CN101921429A - 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 PDF

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CN101921429A
CN101921429A CN2010102555459A CN201010255545A CN101921429A CN 101921429 A CN101921429 A CN 101921429A CN 2010102555459 A CN2010102555459 A CN 2010102555459A CN 201010255545 A CN201010255545 A CN 201010255545A CN 101921429 A CN101921429 A CN 101921429A
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molecular weight
epoxy resin
ultrahigh molecular
weight polypropylene
antioxidant
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CN101921429B (en
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王新鹏
王依民
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Donghua University
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Donghua University
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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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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • 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

Ultrahigh molecular weight polypropylene/epoxy resin composite membrane and preparation method thereof
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 orientation (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 mixture 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 also claims 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, with Japanese Patent JP3497569 (the flat JP08-064194 that grows up), among the JP3258737 (the flat JP06-212006 that grows up).
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 Resins, epoxy to have suitable advantage as the processibility of improving the ultrahigh molecular weight polypropylene film and flexible properties-correcting agent.Its reason is:
1. Resins, epoxy 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 Resins, epoxy is appropriately crosslinked, improved the tensile property that extracts gel fiber greatly.
2. Resins, epoxy 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 the heat-drawn wire height 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 composition, described composite membrane thickness is 10～60 microns, comprise ultrahigh molecular weight polypropylene, high density polyethylene(HDPE), Resins, epoxy, solidifying agent, antioxidant 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 Resins, epoxy,
0～10 part in solidifying agent,
0.01～1 part of antioxidant,
Help 0.01～1 part of antioxidant.
As optimized technical scheme:
Aforesaid ultrahigh molecular weight polypropylene/epoxy resin composite membrane, wherein, granularity 80～120 orders of described ultrahigh molecular weight polypropylene, molecular weight
Figure BSA00000232313800021
The molecular weight of described high density polyethylene(HDPE)
Figure BSA00000232313800022
Aforesaid ultrahigh molecular weight polypropylene/epoxy resin composite membrane, wherein, described Resins, epoxy 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:
Figure BSA00000232313800031
Wherein R is H or CH 3Or N=1～6;
The chemical structural formula of described bisphenol A type epoxy resin is:
Figure BSA00000232313800033
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:
Figure BSA00000232313800035
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 antioxidant is selected from 2, and 6-di-tert-butyl methyl phenol or N-Phenyl beta naphthylamine are preferred 2, the 6-di-tert-butyl methyl phenol; The described antioxidant 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), Resins, epoxy, solidifying agent, antioxidant with help antioxidant 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 Resins, epoxy,
0～10 part in solidifying agent,
0.01～1 part of antioxidant,
Help 0.01～1 part of antioxidant.
(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 secondary stretch 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, dimethylbenzene, paraffin oil, polyisobutene, mineral oil 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, molecular weight
Figure BSA00000232313800041
Granularity 80～120 orders of high density polyethylene(HDPE), molecular weight
Described Resins, epoxy 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
Figure BSA00000232313800044
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:
Figure BSA00000232313800052
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 antioxidant is selected from 2, and 6-di-tert-butyl methyl phenol or N-Phenyl beta naphthylamine are preferred 2, the 6-di-tert-butyl methyl phenol; The described antioxidant that helps is two hard ester group pentaerythritol diphosphites.
Composite membrane 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 Resins, epoxy itself can be regarded as a kind of self-reinforced material, in to UHMWPP film tensile process, form certain orientation, the performance of composite membrane is further enhanced.Because Resins, epoxy 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 Resins, epoxy 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 and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications 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
It with weight-average molecular weight 4,000,000 ultrahigh molecular weight polypropylene powder (80 order), weight-average molecular weight is 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 Resins, epoxy and solidifying agent is 9: 1: 0.1: 0.01, the total mass of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and Resins, epoxy 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%, 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, be incubated 1 hour, send into the storage still then, cool to room temperature, add twin screw extruder again, 240 ℃ of fully dissolvings down, extrude continuously with 180 rev/mins speed by twin screw extruder again, extrude under 240 ℃ through volume pump and rectangular orifice, make the frozen glue sheet material that thickness is 1mm by the curtain coating cooling roller, 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 described 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 as follows: 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, tensile strength is measured according to GB/T1040.3-2006, and shrinking percentage is measured according to GB/T12027-2004.
Embodiment 2
Except Resins, epoxy 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 membrane.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 Resins, epoxy type is bisphenol A-type (n=1), and solvent is a dimethylbenzene, and weight content is 74.87%, and extraction agent is a methylene dichloride, and other prepare composite membrane all by embodiment 1 described preparation process.The performance test results is as shown in table 1.
Embodiment 4
Except Resins, epoxy 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 membrane.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 Resins, epoxy type is bisphenol S (n=1), and solvent is a paraffin oil, and weight content is 79.87%, and extraction agent is hydrocarbon, and other prepare composite membrane all by embodiment 3 described preparation processes.The performance test results is as shown in table 1.
Embodiment 6
Except Resins, epoxy 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 membrane.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 Resins, epoxy 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-Phenyl beta naphthylamine, and other prepare composite membrane all by embodiment 5 described preparation processes.The performance test results is as shown in table 2.
Embodiment 8
Except Resins, epoxy 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 membrane.The performance test results is as shown in table 2.
Embodiment 9
It with weight-average molecular weight 4,000,000 ultrahigh molecular weight polypropylene powder (120 order), weight-average molecular weight is 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 Resins, epoxy and solidifying agent is 9: 1: 0.001: 0.001, the total mass of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and Resins, epoxy and solidifying agent and the mass ratio of mineral oil are 1: 9, oxidation inhibitor is the N-Phenyl beta naphthylamine, 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, be incubated 2 hours, send into the storage still then, cool to room temperature, add twin screw extruder again, 220 ℃ of fully dissolvings down, extrude continuously with 160 rev/mins speed by twin screw extruder again, extrude under 220 ℃ through volume pump and rectangular orifice, make the frozen glue sheet material that thickness is 1mm by the curtain coating cooling roller, 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 described 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
It with weight-average molecular weight 4,000,000 ultrahigh molecular weight polypropylene powder (120 order), weight-average molecular weight is 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 Resins, epoxy and solidifying agent is 9: 1: 2: 1, the total mass of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) and Resins, epoxy and solidifying agent and the mass ratio of mineral oil are 23.2: 86.8, oxidation inhibitor is the N-Phenyl beta naphthylamine, 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, be incubated half hour, send into the storage still then, cool to room temperature, add twin screw extruder again, 220 ℃ of fully dissolvings down, extrude continuously with 160 rev/mins speed by twin screw extruder again, extrude under 220 ℃ through volume pump and rectangular orifice, make the frozen glue sheet material that thickness is 1mm by the curtain coating cooling roller, 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 described 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
It with weight-average molecular weight 4,000,000 ultrahigh molecular weight polypropylene powder (80 order), weight-average molecular weight is 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, wherein the mass ratio of ultrahigh molecular weight polypropylene and high density polyethylene(HDPE) is 9: 1, 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-Phenyl beta naphthylamine, content is 0.01%, 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, be incubated half hour, send into the storage still then, cool to room temperature, add twin screw extruder again, 250 ℃ of fully dissolvings down, extrude continuously with 250 rev/mins speed by twin screw extruder again, extrude under 260 ℃ through volume pump and rectangular orifice, make the frozen glue sheet material that thickness is 1mm by the curtain coating cooling roller, 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 described 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 membrane by as above comparative example 1 described preparation process.Performance test methods and result are as shown in table 2.
Table 1
Figure BSA00000232313800091
Table 2
Figure BSA00000232313800101

