CN110483884A - A kind of high-fire resistance microporous polypropylene membrane and preparation method thereof - Google Patents
A kind of high-fire resistance microporous polypropylene membrane and preparation method thereof Download PDFInfo
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- CN110483884A CN110483884A CN201910317248.3A CN201910317248A CN110483884A CN 110483884 A CN110483884 A CN 110483884A CN 201910317248 A CN201910317248 A CN 201910317248A CN 110483884 A CN110483884 A CN 110483884A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention provides a kind of high-fire resistance microporous polypropylene membranes and preparation method thereof, and the microporous barrier includes following raw materials according: polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate.Solving microporous polypropylene membrane in the prior art, there are the technical problems of heat resistance difference.The present invention is using specific formula masterbatch, the polyethylene terephthalate of certain content is added into polypropylene, polypropylene beta crystal nucleating agent, it is much better than polyacrylic feature using melting point polyester, reduce the percent thermal shrinkage of microporous polypropylene membrane under high temperature, to improve microporous polypropylene membrane heat resistance, the microporous polypropylene membrane of high heat resistance is obtained.
Description
Technical field
The present invention relates to microporous membrane technology field more particularly to a kind of high-fire resistance microporous polypropylene membrane and its preparation sides
Method.
Background technique
Microporous polypropylene membrane has many advantages, such as that chemical stability is high, the molding of low in cost, easy processing, be current driving force lithium from
The sub- most commonly used diaphragm material of battery.But there is heat resistance difference in microporous polypropylene membrane, polyacrylic fusing point is 163
DEG C, melting, which can occur, for diaphragm when battery thermal runaway causes positive and negative anodes to contact, and leads to that the accidents such as short circuit or explosion occur.
At present mainly by coating Al on the surface of polypropylene/olefin diaphragm2O3、SiO2The modes of Nano Ceramic Particles improves
The heat resistance of battery.However there are coatings to be unevenly distributed, ceramic particle " shedding ", the heat resistance for leading to diaphragm for coating diaphragm
It not can effectively solve.
Summary of the invention
The embodiment of the invention provides a kind of high-fire resistance microporous polypropylene membranes and preparation method thereof, solve in the prior art
There are the technical problems of heat resistance difference for microporous polypropylene membrane.
In view of the above problems, the present invention provides a kind of high-fire resistance microporous polypropylene membrane and preparation method thereof, first party
Face, the present invention provides a kind of high-fire resistance microporous polypropylene membranes, and the microporous barrier includes following raw materials according: polypropylene, polypropylene beta
Crystal-type nucleater and polyethylene terephthalate.
Preferably, polyethylene terephthalate content is 0.1wt%-15wt% in the raw material.
Preferably, the quality that polypropylene beta crystal nucleating agent accounts for polypropylene/polypropylene beta crystal-type nucleater in the raw material is divided
Number is 0.5%-3%.
Preferably, the microporous barrier with a thickness of 12-16 μm；Longitudinal heat of the microporous barrier is received after preservation 1h at 90 DEG C
Shrinkage is 0.8-0.9%, and lateral percent thermal shrinkage is 0.4-0.5%；Longitudinal heat of the microporous barrier is received after preservation 1h at 105 DEG C
Shrinkage is 1-1.5%, and lateral percent thermal shrinkage is 0.5-1%.
Second aspect, the present invention provides a kind of preparation methods of high-fire resistance microporous polypropylene membrane, which comprises
Polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate are uniformly mixed, mixed raw material is squeezed out,
Mixing, prepares the formula masterbatch of different substrate materials content；The formula masterbatch is prepared into prefabricated diaphragm；To the prefabricated diaphragm into
The two-way asynchronous stretching of row, is made the microporous polypropylene membrane.
Preferably, prefabricated diaphragm is prepared into for masterbatch is formulated using the method for squeezing out curtain coating.
Preferably, the extrudate flow delay extruder uses single screw extrusion machine, and die temperature range is 240-250 DEG C,
Casting roller temperature range is 120-130 DEG C.
Preferably, longitudinal stretching (MD) temperature is 100 DEG C in the two-way asynchronous drawing process, and tensile speed is 1mm/s,
Stretching ratio is 5.5 times.
Preferably, cross directional stretch (TD) temperature is 130 DEG C in the two-way asynchronous drawing process, and tensile speed is 0.5mm/
S, stretching ratio are 3 times.
