CN105457506B - A kind of resistance to oxidation milipore filter and preparation method thereof - Google Patents
A kind of resistance to oxidation milipore filter and preparation method thereof Download PDFInfo
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- CN105457506B CN105457506B CN201610019502.8A CN201610019502A CN105457506B CN 105457506 B CN105457506 B CN 105457506B CN 201610019502 A CN201610019502 A CN 201610019502A CN 105457506 B CN105457506 B CN 105457506B
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- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- 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
- B01D67/0013—Casting processes
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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Abstract
The invention discloses a kind of resistance to oxidation milipore filter and preparation method thereof, belong to field of material preparation.Prepare resistance to oxidation milipore filter the key component of raw material and the mass fraction of each key component be：PVDF powders：100 parts；Solvent：40 60 parts；Antioxidant：0.5 1 parts, antioxidant is reacted to obtain by dendroid polyethyleneimine, chain alkyl amine substance and phenols or ester type compound.Long chain alkane amine substance can neutralize and adsorb the HCl discharged in PVDF decomposable processes in the resistance to oxidation milipore filter of the present invention, and the double bond formed with PVDF by decomposition carries out addition reaction, so as to improve the antioxygenic property of PVDF materials.
Description
Technical field
The invention belongs to field of material preparation, more specifically to a kind of resistance to oxidation milipore filter and preparation method thereof.
Background technology
Most milipore filters is used at present as PVDF materials.What conventional film materials industry was lifted is the hydrophily and high pass of film
Amount, but as water quality requirement and recycle-water ratio increasingly improve, the materialized pretreatment means such as oxidation are also constantly being strengthened, and cause
Also more and more higher is required to the oxidative resistance of milipore filter.
At present, existing document and patent report into PVDF materials by adding oxidation resistant material, so as to reach raising film
The purpose of oxidation resistent susceptibility.For example, Chinese Patent Application No. is CN201310097069, application publication date is 03 month 2013 25
The patent application document of day discloses a kind of polyvinyl alcohol formal layer and poly- bipropenyl phthalic acid ester layer lifting film
Material against oxidative agent performance.Chinese Patent Application No. is CN200910220545, and application publication date is on December 01st, 2009
Patent application document (publication number CN101721927B) discloses a kind of doping naphthyridine ketone structure copolymerization aryl ether sulfone lifting film
Material against oxidative agent performance.Chinese Patent Application No. is CN200510011473, and application publication date is on 03 25th, 2005
Patent application document (publication number CN1695778B) discloses a kind of doping polyether sulphone or PAEK lifting membrane material oxytolerant
Agent performance.
But dendroid polyethyleneimine, chain alkyl amine substance and phenols or ester type compound are adulterated in PVDF
Antioxidant is compounded, the method for preparing resistance to oxidation milipore filter has not been reported.
The content of the invention
1. to solve the problems, such as
For existing milipore filter oxidizable during high oxidative water body use the problem of, the present invention provides a kind of oxytolerant
Change milipore filter and preparation method thereof.
2. technical scheme
In order to solve the problems of the prior art, the key component of the raw material of the milipore filter prepared by the present invention includes PVDF
Powder, solvent and antioxidant, specifically, technical scheme is as follows：
A kind of resistance to oxidation milipore filter, prepare the key component of the raw material of the resistance to oxidation milipore filter and the weight of each key component
Number is：PVDF powders：100 parts；Solvent：40-60 parts；Antioxidant：0.5-1 parts.
Preferably, described solvent is dimethyl acetamide, dimethylformamide, dimethyl sulfoxide (DMSO) or N- crassitudes
One or more in ketone.
Preferably, described antioxidant is formed by monomer A, monomer B and monomer C copolymerzation with cross-linkings, and wherein monomer A is branch
Shaped polyethylene imines；Monomer B is chain alkyl amine substance；Monomer C is phenols or ester type compound.
Preferably, the structural formula of described dendroid polyethyleneimine is：
Wherein, n 100-1000, the molecular weight of dendroid polyethyleneimine is 50000-500000.
