CN110894253B - Nonionic fluorine-containing amphiphilic polymer and separation membrane containing same - Google Patents

Nonionic fluorine-containing amphiphilic polymer and separation membrane containing same Download PDF

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CN110894253B
CN110894253B CN201811062843.9A CN201811062843A CN110894253B CN 110894253 B CN110894253 B CN 110894253B CN 201811062843 A CN201811062843 A CN 201811062843A CN 110894253 B CN110894253 B CN 110894253B
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fluorine
nonionic
amphiphilic polymer
molecular weight
containing amphiphilic
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CN110894253A (en
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朱宝库
王纳川
陈忱
章鹏
周名勇
肖玲
赵斌
王俊
陈清
陈良刚
沈宇杰
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Hainan Litree Purifying Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone

Abstract

The invention discloses a nonionic fluorine-containing amphiphilic polymer and a separation membrane containing the same. The non-ionic fluorine-containing amphiphilic copolymer is polymerized by using fluorine-containing macromolecules as a dispersing agent, using micromolecular esters as a solubilizer and using fluorine-containing monomers and other non-ionic hydrophilic monomers as raw materials by adopting a free radical suspension polymerization method. The fluorine-containing macromolecular dispersing agent is obtained by solution copolymerization of a fluorine-containing ethyl monomer and a nonionic hydrophilic monomer in an organic solvent. The fluorine-containing macromolecular dispersing agent adopted by the invention has excellent dispersing effect on fluorine-containing monomers, and the micromolecule ester solubilizer can increase the intermiscibility of hydrophilic monomers and fluorine-containing monomers, so that the highly hydrophilic fluorine-containing amphiphilic copolymer can be prepared. The nonionic fluorine-containing amphiphilic polymer can be independently used for preparing or blended with other resins to prepare a high-hydrophilicity separation membrane, and has good hydrophilicity, low cost and good application prospect compared with the existing fluorine-containing separation membrane material.

Description

Nonionic fluorine-containing amphiphilic polymer and separation membrane containing same
Technical Field
The invention belongs to the field of high molecular materials, and particularly relates to a nonionic fluorine-containing amphiphilic polymer and a separation membrane containing the same.
Background
Fluorine atoms have strong electronegativity, low polarizability, weak van der waals force and high bond energy (485.3kJ/mol) of C-F bonds, so that the fluorine-containing polymer has outstanding heat resistance, solvent resistance, acid and alkali corrosion resistance, excellent weather resistance and flame resistance, unique low surface energy and the like. The fluorine-containing polymers are mainly classified into fluorine-containing olefin polymers and fluorine-containing acrylate polymers. The fluorine-containing olefins mainly include polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), and Polytetrafluoroethylene (PTFE). Polyvinylidene fluoride (PVDF) has better chemical stability, heat resistance and mechanical property, and ultraviolet irradiation resistance, aging resistance and other properties; the PVDF has the advantages of tight arrangement among molecular chains, higher crystallinity, larger hydrophobicity and poor alkali tolerance. Therefore, PVDF is a novel material with excellent comprehensive performance, and has attracted great interest in the fields of fluorocarbon coatings, petrochemical industry, membrane separation and the like in recent years. Polychlorotrifluoroethylene (PCTFE) has high crystallinity, and has the characteristics of high transparency, high hardness, strong rigidity and good creep resistance. As the molecular structure contains more fluorine atoms, the product has non-hygroscopicity and air impermeability, and chlorine atoms are introduced into the molecules, so that the processing performance is improved, but the heat resistance is poor. It is commonly used as corrosion-resistant, electronic instrument parts and moistureproof and anti-sticking coatings on chemical equipment. Polytetrafluoroethylene (PTFE) has outstanding temperature resistance and high lubricity, has excellent chemical stability, is inert to most chemicals and solvents, and can resist strong acid, strong alkali, water and various organic solvents. It is often used for manufacturing rods, tubes, plates, cable materials, raw material belts, anti-sticking coatings and the like. The fluorine-containing acrylate not only retains the hydrophobic and oleophobic properties of the fluorine-containing polymer, but also has the adhesive property of an acrylate polymer, but because the fluorine-containing acrylate has higher inertia and is difficult to dissolve in water and common solvents, the fluorine-containing acrylate is usually subjected to emulsion polymerization with monomers such as (methyl) acrylate, styrene and the like to obtain a binary or ternary copolymer, and the fluorine-containing acrylate is widely applied to textile industry and coating industry to endow a substrate with excellent water and oil repellent effects.
At present, research on fluorine-containing copolymers and preparation methods thereof is reported at home and abroad. Chinese patent (CN 107848947a) discloses a fluorine-containing compound, a living polymerization initiator, a fluorine-containing polymer, a method for producing a fluorine-containing polymer, and a resist composition, which are easily available, are suitable for use as an initiator for living radical polymerization, are free from foreign matter, are excellent in liquid repellency such as water repellency, and can be suitably used as a leveling agent in a resist composition. The fluorine-containing compound is used only as an initiator for living polymerization, and does not improve hydrophilicity. Chinese patent (CN101481438A) discloses a random copolymerization fluorine-containing macromolecular emulsifier and a preparation method thereof, wherein the macromolecular emulsifier consisting of fluorine-containing chain links and hydrophilic chain links is prepared by adopting free radical polymerization. The molecular weight of the copolymer is only about 1 ten thousand, and the copolymer can only be used as an emulsifier and cannot meet the requirements of diversified fluorine-containing products. Chinese patent (CN 105008418A) discloses a hydrophilic fluoropolymer, which contains a functional group of hydroxyl, carboxyl or sulfonic group to provide hydrophilicity. Although the selectivity of hydrophilic groups is increased, the hydrophilic groups are grafted to the main chain of the fluorine polymer, belonging to the graft polymer, and the grafting rate is only about 1 wt%. While many other documents report the use of Atom Transfer Radical Polymerization (ATRP) to graft various groups onto the surface or polymer chains of PVDF or PTFE, the overall grafting rate still does not exceed 20 wt%. Only the side chain or the surface of the product is modified, and the main chain in the polymer is not fundamentally changed. Chinese patent (CN201510058126A) discloses a non-ionic functional fluorine-containing polymer and a preparation method thereof, wherein the functional fluorine-containing polymer takes a fluorine-containing monomer, a graftable active monomer and a hydrophilic functional monomer as comonomers, an active precursor polymer with a main chain containing an atom transfer radical polymerization active side group is polymerized in an aqueous dispersion system, then the active side group is utilized to initiate the non-ionic functional monomer on a solid-liquid interface to carry out interface atom transfer radical polymerization in an alkaline environment, and the anionic functional fluorine-containing polymer containing a non-ionic side chain is polymerized. The method can improve the content of the hydrophilic monomer to 70 wt% at most, which is higher than the content of the hydrophilic component in the existing fluorine-containing copolymer. However, two important problems remain unsolved in this patent: firstly, in the non-ionic functionalized fluorine-containing polymer, a hydrophilic chain segment is a non-ionic functionalized chain link F2 which is grafted on a polymer main chain as a graft chain segment and belongs to a graft polymer, and the non-ionic functionalized chain segment is not a conventional main chain copolymer of two monomers, so that the properties of the main chain and the graft chain in the polymer chain are greatly different, the defects of phase separation or performance are easily caused when a polymer product is prepared, and the chemical bond of the graft chain segment and the main chain is not stable; in the conventional random copolymer, the two performance monomers are randomly distributed and are connected by strong carbon-carbon bonds, so that the random copolymer is very stable, and the performance of the whole polymer chain is uniform and stable, so that the conventional copolymerization is the fundamental modification of a main chain monomer and is a qualitative change. On the other hand, the graft modification of the copolymer is an alternative method which cannot change the original structure of the polymer main chain under the condition that the common copolymerization modification cannot be realized. Secondly, in order to modify the grafting, the main chain must be damaged to a certain extent so as to contain active sites or defect points, and then other monomers are grafted onto the main chain by using the active sites or defect points, which is extremely complicated. And the active side group makes the active site very unstable, so that the atom transfer radical polymerization described in the patent can not be completed due to very easy degradation, and therefore, a harsh reaction environment is required for protecting the atom transfer radical polymerization and an expensive catalyst system is adopted for realizing stable polymerization. Thus, in this patent, from the viewpoint of the structure of the polymer, it is not a conventional copolymer of two monomers; from the perspective of the preparation method of the polymer, the synthetic steps are very complicated, and the steps of the four monomers and the two types of polymerization are involved, wherein the coordination of the active residue in the atom transfer radical polymerization is very complicated, and strict oxygen-free conditions are required. Thus, this patent, although achieving an increase in hydrophilic monomer components, is still an unconventional and extremely complicated scheme that is difficult to industrialize.
