CN101786310A - Method for preparing microporous polysulfones foam material by injection molding of supercritical fluid - Google Patents
Method for preparing microporous polysulfones foam material by injection molding of supercritical fluid Download PDFInfo
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- CN101786310A CN101786310A CN201010022664A CN201010022664A CN101786310A CN 101786310 A CN101786310 A CN 101786310A CN 201010022664 A CN201010022664 A CN 201010022664A CN 201010022664 A CN201010022664 A CN 201010022664A CN 101786310 A CN101786310 A CN 101786310A
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Abstract
The invention provides a method for preparing a microporous polysulfones foam material by injection molding of a supercritical fluid. The steps of the method are as follows: (1) the supercritical fluid is injected into a polysulfones melt melted in a homogenization section of a screw extruder to form homogeneous-phase solution; (2) the homogeneous-phase solution is extruded by the screw extruder and then injected into a mould with the temperature of 100 to 140 DEG C, and then the microporous polysulfones foam material is produced. The supercritical fluid is supercritical N2 or CO2; and a polysulfones polymer includes but is not limited to polysulfone or polyether sulfone. The invention has the remarkable advantage that the method in the invention can prepare the microporous polysulfones foam material with light weight, high tensile strength, high impact strength and high bending strength.
Description
Technical field
This patent relates to the method that a kind of injection molding of supercritical fluid prepares micropore polysulfones expanded material.
Background technology
Polysulfones-like polymer is a kind of resistant to elevated temperatures special engineering plastics, has the excellent comprehensive performance, as hear resistance, and non-oxidizability, hydrolytic resistance and anti-flammability etc. are widely used in electric, electronics, machinery, medical treatment, chemical industry, food and aerospace field.
Microcellular foam is meant that cell diameter is 1 μ m～50 μ m, and cell density is 10
9～10
12Cells/cm
3Foamed plastics.
Therefore on the one hand microcellular foam is because abscess is very little, and quantity is very big, and it can keep the advantage of general foamed plastics: light weight, material-saving, can absorb shock loading, sound insulation and heat-proof quality are good, denominators such as specific strength height; On the other hand, because abscess-size is less than the original defective of material internal, so the existence of abscess can not reduce the intensity of material, can make original crack tip passivation in the material on the contrary, help organizing the expansion of crackle under the stress effect, thereby improved the mechanical property of foamed plastics.Because therefore microcellular foam can be less to keep its mechanical property to lose under the prerequisite that obviously reduces product weight, and can make automobile to improve otherwise performance, there is special using value in fields such as aircraft and various transportation equipments.At present, micropore plastic product just is being applied to many industrial circles, as industries such as Aero-Space, automobile, medicine, electronics, packagings for foodstuff, the infusion of financial resources of increasing plastic processing enterprise is transformed existing injector, utilize the micropore injection process to produce, improve Enterprises'Competitiveness.
Adopt conventional method, as [1]
J, Gendron R,
L.Ultrasoniccharacterization performed during chemical foaming of cross-linked polyolefins[J] .Polymer Testing, 2004,23 (2): 125-130. and document [2] Matuana LM, Faruk O, Diaz CA.Cell morphology of extrusion foamed poly (lactic acid) using endothermic chemicalfoaming agent[J] .Bioresource Technology, 2009,100 (23): the abscess of the foamed plastics that 5947-5954. is prepared is bigger, when foam is stressed, abscess usually becomes the cradle of foam crackle, has reduced the intensity of material.Compare the not solid plastic of foaming, microcellular foam not only density can reduce outside 5%～95%, and have the following advantages: high toughness (can reach entity 5 times), the low coefficient of heat conduction, high impact strength (can reach entity 5 times), low dielectric constant, see document: [3] J.D.Gaspari.Microcellular foams[J] .Plastics Technology, 1993,2:63-65. and document [4] MatuanaLM, Park CB, Balatinecz JJ.Structures and mechanical properties of microcellularfoamed polyvinyl chloride[J] .Cellular polymers, 1998, the record of 17:1-16..