Preferably, the structural formula of described chain alkyl amine substance is：
In formula, m 10-12, R are methyl or ethyl, and X is halogens.
Preferably, described chain alkyl amine substance is DTAC, trimethyl bromine
Change ammonium, dodecyl dimethyl ethyl phosphonium bromide ammonium, dodecyldimethylamine base ethyl phosphonium bromide ammonium, dodecyldimethylamine base ethylmercury chloride
One or more in ammonium, tridecyl trimethylammonium bromide etc.；Described monomer C is butylhydroxy fennel phenol, the four seasons penta 4
Alcohol ester and the tert-butyl group are to one kind in two benzenediols.
A kind of preparation method of above-mentioned resistance to oxidation milipore filter, specific preparation process are：
(1) monomer A, monomer B and monomer C reactions are prepared into antioxidant in proportion；
(2) PVDF powders are dissolved in solvent in proportion, add antioxidant, stir, after deaeration curing, used
Traditional phase transition method stands casting solution, gel, knifing, you can synthesis polyvinylidene fluoride (PVDF) ultrafiltration membrane.
Preferably, the preparation method of antioxidant is in step (1)：Monomer A, monomer B and monomer C are sent out in a kettle
Raw polymerisation, reaction temperature are 40~80 DEG C, and the reaction time is 24~48h；Reaction is evaporated under reduced pressure after terminating and can obtain institute
The antioxidant stated.
Preferably, monomer A, monomer B and monomer C mol ratio are 1：(0.1-0.4)：(0.01-0.05).
Polyethyleneimine (PEI) is a kind of macromolecule organic, generally has linear and two kinds of forms of dendroid, is just
One of maximum a kind of macromolecule organic of charge density；Dendritic structure can play a part of crosslinking agent, Ke Yiyu simultaneously
Other macromolecules form high crosslinking space net structure, and the structural molecule amount is big, stable performance, not easily runs off, can be stably
It is present in PVDF.But at present, by the way that this dendrimer crosslinking agents of PEI are applied in the preparation of PVDF ultrafiltration membrane
There is not yet document report, the present invention create by dendroid polyethyleneimine and chain alkyl amine substance and phenols or esters
Compound reacts the antioxidant that a kind of high cross-linked structure in space is prepared, and using this antioxidant as milipore filter
A kind of milipore filter of resistance to oxidation is prepared in additive.The modification PVDF ultrafiltration membrane synthesized in the present invention has preparation process simple
Singly, the advantages that required raw material type is few, and product qualification rate is high, while its oxidation resistent susceptibility is obvious.
3. beneficial effect
(1) antioxidant that the present invention synthesizes is the high cross-linked structure in space, and what can be stablized is present in PVDF, no
It is easy to run off, there is preferable oxidation resistent susceptibility；
(2) long chain alkane amine substance can be neutralized and adsorbed in PVDF decomposable processes in the antioxidant that the present invention synthesizes
The HCl of release, and addition reaction is carried out with the double bond of formation, so as to improve the antioxygenic property of PVDF materials；
(3) in building-up process of the present invention caused C=C double bonds and and phenols functional group can also absorb and shielding part
Divide harmful energy of ultraviolet region, catch the living radical by ultraviolet excitation, be quenched excited state molecule, decompose ultraviolet light production
Raw peroxide, therefore, resistance to oxidation aeration flexible pipe of the invention have the advantages that oxidation resistance is strong, service life is long；
(4) the resistance to oxidation milipore filter synthesis technique prepared by the present invention is simple, and raw material is cheap and easy to get, high yield rate, performance
It is excellent, environmentally friendly.
Embodiment
The present invention is further described below with reference to specific embodiment.
