CN110894251A - Tertiary amine derivative type chlorine-containing amphiphilic polymer and separation membrane prepared from same - Google Patents

Tertiary amine derivative type chlorine-containing amphiphilic polymer and separation membrane prepared from same Download PDF

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CN110894251A
CN110894251A CN201811062841.XA CN201811062841A CN110894251A CN 110894251 A CN110894251 A CN 110894251A CN 201811062841 A CN201811062841 A CN 201811062841A CN 110894251 A CN110894251 A CN 110894251A
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chlorine
tertiary amine
amine derivative
derivative type
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CN110894251B (en
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朱宝库
王纳川
章鹏
孙创超
肖玲
王俊
赵斌
刘孝民
刘征波
周名勇
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Mount Huangshan Dream High Polymer 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
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/08—Vinylidene chloride
    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • 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
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • 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
    • 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
    • C08F228/00—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 bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—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 bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur

Abstract

The invention discloses a tertiary amine derivative type chlorine-containing amphiphilic polymer and a separation membrane prepared from the same. The tertiary amine derivative type chlorine-containing amphiphilic copolymer is polymerized by taking chlorine-containing macromolecules as a dispersing agent, taking micromolecular esters as a solubilizer and taking chlorine-containing monomers and tertiary amine derivative type hydrophilic monomers as raw materials by adopting a free radical suspension polymerization method. The chlorine-containing macromolecular dispersing agent is obtained by carrying out solution copolymerization on a chlorine-containing monomer and a tertiary amine derivative type hydrophilic monomer in an organic solvent. The invention adopts the chlorine-containing macromolecular dispersant, has excellent dispersing effect on chlorine-containing monomers, and the micromolecular ester solubilizer can improve the intermiscibility of the hydrophilic monomer and the chlorine-containing monomers, thereby preparing the high-hydrophilicity chlorine-containing amphiphilic copolymer. The tertiary amine derivative type chlorine-containing copolymer can be independently used for preparing separation membranes or can be blended with other resins to prepare separation membranes, and compared with the existing chlorine-containing separation membrane materials, the tertiary amine derivative type chlorine-containing copolymer has the advantages of good hydrophilicity, pollution resistance, low cost and good application prospect.

Description

Tertiary amine derivative type chlorine-containing amphiphilic polymer and separation membrane prepared from same
Technical Field
The invention belongs to the field of high molecular materials, and particularly relates to a tertiary amine derivative type chlorine-containing amphiphilic polymer and a separation membrane prepared from the same.
Background
Polyvinyl chloride is a non-toxic, odorless white powder. It has good chemical stability and plasticity. Except a few organic solvents, the paint can resist acid, alkali and salt at normal temperature; PVC has poor thermal stability and light resistance, and can start to decompose and change color at the temperature of more than 140 ℃. Based on the characteristics, the PVC is mainly used for the fields of production of profiles, special-shaped materials, pipe fittings, plates, sheets, cable sheaths, hard or soft tubes, blood transfusion equipment, films and the like. And in the using process, the application field of PVC is greatly expanded by continuously researching modification.
The polyvinylidene chloride has the characteristics of flame resistance, corrosion resistance, good air tightness and the like. Because of its strong polarity, it is insoluble in common solvents at normal temperature. The disadvantages are poor light and heat stability and difficult processing. Can be made into sheets, pipes, moldings, films and fibers. In order to overcome the disadvantages of poor solubility and difficult processing, vinylidene chloride is usually copolymerized with a small amount (15% to 20%) of monomers such as vinyl chloride, acrylonitrile, and acrylic esters to obtain binary or ternary copolymers. Vinylidene chloride copolymers are also used as coatings, adhesives, and the like.
At present, studies on polyvinyl chloride-based copolymers and methods for producing the same have been reported at home and abroad. The comparisons are representative of: chinese patent (CN101402701A) discloses a method for producing a chloroethylene-vinyl acetate-maleic anhydride terpolymer which has good hydrophilicity and can be used for preparing a hydrophilic component of a PVC filtering membrane. Chinese patent (CN200880124880.6) reports a composition of vinylidene chloride copolymer, which is a (meth) acrylic monomer among monomers copolymerized with vinylidene chloride, and the copolymer can be used for preparing a packaging bag of a multilayer film. Most of the comonomers in the existing vinyl chloride copolymer are oil-soluble monomers (such as vinyl acetate, acrylate and the like), and although the copolymerization content can reach 10-20 wt%, the prepared copolymer has poor hydrophilicity. When a water-soluble monomer (e.g., maleic anhydride, acrylic acid, etc.) is used as a comonomer, the content of the water-soluble monomer component in the copolymer is particularly low, being only 5% by weight or less. While many other documents report the use of Atom Transfer Radical Polymerization (ATRP) to graft various groups onto the surface or polymer chains of PVC, the overall grafting yield 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 patents (CN201510058518.5 and CN2015100591133) disclose a cationic (non-) ionic functionalized vinyl chloride polymer and a preparation method thereof, wherein the functionalized vinyl chloride polymer takes a chlorine-containing monomer, a graftable active monomer and a hydrophilic functionalized monomer as comonomers, and is polymerized into an active precursor polymer with a main chain containing an atom transfer radical polymerization active side group in an aqueous dispersion system, and then the active side group is used for initiating the cationic (non-) ionic functionalized monomer to carry out interfacial atom transfer radical polymerization on a solid-liquid interface in an alkaline environment to polymerize and form the anionic functionalized chlorine-containing polymer with a cationic (non-) ionic side chain. The method can increase the content of the hydrophilic monomer to 70 wt% at most, which is higher than the content of the hydrophilic component in the existing chlorine-containing copolymer. However, there are two important problems that are not solved in this patent: firstly, in the cation (non) ion functionalized chlorine-containing polymer, the hydrophilic segment is cation (non) ion functionalized chain link F2 which is grafted on the polymer main chain as a grafting segment and belongs to a grafting polymer, and is not a conventional main chain copolymer of two monomers, which can cause great difference of properties of the main chain and the grafting chain in the polymer chain, easily cause phase separation or performance defect when preparing a polymer product, and the chemical bond of the grafting 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 active site 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 chlorine-containing main chain copolymer can reach 10-20 wt%; the water-soluble monomer (such as carboxyl, hydroxyl, sulfonic acid group and the like) has the copolymerization content of less than 5wt percent. In addition, although the content of the hydrophilic functionalized monomer can be increased by adopting a living radical polymerization method (China CN201510058518.5 and CN2015100591133), the prepared chlorine-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 polymer main chain; in addition, four types of monomers are needed to increase the content of the hydrophilic component, two polymerization methods are adopted, the steps are very complicated, and the large-scale application is difficult. 