, and U.S. Pat 6,824,865, US6,666,969, US6,566,012, US6; 245,272, US6,153,133, US6,096,213, US5,993,954, US5,922; 492, US5,853,633, US5,830,554, US5,786,396, US5,741,848, US5; 281,491, US5,051,183, US4,873,034, US4,734,196, US4,650; 730, US4,620,955, US4,600,633, US4,588,633, US4,593,256 and Japanese Patent JP3497569 (the flat JP08-064194 of growing up), JP3258737 (the flat JP06-212006 that grows up) in.
In a kind of end-use---be used for the barrier film of secondary lithium battery, exist and keep or when increasing its intensity (being disruptive strength) and reduce the lasting requirement of the thickness of film.
Therefore, need new film to satisfy these and other requirement.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of ultrahigh molecular weight polypropylene/epoxy resin composite membrane, and adopt wet method to prepare the method for ultrahigh molecular weight polypropylene/epoxy resin composite membrane, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention:
The present invention selects epoxy resin to have suitable advantage as the processibility of improving the ultrahigh molecular weight polypropylene film and flexible properties-correcting agent.Its reason is:
1. epoxy resin is appropriately crosslinked in composite solution, has improved the stability of flow of ultrahigh molecular weight polypropylene greatly, has avoided the melt fracture that produces because of hypertonia.In addition, because epoxy resin is appropriately crosslinked, improved the tensile property that extracts gel fiber greatly.
2. epoxy resin is polar, has improved the solubility property of solvent after the adding, makes that the dissolving of ultrahigh molecular weight polypropylene in solvent is more complete.
3. cause heat-drawn wire high behind the cross linking of epoxy resin, can improve the hot closing temperature of film.Since be partial cross-linked, therefore also little to the influence of its tensile property.
Technical scheme of the present invention:
Ultrahigh molecular weight polypropylene/epoxy resin composite membrane of the present invention is a kind of compsn; Described composite package thickness is 10～60 microns; Comprise ultrahigh molecular weight polypropylene, high density polyethylene(HDPE), epoxy resin, solidifying agent, inhibitor and help antioxidant ingredients, each component by weight:
Ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE) add up to 100 parts,
Wherein, the ratio of ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE) is: 1～9: 9～1,
0.01～20 part of epoxy resin,
0～10 part in solidifying agent,
0.01～1 part of inhibitor,
Help 0.01～1 part of inhibitor.
As optimized technical scheme:
Aforesaid ultrahigh molecular weight polypropylene/epoxy resin composite membrane; Wherein, Granularity 80～120 orders of described ultrahigh molecular weight polypropylene; The aforesaid ultrahigh molecular weight polypropylene/epoxy resin composite membrane of molecular weight
of the described high density polyethylene(HDPE) of molecular weight
; Wherein, described epoxy resin be selected from aliphatic epoxy resin,
In bisphenol A type epoxy resin, bisphenol-s epoxy resin and the bisphenol f type epoxy resin one or several;
The chemical structural formula of described aliphatic epoxy resin is:
Wherein R is H or CH
3Or
N=1～6;
The chemical structural formula of described bisphenol A type epoxy resin is:
N=1～6 wherein;
The chemical structural formula of described bisphenol-s epoxy resin is:
N=1～6 wherein;
The chemical structural formula of described bisphenol f type epoxy resin is:
N=1～6 wherein;
Aforesaid ultrahigh molecular weight polypropylene/epoxy resin composite membrane; Wherein, Described solidifying agent is selected from one or several in amine or the anhydrides; Preferred mphenylenediamine of amine or p-diaminodiphenyl, preferred Tetra Hydro Phthalic Anhydride of anhydrides (THPA) or methyl tetrahydrophthalic anhydride (MTHPA) or Tetra hydro Phthalic anhydride (PA).
