CN108559265A - A kind of Thermo-sensitive polysulfones graft copolymer and Thermo-sensitive PS membrane - Google Patents
A kind of Thermo-sensitive polysulfones graft copolymer and Thermo-sensitive PS membrane Download PDFInfo
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- CN108559265A CN108559265A CN201810347461.4A CN201810347461A CN108559265A CN 108559265 A CN108559265 A CN 108559265A CN 201810347461 A CN201810347461 A CN 201810347461A CN 108559265 A CN108559265 A CN 108559265A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses the structure of a kind of Thermo-sensitive polysulfones graft copolymer and Thermo-sensitive PS membrane, the Thermo-sensitive polysulfones graft copolymer is shown in formula I.The preparation method of Thermo-sensitive PS membrane includes the following steps：Thermo-sensitive polysulfones graft copolymer and polysulfones are added in solvent, stir evenly to obtain Casting solution；Casting solution cleans and removes bubble removing, spreads to uniform film on a glass, immerses in coagulating bath thermostatic water bath 2~24 hours, gel, solidification occur for casting solution, it places after taking-up and is impregnated 24 hours or more in distilled water, dried after finally being rinsed with distilled water, Thermo-sensitive PS membrane is made.The graft copolymer side-chains of the present invention have LCST and UCST adjustable characteristics, therefore can assign polysulfones blend film LCST and UCST adjustable characteristic.
Description
Technical field
The invention belongs to functional high molecule material fields, and in particular to a kind of Thermo-sensitive polysulfones graft copolymer and temperature sensitive
Property PS membrane and its preparation method and use.The Thermo-sensitive polysulfones graft copolymer and Thermo-sensitive PS membrane of the present invention has can
The LCST (lower critical solution temperature) and UCST (high critical solution temperature) of adjusting.
Background technology
Membrane separation technique is to originate in a kind of new separation technology in 20th century, it is utilized with natural or artificial synthesized height
Molecular film is medium, using outside energy or chemical potential difference as motive force, target substance is pushed to pass through, to divide material
From, purification.The technology has many advantages, such as to efficiently separate, low energy consumption, without phase-change, equipment it is simple, easy to operate, be widely used in eating
All conglomeraties such as product, drug, metallurgy, chemical industry, electric power, are especially concerned by people in terms of water and wastewater treatment, and by
Being considered this century most has one of the water technology of development potentiality.
The core component of membrane separation technique is membrane material, mainly there is two class of inorganic material film and organic film material.Organic film
It is based on organic high molecular layer because of the membrane material that advantage is numerous and is produced and is applied extensively, therefore applied at present.It can be with
There are many organic material of film forming, and common organic material has cellulose family, polysulfones, polyacrylonitrile (PAN), Kynoar
(PVDF), the engineerings high molecular material such as polyether-ketone (PEK), polyimides (PI).These organic film materials can be applied to very much
Occasion, and there is certain application advantage, but due to the limitation of self-characteristic, there is also certain limitations in the application.It is special
It is not being growing with application of membrane separation technology field, the performance requirement of membrane material is also continuously improved, therefore, improves film
The performance of material seems significant to prepare satisfactory membrane material.
The physicochemical characteristics of stimulating responsive polymer consumingly relies on extraneous various incentive conditions, such as electric field, magnetic
Field, light, oxidation-reduction potential, ionic strength, temperature and pH value etc..This stimuli responsive characteristic so that this kind of polymer material can
To be applied to the various aspects such as Separation of Proteins film, sensor, drug conveying, thus cause everybody extensive concern.And it will thorn
Membrane material stimulating responsive characteristic can be assigned to which stimulating responsive be prepared applied to membrane material by swashing responsive polymer
Film.There are many kinds of the methods for preparing stimulating responsive film：Including layer assembly, nano particle immobilized, blending or it is graft-polymerized
Object segment.
So far, only patent of invention CN104190273B discloses one kind by changing filming technology to improve
PVDF-g-PNIPAAm films Thermo-sensitive and hydrophilic method, mainly promote temperature sensing polymer chain by the optimization of film-forming process
Section PNIPAAm is enriched with to film surface, to improve the Thermo-sensitive of film.Generally, in terms of temperature sensing polymer membrane material
Patent is totally less, and not seeing especially has high critical inversion temperature (LCST) and high critical inversion temperature
(UCST) correlative study of polymeric film material is adjusted.
