CN115651408B - Temperature-sensitive polyethersulfone composite material and application thereof in preparation of intelligent ultrafiltration membrane for temperature responsiveness - Google Patents
Temperature-sensitive polyethersulfone composite material and application thereof in preparation of intelligent ultrafiltration membrane for temperature responsiveness Download PDFInfo
- Publication number
- CN115651408B CN115651408B CN202211190738.XA CN202211190738A CN115651408B CN 115651408 B CN115651408 B CN 115651408B CN 202211190738 A CN202211190738 A CN 202211190738A CN 115651408 B CN115651408 B CN 115651408B
- Authority
- CN
- China
- Prior art keywords
- temperature
- sensitive
- parts
- composite material
- polyethersulfone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 115
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 83
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012528 membrane Substances 0.000 title claims abstract description 18
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 18
- 230000004043 responsiveness Effects 0.000 title claims abstract description 7
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 53
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000002041 carbon nanotube Substances 0.000 claims description 28
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 28
- 239000003365 glass fiber Substances 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 25
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 20
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 18
- 235000011152 sodium sulphate Nutrition 0.000 claims description 18
- 239000012986 chain transfer agent Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 5
- 229940082004 sodium laurate Drugs 0.000 claims description 5
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- GQECANUIPBFPLA-UHFFFAOYSA-N 2-(carboxymethylsulfanylcarbothioylsulfanyl)acetic acid Chemical compound OC(=O)CSC(=S)SCC(O)=O GQECANUIPBFPLA-UHFFFAOYSA-N 0.000 description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 7
- 235000013539 calcium stearate Nutrition 0.000 description 7
- 239000008116 calcium stearate Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000011160 research Methods 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of ultrafiltration membrane materials, and particularly discloses a temperature-sensitive polyethersulfone composite material and application thereof in preparation of an intelligent ultrafiltration membrane for temperature responsiveness. The temperature-sensitive polyethersulfone composite material comprises the following raw material components in parts by weight: 70-100 parts of polyether sulfone resin; 20-30 parts of temperature-sensitive block polymer; 5-10 parts of a composite reinforcing agent; 1-3 parts of dispersing agent. The temperature-sensitive polyethersulfone composite material is used for preparing the ultrafiltration membrane, so that the ultrafiltration membrane not only has temperature sensitivity, but also has better tensile strength.
Description
Technical Field
The invention relates to the technical field of ultrafiltration membrane materials, in particular to a temperature-sensitive polyethersulfone composite material and application thereof in preparing an intelligent ultrafiltration membrane for temperature responsiveness.
Background
Ultrafiltration membrane refers to an artificial permeable membrane used in the ultrafiltration process; wherein, materials such as cellulose acetate, cellulose acetate esters, polyethylene, polysulfone, polyamide and the like are common materials for preparing ultrafiltration membranes.
The intelligent ultrafiltration membrane with temperature responsiveness is prepared from a polymer with sensitivity to temperature; the pore diameter or the surface property can be changed according to the change of the temperature, so that different ultrafiltration effects at different temperatures are realized.
In order to obtain a polymer with sensitivity, a thermosensitive block polymer can be added into the polymer in general; for example, the temperature-sensitive ultrafiltration membrane is prepared by adding a temperature-sensitive amphiphilic polymer into a polyvinylidene fluoride membrane material in Chinese patent No. CN 103418255A.
However, the inventor finds that the temperature-sensitive block polymer is added into the polyethersulfone material in the research, and the prepared temperature-sensitive polyethersulfone composite material has temperature-sensitive performance; but its tensile strength is insufficient and needs to be further improved.
Disclosure of Invention
In order to overcome at least one technical problem existing in the prior art, the invention firstly provides a temperature-sensitive polyethersulfone composite material. The temperature-sensitive polyether sulfone composite material has temperature-sensitive performance by adding the temperature-sensitive block polymer into the polyether sulfone material; meanwhile, the tensile strength of the temperature-sensitive polyethersulfone composite material is also improved by adding the composite reinforcing agent.