Said one or multiple technical solutions in the embodiment of the present application at least have following one or more technology effects
Fruit:
1, a kind of high-fire resistance microporous polypropylene membrane provided in an embodiment of the present invention, the microporous barrier includes following raw materials according:
Polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate.Formula masterbatch prepared by the present invention is to poly- third
Be added polyethylene terephthalate in alkene, polypropylene beta crystal nucleating agent, polyethylene terephthalate fusing point 250 DEG C with
On, the defect of existing MIcroporous polyolefin film poor heat resistance can be overcome, effectively high temperature lower diaphragm plate is prevented to be heat-shrinked, while being solved existing
There is the problems such as ceramic coating membrane is at high cost, coating is uneven, ceramic particle falls off, solves polypropylene microporous in the prior art
There are the technical problems of heat resistance difference for film.Reach poly- to benzene two by being added into polypropylene, polypropylene beta crystal nucleating agent
Formic acid ethylene glycol can overcome the defect of existing MIcroporous polyolefin film poor heat resistance, effectively high temperature lower diaphragm plate be prevented to be heat-shrinked
Technical effect.
2, the preparation method of a kind of high-fire resistance microporous polypropylene membrane provided in an embodiment of the present invention, which comprises
Polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate are uniformly mixed, mixed raw material is squeezed out,
Mixing, prepares the formula masterbatch of different substrate materials content；The formula masterbatch is prepared into prefabricated diaphragm；To the prefabricated diaphragm into
The two-way asynchronous stretching of row, is made the microporous polypropylene membrane.The present invention is brilliant to polypropylene, polypropylene beta when preparation is formulated masterbatch
The polyethylene terephthalate of certain content is added in type nucleating agent, is much better than polyacrylic feature using melting point polyester,
The percent thermal shrinkage for reducing microporous polypropylene membrane under high temperature, to improve microporous polypropylene membrane heat resistance.The present invention is using specific
Formula masterbatch, can get high heat resistance microporous polypropylene membrane.There is heat resistance by the microporous barrier that this method is produced
The good advantage of energy, and reduce costs.Solving microporous polypropylene membrane in the prior art, there are the technical problems of heat resistance difference.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects of the present invention, feature and advantage can
It is clearer and more comprehensible, the followings are specific embodiments of the present invention.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please are not constituted an undue limitation on the present application for explaining the application.In the accompanying drawings:
Fig. 1 is a kind of flow diagram of the preparation method of high-fire resistance microporous polypropylene membrane of the embodiment of the present invention；
Fig. 2 is the stereoscan photograph of microporous barrier prepared by the embodiment of the present invention 1；
Fig. 3 is that pp material used in the embodiment of the present invention and polyethylene terephthalate raw material melt heating curve.
Specific embodiment
The embodiment of the invention provides a kind of high-fire resistance microporous polypropylene membranes and preparation method thereof, for solving existing skill
There are the technical problems of heat resistance difference for microporous polypropylene membrane in art.
Technical solution general thought provided by the invention is as follows:
Microporous barrier includes following raw materials according: polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate.This
The formula masterbatch for inventing preparation, is that polyethylene terephthalate is added into polypropylene, polypropylene beta crystal nucleating agent, poly- pair
Phthalic acid ethylene glycol fusing point can overcome the defect of existing MIcroporous polyolefin film poor heat resistance, effectively prevent at 250 DEG C or more
High temperature lower diaphragm plate is heat-shrinked, and has been reached by the way that poly terephthalic acid second two is added into polypropylene, polypropylene beta crystal nucleating agent
Alcohol can overcome the defect of existing MIcroporous polyolefin film poor heat resistance, the technical effect for effectively high temperature lower diaphragm plate being prevented to be heat-shrinked.
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Embodiment 1
The embodiment of the invention provides a kind of high-fire resistance microporous polypropylene membranes, and the microporous barrier includes following raw materials according: poly-
Propylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate.
Further, polyethylene terephthalate content is 0.1wt%-15wt% in the raw material.
Further, polypropylene beta crystal nucleating agent accounts for the quality of polypropylene/polypropylene beta crystal-type nucleater in the raw material
Score is 0.5%-3%.
Further, the microporous barrier with a thickness of 12-16 μm；The longitudinal direction of the microporous barrier is hot after preservation 1h at 90 DEG C
Shrinking percentage is 0.8-0.9%, and lateral percent thermal shrinkage is 0.4-0.5%；The longitudinal direction of the microporous barrier is hot after preservation 1h at 105 DEG C
Shrinking percentage is 1-1.5%, and lateral percent thermal shrinkage is 0.5-1%.
