阅读说明：本技术 一种高分子膜及其制备方法 (Polymer film and preparation method thereof ) 是由 毛泽龙 于 2020-11-09 设计创作，主要内容包括：本发明公开了一种高分子膜及其制备方法,所述高分子膜,以重量份为单位,包括以下原料：全氟磺酸树脂92-135份、脲醛树脂20-40份、壳聚糖12-23份、微晶纤维素6-10份、石墨烯微片1-2份、纳米碳化硅8-13份、堇青石粉6-15份、纳米陶瓷粉8-12份、氯化石蜡5-9份、硬脂酸7-16份、脂肪醇聚氧乙烯醚硫酸钠0.7-1.3份、三甲基硅醇钾4-6份、乙醇锌1.6-3.5份,所述高分子膜经过制备基料、制备表面改性填料、高温剪切、塑化、热定型等步骤制得的。本发明的高分子膜的纵向拉伸强度较大,达到了127.3MPa以上,膜性能优异,可满足实际使用时的需可满足应用需求,可大力推广应用。(The invention discloses a polymer film and a preparation method thereof, wherein the polymer film comprises the following raw materials in parts by weight: 92-135 parts of perfluorinated sulfonic acid resin, 20-40 parts of urea-formaldehyde resin, 12-23 parts of chitosan, 6-10 parts of microcrystalline cellulose, 1-2 parts of graphene microchip, 8-13 parts of nano silicon carbide, 6-15 parts of cordierite powder, 8-12 parts of nano ceramic powder, 5-9 parts of chlorinated paraffin, 7-16 parts of stearic acid, 0.7-1.3 parts of fatty alcohol polyoxyethylene ether sodium sulfate, 4-6 parts of trimethylsilanolate and 1.6-3.5 parts of zinc alcohol, and the polymer film is prepared by the steps of preparing a base material, preparing a surface modified filler, shearing at high temperature, plasticizing, heat setting and the like. The polymer film has high longitudinal tensile strength reaching over 127.3MPa, excellent film performance, capacity of meeting practical use requirement and application requirement, and capacity of being popularized and applied widely.)

1. The polymer film is characterized by comprising the following raw materials in parts by weight: 92-135 parts of perfluorinated sulfonic acid resin, 20-40 parts of urea-formaldehyde resin, 12-23 parts of chitosan, 6-10 parts of microcrystalline cellulose, 1-2 parts of graphene microchip, 8-13 parts of nano silicon carbide, 6-15 parts of cordierite powder, 8-12 parts of nano ceramic powder, 5-9 parts of chlorinated paraffin, 7-16 parts of stearic acid, 0.7-1.3 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 4-6 parts of potassium trimethylsilanolate and 1.6-3.5 parts of zinc ethoxide;

the preparation method of the polymer film comprises the following steps:

s1: heating and melting the perfluorinated sulfonic acid resin and the urea-formaldehyde resin to obtain a liquid sizing material, adding the chlorinated paraffin and the stearic acid into the liquid sizing material, continuously heating and stirring, and cooling to room temperature to obtain a base material;

s2: uniformly mixing microcrystalline cellulose, graphene nanoplatelets, nano silicon carbide, cordierite powder and nano ceramic powder, heating, stirring, adding sodium fatty alcohol-polyoxyethylene ether sulfate, potassium trimethylsilanolate and zinc ethoxide, uniformly mixing, heating, stirring, and cooling to room temperature to obtain a surface modified filler;

s3: and (3) heating and stirring the base material prepared in the step S1, the surface modified filler prepared in the step S2 and chitosan, then shearing at high temperature, plasticizing, stirring and blending in an extruder to obtain a mixed melt, then conveying the melt into a die head, cooling and solidifying on a rapid cooling roller to obtain a sheet, and then carrying out biaxial stretching, extraction and heat setting to obtain the polymer film.