The technical problems to be solved by the invention are realized by the following technical scheme:
the temperature-sensitive polyethersulfone composite material comprises the following raw material components in parts by weight:
70-100 parts of polyether sulfone resin; 20-30 parts of temperature-sensitive block polymer; 5-10 parts of a composite reinforcing agent; 1-3 parts of dispersing agent.
Preferably, the temperature-sensitive polyethersulfone composite material comprises the following raw material components in parts by weight:
80-90 parts of polyether sulfone resin; 20-25 parts of temperature-sensitive block polymer; 6-8 parts of a composite reinforcing agent; 1-2 parts of dispersing agent.
Most preferably, the temperature-sensitive polyethersulfone composite material comprises the following raw material components in parts by weight:
80 parts of polyether sulfone resin; 25 parts of temperature-sensitive block polymer; 6 parts of a composite reinforcing agent; 2 parts of dispersing agent.
Preferably, the thermosensitive block polymer is prepared by the following method:
adding a polymerization monomer, a chain transfer agent and an initiator into an organic solvent to perform polymerization reaction; and after the reaction is finished, the thermosensitive block polymer is obtained.
Preferably, the molar ratio of the polymerization monomer to the chain transfer agent to the initiator is 20-40:10:1.
Most preferably, the molar ratio of the polymerized monomer, chain transfer agent and initiator is 30:10:1.
Preferably, the polymeric monomer is selected from N-vinylcaprolactam and/or N-isopropylacrylamide.
According to the invention, the temperature-sensitive block polymer obtained by polymerizing the N-vinyl caprolactam and/or N-isopropyl acrylamide serving as monomers is added, so that the prepared temperature-sensitive polyethersulfone composite material has temperature-sensitive performance.
Preferably, the composite reinforcing agent consists of glass fibers and carbon nanotubes;
preferably, the weight ratio of the glass fiber to the carbon nano tube is 2-4: 1.
most preferably, the weight ratio of the glass fiber to the carbon nano tube is 3:1.
according to the invention, the tensile strength of the prepared temperature-sensitive polyethersulfone composite material is improved by adding the composite reinforcing agent consisting of the glass fiber and the carbon nano tube.
Preferably, the composite reinforcing agent is a modified composite reinforcing agent, and the modified composite reinforcing agent is prepared by the following method:
(1) Adding glass fiber and carbon nano tube into water, and carrying out ultrasonic treatment to obtain dispersion liquid;
(2) Adding lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate into the dispersion liquid, continuing to disperse, and taking solid after the dispersion is finished to obtain the modified composite reinforcing agent.
The inventor finds that the tensile strength of the thermosensitive polyethersulfone composite material prepared by adding the thermosensitive block polymer is improved but the amplitude of the improvement is not large by simply adding 5-10 parts by weight of the composite reinforcing agent into the thermosensitive polyethersulfone composite material. The inventors have surprisingly found in the research that the modified composite reinforcing agent obtained by modifying the glass fiber and the carbon nano tube by the method provided by the invention has a far greater improvement range of the tensile strength of the temperature-sensitive polyethersulfone composite material provided by the invention than that of the glass fiber and the carbon nano tube which are not modified.
The inventors again emphasized that the addition of sodium laurate monoethanolamide sulfate and calcium lignosulfonate in step (2) was critical; research shows that the modified composite reinforcing agent prepared by simultaneously adding lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate can greatly improve the tensile strength of the temperature-sensitive polyether sulfone composite material compared with an unmodified composite reinforcing agent; however, the tensile strength of the temperature-sensitive polyethersulfone composite material of the present invention cannot be greatly improved by adding sodium laurate monoethanolamide sulfate alone or calcium lignosulfonate alone or by adding other components; meanwhile, the modified composite reinforcing agent prepared by adding lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate can synergistically improve the tensile strength of the temperature-sensitive polyether sulfone composite material.
Preferably, the weight ratio of the glass fiber to the carbon nano tube is 2-4: 1.
most preferably, the weight ratio of the glass fiber to the carbon nano tube is 3:1.
preferably, the carbon nanotubes are multiwall carbon nanotubes.
Preferably, the weight ratio of the added lauric acid monoethanolamide sodium sulfate to the calcium lignosulfonate to the dispersion is 8-15:5-10:100;
most preferably, the weight ratio of the lauric acid monoethanolamide sodium sulfate to the calcium lignosulfonate added to the dispersion is 10:7:100.