In a word, the copolymerization content of oil-soluble monomers (such as vinyl acetate, acrylate and the like) in the comonomers in the existing fluorine-containing main chain copolymer can reach 10-20 wt%; the water-soluble monomer (such as carboxyl, hydroxyl, sulfonic group and the like) has the copolymerization content of less than 1wt percent. In addition, although the content of the hydrophilic functionalized monomer can be improved by adopting a living radical polymerization method (such as Chinese CN201510058126A), the prepared fluorine-containing copolymer is a graft copolymer, the hydrophilic monomer component is not on the main chain, and the uniformity and the stability of the copolymer are poor, wherein the uniformity refers to the uniformity of the distribution of the hydrophilic monomer component on the polymer chain, and the stability refers to the link firmness of the graft chain and the main chain of the polymer; in addition, four types of monomers are needed to increase the content of the hydrophilic component, and two polymerization methods have extremely complex steps and are difficult to be applied in a large scale. Therefore, in the prior art, the content of the hydrophilic monomer is difficult to increase, or a complex ATRP method is used for grafting the hydrophilic component to a side chain, and the content of the hydrophilic monomer component on a main chain cannot be greatly increased.
Disclosure of Invention
In order to overcome the defects of the prior art, the technical problem to be solved by the invention is to provide a nonionic fluorine-containing amphiphilic polymer and a separation membrane containing the same, wherein the nonionic fluorine-containing amphiphilic polymer contains a hydrophobic fluorine-containing monomer and a nonionic hydrophilic monomer, and the content of a hydrophilic component can be adjusted at will within the range of 1-70 wt%; and the hydrophobic component and the hydrophilic component can be respectively selected, so that the key problem that the hydrophilic monomer component cannot be greatly improved on the main chain is solved.
Different from the prior art, the nonionic fluorine-containing amphiphilic copolymer and the separation membrane prepared from the same provided by the invention solve the following problems in the prior art:
(1) the copolymerization content of oil-soluble monomers (such as vinyl acetate, acrylate and the like) in comonomers in the existing fluorine-containing main chain copolymer can reach 10-20 wt%; the water-soluble monomer (such as carboxyl, hydroxyl, sulfonic group and the like) has the copolymerization content of less than 1wt percent. The technology of the invention greatly widens the variety of hydrophilic monomers copolymerized with the fluorine-containing monomer, and the hydrophilic monomers can be selected from any one or more of vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol monoallyl ether, hydroxymethyl acrylamide, hydroxyethyl acrylamide and hydroxypropyl methacrylamide. These hydrophilic functionalized monomers have very good hydrophilic properties. Furthermore, the content of the hydrophilic functional monomer in the nonionic fluorine-containing amphiphilic polymer provided by the invention can reach 70 wt%, which is far higher than that of the hydrophilic component in the existing fluorine-containing copolymer, and the hydrophilic functional monomer component in the copolymer can be randomly adjusted between 1 wt% and 70 wt%.
(2) Although the method of atom transfer radical graft copolymerization, as reported in chinese patent CN201510058126A and related documents, can increase the content of hydrophilic components, the synthesized copolymer is a graft polymer, the graft segment is unstable, the preparation method is very complex, the conditions are very harsh, and industrial production cannot be realized. The invention realizes the copolymerization of the fluorine-containing monomer and the nonionic hydrophilic monomer in the main chain, and is a binary main chain copolymer of the fluorine-containing monomer and the nonionic hydrophilic monomer. Such copolymers contain a polymeric backbone of only two monomers and no other graft units and third monomers, since the addition of graft units and third units necessarily affects the performance of the amphipathic copolymer. The graft polymer containing the graft unit is liable to cause phase separation or performance defects in the preparation of a polymer article, and the chemical bond connecting the graft segment and the main chain is not so stable, and in addition, in order to modify the graft, the main chain must be damaged to some extent to contain active sites or defect points, and then other monomers are grafted to the main chain by using the active sites or defect points, which is extremely complicated in procedure. And the active side group makes the active site very unstable, so that the atom transfer radical polymerization described in the patent can not be completed due to very easy degradation, and therefore, a harsh reaction environment is required for protecting the atom transfer radical polymerization and an expensive catalyst system is adopted for realizing stable polymerization. The third unit inevitably affects the polymerization activity of the two original comonomers, and the uncertainty of performance change is inevitably brought about after the third monomer is copolymerized to the main chain of the polymer. In summary, the copolymers comprising the graft units or the third monomer are also completely different copolymers from the binary backbone copolymers of the present invention, and there are great differences in structure and properties. The nonionic fluorine-containing amphiphilic polymer provided by the invention has stable performance, and greatly improves the hydrophilic component. And the process is simple and easy to implement and easy to industrialize.
(3) The existing fluorine-containing polymer separation membrane is mainly a hydrophobic membrane, and the hydrophilic type is very poor due to high fluorine content. The invention provides a non-ionic fluorine-containing amphiphilic polymer raw material for the fluorine-containing polymer separation membrane, and the amphiphilic polymer material can be used for preparing the fluorine-containing polymer membrane with excellent hydrophilicity and pollution resistance by using the conventional separation membrane preparation process, thereby greatly expanding the application range of the fluorine-containing polymer separation membrane.