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 chlorine-containing amphiphilic copolymer based on a tertiary amine derivative and a separation membrane prepared from the copolymer. The tertiary amine derivative type chlorine-containing amphiphilic polymer comprises a hydrophobic chlorine-containing monomer and a tertiary amine derivative type hydrophilic monomer, and the content of a hydrophilic component can be adjusted at will within the range of 1-70%; 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 tertiary amine derivative type chlorine-containing amphiphilic copolymer and the separation membrane prepared from the copolymer provided by the invention solve the following problems in the prior art:
(1) in the comonomers in the existing copolymer containing the chlorine main chain, the copolymerization content of oil-soluble monomers (such as vinyl acetate, acrylate and the like) can reach 10-20 wt%; the water-soluble monomer (such as carboxyl, hydroxyl, sulfonic acid group and the like) has the copolymerization content of less than 5wt percent. The technology of the invention greatly widens the variety of hydrophilic monomers copolymerized with chlorine-containing monomers, and the tertiary amine derivative type hydrophilic monomer can be selected from any one or more of trimethyl allyl ammonium chloride, 2-methacryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, betaine methacrylate sulfonate, betaine methacrylate carboxylate, betaine methacrylate sulfonate and betaine methacrylate carboxylate. These hydrophilic monomers of the tertiary amine derivative type have very good hydrophilic properties. Furthermore, the content of the tertiary amine derivative type hydrophilic monomer in the tertiary amine derivative type chlorine-containing amphiphilic polymer provided by the invention can reach 70 wt%, which is far higher than that of the hydrophilic component in the existing chlorine-containing copolymer, and the content of the tertiary amine derivative type hydrophilic monomer in the copolymer can be adjusted at will between 1 wt% and 70 wt%.
(2) Although the method of atom transfer radical graft copolymerization reported in chinese patents (CN201510058518.5 and CN2015100591133) 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 chlorine-containing monomer and the tertiary amine derivative type hydrophilic monomer in the main chain, and is a binary main chain copolymer of the chlorine-containing monomer and the tertiary amine derivative type 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 defects in phase separation or performance in preparing a polymer article, and the chemical bond connecting the graft segment and the main chain is not so stable, and in order to modify the graft, the main chain must be broken to a certain 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. 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 to protect the atom transfer radical polymerization and an expensive catalyst system is adopted to realize stable polymerization. The third monomer is contained, so that the polymerization activity of the two original comonomers is necessarily influenced, and uncertainty of performance change is necessarily 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 the structure and properties thereof may be greatly different. The tertiary amine derivative type chlorine-containing amphiphilic polymer provided by the invention has stable performance, and greatly improves hydrophilic components. And the process is simple and easy to implement and easy to industrialize.
(3) The existing chlorine-containing polymer separation membrane is mainly a hydrophobic membrane, and the hydrophilic type is extremely poor due to the high chlorine content. The invention provides a tertiary amine derivative type chlorine-containing amphiphilic polymer raw material for the chlorine-containing polymer separation membrane, and the chlorine-containing polymer membrane with excellent hydrophilicity and pollution resistance can be prepared by using the amphiphilic polymer material by using a conventional separation membrane preparation process, so that the application range of the chlorine-containing polymer separation membrane is greatly expanded.
In the existing copolymerization technology, due to the hydrophobicity of the chlorine-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 difficult 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 tertiary amine derivative type chlorine-containing amphiphilic polymer only containing the main chain copolymerization of two monomers of chlorine-containing monomers and tertiary amine derivative type hydrophilic monomers, and the content of the tertiary amine derivative type 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 tertiary amine derivative type chlorine-containing amphiphilic polymer, an innovative solution is adopted. One is that a chlorine-containing macromolecular dispersant is specially designed for preparing the tertiary amine derivative type chlorine-containing amphiphilic copolymer, wherein a hydrophobic chlorine-containing monomer and a tertiary amine derivative type hydrophilic monomer are introduced into the chlorine-containing macromolecular dispersant. Secondly, the solubilizer and the extractant are matched with the important chlorine-containing macromolecular dispersant, and finally the tertiary amine derivative type hydrophilic monomer is gradually added. The solution is that necessary processes for preparing the tertiary amine derivative type chlorine-containing amphiphilic copolymer supplement each other, the essential processes are all absent, the content of the tertiary amine derivative type hydrophilic component is randomly adjusted between 1 wt% and 70 wt%, and the preparation method is simple and easy to implement and easy to industrialize.
Finally, the novel tertiary amine derivative type chlorine-containing amphiphilic copolymer can be used as a raw material, and the following chlorine-containing amphiphilic copolymer separation membranes are prepared by adopting a conventional membrane preparation process:
the invention provides a separation membrane of a cationic chlorine-containing amphiphilic copolymer, which contains a tertiary amine derivative type chlorine-containing amphiphilic copolymer when a tertiary amine derivative type hydrophilic monomer B is selected from trimethyl allyl ammonium chloride, 2-methacryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride and acryloyloxyethyl trimethyl ammonium chloride, or a substance after quaternization reaction of the tertiary amine derivative type chlorine-containing amphiphilic copolymer when the tertiary amine derivative type hydrophilic monomer B is selected from dimethylaminoethyl methacrylate, diethaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide and dimethylaminopropyl acrylamide.