The invention also provides application of the temperature-sensitive polyethersulfone composite material in preparation of an intelligent ultrafiltration membrane for temperature responsiveness.
The beneficial effects are that: the invention provides a brand new temperature-sensitive polyethersulfone composite material; the temperature-sensitive polyether sulfone composite material has temperature-sensitive performance by adding the temperature-sensitive block polymer into the polyether sulfone material; meanwhile, the tensile strength of the temperature-sensitive polyethersulfone composite material is also improved by adding the composite reinforcing agent. In particular, the modified composite reinforcing agent obtained by modifying the glass fiber and the carbon nano tube by the method can further greatly improve the tensile strength of the temperature-sensitive polyethersulfone composite material compared with an unmodified composite reinforcing agent. Therefore, the temperature-sensitive polyethersulfone composite material is used for preparing the ultrafiltration membrane, so that the ultrafiltration membrane not only has temperature sensitivity, but also has better tensile strength.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
The polyethersulfone resin used in the following examples is polyethersulfone under the brand name E6020P of Basf brand; other sources not noted are conventional materials available commercially to those skilled in the art.
Example 1 preparation of temperature-sensitive polyethersulfone composite Material
The raw materials comprise the following components in parts by weight: 80 parts of polyether sulfone resin; 25 parts of temperature-sensitive block polymer; 6 parts of a composite reinforcing agent; 2 parts of dispersing agent calcium stearate;
the thermosensitive block polymer is prepared by the following method: adding N-isopropyl acrylamide, a chain transfer agent bis (carboxymethyl) trithiocarbonate and an initiator azodiisobutyronitrile with the molar ratio of 30:10:1 into an organic solvent 1, 4-dioxane with the total weight of 8 times of the raw materials, and carrying out polymerization reaction for 8 hours at 65 ℃ under the protection of nitrogen; obtaining a product after the reaction is finished, and obtaining the temperature-sensitive block polymer;
the weight ratio of the composite reinforcing agent is 3:1 and multi-wall carbon nanotubes.
The preparation method comprises the following steps: and (3) putting the raw materials in parts by weight into a double-screw extruder for melt extrusion to obtain the temperature-sensitive polyethersulfone composite material.
Example 2 preparation of temperature-sensitive polyethersulfone composite Material
The raw materials comprise the following components in parts by weight: 80 parts of polyether sulfone resin; 25 parts of temperature-sensitive block polymer; 6 parts of modified composite reinforcing agent; 2 parts of dispersing agent calcium stearate;
the thermosensitive block polymer is prepared by the following method: adding N-isopropyl acrylamide, a chain transfer agent bis (carboxymethyl) trithiocarbonate and an initiator azodiisobutyronitrile with the molar ratio of 30:10:1 into an organic solvent 1, 4-dioxane with the total weight of 8 times of the raw materials, and carrying out polymerization reaction for 8 hours at 65 ℃ under the protection of nitrogen; obtaining a product after the reaction is finished, and obtaining the temperature-sensitive block polymer;
the modified composite reinforcing agent is prepared by the following method:
(1) The weight ratio is 3:1, adding glass fiber and carbon nano tube into water with the weight being 10 times that of the glass fiber and carbon nano tube, and carrying out ultrasonic treatment for 30min to disperse liquid;
(2) Adding lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate into the dispersion liquid, continuing to disperse, and taking solid after the dispersion is finished to obtain the modified composite reinforcing agent;
wherein the weight ratio of the added lauric acid monoethanolamide sodium sulfate to the dispersion liquid is 10:7:100.
The preparation method comprises the following steps: and (3) putting the raw materials in parts by weight into a double-screw extruder for melt extrusion to obtain the temperature-sensitive polyethersulfone composite material.