Aforesaid ultrahigh molecular weight polypropylene/epoxy resin composite membrane, wherein, described inhibitor is selected from 2, and 6-di-tert-butyl methyl phenol or N-PBNA are preferred 2, the 6-di-tert-butyl methyl phenol; The described inhibitor that helps is two hard ester group pentaerythritol diphosphites.
In order on the basis of not damaging the original excellent properties of ultrahigh molecular weight polypropylene film, to improve the processibility and the snappiness of UHMWPP film better; Its preparation method is very crucial; The invention provides a kind of ultrahigh molecular weight polypropylene/epoxy resin composite membrane and preparation method thereof, this method comprises the steps:
(1) with ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE), epoxy resin, solidifying agent, inhibitor with help inhibitor in solvent, to mix; Each component is by weight:
Ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE) add up to 100 parts,
Wherein, the ratio of ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE) is: 1～9: 9～1,
0.01～20 part of epoxy resin,
0～10 part in solidifying agent,
0.01～1 part of inhibitor,
Help 0.01～1 part of inhibitor.
(2) under the nitrogen protection effect, be warming up to 100～125 ℃, heat-up rate is controlled at 0.5～5 ℃/min, and the speed with 30～60 commentaries on classics/min stirs simultaneously, is incubated 0.5～2 hour, obtains aaerosol solution;
(3) aaerosol solution makes uniform composite solution through twin-screw mixer, and temperature is controlled at 110～300 ℃, and screw speed is at 120～250 rev/mins;
(4) fully the dissolved composite solution is extruded through rectangular orifice under 220～250 ℃, and the curtain coating cooling makes the frozen glue sheet material;
(5) the frozen glue sheet material passes through extraction and at 90～125 ℃ following 3～8 times redrawing and 128～145 ℃ of following heat setting types 2～10 minutes, can obtain ultrahigh molecular weight polypropylene/epoxy resin composite membrane.
The weight percentage of described solvent is 75～95%, and described solvent is selected from one or more in toluene, YLENE, Yellow Protopet 2A, polyisobutene, MO or the white oil; Described extraction agent is selected from one or more in gasoline, methylene dichloride, tetrachloroethane or the hydrocarbon extraction agent.
Granularity 80～120 orders of described ultrahigh molecular weight polypropylene; Granularity 80～120 orders of molecular weight
high density polyethylene(HDPE), molecular weight
Described epoxy resin is selected from one or several in aliphatic epoxy resin, bisphenol A type epoxy resin, bisphenol-s epoxy resin and the bisphenol f type epoxy resin;
The chemical structural formula of described aliphatic epoxy resin is:
Wherein R is H or CH
3Or
N=1～6;
The chemical structural formula of described bisphenol A type epoxy resin is:
N=1～6 wherein;
The chemical structural formula of described bisphenol-s epoxy resin is:
N=1～6 wherein;
The chemical structural formula of described bisphenol f type epoxy resin is:
N=1～6 wherein;
Described solidifying agent is selected from one or several in amine or the anhydrides, preferred mphenylenediamine of amine or p-diaminodiphenyl, the preferred Tetra Hydro Phthalic Anhydride of anhydrides or methyl tetrahydrophthalic anhydride or Tetra hydro Phthalic anhydride; Described inhibitor is selected from 2, and 6-di-tert-butyl methyl phenol or N-PBNA are preferred 2, the 6-di-tert-butyl methyl phenol; The described inhibitor that helps is two hard ester group pentaerythritol diphosphites.
Composite package of the present invention can overcome the shortcoming that prior art exists to a great extent, obtains the UHMWPP film of high comprehensive performance, can expand it in many-sided application.Because epoxy resin itself can be regarded as a kind of self-reinforced material, in to UHMWPP film tensile process, form certain orientation, the performance of composite package is further enhanced.Because epoxy resin has a lot of premium propertiess, it has good processibility, thermotolerance and creep resistance shape, according to the consistency principle of matrix material, can reach processibility and the stable on heating purpose of improving the UHMWPP film theoretically.