In the existing copolymerization technology, due to the hydrophobicity of the fluorine-containing monomer and the hydrophilicity of the hydrophilic monomer, the content of the hydrophilic component in the copolymer is extremely low when the two monomers are subjected to free radical suspension copolymerization, and the problem of copolymerization is solved. In addition, although the atom transfer radical grafting method which can obviously increase the content of the hydrophilic component is used for realizing the increase and adjustment of the content of the hydrophilic component in the copolymer, the obtained graft copolymer which is only on the active site of the main chain of the copolymer has the problems that the instability of the graft chain segment and the complex preparation scheme are still unavoidable. In order to solve the problem, the invention adopts a simple free radical suspension polymerization method to prepare the nonionic fluorine-containing amphiphilic polymer which only contains the main chain copolymerization of fluorine-containing monomers and nonionic hydrophilic monomers, and the content of the nonionic hydrophilic component can be adjusted between 1 and 70 weight percent, thereby achieving the purpose of adjusting the performance of the copolymer. The method solves the problems of low selectivity of a hydrophilic component and a hydrophilic monomer in the conventional copolymerization, and also solves the problems that the introduction of the hydrophilic component into a polymer main chain cannot be realized and the process is complicated in the graft copolymerization by an atom transfer radical polymerization method.
In the preparation steps of the nonionic fluorine-containing amphiphilic polymer, an innovative solution is adopted. One is that a fluorine-containing macromolecular dispersant is specially designed for preparing the non-ionic fluorine-containing amphiphilic copolymer, wherein hydrophobic fluorine-containing monomers and non-ionic hydrophilic monomers are introduced into the fluorine-containing macromolecular dispersant. Secondly, the solubilizer, the extractant and the important fluorine-containing macromolecular dispersant are mutually matched, and finally the non-ionic hydrophilic monomer is gradually added. The solution is necessary process for preparing the nonionic fluorine-containing amphiphilic copolymer, which is complementary to each other, is not necessary, realizes the random adjustment of the content of the nonionic hydrophilic component between 1 and 70 weight percent, and has simple and easy preparation method and easy industrialization.
Finally, the novel nonionic fluorine-containing amphiphilic copolymer can be used as a raw material, and a conventional membrane preparation process is adopted to prepare the nonionic fluorine-containing amphiphilic separation membrane, so that the hydrophilicity of the novel nonionic fluorine-containing amphiphilic copolymer is remarkably improved compared with that of the conventional fluorine-containing polymer separation membrane, and the novel nonionic fluorine-containing amphiphilic copolymer has excellent hydrophilicity and contamination resistance.
Therefore, the invention adopts the following technical scheme:
a nonionic fluorine-containing amphiphilic polymer characterized by: the nonionic fluorine-containing amphiphilic polymer is a polymer consisting of fluorine-containing chain links and nonionic hydrophilic chain links, and the structural formula of the nonionic fluorine-containing amphiphilic polymer is shown as follows:
Figure GDA0002072751060000041
in the formula:
the fluorine-containing chain link is formed by polymerizing a fluorine-containing monomer A, and the structure of the fluorine-containing chain link unit-A-is
Figure GDA0002072751060000042
The nonionic hydrophilic chain link is formed by polymerizing a nonionic hydrophilic monomer B, and the structure of the nonionic hydrophilic chain link unit-B-is as follows:
Figure GDA0002072751060000051
in the formula:
R1selected from H, F;
R2selected from H, F;
R3selected from H, CH3；
R4Is selected from
Figure GDA0002072751060000052
COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH、CH2O(CH2CH2O)nH、CO(OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、CONHCH2CHOHCH3、CONHCH2CH2OH、
a. b and n are integers which are more than or equal to 1; preferably, a/b is 250/1-1.5/1; preferably, a/b is 10/1 to 1/1.
Further, the monomer corresponding to the fluorine-containing monomer A is any one or more of vinyl fluoride, vinylidene fluoride and tetrafluoroethylene, and the structural formula is as follows:
Figure GDA0002072751060000053
in the formula:
R1selected from H, F;
R2selected from H, F.
Further, the monomer corresponding to the non-ionic hydrophilic monomer B is any one or more of vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol monoallyl ether, hydroxymethyl acrylamide, hydroxyethyl acrylamide and hydroxypropyl methacrylamide, and the structural formula is as follows:
Figure GDA0002072751060000054
in the formula:
R3selected from H, CH3；
R4Is selected from
Figure GDA0002072751060000061
COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH、CH2O(CH2CH2O)nH、CO(OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、CONHCH2CHOHCH3、CONHCH2CH2OH；
n is an integer greater than 1.
Further, the number average molecular weight of the nonionic fluorine-containing amphiphilic polymer is 10-100 ten thousand daltons.
The invention also provides a preparation method of the nonionic fluorine-containing amphiphilic polymer, which comprises the following steps:
(1) preparation of a solubilization dispersion liquid: adding the fluorine-containing monomer A, fluorine-containing macromolecular dispersant solution, hydrophobic initiator and solubilizer into the water phase, and dispersing under the action of mechanical stirring or adding into a high-pressure homogenizer or an ultrasonic emulsifier for emulsification to obtain stable dispersion liquid;
(2) polymerization of amphiphilic copolymers containing fluorine: heating to 40-80 ℃ for polymerization reaction, gradually adding a non-ionic hydrophilic monomer B into the dispersion liquid obtained in the step (1), and filtering to obtain a fluorine-containing amphiphilic copolymer wet material after the reaction is finished;
(3) extracting the solubilizer: adding the fluorine-containing amphiphilic copolymer wet material obtained in the step (2) into an extracting agent, removing the solubilizer in the fluorine-containing amphiphilic copolymer wet material, and drying to obtain the fluorine-containing amphiphilic copolymer
Preferably, the fluorine-containing monomer A in the step (1) is selected from any one or more of vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene;
preferably, the fluorine-containing macromolecular dispersant solution in the step (1) consists of 10-50 wt% of fluorine-containing macromolecular dispersant and the balance of organic solvent.
Preferably, the solubilizer in step (1) is selected from any one or more of propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, methyl propionate, ethyl propionate, butyl propionate, hexyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, hexyl butyrate;
preferably, the hydrophobic initiator described in step (1) is an initiator known in the art of free radical polymerization. More preferably, the initiator is selected from any one or any more of bis (2-ethylhexyl) peroxydicarbonate (EHP), azobisisobutyronitrile and dibenzoyl peroxide.
Preferably, the adding amount of the fluorine-containing macromolecular dispersant solution in the step (1) is 0.5-5% of the total mass of the fluorine-containing monomer.
Preferably, the hydrophobic initiator is added in the step (1) in a conventional amount well known in the field of radical polymerization.