Example 3 preparation of temperature-sensitive polyethersulfone composite Material
The raw materials comprise the following components in parts by weight: 70 parts of polyether sulfone resin; 30 parts of temperature-sensitive block polymer; 5 parts of modified composite reinforcing agent; 1 part of dispersant calcium stearate;
the thermosensitive block polymer is prepared by the following method: adding N-isopropyl acrylamide, a chain transfer agent bis (carboxymethyl) trithiocarbonate and an initiator azodiisobutyronitrile with the molar ratio of 30:10:1 into an organic solvent 1, 4-dioxane with the total weight of 8 times of the raw materials, and carrying out polymerization reaction for 8 hours at 65 ℃ under the protection of nitrogen; obtaining a product after the reaction is finished, and obtaining the temperature-sensitive block polymer;
the modified composite reinforcing agent is prepared by the following method:
(1) The weight ratio is 2:1, adding glass fiber and carbon nano tube into water with the weight being 10 times that of the glass fiber and carbon nano tube, and carrying out ultrasonic treatment for 30min to disperse liquid;
(2) Adding lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate into the dispersion liquid, continuing to disperse, and taking solid after the dispersion is finished to obtain the modified composite reinforcing agent;
wherein the weight ratio of the added lauric acid monoethanolamide sodium sulfate to the dispersion liquid is 15:5:100.
The preparation method comprises the following steps: and (3) putting the raw materials in parts by weight into a double-screw extruder for melt extrusion to obtain the temperature-sensitive polyethersulfone composite material.
Example 4 preparation of temperature-sensitive polyethersulfone composite Material
The raw materials comprise the following components in parts by weight: 100 parts of polyether sulfone resin; 20 parts of temperature-sensitive block polymer; 10 parts of modified composite reinforcing agent; 3 parts of dispersing agent calcium stearate;
the thermosensitive block polymer is prepared by the following method: adding N-isopropyl acrylamide, a chain transfer agent bis (carboxymethyl) trithiocarbonate and an initiator azodiisobutyronitrile with the molar ratio of 30:10:1 into an organic solvent 1, 4-dioxane with the total weight of 8 times of the raw materials, and carrying out polymerization reaction for 8 hours at 65 ℃ under the protection of nitrogen; obtaining a product after the reaction is finished, and obtaining the temperature-sensitive block polymer;
the modified composite reinforcing agent is prepared by the following method:
(1) The weight ratio is 4:1, adding glass fiber and carbon nano tube into water with the weight being 10 times that of the glass fiber and carbon nano tube, and carrying out ultrasonic treatment for 30min to disperse liquid;
(2) Adding lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate into the dispersion liquid, continuing to disperse, and taking solid after the dispersion is finished to obtain the modified composite reinforcing agent;
wherein the weight ratio of the added lauric acid monoethanolamide sodium sulfate to the dispersion liquid is 8:10:100.
The preparation method comprises the following steps: and (3) putting the raw materials in parts by weight into a double-screw extruder for melt extrusion to obtain the temperature-sensitive polyethersulfone composite material.
Comparative example 1 preparation of temperature sensitive polyethersulfone composite Material
The raw materials comprise the following components in parts by weight: 80 parts of polyether sulfone resin; 25 parts of temperature-sensitive block polymer; 2 parts of dispersing agent calcium stearate;
the thermosensitive block polymer is prepared by the following method: adding N-isopropyl acrylamide, a chain transfer agent bis (carboxymethyl) trithiocarbonate and an initiator azodiisobutyronitrile with the molar ratio of 30:10:1 into an organic solvent 1, 4-dioxane with the total weight of 8 times of the raw materials, and carrying out polymerization reaction for 8 hours at 65 ℃ under the protection of nitrogen; and taking a product after the reaction is finished to obtain the temperature-sensitive block polymer.
The preparation method comprises the following steps: and (3) putting the raw materials in parts by weight into a double-screw extruder for melt extrusion to obtain the temperature-sensitive polyethersulfone composite material.
Comparative example 1 does not add a reinforcing agent.
