CN101580600B - Method for preparing perfluoroethylene-propylene microcellular foam material - Google Patents
Method for preparing perfluoroethylene-propylene microcellular foam material Download PDFInfo
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- CN101580600B CN101580600B CN2009100533109A CN200910053310A CN101580600B CN 101580600 B CN101580600 B CN 101580600B CN 2009100533109 A CN2009100533109 A CN 2009100533109A CN 200910053310 A CN200910053310 A CN 200910053310A CN 101580600 B CN101580600 B CN 101580600B
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- perfluoroethylene
- propylene
- foam material
- microcellular foam
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Abstract
The invention relates to a method for preparing perfluoroethylene-propylene microcellular foam material, belonging to the technical field of macromolecule foam material, comprising the following steps: placing the perfluoroethylene-propylene in a sealed container containing carbon dioxide fluid in supercritical state to carry out swelling treatment; carrying out fast pressure relief treatment on the sealed container to facilitate the carbon dioxide dissolved in the perfluoroethylene-propylene to supersaturate and foam, thus obtaining the perfluoroethylene-propylene microcellular foam material.The method of the invention is simple and feasible; therefore, FEP microcellular foam material with fine electrical property and with vesicle being below 200nm can be prepared.
Description
Technical field
That the present invention relates to is a kind of preparation method of high molecular foam material technical field, specifically is a kind of perfluoroethylene-propylene (FEP, Fluorinated-ethylene-propylene) preparation method of microcellular foam material.
Background technology
Microcellular plastics is a kind of material of excellent performance, shows good mechanical property, thermal characteristics and processing characteristics.Compare with the plastics of not foaming, microcellular plastics density can reduce by 5%～98%, and shock strength can improve 5 times, and toughness improves 5 times, and rigid mass prolongs 5 times fatigue lifetime than high 3～5 times, has lower thermal conductivity and dielectric coefficient.Because these particular performances make that the Application Areas of microcellular plastics is very broad.The very suitable manufacturing package of microcellular plastics, thin-walled cover, electricity and thermal insulator can be applicable to packaging box piece, large-scale housing product, material of construction, automobile inner decorative piece, household appliances, sports equipment, information engineering articles for use, medical and hygiene article etc.In addition, the open cell type microcellular plastics can be realized the heterogeneous separation of less energy-consumption on chemical industry, pharmaceutically the medicine of complexity being separated purification, can be widely used in the battery separator barrier film aspect the energy, lead acid cell is exempted safeguarded, and improve cold-start performance greatly.
The preparation method of microcellular plastics mainly is divided into two kinds of chemical process and physical methods.The organism that chemical foaming generally adopts Cellmic C 121 etc. at high temperature can decompose to produce gas is as whipping agent, and organic blowing agent decomposes the back and has residually in material, is difficult to be competent under some environments for use high to material requirements (in as human body etc.).Traditional physical foaming method is the thermodynamic state that changes gas gradually, and the abscess-size of Chan Shenging is inhomogeneous like this, causes the performance of expanded plastic to be subjected to certain influence.
Supercritical gas foaming also is a kind of foaming method of physics, but it and traditional physical blowing have bigger difference.Thermodynamic state changes rapidly in the supercritical gas foamed forming process, and its nucleation rate and complex quantity substantially exceed general physical blowing.Moreover the mass transfer coefficient height of supercritical gas can reach concentration balance in the short period of time, thereby shorten process period.Selecting carbonic acid gas for use then is because its environment-friendly and green as whipping agent, environmentally safe, and critical condition reaches easily, and it has the very strong dissolving power that penetrates in high molecular polymer, helps to improve the effect of foaming.
FEP is that a kind of high and low temperature resistance is good, and wear resistance is good, the macromolecule polymer material that self-lubricating property is good.Its electrical insulating property excellence, and be not subjected to the influence of Working environment, humidity, temperature and frequency, have good arc resistance.Has good chemical resistance simultaneously.Also have the physiology inertia, can implant into body in, toxicological harmless.
Supercritical co foaming FEP can combine the foaming technique of this green of supercritical co and the good performance of FEP material itself, and therefore the foam material that can prepare will possess better performance, satisfy the requirement of association area development.Find through searching document, very rare for the research of supercritical co foaming FEP at present.
In sum, the professional is making great efforts to prepare the FEP microcellular foam material with excellent electrical of abscess-size below 200nm, does not find the report of correlation technique document so far as yet.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of preparation method of perfluoroethylene-propylene microcellular foam material is provided, compare that its abscess-size of foam material that traditional preparation method obtains is littler, cell density is higher, possesses better electrical property.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
The first step, perfluoroethylene-propylene placed contain supercritical carbon dioxide fluidic encloses container and carry out swelling treatment.
