CN1321727C - Novel reverse osmosis antioxidant compound membrane of polyamide and its preparing method - Google Patents
Novel reverse osmosis antioxidant compound membrane of polyamide and its preparing method Download PDFInfo
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- CN1321727C CN1321727C CNB2004100681555A CN200410068155A CN1321727C CN 1321727 C CN1321727 C CN 1321727C CN B2004100681555 A CNB2004100681555 A CN B2004100681555A CN 200410068155 A CN200410068155 A CN 200410068155A CN 1321727 C CN1321727 C CN 1321727C
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Abstract
The present invention relates to a novel compound polyamide reverse osmosis film and a preparation method thereof. The compound reverse osmosis film obtained by the method can reach good effect on water fluxes and desalinization ratios. In the present invention, high molecular materials which has the characteristics of good hydrophilicity, stable mechanicalness, etc. generate polymerization reactions or polycondensation reactions on a porous supporting film according to definite technologic steps and according to definite technologic conditions to form an ultrathin functional film. The method has simple technology of compound film preparation, and relatively controllable technologic conditions, and accordingly the cost is reduced, furthermore, the present invention is favorable to the popularization and the use of high molecular compound materials which has high performance and relatively high prices. The present invention can be widely used for the separation of various kinds of liquid, particularly the separation of water solutions, and can be used in the technology of pure water preparation and sewage treatment.
Description
Technical field
The invention belongs to a kind of novel polyamide reverse osmosis composite membrane and preparation method thereof.
Background technology
Reverse osmosis composite membrane is that one deck ultrathin functional layer is deposited to suitable micropore support membrane surface, aperture, and depositional mode mainly contains surface-coated, interfacial polycondensation and in-situ polymerization etc.
Composite membrane has many advantages than asymmetric membrane: it can make every layer to reach optimum performance by cutting out.Ultrathin functional layer can be optimized to desirable selection permeability, and support membrane can reach best intensity and pressure tightness.In addition, composite membrane can make the material that is difficult to form asymmetric membrane form ultrathin membrane, as because solvent limitation and crosslinking polymer can form composite membrane by in-situ polymerization or interfacial polycondensation; The material of ultrathin membrane can be selected the new material of high-performance (price is expensive) for use.
Salt rejection rate and water flux are two important parameters estimating reverse osmosis membrane, and salt rejection rate R is defined as: under fixed operating condition, and feeding liquid salinity (c
f) with penetrating fluid in salinity (c
p) poor, again divided by the feeding liquid salinity.
Water flux is defined as: under certain operating condition, see through the volume of the water of elementary membrane area in the unit interval, its unit is 1/m
2.h.
The operating condition that adopts among the present invention is: the sodium-chloride water solution of 2000mg/L, operating pressure are 1.0-1.6MPa, and operating temperature is 22 ℃--25 ℃.
Polyamide has acid amides functional group (CO-NH-), good hydrophilic property, and its mechanical stability, heat endurance and hydrolytic stability are all fine, are specially adapted to reverse osmosis process.On the polysulfones support membrane, become the composite membrane kind of present combination property optimum by the reverse osmosis membrane of the compound one deck aromatic polyamides of interfacial polycondensation ultrathin functional layer gained.
US Patent4 in 1981 such as Cadotte, 277,344 adopt interface polycondensation to pass through the compound one deck aromatic polyamides of interfacial polycondensation film on the polysulfones support membrane, this film is that the polysulfones support membrane is immersed in the buffer solution of m-phenylene diamine (MPD), after extracting, pyromellitic trimethylsilyl chloride solution in the covering, reaction a period of time post rinse, and carry out post processing.This film ultrathin functional layer is mainly crosslinked aromatic polyamides, and its chemical structural formula can be expressed as:
Uemura etc. were at US Patent4 in 1988, adopting interface polycondensation in 761,234 is crosslinking agent with equal benzene triamine, reacts compound one deck aromatic polyamides film with m-phthaloyl chloride on support membrane, salt rejection rate is greater than 99%, but its used equal benzene triamine is difficult to obtain.The chemical structural formula of aromatic polyamides can be expressed as in its compound ultrathin functional layer:
In addition, US Patent5,576,057, US Patent5,989,426, US Patent6,162,358, USPatent6,464, patents such as 873 also are that the polysulfones support membrane is immersed in the polyamine aqueous solution, immerse polynary solution of acid chloride after extracting again, and reaction a period of time post rinse also carries out post processing and obtains product.