Invention content
The shortcomings that in order to overcome existing organic film material to utilize temperature sensing polymer method of modifying and insufficient, of the invention head
Be designed to provide a kind of Thermo-sensitive polysulfones graft copolymer, with adjustable LCST (lower critical solution temperature) and
UCST (high critical solution temperature).
Another object of the present invention is to provide a kind of Thermo-sensitive PS membranes, by above-mentioned Thermo-sensitive polysulfones graft copolymer
It is made.
It is still another object of the present invention to provide the purposes of above-mentioned copolymer and PS membrane.
The purpose of the invention is achieved by the following technical solution：
A kind of Thermo-sensitive polysulfones graft copolymer, structure are shown in formula I：
In formula, the range of x is 0~1；
The integer that m is 10~150, the integer that n is 80~200.
The synthetic method of above-mentioned Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) mix monomer, chloromethyl polysulphone, aglucon and catalyst are added in solvent；Mixed system deoxygenation is laggard
Row polymerisation, 1~10h is reacted at 55~95 DEG C, and product washing of precipitate obtains polymer after room temperature in vacuo drying；
(2) step (1) resulting polymers and imidazoles are dissolved in N, in N '-dimethyl formamide, in 65~85 DEG C of oil baths
Middle reaction 10~for 24 hours, room temperature is dried in vacuo to obtain Thermo-sensitive polysulfones graft copolymer after product washing of precipitate；
Mix monomer described in step (1) includes glycidyl methacrylate and 2- (2- methoxy ethoxies) ethyl
Methacrylate, molar ratio are 0/100~100/0；
The molar ratio of monomer and chloromethyl polysulphone described in step (1) is 5/1~500/1, preferably 20/1~100/1；
Aglucon described in step (1) can be 2,2 '-bipyridyls, 4,4 '-dinonyl bipyridyls or pentamethyl divinyl three
One kind in amine；
The molar ratio of aglucon and chloromethyl polysulphone unit described in step (1) is 0.1/1.0~10/1, it is preferable that is rubbed
You are than being 0.5/1.0~5/1.
Solvent described in step (1) can be one or more of toluene, tetrahydrofuran, methyl phenyl ethers anisole, cyclohexanone or butanone；
The volume ratio of solvent and monomer described in step (1) is 10/1~0.5/1.0, preferably 5/1~0.5/1.0.
Catalyst described in step (1) is stannous chloride or its mixture with copper chloride, cuprous bromide or itself and bromination
The mixture of copper；The molar ratio of catalyst and chloromethyl polysulphone is 0.1/1.0~10/1, preferably 0.5/1.0~5/1.If
The molar ratio of addition copper chloride, copper chloride and stannous chloride is 0.05/1.00~0.2/1.0, if addition copper bromide, copper bromide
Molar ratio with cuprous bromide is 0.05/1.00~0.2/1.0.
The solvent used in washing of precipitate described in step (1) can be one in n-hexane, hexamethylene, ether or petroleum ether
Kind or more；
A concentration of 5~100g/L of the product of step (1) described in step (2) in n,N-Dimethylformamide solution,
It is preferred that 30~50g/L；
The mass ratio of imidazoles and the product of step (1) described in step (2) is 10/1~1/1, preferably 7/1~4/1；
The solvent used in washing of precipitate described in step (2) can be one or more of n-hexane, ether or petroleum ether.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) above-mentioned Thermo-sensitive polysulfones graft copolymer and polysulfones are added in solvent, it is molten to obtain casting film for stirring and dissolving
Liquid；
(2) Casting solution is cleaned and removes bubble removing, spread to uniform film using the tape casting on a glass, immerse temperature
It it is 2~24 hours in 10~80 DEG C of coagulating bath thermostatic water bath, gel, solidification occur for casting solution, are put under room temperature after taking-up
It sets in distilled water and impregnates 24 hours or more, dried after finally being rinsed with distilled water, Thermo-sensitive PS membrane is made；
The mass ratio of Thermo-sensitive polysulfones graft copolymer and polysulfones described in step (1) is 1:1-1:20；
Solvent described in step (1) is N, N '-dimethyl acetamide (DMAc), N, N '-dimethyl formamide (DMF) or N-
One kind in methyl pyrrolidone (NMP)；
Step (2) described film thickness is 100-300 μm；
Coagulating bath described in step (2) is deionized water or containing the aqueous solution that mass concentration is 0~20% additive, is added
It is two in ethyl alcohol, acetone, dimethylacetylamide, dimethylformamide, N-Methyl pyrrolidone, sodium chloride or sodium sulphate to add agent
Kind or more.