Comparative example 2 preparation of temperature sensitive polyethersulfone composite Material
The raw materials comprise the following components in parts by weight: 80 parts of polyether sulfone resin; 25 parts of temperature-sensitive block polymer; 6 parts of modified composite reinforcing agent; 2 parts of dispersing agent calcium stearate;
the thermosensitive block polymer is prepared by the following method: adding N-isopropyl acrylamide, a chain transfer agent bis (carboxymethyl) trithiocarbonate and an initiator azodiisobutyronitrile with the molar ratio of 30:10:1 into an organic solvent 1, 4-dioxane with the total weight of 8 times of the raw materials, and carrying out polymerization reaction for 8 hours at 65 ℃ under the protection of nitrogen; obtaining a product after the reaction is finished, and obtaining the temperature-sensitive block polymer;
the modified composite reinforcing agent is prepared by the following method:
(1) The weight ratio is 3:1, adding glass fiber and carbon nano tube into water with the weight being 10 times that of the glass fiber and carbon nano tube, and carrying out ultrasonic treatment for 30min to disperse liquid;
(2) Adding lauric acid monoethanolamide sodium sulfate into the dispersion liquid, continuing to disperse, and taking solid after the dispersion is finished to obtain the modified composite reinforcing agent;
wherein, the weight ratio of the lauric acid monoethanolamide sodium sulfate added to the dispersion liquid is 17:100.
The preparation method comprises the following steps: and (3) putting the raw materials in parts by weight into a double-screw extruder for melt extrusion to obtain the temperature-sensitive polyethersulfone composite material.
Comparative example 2 in the modification of the composite reinforcing agent, the composite reinforcing agent was modified by adding only sodium laurate monoethanolamide sulfate.
Comparative example 3 preparation of temperature sensitive polyethersulfone composite Material
The raw materials comprise the following components in parts by weight: 80 parts of polyether sulfone resin; 25 parts of temperature-sensitive block polymer; 6 parts of modified composite reinforcing agent; 2 parts of dispersing agent calcium stearate;
the thermosensitive block polymer is prepared by the following method: adding N-isopropyl acrylamide, a chain transfer agent bis (carboxymethyl) trithiocarbonate and an initiator azodiisobutyronitrile with the molar ratio of 30:10:1 into an organic solvent 1, 4-dioxane with the total weight of 8 times of the raw materials, and carrying out polymerization reaction for 8 hours at 65 ℃ under the protection of nitrogen; obtaining a product after the reaction is finished, and obtaining the temperature-sensitive block polymer;
the modified composite reinforcing agent is prepared by the following method:
(1) The weight ratio is 3:1, adding glass fiber and carbon nano tube into water with the weight being 10 times that of the glass fiber and carbon nano tube, and carrying out ultrasonic treatment for 30min to disperse liquid;
(2) Adding calcium lignosulfonate into the dispersion liquid, continuing to disperse, and taking solid after the dispersion is finished to obtain the modified composite reinforcing agent;
wherein the weight ratio of the added calcium lignosulfonate to the dispersion liquid is 17:100.
The preparation method comprises the following steps: and (3) putting the raw materials in parts by weight into a double-screw extruder for melt extrusion to obtain the temperature-sensitive polyethersulfone composite material.
Comparative example 3 in the modification of the composite reinforcing agent, the composite reinforcing agent was modified by adding only calcium lignosulfonate.
The tensile strength test results of the temperature-sensitive polyethersulfone composite materials prepared in examples 1 to 4 and comparative examples 1 to 3 are shown in Table 1.
Table 1.
As can be seen from the experimental data in Table 1, the tensile strength of the temperature-sensitive polyethersulfone composite material prepared by adding the temperature-sensitive block polymer into the polyethersulfone material in comparative example 1 is only 71MPa. In the embodiment 1, the tensile strength of the prepared temperature-sensitive polyethersulfone composite material is improved by adding the composite reinforcing agent consisting of glass fibers and carbon nanotubes.
As can be seen from the experimental data in table 1, the tensile strength of the temperature-sensitive polyethersulfone composite materials prepared in examples 2 to 4 is significantly higher than that of the materials in example 1 and comparative example 1; this illustrates: in the embodiment 1, the tensile strength of the temperature-sensitive polyethersulfone composite material is improved by adding the composite reinforcing agent consisting of glass fibers and carbon nanotubes, but the improvement is not large; in the embodiments 2 to 4, the modified composite reinforcing agent obtained by modifying the glass fiber and the carbon nano tube by the method of the invention can greatly improve the tensile strength of the temperature-sensitive polyethersulfone composite material; the improvement amplitude of the tensile strength of the temperature-sensitive polyethersulfone composite material is far greater than that of the glass fiber and the carbon nano tube added with the unmodified glass fiber.
