CN107936560A - A kind of polyether sulfone composite modification material and preparation method thereof - Google Patents
A kind of polyether sulfone composite modification material and preparation method thereof Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention discloses a kind of polyether sulfone composite modification material and preparation method thereof, including following parts by weight raw material to be prepared：20 30 parts of polytetrafluoroethylene (PTFE), 55 75 parts of polyether sulfone, 15 20 parts of nano-calcium carbonate, 5 10 parts of modifying agent, 0.3 0.8 parts of coupling agent, 0.3 0.5 parts of crosslinking agent, 13 parts of ultra-violet absorber, 13 parts of antioxidant；The present invention is for composite by the nano-calcium carbonate Jing Guo specific aim modification and polyether sulfone, and nano-calcium carbonate is set to be dispersed in polyether sulfone system, obtained polyether sulfone composite modification material ageing-resistant performance is excellent, is conducive to application of the polyether sulfone in more areas.
Description
Technical field
The present invention relates to modified poly (ether-sulfone) Material Field, and in particular to a kind of polyether sulfone composite modification material and its preparation side
Method.
Background technology
Polyether sulfone is, the right and wrong obtained with diphenyl ether condensation by the double sulphonyl chlorodiphenyl ethers of 4,4'- under anhydrous ferric chloride catalysis
Crystalline state polymer, is a kind of thermoplastic engineering plastic.Due to heat resistance, hot water resistance, creep resistance, dimensional stability,
The excellent comprehensive performance such as impact resistance, chemical proofing, nontoxic, fire-retardant, so for a long time in electronics, electric appliance, machinery, vapour
Car, medical apparatus, food processing and the field such as stickness paint is not widely used.
With the continuous improvement that people require material ageing-resistant performance, the polyether sulfone without ageing-resistant modification has been difficult to full
Sufficient demand, thus, ageing-resistant modification is carried out to polyether sulfone and is necessitated.Now to the ageing-resistant modification processing method kind of polyether sulfone
Class is various, and modified effect is also fine, especially with the appearance and application of nano material, the resistance to ag(e)ing increase effect of polyether sulfone
Significantly, polyether sulfone is enable largely to be used in more areas, but there is also deficiency.Although nano material has ageing-resistant enhancing effect
It is good, the advantages of additive amount is small, but there is also difficulties in dispersion, it is of high cost the defects of.In ageing-resistant modifying process is carried out, nanometer material
The scattered inequality of material can influence its ageing-resistant effect, and obtained modified material resistance to ag(e)ing is relatively low, production to modified material and should
With adversely affecting.
The content of the invention
The defects of it is an object of the invention to overcome existing polyether sulfone composite modification material resistance to ag(e)ing poor, there is provided a kind of
Polyether sulfone composite modification material and preparation method thereof；The present invention is by the nano-calcium carbonate and polyether sulfone Jing Guo specific aim modification
It is for composite, and nano-calcium carbonate is dispersed in polyether sulfone system, obtained polyether sulfone composite modification material is ageing-resistant
Excellent performance, is conducive to application of the polyether sulfone in more areas.
In order to realize foregoing invention purpose, the present invention provides a kind of polyether sulfone composite modification material, including following weight
Part raw material are prepared：15-20 parts of nano-calcium carbonate, 5-10 parts of modifying agent, 20-30 parts of polytetrafluoroethylene (PTFE), 55-75
Part polyether sulfone, 0.3-0.8 part of coupling agent, 0.3-0.5 parts of crosslinking agent, 1-3 parts of ultra-violet absorber, 1-3 parts resist
Oxygen agent.
A kind of above-mentioned polyether sulfone composite modification material, can increase resin material resistance to ag(e)ing according to nano-calcium carbonate and crosslinking
Basic principle, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, come improve nano-calcium carbonate with
Compatibility between polyether sulfone, and make nano-calcium carbonate disperse evenly, to make nano-calcium carbonate to polyether sulfone in polyether sulfone
Resistance to ag(e)ing humidification is more preferable, also modified polyether sulfone composite modification material is existed by controlling the degree of polymerization of polyether sulfone
Reach optimum balance relation between resistance to ag(e)ing and processability, so that the polyether sulfone composite modification material made is with excellent
Resistance to ag(e)ing under conditions of, it may have excellent processability, allows it to be applied in more areas.
