CN101914242A - Ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane - Google Patents
Ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane Download PDFInfo
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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
- B29C48/92—Measuring, controlling or regulating
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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
- 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
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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
- 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
Abstract
The invention discloses an ultrahigh molecular weight polypropylene (UHMWPP)/ultrahigh molecular weight polythene (UHMWPE)/epoxy resin composite membrane and a preparation method thereof, wherein the composite membrane contains 100 parts of ultrahigh molecular weight polypropylene and ultrahigh molecular weight polythene 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 secondary antioxidant, wherein the proportion of the ultrahigh molecular weight polypropylene to the ultrahigh molecular weight polythene is 1:9-9:1. The molecular weight of the ultrahigh molecular weight polypropylene is 4,000,000, and the molecular weight of the ultrahigh molecular weight polythene is 500,000. The invention has the advantages that the modifier epoxy resin has excellent performance per se and represents better performance compared with other modifiers compounded with the UHMWPE, especially in the aspects of processability and heat resistance, and moreover, the modifier epoxy resin has very small damage to the original excellent performance of the UHMWPE; the preparation method of the composite membrane is simpler than the implementing method of a high-energy radiation modification method, and required equipment is simple; the production can be directly carried out on the basis of slightly improving the production equipment of the original UHMWPE membrane; and moreover, the addition of the UHMWPP can improve the porosity and the heat resistance of the composite membrane.
Description
Technical field
The present invention relates to ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane and preparation method thereof, particularly ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/the 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 for making the microporous membrane that comprises ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE).
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 UHMWPE 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
Technical conceive of the present invention:
The present invention selects Resins, epoxy to have suitable advantage as the processibility of improving the UHMWPE film and stable on heating 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 polyethylene(UHMWPE) 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 polyethylene(UHMWPE) 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.
4. in addition, the adding of ultrahigh molecular weight polypropylene can improve the porosity and the resistance toheat of composite membrane.
Technical scheme of the present invention:
Ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/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, ultrahigh molecular weight polyethylene(UHMWPE), Resins, epoxy, solidifying agent, antioxidant and help antioxidant ingredients, each component by weight:
Ultrahigh molecular weight polypropylene powder and ultrahigh molecular weight polyethylene(UHMWPE) add up to 100 parts,
Wherein, the ratio of ultrahigh molecular weight polypropylene powder and ultrahigh molecular weight polyethylene(UHMWPE) 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/ultrahigh molecular weight polythene/epoxy resin composite membrane, wherein, granularity 80～120 orders of described ultrahigh molecular weight polyethylene(UHMWPE), molecular weight
The molecular weight of described ultrahigh molecular weight polypropylene
Aforesaid ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane, wherein, 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
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/ultrahigh molecular weight polythene/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/ultrahigh molecular weight polythene/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 ultra high molecular weight polyethylene films, to improve the processibility and the thermotolerance of UHMWPE film better, its preparation method is very crucial, the invention provides a kind of ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane and preparation method thereof, this method comprises the steps:
(1) is 80～120 purpose ultrahigh molecular weight polypropylene powder and a certain amount of Resins, epoxy, solidifying agent, antioxidant with granularity and helps antioxidant in solvent, to mix; Under the nitrogen protection effect, be warming up to 100～125 ℃, heat-up rate is controlled at 0.5～5 ℃/min, is incubated 0.5～2 hour, obtains aaerosol solution;
(2) be that 80～120 purpose ultrahigh molecular weight polyethylene(UHMWPE) powder are respectively with a certain amount of Resins, epoxy, solidifying agent, antioxidant with help antioxidant to mix in solvent with granularity; Under the nitrogen protection effect, be warming up to 125～150 ℃, heat-up rate is controlled at 0.5～5 ℃/min, is incubated 0.5～2 hour, obtains aaerosol solution;
(3) after two of gained kinds of aaerosol solutions mix, make uniform composite solution through twin-screw mixer, 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 220～260 ℃, 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/ultrahigh molecular weight polythene/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 polyethylene(UHMWPE), molecular weight
Described ultrahigh molecular weight polypropylene particles of powder degree 80～120 orders, 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
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 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 UHMWPE 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 UHMWPE 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 UHMWPE 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 UHMWPE composite table, especially aspect processibility and thermotolerance, and also very little to the damage of the original excellent properties of UHMWPE film.
(2) add ultrahigh molecular weight polypropylene and obtain the film strength height, implementation method than high-energy radiation method of modifying is simple, can improve the processibility and the thermotolerance of film simultaneously, and the equipment that requires is simple, can on the production unit of original UHMWPE film, improves a little and directly produce.
(3) in addition, the adding of ultrahigh molecular weight polypropylene can improve the porosity and the resistance toheat of composite membrane.