Summary of the invention
The objective of the invention is to prepare a kind of novel reverse osmosis composite membrane, the composite membrane ultrathin functional layer is except containing the acid amides functional group (CO-NH-), also contain the urea functional group (NH-CO-NH-) or the amido formate functional group (OCO-NH-), the hydrophily of ultrathin functional layer is improved.In addition, phenolic group and aminomethyl are arranged on the aromatic ring of polyamine, be beneficial to the oxidative resistance that strengthens ultrathin functional layer.The chemical structural formula of ultrathin functional layer aromatic polyamides can be expressed as:
X is-NH-CO-NH-or (OCO-NH-) in the formula; Y corresponds to-NH
2Or-OH, also may be-COOH; Z is-CH
2NH
2
The present invention is related novel polyamide reverse osmosis composite membrane, contain on by aromatic rings on the porous support membrane phenolic group and aliphatic polyamine and the polynary acyl chlorides of modified aromatic its interfacial polycondensation with polyamines solution in compound one deck fragrance and the fat polyamide thin layer that mix.
Above-mentioned novel polyamide reverse osmosis composite membrane contains a phenolic group and binary aliphatic or tertiary amine on the described aromatic rings, comprise 2,4 at least, 6-three aminomethyl phenol, 2,6-diaminomethyl phenol and 2, in 4-diaminomethyl phenol and the corresponding derivative thereof one.
Above-mentioned novel polyamide reverse osmosis composite membrane, the polynary acyl chlorides of described modified aromatic comprises in 5-oxygen formyl chloride-isophthaloyl chlorine and the pyromellitic trimethylsilyl chloride at least.
Above-mentioned novel polyamide reverse osmosis composite membrane, the part by weight that contains phenolic group and aliphatic polyamine and the polynary acyl chlorides of described modified aromatic on the described aromatic rings was from 0.1: 1 to 10: 1.
Above-mentioned novel polyamide reverse osmosis composite membrane, interfacial polycondensation contains the dispersing agent C NF of 0.1%---1% with in the polyamines solution, and CNF is the sulfonated products of naphthalene, cresols and formaldehyde condensation products.
Above-mentioned novel polyamide reverse osmosis composite membrane, described support membrane is the UDEL P3500 polysulfones with 16%, and 0.3% water and 0.1% surfactant are dissolved in N, the N-dimethylacetylamide, be coated with and scrape on polyester non-woven fabric, immerse gel in the water then and remove and obtain after desolvating; Wherein surfactant comprises alkyl phenol polyoxy Acetoxon acid esters at least, a kind of in dodecyl sodium sulfate and the alkyl phenol polyoxy Acetoxon hydrochlorate.
The preparation method of preparation novel polyamide reverse osmosis composite membrane, be that polysulfones support membrane single face is immersed in the above-mentioned polyamines solution, carry out the single face interface polymerization reaction with the modified multicomponent solution of acid chloride, the interface polymerization reaction that generates polyamide active layer only carries out on polysulfones support membrane surface, composite membrane dried in the shade in air 1～3 minute, through heat treatment, rinsing afterwards obtains reverse osmosis composite membrane again.
The preparation method of above-mentioned novel polyamide reverse osmosis composite membrane, described heat treatment comprised for two steps, and the first step is to handle 3-5 minute down at 40-70 ℃, and second step was to handle 3-5 minute down at 70-110 ℃.