A kind of above-mentioned polyether sulfone composite modification material, wherein, the nano-calcium carbonate particle diameter is 10-80nm；Nano-sized carbon
Sour calcium particle diameter is smaller, and dispersiveness is poorer, and nano-calcium carbonate particle diameter is bigger, poorer to the ageing-resistant humidification of polyether sulfone；It is preferred that
, the nano-calcium carbonate particle diameter is 30-50nm；Most preferably, the nano-calcium carbonate particle diameter is 40nm.
A kind of above-mentioned polyether sulfone composite modification material, wherein, the modifying agent is dodecyl sodium sulfonate calcium and mercaptan first
The mixture of Ji Xi compositions；The modifying agent can improve the compatibility of nano-calcium carbonate and polyether sulfone and in nano-sized carbon
Sour calcium surface forms polar group, beneficial to scattered；Preferably, dodecyl sodium sulfonate calcium and thiol methyl tin in the modifying agent
The ratio between the amount of material be 1 ︰ 1.
A kind of above-mentioned polyether sulfone composite modification material, wherein, the antioxidant is antioxidant 3314, in antioxidant 626
It is one or two kinds of.The ultra-violet absorber is UV-3813.
A kind of above-mentioned polyether sulfone composite modification material, wherein, the degree of polymerization of polytetrafluoroethylene (PTFE) is bigger, then polyether sulfone after being crosslinked
The resistance to ag(e)ing of composite modification material is poorer, and processability is better, and the polymer of polytetrafluoroethylene (PTFE) is smaller, then polyether sulfone is answered after being crosslinked
The resistance to ag(e)ing of conjunction modified material is better, and processability is poorer, therefore, selects the rational polytetrafluoroethylene (PTFE) degree of polymerization, is that balance is resistance to
The important means of aging and processability.The degree of polymerization of the polytetrafluoroethylene (PTFE) is 80-180；Preferably, the polytetrafluoro
The degree of polymerization of ethene is 100-150；Optimal, the degree of polymerization of the polytetrafluoroethylene (PTFE) is 120；By preferred, what is obtained is poly-
Ether sulfone composite modification material both has excellent resistance to ag(e)ing, it may have preferable processability, is adapted to polyether sulfone in more areas
In promoted and applied.
Wherein, the polyether sulfone degree of polymerization is 600-1200；Preferably, the degree of polymerization of the polyether sulfone is 800-
1100；Most preferably, the degree of polymerization of the polyether sulfone is 1000；By preferred, obtained polyether sulfone composite modification material was both
With excellent resistance to ag(e)ing, it may have preferable processability.
A kind of above-mentioned polyether sulfone composite modification material, wherein, the coupling agent is (the dodecyl benzene sulfonyl of isopropyl three
Base) titanate coupling agent；Isopropyl three (dodecyl benzenesulfonyl) titanate esters can increase nano-calcium carbonate and polyether sulfone and
Compatibility between modified material, improves the performance of polyether sulfone composite modification material.
Wherein, the crosslinking agent is p-methyl benzenesulfonic acid, which can be by the polymer former material of two kinds of different polymerization degrees
The appropriate crosslinking of material, improves the resistance to ag(e)ing of polyether sulfone composite modification material.
A kind of above-mentioned polyether sulfone composite modification material, wherein, its raw material further include dispersant, plasticizer, antistatic additive,
One or more auxiliary agents in coloring agent, brightener；Above-mentioned auxiliary agent can improve the processability of polyether sulfone composite modification material, increase
Its feature etc. is added to act on, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of polyether sulfone composite modification material
Preparation method, comprises the following steps：
（1）Nano-calcium carbonate is handled with coupling agent；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano-calcium carbonate after cladding and polyether sulfone processing for composite in the electric field after mixing, mixture is obtained；
（4）By mixture and polytetrafluoroethylene (PTFE), crosslinking agent, antioxidant, ultra-violet absorber after mixing at place for composite
Reason, obtains polyether sulfone composite modification material.
A kind of preparation method of polyether sulfone composite modification material, first carries out coupling processing with coupling agent to nano-calcium carbonate,
Increase nano-calcium carbonate and modifying agent, the compatibility of polyether sulfone；Again processing is modified to nano-calcium carbonate with modifying agent, and
Its surface forms polar group；Finally the polar group in nano-calcium carbonate surface and polyether sulfone chain is set to polarize using external electric field,
It is powered, by repelling each other between electric charge or attracting principle, while making nano-calcium carbonate dispersed, also can with polyether sulfone chain
Polar group it is bonded so that the ageing-resistant enhancing effect of nano-calcium carbonate is farthest embodied, so as to get change
Property polyether sulfone resistance to ag(e)ing significantly improves；The preparation method is simple and reliable, is suitable for the big rule of polyether sulfone composite modification material
Mould, industrialized production.