The invention has the beneficial effects as follows:
(1) properties-correcting agent epoxy resin itself has excellent performance, reveals better properties than other properties-correcting agent and UHMWPP composite table, especially aspect processibility and thermotolerance, and also very little to the damage of the original excellent properties of UHMWPP film.
(2) obtain the film strength height than adding medium molecular weight polyvinyl; Implementation method than high-energy radiation method of modifying is simple; Can improve the processibility and the snappiness of film simultaneously, and the equipment that requires is simple, can on the production unit of original UHMWPP film, improves a little and directly produce.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With weight-average molecular weight is that 4,000,000 ultrahigh molecular weight polypropylene powder (80 order), weight-average molecular weight are that 100,000 high density polyethylene(HDPE) (80 order), aliphatic epoxy resin (n=1), solidifying agent mphenylenediamine and toluene together add in the swelling still; Stir with 30 rev/mins speed; Reactant is mixed; Wherein the mass ratio of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and epoxy resin and solidifying agent is 9: 1: 0.1: 0.01, and the total mass of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and epoxy resin and solidifying agent and the mass ratio of toluene are 1: 9, oxidation inhibitor is 2; The 6-di-tert-butyl methyl phenol; Content is 0.01%, and aid anti-oxidants is two hard ester group pentaerythritol diphosphites, and content is 0.01%.Reactant is heated to 120 ℃ with the temperature rise rate of 2 ℃/min, is incubated 1 hour, sends into the storage still then; Cool to room temperature adds twin screw extruder again, 240 ℃ of fully dissolvings down; Extrude continuously with 180 rev/mins speed by twin screw extruder again, under 240 ℃, extrude, make the frozen glue sheet material that thickness is 1mm through the curtain coating cooling roller through volume pump and rectangular orifice; Pass through gasoline extraction and biaxial orientation stretching machine then 6 times of 117 ℃ of following longitudinal stretchings; 4 times of cross directional stretchs pass through forming machine then under 128 ℃, finalize the design 5 minutes; Reel with 12 meters/minute speed through up-coiler at last, can obtain said thickness and be 20 microns ultrahigh molecular weight polypropylene/epoxy resin composite membrane.The performance test results is as shown in table 1.Testing method and standard are following: thickness is measured according to GB/T6672-2001; Ventilation property is measured according to ASTM D726; Porosity is measured according to T/SEN004-2007; Puncture intensity is measured according to ASTM D4833-00e1, and tensile strength is measured according to GB/T1040.3-2006, and shrinking percentage is measured according to GB/T12027-2004.
Embodiment 2
Except epoxy resin n value is 6 and solidifying agent to be p-diaminodiphenyl different with embodiment 1, all by embodiment 1 described preparation process, the preparation composite package.The performance test results is as shown in table 1.
Embodiment 3
The ultrahigh molecular weight polypropylene weight-average molecular weight is 3,000,000, and weight content is 12.5%; The high density polyethylene(HDPE) weight-average molecular weight is 500,000, and weight content is 12.5%; The epoxy resin type is bisphenol A-type (n=1), and solvent is a YLENE, and weight content is 74.87%, and extraction agent is a methylene dichloride, and other prepare composite package all by embodiment 1 described preparation process.The performance test results is as shown in table 1.
Embodiment 4
Except epoxy resin n value is 6 and solidifying agent to be p-diaminodiphenyl different with embodiment 3, all by embodiment 3 described preparation processes, the preparation composite package.The performance test results is as shown in table 1.
Embodiment 5
The ultrahigh molecular weight polypropylene weight-average molecular weight is 1,000,000, and weight content is 2%; The high density polyethylene(HDPE) weight-average molecular weight is 1,000,000, and weight content is 18%; The epoxy resin type is bisphenol S (n=1), and solvent is a Yellow Protopet 2A, and weight content is 79.87%, and extraction agent is hydrocarbon, and other prepare composite package all by embodiment 3 described preparation processes.The performance test results is as shown in table 1.
