CN113429618B - Hydrophilic modification method of polyolefin material, hydrophilic polyolefin material and reaction liquid for hydrophilic modification of polyolefin material - Google Patents
Hydrophilic modification method of polyolefin material, hydrophilic polyolefin material and reaction liquid for hydrophilic modification of polyolefin material Download PDFInfo
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- CN113429618B CN113429618B CN201810792452.6A CN201810792452A CN113429618B CN 113429618 B CN113429618 B CN 113429618B CN 201810792452 A CN201810792452 A CN 201810792452A CN 113429618 B CN113429618 B CN 113429618B
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a hydrophilic modification method of a polyolefin material, a hydrophilic polyolefin material and a reaction solution for hydrophilic modification of the polyolefin material, and belongs to the technical field of chemical treatment of the polyolefin material. The hydrophilic modification method of the polyolefin material comprises the steps of carrying out surface oxidation activation treatment on the polyolefin material, and then adopting polyvinylpyrrolidone to graft polymerize; the K value of the polyvinylpyrrolidone is 88-98. The hydrophilic modification method of the polyolefin material has simple process and low cost, and the polyvinylpyrrolidone with K value of 88-98 is used for carrying out graft polymerization on the polyolefin subjected to surface activation, so that the water contact angle of the polyolefin material is greatly reduced, and particularly for the polypropylene material, the water contact angle of the polypropylene material can be reduced from 100-150 ℃ to below 10 ℃ before hydrophilic modification, and the application range of the polyolefin material is greatly expanded.
Description
Technical Field
The invention relates to a hydrophilic modification method of a polyolefin material, a hydrophilic polyolefin material and a reaction solution for hydrophilic modification of the polyolefin material, and belongs to the technical field of chemical treatment of the polyolefin material.
Background
Polyolefin such as polyethylene and polypropylene is a polymer material with low price, excellent chemical stability and thermal stability, the polyolefin material prepared from the polyolefin material is widely applied to the fields of industry, agriculture, medicine, environmental protection, batteries and the like, and particularly polyethylene microporous films and polypropylene microporous films prepared from the polyolefin material are widely applied to the field of lithium ion batteries due to good insulativity and lithium ion conductivity. However, such polyolefin has poor hydrophilicity and is not easily chemically modified because of its low polarity and high crystallinity.
For example, a polypropylene microporous membrane for a lithium ion battery is difficult to infiltrate into the interior of the polypropylene microporous membrane in an aqueous solution, so that the polypropylene microporous membrane cannot be directly applied to the field of the nickel-hydrogen battery and other aqueous batteries. The nickel-hydrogen battery belongs to a secondary battery, and has lower energy density than a lithium ion battery, but the electrolyte is KOH aqueous solution, so that the electrolyte cannot generate flatulence when the temperature is high, and the safety is better. In order to enable the conventional polyolefin microporous membrane to be applied to the field of nickel-hydrogen batteries, the conventional polyolefin microporous membrane needs to be subjected to hydrophilization treatment.
In the prior art, various surface activation treatments such as ozone treatment, plasma treatment, ultraviolet irradiation treatment, high-voltage discharge treatment, corona discharge treatment and the like are required to improve the hydrophilicity of such polyolefin materials. A method for preparing a modified polyolefin nonwoven membrane by glow discharge is disclosed in chinese patent application publication No. CN107887555a, which comprises the steps of: stirring a vinyl silane coupling agent in water to obtain vinyl silicon dioxide nanoparticle hydrosol, adding a hydrophilic grafting monomer and an initiator into the hydrosol, and introducing nitrogen for later use; and (3) passing the polyolefin non-woven diaphragm through a corona processor at a speed of 2-6 m/min under a voltage of 3.0-6.0 kV, then immediately putting the polyolefin non-woven diaphragm into hydrosol containing grafting monomers and initiating silicon nanoparticles for grafting modification, taking out the modified polyolefin non-woven diaphragm after reaction, cleaning and drying to obtain the modified polyolefin non-woven diaphragm. The method can improve the hydrophilicity of the polyolefin non-woven membrane, but has the disadvantages of complex process and high cost.