A kind of preparation method of above-mentioned polyether sulfone composite modification material, wherein, it is preferred that step 1 carries out coupling processing mistake
Cheng Zhongke is aided in using ultrasonic wave；Shaken by the high speed of ultrasonic wave, make nano-calcium carbonate dispersiveness more preferable, and to coupling processing
With facilitation.
A kind of preparation method of above-mentioned polyether sulfone composite modification material, wherein, the electric field energy described in step 3 produces group
Raw polarization, makes group powered, so as to promote the scattered and bonded effect of nano-calcium carbonate, improves the resistance to of modified poly (ether-sulfone)
Aging.
Preferably, the electric field strength is 1.5-2.8kv/m；Electric field strength is too small, and polarization effect is weak, to nano-calcium carbonate
The dispersion effect of calcium is poor；Electric field strength is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces displacement,
Arrangement and the bonded performance for having an impact, may be decreased polyether sulfone composite modification material to strand；Most preferably, it is described
Electric field strength is 2.0-2.5kv/m.
Wherein, it is preferred that the electric field is the constant parallel electric field of direction of an electric field；The constant parallel electric field of direction of an electric field
Best to the polarization effect of polar group, group intermolecular forces are stablized, to the scattered and bonded facilitation of nano-calcium carbonate
Best results.
Compared with prior art, beneficial effects of the present invention：
1st, polyether sulfone composite modification material of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, makes nanometer
Compatibility between calcium carbonate and polyether sulfone is more preferable, and the dispersiveness in polyether sulfone is more preferable, and nano-calcium carbonate is to the resistance to of polyether sulfone
Aging humidification is more preferable.
2nd, polyether sulfone composite modification material of the present invention makes modification by controlling the degree of polymerization of polyether sulfone and polytetrafluoroethylene (PTFE)
Polyether sulfone composite modification material afterwards reaches optimum balance relation between resistance to ag(e)ing and processability, so as to get polyether sulfone answer
Modified material is closed under conditions of with excellent resistance to ag(e)ing, it may have excellent processability.
3rd, the preparation method of polyether sulfone composite modification material of the present invention, using the polarization of external electric field, can promote nanometer
Calcium carbonate is scattered and bonded in polyether sulfone system, and the ageing-resistant enhancing effect of nano-calcium carbonate is more preferable, obtained polyether sulfone
The resistance to ag(e)ing higher of composite modification material.
4th, the preparation method of polyether sulfone composite modification material of the present invention is simple, reliable, is adapted to polyether sulfone composite modification material
Extensive, industrialized production.
Embodiment
With reference to test example and embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）28 parts of nano-calcium carbonate is handled with 0.5 part isopropyl three (dodecyl benzenesulfonyl) titanate esters；
（2）By the nano-calcium carbonate Jing Guo coupling agent treatment 3.5 parts of dodecyl sodium sulfonate calcium and 3.5 parts of thiol methyl tin
Carry out cladding processing；
（3）It is in electric field strength after mixing by the polyether sulfone that the nano-calcium carbonate after cladding is 900 with 65 parts of the degree of polymerization
Extruded in the constant parallel electric field of the direction of an electric field of 2.0kv/m, obtain mixture；
（4）Polytetrafluoroethylene (PTFE) that the mixture that step 3 is obtained and 25 parts of the degree of polymerization are 120,0.4 part of p-methyl benzenesulfonic acid, 2 parts
Ultra-violet absorber, 2 parts of antioxidant extruded after mixing, obtain polyether sulfone composite modification material.
Embodiment 2
（1）15 parts of nano-calcium carbonate is handled with 0.3 part isopropyl three (dodecyl benzenesulfonyl) titanate esters；
（2）By the nano-calcium carbonate Jing Guo coupling agent treatment 2.5 parts of dodecyl sodium sulfonate calcium and 2.5 parts of thiol methyl tin
Carry out cladding processing；
（3）By polyether sulfone that the nano-calcium carbonate after cladding and 55 parts of the degree of polymerization are 1200 after mixing in electric field strength
To be extruded in the electric field of 2.8kv/m, mixture is obtained；
（4）Polytetrafluoroethylene (PTFE) that the mixture that step 3 is obtained and 20 parts of the degree of polymerization are 180,0.3 part of p-methyl benzenesulfonic acid, 1 part
Ultra-violet absorber, 3 parts of antioxidant extruded after mixing, obtain polyether sulfone composite modification material.