2. The polymeric membrane according to claim 1, comprising the following raw materials in parts by weight: 115 parts of perfluorinated sulfonic acid resin, 32 parts of urea-formaldehyde resin, 18 parts of chitosan, 9 parts of microcrystalline cellulose, 1.6 parts of graphene microchip, 10 parts of nano silicon carbide, 9 parts of cordierite powder, 10 parts of nano ceramic powder, 8 parts of chlorinated paraffin, 12 parts of stearic acid, 1 part of fatty alcohol-polyoxyethylene ether sodium sulfate, 5 parts of potassium trimethylsilanolate and 3 parts of zinc ethoxide.

3. The method for preparing a polymer film according to claim 1, wherein in step S1, the perfluorosulfonic acid resin and the urea-formaldehyde resin are heated to 135-152 ℃ and then melted to obtain the liquid rubber.

4. The method as claimed in claim 1, wherein in step S1, the chlorinated paraffin and stearic acid are added to the liquid rubber, the temperature is increased to 172-185 ℃, the mixture is stirred, and the mixture is cooled to room temperature to obtain the base material.

5. The method for preparing a polymer film according to claim 4, wherein the rotation speed of the stirring is 1200-1400 r/min.

6. The method for preparing a polymer membrane according to claim 5, wherein the stirring is performed at a rotation speed of 1200-1400r/min for 0.7-1.5 h.

7. The method for preparing a polymer film according to claim 1, wherein in step S2, the sodium alcohol ether sulfate, the potassium trimethylsilanolate, and the zinc ethoxide are added and mixed uniformly, heated to 140-156 ℃ and stirred at a rotation speed of 1100-1300r/min for 1.5-2.5h, and cooled to room temperature to obtain the surface-modified filler.

8. The method as claimed in claim 1, wherein in step S3, the binder prepared in step S1, the surface modified filler prepared in step S2 and the chitosan are heated to 145 ℃ and then stirred at 1200r/min for 1-1.5h at 1000-.

9. The method of claim 1, wherein in step S3, the extruder is a twin-screw extruder.

10. The method as claimed in claim 1, wherein the step S3 is performed by plasticizing at 154 ℃ and 136 ℃ for 8-25 min.

Technical Field

The invention belongs to the technical field of membrane preparation, and particularly relates to a polymer membrane and a preparation method thereof.

Background

In recent years, lithium batteries have been rapidly developed, but the safety and high performance of lithium batteries have been key problems restricting the development of lithium batteries, and a diaphragm is an electric insulating film with a porous structure, mainly used for isolating a positive electrode and a negative electrode, preventing electrons in the batteries from passing through, and allowing ions in an electrolyte solution to freely pass between the positive electrode and the negative electrode, and the performance of the diaphragm determines the interface structure, the internal resistance and the like of the batteries, and directly influences the characteristics of the batteries, such as capacity, cycle performance and the like.

The Chinese patent application document 'composite stable lithium battery diaphragm (application publication number: CN 105006591A)' discloses a composite stable lithium battery diaphragm, which comprises a polymer base film and a proton conducting material dispersed in the polymer base film, wherein the proton conducting material is composed of graphene nanoplatelets, nano silicon carbide, perfluorinated sulfonic acid resin, cordierite powder and nano ceramic powder, and the mass ratio of the graphene nanoplatelets, the nano silicon carbide, the perfluorinated sulfonic acid resin, the cordierite powder and the nano ceramic powder is 2:3:20:0.5: 1.5. The traditional proton conduction material is changed, and the high-performance materials such as the graphene nanoplatelets are added, so that the prepared electrolyte membrane not only can ensure good conductivity in use, but also can be degraded by microorganisms after being discarded, and the harm of the electrolyte membrane to the environment is reduced. But the longitudinal tensile strength is poor, and the requirement in practical use cannot be met.

Disclosure of Invention

The invention provides a polymer film and a preparation method thereof, which aim to solve the problem that the polymer film prepared by the prior art has poor longitudinal tensile strength.