Embodiment 6
Except epoxy resin n value is 6 and solidifying agent to be methyl tetrahydrophthalic anhydride different with embodiment 5, all by embodiment 5 described preparation processes, the preparation composite package.The performance test results is as shown in table 1.
Embodiment 7
The ultrahigh molecular weight polypropylene weight-average molecular weight is 4,000,000, and weight content is 9%; The high density polyethylene(HDPE) weight-average molecular weight is 1,000,000, and weight content is 1%; The epoxy resin type is Bisphenol F (n=1), and solvent is a polyisobutene, and weight content is 79.87%, and extraction agent is a tetrachloroethane, and oxidation inhibitor is the N-PBNA, and other prepare composite package all by embodiment 5 described preparation processes.The performance test results is as shown in table 2.
Embodiment 8
Except epoxy resin n value be 6 and solidifying agent be methyl tetrahydrophthalic anhydride, the granularity of ultrahigh molecular weight polypropylene and high-density polyethylene powder is 120 orders, different with embodiment 7 outside, all by embodiment 7 described preparation processes, the preparation composite package.The performance test results is as shown in table 2.
Embodiment 9
With weight-average molecular weight is that 4,000,000 ultrahigh molecular weight polypropylene powder (120 order), weight-average molecular weight are that 100,000 high density polyethylene(HDPE) (120 order), bisphenol A epoxide resin (n=1), solidifying agent Tetra hydro Phthalic anhydride and solvent toluene together add in the swelling still; Stir with 60 rev/mins speed; Reactant is mixed; Wherein the mass ratio of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and epoxy resin and solidifying agent is 9: 1: 0.001: 0.001; The total mass of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and epoxy resin and solidifying agent and the mass ratio of MO are 1: 9, and oxidation inhibitor is the N-PBNA, and content is 0.001%; Aid anti-oxidants is two hard ester group pentaerythritol diphosphites, and content is 0.001%.Reactant is heated to 100 ℃ with the temperature rise rate of 0.5 ℃/min, is incubated 2 hours, sends into the storage still then; Cool to room temperature adds twin screw extruder again, 220 ℃ of fully dissolvings down; Extrude continuously with 160 rev/mins speed by twin screw extruder again, under 220 ℃, extrude, make the frozen glue sheet material that thickness is 1mm through the curtain coating cooling roller through volume pump and rectangular orifice; Pass through gasoline extraction and biaxial orientation stretching machine then 8 times of 90 ℃ of following longitudinal stretchings; 6 times of cross directional stretchs pass through forming machine then under 145 ℃, finalize the design 2 minutes; Reel with 12 meters/minute speed through up-coiler at last, can obtain said thickness and be 10 microns ultrahigh molecular weight polypropylene/epoxy resin composite membrane.The performance test results is as shown in table 2.
Embodiment 10
With weight-average molecular weight is that 4,000,000 ultrahigh molecular weight polypropylene powder (120 order), weight-average molecular weight are that 100,000 high density polyethylene(HDPE) (120 order), bisphenol A epoxide resin (n=6), solidifying agent Tetra hydro Phthalic anhydride and solvent xylene together add in the swelling still; Stir with 60 rev/mins speed; Reactant is mixed; Wherein the mass ratio of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and epoxy resin and solidifying agent is 9: 1: 2: 1; The total mass of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and epoxy resin and solidifying agent and the mass ratio of MO are 23.2: 86.8, and oxidation inhibitor is the N-PBNA, and content is 0.1%; Aid anti-oxidants is two hard ester group pentaerythritol diphosphites, and content is 0.1%.Reactant is heated to 125 ℃ with the temperature rise rate of 5 ℃/min, is incubated half hour, sends into the storage still then; Cool to room temperature adds twin screw extruder again, 220 ℃ of fully dissolvings down; Extrude continuously with 160 rev/mins speed by twin screw extruder again, under 220 ℃, extrude, make the frozen glue sheet material that thickness is 1mm through the curtain coating cooling roller through volume pump and rectangular orifice; Pass through dichloromethane extraction and biaxial orientation stretching machine then 4 times of 90 ℃ of following longitudinal stretchings; 3 times of cross directional stretchs pass through forming machine then under 145 ℃, finalize the design 2 minutes; Reel with 12 meters/minute speed through up-coiler at last, can obtain said thickness and be 60 microns ultrahigh molecular weight polypropylene/epoxy resin composite membrane.The performance test results is as shown in table 2.