Embodiment 3
（1）20 parts of nano-calcium carbonate is handled with 0.8 part isopropyl three (dodecyl benzenesulfonyl) titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is carried out with 5 parts of dodecyl sodium sulfonate calcium and 5 parts of thiol methyl tin
Cladding processing；
（3）By polyether sulfone that the nano-calcium carbonate after cladding and 75 parts of the degree of polymerization are 600 after mixing in electric field strength
To be extruded in the constant parallel electric field of the direction of an electric field of 1.5kv/m, mixture is obtained；
（4）Polytetrafluoroethylene (PTFE) that the mixture that step 3 is obtained and 30 parts of the degree of polymerization are 80,0.5 part of p-methyl benzenesulfonic acid, 3 parts
Ultra-violet absorber, 1 part of antioxidant extruded after mixing, obtain polyether sulfone composite modification material.
Comparative example 1
（1）18 parts of nano-calcium carbonate is handled with 0.5 part isopropyl three (dodecyl benzenesulfonyl) titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment and 8 parts of dispersant, the polyether sulfone that 65 parts of the degree of polymerization is 900 are mixed
Extruded after closing uniformly in the constant parallel electric field of the direction of an electric field that electric field strength is 2.0kv/m, obtain mixture；
（3）0.4 part of p-methyl benzenesulfonic acid of polytetrafluoroethylene (PTFE) that the mixture that step 2 is obtained and 25 parts of the degree of polymerization are 120,2 parts
Ultra-violet absorber, 2 parts of antioxidant extruded after mixing, obtain polyether sulfone composite modification material.
Comparative example 2
（1）18 parts of nano-calcium carbonate is handled with 0.5 part isopropyl three (dodecyl benzenesulfonyl) titanate esters；
（2）By the nano-calcium carbonate Jing Guo coupling agent treatment 3.5 parts of dodecyl sodium sulfonate calcium and 3.5 parts of thiol methyl tin
Carry out cladding processing；
（3）By polyether sulfone that the nano-calcium carbonate after cladding and 65 parts of the degree of polymerization are 900,25 parts of the degree of polymerization be 120 it is poly-
Tetrafluoroethene, 0.4 part of p-methyl benzenesulfonic acid, 2 parts of ultra-violet absorber, 2 parts of antioxidant are extruded after mixing, are obtained
Polyether sulfone composite modification material.
Comparative example 3
（1）18 parts of nano-calcium carbonate is handled with 0.5 part isopropyl three (dodecyl benzenesulfonyl) titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is wrapped with 3.5 parts of polystyrene and 3.5 parts of thiol methyl tin
Cover processing；
（3）It is in electric field strength after mixing by the polyether sulfone that the nano-calcium carbonate after cladding is 900 with 65 parts of the degree of polymerization
Extruded in the constant parallel electric field of the direction of an electric field of 2.0kv/m, obtain mixture；
（4）Polytetrafluoroethylene (PTFE) that the mixture that step 3 is obtained and 25 parts of the degree of polymerization are 120,0.4 part of p-methyl benzenesulfonic acid, 2 parts
Ultra-violet absorber, 2 parts of antioxidant extruded after mixing, obtain polyether sulfone composite modification material.
Comparative example 4
（1）18 parts of nano-calcium carbonate is handled with 0.5 part isopropyl three (dodecyl benzenesulfonyl) titanate esters；
（2）By the nano-calcium carbonate Jing Guo coupling agent treatment 3.5 parts of dodecyl sodium sulfonate calcium and 3.5 parts of thiol methyl tin
Carry out cladding processing；
（3）By the polytetrafluoroethylene (PTFE) of the nano-calcium carbonate after cladding and 25 parts of the degree of polymerization for 120,0.4 part of p-methyl benzenesulfonic acid, 2
Part ultra-violet absorber, 2 parts of antioxidant, 65 parts of the degree of polymerization be 900 polyether sulfone be in electric field strength after mixing
Extruded in the constant parallel electric field of the direction of an electric field of 2.0kv/m, obtain polyether sulfone composite modification material.