In order to solve the technical problems, the invention adopts the following technical scheme:

a polymer film comprises the following raw materials in parts by weight: 92-135 parts of perfluorinated sulfonic acid resin, 20-40 parts of urea-formaldehyde resin, 12-23 parts of chitosan, 6-10 parts of microcrystalline cellulose, 1-2 parts of graphene microchip, 8-13 parts of nano silicon carbide, 6-15 parts of cordierite powder, 8-12 parts of nano ceramic powder, 5-9 parts of chlorinated paraffin, 7-16 parts of stearic acid, 0.7-1.3 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 4-6 parts of potassium trimethylsilanolate and 1.6-3.5 parts of zinc ethoxide;

the preparation method of the polymer film comprises the following steps:

s1: heating and melting the perfluorinated sulfonic acid resin and the urea-formaldehyde resin to obtain a liquid sizing material, adding the chlorinated paraffin and the stearic acid into the liquid sizing material, continuously heating and stirring, and cooling to room temperature to obtain a base material;

s2: uniformly mixing microcrystalline cellulose, graphene nanoplatelets, nano silicon carbide, cordierite powder and nano ceramic powder, heating, stirring, adding sodium fatty alcohol-polyoxyethylene ether sulfate, potassium trimethylsilanolate and zinc ethoxide, uniformly mixing, heating, stirring, and cooling to room temperature to obtain a surface modified filler;

s3: and (3) heating and stirring the base material prepared in the step S1, the surface modified filler prepared in the step S2 and chitosan, then shearing at high temperature, plasticizing, stirring and blending in an extruder to obtain a mixed melt, then conveying the melt into a die head, cooling and solidifying on a rapid cooling roller to obtain a sheet, and then carrying out biaxial stretching, extraction and heat setting to obtain the polymer film.

Further, the polymer film comprises the following raw materials in parts by weight: 115 parts of perfluorinated sulfonic acid resin, 32 parts of urea-formaldehyde resin, 18 parts of chitosan, 9 parts of microcrystalline cellulose, 1.6 parts of graphene microchip, 10 parts of nano silicon carbide, 9 parts of cordierite powder, 10 parts of nano ceramic powder, 8 parts of chlorinated paraffin, 12 parts of stearic acid, 1 part of fatty alcohol-polyoxyethylene ether sodium sulfate, 5 parts of potassium trimethylsilanolate and 3 parts of zinc ethoxide.

Further, in step S1, the perfluorosulfonic acid resin and the urea-formaldehyde resin are heated to 135-152 ℃ and then melted to obtain the liquid rubber.

Further, in step S1, the chlorinated paraffin and stearic acid are added into the liquid rubber, the temperature is increased to 172-185 ℃ and the mixture is stirred, and the mixture is cooled to room temperature to obtain the base material.

Further, the rotation speed of the stirring is 1200-1400 r/min.

Further, stirring for 0.7-1.5h at the stirring speed of 1200-1400 r/min.

Further, in step S2, adding sodium fatty alcohol polyoxyethylene ether sulfate, potassium trimethylsilanolate and zinc ethoxide, mixing uniformly, heating to 140-.

Further, in step S3, the temperature of the base material prepared in step S1, the surface modified filler prepared in step S2 and the chitosan is raised to 145 ℃ for stirring at the speed of 1000-.

Further, in step S3, the extruder is a twin-screw extruder.

Further, in step S3, plasticizing is carried out at 154 ℃ for 8-25min and 136 ℃.

The invention has the following beneficial effects:

(1) the polymer film has high longitudinal tensile strength reaching over 127.3MPa, excellent film performance, capacity of meeting the practical requirement and capacity of being popularized and applied widely.