Preferably, the addition amount of the solubilizer in the step (1) is 0.5-5% of the total mass of the fluorine-containing monomer.
Preferably, the non-ionic hydrophilic monomer B in the step (2) is selected from any one or more of vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol monoallyl ether, hydroxymethyl acrylamide, hydroxyethyl acrylamide and hydroxypropyl methacrylamide.
Preferably, the addition amount of the nonionic hydrophilic monomer B in the step (2) is: the fluorine-containing monomer A/nonionic hydrophilic monomer B is 250/1-1.5/1, preferably 250/1-1.5/1.
Preferably, the polymerization reaction in step (2) is selected from suspension polymerization. The polymerization reaction employs reaction temperatures and reaction times well known in the art of free radical polymerization. More preferably, the reaction temperature is 40-80 ℃, and the reaction time is 1-20 hours.
Preferably, the duration of the step-by-step addition of the nonionic hydrophilic monomer B in the step (2) is 0.25 to 2 hours from the end of the temperature rise to the end of the reaction.
Preferably, the extractant in step (3) is selected from any one or more of methanol, ethanol and propanol.
Preferably, the adding amount of the extracting agent in the step (3) is 20-100% of the total mass of the nonionic fluorine-containing amphiphilic polymer.
The invention also provides a fluorine-containing macromolecular dispersant which is a polymer consisting of fluorine-containing chain links and nonionic hydrophilic chain links, and the structural formula of the fluorine-containing macromolecular dispersant is as follows:
Figure GDA0002072751060000071
in the formula:
the fluorine-containing chain link is formed by polymerizing a fluorine-containing monomer A, and the structure of the fluorine-containing chain link unit-A-is
Figure GDA0002072751060000072
The nonionic hydrophilic chain link is formed by polymerizing a nonionic hydrophilic monomer B, and the structure of the nonionic hydrophilic chain link unit-B-is as follows:
Figure GDA0002072751060000073
in the formula:
R1selected from H, F;
R2selected from H, F;
R3selected from H, CH3；
R4Is selected from
Figure GDA0002072751060000081
COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH、CH2O(CH2CH2O)nH、CO(OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、CONHCH2CHOHCH3、CONHCH2CH2OH、
x, y and n are integers which are more than or equal to 1; preferably, x/y is 3/1-1/100; the preferred x/y is 1/1 ~ 1/20.
Further, the monomer corresponding to the fluorine-containing monomer A is any one or more of vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene, and the structural formula is as follows:
Figure GDA0002072751060000082
in the formula:
R1selected from H, F;
R2selected from H, F.
Further, the monomer corresponding to the non-ionic hydrophilic monomer B is any one or more of vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol monoallyl ether, hydroxymethyl acrylamide, hydroxyethyl acrylamide and hydroxypropyl methacrylamide, and the structural formula is as follows:
Figure GDA0002072751060000083
in the formula:
R3selected from H, CH3；
R4Is selected from
Figure GDA0002072751060000084
COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH、CH2O(CH2CH2O)nH、CO(OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、CONHCH2CHOHCH3、CONHCH2CH2OH；
n is an integer greater than 1.
Further, the number average molecular weight of the nonionic fluorine-containing amphiphilic polymer is 0.5-10 ten thousand daltons.
The invention provides a preparation method of the fluorine-containing macromolecular dispersing agent, which comprises the following steps: weighing a fluorine-containing monomer A accounting for 5-50% of the total weight of the monomers, a non-ionic hydrophilic monomer B accounting for 50-95% of the total weight of the monomers and an initiator accounting for 0.1-5% of the total weight of the monomers, and carrying out solution polymerization in an organic solvent at the temperature of 40-120 ℃ to obtain a fluorine-containing macromolecular dispersant solution, wherein the total weight of the monomers is the total weight of the fluorine-containing monomer A and the non-ionic hydrophilic monomer B;
preferably, the fluorine-containing monomer A in the step (A) is selected from any one or more of vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene;
preferably, the hydrophilic functionalized monomer B in step (a) is selected from any one or more of vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol monoallyl ether, hydroxymethyl acrylamide, hydroxyethyl acrylamide and hydroxypropyl methacrylamide.
Preferably, the initiator used in step (a) is any one of azobisisobutyronitrile and benzoyl peroxide.
Preferably, the polymerization reaction in step (a) is selected from solution polymerization. The organic solvent is one or more selected from acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N dimethylformamide, N dimethylacetamide, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and N-alkyl pyrrolidone.
Preferably, the macromolecular dispersant solution in the step is composed of 10-50% of monomer and the balance of organic solvent.
Preferably, the monomer preparation mass ratio in the step is as follows: 5-50% of fluorine-containing monomer and 50-95% of nonionic hydrophilic monomer.
Preferably, the polymerization time in the step is 1 to 20 hours.
The invention also provides a nonionic fluorine-containing amphiphilic copolymer separation membrane, which is characterized by comprising the nonionic fluorine-containing amphiphilic copolymer or the nonionic fluorine-containing amphiphilic copolymer prepared by the method.
Further, the nonionic fluorine-containing amphiphilic copolymer separation membrane is prepared by adopting a preparation process which is commonly known in the field of separation membranes.
Further, the nonionic fluorine-containing amphiphilic copolymer separation membrane provided by the invention can also comprise other resin materials or additive materials according to the use requirements. The other resin materials can be polyvinyl chloride, polypropylene, polyethylene, polyvinylidene fluoride, polycarbonate, nylon and polyether sulfone, and the additive materials can be common inorganic materials, organic micromolecular materials and high molecular materials.
Compared with the prior art, the invention has the beneficial effects that:
1) the nonionic hydrophilic monomer component in the nonionic fluorine-containing amphiphilic polymer provided by the invention has very good hydrophilic performance, and the content of the nonionic hydrophilic monomer component can reach 70 wt%, which is far higher than that of the hydrophilic component in the existing fluorine-containing copolymer; in addition, the proportion of the nonionic functional monomer component in the nonionic functional fluorine-containing polymer can be randomly adjusted between 1 wt% and 70 wt%, so that the nonionic functional fluorine-containing polymer provided by the invention has very flexible applicability.
2) The invention adopts a free radical suspension polymerization method which takes a specific fluorine-containing macromolecular dispersant as a dispersant to polymerize two monomers into the same copolymer main chain instead of graft copolymerization, thereby greatly improving the content of hydrophilic monomer components on the main chain and having good stability and uniformity of the polymer.
3) The free radical suspension polymerization method adopted by the invention has short reaction flow and simple equipment, and is suitable for large-scale production.
4) The invention can prepare the nonionic fluorine-containing amphiphilic polymer membrane with excellent hydrophilicity and pollution resistance by adopting the conventional separation membrane preparation process, thereby greatly expanding the application range of the fluorine-containing polymer separation membrane.
Drawings
FIG. 1 is a scanning electron micrograph of platelets adhered to the surfaces of the P3 membrane, the P8 membrane and the PVDF membrane prepared in example 34.