The preparation method of above-mentioned novel polyamide reverse osmosis composite membrane, described rinsing comprised for two steps, the first step is to be in 15% the pure water solution rinsing 10-40 minute at 30-60 ℃ methyl alcohol part by weight, and second step was in 30-60 ℃ pure water rinsing 10-40 minute.
The preparation method of above-mentioned novel polyamide reverse osmosis composite membrane, the used organic solvent of modified multicomponent solution of acid chloride is a trifluorotrichloroethane, n-hexane, a kind of in heptane and the hendecane etc.
The composite membrane performance of this method preparation obviously is better than the conventional composite membrane that immerses the interfacial polymerization preparation, and easilier in rinse cycle washes out unnecessary polyamine.
Following examples provide the explanation of novel reverse osmosis composite membrane and their desalting performance.Yet these embodiment only provide as an illustration rather than limit the present invention.
The specific embodiment
Embodiment 1-2 is with 16% UDEL P3500 polysulfones, 0.3% water and 0.1% polyoxyethylene nonyl phenyl Acetoxon acid esters are dissolved in N, and the N-dimethylacetylamide is coated with and scrapes on polyester non-woven fabric, immerse then in the water to remove and obtain the support membrane that molecular cut off is 2-3 ten thousand after desolvating, hygrometric state is preserved standby.
It is in 2% the aqueous solution (2 that the polysulfones support membrane single face of hygrometric state is immersed in the polyamine part by weight, 4,6-three aminomethyl phenol, 2,6-diaminomethyl phenol and 2,4-diaminomethyl phenol) 2 minutes after extracting with squeegee roll extrusion support membrane surface, is that 0.1% cyclohexane solution single face contacts and carries out interface polymerization reaction 20-40 second with polynary acyl chlorides part by weight.Composite membrane dried in the shade in air 2 minutes, and again through two step heat treatments: the first step is to handle 3-5 minute down at 40-70 ℃, and second step was to handle 3-5 minute down at 70-110 ℃.Then carry out two step rinsings again: the first step is to be in 15% the aqueous solution rinsing 10-40 minute at 30-60 ℃ methyl alcohol part by weight, and second step was in 30-60 ℃ water rinsing 10-40 minute.The composite membrane of preparation is kept in the water, and at the sodium-chloride water solution of 2000mg/L, operating pressure is 1.5MPa, and operating temperature is its desalting performance of test under 22 ℃ the condition.
| Embodiment | Polynary acyl chlorides | Polyamine | Flux (l/m2.h) | Salt rejection rate |
| 1 2 | Pyromellitic trimethylsilyl chloride 5-oxygen formyl chloride-isophthaloyl chlorine | 2,4,6-three aminomethyl phenol 2.4,6-three aminomethyl phenol | 31.8 24.0 | 98.1 98.8 |
Embodiment 3-4 is as the embodiment of front, as stated above, adopting the polyamine part by weight is that 2% the aqueous solution (includes 0.2% dispersing agent C NF, this CNF is the sulfonated products of naphthalene, cresols and formaldehyde condensation products), the pyromellitic trimethylsilyl chloride part by weight is that 0.1% cyclohexane solution prepares reverse osmosis composite membrane.The composite membrane of preparation is kept in the water, and at the sodium-chloride water solution of 2000mg/L, operating pressure is 1.0MPa, and operating temperature is its desalting performance of test under 22 ℃ the condition.
These several embodiment investigate the low-pressure performance of film and the effect of dispersant.
| Embodiment | Polynary acyl chlorides | Polyamine | Flux (l/m2.h) | Salt rejection rate |
| 3 4 | Pyromellitic trimethylsilyl chloride 5-oxygen formyl chloride-isophthaloyl chlorine | 2,4,6-three aminomethyl phenol 2,4,6-three aminomethyl phenol | 20.5 16.2 | 98.7 99.0 |
Embodiment 5-6 is as the reverse osmosis composite membrane of the embodiment 1-2 of front, immersed in 20% the glycerine water solution 5 hours, take out airing, after in air, preserving six months, heavily immerse in the water, at the sodium-chloride water solution of 2000mg/L, operating pressure is 1.5MPa, and operating temperature is its desalting performance of test under 22 ℃ the condition.