Embodiment 1
A kind of preparation method of resistance to oxidation milipore filter is：
Step (1)：Example is 1 in molar ratio:0.1:0.01 takes the PEI (after weighing that molecular weight is 50000-100000 scopes
Be configured to the aqueous solution, hereinafter referred to as PEI solution), DTAB and butylhydroxy fennel phenol, by dodecyl
Trimethylammonium bromide and butylhydroxy fennel phenol are placed in reactor, and PEI solution is slowly added dropwise thereto, and it is anti-to be heated to 80 DEG C of mixing
24h is answered, reacts and obtains antioxidant by being evaporated under reduced pressure after terminating；
Step (2)：Take PVDF powders：100 parts；Solvent dimethyl acetamide：40 parts；Antioxidant：0.5 part, stirring is equal
It is even, after deaeration curing, casting solution is stood using traditional phase transition method, gel, knifing, you can synthesis oxytolerant polyvinylidene fluoride
Milipore filter.
The resistance to oxidation milipore filter prepared in the present embodiment is used for oxidation test, resistance to oxidation milipore filter is positioned over into chlorine residue is
Run 90 days in 10000mg/L recycle-water, membrane flux reduces by 1%, shows that the antioxygenic property of resistance to oxidation milipore filter is good.
Embodiment 2
With embodiment 1, difference is the other conditions of this example：
Example is 1 in molar ratio in step (1):0.2:0.03 takes the PEI that molecular weight is 100000-500000 scopes (to weigh
After be configured to the aqueous solution, hereinafter referred to as PEI solution), DTAB and tetrapentaerythritol ester, by dodecyl
Trimethylammonium bromide and tetrapentaerythritol ester are placed in reactor, and PEI solution is slowly added dropwise thereto, and it is anti-to be heated to 40 DEG C of mixing
48h is answered, reacts and obtains antioxidant by being evaporated under reduced pressure after terminating；
Step (2) takes PVDF powders：100 parts；Solvent dimethylformamide：60 parts；Antioxidant：1 part, stir,
After deaeration curing, casting solution is stood using traditional phase transition method, gel, knifing, you can synthesis oxytolerant polyvinylidene fluoride surpasses
Filter membrane.
The resistance to oxidation milipore filter prepared in the present embodiment is used for oxidation test, resistance to oxidation milipore filter is positioned over into chlorine residue is
Run 70 days in 15000mg/L recycle-water, membrane flux reduces by 0.8%, shows that the antioxygenic property of resistance to oxidation milipore filter is good.
Embodiment 3
With embodiment 1, difference is the other conditions of this example：
Example is 1 in molar ratio in step (1):0.4:0.05 takes the PEI that molecular weight is 300000-500000 scopes (to weigh
After be configured to the aqueous solution, hereinafter referred to as PEI solution), dodecyl dimethyl ethyl phosphonium bromide ammonium and the tert-butyl group to two benzenediols, will
Dodecyl dimethyl ethyl phosphonium bromide ammonium and the tert-butyl group are placed in reactor to two benzenediols, and PEI solution is slowly added dropwise thereto, adds
Heat is reacted to 50 DEG C of hybrid reaction 36h and can obtain antioxidant by being evaporated under reduced pressure after terminating；
Step (2) takes PVDF powders：100 parts；Solvent (dimethyl sulfoxide (DMSO):1-METHYLPYRROLIDONE=1:1)：60 parts；It is resistance to
Oxidant：0.6 part, stir, after deaeration curing, stood casting solution using traditional phase transition method, gel, knifing, you can
Synthesize resistance to oxidation polyvinylidene fluoride (PVDF) ultrafiltration membrane.
The resistance to oxidation milipore filter prepared in the present embodiment is used for oxidation test, resistance to oxidation milipore filter is positioned over into chlorine residue is
Run 80 days in 12000mg/L recycle-water, membrane flux reduces by 0.9%, shows that the antioxygenic property of resistance to oxidation milipore filter is good.