The invention also provides an amphoteric chlorine-containing amphiphilic copolymer separation membrane, which contains a tertiary amine derivative type chlorine-containing amphiphilic copolymer of a tertiary amine derivative type hydrophilic monomer B selected from sulfobetaine methacrylate, carboxylic betaine methacrylate, sulfamic betaine methacrylamide, betaine methacrylamide carboxylic acid or a substance obtained by amphoteric reaction of the tertiary amine derivative type chlorine-containing amphiphilic copolymer when the tertiary amine derivative type hydrophilic monomer B is selected from dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide and dimethylaminopropyl acrylamide.
Compared with the existing chlorine-containing polymer separation membrane, the hydrophilicity of the two chlorine-containing amphiphilic polymer separation membranes is obviously improved, and the two chlorine-containing amphiphilic polymer separation membranes have excellent hydrophilicity and contamination resistance.
Therefore, the invention adopts the following technical scheme:
a tertiary amine derivative type chlorine-containing amphiphilic polymer, characterized in that: the tertiary amine derivative type chlorine-containing amphiphilic polymer is a polymer consisting of chlorine-containing chain links and tertiary amine derivative type hydrophilic chain links, and the structural formula of the tertiary amine derivative type chlorine-containing amphiphilic polymer is shown as follows:
Figure BDA0001797552740000061
in the formula:
the chlorine-containing chain link is formed by polymerizing chlorine-containing monomers A, and the structure of the chlorine-containing chain link unit-A-is
Figure BDA0001797552740000062
The tertiary amine derivative type hydrophilic chain link is formed by polymerizing a tertiary amine derivative type hydrophilic monomer B, and the structure of a tertiary amine derivative type hydrophilic chain link unit-B-is as follows:
Figure BDA0001797552740000063
in the formula:
R1selected from H, Cl;
R2selected from H, CH3
R3Is selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、 CH2N(CH2＝CHCH2)(CH3)2Cl、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、 CONHCH2CH2CH2N(CH3)2、COOCH2CH2N+(CH3)2CH2CH2SO3 -、CONHCH2CH2N+(CH3)2CH2CH2SO3 -、COOCH2CH2N+(CH3)2CH2CH2COO-、CONHCH2CH2N+(CH3)2CH2CH2COO-
a. b is an integer greater 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 chlorine-containing monomer A is any one or more of vinyl chloride and vinylidene chloride, and the structural formula is as follows:
Figure BDA0001797552740000064
in the formula:
R1selected from H, Cl.
Further, the monomer corresponding to the tertiary amine derivative type hydrophilic monomer B is any one or more of trimethyl allyl ammonium chloride, 2-methacryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, sulfobetaine methacrylate, carboxylic betaine methacrylate, sulfobetaine methacrylate and carboxylic betaine methacrylamide, and the structural formula is as follows:
Figure BDA0001797552740000071
in the formula:
R2selected from H, CH3；
R3Is selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、 CH2N(CH2＝CHCH2)(CH3)2Cl、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、 CONHCH2CH2CH2N(CH3)2、COOCH2CH2N+(CH3)2CH2CH2SO3 -、CONHCH2CH2N+(CH3)2CH2CH2SO3 -、COOCH2CH2N+(CH3)2CH2CH2COO-、CONHCH2CH2N+(CH3)2CH2CH2COO-。
Further, the tertiary amine derivative type chlorine-containing amphiphilic polymer has the number average molecular weight of 5-15 kilodaltons.
The invention also provides a preparation method of the tertiary amine derivative type chlorine-containing amphiphilic polymer, which comprises the following steps:
(1) preparation of a solubilization dispersion liquid: adding a chlorine-containing monomer A, a chlorine-containing macromolecular dispersant solution, a hydrophobic initiator and a solubilizer into a 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 a stable dispersion liquid;
(2) polymerization of chlorine-containing amphiphilic copolymer: heating to 40-80 ℃ for polymerization reaction, gradually adding a tertiary amine derivative type hydrophilic monomer B into the dispersion liquid obtained in the step (1), and filtering to obtain a chlorine-containing amphiphilic copolymer wet material after the reaction is finished;
(3) extracting the solubilizer: adding the chlorine-containing amphipathic copolymer wet material obtained in the step (2) into an extracting agent, removing the solubilizer in the chlorine-containing amphipathic copolymer wet material, and drying to obtain the chlorine-containing amphipathic copolymer
Preferably, the chlorine-containing monomer A in the step (1) is selected from any one or more of vinyl chloride and vinylidene chloride;
preferably, the chlorine-containing macromolecular dispersant solution in the step (1) consists of 10-50 wt% of chlorine-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, methyl propionate, ethyl propionate, butyl propionate, hexyl propionate, methyl butyrate, ethyl butyrate and butyl 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 addition amount of the chlorine-containing macromolecular dispersant solution in the step (1) is 0.5-5% of the total mass of the chlorine-containing monomers.
Preferably, the hydrophobic initiator is added in step (1) in an amount generally known in the art of radical polymerization.
Preferably, the addition amount of the solubilizer in the step (1) is 0.5-5% of the total mass of the chlorine-containing monomers.
Preferably, the hydrophilic monomer B of the tertiary amine derivative type described in the step (2) is selected from any one or any more of trimethyl allyl ammonium chloride, 2-methacryloyloxyethyltrimethyl ammonium chloride, dimethyldiallyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, sulfobetaine methacrylate, carboxylic betaine methacrylate, sulfonic betaine methacrylamide, and betaine methacrylamide carboxylic acid.
