CN111408285B - Amide hybrid polyester porous separation membrane and preparation method thereof - Google Patents
Amide hybrid polyester porous separation membrane and preparation method thereof Download PDFInfo
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- CN111408285B CN111408285B CN202010288010.5A CN202010288010A CN111408285B CN 111408285 B CN111408285 B CN 111408285B CN 202010288010 A CN202010288010 A CN 202010288010A CN 111408285 B CN111408285 B CN 111408285B
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- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 229920000728 polyester Polymers 0.000 title claims abstract description 51
- 150000001408 amides Chemical class 0.000 title claims abstract description 47
- 238000000926 separation method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005886 esterification reaction Methods 0.000 claims abstract description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims abstract description 10
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003361 porogen Substances 0.000 claims abstract description 7
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000005266 casting Methods 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 6
- 230000015271 coagulation Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 claims 2
- 239000010409 thin film Substances 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 14
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 230000001112 coagulating effect Effects 0.000 description 4
- -1 Polyethylene terephthalate Polymers 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000003368 amide group Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 101150071434 BAR1 gene Proteins 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
本发明公开了一种酰胺杂化聚酯多孔分离膜及其制备方法，其中的酰胺杂化聚酯多孔分离膜由如下重量份数的原料制备而成：改性酰胺杂化聚酯5‑8份；致孔剂3‑5份；溶剂37‑42份；其中：所述改性酰胺杂化聚酯由如下重量份数的原料经酯化缩聚反应制备而成：对苯二甲酸150‑166份；乙二醇70‑80份；己二胺2‑5份；癸二胺4‑6份；1,12‑二氨基十二烷4‑6份；乙二醇锑0.04‑0.06份。本发明制备的多孔分离膜具备优良的渗透率及截留率，可用于高温或溶剂体系。The invention discloses an amide hybrid polyester porous separation membrane and a preparation method thereof, wherein the amide hybrid polyester porous separation membrane is prepared from the following raw materials in parts by weight: modified amide hybrid polyester 5-8 3-5 parts of porogen; 37-42 parts of solvent; wherein: the modified amide hybrid polyester is prepared from the following raw materials in parts by weight through esterification and polycondensation: 150-166 terephthalic acid parts; 70-80 parts of ethylene glycol; 2-5 parts of hexanediamine; 4-6 parts of decanediamine; 4-6 parts of 1,12-diaminododecane; 0.04-0.06 parts of ethylene glycol antimony. The porous separation membrane prepared by the invention has excellent permeability and retention rate, and can be used in high temperature or solvent systems.
Description
Technical Field
The invention relates to the field of polyester synthesis and preparation of porous separation membranes, in particular to an amide hybrid polyester porous separation membrane and a preparation method thereof.
Background
The membrane separation technology plays an increasingly important role in the development of the chemical industry towards more environmentally friendly processes. Especially has high application value in pharmaceutical, petrochemical and food industries. However, the limited availability of solvent resistant membranes is an obstacle to overcome, most membranes cannot be used in non-aqueous solvents or at high temperatures. In addition, scalability and cost are also important factors limiting their development.
Polyethylene terephthalate (PET) has been used in membrane technology, but is mainly used as a non-woven support for multilayer porous membranes, for the preparation of electrospun nanofibers, as well as a woven support or coating for hollow fibers, ion-tracking etched membranes, or more recently as tracking UV membranes. In the prior art, the research of using PET to manufacture a separation membrane is rarely reported. In view of this, the object of the present invention is to produce a porous separation membrane based on PET as a main raw material.
Disclosure of Invention
In order to achieve the above object, one aspect of the present invention provides an amide hybrid polyester porous separation membrane, which has the following technical scheme:
the amide hybrid polyester porous separation membrane is characterized by being prepared from the following raw materials in parts by weight:
5-8 parts of modified amide hybrid polyester;
3-5 parts of a pore-foaming agent;
37-42 parts of a solvent; wherein:
the modified amide hybrid polyester is prepared from the following raw materials in parts by weight through esterification and polycondensation reaction:
150-166 parts of terephthalic acid;
70-80 parts of ethylene glycol;
2-5 parts of hexamethylene diamine;
4-6 parts of decamethylene diamine;
4-6 parts of 1, 12-diaminododecane;
0.04 to 0.06 portion of ethylene glycol antimony.
