CN111875745A - Grafting reaction extrusion production of super-hydrophilic PVDF membrane material and preparation process thereof - Google Patents
Grafting reaction extrusion production of super-hydrophilic PVDF membrane material and preparation process thereof Download PDFInfo
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- CN111875745A CN111875745A CN202010563462.XA CN202010563462A CN111875745A CN 111875745 A CN111875745 A CN 111875745A CN 202010563462 A CN202010563462 A CN 202010563462A CN 111875745 A CN111875745 A CN 111875745A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention discloses a method for producing a super-hydrophilic PVDF membrane material by grafting reaction extrusion, wherein in the extrusion process of the PVDF membrane material, a functional monomer with extremely high hydrophilicity, namely choline polyphosphate ethylene glycol acrylate and another antibacterial monomer with synergistic effect, namely 2-methyl-2-acrylic acid-2-sulfoethyl ester, are added, and the grafting reaction is carried out on molecular chains of the PVDF membrane material under the action of an initiator 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane (DBPH) and a catalyst ammonium ceric nitrate. The PVDF prepared by the grafting reaction not only maintains the original comprehensive performance of the PVDF, but also greatly improves the water flux from the temperature of 90 ℃ before the static contact angle is not changed to the temperature of 15 ℃ after the grafting modification, and shows the super-hydrophilicity of the PVDF membrane material.
Description
Technical Field
The invention relates to a method for producing a super-hydrophilic PVDF membrane material by grafting reaction and extrusion.
Background
Polyvinylidene fluoride (PVDF) is an excellent polymer material, has the characteristics of high strength, high temperature resistance and the like, and is widely applied to biopharmaceuticals, automobile decorations, home appliance shells and the like. But because the PVDF membrane material has strong hydrophobicity, serious membrane pollution is easily caused, the service life of the PVDF membrane material is shortened, and the application range of the PVDF membrane material is limited. The method is characterized in that the surface modification is carried out on the PVDF membrane material or the hydrophilic organic matter is added by a blending method to enhance the hydrophilicity of the PVDF membrane material, but the storage effect is poor, or the compatibility between the hydrophilic organic matter and the PVDF by the blending method is poor, and the PVDF membrane material is easy to fall off after the membrane is formed.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of poor antibacterial performance and poor antibacterial performance of a PVDF material in the prior art, and provides a super-hydrophilic PVDF membrane material obtained through a grafting reaction and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the super-hydrophilic PVDF membrane material produced by the grafting reaction extrusion comprises the following components in parts by weight:
100 parts of PVDF
5-7 parts of choline polyphosphate ethylene glycol acrylate
1-1.5 parts of 2-methyl-2-acrylic acid-2-sulfoethyl ester
0.3-0.5 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane
0.2-0.3 part of ammonium ceric nitrate.
Preferably, the composition comprises the following components in parts by weight:
100 parts of PVDF
6 parts of choline polyphosphate ethylene glycol acrylate
2-methyl-2-propenoic acid-2-sulfoethyl ester 1.2 weight portions
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.4 part
0.2-0.3 part of ammonium ceric nitrate.
The preparation process for producing the super-hydrophilic PVDF membrane material by grafting reaction extrusion is characterized by comprising the following steps:
s1, extruding on a double-screw extruder with the length-diameter ratio L/D being 48, wherein the double-screw extruder is provided with 12 sections and 2 feed inlets, the first feed inlet is positioned at the position of the extruder 1D, and the second feed inlet is positioned at the position of SD of the fifth section of the extruder;
s2, feeding PVDF from a feed inlet 1# of a first section 1D of the twin-screw extruder;
s3, mixing the choline ethylene glycol polyphosphate, 2-methyl-2-acrylic acid-2-sulfoethyl ester, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and cerium ammonium nitrate according to a ratio, and feeding from a second feeding port 2# of the double-screw extruder; the extrusion processing temperature is gradually increased from 140-150 ℃ of the first section to 250 ℃ of the eighth section, and the extrusion temperature of the tail section of the extruder is gradually reduced to 170-180 ℃.
Further, the process temperature of each section in S4 is set as follows:
140 to 150 ℃, 160 to 170 ℃, 170 to 180 ℃, 180 to 190 ℃, 190 to 200 ℃, 210 to 220 ℃, 230 to 240 ℃, 240 to 250 ℃, 220 to 230 ℃, 210 to 220 ℃, 190 to 195 ℃ and 170 to 180 ℃.