Detailed Description
The following will describe in detail the method for preparing the nonionic fluorine-containing amphiphilic polymer according to the present invention with reference to specific examples. The procedure was the same as described in the summary of the invention for all examples, and the parameters in the table are the respective conditions of execution and the structure of the copolymer obtained. It should be noted that the embodiments described are not intended to limit the invention, and all modifications that can be derived or suggested by those skilled in the art from the disclosure of the present invention should be considered within the scope of the present invention.
Example 1
Synthesizing a nonionic fluorine-containing amphiphilic polymer P1 taking a fluorine-containing macromolecular dispersant D1 solution as a dispersant:
100g of N, N-Dimethylacetamide (DMAC), 6g of vinylidene fluoride, 8g of vinyl pyrrolidone and 0.1g of initiator Benzoyl Peroxide (BPO) are added into a reactor, and dissolved and stirred at room temperature for 30 minutes under the condition of introducing nitrogen to remove oxygen in the system. The temperature was raised to 60 ℃ in the presence of reflux to carry out the polymerization. After 6 hours of reaction, heating was stopped and air was introduced to terminate the reaction. To obtain a fluorine-containing macromolecular dispersing agent D1 solution. 2000ml of deionized water, 1.2g of D1 solution and 1g of initiator bis (2-ethylhexyl) peroxydicarbonate (EHP) are added into a stainless steel reaction kettle, the stainless steel reaction kettle is vacuumized and filled with nitrogen for 3 times, then 1500g of vinylidene fluoride and 7.5g of solubilizer ethyl acetate are added, and the mixture is pre-dispersed and stirred for 30 minutes at room temperature. The temperature was raised to 40 ℃ polymerization temperature, and 15g of vinylpyrrolidone was gradually added dropwise to carry out polymerization. After 12 hours of reaction, air was introduced into the system to terminate the reaction. Discharging, filtering, washing, extracting solubilizer dodecylamine by using 500g of methanol, and drying at 50 ℃ to obtain the nonionic fluorine-containing amphiphilic polymer P1.
The method for characterizing the structures and the performances of the synthesized fluorine-containing macromolecular dispersant D1 solution and the nonionic fluorine-containing amphiphilic polymer P1 comprises the following steps:
1. structural characterization: by using1H-NMR nuclear magnetic resonance spectrum analysis of the structure. The dispersant macromolecule D1 obtained by drying the obtained dispersant solution and the polymer P1 obtained by dissolving the dispersant macromolecule D1 and the polymer P1 in deuterated DFM, respectively, were subjected to nuclear magnetic testing.
2. And (3) performance characterization: the molecular weight was analyzed by Gel Permeation Chromatography (GPC). The resulting dispersant macromolecule D1 and polymer P1 were dissolved in DMF, respectively, for GPC testing.
The content of the nonionic hydrophilic monomer component in D1 in this example was 57.1 wt%, and the number average molecular weight Mn of D1 was 5K, as measured by polymer 1H-NMR spectrum and GPC; molecular weight distribution PDI 1.5; the content of the nonionic hydrophilic monomer component in the P1 is 1.04 wt%, and the number average molecular weight Mn of the P1 is 100K; molecular weight distribution PDI 1.6;
example 2
Synthesizing a nonionic fluorine-containing amphiphilic polymer P2 taking a fluorine-containing macromolecular dispersant D2 solution as a dispersant:
the synthesis of D2 and P2 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D2 and P2 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D2 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P2 are shown in Table 4.
Example 3
Synthesizing a nonionic fluorine-containing amphiphilic polymer P3 taking a fluorine-containing macromolecular dispersant D3 solution as a dispersant:
the synthesis of D3 and P3 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D3 and P3 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D3 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P3 are shown in Table 4.
Example 4
Synthesizing a nonionic fluorine-containing amphiphilic polymer P4 taking a fluorine-containing macromolecular dispersant D4 solution as a dispersant:
the synthesis of D4 and P4 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D4 and P4 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D4 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P4 are shown in Table 4.
Example 5
Synthesizing a nonionic fluorine-containing amphiphilic polymer P5 taking a fluorine-containing macromolecular dispersant D5 solution as a dispersant:
the synthesis of D5 and P5 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D5 and P5 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D5 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P5 are shown in Table 4.
Example 6
Synthesizing a nonionic fluorine-containing amphiphilic polymer P6 taking a fluorine-containing macromolecular dispersant D6 solution as a dispersant:
the synthesis of D6 and P6 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D6 and P6 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D6 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P6 are shown in Table 4.
Example 7
Synthesizing a nonionic fluorine-containing amphiphilic polymer P7 taking a fluorine-containing macromolecular dispersant D7 solution as a dispersant:
the synthesis of D7 and P7 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D7 and P7 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D7 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P7 are shown in Table 4.
Example 8
Synthesizing a nonionic fluorine-containing amphiphilic polymer P8 taking a fluorine-containing macromolecular dispersant D8 solution as a dispersant:
the synthesis of D8 and P8 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D8 and P8 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D8 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P8 are shown in Table 4.
Example 9
Synthesizing a nonionic fluorine-containing amphiphilic polymer P9 taking a fluorine-containing macromolecular dispersant D9 solution as a dispersant:
the synthesis of D9 and P9 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D9 and P9 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D9 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P9 are shown in Table 4.
Example 10
Synthesizing a nonionic fluorine-containing amphiphilic polymer P10 taking a fluorine-containing macromolecular dispersant D10 solution as a dispersant:
the synthesis of D10 and P10 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D10 and P10 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D10 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P10 are shown in Table 4.
Example 11
Synthesizing a nonionic fluorine-containing amphiphilic polymer P11 taking a fluorine-containing macromolecular dispersant D11 solution as a dispersant:
the synthesis of D11 and P11 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D11 and P11 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D11 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P11 are shown in Table 4.
Example 12
Synthesizing a nonionic fluorine-containing amphiphilic polymer P12 taking a fluorine-containing macromolecular dispersant D12 solution as a dispersant:
the synthesis of D12 and P12 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D12 and P12 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D12 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P12 are shown in Table 4.
Example 13
Synthesizing a nonionic fluorine-containing amphiphilic polymer P13 taking a fluorine-containing macromolecular dispersant D13 solution as a dispersant:
the synthesis of D13 and P13 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D13 and P13 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D13 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P13 are shown in Table 4.
Example 14
Synthesizing a nonionic fluorine-containing amphiphilic polymer P14 taking a fluorine-containing macromolecular dispersant D14 solution as a dispersant:
the synthesis of D14 and P14 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D14 and P14 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D14 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P14 are shown in Table 4.
Example 15
Synthesizing a nonionic fluorine-containing amphiphilic polymer P15 taking a fluorine-containing macromolecular dispersant D15 solution as a dispersant:
the synthesis of D15 and P15 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D15 and P15 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D15 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P15 are shown in Table 4.