In some embodiments, the porogen comprises polyethylene glycol having a molecular weight of 200-.
In some embodiments, the solvent comprises hexafluoroisopropanol.
In some embodiments, the amide linkages in the modified amide hybrid polyester are from 6 to 12 mole%.
The second aspect of the present invention provides a method for preparing an amide hybrid polyester porous separation membrane, which comprises the following steps:
step one, synthesizing modified amide hybrid polyester through esterification and polycondensation:
according to the weight parts, putting 150-166 parts of terephthalic acid, 70-80 parts of ethylene glycol, 2-5 parts of hexamethylene diamine, 4-6 parts of decamethylene diamine, 4-6 parts of 1, 12-diaminododecane and 0.04-0.06 part of ethylene glycol antimony into a reaction kettle, stirring under a nitrogen atmosphere, slowly heating to 220 ℃, starting an esterification reaction, controlling the temperature range of the esterification reaction to be 220-260 ℃, and controlling the reaction time to be 2 hours;
and after the esterification reaction is finished, heating the temperature of the reaction kettle to 265 ℃, slowly vacuumizing, starting polycondensation reaction, and reacting for 2.5 hours when the vacuum degree in the kettle is less than 30Pa to obtain the modified amide hybrid polyester.
Step two, film preparation
Putting 2-5 parts by weight of the modified amide hybrid polyester prepared in the step one, 3-5 parts by weight of a pore-forming agent and 37-42 parts by weight of a solvent into a reaction kettle, stirring and dissolving for 3 hours at 30 ℃, and then standing for 6 hours to obtain a membrane casting solution;
and (3) processing the casting solution into a film with the thickness of 145-155 microns by using a film spreading machine at room temperature, and then putting the film into a coagulating bath at 20 ℃ to obtain the porous separation film.
In some embodiments, the porogen comprises polyethylene glycol having a molecular weight of 200-.
In some embodiments, the coagulation bath comprises one of water, ethanol, or methanol, and the temperature of the coagulation bath is 15-30 ℃.
According to the invention, through a chemical copolymerization method, an amido bond is introduced into a main chain structure of the polyethylene terephthalate to prepare the modified amide structure hybrid polyester with excellent performance. Then, the modified polyester is used for preparing a porous separation membrane through a non-solvent phase conversion method, and the porous separation membrane has excellent permeability and rejection rate and can be used for high temperature or solvent systems.
Detailed Description
The description is further elucidated with reference to specific examples. The description is to be regarded as illustrative and explanatory only and should not be taken as limiting the scope of the invention in any way.
Some of the raw materials used in the examples of the present invention were derived as follows:
terephthalic acid, purchased from jingle chemical products limited, beijing, has a purity of 99%.
Ethylene glycol, purchased from the Chinese petrochemical Beijing Yanshan division, had a purity of 99.8%.
Hexamethylenediamine, decamethylenediamine, 1, 12-diaminododecane, all available from Aladdin reagent (Shanghai) Co., Ltd., purity 99.5%.
Ethylene glycol antimony, purchased from Shanghai Yugong & trade Co., Ltd., with a purity of 99.9%;
polyethylene glycol, available from alatin reagent (shanghai) ltd.
Hexafluoroisopropanol, purchased from denna yofta chemical ltd, with a purity of 99%.