Specifically, microporous barrier of the invention includes following raw materials according: polypropylene, polypropylene beta crystal nucleating agent and poly- to benzene
Naphthalate, polypropylene (abbreviation PP) are a kind of hemicrystalline thermoplastics, and impact resistance with higher is mechanical
Property is tough, and polypropylene (PP) is due to crystallization, and the shrinking percentage of PP is quite high, generally 1.8-2.5%, and the direction of shrinking percentage
The materials such as uniformity ratio PE-HD are far better, and 30% glass additive is added and shrinking percentage can be made to drop to 0.7%.
The polypropylene beta crystal nucleating agent that the present embodiment is selected is terres rares nucleating agent, and model WBG, it can induce beta crystal
Crystallization, makes PP receive the beta crystal of high-content, thus assign product good impact resistance, resistance to heat distorsion and high porosity.
WBG especially suitable for PP-R pipe, automobile, household electrical appliance and other require the product of high impact-resistant and heat distortion temperature, can also
It applies in the production of PP synthetic paper, film etc., there is β crystalline substance high conversion rate, be remarkably improved plastic products toughness.
Polyethylene terephthalate category crystal type saturated polyester, average molecular weight (2-3) × 104, weight are equal with number
The ratio between molecular weight be 1.5-1.8, relative density 1.38-1.40g/cm3,225-256 DEG C of fusing point, 243 DEG C of flowing temperature, glass
Change 80 DEG C of temperature, 80 DEG C of Martin heat resistance, 98 DEG C of heat distortion temperature (1.82MPa), 353 DEG C of decomposition temperature, there is excellent machinery
Performance, rigidity are high, hardness is big, water imbibition very little, good stability of the dimension, good toughness, impact resistance, rub resistance, creep resistance, chemically-resistant
Property is good.
The present embodiment provides a kind of means modified using substrate formula, and the formula masterbatch of preparation is to polypropylene, poly- third
Polyethylene terephthalate is added in alkene beta crystal-type nucleater, polyethylene terephthalate fusing point, can at 250 DEG C or more
It solves the problems, such as that existing polypropylene microporous film heat resistance is low, the defect of existing MIcroporous polyolefin film poor heat resistance can be overcome, it can
The technical effect for effectively high temperature lower diaphragm plate being prevented to be heat-shrinked.
Embodiment 2
Fig. 1 is a kind of flow diagram of the preparation method of high-fire resistance microporous polypropylene membrane in the embodiment of the present invention.This
Inventive embodiments provide a kind of preparation method of high-fire resistance microporous polypropylene membrane, referring to FIG. 1, the described method includes:
Step 10: polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate uniformly being mixed, to mixed
It closes raw material to be squeezed out, mixed, prepares the formula masterbatch of different substrate materials content.
Specifically, using high-speed mixer by polyethylene terephthalate, polypropylene, polypropylene beta crystal nucleating agent
It is uniformly mixed, mixed raw material is squeezed out using double screw extruder, is mixed, the formula masterbatch of different substrate materials content is prepared.
Step 20: the formula masterbatch is prepared into prefabricated diaphragm.
Further, prefabricated diaphragm is prepared into for masterbatch is formulated using the method for squeezing out curtain coating.
Further, the extrudate flow delay extruder uses single screw extrusion machine, and die temperature range is 240-250
DEG C, casting roller temperature range is 120-130 DEG C.
The use of the polypropylene beta crystal nucleating agent is to obtain Beta-crystalline polyacrylic in casting processes.
Step 30: two-way asynchronous stretching being carried out to the prefabricated diaphragm, the microporous polypropylene membrane is made.
Further, longitudinal stretching (MD) temperature is 100 DEG C in the two-way asynchronous drawing process, and tensile speed is 1mm/
S, stretching ratio are 5.5 times.
Further, cross directional stretch (TD) temperature is 130 DEG C in the two-way asynchronous drawing process, and tensile speed is
0.5mm/s, stretching ratio are 3 times.
Specifically, carrying out two-way asynchronous stretching to prefabricated film using film biaxial tension experimental provision, i.e., respectively along longitudinal direction
Prefabricated diaphragm is applied with transverse direction and is stretched.Longitudinal stretching (MD) temperature is 100 DEG C in the two-way asynchronous drawing process, stretches speed
Degree is 1mm/s, and stretching ratio is 5.5 times；Cross directional stretch (TD) temperature is 130 DEG C, and tensile speed is 0.5mm/s, stretching ratio
It is 3 times.