(2) The simultaneous addition of the sodium fatty alcohol-polyoxyethylene ether sulfate, the potassium trimethylsilanolate and the zinc ethoxide plays a synergistic role in the preparation of the polymer film, and the longitudinal tensile strength is synergistically improved because: the sodium fatty alcohol-polyoxyethylene ether sulfate has good activation and dispersion effects, can increase the pores on the surfaces of the perfluorinated sulfonic acid resin and the urea-formaldehyde resin, and enables potassium trimethylsilanolate to permeate the interiors of the perfluorinated sulfonic acid resin and the urea-formaldehyde resin to form a stable connection structure, so that the sodium fatty alcohol-polyoxyethylene ether sulfate can promote the effects of zinc alcohol, the perfluorinated sulfonic acid resin and the urea-formaldehyde resin; the potassium trimethylsilanolate has strong permeability, can improve the adhesion between the perfluorinated sulfonic acid resin, the urea-formaldehyde resin and the zinc ethylate, enables the perfluorinated sulfonic acid resin, the urea-formaldehyde resin and the zinc ethylate to be uniformly dispersed in the perfluorinated sulfonic acid resin and the urea-formaldehyde resin, provides an acting point for the surface modification of the perfluorinated sulfonic acid resin and the urea-formaldehyde resin, and is beneficial to improving the longitudinal tensile strength of a polymer film.

(3) The longitudinal tensile strength of the polymer film prepared by the invention is obviously superior to that of the polymer film prepared by the prior art, and is at least higher than 84.8 percent, thereby solving the technical problem that the polymer film prepared by the prior art has poorer longitudinal tensile strength.

Detailed Description

In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.

In an embodiment, the polymer film comprises the following raw materials in parts by weight: 92-135 parts of perfluorinated sulfonic acid resin, 20-40 parts of urea-formaldehyde resin, 12-23 parts of chitosan, 6-10 parts of microcrystalline cellulose, 1-2 parts of graphene microchip, 8-13 parts of nano silicon carbide, 6-15 parts of cordierite powder, 8-12 parts of nano ceramic powder, 5-9 parts of chlorinated paraffin, 7-16 parts of stearic acid, 0.7-1.3 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 4-6 parts of potassium trimethylsilanolate and 1.6-3.5 parts of zinc ethoxide;

the preparation method of the polymer film comprises the following steps:

s1: heating the perfluorinated sulfonic acid resin and the urea-formaldehyde resin to 135-;

s2: uniformly mixing microcrystalline cellulose, graphene nanoplatelets, nano silicon carbide, cordierite powder and nano ceramic powder, heating, stirring, adding sodium fatty alcohol-polyoxyethylene ether sulfate, potassium trimethylsilanolate and zinc ethoxide, uniformly mixing, heating to 140-156 ℃, stirring at the rotating speed of 1100-1300r/min for 1.5-2.5h, and cooling to room temperature to obtain a surface modified filler;

s3: heating the base material prepared in the step S1, the surface modified filler prepared in the step S2 and chitosan to 145 ℃, stirring at the rotating speed of 1000-1200r/min for 1-1.5h, then shearing at high temperature in a double-screw extruder, plasticizing at 154 ℃ of 136-154 ℃ for 8-25min, stirring, blending to obtain a mixed melt, then conveying the melt into a die head, cooling and solidifying on a quick cooling roller to obtain a sheet, and then performing biaxial tension, extraction and heat setting to obtain the polymer film.

The present invention is illustrated by the following more specific examples.

Example 1

A polymer film comprises the following raw materials in parts by weight: 95 parts of perfluorinated sulfonic acid resin, 22 parts of urea-formaldehyde resin, 14 parts of chitosan, 6 parts of microcrystalline cellulose, 1 part of graphene microchip, 8 parts of nano silicon carbide, 7 parts of cordierite powder, 8 parts of nano ceramic powder, 5 parts of chlorinated paraffin, 7 parts of stearic acid, 0.8 part of fatty alcohol-polyoxyethylene ether sodium sulfate, 4.2 parts of potassium trimethylsilanolate and 2 parts of zinc ethylate;

the preparation method of the polymer film comprises the following steps:

s1: heating perfluorinated sulfonic acid resin and urea-formaldehyde resin to 138 ℃ and then melting to obtain a liquid rubber material, then adding chlorinated paraffin and stearic acid into the liquid rubber material, continuously heating to 175 ℃, stirring at the rotating speed of 1200r/min for 1.5h, and cooling to room temperature to obtain a base material;