Example 1
Step one, synthesizing modified amide hybrid polyester through esterification and polycondensation:
according to the weight portion, 166 portions of terephthalic acid, 70 portions of ethylene glycol, 2.8 portions of hexamethylene diamine, 4.1 portions of decamethylene diamine, 4.8 portions of 1, 12-diaminododecane and 0.04 portion of ethylene glycol antimony are put into a reaction kettle, stirred under the atmosphere of nitrogen, and then slowly heated to 220 ℃ to start the esterification reaction, wherein the temperature range of the esterification reaction is controlled to be 220-260 ℃ and the reaction time is 2 hours;
after the esterification reaction is finished, the temperature of the reaction kettle is raised to 265 ℃, the reaction kettle is slowly vacuumized, the polycondensation reaction is started, and when the vacuum degree in the kettle is less than 30Pa, the reaction is carried out for 2.5 hours, so that the modified amide hybrid polyester with the amido bond content of 6-12mol% is obtained.
Step two, film preparation
Taking 5g of modified amide hybrid polyester, 3g of polyethylene glycol with molecular weight of 200 and 42g of hexafluoroisopropanol, stirring and dissolving for 3 hours at 30 ℃, and then standing for 6 hours to obtain a casting solution.
Preparing the membrane casting solution into a membrane with the thickness of 145 microns by adopting a membrane spreading machine at room temperature, and then putting the membrane casting solution into an ethanol coagulating bath at 15 ℃ to obtain the porous separation membrane.
Example 2
The preparation steps of the amide hybrid polyester porous separation membrane of the present example are as follows:
step one, synthesizing modified amide hybrid polyester through esterification and polycondensation:
putting 150 parts by weight of terephthalic acid, 80 parts by weight of ethylene glycol, 2 parts by weight of hexamethylene diamine, 6 parts by weight of decamethylene diamine, 5 parts by weight of 1, 12-diaminododecane and 0.05 part by weight of ethylene glycol antimony into a reaction kettle, stirring under the atmosphere of nitrogen, slowly heating to 220 ℃, starting an esterification reaction, controlling the temperature range of the esterification reaction to be 220-260 ℃, and controlling the reaction time to be 2 hours;
after the esterification reaction is finished, the temperature of the reaction kettle is raised to 265 ℃, the reaction kettle is slowly vacuumized, the polycondensation reaction is started, and when the vacuum degree in the kettle is less than 30Pa, the reaction is carried out for 2.5 hours, so as to obtain the modified amide hybrid polyester with the amide bond content of 6-12 mol%.
Step two, film preparation
And (3) taking 8g of the modified amide hybrid polyester prepared in the step one, 5g of polyethylene glycol with the molecular weight of 600 and 37g of hexafluoroisopropanol, stirring and dissolving for 3 hours at the temperature of 30 ℃, and standing for 6 hours to obtain a casting solution.
Preparing the membrane casting solution into a membrane with the thickness of 150 microns by adopting a membrane spreading machine at room temperature, and then putting the membrane into a methanol coagulating bath at the temperature of 20 ℃ to obtain the porous separation membrane.
Example 3
The preparation steps of the amide hybrid polyester porous separation membrane of the present example are as follows:
step one, synthesizing modified amide hybrid polyester through esterification and polycondensation:
putting 160 parts by weight of terephthalic acid, 75 parts by weight of ethylene glycol, 4 parts by weight of hexamethylene diamine, 5 parts by weight of decamethylene diamine, 6 parts by weight of 1, 12-diaminododecane and 0.06 part by weight of ethylene glycol antimony into a reaction kettle, stirring under the atmosphere of nitrogen, slowly heating to 220 ℃, starting an esterification reaction, controlling the temperature range of the esterification reaction to be 220-260 ℃, and controlling the reaction time to be 2 hours;
after the esterification reaction is finished, the temperature of the reaction kettle is raised to 265 ℃, the reaction kettle is slowly vacuumized, the polycondensation reaction is started, and when the vacuum degree in the kettle is less than 30Pa, the reaction is carried out for 2.5 hours, so that the modified amide hybrid polyester with the amido bond content of 6-12mol% is obtained.