Adopt the cellular plastic injection moulding method of supercritical fluid, being to prepare the more advanced technology of microcellular foam at present, is just to begin to carry out the injection moulding new technology that is used to prepare the microcellular foam goods with broad prospect of application that industry is promoted abroad in recent years.This technology is with the gas (N of supercriticality
2Or CO
2) go in the polymer melt by the injector to inject that is installed on the injector machine barrel, form the polymer/gas system of single homogeneous phase.Subsequently, melt is gone into mold cavity by fast injection, along with pressure drop, supercritical gas is overflowed, form the countless diameters micropore between 1-50 μ m usually, last micropore melt cooling and shaping and to obtain cell size even, the micropore plastic product that is evenly distributed in die cavity.Mucell technology, FIM forming technique, Ergocell technology can success produce micropore plastic product, yet that Mucell is commercialization is best, the cellular plastic injection molding technology that is most widely used.
Compare with traditional injection process, adopt supercritical fluid cellular plastic process of injection molding to have advantages such as energy-saving and cost-reducing, that product properties is excellent, molding cycle is short, save material.The huge ability that the cellular plastic process of injection molding provides the traditional injection moulding process not had is for development of new plastic product, optimization injection technique and reduction product cost have been opened up wide space.And supercritical fluid is widely used in Polymer Processing with its special nature, mainly comprises: polymer modification, compound, synthetic, granulation etc., and especially aspect microporous foam.In these areas, overcritical N
2Or CO
2Be most widely used, it is cleaning and the very wide solvent of the scope of application, is the harmful organic solvent of environment and the best substitute of fluorochlorohydrocarbon.Overcritical N
2(scN
2) or supercritical CO
2(scCO
2) except general features, also have many characteristics with supercritical fluid.They be inexpensive, do not fire, nontoxic, and wide material sources, be easy to reclaim.Supercritical fluid can be with glass transition temperature, fusing point and the viscosity (because increase of free volume) of obvious reduction polymer to the plastication of polymer, make that polymer can be to process under lower temperature, and it has changed the physical property of the polymer of polymer, as density, diffusivity, expanding volume.
But, because polysulfones-like polymer is a kind of more special high molecular polymer, have that forming temperature is higher, melt strength is lower under the high temperature, supercritical fluid is the low shortcoming that is unfavorable for microporous foam that waits of solubility therein, therefore, can adopt the injection molding method of cellular plastic of supercritical fluid, preparation polysulfones microcellular foam material be the problem that those skilled in the art extremely pay close attention to.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing microporous polysulfones foam material by injection molding of supercritical fluid is to satisfy the needs of relevant field development.
Technical conceive of the present invention is such:
The present invention's imagination is utilized overcritical N
2Or CO
2For the blowing agent injection mo(u)lding prepares the polysulfones microcellular foam material.N
2And CO
2It is the blowing agent of the preparation microcellular foam of the best.If both concentration in molten polymer is identical, the abscess of nitrogen gas generation is just littler than the carbon dioxide so, because the diffusion rate of nitrogen in melt is lower.Greater than carbon dioxide, the polymer melt of nitrogen gas foaming can produce more complex to the single-phase liquation of polymer melt/blowing agent like this to the driving force of nitrogen.Therefore for obtaining more less good foam structure, selecting nitrogen usually is the blowing agent of polysulfones microcellular foam material.The mechanical property of polyether sulfone microcellular foam material mainly is limited by foam structure (comprising: abscess-size, cell density, distribution of cells and cell orientation), and molecular chain orientation.The typical distribution of cells of micropore injection moulding goods mainly comprises the cortex that does not foam, the shear layer that orientation takes place abscess, and abscess is spherical sandwich layer.Abscess-size is more little, and density is big more, distribute even more and the orientation weak more, the mechanical property of material is good more.The molecular chain orientation of microcellular foam goods streamwise has material impact to mechanical strength.Arrange in order along stress direction at the material internal strand, under the certain situation of chemical bond energy, macroscopical intensity of material streamwise will be significantly improved, and will significantly weaken perpendicular to macroscopical intensity of flow direction.Machined parameters has material impact to foam structure and molecular chain orientation, and then influences the mechanical property of material.As: higher melten gel amount, SCF content, moderate injection pressure, injection speed, lower melt temperature, mold temperature help obtaining higher draw tensile strength.Impact strength and bending strength increase along with the raising of melten gel amount and SCF content, along with first the increase afterwards of the raising of injection pressure, injection speed, melt temperature, mold temperature reduces.This shows by optimizing technology, control foam structure and molecular chain orientation, the micropore polysulfones expanded material that must obtain having higher mechanical property.