Example 16
Synthesizing a nonionic fluorine-containing amphiphilic polymer P16 taking a fluorine-containing macromolecular dispersant D16 solution as a dispersant:
the synthesis of D16 and P16 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D16 and P16 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D16 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P16 are shown in Table 4.
Example 17
Synthesizing a nonionic fluorine-containing amphiphilic polymer P17 taking a fluorine-containing macromolecular dispersant D17 solution as a dispersant:
the synthesis of D17 and P17 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D17 and P17 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D17 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P17 are shown in Table 4.
Example 18
Synthesizing a nonionic fluorine-containing amphiphilic polymer P18 taking a fluorine-containing macromolecular dispersant D18 solution as a dispersant:
the synthesis of D18 and P18 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D18 and P18 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D18 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P18 are shown in Table 4.
Example 19
Synthesizing a nonionic fluorine-containing amphiphilic polymer P19 taking a fluorine-containing macromolecular dispersant D19 solution as a dispersant:
the synthesis of D19 and P19 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D19 and P19 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D19 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P19 are shown in Table 4.
Example 20
Synthesizing a nonionic fluorine-containing amphiphilic polymer P20 taking a fluorine-containing macromolecular dispersant D20 solution as a dispersant:
the synthesis of D20 and P20 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D20 and P20 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D20 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P20 are shown in Table 4.
Example 21
Synthesizing a nonionic fluorine-containing amphiphilic polymer P21 taking a fluorine-containing macromolecular dispersant D21 solution as a dispersant:
the synthesis of D21 and P21 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D21 and P21 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D21 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P21 are shown in Table 4.
Example 22
Synthesizing a nonionic fluorine-containing amphiphilic polymer P22 taking a fluorine-containing macromolecular dispersant D22 solution as a dispersant:
the synthesis of D22 and P22 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D22 and P22 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D22 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P22 are shown in Table 4.
Example 23
Synthesizing a nonionic fluorine-containing amphiphilic polymer P23 taking a fluorine-containing macromolecular dispersant D23 solution as a dispersant:
the synthesis of D23 and P23 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D23 and P23 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D23 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P23 are shown in Table 4.
Example 24
Synthesizing a nonionic fluorine-containing amphiphilic polymer P24 taking a fluorine-containing macromolecular dispersant D24 solution as a dispersant:
the synthesis of D24 and P24 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D24 and P24 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D24 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P24 are shown in Table 4.
Example 25
Synthesizing a nonionic fluorine-containing amphiphilic polymer P25 taking a fluorine-containing macromolecular dispersant D25 solution as a dispersant:
the synthesis of D25 and P25 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D25 and P25 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D25 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P25 are shown in Table 4.
Example 26
Synthesizing a nonionic fluorine-containing amphiphilic polymer P26 taking a fluorine-containing macromolecular dispersant D26 solution as a dispersant:
the synthesis of D26 and P26 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D26 and P26 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D26 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P26 are shown in Table 4.
Example 27
Synthesizing a nonionic fluorine-containing amphiphilic polymer P27 taking a fluorine-containing macromolecular dispersant D27 solution as a dispersant:
the synthesis of D27 and P27 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D27 and P27 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D27 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P27 are shown in Table 4.
Example 28
Synthesizing a nonionic fluorine-containing amphiphilic polymer P28 taking a fluorine-containing macromolecular dispersant D28 solution as a dispersant:
the synthesis of D28 and P28 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D28 and P28 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D28 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P28 are shown in Table 4.
Example 29
Synthesizing a nonionic fluorine-containing amphiphilic polymer P29 taking a fluorine-containing macromolecular dispersant D29 solution as a dispersant:
the synthesis of D29 and P29 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D29 and P29 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D29 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P29 are shown in Table 4.
Example 30
Synthesizing a nonionic fluorine-containing amphiphilic polymer P30 taking a fluorine-containing macromolecular dispersant D30 solution as a dispersant:
the synthesis of D30 and P30 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D30 and P30 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D30 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P30 are shown in Table 4.
Example 31
Synthesizing a nonionic fluorine-containing amphiphilic polymer P31 taking a fluorine-containing macromolecular dispersant D31 solution as a dispersant:
the synthesis of D31 and P31 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D31 and P31 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D31 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P31 are shown in Table 4.
Example 32
Synthesizing a nonionic fluorine-containing amphiphilic polymer P32 taking a fluorine-containing macromolecular dispersant D32 solution as a dispersant:
the synthesis of D32 and P32 is as described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The D32 and P32 structural and performance characterization methods were the same as those of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of D32 are shown in Table 3; the content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of P32 are shown in Table 4.
Example 33
This example illustrates the excellent hydrophilic properties of nonionic fluorine-containing amphiphilic polymers compared to conventional fluoropolymers. The method comprises the following steps:
(1) preparation of P1-P32 films: respectively dissolving 20g of the copolymers P1-P32 prepared in examples 1-32 in 100g of N, N-dimethylacetamide to prepare a membrane preparation solution; scraping the film-forming liquid on a glass sheet to form a liquid film, immersing the liquid film into water at 40 ℃ for curing to form a film, and washing for 12 hours to obtain the P1-P32 films.
(2) Preparation of PVDF membrane: dissolving 20g of polyvinylidene fluoride in 100g of N, N-dimethylacetamide to prepare a membrane preparation solution; scraping the film-forming liquid on a glass sheet to form a liquid film, soaking the liquid film into water of 40 ℃ for curing and film-forming, and washing for 12 hours to obtain the PVDF film.
(3) The membrane was washed three times with deionized water and absolute ethanol for contact angle experiments.
The initial contact angles and the post-30 s contact angles of the membranes are shown in table 5, and it can be seen that the initial contact angles of the membranes from P1 to P32 are far smaller than the contact angle of the common PVDF membrane, in addition, the contact angles after 30s indicate the dynamic change rate of the contact angles of the membranes, and it can be seen that the reduction rate of the contact angles of the membranes from P1 to P32 is far higher than the reduction rate of the contact angle of the common PVDF membrane, and the two contact angle test data indicate that the hydrophilic performance of the membranes from P1 to P32 is very excellent; and by comparing the relation between the contact angle of the P1-P32 film and the content of the nonionic hydrophilic monomer component in the polymer, the contact angle of the prepared film is changed along with the change of the content of the nonionic functional monomer component in the polymer, and the film has adjustability.
This example clearly shows that the nonionic fluorine-containing amphiphilic polymer synthesized by the present invention can prepare a separation membrane material with excellent hydrophilic properties.
Example 34
This example illustrates the anti-fouling properties of a nonionic fluorine-containing amphiphilic polymer as compared to a conventional fluoropolymer. The method comprises the following steps:
(1) preparation of P1-P32 films: respectively dissolving 20g of the copolymers P1-P32 prepared in examples 1-32 in 100g of N, N-dimethylacetamide to prepare a membrane preparation solution; scraping the film-forming liquid on a glass sheet to form a liquid film, immersing the liquid film into water at 40 ℃ for curing to form a film, and washing for 12 hours to obtain the P1-P32 films.