These several embodiment are after investigating such film long-term storage, the stability of performance
| Embodiment | Polynary acyl chlorides | Polyamine | Flux (l/m 2.h) | Salt rejection rate |
| 5 6 | Pyromellitic trimethylsilyl chloride 5-oxygen formyl chloride-isophthaloyl chlorine | 2,4,6-three aminomethyl phenol 2,4,6-three aminomethyl phenol | 28.6 25.3 | 98.2 98.7 |
Embodiment 7-8 is as the reverse osmosis composite membrane of the embodiment 1-2 of front, and at the sodium-chloride water solution of 2000mg/L, operating pressure is 1.5MPa, and operating temperature is to test its desalination and flux performance under 22 ℃ the condition in continuous 60 days.
These several embodiment are the stability of investigating the longer-term operation of such film properties.Embodiment 7 is an initial performance, and embodiment 8 is continuous 60 days postrun performances.
| Embodiment | Polynary acyl chlorides | Polyamine | Flux (l/m 2.h) | Salt rejection rate |
| 7 8 | Pyromellitic trimethylsilyl chloride 5-oxygen formyl chloride-isophthaloyl chlorine | 2,4,6-three aminomethyl phenol 2,4,6-three aminomethyl phenol | 29.5 26.5 | 98.0 98.4 |
Embodiment 9-10 is immersed in pH=8 as the reverse osmosis composite membrane of the embodiment 1-2 of front with film, in the aqueous solution of the NaClO of 500mg/L after 48 hours its salt rejection rate drop to 97.6 and 98.4 respectively from 98.1%, 98.8%.Test condition is: the sodium-chloride water solution of 2000mg/L, operating pressure are 1.5MPa, and operating temperature is 22 ℃.
Claims (8)
1. novel polyamide reverse osmosis composite membrane, it is characterized in that, containing a phenolic group and binary aliphatic or tertiary amine on by aromatic rings on the porous support membrane, at least comprise 2,4,6-three aminomethyl phenol, 2,6-diaminomethyl phenol and 2, in 4-diaminomethyl phenol and the corresponding derivative thereof one with contain 5-oxygen formyl chloride-isophthaloyl chlorine, pyromellitic trimethylsilyl chloride at least in a kind of interfacial polycondensation with the solution of the dispersing agent C NF that contains 0.1%---1% in compound one deck fragrance and the fat polyamide thin layer that mix.
2. novel polyamide reverse osmosis composite membrane as claimed in claim 1 is characterized in that, the part by weight that contains phenolic group and aliphatic polyamine and the polynary acyl chlorides of described modified aromatic on the described aromatic rings was from 0.1: 1 to 10: 1.
3. novel polyamide reverse osmosis composite membrane as claimed in claim 1, it is characterised in that interfacial polycondensation is the sulfonated products of naphthalene, cresols and formaldehyde condensation products with dispersing agent C NF.
4. novel polyamide reverse osmosis composite membrane as claimed in claim 1, it is characterized in that, described support membrane is the UDEL P3500 polysulfones with 16%, 0.3% water and 0.1% surfactant are dissolved in N, the N-dimethylacetylamide, be coated with and scrape on polyester non-woven fabric, immerse gel in the water then and remove and obtain after desolvating; Wherein surfactant comprises alkyl phenol polyoxy Acetoxon acid esters at least, a kind of in dodecyl sodium sulfate and the alkyl phenol polyoxy Acetoxon hydrochlorate.