Disclosure of Invention
The invention aims to provide a hydrophilic modification method of a polyolefin material, which is simple in process and low in cost.
The invention also provides a hydrophilic polyolefin material prepared by the hydrophilic modification method and a reaction solution for hydrophilic modification of the polyolefin material.
In order to achieve the above object, the hydrophilic modification method of the polyolefin material of the present invention adopts the following technical scheme:
a hydrophilic modification method of polyolefin material comprises performing surface oxidation activation treatment on polyolefin material, and then adopting polyvinylpyrrolidone to graft polymerize; the K value of the polyvinylpyrrolidone is 88-98.
The hydrophilic modification method of the polyolefin material has simple process and low cost, and the polyvinylpyrrolidone with K value of 88-98 is used for carrying out graft polymerization on the polyolefin subjected to surface activation, so that the water contact angle of the polyolefin material is greatly reduced, and particularly for the polypropylene material, the water contact angle of the polypropylene material can be reduced from 100-150 ℃ to below 10 ℃ before hydrophilic modification, and the application range of the polyolefin material is greatly expanded.
The surface oxidation activation treatment is corona discharge treatment. In the corona discharge treatment process, polyolefin molecules can be subjected to chemical bond fracture in a high-frequency and high-pressure environment, so that the surface roughness and the surface area of a polyolefin material are increased, meanwhile, a large amount of ozone is generated by a corona device during discharge, and the ozone serving as a strong oxidant can be subjected to hydrogen abstraction reaction on the surface of the polyolefin material to form unsaturated bonds.
The graft polymerization is carried out under an initiator; the initiator is at least one of butanedione, diphenyl ketone and xanthone.
Preferably, the polyolefin material is a polypropylene material.
Further preferably, the polyolefin material is a polypropylene microporous membrane. The water contact angle of the polypropylene microporous membrane is 100-150 degrees, the polypropylene microporous membrane is not soaked after being contacted with KOH solution, the water contact angle of the polypropylene microporous membrane is reduced to below 10 degrees after being modified by adopting the hydrophilic modification method, so that the polypropylene microporous membrane is easy to soak after being contacted with the KOH solution, and the defect that the conventional polypropylene microporous membrane cannot be applied to a nickel-hydrogen battery can be overcome by adopting the polypropylene microporous membrane modified by adopting the hydrophilic modification method.
Preferably, the polypropylene microporous membrane has a porosity of 43 to 50%. The aperture of the polypropylene microporous membrane is 50-120 nm.
Preferably, the grafting polymerization is to soak the polyolefin material subjected to surface oxidation activation treatment in a reaction solution; the reaction solution comprises the following components in percentage by mass: 5 to 30 percent of polyvinylpyrrolidone, 0.5 to 2 percent of initiator and the balance of solvent.
Preferably, the solvent is a mixture of an organic solvent and water. The organic solvent is at least one of dimethylacetamide, ethanol and acetone. The mass ratio of the organic solvent to the water is 3-5:1.
Preferably, the soaking time is 5-10 min.
Preferably, the hydrophilic modification method of the polyolefin material further comprises the step of drying the polyolefin material subjected to graft polymerization at 50-80 ℃. The drying treatment time is 15-30 min.
The hydrophilic polyolefin material adopts the following technical scheme:
a hydrophilic polyolefin material prepared by the hydrophilic modification method of the polyolefin material.
The hydrophilic polyolefin material has a low water contact angle, can be well infiltrated by water, and has a wide application prospect.
The reaction liquid for hydrophilic modification of polyolefin materials adopts the following technical scheme:
the reaction liquid for hydrophilic modification of the polyolefin material comprises the following components in percentage by mass: 5 to 30 percent of polyvinylpyrrolidone, 0.5 to 2 percent of initiator and the balance of solvent; the K value of the polyvinylpyrrolidone is 88-98.
The reaction liquid for hydrophilic modification of the polyolefin material can greatly reduce the contact angle of the polyolefin material when being used for hydrophilic modification of the polyolefin material.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments.
The pore diameter of the polypropylene microporous membrane adopted in the specific embodiment is 50-120 nm.
