CN114891265A - Method for modifying and functionalizing inner surface of tubular perforated material - Google Patents
Method for modifying and functionalizing inner surface of tubular perforated material Download PDFInfo
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- CN114891265A CN114891265A CN202210348283.3A CN202210348283A CN114891265A CN 114891265 A CN114891265 A CN 114891265A CN 202210348283 A CN202210348283 A CN 202210348283A CN 114891265 A CN114891265 A CN 114891265A
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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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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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
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- C08J2203/06—CO2, N2 or noble gases
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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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
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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
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- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The application discloses a method for modifying and functionalizing the inner surface of a tubular perforated material, which comprises the following steps: (S1) obtaining a tubular open-cell material; (S2) allowing a modifying reagent to flow through the inside of the tubular open-pore material by a power source, and modifying to obtain the modified material. The method comprises the steps that a modification reagent is driven into or drawn out from one end of a tubular perforated material through an external power source, so that the modification reagent flows through an internal channel of the tubular perforated material in a large quantity; the collected modifying reagent solution is extracted by the power source, so that the modifying reagent circularly flows in the inner channel of the tubular open-pore material, and the modification and functionalization of the three-dimensional open-pore material with the compact surface layer are completed, thereby improving the utilization rate of the modifying reagent and saving the cost; the method can endow the material with the functions of adsorption, separation, enrichment, filtration and the like in one step by changing the internal coating material.
Description
Technical Field
The application relates to a method for modifying and functionalizing the inner surface of a tubular open-cell material, belonging to the field of functionalization of the inner surface of a polymer high-open-cell material.
Background
The porous material such as active carbon has wide application in industrial production and daily life, and the high-open-pore material with a compact skin layer has good application prospect in the fields of filtration, adsorption and separation due to the high specific surface area and the integrated compact skin layer, such as PP-based supercritical fluid (CO) with chemical resistance, weather resistance and stable performance 2 、N 2 ) Extruding the foamed material. However, the high open pore size and the high specific surface area are difficult to meet the complex application requirements, so that specific functional modification needs to be performed on the interior of the material to endow the material with functions of separation, adsorption, filtration, enrichment and the like.
At present, the modification of the porous material is mainly directed at a two-dimensional material and a porous three-dimensional material without a skin layer, the modification of the material does not need complex technology, and a modification reagent enters the interior of the material through physical oscillation, plasma treatment or an immersion method, so that the interior modification of the material can be realized. For example, chinese patent CN101439265A discloses a hydrophilic modification method for polymer microporous membrane. The method comprises adsorbing organic monomer on the surface of polymer microporous membrane, placing between two discharge electrodes for dielectric barrier discharge, performing normal pressure dielectric barrier discharge plasma treatment, and cleaning and drying to obtain hydrophilic polymer microporous membrane. The method has the characteristics of simple process, convenient operation, high processing speed, good and lasting treatment effect, low cost, difficult environmental pollution, energy conservation and the like. Chinese patent CN108252110B discloses a method for depositing polymer material on the surface of fabric and the fabric prepared by the method. The method endows the material with functionality by depositing the curing agent on the surface of the fabric and then reacting with the curing agent after electrostatic spinning deposition, and improves the washing resistance of the material.
Internal modification of three-dimensional commercial sponge cellular materials without a dense skin has also employed impregnation and shaking to get the modifying agent into the interior of the material. For example, Chinese patent CN111592683A discloses a super-hydrophobic oil-absorbing sponge, a preparation method and an application thereof, wherein a modification reagent is prepared by mixing optical cement, silica particles, disulfide particles and solvent tetrahydrofuran, and the sponge is immersed in the modification reagent. The method is simple, the reagent is easy to obtain, the method is economic and environment-friendly, and no expensive equipment is needed. Chinese invention patent CN112808032A discloses a method for enhancing the hydrophobic property of a PVDF hollow fiber membrane. The PVDF hollow fiber membrane treated by polyethylene glycol is immersed in the PVEF/PVC composite membrane casting solution doped with nano graphite, so that the hydrophobicity of the PVDF hollow fiber membrane is obviously improved.