Described swelling treatment is meant: it is 40 ℃ that encloses container is provided with temperature, and air pressure is under the environment of 8～20MPa at least 2 hours, and carbonic acid gas fully obtains dissolving;
Described supercritical carbon dioxide fluid is meant the temperature of carbonic acid gas greater than 31.1 ℃, and pressure is higher than 7.4MPa.
The volume of described perfluoroethylene-propylene is smaller or equal to the volumetrical 1/20th of encloses container.
Second step, encloses container is carried out fast pressure relief treatment, carbon dioxide dissolved is carried out supersaturation foaming in the perfluoroethylene-propylene, prepares perfluoroethylene-propylene microcellular foam material.
Described fast pressure relief treatment is meant: the release speed that encloses container is at least 5MPa/s with release speed is unloaded and is depressed into normal pressure.
The mean cell diameter of described perfluoroethylene-propylene microcellular foam material is 70 ~ 168nm, cell density 1.92 * 10
12~ 6.77 * 10
13/ cm
3
The foaming method of the supercritical co that the present invention adopts is a kind of method of novel green, can not cause any pollution to environment, thus can be by the simple FEP microcellular foam material with excellent electrical of method preparation abscess-size below 200nm.
Description of drawings
Fig. 1 is the sample of the embodiment profile scanning Electronic Speculum figure that quenches;
Fig. 2 is the sample cell diameter distribution plan of embodiment.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The first step, the FEP raw material is put into autoclave.The volume of FEP is not more than 1/20th of autoclave volume, and guaranteeing has enough space foamings.Close autoclave, steel cylinder is communicated with autoclave, carry out low pressure CO 2 and purge, continue several minutes.Autoclave is put into 40 ℃ of water-baths, with high-pressure pump carbonic acid gas is charged into autoclave to pressure and reach 8MPa, swelling two hours.
Second goes on foot, autoclave is taken out, and fast pressure relief to gauge pressure is a normal pressure, and release speed is 5MPa/s.
Present embodiment detects evaluation in the following manner:
Adopt scanning electron microscope (SEM) to the foaming FEP sample section analysis of quenching, to investigate cell density and the cell diameter size of foaming FEP.Analytical instrument is the Japanese Hitachi High-Technologies S-2150 of company type scanning electron microscope.
As shown in Figure 1, for the FEP foaming sample profile scanning Electronic Speculum figure that quenches, magnification and size have been indicated among the figure.Statistics micropore number n is determined photo area A (cm from the SEM photo
2) and foaming before and after the ratio η of density.Document Hani E.Naguib is adopted in the calculating of cell density, Chul B.Park.Strategies forAchieving Ultra Low-Density Polypropylene Foams.Polymer Engineering andScience, 42 (7): the method that 1481-1492 (2004) provides, cell density N
pFor:
As depicted in figs. 1 and 2, the mean cell diameter of gained foaming sample is 168nm, and cell density is 1.92 * 10
12/ cm
3From cell morphology, abscess is spherical in shape.
Embodiment 2
The first step, the FEP raw material is put into autoclave.The volume of FEP is not more than 1/20th of autoclave volume, and guaranteeing has enough space foamings.Close autoclave, steel cylinder is communicated with autoclave, carry out low pressure CO 2 and purge, continue several minutes.Autoclave is put into 40 ℃ of water-baths, with high-pressure pump carbonic acid gas is charged into autoclave to pressure and reach 14MPa, swelling two hours.
Second goes on foot, autoclave is taken out, and fast pressure relief to gauge pressure is a normal pressure, and release speed is 5MPa/s.
The mean cell diameter of gained foaming sample is 89nm, and cell density is 4.51 * 10
13/ cm
3
Embodiment 3
The first step, the FEP raw material is put into autoclave.The volume of FEP is not more than 1/20th of autoclave volume, and guaranteeing has enough space foamings.Close autoclave, steel cylinder is communicated with autoclave, carry out low pressure CO 2 and purge, continue several minutes.Autoclave is put into 40 ℃ of water-baths, with high-pressure pump carbonic acid gas is charged into autoclave to pressure and reach 20MPa, swelling two hours.
Second goes on foot, autoclave is taken out, and fast pressure relief to gauge pressure is a normal pressure, and release speed is 5MPa/s.