As can be seen from the experimental data in Table 1, the tensile strength of the temperature-sensitive polyethersulfone composite material prepared in comparative examples 2 and 3 is compared with that of the temperature-sensitive polyethersulfone composite material prepared in example 1, and the improvement amplitude is not large; much smaller than example 2; this illustrates: the addition of lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate in step (2) is critical; the tensile strength of the temperature-sensitive polyether sulfone composite material can be greatly improved by adding the modified composite reinforcing agent prepared by lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate; however, the tensile strength of the temperature-sensitive polyethersulfone composite material of the present invention cannot be greatly improved by adding sodium laurate monoethanolamide sulfate alone or calcium lignosulfonate alone or by adding other components; meanwhile, the modified composite reinforcing agent prepared by adding lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate can synergistically improve the tensile strength of the temperature-sensitive polyether sulfone composite material.
Claims (10)
1. The temperature-sensitive polyethersulfone composite material is characterized by comprising the following raw material components in parts by weight:
70-100 parts of polyether sulfone resin; 20-30 parts of temperature-sensitive block polymer; 5-10 parts of a composite reinforcing agent; 1-3 of dispersing agent;
the composite reinforcing agent is a modified composite reinforcing agent, and the modified composite reinforcing agent is prepared by the following method:
(1) Adding glass fiber and carbon nano tube into water, and carrying out ultrasonic treatment to obtain dispersion liquid;
(2) Adding lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate into the dispersion liquid, continuing to disperse, and taking solid after the dispersion is finished to obtain the modified composite reinforcing agent;
the weight ratio of the glass fiber to the carbon nano tube is 2-4: 1.
2. the temperature-sensitive polyethersulfone composite material according to claim 1, comprising the following raw material components in parts by weight:
80-90 parts of polyether sulfone resin; 20-25 parts of temperature-sensitive block polymer; 6-8 parts of a composite reinforcing agent; 1-2 parts of dispersing agent.
3. The temperature-sensitive polyethersulfone composite material according to claim 1, comprising the following raw material components in parts by weight:
80 parts of polyether sulfone resin; 25 parts of temperature-sensitive block polymer; 6 parts of a composite reinforcing agent; 2 parts of dispersing agent.
4. The temperature-sensitive polyethersulfone composite material of claim 1, wherein the temperature-sensitive block polymer is prepared by the following method:
adding a polymerization monomer, a chain transfer agent and an initiator into an organic solvent to perform polymerization reaction; and after the reaction is finished, the thermosensitive block polymer is obtained.
5. The temperature-sensitive polyethersulfone composite material according to claim 4, wherein the molar ratio of the polymerized monomer, the chain transfer agent and the initiator is 20-40:10:1.
6. The temperature-sensitive polyethersulfone composite material according to claim 5, characterized in that said polymeric monomer is chosen from N-vinylcaprolactam and/or N-isopropylacrylamide.
7. The temperature-sensitive polyethersulfone composite material according to claim 1, wherein the weight ratio of glass fiber to carbon nanotubes is 3:1.
8. the temperature-sensitive polyethersulfone composite material according to claim 1, wherein the weight ratio of the added lauric acid monoethanolamide sodium sulfate and calcium lignosulfonate to the dispersion is 8-15:5-10:100.
9. The temperature-sensitive polyethersulfone composite material of claim 8, wherein the weight ratio of the added sodium laurate monoethanolamide sulfate and calcium lignosulfonate to the dispersion is 10:7:100.