5. the preparation method of a novel polyamide reverse osmosis composite membrane, it is characterized in that, polysulfones support membrane single face is immersed in the polyamines solution of aforesaid right requirement 1, carry out the single face interface polymerization reaction with the modified multicomponent solution of acid chloride, the interface polymerization reaction that generates polyamide active layer only carries out on polysulfones support membrane surface, composite membrane dried in the shade in air 1～3 minute, and again through heat treatment, rinsing afterwards obtains reverse osmosis composite membrane.
6. the preparation method of novel polyamide reverse osmosis composite membrane as claimed in claim 5 is characterized in that, described heat treatment comprised for two steps, and the first step is to handle 3-5 minute down at 40-70 ℃, and second step was to handle 3-5 minute down at 70-110 ℃.
7. the preparation method of novel polyamide reverse osmosis composite membrane as claimed in claim 5, it is characterized in that, described rinsing comprised for two steps, the first step is to be in 15% the pure water solution rinsing 10-40 minute at 30-60 ℃ methyl alcohol part by weight, and second step was in 30-60 ℃ pure water rinsing 10-40 minute.
8. the preparation method of novel polyamide reverse osmosis composite membrane as claimed in claim 5 is characterized in that, the used organic solvent of modified multicomponent solution of acid chloride is a trifluorotrichloroethane, n-hexane, a kind of in heptane and the hendecane.
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| CNB2004100681555A CN1321727C (en) | 2004-11-12 | 2004-11-12 | Novel reverse osmosis antioxidant compound membrane of polyamide and its preparing method |
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| CNB2004100681555A CN1321727C (en) | 2004-11-12 | 2004-11-12 | Novel reverse osmosis antioxidant compound membrane of polyamide and its preparing method |
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| CN1321727C true CN1321727C (en) | 2007-06-20 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8193896B2 (en) * | 2008-08-15 | 2012-06-05 | Martin Weinberg | Polyamide electrical insulation for use in liquid filled transformers |
| CN102125809A (en) * | 2010-01-13 | 2011-07-20 | 武少禹 | Method for improving performance of reverse osmosis composite membrane through vapor treatment |
| CN102133506B (en) * | 2011-02-28 | 2013-01-09 | 浙江理工大学 | Polyamide composite nanofiltration membrane |
| WO2014126626A1 (en) | 2013-02-15 | 2014-08-21 | Empire Technology Development Llc | Phenolic epoxy compounds |
| EP3008125A4 (en) | 2013-06-13 | 2016-12-07 | Empire Technology Dev Llc | Multi-functional phenolic resins |
| EP3077364A4 (en) | 2013-12-02 | 2017-11-08 | Empire Technology Development LLC | Novel gemini surfactants and their use |
| CN105642137B (en) * | 2015-12-31 | 2018-06-12 | 南京理工大学 | Reverse osmosis membrane, preparation method and application thereof |
| CN110917912B (en) * | 2019-12-09 | 2021-09-24 | 南京惟新环保装备技术研究院有限公司 | Internal pressure type composite hollow fiber nanofiltration membrane yarn and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593588A (en) * | 1995-07-07 | 1997-01-14 | Korea Institute Of Science And Technology | Composite reverse osmosis membrane having active layer of aromatic polyester or copolymer of aromatic polyester and aromatic polyamide |
| CN1257748A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Alcohol-water system modifying process for inner interface of inverse osmosis membrane |
| CN1436815A (en) * | 2002-02-07 | 2003-08-20 | 四川大学 | Prepn of lateral hydroxyl group containing polyimide/SiO2 hybrid film |
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2004
- 2004-11-12 CN CNB2004100681555A patent/CN1321727C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593588A (en) * | 1995-07-07 | 1997-01-14 | Korea Institute Of Science And Technology | Composite reverse osmosis membrane having active layer of aromatic polyester or copolymer of aromatic polyester and aromatic polyamide |
| CN1257748A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Alcohol-water system modifying process for inner interface of inverse osmosis membrane |
| CN1436815A (en) * | 2002-02-07 | 2003-08-20 | 四川大学 | Prepn of lateral hydroxyl group containing polyimide/SiO2 hybrid film |
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