Step two, film preparation
And (3) taking 6g of the modified amide hybrid polyester prepared in the step one, 4g of polyethylene glycol with the molecular weight of 800 and 40g of hexafluoroisopropanol, stirring and dissolving for 3 hours at the temperature of 30 ℃, and standing for 6 hours to obtain a casting solution.
Preparing the casting solution into a film with the thickness of 155 microns by adopting a film spreading machine at room temperature, and then putting the film into a 25 ℃ water coagulation bath to obtain the porous separation film.
Example 4
The preparation steps of the amide hybrid polyester porous separation membrane of the present example are as follows:
step one, synthesizing modified amide hybrid polyester through esterification and polycondensation:
putting 158 parts of terephthalic acid, 78 parts of ethylene glycol, 5 parts of hexamethylene diamine, 4.5 parts of decamethylene diamine, 4 parts of 1, 12-diaminododecane and 0.05 part of ethylene glycol antimony into a reaction kettle according to parts by weight, stirring under a nitrogen atmosphere, slowly heating to 220 ℃, starting an esterification reaction, controlling the temperature range of the esterification reaction to be 220-260 ℃, and controlling the reaction time to be 2 hours;
after the esterification reaction is finished, the temperature of the reaction kettle is raised to 265 ℃, the reaction kettle is slowly vacuumized, the polycondensation reaction is started, and when the vacuum degree in the kettle is less than 30Pa, the reaction is carried out for 2.5 hours, so that the modified amide hybrid polyester with the amido bond content of 6-12mol% is obtained.
Step two, film preparation
And (3) taking 7g of the modified amide hybrid polyester prepared in the step one, 4.5g of polyethylene glycol with the molecular weight of 1000 and 41g of hexafluoroisopropanol, stirring and dissolving for 3 hours at the temperature of 30 ℃, and standing for 6 hours to obtain a casting solution.
Preparing the membrane casting solution into a membrane with the thickness of 150 microns by adopting a membrane spreading machine at room temperature, and then putting the membrane into an ethanol coagulating bath at the temperature of 25 ℃ to obtain the porous separation membrane.
The results of the performance tests of the amide hybrid polyester porous separation membranes obtained in examples 1 to 4 are shown in table 1.
TABLE 1
| Permeability of DMF at 75 ℃ under 2 bar (L m-2 h-1 bar-1) | Retention of PEG-50 in DMF solution (%) | |
| Example 1 | 147 | 92.7 |
| Example 2 | 176 | 90.9 |
| Example 3 | 169 | 90.4 |
| Example 4 | 189 | 90.1 |
According to the invention, through a chemical copolymerization method, an amido bond is introduced into a main chain structure of the polyethylene terephthalate to prepare the modified amide structure hybrid polyester with excellent performance. Then, the modified polyester is used for preparing a porous separation membrane with the thickness of 100-200 microns by a non-solvent phase conversion method. As can be seen from the test results in table 1, the porous separation membrane has excellent permeability and rejection rate, and can be used for high temperature or solvent systems.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
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| CN202010288010.5A CN111408285B (en) | 2020-04-14 | 2020-04-14 | Amide hybrid polyester porous separation membrane and preparation method thereof |
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| CN109134850A (en) * | 2017-06-16 | 2019-01-04 | 上海凯赛生物技术研发中心有限公司 | Polyesteramide and preparation method thereof and the fiber as made from the polyesteramide |
| CN109880083A (en) * | 2019-03-05 | 2019-06-14 | 哈尔滨工业大学无锡新材料研究院 | A kind of impact-resistant amide hybrid polyester and preparation method thereof |
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| CN109134850A (en) * | 2017-06-16 | 2019-01-04 | 上海凯赛生物技术研发中心有限公司 | Polyesteramide and preparation method thereof and the fiber as made from the polyesteramide |
| CN109880083A (en) * | 2019-03-05 | 2019-06-14 | 哈尔滨工业大学无锡新材料研究院 | A kind of impact-resistant amide hybrid polyester and preparation method thereof |
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