(2) Preparation of PVDF membrane: dissolving 20g of polyvinylidene fluoride in 100g of N, N-dimethylacetamide to prepare a membrane preparation solution; scraping the film-forming liquid on a glass sheet to form a liquid film, soaking the liquid film into water of 40 ℃ for curing and film-forming, and washing for 12 hours to obtain the PVDF film.
(3) The membrane was washed three times with deionized water, soaked in phosphate buffered saline (PBS solution) for 24h, the buffer removed and Platelet Rich Plasma (PRP) was added at 37 ℃. After 120min of soaking, the membrane was rinsed 3 times with PBS solution to remove non-adhered platelets, and then the adhered platelets were fixed with 2.5% wt aqueous glutaraldehyde solution. Rinsing with PBS solution for 3 times after 30min, sequentially soaking in ethanol solutions with different concentrations (50%, 70%, 80%, 90%, 95%, 100%) for 30min, and gradually dehydrating. After air-drying at room temperature, the adhesion of platelets to the membrane material surface was observed by scanning electron microscopy (JSM-5510 LV).
The surface of the P3 membrane, P8 membrane and PVDF membrane was adhered with platelets as shown in FIG. 1, and the surface of the other membranes was adhered with platelets as shown in Table 6. It is evident from fig. 1 and table 6 that the P1-P32 membranes have very little adhesion to platelets, whereas the conventional PVDF membrane has much platelet adhesion on its surface.
This example clearly shows that the synthesized nonionic fluorine-containing amphiphilic polymer of the present invention has anti-platelet adhesion performance, which indicates that its anti-pollution performance is excellent.
Comparative example 1
Synthesis of nonionic fluorine-containing amphiphilic polymer CP3 with common dispersant as dispersant:
CP3 Synthesis Process referring to example 3, the dispersant used polyvinyl alcohol as the dispersant, and other formulations and process parameters were consistent with those of P3 synthesis.
The CP3 structure and performance characterization method was the same as that of example 1. The content of the nonionic hydrophilic monomer component, the molecular weight and the molecular weight distribution of CP3 are shown in table 4.
This comparative example shows that the content of the nonionic hydrophilic monomer component was only 1.5% when polyvinyl alcohol was used instead of the exclusive dispersant D3. The special dispersant is a key formula for synthesizing high-content hydrophilic components.
Comparative example 2
Synthesis of graft type hydrophilic segment fluoropolymer GP3 (see patent CN201510058126A example 1):
2000ml of deionized water, 1.2g of polyvinyl alcohol (PVA) as an additive, 0.4g of hydroxypropyl methylcellulose (HPMC) as an additive, 1g of bis (2-ethylhexyl) peroxydicarbonate (EHP) as an initiator, 1000g of trifluoroethylene, 27.19g of hydroxyethyl acrylate and 4.85g of allyl 2-bromo-2-methylpropionate were added to a stainless steel reaction vessel, and the mixture was subjected to predispersion stirring at room temperature for 30 minutes after repeated 3 times of vacuum-pumping and nitrogen-charging. The temperature was raised to 47 ℃ polymerization temperature to carry out polymerization reaction. Reacting for 12 hours, stopping heating when the pressure drop in the kettle reaches 0.2MPa, naturally volatilizing for 15 minutes, introducing air for 5 minutes, vacuumizing and filling nitrogen for three times, adding 336.31g of hydroxypropyl methacrylate, 10g of copper, 10g of cuprous chloride and 20g of 2,2' -bipyridyl (bpy), and then controlling the temperature to be 70 ℃ to react for 24 hours. And after the reaction is finished, introducing air into the system to terminate the reaction. Discharging, filtering, washing and drying at 50 ℃ to obtain the graft hydrophilic chain segment fluorine-containing polymer GP 3.
GP3 was prepared according to the procedure of example 33 to obtain GP3 film. After soaking the GP3 film and the P3 film simultaneously in a solution at pH 2 and pH 14 for 12h, the contact angle was measured. It was found that the contact angle before GP3 immersion was 44 °, the contact angle after immersion was 68 °, and the hydrophilic effect was significantly reduced. And the contact angle of P3 before soaking is 45 degrees, the contact angle after soaking is 44 degrees, and the hydrophilic effect is unchanged. The stability of the grafted hydrophilic component of graft polymer GP3 was shown to be weaker than that of the backbone copolymer P3.
TABLE 1
Figure GDA0002072751060000181
Figure GDA0002072751060000191
Figure GDA0002072751060000201
Figure GDA0002072751060000211
Figure GDA0002072751060000221
TABLE 2
Figure GDA0002072751060000231
TABLE 3
Figure GDA0002072751060000241
TABLE 4
Figure GDA0002072751060000242
Figure GDA0002072751060000251
TABLE 5
Film numbering Initial contact Angle/° C Contact angle/DEG after 30s Film numbering Initial contact Angle/° C Contact angle/DEG after 30s
P1 83 75 P18 67 64
P2 87 85 P19 68 55
P3 45 15 P20 64 56
P4 77 58 P21 68 51
P5 75 55 P22 64 54
P6 76 53 P23 64 52
P7 72 49 P24 57 48
P8 71 46 P25 55 49
P9 69 45 P26 54 42
P10 68 45 P27 44 23
P11 50 28 P28 43 22
P12 46 22 P29 42 19
P13 46 18 P30 41 19
P14 75 54 P31 46 24
P15 75 55 P32 41 15
P16 74 56 PVDF 89 81
P17 79 54
TABLE 6
Figure GDA0002072751060000252
Figure GDA0002072751060000261
● ● high adhesion; ● amount of stiction; low adhesion level; O.O. very low adhesion

Claims (21)

1. A nonionic fluorine-containing amphiphilic polymer characterized by: the nonionic fluorine-containing amphiphilic polymer is a polymer consisting of fluorine-containing chain links and nonionic hydrophilic chain links, and the structural formula of the nonionic fluorine-containing amphiphilic polymer is shown as follows:
Figure FDA0003161412970000011
in the formula:
the fluorine-containing chain link is formed by polymerizing a fluorine-containing monomer A, and the structure of the fluorine-containing chain link unit-A-is
Figure FDA0003161412970000012
The nonionic hydrophilic chain link is formed by polymerizing a nonionic hydrophilic monomer B, and the structure of the nonionic hydrophilic chain link unit-B-is as follows:
Figure FDA0003161412970000013
in the formula:
R1selected from H, F;
R2selected from H, F;
R3selected from H, CH3；
R4Is selected from
Figure FDA0003161412970000014
COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH、CH2O(CH2CH2O)nH、CO(OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、CONHCH2CHOHCH3、CONHCH2CH2OH；
a. b and n are integers which are more than or equal to 1.