The mean cell diameter of gained foaming sample is 70nm, and cell density is 6.77 * 10
13/ cm
3
Claims (3)
1. the preparation method of a perfluoroethylene-propylene microcellular foam material is characterized in that, comprises the steps:
The first step, perfluoroethylene-propylene placed contain supercritical carbon dioxide fluidic encloses container and carry out swelling treatment;
Second step, encloses container is carried out fast pressure relief treatment, carbon dioxide dissolved is carried out supersaturation foaming in the perfluoroethylene-propylene, prepares perfluoroethylene-propylene microcellular foam material;
Described swelling treatment is meant: it is 40 ℃ that encloses container is provided with temperature, and air pressure is under the environment of 8～20MPa at least 2 hours, and carbonic acid gas fully obtains dissolving;
Described fast pressure relief treatment is meant: the release speed that encloses container is at least 5MPa/s with release speed is unloaded and is depressed into normal pressure.
2. the preparation method of perfluoroethylene-propylene microcellular foam material according to claim 1 is characterized in that, the volume of the perfluoroethylene-propylene described in the first step is smaller or equal to the volumetrical 1/20th of encloses container.
3. the preparation method of perfluoroethylene-propylene microcellular foam material according to claim 1 is characterized in that, the mean cell diameter of described perfluoroethylene-propylene microcellular foam material is 70～168nm, cell density 1.92 * 10
12～6.77 * 10
13/ cm
3
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| CN2009100533109A CN101580600B (en) | 2009-06-18 | 2009-06-18 | Method for preparing perfluoroethylene-propylene microcellular foam material |
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|---|---|---|---|
| CN2009100533109A CN101580600B (en) | 2009-06-18 | 2009-06-18 | Method for preparing perfluoroethylene-propylene microcellular foam material |
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| CN101580600B true CN101580600B (en) | 2011-06-01 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109081936A (en) * | 2017-06-14 | 2018-12-25 | 宁波绿色方舟环境科技有限公司 | A kind of fluoropolymer cellular material and preparation method thereof |
| CN109078509B (en) * | 2017-06-14 | 2020-10-23 | 宁波绿色方舟环境科技有限公司 | Fluorinated ethylene propylene hollow fiber membrane and preparation method thereof |
| CN109735030A (en) * | 2018-12-13 | 2019-05-10 | 济南赛辰高分子材料有限公司 | A kind of fluorine Material Physics foaming nucleation masterbatch |
| CN115124801B (en) * | 2022-07-12 | 2024-02-13 | 浙江巨化新材料研究院有限公司 | FEP (fluorinated ethylene propylene) physically foamed cable insulating layer material for signal transmission and preparation method thereof |
| CN116144127A (en) * | 2022-07-28 | 2023-05-23 | 四川大学 | Low dielectric loss PTFE in-situ fiber FEP microporous material, preparation method and application thereof in wave-transparent material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169359A (en) * | 1996-05-22 | 1998-01-07 | 纳幕尔杜邦公司 | Foamed fluoropolymer |
| CN1908053A (en) * | 2006-08-14 | 2007-02-07 | 华东理工大学 | Method of preparing siliceous polypropylene nano foaming material using supercritical carbon dioxide technique |
| CN101386685A (en) * | 2008-10-30 | 2009-03-18 | 上海交通大学 | Method for preparing poly hexane diacid-terephthalic acid-butylene terephthalate foaming material |
-
2009
- 2009-06-18 CN CN2009100533109A patent/CN101580600B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169359A (en) * | 1996-05-22 | 1998-01-07 | 纳幕尔杜邦公司 | Foamed fluoropolymer |
| US5912278A (en) * | 1996-05-22 | 1999-06-15 | E. I. Du Pont De Nemours And Company | Foamed fluoropolymer |
| CN1908053A (en) * | 2006-08-14 | 2007-02-07 | 华东理工大学 | Method of preparing siliceous polypropylene nano foaming material using supercritical carbon dioxide technique |
| CN101386685A (en) * | 2008-10-30 | 2009-03-18 | 上海交通大学 | Method for preparing poly hexane diacid-terephthalic acid-butylene terephthalate foaming material |
Non-Patent Citations (2)
| Title |
|---|
| Larissa Zirkel 等.Foaming of thin films of a fluorinated ethylene propylene copolymer using supercritical carbon dioxide.《The Journal of Supercritical Fluids》.2009,第49卷(第1期),103-110. |
| Larissa Zirkel等.Foaming of thin films of a fluorinated ethylene propylene copolymer using supercritical carbon dioxide.《The Journal of Supercritical Fluids》.2009,第49卷(第1期),103-110. * |
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