The principle of the present invention is：Being grafted on polysulfones main chain using atom transfer radical polymerization (ATRP) method is had
Then it is directly blended and is film-made with polysulfones base material, obtained novel by the graft copolymer of LCST and UCST adjustable characteristic side chains
Thermo-sensitive PS membrane.All it is polysulfones macromolecular, graft polymers and film forming due to graft polymers main chain and at film base material
Base material is easy to carry out blending film forming.And pendant graft polymer chains have water solubility, its can be kept hydrophilic by controlling membrance casting condition
Property segment is distributed in film and fenestra wall surface.Since itself has LCST and UCST adjustable characteristics again, can make final
The polymer blend membrane of formation has LCST and UCST adjustable characteristics.
The present invention has the following advantages and effects with respect to the prior art：
(1) graft copolymer backbone used in the present invention is identical with film base material material essence, therefore is very beneficial for being blended
Film forming.
(2) graft copolymer side-chains of the invention have LCST and UCST adjustable characteristics, therefore it is total to assign polysulfones
Mixed film LCST and UCST adjustable characteristic.
(3) present invention's has the preparation of LCST and UCST adjustable characteristic novel temperature-sensitive polysulfones membrane process very simple,
Performance is special, can be applied to smart membrane Material Field.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) 29.9g polysulfones and 1500ml chloroforms are added in the round-bottomed flask of 2000ml, being stirred at room temperature makes polysulfones dissolve,
Then 20g paraformaldehydes, 1.6ml butters of tin and 85.1ml trim,ethylchlorosilanes is added, system is warming up to 52 DEG C of reaction 20h,
After reaction terminating, product precipitates in methyl alcohol, and filtering, filter cake is washed with methanol, and 40 DEG C of vacuum drying obtain chloromethyl polysulphone production
Object (reaction of generation is shown below), it is 0.53 that nuclear-magnetism, which measures its degree of substitution, i.e., has 0.53 on each polysulfones repetitive unit
Chloro-methyl group；
(2) 10g glycidyl methacrylate, 10g 2- (2- methoxyl group ethoxies are added in the round-bottomed flask of 100ml
Base) ethylmethyl acrylate, chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides obtained by 5g steps (1)
With 0.1g copper chlorides.Lead to argon gas Gu after mixed system dissolving and steep 30min deoxygenations, polymerisation 2h, reaction production are carried out at 80 DEG C
Object is deposited in ether, and filtering, filter cake is washed with ether, then dried to constant weight in room temperature in vacuo, obtain polysulfones graft copolymerization
Object；The structure of polymer is shown below；
(3) polysulfones graft copolymer and 25g imidazoles obtained by 5g steps (1) are dissolved in 150mL N, N '-dimethyl formyl
It in amine, is reacted in 70 DEG C of oil baths for 24 hours, room temperature is dried in vacuo to obtain the polysulfones with LCST characteristic side chains after product washing of precipitate
Graft copolymer；The structure of polymer is shown below；
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 2g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 150mL DMF, stirring and dissolving,
Obtain Casting solution；
(2) Casting solution obtained by step (1) is cleaned and removes bubble removing, the tape casting is utilized on horizontal clean glass plate
Spread to uniform film, it is 300 μm to scrape film thickness, immerses temperature and is in 50 DEG C of coagulating bath thermostatic water bath, casting solution by gel,
Solidification, and be placed in coagulating bath 24 hours, it places impregnated 24 hours in distilled water under room temperature, fully rinsed with distilled water
It dries at room temperature afterwards and obtains novel temperature-sensitive PS membrane.