Example 1
The reaction liquid for hydrophilic modification of polyolefin in the embodiment comprises the following components in percentage by mass: 8% of polyvinylpyrrolidone, 1% of benzophenone and the balance of solvent; the solvent is prepared by mixing dimethylacetamide and deionized water according to a mass ratio of 8:2; when the reaction liquid is prepared, polyvinylpyrrolidone, benzophenone and solvent are added into a stirring kettle according to the proportion, and the mixture is uniformly mixed; the K value of the polyvinylpyrrolidone used is 90.
The polyolefin material of this embodiment is a polypropylene microporous membrane with a porosity of 45%, and the hydrophilic modification method comprises the following steps:
1) Fixing a conventional polypropylene microporous membrane to be treated in an unreeling mechanism, controlling the polypropylene microporous membrane to enter a corona device with a treatment voltage of 220V according to the speed of 15m/min by a motor, and carrying out corona discharge treatment for 1min in the corona device;
2) Immersing the polypropylene microporous membrane subjected to corona discharge treatment into a reaction solution at the temperature of 22 ℃ at the speed of 15m/min, and immersing for 8min in the reaction solution;
3) Sequentially passing the soaked polypropylene microporous membrane through two containers filled with deionized water to respectively carry out first cleaning and second cleaning; controlling the temperature of deionized water to be 25 ℃ in the cleaning process;
4) And then the cleaned polypropylene microporous membrane is sent into a baking oven to be dried at 75 ℃ for 20min, and the dried polypropylene microporous membrane is pulled to a winding structure to form a winding core, so that the production process of the hydrophilic polypropylene microporous membrane is completed.
The hydrophilic polyolefin material of this example was produced by the hydrophilic modification method of this example.
The water contact angle of the polypropylene microporous membrane before hydrophilic modification is 120 degrees, the water contact angle after modification by the hydrophilic modification method of the embodiment is 8 degrees, obvious pore blocking is avoided, the contact angle of an alkaline solution is basically consistent with the contact angle of water, and the requirement of the alkaline battery on the circularity can be met.
Example 2
The reaction liquid for hydrophilic modification of polyolefin in the embodiment comprises the following components in percentage by mass: 6% of polyvinylpyrrolidone, 2% of benzophenone and the balance of solvent; the solvent is prepared by mixing dimethylacetamide and deionized water according to a mass ratio of 8:2; when the reaction liquid is prepared, polyvinylpyrrolidone, benzophenone and solvent are added into a stirring kettle according to the proportion, and the mixture is uniformly mixed; the K value of the polyvinylpyrrolidone used was 95.
The polyolefin material of this example is a polypropylene microporous membrane with a porosity of 47%, and the hydrophilic modification method comprises the following steps:
1) Fixing a conventional polypropylene microporous membrane to be treated in an unreeling mechanism, controlling the polypropylene microporous membrane to enter a corona device with a treatment voltage of 220V according to the speed of 12m/min by a motor, and carrying out corona discharge treatment for 1min in the corona device;
2) Immersing the polypropylene microporous membrane subjected to corona discharge treatment into a reaction solution at the temperature of 22 ℃ at the speed of 12m/min, and immersing for 8min in the reaction solution;
3) Sequentially passing the soaked polypropylene microporous membrane through two containers filled with deionized water to respectively carry out first cleaning and second cleaning; controlling the temperature of deionized water to be 25 ℃ in the cleaning process;
4) And then the cleaned polypropylene microporous membrane is sent into a baking oven to be dried at 75 ℃ for 20min, and the dried polypropylene microporous membrane is pulled to a winding structure to form a winding core, so that the production process of the hydrophilic polypropylene microporous membrane is completed.
The hydrophilic polyolefin material of this example was produced by the hydrophilic modification method of this example.
The water contact angle of the polypropylene microporous membrane before hydrophilic modification is 120 degrees, the water contact angle after modification by the hydrophilic modification method of the embodiment is 6 degrees, obvious pore blocking is avoided, the contact angle of an alkaline solution is basically consistent with the contact angle of water, and the requirement of the alkaline battery on the circularity can be met.