Claims (10)

1. ultrahigh molecular weight polypropylene/epoxy resin composite membrane, it is characterized in that: described composite membrane thickness is 10～60 microns, comprise ultrahigh molecular weight polypropylene, high density polyethylene(HDPE), Resins, epoxy, solidifying agent, antioxidant 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 Resins, epoxy,
0～10 part in solidifying agent,
0.01～1 part of antioxidant,
Help 0.01～1 part of antioxidant.
2. ultrahigh molecular weight polypropylene/epoxy resin composite membrane according to claim 1 is characterized in that, described ultrahigh molecular weight polypropylene particles of powder degree 80～120 orders, molecular weight
Figure FSA00000232313700011
Granularity 80～120 orders of described high-density polyethylene powder, molecular weight
Figure FSA00000232313700012
3. ultrahigh molecular weight polypropylene/epoxy resin composite membrane according to claim 1, it is characterized in that described Resins, epoxy 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:
Figure FSA00000232313700013
Wherein R is H or CH 3Or
Figure FSA00000232313700014
N=1～6;
The chemical structural formula of described bisphenol A type epoxy resin is:
Figure FSA00000232313700015
N=1～6 wherein;
The chemical structural formula of described bisphenol-s epoxy resin is:
Figure FSA00000232313700021
N=1～6 wherein;
The chemical structural formula of described bisphenol f type epoxy resin is:
Figure FSA00000232313700022
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, preferred mphenylenediamine of amine or p-diaminodiphenyl, the preferred Tetra Hydro Phthalic Anhydride of anhydrides 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 antioxidant is selected from 2, and 6-di-tert-butyl methyl phenol or N-Phenyl beta naphthylamine are preferred 2, the 6-di-tert-butyl methyl phenol; The described antioxidant 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), Resins, epoxy, solidifying agent, antioxidant with granularity and helps antioxidant 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 Resins, epoxy,
0～10 part in solidifying agent,
0.01～1 part of antioxidant,
Help 0.01～1 part of antioxidant.
(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 secondary stretch 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, dimethylbenzene, paraffin oil, polyisobutene, mineral oil or the white oil; 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 is characterized in that, described ultrahigh molecular weight polypropylene particles of powder degree 80～120 orders, molecular weight
Figure FSA00000232313700031
Granularity 80～120 orders of described high-density polyethylene powder, molecular weight 1 × 10 5 ≤ M ‾ W ≤ 1 × 10 6 .
9. method according to claim 6 is characterized in that described Resins, epoxy 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:
Figure FSA00000232313700033
Wherein R is H or CH 3Or
Figure FSA00000232313700034
N=1～6;
The chemical structural formula of described bisphenol A type epoxy resin is:
Figure FSA00000232313700035
N=1～6 wherein;
The chemical structural formula of described bisphenol-s epoxy resin is:
Figure FSA00000232313700036
N=1～6 wherein;
The chemical structural formula of described bisphenol f type epoxy resin is:
Figure FSA00000232313700041
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, 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 antioxidant is selected from 2, and 6-di-tert-butyl methyl phenol or N-Phenyl beta naphthylamine are preferred 2, the 6-di-tert-butyl methyl phenol; The described antioxidant that helps is two hard ester group pentaerythritol diphosphites.
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