Embodiment 4
With embodiment 1, difference is the other conditions of this example：
Example is 1 in molar ratio in step (1):0.2:0.02 takes the PEI that molecular weight is 400000-500000 scopes (to weigh
After be configured to the aqueous solution, hereinafter referred to as PEI solution), dodecyldimethylamine base ethyl tertiary amine and the tert-butyl group to two benzenediols, by ten
Tetraalkyl dimethyl ethyl ammonium bromide and the tert-butyl group are placed in reactor to two benzenediols, and PEI solution is slowly added dropwise thereto, heating
To 45 DEG C of hybrid reaction 42h, react and can obtain antioxidant by being evaporated under reduced pressure after terminating；
Step (2) takes PVDF powders：100 parts；Solvent dimethyl sulfoxide (DMSO)：50 parts；Antioxidant：0.7 part, stir,
After deaeration curing, casting solution is stood using traditional phase transition method, gel, knifing, you can synthesis oxytolerant polyvinylidene fluoride surpasses
Filter membrane.
The resistance to oxidation milipore filter prepared in the present embodiment is used for oxidation test, resistance to oxidation milipore filter is positioned over into chlorine residue is
Run 100 days in 11000mg/L recycle-water, membrane flux reduces by 0.6%, shows that the antioxygenic property of resistance to oxidation milipore filter is good.
Embodiment 5
With embodiment 1, difference is the other conditions of this example：
Example is 1 in molar ratio in step (1):0.1:0.02 takes the PEI (after weighing that molecular weight is 50000-500000 scopes
Be configured to the aqueous solution, hereinafter referred to as PEI solution), dodecyldimethylamine base ethyl ammonium chloride and tetrapentaerythritol ester, by the tetradecane
Base dimethyl ethyl ammonium chloride and tetrapentaerythritol ester are placed in reactor, and PEI solution is slowly added dropwise thereto, are heated to 52 DEG C and mix
Reaction 28h is closed, reacts and can obtain antioxidant by being evaporated under reduced pressure after terminating；
Step takes PVDF powders in (2)：100 parts；Solvent N-methyl pyrilidone：60 parts；Antioxidant：0.5 part, stirring
Uniformly, after deaeration curing, casting solution is stood using traditional phase transition method, gel, knifing, you can synthesis resistance to oxidation polyvinylidene fluoride
Alkene milipore filter.
The resistance to oxidation milipore filter prepared in the present embodiment is used for oxidation test, resistance to oxidation milipore filter is positioned over into chlorine residue is
Run 90 days in 16000mg/L recycle-water, membrane flux reduces by 1%, shows that the antioxygenic property of resistance to oxidation milipore filter is good.
Embodiment 6
With embodiment 1, difference is the other conditions of this example：
Example is 1 in molar ratio in step (1):0.3:0.04 takes the PEI that molecular weight is 400000-500000 scopes (to weigh
After be configured to the aqueous solution, hereinafter referred to as PEI solution), dodecyldimethylamine base ethyl phosphonium bromide ammonium and tridecyl trimethyl bromination
Ammonium mixture, tetrapentaerythritol ester, by dodecyldimethylamine base ethyl phosphonium bromide ammonium and tridecyl trimethylammonium bromide mixture,
Tetrapentaerythritol ester is placed in reactor, and PEI solution is slowly added dropwise thereto, is heated to 45 DEG C of hybrid reaction 42h, wherein, ten
Tetraalkyl dimethyl ethyl ammonium bromide and tridecyl trimethylammonium bromide molar ratio are 1:1, reaction passes through decompression after terminating
Distillation can obtain antioxidant；
Step takes PVDF powders in (2)：100 parts；Solvent N-methyl pyrilidone：50 parts；Antioxidant：0.6 part, stirring
Uniformly, after deaeration curing, casting solution is stood using traditional phase transition method, gel, knifing, you can synthesis resistance to oxidation polyvinylidene fluoride
Alkene milipore filter.
The resistance to oxidation milipore filter prepared in the present embodiment is used for oxidation test, resistance to oxidation milipore filter is positioned over into chlorine residue is
Run 70 days in 14000mg/L recycle-water, membrane flux reduces by 0.6%, shows that the antioxygenic property of resistance to oxidation milipore filter is good.