In following example 3, embodiment 4 and embodiment 5, the polypropylene trade mark of selection is F401, poly terephthalic acid second
The diol ester trade mark is FG620, and polypropylene beta crystal nucleating agent is terres rares nucleating agent, model WBG, wherein polyacrylic fusing point
It is 163 DEG C, polyethylene terephthalate fusing point is 254 DEG C (see Fig. 3).
Embodiment 3
Polypropylene, polypropylene beta crystal nucleating agent, polyethylene terephthalate are uniformly mixed using high-speed mixer
It closes, mixed raw material is squeezed out using double screw extruder, is mixed, preparing polyethylene terephthalate content is
0.1% formula masterbatch, polypropylene beta crystal nucleating agent accounts for the mass fraction of polypropylene/polypropylene beta crystal-type nucleater and is in masterbatch
1.5%.Masterbatch is formulated after single screw extrusion machine squeezes out, prefabricated diaphragm is made in molding on casting machine.
Extrudate flow delay die temperature is set as 240 DEG C, and roller temperature is set as 120 DEG C.
Two-way asynchronous stretching is carried out to prefabricated film using film biaxial tension experimental provision.Longitudinal stretching (MD) temperature is
100 DEG C, tensile speed is 1mm/s, and stretching ratio is 5.5 times；Cross directional stretch (TD) temperature is 130 DEG C, and tensile speed is
0.5mm/s, stretching ratio are 3 times.It is final to obtain microporous polypropylene membrane.Each base of masterbatch is formulated in microporous polypropylene membrane preparation process
The content of material, drawing process are as shown in table 1.Using microporous barrier surface micropore pattern described in scanning electronic microscope observation, as a result
See that Fig. 2, Fig. 2 give the stereoscan photograph of the microporous barrier of the preparation of embodiment 1.By the microporous barrier at 90 DEG C and 105 DEG C
After keeping 1h respectively, its longitudinally, laterally percent thermal shrinkage is tested, the results are shown in Table 2.
Embodiment 4
Using high-speed mixer by a certain proportion of polypropylene, polypropylene beta crystal nucleating agent, polyethylene terephthalate
Ester uniformly mixes, and is squeezed out, is mixed to mixed raw material using double screw extruder, prepared polyethylene terephthalate and contain
The formula masterbatch for being 8% is measured, it is 0.5% that polypropylene beta crystal nucleating agent, which accounts for polypropylene/nucleating agent mass fraction, in masterbatch.Match
Square masterbatch is after single screw extrusion machine squeezes out, and prefabricated diaphragm is made in molding on casting machine.
Extrudate flow delay die temperature is set as 245 DEG C, and roller temperature is set as 130 DEG C.
Two-way asynchronous stretching is carried out to prefabricated film using film biaxial tension experimental provision.Longitudinal stretching (MD) temperature is
100 DEG C, tensile speed is 1mm/s, and stretching ratio is 5.5 times；Cross directional stretch (TD) temperature is 130 DEG C, and tensile speed is
0.5mm/s, stretching ratio are 3 times.It is final to obtain microporous polypropylene membrane.Each base of masterbatch is formulated in microporous polypropylene membrane preparation process
The content of material, drawing process are as shown in table 1.After the microporous barrier is kept 1h respectively at 90 DEG C and 105 DEG C, it is vertical to test it
To, lateral percent thermal shrinkage, it the results are shown in Table 2.
Embodiment 5
Using high-speed mixer by a certain proportion of polypropylene, polypropylene beta crystal nucleating agent, polyethylene terephthalate
Ester uniformly mixes, and is squeezed out, is mixed to mixed raw material using double screw extruder, prepared polyethylene terephthalate and contain
The formula masterbatch for being 15% is measured, it is 3% that polypropylene beta crystal nucleating agent, which accounts for polypropylene/nucleating agent mass fraction, in masterbatch.Formula
Masterbatch is after single screw extrusion machine squeezes out, and prefabricated diaphragm is made in molding on casting machine.
Extrudate flow delay die temperature is set as 250 DEG C, and roller temperature is set as 125 DEG C.