The above method, although simple and easy to operate, has difficulty in solving the problem of internal modification of materials having a dense skin.
The preparation method of polyolefin extrusion foaming material is disclosed, mainly utilizes the difference of internal structure caused by gradient change of temperature from center to edge after melt extrusion die head, generally selects incompatible polymer system to promote cell breakage in foaming process, thereby improving the aperture ratio of material to broaden its application, and fully utilizes the performance advantage of polyolefin material under specific environment.
The extrusion foaming material has the characteristics of compact skin, high open pore structure, high specific surface area and certain flux in the preparation process, and meanwhile, the incomplete foam wall after opening pores has a certain interception function. In addition, the composite material has good chemical resistance and weather resistance, so that the composite material can be applied to the fields of filtration, adsorption, separation and the like. However, due to its dense skin, the current technical modification and functionalization techniques have difficulty in achieving controllable coating modification of the interior of the material, and severely limit the functional application of polyolefin materials.
Disclosure of Invention
According to one aspect of the application, a method for modifying and functionalizing the inner surface of a tubular open-pore material is provided, wherein a modifying reagent is introduced from one end of the tubular open-pore material through an external power source, so that the modifying reagent flows into an inner channel of the tubular open-pore material according to a designed flow rate; flowing the modifying solution into the other port, so that the modifying reagent circularly flows in the inner channel of the tubular open-pore material; the method can endow the material with the functions of adsorption, separation, enrichment, filtration and the like in one step by changing the internal coating material.
A method for modifying and functionalizing the inner surface of a tubular open-pore material comprises the following steps:
(S1) obtaining a tubular open-cell material;
(S2) allowing a modifying reagent to flow through the inside of the tubular open-pore material by a power source, and modifying to obtain the modified material.
Alternatively, in the step (S2), the modifying agent is injected from one end of the tubular opening material through a power source, or
And drawing the modifying reagent from one end of the tubular open-pore material by a power source for modification.
Optionally, one end of the tubular perforated material is connected to the power source through an external pipe.
Optionally, the tubular perforated material is affixed to an external conduit.
Optionally, in step (S2), the modifying reagent flows through the tubular open-pore material and is collected into a solution, and the solution is the modifying reagent.
Optionally, the outflow end of the tubular perforated material is placed in the solution, and the external pipeline connected with the other end of the power source is placed in the solution.
Optionally, the tubular apertured material is a strip of material.
Optionally, the geometric shape of the tubular open-cell material is selected from one of cylindrical and long strip.
Optionally, the length-diameter ratio of the tubular open-cell material is 1-200;
preferably, the length-diameter ratio of the tubular open-cell material is 1-50.
Optionally, the aspect ratio of the tubular, open-celled material is independently selected from any value or range of values between any two of 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 70, 90, 120, 140, 160, 180, 200.
Optionally, the compact skin layer of the tubular open-cell material is 0.0001 mm-0.1 mm;
preferably, the compact skin layer of the tubular open-pore material is 0.0001 mm-0.01 mm.
Optionally, the size of the internal open pore structure of the tubular open pore material is 1-500 μm;
preferably, the size of the internal open pore structure of the tubular open pore material is 1-200 μm.
Optionally, the tubular open-cell material has a high open cell content in the range of 85% to 99%;
preferably, it ranges from 90% to 99%.
Optionally, the monomer of the modifying reagent is selected from at least one of dopamine, cellulose derivatives, chitosan, hyaluronic acid, starch, polyacrylic acids, thiolated polymers, and polyethyleneimine.
The modifying reagent is the monomer and the combination of the modifying reagent and a functional reagent (MOF).
Optionally, the power source is selected from one of a compound peristaltic pump and a plunger pump.
Optionally, in the step (S2), the injection modification time is 2h to 24 h;
preferably, the time for injection modification is 2h to 12 h.
Optionally, the time for injecting the modification is independently selected from any value of 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, or a range value between any two.
Optionally, after finishing the injection modification, drying the tubular perforated material.