Comparative example 1
With weight-average molecular weight is that 4,000,000 ultrahigh molecular weight polypropylene powder (80 order), weight-average molecular weight are that 100,000 high density polyethylene(HDPE) (80 order) and solvent xylene together add in the swelling still; Stir with 30 rev/mins speed; Reactant is mixed, and wherein the mass ratio of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) is 9: 1, and the total mass of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and the mass ratio of white oil are 1: 9; Oxidation inhibitor is the N-PBNA; Content is 0.01%, and aid anti-oxidants is two hard ester group pentaerythritol diphosphites, and content is 0.01%.Reactant is heated to 125 ℃ with the temperature rise rate of 5 ℃/min, is incubated half hour, sends into the storage still then; Cool to room temperature adds twin screw extruder again, 250 ℃ of fully dissolvings down; Extrude continuously with 250 rev/mins speed by twin screw extruder again, under 260 ℃, extrude, make the frozen glue sheet material that thickness is 1mm through the curtain coating cooling roller through volume pump and rectangular orifice; Pass through dichloromethane extraction and biaxial orientation stretching machine then 6 times of 125 ℃ of following longitudinal stretchings; 4 times of cross directional stretchs pass through forming machine then under 128 ℃, finalize the design 10 minutes; Reel with 12 meters/minute speed through up-coiler at last, can obtain said thickness and be 20 microns ultrahigh molecular weight polypropylene/epoxy resin composite membrane.The performance test results is as shown in table 2.
Comparative example 2
Except add 0.1% bisphenol A epoxide resin and comparative example 1 different, other all prepare composite package by as above comparative example 1 described preparation process.Performance test methods and result are as shown in table 2.
Table 1
Table 2
Claims (10)
1. ultrahigh molecular weight polypropylene/epoxy resin composite membrane; It is characterized in that: described composite package thickness is 10～60 microns; Comprise ultrahigh molecular weight polypropylene, high density polyethylene(HDPE), epoxy resin, solidifying agent, inhibitor and help antioxidant ingredients, each component by weight:
Ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE) add up to 100 parts,
Wherein, ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE) are 1～9: 9～1
0.01～20 part of epoxy resin,
0～10 part in solidifying agent,
0.01～1 part of inhibitor,
Help 0.01～1 part of inhibitor.
2. ultrahigh molecular weight polypropylene/epoxy resin composite membrane according to claim 1; It is characterized in that; Described ultrahigh molecular weight polypropylene particles of powder degree 80～120 orders; Granularity 80～120 orders of the described high-density polyethylene powder of molecular weight
, molecular weight
3. ultrahigh molecular weight polypropylene/epoxy resin composite membrane according to claim 1; It is characterized in that described epoxy resin is selected from one or several in aliphatic epoxy resin, bisphenol A type epoxy resin, bisphenol-s epoxy resin and the bisphenol f type epoxy resin;
The chemical structural formula of described aliphatic epoxy resin is:
Wherein R is H or CH
3Or
N=1～6;
The chemical structural formula of described bisphenol A type epoxy resin is:
N=1～6 wherein;
The chemical structural formula of described bisphenol-s epoxy resin is:
N=1～6 wherein;
The chemical structural formula of described bisphenol f type epoxy resin is:
N=1～6 wherein.