Embodiment 2
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) 30g glycidyl methacrylate, 3g 2- (2- methoxyl group ethoxies are added in the round-bottomed flask of 100ml
Base) ethylmethyl acrylate, chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides obtained by 5g steps (1)
With 0.1g copper chlorides.Lead to argon gas Gu after mixed system dissolving and steep 30min deoxygenations, polymerisation 2h, reaction production are carried out at 80 DEG C
Object is deposited in ether, and filtering, filter cake is washed with ether, then dried to constant weight in room temperature in vacuo, obtain polysulfones graft copolymerization
Object；
(3) 5g polysulfones graft copolymer and 35g imidazoles are dissolved in 250mL N, in N '-dimethyl formamide, at 85 DEG C
15h is reacted in oil bath, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with UCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 8g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 200mL DMF, stirring and dissolving,
Obtain Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 200 μm to scrape film thickness, is immersed in the coagulating bath thermostatic water bath that temperature is 30 DEG C, and casting solution passes through gel, solidification, and
It is placed in coagulating bath 12 hours, places impregnated 24 hours in distilled water under room temperature, in room temperature after fully being rinsed with distilled water
Under dry and obtain novel temperature-sensitive PS membrane.
Embodiment 3
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) 30g glycidyl methacrylate, 5g 2- (2- methoxyl group ethoxies are added in the round-bottomed flask of 100ml
Base) ethylmethyl acrylate, chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides obtained by 5g steps (1)
With 0.1g copper chlorides.Lead to argon gas Gu after mixed system dissolving and steep 30min deoxygenations, polymerisation 2h, reaction production are carried out at 80 DEG C
Object is deposited in ether, and filtering, filter cake is washed with ether, then dried to constant weight in room temperature in vacuo, obtain polysulfones graft copolymerization
Object；
(3) 5g polysulfones graft copolymer and 15g imidazoles are dissolved in 150mL N, in N '-dimethyl formamide, at 75 DEG C
15h is reacted in oil bath, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with UCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 5g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 180mL DMF, stirring and dissolving,
Obtain Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 250 μm to scrape film thickness, is immersed in the coagulating bath thermostatic water bath that temperature is 70 DEG C, and casting solution passes through gel, solidification, and
It is placed in coagulating bath 12 hours, places impregnated 24 hours in distilled water under room temperature, in room temperature after fully being rinsed with distilled water
Under dry and obtain novel temperature-sensitive PS membrane.
Embodiment 4
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) 30g glycidyl methacrylate, 8g 2- (2- methoxyl group ethoxies are added in the round-bottomed flask of 100ml
Base) ethylmethyl acrylate, chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides obtained by 5g steps (1)
With 0.05g copper chlorides.Lead to argon gas Gu after mixed system dissolving and steep 30min deoxygenations, polymerisation 3h, reaction production are carried out at 85 DEG C
Object is deposited in ether, and filtering, filter cake is washed with ether, then dried to constant weight in room temperature in vacuo, obtain polysulfones graft copolymerization
Object；
(3) 5g polysulfones graft copolymer and 25g imidazoles are dissolved in 150mL N, in N '-dimethyl formamide, at 70 DEG C
It is reacted in oil bath for 24 hours, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with LCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 2g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 150mL DMF, stirring and dissolving,
Obtain Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 100 μm to scrape film thickness, is immersed in the coagulating bath thermostatic water bath that temperature is 50 DEG C, and casting solution passes through gel, solidification, and
It is placed in coagulating bath 24 hours, places impregnated 24 hours in distilled water under room temperature, in room temperature after fully being rinsed with distilled water
Under dry and obtain novel temperature-sensitive PS membrane.