Preferably, the amount of the tertiary amine derivative type hydrophilic monomer B added in step (2) is: the chlorine-containing monomer A/tertiary amine derivative type hydrophilic monomer B is 250/1-1.5/1, and the preferable A/B is 10/1-1/1.
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 time for gradually adding the tertiary amine derivative type hydrophilic monomer B in the step (2) is 0.25 to 2 hours from the end of temperature rise to the end of reaction.
Preferably, the extractant in the step (3) is selected from any one or more of methanol, ethanol and propanol.
Preferably, the addition amount of the extracting agent in the step (3) is 20-100% of the total mass of the tertiary amine derivative type chlorine-containing amphiphilic polymer.
The invention also provides a chlorine-containing macromolecular dispersant, which is a polymer consisting of chlorine-containing links and tertiary amine derivative type hydrophilic links, and the structural formula of the chlorine-containing macromolecular dispersant is shown as follows:
Figure BDA0001797552740000091
in the formula:
the chlorine-containing chain link is formed by polymerizing chlorine-containing monomers A, and the structure of the chlorine-containing chain link unit-A-is
Figure BDA0001797552740000092
The tertiary amine derivative type hydrophilic chain link is formed by polymerizing a tertiary amine derivative type hydrophilic monomer B, and the structure of a tertiary amine derivative type hydrophilic chain link unit-B-is as follows:
Figure BDA0001797552740000093
in the formula:
R1selected from H, Cl;
R2selected from H, CH3
R3Is selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、 CH2N(CH2＝CHCH2)(CH3)2Cl、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、 CONHCH2CH2CH2N(CH3)2、COOCH2CH2N+(CH3)2CH2CH2SO3 -、CONHCH2CH2N+(CH3)2CH2CH2SO3 -、COOCH2CH2N+(CH3)2CH2CH2COO-、CONHCH2CH2N+(CH3)2CH2CH2COO-；
x and y are integers greater 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 chlorine-containing monomer A is any one or more of vinyl chloride and vinylidene chloride, and the structural formula is as follows:
Figure BDA0001797552740000101
in the formula:
R1selected from H, Cl.
Further, the monomer corresponding to the tertiary amine derivative type hydrophilic monomer B is any one or more of trimethyl allyl ammonium chloride, 2-methacryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, sulfobetaine methacrylate, carboxylic betaine methacrylate, sulfobetaine methacrylate and carboxylic betaine methacrylamide, and the structural formula is as follows:
Figure BDA0001797552740000102
in the formula:
R2selected from H, CH3；
R3Is selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、 CH2N(CH2＝CHCH2)(CH3)2Cl、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、 CONHCH2CH2CH2N(CH3)2、COOCH2CH2N+(CH3)2CH2CH2SO3 -、CONHCH2CH2N+(CH3)2CH2CH2SO3 -、COOCH2CH2N+(CH3)2CH2CH2COO-、CONHCH2CH2N+(CH3)2CH2CH2COO-。
Further, the tertiary amine derivative type chlorine-containing amphiphilic polymer has a number average molecular weight of 0.2 to 2 kilodaltons.
The invention provides a preparation method of a chlorine-containing macromolecular dispersant, which comprises the following steps: weighing 5-50% of chlorine-containing monomer A, 50-95% of tertiary amine derivative type hydrophilic monomer B and 0.1-5% of initiator by weight 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 chlorine-containing macromolecular dispersing agent solution, wherein the total weight of the monomers is the total weight of the chlorine-containing monomer A and the tertiary amine derivative type hydrophilic monomer B;
preferably, the chlorine-containing monomer A in the step (A) is selected from any one or more of vinyl chloride and vinylidene chloride;
preferably, the hydrophilic monomer B of tertiary amine derivative type in step (A) is selected from any one or any more of trimethyl allyl ammonium chloride, 2-methacryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, sulfobetaine methacrylate, carboxylic betaine methacrylate, sulfonic betaine methacrylamide, and carboxylic betaine 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 agent in the step consists 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 chlorine-containing monomer and 50-95% of tertiary amine derivative type hydrophilic monomer.
Preferably, the polymerization time in the step is 1 to 20 hours.
The tertiary amine derivative type chlorine-containing amphiphilic copolymer provided by the invention can be used as a raw material, and the following two chlorine-containing amphiphilic copolymer separation membranes can be prepared by adopting a conventional membrane preparation process:
the invention also provides a cationic chlorine-containing amphiphilic copolymer separation membrane, which contains the tertiary amine derivative type chlorine-containing amphiphilic polymer, wherein the tertiary amine derivative type hydrophilic monomer B of the tertiary amine derivative type chlorine-containing amphiphilic polymer is selected from trimethyl allyl ammonium chloride, 2-methacryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride and acryloyloxyethyl trimethyl ammonium chloride.
The invention also provides a cationic chlorine-containing amphiphilic copolymer separation membrane, which contains a product obtained after the quaternization reaction of the tertiary amine derivative type chlorine-containing amphiphilic polymer, wherein the tertiary amine derivative type hydrophilic monomer B of the tertiary amine derivative type chlorine-containing amphiphilic polymer is selected from dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide and dimethylaminopropyl acrylamide. I.e., the films prepared in examples 16-18.
Further, the preparation method of the cationic chlorine-containing amphiphilic copolymer separation membrane is a known membrane preparation method in the field of separation membranes.
Further, the quaternary ammonium salt of the tertiary amine derivative type chlorine-containing amphiphilic copolymer after the quaternary ammonium reaction can be obtained by the quaternary ammonium reaction before the membrane is made, or can be obtained by the quaternary ammonium reaction after the membrane is made.
Further, the quaternization reaction employs a quaternization method well known in the art.