Claims (9)
- A kind of 1. resistance to oxidation milipore filter, it is characterised in that：Prepare the key component of the raw material of the resistance to oxidation milipore filter and each master The parts by weight for wanting component are：PVDF powders：100 parts；Solvent：40-60 parts；Antioxidant：0.5-1 parts；Described solvent is One or more mixing in dimethyl acetamide, dimethylformamide, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE；It is described Antioxidant formed by monomer A, monomer B and monomer C copolymerzation with cross-linkings；Described monomer A is dendroid polyethyleneimine；It is described Monomer B be chain alkyl amine substance；Described monomer C is phenols or ester type compound.
- A kind of 2. resistance to oxidation milipore filter according to claim 1, it is characterised in that：Described dendroid polyethyleneimine Structural formula is：Wherein, n 100-1000, the molecular weight of described dendroid polyethyleneimine is 50000-500000.
- A kind of 3. resistance to oxidation milipore filter according to claim 1, it is characterised in that：Described chain alkyl amine substance Structural formula is：In formula, m 10-12, R are methyl or ethyl, and X is halogens.
- A kind of 4. resistance to oxidation milipore filter according to claim 3, it is characterised in that：Described chain alkyl amine substance is DTAC, DTAB, dodecyl dimethyl ethyl phosphonium bromide ammonium, myristyl two One or more in Methylethyl ammonium bromide, dodecyldimethylamine base ethyl ammonium chloride, tridecyl trimethylammonium bromide.
- A kind of 5. resistance to oxidation milipore filter according to claim 1, it is characterised in that：Described monomer C is butylhydroxy fennel Fragrant phenol, tetrapentaerythritol ester or the tert-butyl group are to one kind in two benzenediols.
- A kind of 6. resistance to oxidation milipore filter as claimed in any of claims 1 to 5, it is characterised in that：Described oxytolerant Change milipore filter and be placed on chlorine residue to be run 70-100 days in 10000-16000mg/L recycle-water, membrane flux reduces 0.6%-1%.
- 7. a kind of preparation method of resistance to oxidation milipore filter described in claim 1, main preparation process are：（1）Monomer A, monomer B and monomer C reactions are prepared into antioxidant in proportion；（2）Take 100 parts of Kynoar powders to be dissolved in 40-60 part solvents, take step（1）Obtained antioxidant 0.5-1 Part, stir, after deaeration curing, stood casting solution using traditional phase transition method, gel, knifing, you can synthesis gathers inclined fluorine Ethene milipore filter.
- A kind of 8. preparation method of resistance to oxidation milipore filter according to claim 7, it is characterised in that：Step（1）Middle oxytolerant The preparation method of agent is：Polymerisation is occurred into a kettle for monomer A, monomer B and monomer C, reaction temperature is 40 ~ 80 DEG C, the reaction time is 24 ~ 48 h；Reaction is evaporated under reduced pressure after terminating and can obtain described antioxidant.
- A kind of 9. preparation method of resistance to oxidation milipore filter according to claim 8, it is characterised in that：Monomer A, monomer B and Monomer C mol ratio is 1：（0.1-0.4）：（0.01-0.05）.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1695778A (en) * | 2005-03-25 | 2005-11-16 | 清华大学 | Ultrafiltration membrane of hollow fiber made form polyarylether sulfone or polyarylether ketone of containing phenolphthalein lateral group, and preparation method |
| CN104174299A (en) * | 2014-07-30 | 2014-12-03 | 中国海洋大学 | High-flux positive osmosis membrane based on ultrathin support layer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060049102A1 (en) * | 2004-09-03 | 2006-03-09 | Miller Jeffrey T | Ionic polymer membranes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1695778A (en) * | 2005-03-25 | 2005-11-16 | 清华大学 | Ultrafiltration membrane of hollow fiber made form polyarylether sulfone or polyarylether ketone of containing phenolphthalein lateral group, and preparation method |
| CN104174299A (en) * | 2014-07-30 | 2014-12-03 | 中国海洋大学 | High-flux positive osmosis membrane based on ultrathin support layer and preparation method thereof |
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