Embodiment 5
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) 20g glycidyl methacrylate, 10g 2- (2- methoxyl group ethoxies are added in the round-bottomed flask of 100ml
Base) ethylmethyl acrylate, chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides obtained by 4g steps (1)
With 0.05g copper chlorides.Lead to argon gas Gu after mixed system dissolving and steep 30min deoxygenations, polymerisation 3h, reaction production are carried out at 85 DEG C
Object is deposited in ether, and filtering, filter cake is washed with ether, then dried to constant weight in room temperature in vacuo, obtain polysulfones graft copolymerization
Object；
(3) 5g polysulfones graft copolymer and 30g imidazoles are dissolved in 250mL N, in N '-dimethyl formamide, at 85 DEG C
15h is reacted in oil bath, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with LCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 6g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 200mL DMF, stirring and dissolving,
Obtain Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 150 μm to scrape film thickness, is immersed in the coagulating bath thermostatic water bath that temperature is 30 DEG C, and casting solution passes through gel, solidification, and
It is placed in coagulating bath 10 hours, places impregnated 24 hours in distilled water under room temperature, in room temperature after fully being rinsed with distilled water
Under dry and obtain novel temperature-sensitive PS membrane.
Embodiment 6
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) chloromethane obtained by 10g glycidyl methacrylate, 20g steps (1) is added in the round-bottomed flask of 100ml
Base polysulfones, 5g bipyridines, 50ml toluene, 1g stannous chlorides and 0.05g copper chlorides.Lead to argon gas Gu bubbles after mixed system dissolving
30min deoxygenations carry out polymerisation 3h at 85 DEG C, and reaction product is deposited in ether, filter, and filter cake is washed with ether, so
It is dried afterwards to constant weight in room temperature in vacuo, obtains polysulfones graft copolymer；
(3) 5g polysulfones graft copolymer and 15g imidazoles are dissolved in 150mL N, in N '-dimethyl formamide, at 75 DEG C
15h is reacted in oil bath, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with LCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 4g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 180mL DMF, stirring and dissolving,
Obtain Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 300 μm to scrape film thickness, and it is 70 DEG C of 10% ethanol solution constant temperature coagulating bath to immerse temperature, and casting solution is by gel, solid
Change, and be placed in coagulating bath 2 hours, places impregnated 24 hours in distilled water under room temperature, after fully being rinsed with distilled water
It dries at room temperature and obtains novel temperature-sensitive PS membrane.
Embodiment 7
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) 7g glycidyl methacrylate, 30g 2- (2- methoxyl group ethoxies are added in the round-bottomed flask of 100ml
Base) ethylmethyl acrylate, chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides obtained by 5g steps (1)
With 0.2g copper chlorides.Lead to argon gas Gu after mixed system dissolving and steep 30min deoxygenations, polymerisation 1.5h, reaction are carried out at 85 DEG C
Product is deposited in ether, and filtering, filter cake is washed with ether, then dried to constant weight in room temperature in vacuo, obtains polysulfones grafting altogether
Polymers；
(3) 5g polysulfones graft copolymer and 20g imidazoles are dissolved in 150mL N, in N '-dimethyl formamide, at 70 DEG C
It is reacted in oil bath for 24 hours, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with LCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 5g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 150mL DMF, stirring and dissolving,
Obtain Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 250 μm to scrape film thickness, is immersed in the coagulating bath thermostatic water bath that temperature is 50 DEG C, and casting solution passes through gel, solidification, and
It is placed in coagulating bath 2 hours, places impregnate 24 hours in distilled water under room temperature, after fully being rinsed with distilled water at room temperature
It dries and obtains novel temperature-sensitive PS membrane.
Embodiment 8
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) 5g glycidyl methacrylate, 30g 2- (2- methoxyl group ethoxies are added in the round-bottomed flask of 100ml
Base) ethylmethyl acrylate, chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides obtained by 5g steps (1)
With 0.2g copper chlorides.Lead to argon gas Gu after mixed system dissolving and steep 30min deoxygenations, polymerisation 1.5h, reaction are carried out at 85 DEG C
Product is deposited in ether, and filtering, filter cake is washed with ether, then dried to constant weight in room temperature in vacuo, obtains polysulfones grafting altogether
Polymers；
(3) 5g polysulfones graft copolymer and 50g imidazoles are dissolved in 250mL N, in N '-dimethyl formamide, at 85 DEG C
15h is reacted in oil bath, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with LCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 4g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 180mL DMF, stirring and dissolving,
Obtain Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 200 μm to scrape film thickness, is immersed in the coagulating bath thermostatic water bath that temperature is 70 DEG C, and casting solution passes through gel, solidification, and
It is placed in coagulating bath 2 hours, places impregnate 24 hours in distilled water under room temperature, after fully being rinsed with distilled water at room temperature
It dries and obtains novel temperature-sensitive PS membrane.