Preferably, the quaternization method adopts a quaternization reagent known in the field, and the quaternization reaction temperature and the reaction time; more preferably, the quaternizing agent is methyl iodide, methyl bromide or benzyl chloride.
The invention also provides an amphoteric chlorine-containing amphiphilic copolymer separation membrane, which contains the tertiary amine derivative type chlorine-containing amphiphilic polymer, wherein the tertiary amine derivative type hydrophilic monomer B of the tertiary amine derivative type chlorine-containing amphiphilic polymer is selected from methacrylic acid sulfobetaine, methacrylic acid carboxylic acid betaine, methacrylamide sulfobetaine and methacrylamide carboxylic acid betaine.
The invention also provides an amphoteric chlorine-containing amphiphilic copolymer separation membrane, which contains a product obtained after the amphoteric reaction of the tertiary amine derivative type chlorine-containing amphiphilic polymer, wherein the tertiary amine derivative type hydrophilic monomer B of the tertiary amine derivative type chlorine-containing amphiphilic polymer is selected from dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide and dimethylaminopropyl acrylamide. I.e., the films prepared in examples 19-21.
Further, the preparation method of the amphoteric chlorine-containing amphiphilic copolymer separation membrane is a membrane preparation method known in the field of separation membranes.
Furthermore, the substance after the amphoteric reaction of the tertiary amine derivative type chlorine-containing amphiphilic copolymer can be obtained by the amphoteric reaction before membrane preparation and also can be obtained by the amphoteric reaction after membrane preparation.
Further, the amphoteric reaction employs an amphoteric method well known in the art.
Preferably, the amphoteric method adopts amphoteric reagents known in the art, and the amphoteric reaction temperature and the amphoteric reaction time are adopted; more preferably, the amphiprotic reagent is 1, 3-propane sultone, 1, 4-butane sultone and sodium chloroacetate.
Further, the separation membrane of the tertiary amine derivative type chlorine-containing amphiphilic copolymer 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 micromolecule materials and high polymer materials.
Compared with the prior art, the invention has the beneficial effects that:
1) the tertiary amine derivative type hydrophilic monomer component in the tertiary amine derivative type chlorine-containing amphiphilic polymer provided by the invention has very good hydrophilic performance, and the content of the tertiary amine derivative type hydrophilic monomer component can reach 70 wt%, which is far higher than that of the hydrophilic component in the existing chlorine-containing copolymer; in addition, the proportion of the component B of the tertiary amine derivative type hydrophilic monomer in the tertiary amine derivative type chlorine-containing amphiphilic polymer can be adjusted at will between 1 and 70 wt%, so that the tertiary amine derivative type chlorine-containing amphiphilic polymer provided by the invention has very flexible applicability.
2) The invention adopts a free radical suspension polymerization method which takes a specific chlorine-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) According to the invention, the tertiary amine derivative type chlorine-containing amphiphilic polymer can be prepared into the cationic chlorine-containing amphiphilic copolymer separation membrane and the amphoteric chlorine-containing amphiphilic copolymer separation membrane which are excellent in hydrophilicity and pollution resistance by adopting a conventional separation membrane preparation process, so that the application range of the chlorine-containing polymer separation membrane is greatly expanded.
Drawings
FIG. 1 is a scanning electron micrograph of platelets adhered to the surfaces of YP1 film, LP8 film and PVC film prepared in example.
Detailed Description
The following will describe in detail the process for preparing a chlorine-containing amphiphilic polymer of the tertiary amine derivative type according to the invention with 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 present invention, and all modifications that can be derived or suggested by a person skilled in the art from the present disclosure should be considered as the protection scope of the present invention.
Example 1
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P1 taking a chlorine-containing macromolecular dispersant D1 solution as a dispersant:
100g of N, N-Dimethylacetamide (DMAC), 6g of vinylidene chloride, 20g of a 50% aqueous solution of trimethylallylammonium chloride and 0.1g of Benzoyl Peroxide (BPO) as an initiator 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. A chlorine-containing macromolecular dispersion D1 solution was obtained. 2000ml of deionized water, 1.2g of D1 solution and 1g of initiator di (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 chloride 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 is raised to 40 ℃ for polymerization, and 30g of 50% aqueous solution of trimethyl allyl ammonium chloride is gradually dropped to carry out polymerization reaction. After 12 hours of reaction, air was introduced into the system to terminate the reaction. Discharging, filtering, washing, extracting solubilizer ethyl acetate by using 500g of methanol, and drying at 50 ℃ to obtain the tertiary amine derivative type chlorine-containing amphiphilic polymer P1.
The structural and performance characterization method of the synthesized chlorine-containing macromolecular dispersant D1 solution and the tertiary amine derivative type chlorine-containing amphiphilic polymer P1 comprises the following steps:
1. structural characterization: by using1H-NMR nuclear magnetic resonance spectrum analysis of the structure. The obtained dispersant macromolecule D1 was obtained by drying the obtained dispersant solution, and the obtained polymer P1 was dissolved in deuterated DFM, respectively, for 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 tertiary amine derivative type hydrophilic monomer component in D1 in this example was 58.5 wt%, and the number average molecular weight Mn of D1 was 3.5K by a polymer 1H-NMR spectrum and GPC measurement; molecular weight distribution PDI 1.6; the content of the tertiary amine derivative type hydrophilic monomer component in the P1 is 3.5 wt%, and the number average molecular weight Mn of the P1 is 130K; molecular weight distribution PDI 1.6;
example 2
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P2 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D2 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P2 are shown in Table 3.
Example 3
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P3 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D3 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P3 are shown in Table 3.
Example 4
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P4 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D4 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P4 are shown in Table 3.
Example 5
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P5 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D5 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P5 are shown in Table 3.
Example 6
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P6 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D6 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P6 are shown in Table 3.
Example 7
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P7 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D7 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P7 are shown in Table 3.
Example 8
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P8 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D8 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P8 are shown in Table 3.