Optionally, the drying temperature is 50 ℃ to 100 ℃.
The invention mainly aims to provide a method for modifying the inner surface of a material with a large length-diameter ratio, a compact skin layer and a large number of open pore structures inside, wherein the material has the compact skin layer, the thickness of the material is small, and the macroscopic shape and the open pore rate of the material can be regulated and controlled. Meanwhile, the invention provides a supercritical carbon dioxide extrusion foaming preparation method of a long-distance tubular open-cell material, which comprises the following specific steps:
the preparation process mainly comprises the following steps: (1) premixing polyolefin, elastomer and nucleating agent; (2) adding the premix into an extruder for melt extrusion foaming; (3) a circular opening die is adopted; (4) the foam structure is controlled by regulating and controlling the pressure drop, the foaming temperature and the size of the neck ring mold.
Furthermore, the extruder used in the preparation process of the foam material is a double-stage single-screw tandem extruder, but is not limited to such equipment, and extrusion foaming equipment with similar extrusion foaming functions is included, such as a single-screw extrusion foaming unit, a double-screw extrusion foaming unit, an extrusion foaming unit with double screws at the upper stage and a single screw at the lower stage, and other various types of tandem units;
further, a high-pressure fluid injection pump is used together with the extrusion foaming unit and is used for stably injecting supercritical fluid into the matrix;
further, a melt pump is used together with the extrusion foaming unit for stabilizing and balancing the pressure of the polymer melt;
further, a tractor used in the foaming process of the material is used for dragging the foam pipe;
further, the supercritical fluid used in the foaming process of the material includes supercritical carbon dioxide, supercritical nitrogen gas, etc., preferably supercritical N 2 And supercritical CO 2 ；
Further, the geometrical shape of the foam material is cylindrical or quadrilateral, including circular, square and rectangular, preferably cylindrical, preferably circular die;
further, the diameter of the circular die is 0.5-5mm, preferably 0.5-1.5 mm;
furthermore, the foam material has adjustable geometrical size, the diameter is 8-20mm, preferably 10-15mm,
furthermore, the foam has a dense skin layer with a controllable thickness of 0.0001-0.1mm, preferably 0.0001-0.01mm,
further, the foam material has an internal open-cell structure including a reticulated structure, an open-cell cellular structure, a filamentous structure, and the like,
further, the foam has an internal open-cell structure of 1 to 500. mu.m, preferably 1 to 200 μm;
further, the foam has a high open cell content in the range of 85 to 99%, preferably 90 to 99%,
after the structure is adopted, the invention expands the functional application of the material in the fields of filtration, adsorption, separation and the like aiming at the characteristics of high open pore and high specific surface area of the material, and the modification steps are as follows:
(1) aiming at different application fields, different reagents are adopted to prepare solutions with concentration gradient change, preferably solutions with low concentration and strong functionality, preferably cheap reagents with commercial grade, convenience and easy availability;
(2) further, the solute used in the solution in the step (1) has good adhesion on the inner surface of the material, and comprises cellulose derivatives, chitosan, hyaluronic acid, starch, polyacrylic acids, sulfhydrylation polymers, polyethyleneimine and the like;
(3) further, a reciprocating peristaltic pump is used as a power source, and the peristaltic pump selects the specification of the silicone tube according to the diameter of the material;
(4) connecting the material with one end of a silicone tube matched with the peristaltic pump, and using a clamp to ensure stable connection;
(5) the material and the other end of the silicone tube are simultaneously placed in the prepared modified solution, so that the material and the silicone tube are still below the liquid level of the solution in the container when the peristaltic pump operates normally, and the solution is ensured to circulate;
(6) the solution continuously flows in the material under the action of the peristaltic pump, is adhered to the inner surface of the material through chemical reaction of the solution during the flowing process,
(7) the reaction time is controlled to be 2-24h, preferably 2-12 h;
(8) after the reaction is complete, the material is removed and dried in a forced air oven, the temperature range being set according to the nature of the solution, generally between 50 and 100 ℃.