Embodiment 9
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) 25g 2- (2- methoxy ethoxies) ethylmethyl acrylate, 5g steps are added in the round-bottomed flask of 100ml
Suddenly chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides and 0.2g copper chlorides obtained by (1).Mixed system dissolves
Lead to argon gas Gu afterwards and steep 30min deoxygenations, polymerisation 1.5h is carried out at 85 DEG C, reaction product is deposited in ether, is filtered, filter cake
It is washed with ether, is then dried to constant weight in room temperature in vacuo, obtain polysulfones graft copolymer；
(3) 5g polysulfones graft copolymer and 50g imidazoles are dissolved in 250mL N, in N '-dimethyl formamide, at 85 DEG C
15h is reacted in oil bath, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with LCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 15g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 250mL DMF, stirring is molten
Solution, obtains Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 250 μm to scrape film thickness, and it is 70 DEG C of 20% ethanol solution constant temperature coagulating bath to immerse temperature, and casting solution is by gel, solid
Change, and be placed in coagulating bath 2 hours, places impregnated 24 hours in distilled water under room temperature, after fully being rinsed with distilled water
It dries at room temperature and obtains novel temperature-sensitive PS membrane.
Embodiment 10
A kind of synthetic method of Thermo-sensitive polysulfones graft copolymer, includes the following steps：
(1) with 1 step of embodiment (1)；
(2) 25g 2- (2- methoxy ethoxies) ethylmethyl acrylate, 10g are added in the round-bottomed flask of 100ml
Chloromethyl polysulphone, 5g bipyridines, 50ml toluene, 1g stannous chlorides and 0.2g copper chlorides obtained by step (1).Mixed system is molten
Lead to argon gas Gu after solution and steep 30min deoxygenations, polymerisation 1.5h is carried out at 85 DEG C, reaction product is deposited in ether, is filtered, filter
Cake is washed with ether, is then dried to constant weight in room temperature in vacuo, is obtained polysulfones graft copolymer；
(3) 5g polysulfones graft copolymer and 30g imidazoles are dissolved in 250mL N, in N '-dimethyl formamide, at 80 DEG C
15h is reacted in oil bath, room temperature is dried in vacuo to obtain the polysulfones graft copolymer with LCST characteristic side chains after product washing of precipitate.
A kind of Thermo-sensitive PS membrane, preparation method includes the following steps：
(1) 10g Thermo-sensitive polysulfones graft copolymers and 20g commercialization polysulfones are dissolved in 200mL DMF, stirring is molten
Solution, obtains Casting solution；
(2) Casting solution is cleaned and removes bubble removing, spread to using the tape casting on horizontal clean glass plate uniformly thin
Film, it is 250 μm to scrape film thickness, and it is 30 DEG C of 10% ethanol solution constant temperature coagulating bath to immerse temperature, and casting solution is by gel, solid
Change, and be placed in coagulating bath 2 hours, places impregnated 24 hours in distilled water under room temperature, after fully being rinsed with distilled water
It dries at room temperature and obtains novel temperature-sensitive PS membrane.
Comparative example 1
A kind of PS membrane, is made by following steps：
(1) 30g commercialization polysulfones is dissolved in 250mL DMF, stirring and dissolving obtains Casting solution；
(2) Casting solution obtained by step (3) is cleaned and removes bubble removing, the tape casting is utilized on horizontal clean glass plate
Uniform film is spread to, it is 250 μm to scrape film thickness, immerses the 20% ethanol solution constant temperature coagulating bath that temperature is 70 DEG C, casting solution warp
Gel, solidification are crossed, and is placed in coagulating bath 2 hours, places impregnated 24 hours in distilled water under room temperature, filled with distilled water
Divide after rinsing to dry at room temperature and obtains PS membrane.
The hydrophilic modifying PVDF microfiltration membranes that embodiment and comparative example is prepared are tested for the property below.Test method
It is as follows：
Membrane flux is tested：
Deionization is poured into ultrafiltration cup, the precompressed 30min under the pressurization of 0.1mpa nitrogen then calculates 100mL penetrating fluids
Time used calculates membrane flux.