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
With weight-average molecular weight be 4,000,000 ultrahigh molecular weight polyethylene(UHMWPE) powder (80 order) and weight-average molecular weight be 500,000 ultrahigh molecular weight polypropylene powder (80 order) respectively with aliphatic epoxy resin (n=1), solidifying agent mphenylenediamine and solvent toluene together add in the swelling still, stir with 30 rev/mins speed, reactant is mixed, wherein the mass ratio of ultrahigh molecular weight polyethylene(UHMWPE) and ultrahigh molecular weight polypropylene and Resins, epoxy and solidifying agent is 9: 1: 0.1: 0.01, the total mass of ultrahigh molecular weight polyethylene(UHMWPE) and ultrahigh molecular weight polypropylene 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 ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane of 20 microns.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 polyethylene(UHMWPE) weight-average molecular weight is 3,000,000, and weight content is 12.5%; The ultrahigh molecular weight polypropylene 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 polyethylene(UHMWPE) weight-average molecular weight is 1,000,000, and weight content is 2%; The ultrahigh molecular weight polypropylene weight-average molecular weight is 4,000,000, 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 polyethylene(UHMWPE) weight-average molecular weight is 4,000,000, and weight content is 9%; The ultrahigh molecular weight polypropylene weight-average molecular weight is 500,000, 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, ultrahigh molecular weight polypropylene and ultrahigh molecular weight polyethylene(UHMWPE) particles of powder degree are 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
With weight-average molecular weight be 4,000,000 ultrahigh molecular weight polyethylene(UHMWPE) powder (120 order) and weight-average molecular weight be 500,000 ultrahigh molecular weight polypropylene powder (120 order) respectively with 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 polyethylene(UHMWPE) and ultrahigh molecular weight polypropylene and Resins, epoxy and solidifying agent is 9: 1: 0.001: 0.001, the total mass of ultrahigh molecular weight polypropylene and ultrahigh molecular weight polyethylene(UHMWPE) 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 ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane of 10 microns.The performance test results is as shown in table 2.
Embodiment 10
With weight-average molecular weight be 4,000,000 ultrahigh molecular weight polyethylene(UHMWPE) powder (120 order) and weight-average molecular weight be 500,000 ultrahigh molecular weight polypropylene powder (120 order) respectively with 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 polyethylene(UHMWPE) and ultrahigh molecular weight polypropylene and Resins, epoxy and solidifying agent is 9: 1: 2: 1, the total mass of ultrahigh molecular weight polypropylene and ultrahigh molecular weight polyethylene(UHMWPE) 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 ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane of 60 microns.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 polyethylene(UHMWPE) powder (80 order) and weight-average molecular weight are that 500,000 ultrahigh molecular weight polypropylene powder (80 order) together adds in the swelling still with solvent xylene respectively, stir with 30 rev/mins speed, reactant is mixed, wherein the mass ratio of ultrahigh molecular weight polyethylene(UHMWPE) and ultrahigh molecular weight polypropylene is 9: 1, the total mass of ultrahigh molecular weight polypropylene and ultrahigh molecular weight polyethylene(UHMWPE) 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 polyethylene/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
Table 2
Claims (10)
1. ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/epoxy resin composite membrane, it is characterized in that: described composite membrane thickness is 10～60 microns, comprise ultrahigh molecular weight polypropylene, ultrahigh molecular weight polyethylene(UHMWPE), Resins, epoxy, solidifying agent, antioxidant and help antioxidant ingredients, each component by weight:
100 parts in ultrahigh molecular weight polypropylene and ultrahigh molecular weight polyethylene(UHMWPE) powder
Ultrahigh molecular weight polypropylene and ultrahigh molecular weight polyethylene(UHMWPE) ratio 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/ultrahigh molecular weight polythene/epoxy resin composite membrane according to claim 1 is characterized in that, described ultrahigh molecular weight polyethylene(UHMWPE) particles of powder degree 80～120 orders, molecular weight
3. ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/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
4. ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/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:
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.
5. ultrahigh molecular weight polypropylene/ultrahigh molecular weight polythene/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; Described antioxidant is selected from 2, the 6-di-tert-butyl methyl phenol, and the N-Phenyl beta naphthylamine: 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/ultrahigh molecular weight polythene/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 a certain amount of Resins, epoxy, solidifying agent, antioxidant with granularity and helps antioxidant in solvent, to mix; 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;
(2) be that 80～120 purpose ultrahigh molecular weight polyethylene(UHMWPE) powder are respectively with a certain amount of Resins, epoxy, solidifying agent, antioxidant with help antioxidant to mix in solvent with granularity; Under the nitrogen protection effect, be warming up to 125～150 ℃, 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) after two of gained kinds of aaerosol solutions mix, make uniform composite solution through twin-screw mixer, 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/ultrahigh molecular weight polythene/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, poly-different T alkene, 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 polyethylene(UHMWPE) particles of powder degree 80～120 orders, molecular weight
Described ultrahigh molecular weight polypropylene particles of powder degree 80～120 orders, molecular weight
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:
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, 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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