Method of the present invention comprises the steps:
(1) supercritical fluid is injected the polysulfones melt of screw extruder homogenizing zone fusion, form homogeneous phase solution;
(2) extrude by described screw extruder then, it is in 100～140 ℃ of moulds that described homogeneous phase liquation is injected into temperature, obtains micropore polysulfones expanded material;
The preferred overcritical N of described supercritical fluid
2Or supercritical CO
2
Described polysulfones-like polymer includes but not limited to polysulfones or polyether sulfone;
Described supercritical fluid refers to, and the temperature and pressure of described fluid all is in it more than critical point;
Preferably, when described supercritical fluid be overcritical N
2The time, its temperature is 330～380 ℃, pressure is 19～24MPa; When described supercritical fluid is a supercritical CO
2The time, its temperature is 330～380 ℃, pressure is 19～24MPa;
Pressure differential between mould and the screw extruder is 18.9～23.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 40～60cm
3/ s makes described homogeneous phase liquation owing to pressure drop, and the thermodynamic phase that causes drives the abscess nucleation, growth;
The weight ratio of described supercritical fluid and described polysulfones-like polymer is:
Overcritical N
2: described polysulfones-like polymer=1: 250～1: 111;
Supercritical CO
2: described polysulfones-like polymer=1: 83～1: 37;
Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 5～10s;
Obtain the polysulfones microcellular foam material under these conditions, its abscess-size can be as small as 10 μ m, with respect to the entity that does not foam, and the micropore polyether sulfone goods loss of weight 20% of high tensile, loss of tensile strength is in 20%, and specific strength improves about 20%; Impact strength improves 40%, improves about 90% than impact strength; In the bending strength loss 5%, improve about 20% than bending strength.Improve and flow than obtaining the more polysulfones microcellular foam material of high-amplitude loss of weight.
Can see by above-mentioned disclosed technical scheme, advantage of the present invention is very significant, adopt the method for preparing micropore polysulfones expanded material with the supercritical fluid for blowing agent injection moulding of the present invention, can make the high light-weighted micropore polysulfones expanded material of high tensile, high impact and high bending strength.
Description of drawings
Fig. 1 is a Mucell injection moulding microporous foam system architecture schematic diagram.
Fig. 2 is the SEM figure of streamwise section of the product of embodiment 1.
Fig. 3 is the SEM figure of the product perpendicular flow direction section of embodiment 1.
The specific embodiment
Referring to Fig. 1, Fig. 1 is the Mucell injection moulding microporous foam system that adopts among the embodiment, described Mucell injection moulding microporous foam system is a kind of common injection moulding microporous foam system, at document Hyde LJ, Kishbaugh LA, Katterman JA.How Microcellular Foam Molding Changes the CostStructure of Injection Molded Automotive Components:A Review of the Process andAutomotive Applications.SAE 2002 World Congress.Detroit, among the Michigan:the SAEPublications Group 2002., it there is detailed description, comprises that mainly draw ratio is 24: 1 a Mucell plasticized screw extruder 1, the injection control module 2 that is connected with described screw extruder 1, the die unit 3 that is connected with described injection control module 2, be arranged on the material inlet 4 and the supercritical fluid inlet 5 that is arranged on screw extruder 1 middle part of screw extruder 1 end.
Embodiments of the invention, the screw extruder model of employing is JM80MKIV, male group provides by shake.
(1) supercritical fluid is injected the polysulfones melt of screw extruder homogenizing zone fusion, form homogeneous phase solution.
(2) extrude by described screw extruder then, described homogeneous phase liquation is injected in the temperature mould, obtain micropore polysulfones expanded material.