Example 9
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P9 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D9 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P9 are shown in Table 3.
Example 10
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P10 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D10 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P10 are shown in Table 3.
Example 11
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P11 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D11 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P11 are shown in Table 3.
Example 12
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P12 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D12 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P12 are shown in Table 3.
Example 13
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P13 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D13 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P13 are shown in Table 3.
Example 14
Synthesizing a tertiary amine derivative type chlorine-containing amphiphilic polymer P14 taking a chlorine-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, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of D14 are shown in Table 3; the content, molecular weight and molecular weight distribution of the tertiary amine derivative type hydrophilic monomer component of P14 are shown in Table 3.
Example 15:
this example illustrates that cationic chlorine-containing amphiphilic polymer separation membranes (YP) and amphoteric chlorine-containing amphiphilic polymer separation membranes (LP) prepared from tertiary amine derivative type chlorine-containing amphiphilic polymer have superior hydrophilic properties compared to separation membranes prepared from general chlorine-containing polymer. The method comprises the following steps:
(1) preparation of YP 1-YP 4 films: respectively dissolving 20g of the copolymers P1-P4 prepared in examples 1-4 in 100g of N, N-dimethylacetamide to prepare a membrane preparation solution; and 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 YP 1-YP 13 films.
(2) Preparation of LP 11-LP 14 membranes: respectively dissolving 20g of the copolymers P20-P32 prepared in examples 11-14 in 100g of N, N-dimethylacetamide to prepare a membrane preparation solution; and scraping the film-forming liquid on a glass sheet to form a liquid film, soaking the liquid film into water at 40 ℃ for curing to form a film, and washing for 12 hours to obtain LP 11-LP 14 films.
(3) Preparing a PVC film: 20g of polyvinylidene chloride is dissolved in 100g of N, N-dimethylacetamide to prepare membrane preparation liquid; scraping the film-forming liquid on a glass sheet to form a liquid film, immersing the liquid film into water of 40 ℃ for curing and film-forming, and washing for 12 hours to obtain the PVC film.
(4) The membrane was washed three times with deionized water and absolute ethanol for contact angle experiments.
Example 16
YP5 films were prepared using the P5 quaternization reaction synthesized in example 5:
20g of the copolymer P5 prepared in example 5 was dissolved in 100g of N, N-dimethylacetamide to prepare a film-forming solution; at room temperature, 5g of methyl iodide is added, and stirring is continued for 6 hours; 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 YP5 film. The membrane was washed three times with deionized water and absolute ethanol for contact angle experiments.
Example 17
YP6 films were prepared using the P6 quaternization reaction synthesized in example 6:
20g of the copolymer P6 prepared in example 6 was dissolved in 100g of N, N-dimethylacetamide to prepare a film-forming solution; at room temperature, adding 5g of methyl bromide, and continuing stirring for 4 hours; 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 YP6 film. The membrane was washed three times with deionized water and absolute ethanol for contact angle experiments.
Example 18
YP7 films were prepared using the P16 quaternization reaction synthesized in example 7:
20g of the copolymer P7 prepared in example 7 was dissolved in 100g of N, N-dimethylacetamide to prepare a film-forming solution; scraping the film-forming liquid on a glass sheet into a liquid film, immersing the liquid film into water at 40 ℃ for curing and film-forming, and washing for 12 hours; soaking the washed membrane in 50% benzyl chloride ethanol solution at 40 deg.C for 1 hr; YP7 films were obtained after 12h of washing. The membrane was washed three times with deionized water and absolute ethanol for contact angle experiments.
Example 19
LP8 membranes were prepared using the amphoteric reaction of P8 synthesized in example 8:
20g of the copolymer P8 prepared in example 8 was dissolved in 100g of N, N-dimethylacetamide to prepare a film-forming solution; at 65 ℃, adding 6g of 1, 3-propane sulfonic acid lactone, and continuing stirring for 12 hours; scraping the film-forming liquid on a glass sheet to form a liquid film, soaking the liquid film into water at 40 ℃ for curing to form a film, and washing for 12 hours to obtain the LP8 film. The membrane was washed three times with deionized water and absolute ethanol for contact angle experiments.
Example 20
LP9 membranes were prepared using the amphoteric reaction of P9 synthesized in example 9:
20g of the copolymer P9 prepared in example 9 was dissolved in 100g of N, N-dimethylacetamide to prepare a film-forming solution; at 70 ℃, 6g of 1, 4-butane sulfonic acid lactone is added, and the stirring is continued for 10 hours; scraping the film-forming liquid on a glass sheet to form a liquid film, soaking the liquid film into water at 40 ℃ for curing to form a film, and washing for 12 hours to obtain the LP9 film. The membrane was washed three times with deionized water and absolute ethanol for contact angle experiments.
Example 21
LP10 membranes were prepared using the amphoteric reaction of P10 synthesized in example 10:
20g of the copolymer P10 prepared in example 10 was dissolved in 100g of N, N-dimethylacetamide to prepare a film-forming solution; scraping the film-forming liquid on a glass sheet into a liquid film, immersing the liquid film into water at 40 ℃ for curing and film-forming, and washing for 12 hours; soaking the washed membrane in 50% sodium chloroacetate ethanol solution at 55 deg.C for 6 hr; washing with dilute hydrochloric acid for 1 minute and pure water for 12 hours to obtain the LP10 membrane. The membrane was washed three times with deionized water and absolute ethanol for contact angle experiments.