4. ultrahigh molecular weight polypropylene/epoxy resin composite membrane according to claim 1; It is characterized in that; Described solidifying agent is selected from one or several in amine or the anhydrides; Amine is mphenylenediamine or p-diaminodiphenyl, and anhydrides is Tetra Hydro Phthalic Anhydride or methyl tetrahydrophthalic anhydride or Tetra hydro Phthalic anhydride.
5. ultrahigh molecular weight polypropylene/epoxy resin composite membrane according to claim 1 is characterized in that described inhibitor is selected from 2,6-di-tert-butyl methyl phenol or N-PBNA; The described inhibitor that helps is two hard ester group pentaerythritol diphosphites.
6. prepare the method for the described ultrahigh molecular weight polypropylene/epoxy resin composite membrane of claim 1, it is characterized in that, this method comprises the steps:
(1) is 80～120 purpose ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE), epoxy resin, solidifying agent, inhibitor with granularity and helps inhibitor in solvent, to mix; Each component is by weight: ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE) add up to 100 parts,
Wherein, the ratio of ultrahigh molecular weight polypropylene powder and high density polyethylene(HDPE) is: 1～9: 9～1,
0.01～20 part of epoxy resin,
0～10 part in solidifying agent,
0.01～1 part of inhibitor,
Help 0.01～1 part of inhibitor;
(2) under the nitrogen protection effect, be warming up to 100～125 ℃, heat-up rate is controlled at 0.5～5 ℃/min, and the speed with 30～60 commentaries on classics/min stirs simultaneously, is incubated 0.5～2 hour, obtains aaerosol solution;
(3) aaerosol solution makes uniform composite solution through twin-screw mixer, and temperature is controlled at 110～300 ℃, and screw speed is at 120～250 rev/mins;
(4) fully the dissolved composite solution is extruded through rectangular orifice under 220～250 ℃, and the curtain coating cooling makes the frozen glue sheet material;
(5) the frozen glue sheet material passes through extraction and at 90～125 ℃ following 3～8 times redrawing and 128～145 ℃ of following heat setting types 2～10 minutes, can obtain ultrahigh molecular weight polypropylene/epoxy resin composite membrane.
7. method according to claim 6 is characterized in that, the weight percentage of described solvent is 75～95%, and described solvent is selected from one or more in toluene, YLENE, Yellow Protopet 2A or the polyisobutene; Described extraction agent is selected from one or more in gasoline, methylene dichloride, tetrachloroethane or the hydrocarbon extraction agent.
8. method according to claim 6; It is characterized in that; Described ultrahigh molecular weight polypropylene particles of powder degree 80～120 orders; Granularity 80～120 orders of the described high-density polyethylene powder of molecular weight
, molecular weight
9. method according to claim 6 is characterized in that described epoxy resin is selected from one or several in aliphatic epoxy resin, bisphenol A type epoxy resin, bisphenol-s epoxy resin and the bisphenol f type epoxy resin;
The chemical structural formula of described aliphatic epoxy resin is:
Wherein R is H or CH
3Or
N=1～6;
The chemical structural formula of described bisphenol A type epoxy resin is:
N=1～6 wherein;
The chemical structural formula of described bisphenol-s epoxy resin is:
N=1～6 wherein;
The chemical structural formula of described bisphenol f type epoxy resin is:
N=1～6 wherein.
10. method according to claim 6; It is characterized in that; Described solidifying agent is selected from one or several in amine or the anhydrides, and amine is mphenylenediamine or p-diaminodiphenyl, and anhydrides is Tetra Hydro Phthalic Anhydride or methyl tetrahydrophthalic anhydride or Tetra hydro Phthalic anhydride; Described inhibitor is selected from 2,6-di-tert-butyl methyl phenol or N-PBNA; The described inhibitor that helps is two hard ester group pentaerythritol diphosphites.
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