(9) More specifically, the invention can control the functionalization degree of the material according to the pore structure in the material, the concentration of the solution and the reaction time, endow the material with a specific function and meet the application requirements of the material in different fields.
(10) The invention adopts supercritical CO 2 The PP/TPU composite open-cell foam material integrally prepared by extrusion foaming comprises the following specific steps:
supercritical CO 2 The PP/TPU composite foam material prepared by extrusion integral foaming is used as a matrix and has a compact skin layer, a small number of closed-cell structural cells are close to the skin layer, and a large number of open-cell structural cells are arranged inside the skin layer.
Furthermore, the compact skin layer of the foam material is 0.0001-0.01mm,
further, the expansion ratio of the foam is 15 to 25 times, preferably 20 to 25 times,
further, the foam has a high open cell content of 85 to 99%, preferably 90 to 99%.
The beneficial effects that this application can produce include:
1) according to the modification and functionalization method for the inner surface of the tubular perforated material, the modification reagent is driven into or drawn out from one end of the tubular perforated material through an external power source, so that the modification reagent flows into an internal channel of the tubular perforated material in a large amount; and the collected modifying reagent solution is extracted by the power source, so that the modifying reagent circularly flows in the inner channel of the tubular open-pore material, and the modification and functionalization of the three-dimensional open-pore material with the compact surface layer are completed, thereby improving the utilization rate of the modifying reagent and saving the cost.
2) According to the modification and functionalization method for the inner surface of the tubular open-pore material, the functions of adsorption, separation, enrichment, filtration and the like can be given to the material in one step by changing the coating material in the inner part of the modification and functionalization method.
Drawings
FIG. 1 shows the internal modification process of PP/TPU high open-cell foam prepared in example 1 of the present application: a is a picture of a physical device, and b is a schematic diagram.
Fig. 2 is optical pictures before and after internal modification of the PP/TPU high open-cell material prepared in example 1 of the present application, wherein a is before modification and b is after modification.
FIG. 3 is an electron micrograph of the unmodified PP/TPU high open cell foam prepared in example 1 of the present application.
FIG. 4 is an electron microscope image of the PP/TPU high open-cell foam material prepared in example 1 of the present application after modification.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
And carrying out morphology analysis by using an EVO 18 type scanning electron microscope.
PP/TPU refers to polypropylene/thermoplastic polyurethane elastomer rubber.
Example 1
By using supercritical CO 2 Extruding and foaming integrally prepared PP/TPU foam;
modification and functionalization of PP/TPU foam:
connecting PP/TPU foam with the diameter of 8mm and the opening rate of 90% with one end of a silicone tube matched with a peristaltic pump, as shown in figure 1;
placing the silicone tube in a peristaltic pump clamp, and switching on a power supply of the peristaltic pump;
selecting a commercial grade dopamine prepared solution with self-polymerization and good adhesion characteristics as a modifying reagent, preparing a 3mg/mL dopamine hydrochloride solution with the volume of 150mL, and placing the solution in a 200mL beaker for later use;
immediately putting the foam material and the other end of the silicone tube into the solution at the same time, starting a power supply of a peristaltic pump to enable the solution to flow through the foam material through the silicone tube and adhere to the inner wall of the material by self-polymerization;
the reaction is continuously carried out for 6h, the foam material is switched to the direction and is connected into a silicone tube, and the steps are carried out again;
washing the modified foam material with deionized water for 3min to remove residual solution and incompletely adhered polydopamine;
drying the cleaned foam material in a forced air drying oven at 70 ℃ for 12h, as shown in figure 2;
meanwhile, in the modification process, substances with functionality (such as porous MOF) can be brought into the foam together to endow the foam with different functions. The modified foam material has the microscopic morphology shown in FIG. 4, and it can be seen that the inner wall of the foam is uniformly coated with polydopamine.
Example 2
The same procedure as in example 1 was followed except that the solution was formulated into a hyaluronic acid solution, to obtain a modified PP/TPU foam.