Comparative example 5
（1）18 parts of nano-calcium carbonate is handled with 0.5 part isopropyl three (dodecyl benzenesulfonyl) titanate esters；
（2）By the nano-calcium carbonate Jing Guo coupling agent treatment 3.5 parts of dodecyl sodium sulfonate calcium and 3.5 parts of thiol methyl tin
Carry out cladding processing；
（3）It is in electric field strength after mixing by the polyether sulfone that the nano-calcium carbonate after cladding is 500 with 65 parts of the degree of polymerization
Extruded in the constant parallel electric field of the direction of an electric field of 2.0kv/m, obtain mixture；
（4）The mixture that step 3 is obtained and 25 parts of the degree of polymerization are 50 polytetrafluoroethylene (PTFE), 2 parts of ultra-violet absorber, 2
The antioxidant, 0.4 part of p-methyl benzenesulfonic acid of part are extruded after mixing, obtain polyether sulfone composite modification material.
By the polyether sulfone composite modification material in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, records number
According to as follows：
| Performance | Ageing resistance | Processability |
| Embodiment 1 | ++++++ | ++++ |
| Embodiment 2 | ++++++ | ++++ |
| Embodiment 3 | ++++++ | ++++ |
| Comparative example 1 | ++++ | ++++ |
| Comparative example 2 | ++++ | ++++ |
| Comparative example 3 | ++++ | ++++ |
| Comparative example 4 | ++++ | ++++ |
| Comparative example 5 | ++++++ | ++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the polyether sulfone composite modification material of the present invention being prepared in embodiment 1-3,
Nano-calcium carbonate is uniformly dispersed, and good with the compatibility of polyether sulfone, composite modification material resistance to ag(e)ing is good, and processability is good；And contrast
In example 1, modifying agent is not used processing is modified to nano-calcium carbonate, although adding dispersant, nano-calcium carbonate disperses
Effect is poor, and the poor compatibility with polyether sulfone, the resistance to ag(e)ing of composite modification material significantly reduces；In comparative example 2 not in the electric field
Processing for composite, nano-calcium carbonate dispersion effect is poor, and the resistance to ag(e)ing of composite modification material significantly reduces；Change in comparative example 3
Property agent is not the application defined, and nano-calcium carbonate dispersion effect is poor, and the resistance to ag(e)ing of composite modification material significantly reduces；It is right
Cross-linking reaction equally carries out in the electric field in ratio 4, and electric field has a negative impact cross-linking reaction, so as to get composite modified material
The resistance to ag(e)ing of material reduces；The polyether sulfone and the polytetrafluoroethylene (PTFE) degree of polymerization used in comparative example 5 is too small, although ageing-resistant after compound
Property increased, but its processability significantly reduces, and is unfavorable for the application of polyether sulfone composite modification material.
Claims (10)
1. a kind of polyether sulfone composite modification material, it is characterised in that be prepared including following parts by weight raw material：20-30 parts
Polytetrafluoroethylene (PTFE), 55-75 parts of polyether sulfone, 15-20 parts of nano-calcium carbonate, 5-10 parts of modifying agent, 0.3-0.8 parts of idol
Join agent, 0.3-0.5 parts of crosslinking agent, 1-3 parts of ultra-violet absorber, 1-3 parts of antioxidant；The modifying agent is dodecyl
Sulfoacid calcium and the mixture of thiol methyl tin composition；The coupling agent is even for isopropyl three (dodecyl benzenesulfonyl) titanate esters
Join agent, the crosslinking agent is p-methyl benzenesulfonic acid；The degree of polymerization of the polytetrafluoroethylene (PTFE) is 80-180；The polyether sulfone degree of polymerization is
600-1200。
2. composite modification material according to claim 1, it is characterised in that in the modifying agent dodecyl sodium sulfonate calcium with
The ratio between amount of material of thiol methyl tin is 1 ︰ 1.
3. composite modification material according to claim 1, it is characterised in that the degree of polymerization of the polytetrafluoroethylene (PTFE) is 100-
150。
4. composite modification material according to claim 3, it is characterised in that the degree of polymerization of the polytetrafluoroethylene (PTFE) is 120.
5. composite modification material according to claim 1, it is characterised in that the polyether sulfone degree of polymerization is 800-1100.
6. composite modification material according to claim 5, it is characterised in that the polyether sulfone degree of polymerization is 1000.
7. a kind of preparation method of the composite modification material as described in claim 1-6, it is characterised in that comprise the following steps：
（1）Nano-calcium carbonate is handled with coupling agent；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano-calcium carbonate after cladding and polyether sulfone processing for composite in the electric field after mixing, mixture is obtained；
（4）By mixture and polytetrafluoroethylene (PTFE), crosslinking agent, antioxidant, ultra-violet absorber after mixing at place for composite
Reason, obtains polyether sulfone composite modification material.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric field strength is 1.5-2.8kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric field strength is 2.0-2.5kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field is put down for direction of an electric field is constant
Row electric field.
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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