Two-way asynchronous stretching is carried out to prefabricated film using film biaxial tension experimental provision.Longitudinal stretching (MD) temperature is
100 DEG C, tensile speed is 1mm/s, and stretching ratio is 5.5 times；Cross directional stretch (TD) temperature is 130 DEG C, and tensile speed is
0.5mm/s, stretching ratio are 3 times.It is final to obtain microporous polypropylene membrane.Each base of masterbatch is formulated in microporous polypropylene membrane preparation process
The content of material, drawing process are as shown in table 1.After the microporous barrier is kept 1h respectively at 90 DEG C and 105 DEG C, it is vertical to test it
To, lateral percent thermal shrinkage, it the results are shown in Table 2.
Comparative example
A certain proportion of polypropylene, polypropylene beta crystal nucleating agent are uniformly mixed using high-speed mixer, using twin-screw
Extruder squeezes out mixed raw material, is mixed, preparation formula masterbatch, and polypropylene beta crystal nucleating agent accounts for polypropylene/poly- in masterbatch
The mass fraction of propylene beta crystal-type nucleater is 0.5%.Masterbatch is formulated after single screw extrusion machine squeezes out, is formed on casting machine
Prefabricated diaphragm is made.
Extrudate flow delay die temperature is set as 240 DEG C, and roller temperature is set as 125 DEG C.
Two-way asynchronous stretching is carried out to prefabricated film using film biaxial tension experimental provision.Longitudinal stretching (MD) temperature is
100 DEG C, tensile speed is 1mm/s, and stretching ratio is 5.5 times；Cross directional stretch (TD) temperature is 130 DEG C, and tensile speed is
0.5mm/s, stretching ratio are 3 times.It is final to obtain microporous polypropylene membrane.Each base of masterbatch is formulated in microporous polypropylene membrane preparation process
The content of material, drawing process are as shown in table 1.After the microporous barrier is kept 1h respectively at 90 DEG C and 105 DEG C, it is vertical to test it
To, lateral percent thermal shrinkage, it the results are shown in Table 2.
1 microporous polypropylene membrane master batch formulation of table and drawing process condition
2 PP microporous barrier percent thermal shrinkage test result of table
As can be seen from Table 2, the present invention is made when preparation is formulated masterbatch using high mixer mixed at high speed, twin-screw extrusion
The mode of grain, is added polyethylene terephthalate into polypropylene, polypropylene beta crystal nucleating agent system, microporous barrier it is resistance to
Hot property is significantly improved than comparative example, and then has prepared the microporous polypropylene membrane of high-fire resistance.The present invention is matched using substrate
Just modified means, solve the problems, such as that existing polypropylene microporous film heat resistance is low, high heat resistance have been made using bidirectional extending method
The microporous barrier of performance.
Said one or multiple technical solutions in the embodiment of the present application at least have following one or more technology effects
Fruit:
1, a kind of high-fire resistance microporous polypropylene membrane provided in an embodiment of the present invention, the microporous barrier includes following raw materials according:
Polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate.Formula masterbatch prepared by the present invention is to poly- third
Be added polyethylene terephthalate in alkene, polypropylene beta crystal nucleating agent, polyethylene terephthalate fusing point 250 DEG C with
On, the defect of existing MIcroporous polyolefin film poor heat resistance can be overcome, effectively high temperature lower diaphragm plate is prevented to be heat-shrinked, while being solved existing
There is the problems such as ceramic coating membrane is at high cost, coating is uneven, ceramic particle falls off, solves polypropylene microporous in the prior art
There are the technical problems of heat resistance difference for film.Reach poly- to benzene two by being added into polypropylene, polypropylene beta crystal nucleating agent
Formic acid ethylene glycol can overcome the defect of existing MIcroporous polyolefin film poor heat resistance, effectively high temperature lower diaphragm plate be prevented to be heat-shrinked
Technical effect.
2, the preparation method of a kind of high-fire resistance microporous polypropylene membrane provided in an embodiment of the present invention, which comprises
Polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate are uniformly mixed, mixed raw material is squeezed out,
Mixing, prepares the formula masterbatch of different substrate materials content；The formula masterbatch is prepared into prefabricated diaphragm；To the prefabricated diaphragm into
The two-way asynchronous stretching of row, is made the microporous polypropylene membrane.The present invention is brilliant to polypropylene, polypropylene beta when preparation is formulated masterbatch
The polyethylene terephthalate of certain content is added in type nucleating agent, is much better than polyacrylic feature using melting point polyester,
The percent thermal shrinkage for reducing microporous polypropylene membrane under high temperature, to improve microporous polypropylene membrane heat resistance.The present invention is using specific
Formula masterbatch, can get high heat resistance microporous polypropylene membrane.There is heat resistance by the microporous barrier that this method is produced
The good advantage of energy, and reduce costs.Solving microporous polypropylene membrane in the prior art, there are the technical problems of heat resistance difference.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications can be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.