s2: uniformly mixing microcrystalline cellulose, graphene nanoplatelets, nano silicon carbide, cordierite powder and nano ceramic powder, heating, stirring, adding sodium fatty alcohol-polyoxyethylene ether sulfate, potassium trimethylsilanolate and zinc ethoxide, uniformly mixing, heating to 142 ℃, stirring at the rotating speed of 1100r/min for 2.5h, and cooling to room temperature to obtain a surface modified filler;

s3: heating the base material prepared in the step S1, the surface modified filler prepared in the step S2 and chitosan to 134 ℃, stirring at the rotating speed of 1000r/min for 1.5h, shearing at high temperature in a double-screw extruder, plasticizing at 138 ℃ for 23min, stirring, blending to obtain a mixed melt, conveying the melt into a die head, cooling and solidifying on a rapid cooling roller to obtain a sheet, and then performing bidirectional stretching, extraction and heat setting to obtain the polymer film.

Example 2

A polymer film comprises the following raw materials in parts by weight: 115 parts of perfluorinated sulfonic acid resin, 32 parts of urea-formaldehyde resin, 18 parts of chitosan, 9 parts of microcrystalline cellulose, 1.6 parts of graphene microchip, 10 parts of nano silicon carbide, 9 parts of cordierite powder, 10 parts of nano ceramic powder, 8 parts of chlorinated paraffin, 12 parts of stearic acid, 1 part of fatty alcohol-polyoxyethylene ether sodium sulfate, 5 parts of potassium trimethylsilanolate and 3 parts of zinc ethoxide;

the preparation method of the polymer film comprises the following steps:

s1: heating perfluorinated sulfonic acid resin and urea resin to 145 ℃ and then melting to obtain a liquid rubber material, adding chlorinated paraffin and stearic acid into the liquid rubber material, continuously heating to 180 ℃, stirring at the rotating speed of 1300r/min for 1h, and cooling to room temperature to obtain a base material;

s2: uniformly mixing microcrystalline cellulose, graphene nanoplatelets, nano silicon carbide, cordierite powder and nano ceramic powder, heating, stirring, adding sodium fatty alcohol-polyoxyethylene ether sulfate, potassium trimethylsilanolate and zinc ethoxide, uniformly mixing, heating to 150 ℃, stirring at the rotating speed of 1200r/min for 2h, and cooling to room temperature to obtain a surface modified filler;

s3: heating the base material prepared in the step S1, the surface modified filler prepared in the step S2 and chitosan to 140 ℃, stirring at the rotating speed of 1100r/min for 1.3h, shearing at high temperature in a double-screw extruder, plasticizing at 145 ℃ for 18min, stirring, blending to obtain a mixed melt, conveying the melt into a die head, cooling and solidifying on a rapid cooling roller to obtain a sheet, and then performing bidirectional stretching, extraction and heat setting to obtain the polymer film.

Example 3

A polymer film comprises the following raw materials in parts by weight: 130 parts of perfluorinated sulfonic acid resin, 38 parts of urea-formaldehyde resin, 21 parts of chitosan, 10 parts of microcrystalline cellulose, 2 parts of graphene microchip, 12 parts of nano silicon carbide, 14 parts of cordierite powder, 12 parts of nano ceramic powder, 9 parts of chlorinated paraffin, 15 parts of stearic acid, 1.2 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 6 parts of potassium trimethylsilanolate and 3.2 parts of zinc ethoxide;

the preparation method of the polymer film comprises the following steps:

s1: heating perfluorinated sulfonic acid resin and urea-formaldehyde resin to 150 ℃ and then melting to obtain a liquid rubber material, then adding chlorinated paraffin and stearic acid into the liquid rubber material, continuously heating to 182 ℃, stirring at the rotating speed of 1400r/min for 0.8h, and cooling to room temperature to obtain a base material;