Described supercritical fluid is overcritical N
2Its temperature is 330 ℃, and pressure is 19MPa;
Described polysulfones-like polymer is a polysulfones;
The temperature of mould is 100 ℃, and the pressure differential between mould and the screw extruder is 18.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 40cm
3/ s;
Overcritical N
2With the weight ratio of polysulfones-like polymer be:
Overcritical N
2: described polysulfones-like polymer=1: 250; Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 5s;
Adopt the method for ASTM to detect, under this processing conditions, the entity loss of weight that the microporous foam polyether sulfone tensile bars of acquisition does not foam relatively is 10%, loss of tensile strength 7.7%, and specific tensile strength has improved 2.6%.Impact strength improves 48.1%, improves 63.3% than impact strength; Bending strength loss 2.8% improves 8.3% than bending strength.
The SEM figure of streamwise section sees Fig. 1.The SEM figure of perpendicular flow direction section sees Fig. 2.
Adopt the method identical with embodiment 1, wherein:
Described supercritical fluid is overcritical N
2Its temperature is 380 ℃, and pressure is 24MPa;
Described polysulfones-like polymer is a polysulfones, and the temperature of mould is 140 ℃, and the pressure differential between mould and the screw extruder is 23.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 60cm
3/ s;
Overcritical N
2With the weight ratio of polysulfones-like polymer be:
Overcritical N
2: described polysulfones-like polymer=1: 111;
Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 10s;
Adopt the method for ASTM to detect, under this processing conditions, the entity loss of weight that the microporous foam polyether sulfone tensile bars of acquisition does not foam relatively is 20%, loss of tensile strength 19%, and specific tensile strength improves 18.6%; Impact strength improves 40%, improves 86.9% than impact strength; Bending strength loss 4.6% improves 19.4% than bending strength.
Adopt the method identical with embodiment 1, wherein:
Described supercritical fluid is a supercritical CO
2Its temperature is 330 ℃, and pressure is 19MPa;
Described polysulfones-like polymer is a polysulfones, and the temperature of mould is 100 ℃, and the pressure differential between mould and the screw extruder is 18.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 40cm
3/ s;
Supercritical CO
2With the weight ratio of polysulfones-like polymer be:
Supercritical CO
2: polysulfones-like polymer=1: 83;
Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 5s;
Adopt the method for ASTM to detect, under this processing conditions, the entity loss of weight that the microporous foam polyether sulfone tensile bars of acquisition does not foam relatively is 10%, loss of tensile strength 8.3%, and specific tensile strength has improved 3.5%.Impact strength improves 51%, improves 58.4% than impact strength; Bending strength loss 3.1% improves 7.9% than bending strength.
Adopt the method identical with embodiment 1, wherein:
Described supercritical fluid is a supercritical CO
2Its temperature is 380 ℃, and pressure is 24MPa;
Described polysulfones-like polymer is a polysulfones, and the temperature of mould is 140 ℃, and the pressure differential between mould and the screw extruder is 23.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 60cm
3/ s;
Overcritical N
2With the weight ratio of polysulfones-like polymer be:
Supercritical fluid: described polysulfones-like polymer=1: 37; Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 10s;
Adopt the method for ASTM to detect, under this processing conditions, the entity loss of weight that the microporous foam polyether sulfone tensile bars of acquisition does not foam relatively is 20%, loss of tensile strength 15%, and specific tensile strength improves 20.3%; Impact strength improves 42%, improves 85.5% than impact strength; Bending strength loss 5.3% improves 21.2% than bending strength.
Adopt the method identical with embodiment 1, wherein:
Described supercritical fluid is overcritical N
2Its temperature is 330 ℃, and pressure is 19MPa;
Described polysulfones-like polymer is a polyether sulfone, and the temperature of mould is 100 ℃, and the pressure differential between mould and the screw extruder is 18.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 40cm
3/ s;
Overcritical N
2With the weight ratio of polysulfones-like polymer be:
Supercritical fluid: described polysulfones-like polymer=1: 250;
Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 5s;
Adopt the method for ASTM to detect, under this processing conditions, the entity loss of weight that the microporous foam polyether sulfone tensile bars of acquisition does not foam relatively is 10%, loss of tensile strength 7%, and specific tensile strength has improved 3.4%; Impact strength improves 51%, improves 70% than impact strength; Bending strength loss 3.1% improves 10% than bending strength.