Example 3
The same procedure as in example 1 was followed, except that the solution was prepared as a chitosan solution, to obtain a modified PP/TPU foam.
Example 4
The same procedure as in example 1 was followed except that the solution was formulated into a tannic acid solution to obtain a modified PP/TPU foam.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for modifying and functionalizing an inner surface of a tubular porous material, comprising the steps of:
(S1) obtaining a tubular open-cell material;
(S2) allowing a modifying reagent to flow through the inside of the tubular open-pore material by a power source, and modifying to obtain the modified material.
2. The modifying and functionalizing method according to claim 1, wherein in the step (S2), a modifying agent is injected from one end of said tubular opening material by a power source, or
Extracting the modifying reagent from one end of the tubular open-pore material through a power source for modification;
preferably, one end of the tubular open-pore material is connected with the power source through an external pipeline;
preferably, the tubular perforated material is fixedly connected with an external pipeline.
3. The modification and functionalization method according to claim 1, wherein in the step (S2), the modifying reagent flows through the tubular open-cell material and then is collected into a solution, and the solution is the modifying reagent;
preferably, the outflow end of the tubular perforated material is placed in the solution, and the external pipeline connected with the other end of the power source is placed in the solution.
4. The modification and functionalization method according to claim 1, wherein the tubular perforated material is a strip material;
preferably, the geometric shape of the tubular open-cell material is selected from one of cylindrical and long strip.
5. The modification and functionalization method according to claim 1, wherein the aspect ratio of the tubular open-cell material is 1 to 200;
preferably, the length-diameter ratio of the tubular open-cell material is 1-50;
preferably, the compact skin layer of the tubular open-pore material is 0.0001 mm-0.1 mm;
preferably, the compact skin layer of the tubular open-pore material is 0.0001 mm-0.01 mm.
6. The modification and functionalization method according to claim 1, wherein the size of the internal open cell structure of the tubular open cell material is 1 μm to 500 μm;
preferably, the size of the internal open pore structure of the tubular open pore material is 1-200 μm;
preferably, the tubular open-cell material has a high open-cell content in the range of 85% to 99%;
preferably, it ranges from 90% to 99%.
7. The method of claim 1, wherein the monomer of the modifying agent is at least one selected from dopamine, cellulose derivatives, chitosan, hyaluronic acid, starch, polyacrylic acids, thiolated polymers, and polyethylene imine.
8. The method of claim 1, wherein the power source is selected from the group consisting of a compound peristaltic pump and a plunger pump.
9. The method according to claim 1, wherein in the step (S2), the injection modification time is 2-24 h;
preferably, the time for injection modification is 2h to 12 h.
10. The modification and functionalization method according to claim 1, wherein after the injection modification is finished, the tubular open-cell material is dried;
preferably, the drying temperature is 50-100 ℃.
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| EP0152491A1 (en) * | 1983-12-07 | 1985-08-28 | John Albert Avery Bradbury | Composite foamed articles and process for their production |
| JP2005169386A (en) * | 2003-11-17 | 2005-06-30 | Kanagawa Acad Of Sci & Technol | Method of partial-chemical-modifying microchannel inner surface and microchannel structure |
| CN104248913A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrophilization modification method of polyolefin hollow fiber ultrafiltration membrane |
| CN109705465A (en) * | 2018-12-29 | 2019-05-03 | 中国科学院宁波材料技术与工程研究所 | A kind of hollow foam polyolefin material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0152491A1 (en) * | 1983-12-07 | 1985-08-28 | John Albert Avery Bradbury | Composite foamed articles and process for their production |
| JP2005169386A (en) * | 2003-11-17 | 2005-06-30 | Kanagawa Acad Of Sci & Technol | Method of partial-chemical-modifying microchannel inner surface and microchannel structure |
| CN104248913A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrophilization modification method of polyolefin hollow fiber ultrafiltration membrane |
| CN109705465A (en) * | 2018-12-29 | 2019-05-03 | 中国科学院宁波材料技术与工程研究所 | A kind of hollow foam polyolefin material and preparation method thereof |
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