The initial contact angles and the post-contact angles of 30s of the separation membranes prepared in examples 15 to 21 are shown in table 5, and it can be seen that the initial contact angles of YP1 to YP7 membranes and LP8 to LP14 membranes are far smaller than the contact angle of the common PVC membranes, and in addition, the contact angle after 30s indicates the dynamic contact angle change rate of the membranes, and it can be seen that the contact angle reduction rates of YP1 to YP7 membranes and LP8 to LP14 membranes are far higher than the reduction rate of the contact angle of the common PVC membranes, and the two contact angle test data show that the YP1 to YP7 membranes and LP8 to LP14 membranes have very excellent hydrophilic performance; and by comparing the contact angles of the YP 1-YP 16 films and the LP 17-LP 32 films with the content of the tertiary amine derivative type hydrophilic monomer component in the polymer, the contact angle of the prepared film can be seen to change along with the content of the tertiary amine derivative type hydrophilic monomer component in the polymer, and the film has adjustability.
This example clearly shows that the tertiary amine derivative type chlorine-containing amphiphilic polymer synthesized by the present invention can prepare excellent chlorine-containing amphiphilic polymer separation membrane material.
Example 22:
this example illustrates that cationic chlorine-containing amphiphilic polymer separation membranes (YP) and amphoteric chlorine-containing amphiphilic polymer separation membranes (LP) prepared from tertiary amine derivative type chlorine-containing amphiphilic polymer have anti-contamination properties compared to separation membranes prepared from conventional chlorine-containing polymer. The method comprises the following steps:
(1) preparation of YP 1-YP 7 films and LP 8-LP 14 films: same as in examples 15-21.
(2) 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).
Platelets adhered to the surfaces of YP1, LP8, and PVC membranes prepared in example 22 are shown in fig. 1, and platelets adhered to the surfaces of other membranes are shown in table 5. It is apparent from fig. 1 and table 5 that YP 1-YP 7 films and LP 8-LP 14 films have very little adhesion to platelets, whereas ordinary PVC film surfaces have much platelet adhesion.
The embodiment clearly shows that the tertiary amine derivative type chlorine-containing amphiphilic polymer synthesized by the invention can be used for preparing a chlorine-containing amphiphilic polymer separation membrane material with excellent anti-platelet adhesion and anti-pollution performance.
Comparative example 1
Synthesis of tertiary amine derivative type chlorine-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 tertiary amine derivative type hydrophilic monomer component, the molecular weight and the molecular weight distribution of CP3 are shown in table 3.
This comparative example shows that when polyvinyl alcohol was used in place of the exclusive dispersant D3, the content of the tertiary amine derivative type hydrophilic monomer component was only 0.5%. The special dispersant is a key formula for synthesizing high content of hydrophilic components.
Comparative example 2
Synthesis of the graft type hydrophilic segment chlorine-containing polymer GP3 (see patent CN201510058518.5 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 vinylidene chloride, 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 345g of dimethyl diallyl ammonium chloride, 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 type hydrophilic chain segment chlorine-containing polymer GP 3.
GP3 was formed into a film by the procedure of example 15 to obtain GP3 film. After soaking GP3 film and YP3 film simultaneously in a solution at pH 2 and pH 14 for 12h, the contact angle was measured after washing with pure water. The contact angle of GP3 was found to be 45 before soaking and 62 after soaking, with the hydrophilic effect being significantly reduced. While the contact angle before soaking of YP3 was 44 degrees, the contact angle after soaking was 44 degrees, and the hydrophilic effect was unchanged. The stability of the grafted hydrophilic component of graft polymer GP3 was shown to be less than that of the backbone copolymer P3.
TABLE 1
Figure BDA0001797552740000211
Figure BDA0001797552740000221
Figure BDA0001797552740000231
TABLE 2
Figure BDA0001797552740000232
Figure BDA0001797552740000241
TABLE 3
Figure BDA0001797552740000242
TABLE 4
Figure BDA0001797552740000243
Figure BDA0001797552740000251
TABLE 5
Film numbering Amount of platelet adhesion Film numbering Amount of platelet adhesion
YP1 ● LP8 ○○
YP2 ● LP9 ○○
YP3 ○ LP10 ○○
YP4 ○ LP11 ○○
YP5 ○○ LP2 ○○
YP6 ○○ LP13 ○○
YP7 ○○ LP14 ○○
PVC ●●
● ● high adhesion, ● medium adhesion, ○ low adhesion, ○○ very low adhesion.

Claims (10)

1. A tertiary amine derivative type chlorine-containing amphiphilic polymer, characterized in that: the tertiary amine derivative type chlorine-containing amphiphilic polymer is a polymer consisting of chlorine-containing chain links and tertiary amine derivative type hydrophilic chain links, and the structural formula of the tertiary amine derivative type chlorine-containing amphiphilic polymer is shown as follows:
Figure FDA0001797552730000011
in the formula:
the chlorine-containing chain link is formed by polymerizing chlorine-containing monomers A, and the structure of the chlorine-containing chain link unit-A-is
Figure FDA0001797552730000012
The tertiary amine derivative type hydrophilic chain link is formed by polymerizing a tertiary amine derivative type hydrophilic monomer B, and the structure of a tertiary amine derivative type hydrophilic chain link unit-B-is as follows:
Figure FDA0001797552730000013
in the formula:
R1selected from H, Cl;
R2selected from H, CH3
R3Is selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2＝CHCH2)(CH3)2Cl、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2、COOCH2CH2N+(CH3)2CH2CH2SO3 -、CONHCH2CH2N+(CH3)2CH2CH2SO3 -、COOCH2CH2N+(CH3)2CH2CH2COO-、CONHCH2CH2N+(CH3)2CH2CH2COO-；
a. b is an integer greater than or equal to 1; preferably, a/b is 250/1-1.5/1; preferably, a/b is 10/1 to 1/1.
2. The tertiary amine derivative type chlorine-containing amphiphilic polymer according to claim 1, characterized in that: the structural formula of the chlorine-containing monomer A is as follows:
Figure FDA0001797552730000021
in the formula:
R1selected from H, Cl.
Preferably, the chlorine-containing monomer A is selected from any one or more of vinyl chloride and vinylidene chloride.