Embodiment 6
Adopt the method identical with embodiment 1, wherein:
Described supercritical fluid is overcritical N
2Its temperature is 380 ℃, and pressure is 24MPa;
Described polysulfones-like polymer is a polyether sulfone, and the temperature of mould is 140 ℃, and the pressure differential between mould and the screw extruder is 23.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 60cm
3/ s;
Overcritical N
2With the weight ratio of polysulfones-like polymer be: overcritical N
2: described polysulfones-like polymer=1: 111;
Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 10s;
Adopt the method for ASTM to detect, under this processing conditions, the entity loss of weight that the microporous foam polyether sulfone tensile bars of acquisition does not foam relatively is 20%, loss of tensile strength 15%, and specific tensile strength improves 20%; Impact strength improves 40%, improves 90% than impact strength; , bending strength loss 5.2% improves 21.5% than bending strength.
Embodiment 7
Adopt the method identical with embodiment 1, wherein:
Described supercritical fluid is a supercritical CO
2Its temperature is 330 ℃, and pressure is 19MPa;
Described polysulfones-like polymer is a polyether sulfone, and the temperature of mould is 100 ℃, and the pressure differential between mould and the screw extruder is 18.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 40cm
3/ s;
Overcritical N
2With the weight ratio of polysulfones-like polymer be:
Overcritical N
2: described polysulfones-like polymer=1: 83;
Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 5s;
Adopt the method for ASTM to detect, under this processing conditions, the entity loss of weight that the microporous foam polyether sulfone tensile bars of acquisition does not foam relatively is 10%, loss of tensile strength 7.3%, and specific tensile strength has improved 3.8%; Impact strength improves 47%, improves 70.6% than impact strength; Bending strength loss 3.3% improves 10.5% than bending strength.
Embodiment 8
Adopt the method identical with embodiment 1, wherein:
Described supercritical fluid is a supercritical CO
2Its temperature is 380 ℃, and pressure is 24MPa;
Described polysulfones-like polymer is a polyether sulfone, and the temperature of mould is 140 ℃, and the pressure differential between mould and the screw extruder is 23.9MPa, and the injection speed when the homogeneous phase liquation is injected in the mould is 60cm
3/ s;
Overcritical N
2With the weight ratio of polysulfones-like polymer be:
Overcritical N
2: described polysulfones-like polymer=1: 37;
Supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 10s;
Adopt the method for ASTM to detect, under this processing conditions, the entity loss of weight that the microporous foam polyether sulfone tensile bars of acquisition does not foam relatively is 20%, loss of tensile strength 13%, and specific tensile strength improves 22%; Impact strength improves 41%, improves 88.8% than impact strength; , bending strength loss 5.3% improves 22.3% than bending strength.
Claims (8)
1. the method for preparing microporous polysulfones foam material by injection molding of supercritical fluid is characterized in that, comprises the steps:
(1) supercritical fluid is injected the polysulfones melt of screw extruder homogenizing zone fusion, form homogeneous phase solution;
(2) extrude by described screw extruder then, it is in the mould that described homogeneous phase liquation is injected into temperature, obtains micropore polysulfones expanded material.
Described supercritical fluid is overcritical N
2Or supercritical CO
2
Described polysulfones-like polymer includes but not limited to polysulfones or polyether sulfone.
2. method according to claim 1 is characterized in that, it is in 100～140 ℃ of moulds that described homogeneous phase liquation is injected into temperature, obtains micropore polysulfones expanded material.
3. method according to claim 2 is characterized in that, described supercritical fluid is overcritical N
2, its temperature is 330～380 ℃, pressure is 19～24MPa.
4. method according to claim 2 is characterized in that, described supercritical fluid is a supercritical CO
2, its temperature is 330～380 ℃, pressure is 19～24MPa.
5. according to claim 3 or 4 described methods, it is characterized in that the pressure differential between mould and the screw extruder is 18.9～23.9MPa, the injection speed when the homogeneous phase liquation is injected in the mould is 40～60cm
3/ s.
6. according to claim 3 or 4 described methods, it is characterized in that supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 5～10s.
7. method according to claim 5 is characterized in that, supercritical fluid and the polysulfones-like polymer time of staying in screw extruder is 5～10s.