2. The nonionic fluorine-containing amphiphilic polymer according to claim 1, characterized in that: in the structural formula of the fluorine-containing monomer, a/b is 250/1-1.5/1.
3. The nonionic fluorine-containing amphiphilic polymer according to claim 2, characterized in that: in the structural formula of the fluorine-containing monomer, a/b is 10/1-1/1.
4. The nonionic fluorine-containing amphiphilic polymer according to claim 1, characterized in that: the structural formula of the fluorine-containing monomer A is as follows:
Figure FDA0003161412970000021
in the formula:
R1selected from H, F;
R2selected from H, F.
5. The nonionic fluorine-containing amphiphilic polymer according to claim 4, characterized in that: the fluorine-containing monomer A is selected from one or more of vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene.
6. The nonionic fluorine-containing amphiphilic polymer according to claim 1, characterized in that: the structural formula of the nonionic hydrophilic monomer B is as follows:
Figure FDA0003161412970000022
in the formula:
R3selected from H, CH3；
R4Is selected from
Figure FDA0003161412970000023
COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH、CH2O(CH2CH2O)nH、CO(OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、CONHCH2CHOHCH3、CONHCH2CH2OH；
n is an integer greater than 1.
7. The nonionic fluorine-containing amphiphilic polymer according to claim 1 or 6, characterized in that: the non-ionic hydrophilic monomer B is selected from any one or more of vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol monoallyl ether, hydroxymethyl acrylamide, hydroxyethyl acrylamide and hydroxypropyl methacrylamide.
8. The method for preparing a nonionic fluorine-containing amphiphilic polymer according to claim 1, wherein the method comprises the following steps:
(1) preparation of a solubilization dispersion liquid: adding the fluorine-containing monomer A, a fluorine-containing macromolecular dispersant solution, a hydrophobic initiator and a solubilizer into a water phase to obtain a stable dispersion liquid;
(2) polymerization of fluorine-containing amphiphilic polymer: heating to 40-80 ℃ for polymerization reaction, gradually adding a non-ionic hydrophilic monomer B into the dispersion liquid obtained in the step (1), and filtering to obtain a fluorine-containing amphiphilic polymer wet material after the reaction is finished;
(3) extracting the solubilizer: and (3) adding the fluorine-containing amphiphilic polymer wet material obtained in the step (2) into an extracting agent, removing the solubilizer in the fluorine-containing amphiphilic polymer wet material, and drying to obtain the non-ionic fluorine-containing amphiphilic polymer.
9. The method according to claim 8, wherein the solubilizer is selected from any one or more of propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, butyl propionate, hexyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, hexyl butyrate.
10. The method according to claim 8, wherein the extractant is selected from any one or more of methanol, ethanol, and propanol.
11. The method according to claim 8, wherein the fluorine-containing macromolecular dispersant solution comprises 10 to 50 wt% of the fluorine-containing macromolecular dispersant and the balance of an organic solvent.
12. The method for preparing a nonionic fluorine-containing amphiphilic polymer according to claim 8, wherein the fluorine-containing macromolecular dispersant is a polymer consisting of fluorine-containing chain segments and nonionic hydrophilic chain segments, and the structural formula of the fluorine-containing macromolecular dispersant is as follows:
Figure FDA0003161412970000031
in the formula:
the fluorine-containing chain link is formed by polymerizing a fluorine-containing monomer A, and the structure of the fluorine-containing chain link unit-A-is
Figure FDA0003161412970000041
The nonionic hydrophilic chain link is formed by polymerizing a nonionic hydrophilic monomer B, and the structure of the nonionic hydrophilic chain link unit-B-is as follows:
Figure FDA0003161412970000042
in the formula:
R1selected from H, F;
R2selected from H, F;
R3selected from H, CH3；
R4Is selected from
Figure FDA0003161412970000043
COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH、CH2O(CH2CH2O)nH、CO(OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、CONHCH2CHOHCH3、CONHCH2CH2OH；
x, y and n are integers greater than or equal to 1.
13. The method for preparing the nonionic fluorine-containing amphiphilic polymer according to claim 12, wherein in the structural formula of the fluorine-containing macromolecular dispersing agent, x/y is 3/1-1/100.
14. The method for preparing the nonionic fluorine-containing amphiphilic polymer according to claim 13, wherein in the structural formula of the fluorine-containing macromolecular dispersing agent, x/y is 1/1-1/20.
15. The method for preparing a nonionic fluorine-containing amphiphilic polymer according to any one of claims 8 to 14, wherein the method for preparing the fluorine-containing macromolecular dispersing agent comprises the following steps: weighing 5-50% of fluorine-containing monomer A, 50-95% of nonionic hydrophilic monomer B and 0.1-5% of initiator by weight based on the total weight of the monomers, and carrying out solution polymerization in an organic solvent at the temperature of 40-120 ℃ to obtain a macromolecular dispersant solution as claimed in claim 1, wherein the total weight of the monomers is the total weight of the fluorine-containing monomer A and the nonionic hydrophilic monomer B.
16. The method according to claim 15, wherein the organic solvent is one or more selected from the group consisting of acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N dimethylformamide, N dimethylacetamide, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and N-alkylpyrrolidone.
17. The method according to claim 15, wherein the step of preparing the nonionic fluorine-containing amphiphilic polymer comprises: the structural formula of the fluorine-containing monomer A is as follows:
Figure FDA0003161412970000051
in the formula:
R1selected from H, F;
R2selected from H, F.
18. The method according to claim 17, wherein the step of preparing the nonionic fluorine-containing amphiphilic polymer comprises: the fluorine-containing monomer A is selected from one or more of vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene.
19. The method according to claim 15, wherein the step of preparing the nonionic fluorine-containing amphiphilic polymer comprises: the structural formula of the nonionic hydrophilic monomer B is as follows:
Figure FDA0003161412970000052
in the formula:
R3selected from H, CH3；
R4Is selected from
Figure FDA0003161412970000053
COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH、CH2O(CH2CH2O)nH、CO(OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、CONHCH2CHOHCH3、CONHCH2CH2OH；
n is an integer greater than 1.
20. The method according to claim 19, wherein the step of preparing the nonionic fluorine-containing amphiphilic polymer comprises: the non-ionic hydrophilic monomer B is selected from any one or more of vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol monoallyl ether, hydroxymethyl acrylamide, hydroxyethyl acrylamide and hydroxypropyl methacrylamide.
21. A non-ionic fluorine-containing amphiphilic polymer separation membrane, characterized in that the non-ionic fluorine-containing amphiphilic polymer separation membrane comprises the non-ionic fluorine-containing amphiphilic polymer according to any one of claims 1 to 7 or the non-ionic fluorine-containing amphiphilic polymer prepared according to the method of any one of claims 8 to 20.
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EP1366745A1 (en) * 2002-05-31 2003-12-03 L'oreal Hair compositions containing at least one amphiphilic non-thickening diblock copolymer and at least one film-forming polymer beneficial to hair
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