It is as shown in the table that the flux of Thermo-sensitive PS membrane at different temperatures is prepared in embodiment, comparative example：
Table 1：Flux (the Lm of made Thermo-sensitive PS membrane in embodiment, comparative example-2·h-1) with the variation of coolant-temperature gage
| 15℃ | 25℃ | 38℃ | 50℃ | 65℃ | 80℃ | |
| Embodiment 1 | 753.3 | 876.5 | 985.3 | 1098.2 | 1195.6 | 1198.5 |
| Embodiment 2 | 1152.3 | 1165.6 | 1186.3 | 1126.3 | 1185.2 | 1129.7 |
| Embodiment 3 | 1165.2 | 11.35.8 | 1148.9 | 1158.5 | 1108.2 | 1056.1 |
| Embodiment 4 | 1135.2 | 1162.7 | 1146.3 | 1138.1 | 1076.5 | 978.2 |
| Embodiment 5 | 787.3 | 758.2 | 759.7 | 735.7 | 797.3 | 785.7 |
| Embodiment 6 | 785.2 | 796.5 | 785.6 | 812.3 | 1132.5 | 1152.3 |
| Embodiment 7 | 773.9 | 789.5 | 1031.5 | 1173.2 | 1135.6 | 1181.5 |
| Embodiment 8 | 783.7 | 795.6 | 1178.5 | 1161.8 | 1178.1 | 1185.3 |
| Embodiment 9 | 765.7 | 1178.2 | 1158.6 | 1138.2 | 1176.5 | 1158.2 |
| Embodiment 10 | 758.3 | 1132.1 | 1154.9 | 1165.8 | 1187.5 | 1175.8 |
| Comparative example 1 | 675.8 | 663.8 | 683.9 | 685.6 | 691.2 | 695.8 |
As can be seen from Table 1, graft polymers modified polysulfone film of the invention has apparent relative to comparative example pvdf membrane
Temperature-sensing property, and its temperature-sensing property can be adjusted.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of Thermo-sensitive polysulfones graft copolymer, it is characterised in that structure is shown in formula I：
In formula, the range of x is 0~1.
2. the synthetic method of Thermo-sensitive polysulfones graft copolymer described in claim 1, it is characterised in that include the following steps：
(1) mix monomer, chloromethyl polysulphone, aglucon and catalyst are added in solvent；Gathered after mixed system deoxygenation
Reaction is closed, 1~10h is reacted at 55~95 DEG C, product washing of precipitate obtains polymer after room temperature in vacuo drying；
(2) step (1) resulting polymers and imidazoles are dissolved in N, it is anti-in 65~85 DEG C of oil baths in N '-dimethyl formamide
Answer 10~for 24 hours, room temperature is dried in vacuo to obtain Thermo-sensitive polysulfones graft copolymer after product washing of precipitate；
Mix monomer described in step (1) includes glycidyl methacrylate and 2- (2- methoxy ethoxies) ethyl-methyl
Acrylate, molar ratio are 0/100~100/0.
3. synthetic method according to claim 2, it is characterised in that：
The molar ratio of monomer and chloromethyl polysulphone described in step (1) is 5/1~500/1；
The molar ratio of aglucon and chloromethyl polysulphone unit described in step (1) is 0.1/1.0~10/1.
4. synthetic method according to claim 2, it is characterised in that：Aglucon described in step (1) be 2,2 '-bipyridyls,
One kind in 4,4 '-dinonyl bipyridyls or pentamethyl-diethylenetriamine.
5. synthetic method according to claim 2, it is characterised in that：Catalyst described in step (1) be stannous chloride or
Itself and the mixture of copper chloride, the mixture of cuprous bromide or itself and copper bromide.
6. synthetic method according to claim 2, it is characterised in that：The product of imidazoles and step (1) described in step (2)
Mass ratio be 10/1~1/1.