8. method according to claim 1 is characterized in that, the weight ratio of described supercritical fluid and described polysulfones-like polymer is:
Overcritical N
2: described polysulfones-like polymer=1: 250～1: 111;
Supercritical CO
2: described polysulfones-like polymer=1: 83～1: 37.
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Cited By (8)
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|---|---|---|---|---|
| WO2012033979A1 (en) * | 2010-09-10 | 2012-03-15 | Playtex Products, Inc. | Polymer pellets containing supercritical fluid and methods of making and using |
| CN102443970A (en) * | 2011-10-28 | 2012-05-09 | 中原工学院 | Method for preparing polysulfonate microporous fibre non-woven fabric |
| CN102505165A (en) * | 2011-10-28 | 2012-06-20 | 中原工学院 | Method for preparing polysulfone micro-porous fiber by supercritical fluid meltblown spinning process |
| CN103009540A (en) * | 2011-09-28 | 2013-04-03 | 深圳光启高等理工研究院 | Metamaterial substrate based on controllable dielectric constant and preparation method of substrate |
| CN103382261A (en) * | 2013-07-24 | 2013-11-06 | 大连工业大学 | Method for preparing PPESK-nucleating agent composite material through super-critical CO2 foaming |
| CN103382262A (en) * | 2013-07-24 | 2013-11-06 | 大连工业大学 | Method for preparing PPESK through super-critical CO2 foaming |
| CN111621054A (en) * | 2019-02-27 | 2020-09-04 | 中国科学院宁波材料技术与工程研究所 | Microcellular foam material and preparation method thereof |
| CN114230846A (en) * | 2021-12-30 | 2022-03-25 | 东莞兆阳兴业塑胶制品有限公司 | Supercritical foaming process of PES (polyether sulfone) foaming material |
-
2010
- 2010-01-12 CN CN201010022664A patent/CN101786310A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012033979A1 (en) * | 2010-09-10 | 2012-03-15 | Playtex Products, Inc. | Polymer pellets containing supercritical fluid and methods of making and using |
| CN103347475B (en) * | 2010-09-10 | 2016-06-01 | Edgewell个人护理品牌有限责任公司 | Containing supercritical fluid polymer beads and manufacture method thereof and using method |
| CN103347475A (en) * | 2010-09-10 | 2013-10-09 | 普莱特克斯产品有限责任公司 | Polymer pellets containing supercritical fluid and method of making and using |
| CN103009540A (en) * | 2011-09-28 | 2013-04-03 | 深圳光启高等理工研究院 | Metamaterial substrate based on controllable dielectric constant and preparation method of substrate |
| CN103009540B (en) * | 2011-09-28 | 2015-03-04 | 深圳光启高等理工研究院 | Metamaterial substrate based on controllable dielectric constant and preparation method of substrate |
| CN102505165A (en) * | 2011-10-28 | 2012-06-20 | 中原工学院 | Method for preparing polysulfone micro-porous fiber by supercritical fluid meltblown spinning process |
| CN102443970A (en) * | 2011-10-28 | 2012-05-09 | 中原工学院 | Method for preparing polysulfonate microporous fibre non-woven fabric |
| CN103382261A (en) * | 2013-07-24 | 2013-11-06 | 大连工业大学 | Method for preparing PPESK-nucleating agent composite material through super-critical CO2 foaming |
| CN103382262A (en) * | 2013-07-24 | 2013-11-06 | 大连工业大学 | Method for preparing PPESK through super-critical CO2 foaming |
| CN103382262B (en) * | 2013-07-24 | 2015-02-25 | 大连工业大学 | Method for preparing PPESK through super-critical CO2 foaming |
| CN111621054A (en) * | 2019-02-27 | 2020-09-04 | 中国科学院宁波材料技术与工程研究所 | Microcellular foam material and preparation method thereof |
| CN111621054B (en) * | 2019-02-27 | 2022-09-06 | 中国科学院宁波材料技术与工程研究所 | Microcellular foam material and preparation method thereof |
| CN114230846A (en) * | 2021-12-30 | 2022-03-25 | 东莞兆阳兴业塑胶制品有限公司 | Supercritical foaming process of PES (polyether sulfone) foaming material |
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Application publication date: 20100728 |