s2: uniformly mixing microcrystalline cellulose, graphene nanoplatelets, nano silicon carbide, cordierite powder and nano ceramic powder, heating, stirring, adding sodium fatty alcohol-polyoxyethylene ether sulfate, potassium trimethylsilanolate and zinc ethoxide, uniformly mixing, heating to 152 ℃, stirring at the rotating speed of 1300r/min for 1.7h, and cooling to room temperature to obtain a surface modified filler;

s3: heating the base material prepared in the step S1, the surface modified filler prepared in the step S2 and chitosan to 143 ℃, stirring at the rotating speed of 1200r/min for 1h, then shearing at high temperature in a double-screw extruder, plasticizing at 150 ℃ for 10min, stirring, blending to obtain a mixed melt, then conveying the melt into a die head, cooling and solidifying on a quick cooling roller to obtain a sheet, and then carrying out bidirectional stretching, extraction and heat setting to obtain the polymer film.

Comparative example 1

The preparation process is basically the same as that of example 2, except that the raw materials for preparing the polymer film lack sodium fatty alcohol-polyoxyethylene ether sulfate, potassium trimethylsilanolate and zinc ethylate.

Comparative example 2

The procedure was substantially the same as in example 2 except that the raw material for preparing the polymer film lacked sodium fatty alcohol-polyoxyethylene ether sulfate.

Comparative example 3

The procedure of example 2 was followed except that potassium trimethylsilanolate was absent from the starting materials used to prepare the polymer film.

Comparative example 4

The preparation process was substantially the same as that of example 2 except that zinc ethoxide was absent from the raw material for preparing the polymer film.

Comparative example 5

A polymer film was prepared by the process of example 1 of the "composite stabilized lithium battery separator" (application publication No. CN 105006591A) in the Chinese patent application document.

The polymer films of examples 1 to 3 and comparative examples 1 to 5 were tested for their longitudinal tensile strength with reference to the GB/T1040.3-2006 test for tensile Properties of plastics, the results of which are shown in the following Table:

experimental project	Longitudinal tensile Strength (MPa)
		Example 1	127.3
Example 2	138.2
		Example 3	132.8
Comparative example 1	84.6
		Comparative example 2	119.1
Comparative example 3	122.4
		Comparative example 4	125.8
Comparative example 5	68.9

(1) From the data of examples 1 to 3, it is clear that the polymer film of the present invention has a large longitudinal tensile strength of 127.3MPa or more, and excellent properties.

(2) As can be seen from the data of example 2 and comparative examples 1 to 4, the simultaneous addition of sodium fatty alcohol-polyoxyethylene ether sulfate, potassium trimethylsilanolate, and zinc ethoxide in the preparation of a polymer film provides a synergistic effect, which synergistically increases the longitudinal tensile strength, because:

the sodium fatty alcohol-polyoxyethylene ether sulfate has good activation and dispersion effects, can increase the pores on the surfaces of the perfluorinated sulfonic acid resin and the urea-formaldehyde resin, and enables potassium trimethylsilanolate to permeate the interiors of the perfluorinated sulfonic acid resin and the urea-formaldehyde resin to form a stable connection structure, so that the sodium fatty alcohol-polyoxyethylene ether sulfate can promote the effects of zinc alcohol, the perfluorinated sulfonic acid resin and the urea-formaldehyde resin; the potassium trimethylsilanolate has strong permeability, can improve the adhesion between the perfluorinated sulfonic acid resin, the urea-formaldehyde resin and the zinc ethylate, enables the perfluorinated sulfonic acid resin, the urea-formaldehyde resin and the zinc ethylate to be uniformly dispersed in the perfluorinated sulfonic acid resin and the urea-formaldehyde resin, provides an acting point for the surface modification of the perfluorinated sulfonic acid resin and the urea-formaldehyde resin, and is beneficial to improving the longitudinal tensile strength of a polymer film.

(3) As can be seen from the data of examples 1-3 and comparative example 5, the longitudinal tensile strength of the polymer film prepared by the invention is obviously superior to that of the polymer film prepared by the prior art, and is at least higher than 84.8%, thus solving the technical problem that the polymer film prepared by the prior art has poor longitudinal tensile strength.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.