Further, the feeding rate of the first feeding port was 85kg/h, the running rate of the twin-screw extruder was 120r/min, and the feeding rate of the second feeding port was 4.2 kg/h.
Furthermore, the average residence time of the materials in the extruder is 1.5-3 min.
The invention has the following beneficial effects: in the process of extruding the PVDF, functional monomer choline polyphosphate ethylene glycol acrylate with extremely strong hydrophilicity and another antibacterial monomer 2-methyl-2-acrylic acid-2-sulfoethyl ester with synergistic effect are added, and grafting reaction is carried out on molecular chains of the PVDF under the action of an initiator 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane (DBPH) and a catalyst ammonium ceric nitrate. The PVDF prepared by the grafting reaction not only maintains the original comprehensive performance of the PVDF, but also greatly improves the water flux from the temperature of 90 ℃ before the static contact angle is not changed to the temperature of 15 ℃ after the grafting modification, and shows the super-hydrophilicity of the PVDF membrane material.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Examples
A super-hydrophilic PVDF membrane material produced by graft reaction extrusion comprises the following components in parts by weight:
100 parts of PVDF
6 parts of choline polyphosphate ethylene glycol acrylate
2-methyl-2-propenoic acid-2-sulfoethyl ester 1.2 weight portions
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.4 part
0.2-0.3 part of ammonium ceric nitrate.
The preparation process for producing the super-hydrophilic PVDF membrane material by grafting reaction extrusion comprises the following steps:
s1, extruding on a double-screw extruder with the length-diameter ratio L/D being 48, wherein the double-screw extruder is provided with 12 sections and 2 feed inlets, the first feed inlet is positioned at the position of the extruder 1D, and the second feed inlet is positioned at the position of SD of the fifth section of the extruder;
s2, feeding PVDF from a feed inlet 1# of a first section 1D of the double-screw extruder, wherein the feeding speed is 85kg/h, and the running speed of the double-screw extruder is 120 r/min;
s3, mixing the choline ethylene glycol polyphosphate, 2-methyl-2-acrylic acid-2-sulfoethyl ester, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and the ammonium ceric nitrate according to the proportion, and feeding the mixture from a second feeding port 2# of the double-screw extruder at a feeding speed of 4.2 kg/h; the extrusion processing temperature of each section is 140-150 ℃, 160-170 ℃, 170-180 ℃, 180-190 ℃, 190-200 ℃, 210-220 ℃, 230-240 ℃, 240-250 ℃, 220-230 ℃, 210-220 ℃, 190-195 ℃ and 170-180 ℃; the average residence time of the materials in the extruder is 1.5-3 min.
Comparative example 1
Method for preparing PVDF membrane material by adding hydrophilic organic matter by blending method
100 parts of PVDF
10 portions of Cellulose Acetate (CA)
40 parts of polyvinyl alcohol (PVA)
The preparation process comprises the steps of sequentially adding PVDF, cellulose acetate and polyvinyl alcohol into a high-speed mixer according to the proportion, stirring for 8-10 minutes, and discharging for later use;
s2, adding the mixture to a twin-screw extruder with the rotating speed of 120r/min at the feeding rate of 85kg/h for extrusion.
The process temperature settings for each section were as follows:
140 to 150 ℃, 170 to 180 ℃, 200 to 210 ℃, 210 to 220 ℃, 220 to 230 ℃, 230 to 240 ℃, 240 to 250 ℃, 220 to 230 ℃, 210 to 220 ℃, 190 to 200 ℃, 180 to 190 ℃ and 170 to 180 DEG C
Comparative example 2
The method for modifying the hydrophobicity of the PVDF membrane material by grafting comprises the following steps:
s1, firstly, carrying out alkali liquor pretreatment before surface grafting modification on the 0.45 mu m PVDF membrane material: preparing a 10% KOH-ethanol solution/water of 1: 1, soaking the PVDF membrane material in the solution at 60 ℃ for 120min, then putting the PVDF membrane material into a constant-temperature drying oven at 50 ℃ for drying for 0.5h, and sealing and storing for later use (the PVDF treated by KOH-ethanol solution can remove hydrogen fluoride on the surface of the membrane to form a carbonic acid conjugated double bond, which is beneficial to a grafting reaction;
s2, preparing an n-propanol solution containing 8% of acrylic acid and 1% of Benzoyl Peroxide (BPO), immersing the PVDF treated by the alkali liquor into the prepared solution, heating the solution in a constant-temperature drying oven at 70 ℃ for 4 hours, taking out a sample, then immersing the sample into deionized water, and cleaning the sample for 24 hours at normal temperature to obtain a test sample.