7. a kind of preparation method of Thermo-sensitive PS membrane, it is characterised in that include the following steps：
(1) Thermo-sensitive polysulfones graft copolymer described in claim 1 and polysulfones are added in solvent, stirring and dissolving is cast
Coating solution；
(2) Casting solution is cleaned and removes bubble removing, spread to uniform film on a glass, it is 10~80 DEG C solidifying to immerse temperature
Admittedly bathing in thermostatic water bath 2~24 hours, gel, solidification occur for casting solution, place in distilled water and impregnate under room temperature after taking-up
It 24 hours or more, is dried after finally being rinsed with distilled water, Thermo-sensitive PS membrane is made.
8. preparation method according to claim 7, it is characterised in that：Thermo-sensitive polysulfones graft copolymerization described in step (1)
The mass ratio of object and polysulfones is 1:1-1:20.
9. a kind of Thermo-sensitive PS membrane, it is characterised in that：It is to be made by the method described in claim 7 or 8.
10. application of the Thermo-sensitive PS membrane in preparing membrane material described in claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114953667A (en) * | 2022-04-24 | 2022-08-30 | 山西阳中新材有限责任公司 | Aerogel-containing temperature-sensitive heat-insulating film and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167785A (en) * | 2011-01-20 | 2011-08-31 | 中科院广州化学有限公司 | Phosphorylated polymer composite film for full vanadium flow battery and preparation method thereof |
| CN103736408A (en) * | 2013-12-31 | 2014-04-23 | 中科院广州化学有限公司 | Polysulfone porous film in response to temperature and acidity, preparation method and application of polysuffone porous film |
| CN103755967A (en) * | 2013-12-31 | 2014-04-30 | 中科院广州化学有限公司 | Thermo-sensitive chiral separation additive and thermo-sensitive polysulfone chiral separation membrane |
| CN104307389A (en) * | 2014-10-11 | 2015-01-28 | 四川大学 | Polyether sulfone temperature stimulus response film and preparation method thereof |
| CN105924587A (en) * | 2016-05-16 | 2016-09-07 | 大连理工大学 | Branched side chain polymer anion exchange membrane and preparation method thereof |
| CN107641177A (en) * | 2016-07-20 | 2018-01-30 | 中国科学院上海应用物理研究所 | A kind of polyether sulfone grafted propylene acrylic monomer copolymer and preparation method thereof |
-
2018
- 2018-04-18 CN CN201810347461.4A patent/CN108559265A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167785A (en) * | 2011-01-20 | 2011-08-31 | 中科院广州化学有限公司 | Phosphorylated polymer composite film for full vanadium flow battery and preparation method thereof |
| CN103736408A (en) * | 2013-12-31 | 2014-04-23 | 中科院广州化学有限公司 | Polysulfone porous film in response to temperature and acidity, preparation method and application of polysuffone porous film |
| CN103755967A (en) * | 2013-12-31 | 2014-04-30 | 中科院广州化学有限公司 | Thermo-sensitive chiral separation additive and thermo-sensitive polysulfone chiral separation membrane |
| CN104307389A (en) * | 2014-10-11 | 2015-01-28 | 四川大学 | Polyether sulfone temperature stimulus response film and preparation method thereof |
| CN105924587A (en) * | 2016-05-16 | 2016-09-07 | 大连理工大学 | Branched side chain polymer anion exchange membrane and preparation method thereof |
| CN107641177A (en) * | 2016-07-20 | 2018-01-30 | 中国科学院上海应用物理研究所 | A kind of polyether sulfone grafted propylene acrylic monomer copolymer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| GANWEI ZHANG等: "Poly(3-imidazolyl-2-hydroxypropyl methacrylate)–a new polymer with a tunable upper critical solution temperature in water", 《POLYM. CHEM》 * |
| JEAN-FRANC等: "Polymerization of Oligo(Ethylene Glycol) (Meth) Acrylates:Toward New Generations of Smart Biocompatible Materials", 《J.POLYM.SCI.PART A:POLYM.CHEM. 》 * |
| 杨卫海等: "具有高临界相转变温度的热敏性高分子材料", 《华东理工大学学报（自然科学版）》 * |
| 王建宇等: "PSF-g-PAA和 PSF-g-PNIPAAm的合成及其共混膜的环境响应性研究", 《高分子学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114953667A (en) * | 2022-04-24 | 2022-08-30 | 山西阳中新材有限责任公司 | Aerogel-containing temperature-sensitive heat-insulating film and preparation method thereof |
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