Obviously, those skilled in the art can carry out various modification and variations without departing from this hair to the embodiment of the present invention
The spirit and scope of bright embodiment.In this way, if these modifications and variations of the embodiment of the present invention belong to the claims in the present invention
And its within the scope of equivalent technologies, then the present invention is also intended to include these modifications and variations.
Claims (9)
1. a kind of high-fire resistance microporous polypropylene membrane, which is characterized in that the microporous barrier includes following raw materials according: polypropylene, poly- third
Alkene beta crystal-type nucleater and polyethylene terephthalate.
2. microporous barrier as described in claim 1, which is characterized in that the content of polyethylene terephthalate in the raw material
For 0.1wt%-15wt%.
3. microporous barrier as described in claim 1, which is characterized in that in the raw material polypropylene beta crystal nucleating agent account for polypropylene/
The mass fraction of polypropylene beta crystal nucleating agent is 0.5%-3%.
4. microporous barrier as described in claim 1, which is characterized in that
The microporous barrier with a thickness of 12-16 μm；
Longitudinal percent thermal shrinkage of the microporous barrier is 0.8-0.9% after preservation 1h at 90 DEG C, and lateral percent thermal shrinkage is 0.4-
0.5%；
Longitudinal percent thermal shrinkage of the microporous barrier is 1-1.5% after preservation 1h at 105 DEG C, and lateral percent thermal shrinkage is 0.5-1%.
5. the preparation method of microporous barrier according to any one of claims 1-4, which is characterized in that the described method includes:
Polypropylene, polypropylene beta crystal nucleating agent and polyethylene terephthalate are uniformly mixed, mixed raw material is squeezed
Out, it mixes, prepares the formula masterbatch of different substrate materials content；
The formula masterbatch is prepared into prefabricated diaphragm；
Two-way asynchronous stretching is carried out to the prefabricated diaphragm, the microporous polypropylene membrane is made.
6. method as claimed in claim 5, which is characterized in that using squeeze out curtain coating method will be formulated masterbatch be prepared into it is prefabricated
Diaphragm.
7. method as claimed in claim 6, which is characterized in that the extrudate flow delay extruder uses single screw extrusion machine,
Die temperature range is 240-250 DEG C, and casting roller temperature range is 120-130 DEG C.
8. method as claimed in claim 5, which is characterized in that longitudinal drawing temperature is in the two-way asynchronous drawing process
100 DEG C, tensile speed is 1mm/s, and stretching ratio is 5.5 times.
9. method as claimed in claim 5, which is characterized in that transverse drawing temperature is in the two-way asynchronous drawing process
130 DEG C, tensile speed is 0.5mm/s, and stretching ratio is 3 times.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290549A (en) * | 2011-05-18 | 2011-12-21 | 新乡市中科科技有限公司 | Polyolefine power battery diaphragm and preparation method thereof |
| CN102604203A (en) * | 2012-01-18 | 2012-07-25 | 成都慧成科技有限责任公司 | Improved microporous polymer film and preparation method thereof |
| CN106700224A (en) * | 2015-07-23 | 2017-05-24 | 中国石化扬子石油化工有限公司 | Polypropylene composition and preparation method thereof |
| CN109608837A (en) * | 2018-12-20 | 2019-04-12 | 四川东方绝缘材料股份有限公司 | A kind of polyester-polyolefin film and preparation method thereof |
-
2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290549A (en) * | 2011-05-18 | 2011-12-21 | 新乡市中科科技有限公司 | Polyolefine power battery diaphragm and preparation method thereof |
| CN102604203A (en) * | 2012-01-18 | 2012-07-25 | 成都慧成科技有限责任公司 | Improved microporous polymer film and preparation method thereof |
| CN106700224A (en) * | 2015-07-23 | 2017-05-24 | 中国石化扬子石油化工有限公司 | Polypropylene composition and preparation method thereof |
| CN109608837A (en) * | 2018-12-20 | 2019-04-12 | 四川东方绝缘材料股份有限公司 | A kind of polyester-polyolefin film and preparation method thereof |
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