Example 3
The reaction liquid for hydrophilic modification of polyolefin in the embodiment comprises the following components in percentage by mass: 30% of polyvinylpyrrolidone, 1.5% of benzophenone and the balance of solvent; the solvent is prepared by mixing acetone and deionized water according to the mass ratio of 6:2; when the reaction liquid is prepared, polyvinylpyrrolidone, benzophenone and solvent are added into a stirring kettle according to the proportion, and the mixture is uniformly mixed; the K value of the polyvinylpyrrolidone used was 88.
The polyolefin material of this embodiment is a polypropylene microporous membrane with a porosity of 50%, and the hydrophilic modification method comprises the following steps:
1) Fixing a conventional polypropylene microporous membrane to be treated in an unreeling mechanism, controlling the polypropylene microporous membrane to enter a corona device with a treatment voltage of 220V according to the speed of 15m/min by a motor, and carrying out corona discharge treatment for 1min in the corona device;
2) Immersing the polypropylene microporous membrane subjected to corona discharge treatment into a reaction solution at a temperature of 20 ℃ at a speed of 15m/min, and immersing the polypropylene microporous membrane in the reaction solution for 10min;
3) Sequentially passing the soaked polypropylene microporous membrane through two containers filled with deionized water to respectively carry out first cleaning and second cleaning; controlling the temperature of deionized water to be 25 ℃ in the cleaning process;
4) And then the cleaned polypropylene microporous membrane is sent into a baking oven to be dried at 80 ℃ for 15min, and the dried polypropylene microporous membrane is pulled to a winding structure to form a winding core, so that the production process of the hydrophilic polypropylene microporous membrane is completed.
The hydrophilic polyolefin material of this example was produced by the hydrophilic modification method of this example.
The water contact angle of the polypropylene microporous membrane before hydrophilic modification is 120 degrees, the water contact angle after modification by the hydrophilic modification method of the embodiment is 7.5 degrees, obvious pore blocking is avoided, the contact angle of an alkaline solution is basically consistent with the contact angle of water, and the requirement of the alkaline battery on the circularity can be met.
Example 4
The reaction liquid for hydrophilic modification of polyolefin in the embodiment comprises the following components in percentage by mass: 20% of polyvinylpyrrolidone, 0.5% of benzophenone and the balance of solvent; the solvent is formed by mixing ethanol and deionized water according to the mass ratio of 10:2; when the reaction liquid is prepared, polyvinylpyrrolidone, benzophenone and solvent are added into a stirring kettle according to the proportion, and the mixture is uniformly mixed; the K value of the polyvinylpyrrolidone used was 98.
The polyolefin material of this embodiment is a polypropylene microporous membrane with a porosity of 43%, and the hydrophilic modification method comprises the following steps:
1) Fixing a conventional polypropylene microporous membrane to be treated in an unreeling mechanism, controlling the polypropylene microporous membrane to enter a corona device with a treatment voltage of 220V according to the speed of 15m/min by a motor, and carrying out corona discharge treatment for 1min in the corona device;
2) Immersing the polypropylene microporous membrane subjected to corona discharge treatment into a reaction solution at the temperature of 25 ℃ at the speed of 15m/min for 5min;
3) Sequentially passing the soaked polypropylene microporous membrane through two containers filled with deionized water to respectively carry out first cleaning and second cleaning; controlling the temperature of deionized water to be 25 ℃ in the cleaning process;
4) And then the cleaned polypropylene microporous membrane is sent into a baking oven to be dried at 50 ℃ for 30min, and the dried polypropylene microporous membrane is pulled to a winding structure to form a winding core, so that the production process of the hydrophilic polypropylene microporous membrane is completed.
The hydrophilic polyolefin material of this example was produced by the hydrophilic modification method of this example.
The water contact angle of the polypropylene microporous membrane before hydrophilic modification is 120 degrees, the water contact angle after modification by the hydrophilic modification method of the embodiment is 4 degrees, obvious pore blocking is avoided, the contact angle of an alkaline solution is basically consistent with the contact angle of water, and the requirement of the alkaline battery on the circularity can be met.
Comparative example 1
The hydrophilic modification method of the polyolefin material of this comparative example was identical to that of example 1 except that polyvinylpyrrolidone in the reaction liquid used had a K value of 85. The water contact angle of the hydrophilically modified polypropylene microporous membrane is 25 degrees.
Comparative example 2
The hydrophilic modification method of the polyolefin material of this comparative example was identical to that of example 1 except that the K value of polyvinylpyrrolidone in the reaction liquid used was 100. The water contact angle of the hydrophilically modified polypropylene microporous membrane is 3 degrees, but the requirement of charging and discharging of an alkaline battery can not be met due to severe hole blocking.
Claims (6)
1. A method for the hydrophilic modification of a polyolefin material, characterized by: comprises the steps of carrying out surface oxidation activation treatment on polyolefin materials, and then adopting polyvinylpyrrolidone for graft polymerization; the K value of the polyvinylpyrrolidone is 88-98; the polyolefin material is a polypropylene microporous membrane; the porosity of the polypropylene microporous membrane is 43-50%, and the pore diameter of the polypropylene microporous membrane is 50-120 nm; the surface oxidation activation treatment is corona discharge treatment; the graft polymerization is to soak the polyolefin material subjected to surface oxidation activation treatment in a reaction solution; the reaction solution comprises the following components in percentage by mass: 5-30% of polyvinylpyrrolidone, 0.5-2% of initiator and the balance of solvent.
2. The method for the hydrophilic modification of a polyolefin material according to claim 1, wherein: the initiator is at least one of butanedione, diphenyl ketone and xanthone.
3. The method for the hydrophilic modification of a polyolefin material according to claim 1, wherein: the solvent is a mixture of an organic solvent and water; the organic solvent is at least one of dimethylacetamide, ethanol and acetone.
4. The method for the hydrophilic modification of a polyolefin material according to claim 1, wherein: the soaking time is 5-10 min.
5. The method for the hydrophilic modification of a polyolefin material according to claim 1, wherein: and drying the polyolefin material subjected to graft polymerization at 50-80 ℃.
6. A hydrophilic polyolefin material produced by the hydrophilic modification method of a polyolefin material according to claim 1.
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| CN201810792452.6A CN113429618B (en) | 2018-07-18 | 2018-07-18 | Hydrophilic modification method of polyolefin material, hydrophilic polyolefin material and reaction liquid for hydrophilic modification of polyolefin material |
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| CN201810792452.6A CN113429618B (en) | 2018-07-18 | 2018-07-18 | Hydrophilic modification method of polyolefin material, hydrophilic polyolefin material and reaction liquid for hydrophilic modification of polyolefin material |
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| CN1654519A (en) * | 2005-03-03 | 2005-08-17 | 北京化工大学 | Reaction liquid for modifying polymer film and modifying method |
| CN1817427A (en) * | 2006-01-13 | 2006-08-16 | 浙江大学 | Polymer microporous modification by corona induced grafting technology |
| US20070043160A1 (en) * | 2003-04-17 | 2007-02-22 | Medtronic Vascular, Inc. | Coating for biomedical devices |
| CN105251095A (en) * | 2015-10-22 | 2016-01-20 | 江苏康诺医疗器械有限公司 | PVC ultra-lubricating catheter and preparation method for same |
| CN107887555A (en) * | 2017-11-10 | 2018-04-06 | 青岛大学 | A kind of method that glow discharge prepares improved polyalkene non-woven membrane |
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Patent Citations (5)
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| US20070043160A1 (en) * | 2003-04-17 | 2007-02-22 | Medtronic Vascular, Inc. | Coating for biomedical devices |
| CN1654519A (en) * | 2005-03-03 | 2005-08-17 | 北京化工大学 | Reaction liquid for modifying polymer film and modifying method |
| CN1817427A (en) * | 2006-01-13 | 2006-08-16 | 浙江大学 | Polymer microporous modification by corona induced grafting technology |
| CN105251095A (en) * | 2015-10-22 | 2016-01-20 | 江苏康诺医疗器械有限公司 | PVC ultra-lubricating catheter and preparation method for same |
| CN107887555A (en) * | 2017-11-10 | 2018-04-06 | 青岛大学 | A kind of method that glow discharge prepares improved polyalkene non-woven membrane |
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