3. The tertiary amine derivative type chlorine-containing amphiphilic polymer according to claim 1, characterized in that: the structural formula of the tertiary amine derivative type hydrophilic monomer B is as follows:
Figure FDA0001797552730000022
in the formula:
R2selected from H, CH3；
R3Is selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2＝CHCH2)(CH3)2Cl、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2、COOCH2CH2N+(CH3)2CH2CH2SO3 -、CONHCH2CH2N+(CH3)2CH2CH2SO3 -、COOCH2CH2N+(CH3)2CH2CH2COO-、CONHCH2CH2N+(CH3)2CH2CH2COO-；
Preferably, the tertiary amine derivative type hydrophilic monomer B is selected from any one or any more of trimethyl allyl ammonium chloride, 2-methacryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, sulfobetaine methacrylate, carboxylic betaine methacrylate, sulfobetaine methacrylamide, and carboxylic betaine methacrylamide.
4. The method according to claim 1, wherein the method comprises the steps of:
(1) preparation of a solubilization dispersion liquid: adding a chlorine-containing monomer A, a chlorine-containing macromolecular dispersant solution, a hydrophobic initiator and a solubilizer into a 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 a stable dispersion liquid;
(2) polymerization of chlorine-containing amphiphilic copolymer: heating to 40-80 ℃ for polymerization reaction, gradually adding a tertiary amine derivative type hydrophilic monomer B into the dispersion liquid obtained in the step (1), and filtering to obtain a chlorine-containing amphiphilic copolymer wet material after the reaction is finished;
(3) extracting the solubilizer: adding the chlorine-containing amphiphilic copolymer wet material obtained in the step (2) into an extracting agent, removing the solubilizer in the chlorine-containing amphiphilic copolymer wet material, and drying to obtain a chlorine-containing amphiphilic copolymer;
preferably, the solubilizer is selected from any one or any 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 and hexyl butyrate; preferably, the extractant is selected from any one or more of methanol, ethanol and propanol.
5. The method for preparing a tertiary amine derivative type chlorine-containing amphiphilic copolymer according to claim 4, wherein the chlorine-containing macromolecular dispersant solution comprises 10-50 wt% of chlorine-containing macromolecular dispersant and the balance of organic solvent.
6. The method for preparing a tertiary amine derivative type chlorine-containing amphiphilic copolymer according to claim 4 or 5, wherein the chlorine-containing macromolecular dispersant is a polymer consisting of chlorine-containing chain segments and tertiary amine derivative type hydrophilic chain segments, and the structural formula of the chlorine-containing macromolecular dispersant is as follows:
Figure FDA0001797552730000031
in the formula:
the chlorine-containing chain link is formed by polymerizing chlorine-containing monomers A, and the structure of the chlorine-containing chain link unit-A-is
Figure FDA0001797552730000032
The tertiary amine derivative type hydrophilic chain link is formed by polymerizing a tertiary amine derivative type hydrophilic monomer B, and the structure of a tertiary amine derivative type hydrophilic chain link unit-B-is as follows:
Figure FDA0001797552730000033
in the formula:
R1selected from H, Cl;
R2selected from H, CH3
R3Is selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2＝CHCH2)(CH3)2Cl、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2、COOCH2CH2N+(CH3)2CH2CH2SO3 -、CONHCH2CH2N+(CH3)2CH2CH2SO3 -、COOCH2CH2N+(CH3)2CH2CH2COO-、CONHCH2CH2N+(CH3)2CH2CH2COO-；
x and y are integers greater than or equal to 1; preferably, x/y is 3/1-1/100; the preferred x/y is 1/1 ~ 1/20.
7. A method for preparing a chlorine-containing amphiphilic copolymer of tertiary amine derivative type according to any one of claims 4 to 6, wherein the method for preparing the chlorine-containing macromolecular dispersant comprises the following steps: weighing 5-50% of chlorine-containing monomer A, 50-95% of tertiary amine derivative type hydrophilic monomer B and 0.1-5% of initiator by weight 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 solution containing the macromolecular dispersant of claim 1; preferably, 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-alkyl pyrrolidone.
8. The process for the preparation of a chlorine-containing amphiphilic copolymer of tertiary amine derivative type according to any one of claims 4 to 7, characterized in that: the structural formula of the chlorine-containing monomer A is as follows:
Figure FDA0001797552730000041
in the formula:
R1selected from H, Cl.
Preferably, the chlorine-containing monomer A is selected from any one or more of vinyl chloride and vinylidene chloride.
9. The process for the preparation of a chlorine-containing amphiphilic copolymer of tertiary amine derivative type according to any one of claims 4 to 7, characterized in that: the structural formula of the tertiary amine derivative type hydrophilic monomer B is as follows:
Figure FDA0001797552730000051
in the formula:
R2selected from H, CH3；
R3Is selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2＝CHCH2)(CH3)2Cl、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2、COOCH2CH2N+(CH3)2CH2CH2SO3 -、CONHCH2CH2N+(CH3)2CH2CH2SO3 -、COOCH2CH2N+(CH3)2CH2CH2COO-、CONHCH2CH2N+(CH3)2CH2CH2COO-。
Preferably, the tertiary amine derivative type hydrophilic monomer B is selected from any one or any more of trimethyl allyl ammonium chloride, 2-methacryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, sulfobetaine methacrylate, carboxylic betaine methacrylate, sulfobetaine methacrylamide, and carboxylic betaine methacrylamide.
10. A cationic chlorine-containing amphiphilic copolymer separation membrane, comprising the tertiary amine derivative type chlorine-containing amphiphilic polymer according to any one of claims 1 to 3, wherein the tertiary amine derivative type hydrophilic monomer B of the tertiary amine derivative type chlorine-containing amphiphilic polymer is selected from the group consisting of trimethylallylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride, dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride.
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