Wherein the 0.45 μm PVDF membrane is purchased from Shanghai Puyi Biotechnology, Inc., and the n-propanol is purchased from Zibohai Zhengcheng chemical industries, Inc.
Typical Performance determination
Test for antibacterial Properties
The special material sources are as follows:
1. choline polyphosphate ethylene glycol acrylate was purchased from Jinjinle (Hunan) chemical Co., Ltd
2. 2-methyl-2-propenoic acid-2-sulfoethyl ester was purchased from Hubei Xinkang pharmaceutical chemical Co., Ltd
3. Ammonium cerium nitrate was purchased from Yamada New materials Co., Ltd, Shandong
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. 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.
Claims (6)
1. The method for producing the super-hydrophilic PVDF membrane material by grafting reaction extrusion is characterized by comprising the following components in parts by weight:
100 parts of PVDF
5-7 parts of choline polyphosphate ethylene glycol acrylate
1-1.5 parts of 2-methyl-2-acrylic acid-2-sulfoethyl ester
0.3-0.5 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane
0.2-0.3 part of ammonium ceric nitrate.
2. The grafting reaction extrusion production super-hydrophilic PVDF film material as described in claim 1, which comprises the following components by weight:
100 parts of PVDF
6 parts of choline polyphosphate ethylene glycol acrylate
2-methyl-2-propenoic acid-2-sulfoethyl ester 1.2 weight portions
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.4 part
0.2-0.3 part of ammonium ceric nitrate.
3. The preparation process for producing the super-hydrophilic PVDF membrane material by the grafting reaction and extrusion as in claim 1, which is characterized by comprising the following steps:
s1, extruding on a double-screw extruder with the length-diameter ratio L/D being 48, wherein the double-screw extruder is provided with 12 sections and 2 feed inlets, the first feed inlet is positioned at the position of the extruder 1D, and the second feed inlet is positioned at the position of SD of the fifth section of the extruder;
s2, feeding PVDF from a feed inlet 1# of a first section 1D of the twin-screw extruder;
s3, mixing the choline ethylene glycol polyphosphate, 2-methyl-2-acrylic acid-2-sulfoethyl ester, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and cerium ammonium nitrate according to a ratio, and feeding from a second feeding port 2# of the double-screw extruder; the extrusion processing temperature is gradually increased from 140-150 ℃ of the first section to 250 ℃ of the eighth section, and the extrusion temperature of the tail section of the extruder is gradually reduced to 170-180 ℃.
4. The preparation process for producing the super-hydrophilic PVDF film material by the grafting reaction extrusion as described in claim 3, wherein the process temperature of each section in S3 is set as follows:
140 to 150 ℃, 160 to 170 ℃, 170 to 180 ℃, 180 to 190 ℃, 190 to 200 ℃, 210 to 220 ℃, 230 to 240 ℃, 240 to 250 ℃, 220 to 230 ℃, 210 to 220 ℃, 190 to 195 ℃ and 170 to 180 ℃.
5. The preparation process for producing the super-hydrophilic PVDF membrane material by the grafting reaction extrusion as described in claim 3, wherein the feeding speed of the first feeding port is 85kg/h, the running speed of the twin-screw extruder is 120r/min, and the feeding speed of the second feeding port is 4.2 kg/h.
6. The preparation process for producing the super-hydrophilic PVDF film material through the grafting reaction and extrusion as in any one of claims 3-5, wherein the average residence time of the materials in the extruder is 1.5-3 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010563462.XA CN111875745A (en) | 2020-06-19 | 2020-06-19 | Grafting reaction extrusion production of super-hydrophilic PVDF membrane material and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010563462.XA CN111875745A (en) | 2020-06-19 | 2020-06-19 | Grafting reaction extrusion production of super-hydrophilic PVDF membrane material and preparation process thereof |
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| CN111875745A true CN111875745A (en) | 2020-11-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024096444A1 (en) * | 2022-11-01 | 2024-05-10 | 한국화학연구원 | Graft modified polymer and preparation method therefor |
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2020
- 2020-06-19 CN CN202010563462.XA patent/CN111875745A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024096444A1 (en) * | 2022-11-01 | 2024-05-10 | 한국화학연구원 | Graft modified polymer and preparation method therefor |
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Application publication date: 20201103 |
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