10. The use of the temperature-sensitive polyethersulfone composite material of claim 1 in the preparation of an intelligent ultrafiltration membrane for temperature responsiveness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211190738.XA CN115651408B (en) | 2022-09-28 | 2022-09-28 | Temperature-sensitive polyethersulfone composite material and application thereof in preparation of intelligent ultrafiltration membrane for temperature responsiveness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211190738.XA CN115651408B (en) | 2022-09-28 | 2022-09-28 | Temperature-sensitive polyethersulfone composite material and application thereof in preparation of intelligent ultrafiltration membrane for temperature responsiveness |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115651408A CN115651408A (en) | 2023-01-31 |
| CN115651408B true CN115651408B (en) | 2023-12-26 |
Family
ID=84984588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211190738.XA Active CN115651408B (en) | 2022-09-28 | 2022-09-28 | Temperature-sensitive polyethersulfone composite material and application thereof in preparation of intelligent ultrafiltration membrane for temperature responsiveness |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115651408B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151599A (en) * | 2014-07-18 | 2014-11-19 | 复旦大学 | Ionic liquid functionalized temperature-responsive composite film and preparation method thereof |
| CN104307389A (en) * | 2014-10-11 | 2015-01-28 | 四川大学 | Polyether sulfone temperature stimulus response film and preparation method thereof |
| CN112126230A (en) * | 2020-09-15 | 2020-12-25 | 暨南大学 | Wear-resistant polyether sulfone composite material and preparation method thereof |
-
2022
- 2022-09-28 CN CN202211190738.XA patent/CN115651408B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151599A (en) * | 2014-07-18 | 2014-11-19 | 复旦大学 | Ionic liquid functionalized temperature-responsive composite film and preparation method thereof |
| CN104307389A (en) * | 2014-10-11 | 2015-01-28 | 四川大学 | Polyether sulfone temperature stimulus response film and preparation method thereof |
| CN112126230A (en) * | 2020-09-15 | 2020-12-25 | 暨南大学 | Wear-resistant polyether sulfone composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115651408A (en) | 2023-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR870000360B1 (en) | High strength polyacrylonitril fiber and it's producing method | |
| CN110078860B (en) | Polyacrylonitrile (PAN) polymers having a low polydispersity index (PDI) and carbon fibers made therefrom | |
| CN111718591A (en) | Lignin-containing bio-based composite material and preparation method thereof | |
| CN111995769B (en) | Controllable dual-temperature-sensitive hydrogel and preparation method thereof | |
| CN112370978A (en) | Polysulfone ultrafiltration membrane and preparation method thereof | |
| CN106632861B (en) | Temperature-sensitive bacteria nano-cellulose composite hydrogel material and preparation method and application thereof | |
| CN107973881A (en) | A kind of preparation of high stretch hydroxyethyl cellulose/polyacrylamide hydrogel | |
| CN115651408B (en) | Temperature-sensitive polyethersulfone composite material and application thereof in preparation of intelligent ultrafiltration membrane for temperature responsiveness | |
| CN112695411B (en) | Preparation method of temperature response type nanofiber dressing | |
| CN108727753B (en) | Preparation method of thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel | |
| KR870001386B1 (en) | High strength high elastic rate polyacryliro nitrilic fiber | |
| CN113603993A (en) | Preparation method of self-healing polymer-nano composite material | |
| CN110860217B (en) | Green preparation method of pressure response type polyvinylidene fluoride hollow fiber membrane | |
| CN104558452B (en) | Preparation method of polyvinylidene fluoride-polyvinylpyrrolidone (PVDF-PVP) block copolymer | |
| CN114588792B (en) | Polyvinyl butyral blending reinforced polyvinylidene chloride ultrafiltration membrane and preparation method thereof | |
| CN106823853B (en) | Self-repairing PP (polypropylene) water treatment membrane and preparation method thereof | |
| WO2000050675A1 (en) | Carbon fibers or sheets made from copolymers of acrylonitrile | |
| CN114479224B (en) | Thermoplastic resin porous foam and preparation method and application thereof | |
| CN115449105A (en) | Preparation method and application of polytetrafluoroethylene stretched film | |
| CN108221075A (en) | A kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance | |
| CN103752178A (en) | Hollow fibre membrane and preparation method thereof | |
| CN112316756A (en) | High-strength and high-retention TIPS hollow fiber membrane and preparation method thereof | |
| CN111715080A (en) | Preparation method of biodegradable high-molecular ultrafiltration membrane | |
| CN110036045B (en) | Method for producing polyacrylonitrile | |
| US3542719A (en) | Process for preparing poly(1,4-benzamide) in situ in a polyacrylic solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |