阅读说明：本技术 使离子交联剂聚合的方法 (Method for polymerizing ionic crosslinking agents ) 是由 赵永红 R.J.麦克唐纳 J.H.巴伯 于 2017-05-15 设计创作，主要内容包括：本公开提供了一种聚合方法,其中使(i)包括季铵基团的离子交联剂和(ii)非离子交联剂在反应溶液中聚合,所述反应溶液的溶剂基本上为丙二醇(PG)和非质子酰胺类溶剂的混合物。该聚合制造阴离子交换聚合物组合物。PG和非质子酰胺类溶剂以约25:75至约70:30的重量比存在,并且反应物和溶剂以产生理论水含量为约35%至约60%(wt/wt)的阴离子交换聚合物组合物的量存在。(The present disclosure provides a polymerization process wherein (i) an ionic crosslinker comprising a quaternary ammonium group and (ii) a non-ionic crosslinker are polymerized in a reaction solution having a solvent that is essentially a mixture of Propylene Glycol (PG) and an aprotic amide-based solvent. The polymerization produces an anion exchange polymer composition. The PG and aprotic amide solvent are present in a weight ratio of about 25:75 to about 70:30, and the reactants and solvent are present in amounts to produce an anion exchange polymer composition having a theoretical water content of about 35% to about 60% (wt/wt).)

1. A method, the method comprising:

polymerizing (i) an ionic crosslinking agent comprising quaternary ammonium groups and (ii) a non-ionic crosslinking agent in a reaction solution consisting essentially of a mixture of Propylene Glycol (PG) and an aprotic amide-based solvent to produce an anion exchange polymer composition,

wherein PG and aprotic amide solvent are present in a weight ratio of about 25:75 to about 70:30, and

wherein the reactants and solvent are present in amounts to produce an anion exchange polymer composition having a theoretical water content of from about 35% to about 60% (wt/wt), such as from about 30% to about 50% (wt/wt).

2. The method of claim 1, wherein the solvent mixture is at least about 95% (v/v) PG and an aprotic amide-based solvent.

3. The process of claim 1, wherein the aprotic amide-based solvent is N-methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF), or a mixture of NMP and DMF.

4. The method of claim 1, wherein the non-ionic crosslinker is:

a. divinylbenzene;

b. ethylene Glycol Dimethacrylate (EGDMA);

c. 1, 3-divinylimidazolidin-2-one (DVI);

d. n, N' -methylenebis (acrylamide) (MBA);

e. n-methacrylaminomethyl-acrylamide; or

f. A reaction product between an acrylamide compound and another acrylamide compound including a hydroxyl group, for example, a reaction product between Methacrylamide (MAA) and N-hydroxymethylacrylamide (NHMA).

5. The method of claim 1, wherein the step of polymerizing further comprises polymerizing the monomer.

6. The method of claim 5, wherein the monomer is:

a. n-vinyl caprolactam (V-Cap);

b. vinylbenzyl chloride (VBC);

c. methacrylamide (MAA); or

d. Ethyl vinyl benzene.

7. The method of claim 1, wherein each polymerizable functional group of each polymerizable reactant is independently selected from a vinyl-based functional group, such as an acrylic functional group or an acrylamide functional group.

8. The method of claim 1, further comprising, prior to polymerizing:

the ionic crosslinker is formed by reacting a tertiary amine compound with an alkylating compound.

9. The method of claim 8, wherein the tertiary amine compound is an olefinic tertiary amine, such as dimethylaminopropyl methacrylamide (DMAPMA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminopropyl acrylamide (DMAPAA), or diethylaminopropyl methacrylamide (DEAPMA).

10. The process of claim 8, wherein the alkylated compound is a polyepoxide or polyhalide.

11. The method of claim 10, wherein the polyhalide is a polybrominated alkane, such as 1, 4-dibromobutane or 1, 6-dibromohexane.

12. The method of claim 10, wherein the polyepoxide is a diepoxide or a triepoxide, such as a diglycidyl ether or a triglycidyl ether.

13. The method of claim 12, wherein the diepoxide is: 1, 3-butadiene diepoxide; dicyclopentadiene dioxide; or cis, cis-11, 12, 14, 15-diepoxyeicosanoic acid methyl ester.

14. The method of claim 12, wherein the diglycidyl ether is: diethylene glycol diglycidyl ether; 1, 2-cyclohexanedicarboxylic acid diglycidyl ester; n, N-diglycidyl-4-glycidyloxyaniline; bisphenol a diglycidyl ether; brominated bisphenol a diglycidyl ether; bisphenol F diglycidyl ether; 1, 4-butanediol diglycidyl ether; 1, 4-butanediyl diglycidyl ether; 1, 4-cyclohexanedimethanol diglycidyl ether; glycerol diglycidyl ether; resorcinol diglycidyl ether; bis [4- (glycidyloxy) phenyl ] methane; bisphenol a propoxylated diglycidyl ether; dimer acid diglycidyl ester; ethylene glycol diglycidyl ether; brominated neopentyl glycol diglycidyl ether; diglycidyl ether-terminated poly (dimethylsiloxane); polyethylene glycol diglycidyl ether; polypropylene glycol diglycidyl ether; or 1, 3-butanediol diglycidyl ether.

15. The method of claim 12, wherein the triglycidyl ether is: tris (2, 3-epoxypropyl) isocyanurate; trimethylolpropane triglycidyl ether; tris (4-hydroxyphenyl) methane triglycidyl ether 2, 6-toluene diisocyanate; tris (4-hydroxyphenyl) methane triglycidyl ether; glycerol propoxyttriglycidyl ether; trimethylolethane triglycidyl ether; or 1,2, 3-glycerol triglycidyl ether.

16. The method of claim 8, wherein forming an ionic crosslinker is performed at a reaction temperature that promotes alkylation but does not promote polymerization.

17. The method of claim 1, wherein polymerizing the ionic crosslinker comprises polymerizing the reactant on a woven or nonwoven backing, such as Polyacrylonitrile (PAN) cloth, polypropylene (PP) cloth, Polyethylene (PE) cloth, polyethylene terephthalate (PET) cloth, or polyvinyl chloride (PVC) cloth.

18. A method, the method comprising:

dissolving dimethylaminopropyl methacrylamide (DMAPMA) in a solvent mixture consisting essentially of (i) Propylene Glycol (PG) and (ii) N-methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF), or both, wherein the two solvents are present in a weight ratio of from about 25:75 to about 70: 30;

dissolving an acid and 1, 4-cyclohexanedimethanol diglycidyl ether (CHDMDGE) or Dibromohexane (DBH) or Dibromobutane (DBB) in the solvent mixture;

raising the temperature of the reaction solution to about 78 ℃ and reacting (a) DMAPMA and (b) CHDMDGE, DBH or DBB to form a quaternary ammonium-containing crosslinker;

reducing the temperature of the reaction solution to about room temperature;

dissolving a nonionic crosslinking agent and a polymerization initiator in the reaction solution to provide a polymerization reaction solution; and

polymerizing the reactants in the reaction solution to form an anion exchange polymer composition;

wherein the process optionally comprises casting the polymerization reaction solution on a cloth backing to produce an anion exchange membrane prior to polymerizing the reactants; and

wherein the method optionally comprises conditioning the anion exchange polymer composition.

19. The method of claim 18, wherein:

a. the acid is hydrochloric acid, methanesulfonic acid, sulfuric acid or phosphoric acid;

b. the cloth backing is as follows: polyacrylonitrile (PAN), polypropylene (PP), Polyethylene (PE), polyethylene terephthalate (PET) cloth, or polyvinyl chloride (PVC);

c. the non-ionic cross-linking agent is: divinylbenzene; ethylene Glycol Dimethacrylate (EGDMA); 1, 3-divinylimidazolidin-2-one (DVI); or N, N' -methylenebis (acrylamide) (MBA);

d. the polymerization initiator is: trimethylbenzoyldiphenylphosphine oxide (TPO); 2,2' -azobis (2-methylpropionic acid) dimethyl ester (V-601); 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride (V-044); or 2,2' -azobis (2-methylpropionamidine) dihydrochloride (V-50); or

e. Any combination thereof.

Brief Description of Drawings

Embodiments of the present disclosure will now be described, by way of example only, with reference to the accompanying drawings.

Fig. 1 shows a table summarizing the amounts of solvents and reactants used in the process according to the present disclosure.

Figure 2 shows a table summarizing the amounts of solvents and reactants used in the process according to the present disclosure.

Fig. 3 shows a table summarizing the amounts of solvent and reactants used in the comparative method.

Detailed description of the invention

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

The endpoints of all ranges reciting the same characteristic are independently combinable and inclusive of the recited endpoint.

The modifier "about" used in connection with an amount is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the tolerance ranges associated with measurement of the particular amount or includes the value to be rounded to the particular amount based on the stated numerical significance).

"optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, or that the subsequently identified material may or may not be present, and that the description includes instances where the event or circumstance occurs or where the material is present, and instances where the event or circumstance does not occur or the material is not present.

In general, the present disclosure provides a polymerization process in which (i) an ionic crosslinker comprising quaternary ammonium groups and (ii) a non-ionic crosslinker are polymerized in a solvent mixture that is essentially a mixture of Propylene Glycol (PG) and an aprotic amide-based solvent, such as N-methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF), or dimethylacetamide (DMAc). Aprotic amide solvents may be referred to as "amide solvents," but are not intended to include protic amide solvents, such as 2-pyrrolidone or N-methylformamide. The PG and amide solvents are present in a weight ratio of about 25:75 to about 70: 30. In particular examples, the weight ratio is about 50:50 to about 70: 30. In a more specific example, the weight ratio is about 60:40 to about 70: 30. The reagents and solvent are present in amounts to produce an anion exchange polymer having a theoretical water content of from about 35% to about 60%.

In the context of the present disclosure, "substantially" a solvent mixture of PG and amide-based solvents refers to a solvent mixture of at least 95% by volume of PG or amide-based solvents. The remainder of the solvent mixture may be a solvent that is soluble with the PG and amide solvent mixture.

The theoretical water content of the polymer is calculated by dividing the total weight of solvent by the total weight of the reagents plus solvent, ignoring the weight of any polymerization initiator or inhibitor. For example, a polymerization comprising a total of 27 grams of crosslinker and optional monomers, dissolved in a total of 20 grams of solvent, will result in a polymer with a theoretical water content of 20/(27+20) = 42.5%. In particular examples of the present disclosure, the theoretical water content is about 35% to about 50%. Water contents of about 40% to about 50% are particularly useful in electrodialysis reversal (EDR) based water treatment methods and systems. Water contents of about 30% to about 45% are particularly useful in Electrodialysis (ED) based water treatment methods and systems.

The ionic crosslinker and the nonionic crosslinker each comprise at least two free radical-based polymerizable groups. The expression "free radical-based polymerizable group" (or "polymerizable group") is understood to mean a functional group which polymerizes under free radical polymerization conditions. When the polymerization includes additional monomers, the optional monomers also include free radical-based polymerizable functional groups. Each polymerizable functional group in each reactant used in the polymerization reaction may be independently selected as long as they are polymerizable under the same polymerization conditions. In one example, the polymerizable functional groups are independently selected from: the polymerizable group on the ionic crosslinker can be a vinyl group, while the polymerizable group on the nonionic crosslinker (linker) can be an acrylate. In this example, if an optional monomer is also included in the reaction mixture, the monomer may include acrylamide.

In some examples according to the present disclosure, each polymerizable group in the reactants used in the polymerization reaction is a vinyl-based functional group. Vinyl-based functional groups include vinyl groups, acrylic groups, and acrylamide groups. Non-limiting examples of compounds having a polymerizable vinyl group include: vinyl benzene; divinylbenzene; 1, 3-divinylimidazolidin-2-one; and N-vinyl caprolactam. Non-limiting examples of compounds having an acrylic group include: dimethylaminoethyl methacrylate (DMAEMA) and Ethylene Glycol Dimethacrylate (EGDMA). Non-limiting examples of compounds having an acrylamide group include: (ii) methacrylamide; n-hydroxymethylacrylamide; n- [3- (dimethylamino) propyl ] methacrylamide; and N, N' -methylenebis (acrylamide). In the context of the present disclosure, all exemplified compounds will be considered to have "vinyl-based functional groups".

The ionic crosslinker comprises at least one quaternary ammonium group and at least two polymerizable groups. The ionic crosslinker may be a reaction product formed from the reaction between a tertiary amine compound and an alkylating compound. The polymerizable group can be part of the tertiary amine compound, the alkylating agent, or both. In some examples, the ionic crosslinker is a reaction product formed from a reaction between two tertiary amine compounds (each comprising a polymerizable group) and a polyalkylated compound. The polyalkylated compound can be, for example, a polyepoxide or a polyhalide, such as a polybromide.

Ionic crosslinkers having at least one quaternary ammonium group are disclosed in WO2013052227 and are incorporated herein by reference. Such ionic crosslinkers can be used in the methods according to the present disclosure.

In particular examples, the ionic crosslinker is formed from the reaction between DMAPMA or DMAEMA and CHDMDGE. The resulting cross-linkers each have the following structure (counter ions not shown):

(formula I)

And

(formula II).

In other specific examples, the ionic crosslinker is formed from the reaction between DMAPMA or DMAEMA and DBB or DBH. The resulting crosslinker has the following structure (counter ion not shown):

(formula III);

(formula IV);

(formula V);

(formula VI).

A solvent mixture of PG: amide based solvents that is substantially from about 25:75 to about 70:30 (wt/wt) may be particularly effective in the methods according to the present disclosure, where DMAPMA or DMAEMA is used to form the ionic crosslinker in situ. Particularly when the weight ratio is from about 50:50 to about 70:30, more particularly when the weight ratio is from about 60:40 to about 70:30, it is believed that the solvent mixture reduces the likelihood of polymerization of DMAPMA or DMAEMA at elevated temperatures that are still suitable for reaction of DMAPMA or DMAEMA with CHDMDGE, DBB or DBH. For example, methods using solvent mixtures according to the present disclosure may form ionic crosslinkers using DMAPMA at temperatures up to about 78 ℃. Methods using solvent mixtures according to the present disclosure can form ionic crosslinkers using DMAEMA at temperatures up to about 50 ℃. The rate of reaction between the tertiary amine and the alkylating agent increases at higher temperatures, and thus it may be desirable to form the ionic crosslinker using DMAPMA at a temperature of about 78 ℃ or DMAEMA at a temperature of about 52 ℃. At these temperatures in the solvent mixture, DMAPMA, DMAEMA or CHDMDGE is substantially free of polymerization. Polymerization of DMAPMA, DMAEMA, or CHDMDGE prior to formation of the ionic crosslinker can prevent formation of an anion exchange membrane (e.g., because the reactants have reacted before they can be polymerized on the cloth), or can result in an anion exchange membrane having undesirable physical properties (e.g., an undesirable soft membrane, or a membrane having an undesirable amount of exfoliation).

As discussed above, the nonionic crosslinking agent in the polymerization reaction includes at least two free radical-based polymerizable groups that are polymerizable under the same polymerization conditions as the polymerizable groups of the ionic crosslinking agent. Examples of nonionic crosslinking agents that can be used in the presently disclosed methods include: divinylbenzene (DVB), Ethylene Glycol Dimethacrylate (EGDMA); 1, 3-divinylimidazolidin-2-one (DVI); and N, N' -methylenebis (acrylamide) (MBA).

The method according to the present disclosure may be used to produce an anion exchange membrane, for example by additionally casting a polymerization reaction solution on a cloth backing prior to polymerizing the reactants. The cloth backing may be woven or non-woven. The backing may be made of, for example, Polyacrylonitrile (PAN), polypropylene (PP), Polyethylene (PE), polyethylene terephthalate (PET), or polyvinyl chloride (PVC). The thickness of the cloth backing can be selected such that the resulting anion exchange membrane is from about 0.1mm to about 0.8 mm. Curing the reactants may include exposing the reaction mixture to an elevated temperature, such as about 50 ℃ to about 120 ℃, and/or to UV light. In a particular method, curing includes increasing the temperature from room temperature to about 120 ℃ using a plurality of heating stations.

In a particular example of a method according to the present disclosure, the method comprises dissolving DMAPMA or DMAEMA and an acid in a solvent mixture without allowing the temperature to exceed a temperature that promotes polymerization of DMAPMA or DMAEMA. In an exemplary process, the solvent mixture is substantially Propylene Glycol (PG) plus NMP, DMF, or a combination of both in a weight ratio of about 25:75 to about 70: 30. The amount of solvent mixture is selected in view of the amount of intended polymerization agent such that the theoretical water content of the final polymer is from about 35% to about 60%.

The acid may be hydrochloric acid, methanesulfonic acid, sulfuric acid or phosphoric acid. A free radical inhibitor, such as monomethyl ether hydroquinone (MeHQ), may optionally be included in the solvent mixture.

The exemplary method may include reducing the temperature of the reaction solution to about room temperature. Reducing the temperature of the solution may include removing a heat source and allowing the reaction solution to equilibrate to room temperature; or actively cooling the reaction solution. In an exemplary method, a vinyl-based crosslinking agent and a polymerization initiator are dissolved in a reaction solution to provide a polymerization reaction solution. Exemplary methods may optionally include dissolving the vinyl-based monomer. The reactants are cured and allowed to polymerize to form the anion exchange polymer composition.

In an exemplary method: the vinyl-based crosslinking agent may independently be: divinylbenzene (DVB); ethylene Glycol Dimethacrylate (EGDMA); 1, 3-divinylimidazolidin-2-one (DVI); or N, N' -methylenebis (acrylamide) (MBA), the vinyl-based monomer may be: n-vinyl caprolactam (V-Cap); vinylbenzyl chloride (VBC); methacrylamide (MAA); or ethylvinylbenzene, and the polymerization initiator may be: trimethylbenzoyldiphenylphosphine oxide (TPO); 2,2' -azobis (2-methylpropionic acid) dimethyl ester (V-601); 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride (V-044); or 2,2' -azobis (2-methylpropionamidine) dihydrochloride (V-50).

The exemplary method can optionally include casting the polymerization reaction solution on a cloth backing prior to polymerizing the reactants to produce the anion exchange membrane. The cloth backing may be: polyacrylonitrile (PAN), polypropylene (PP), Polyethylene (PE) or polyethylene terephthalate (PET) cloth. The exemplary method can optionally include conditioning the anion exchange polymer composition.

In one particular example of this exemplary method, DMAPMA is dissolved in a solvent mixture, MSA is added, and the reaction mixture is heated to 70 ℃ to allow the DMAPMA to react with the MSA to protonate the tertiary amine in DMPAMA. CHDMDGE was added and the reaction mixture was heated to 78 ℃ to allow the protonated DMAPMA to react with CHDMDGE. The reaction mixture was cooled to room temperature. Divinyl benzene and a polymerization initiator are added, the reaction mixture is cast on a cloth backing, and the reaction mixture is cured.

In another specific example of an exemplary method, DMAPMA is dissolved in a solvent mixture. DBH or DBB is added and the reaction mixture is heated to 78 ℃ to allow DMAPMA to react with DBH or DBB. The reaction mixture was cooled to room temperature. Divinyl benzene and a polymerization initiator are added, the reaction mixture is cast on a cloth backing, and the reaction mixture is cured.

In another specific example of this exemplary method, DMAEMA is dissolved in a solvent mixture, MSA is added, and the reaction mixture is heated to 50 ℃ to allow the DMAEMA to react with the MSA to protonate the tertiary amine in the DMAEMA. CHDMDGE was added and the reaction mixture was maintained at 50 ℃ to allow the protonated DMAEMA to react with CHDMDGE. The reaction mixture was cooled to room temperature. Divinyl benzene and a polymerization initiator are added, the reaction mixture is cast on a cloth backing, and the reaction mixture is cured.

In another specific example of an exemplary method, DMAEMA is dissolved in a solvent mixture. DBH or DBB was added and the reaction mixture was heated to 50 ℃ to allow DMAEMA to react with DBH or DBB. The reaction mixture was cooled to room temperature. Divinyl benzene and a polymerization initiator are added, the reaction mixture is cast on a cloth backing, and the reaction mixture is cured.

Examples and comparative examples

Various exemplary methods according to the present disclosure are compared to other methods. The polymerization reaction mixtures in these experiments and comparative experiments were applied to woven or nonwoven fabrics made of polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride or polyethylene terephthalate to produce films.

A summary of the reactants and solvents used to form the polymerization reaction mixture is shown in the figure. The comparative experiment results in an anion exchange membrane having one or more undesirable physical properties.

Tables 1 and 2 show experiments in which the weight ratio of PG to NMP or DMF is from about 25:75 to about 70:30, and in which the theoretical water content is from about 35% to about 60%. Table 3 shows comparative experiments in which (a) the weight ratio of PG to NMP and/or DMF falls outside this range, and/or (b) the reaction lacks a non-ionic crosslinker.

All experiments in table 1 used NMP as the amide-based solvent. Experiments 1-16 used CHDMDGE as the dialkylating agent. Experiments 17 and 18 used Dibromohexane (DBH) as the dialkylating agent. DMAPMA and CHDMDGE or DBH form an ionic crosslinker in situ. Experiments 1-12, 17 and 18 of table 1 used DVB80 as the non-ionic crosslinker. Experiments 13-16 of table 1 used EGDMA as the non-ionic crosslinker.

All experiments in table 2 used DMF as the amide solvent, DBH as the dialkylating agent, and DVB80 as the non-ionic crosslinker. DMAPMA and DBH form an ionic crosslinker in situ.

Comparative experiments 1-6 in Table 3 used CHDMDGE as the dialkylating agent, V-Cap as the monomer, and no nonionic crosslinker. Comparative experiments 7-11 used DBH as the dialkylating agent; using Methacrylamide (MAA), V-Cap or VBC as monomers; and does not include a nonionic crosslinking agent. Comparative experiments 12-14 used DBH as the dialkylating agent and DVB80 as the non-ionic crosslinker, but did not use a mixture of PG and NMP or DMF from about 25:75 to about 70: 30. For the aprotic amide solvents in the comparative experiments, comparative experiment 1 used a 1:1 mixture of NMP and DMF; comparative experiments 2, 9 and 13 used NMP; while comparative experiments 4, 5, 7, 8, 10, 11 and 14 used DMF.

All experiments in tables 1-3 used TPO or V-601 as the initiator. MeHQ was used as a free radical inhibitor. DVB80 was 80% divinylbenzene and 20% ethylvinylbenzene. The moles of nonionic crosslinker and monomer in the table reflect this mixture.

Comparative experiments using 1-propanol as a solvent or as a co-solvent with PG or DMF (results not shown) resulted in anion exchange membranes having one or more undesirable physical properties.

Experiments 1-12, Table 1

MeHQ was dissolved in a solvent mixture of PG/NMP. DMAPMA was dissolved in the solvent mixture and MSA was added slowly enough that the temperature did not exceed 60 ℃. After addition of MSA, the temperature of the reaction mixture was raised to 70 ℃ for 30 minutes. CHDMDGE was added to the solvent mixture and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. DVB80, then TPO, was added to the reaction mixture. The resulting polymeric mixture was cast on PAN and/or PP cloth and sandwiched with mylar (mylar) and glass plates, followed by curing in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours.

Experiments 13-16, Table 1

MeHQ was dissolved in a solvent mixture of PG/NMP. DMAPMA was dissolved in the solvent mixture and MSA was added slowly enough that the temperature did not exceed 60 ℃. After addition of MSA, the temperature of the reaction mixture was raised to 70 ℃ for 30 minutes. CHDMDGE was added to the solvent mixture and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. EGDMA, then TPO, was added to the reaction mixture. The resulting polymeric mixture was cast on PAN and PP cloth and sandwiched with mylar and glass plates, followed by curing in an oven at 90 ℃ for 1 hour. The cured film was conditioned in a 1 n nacl solution for 24 hours.

Experiments 17-18, Table 1

MeHQ was dissolved in a solvent mixture of PG/NMP. DMAPMA was dissolved in the solvent mixture, DBH was added to the solvent mixture, and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. DVB80, then TPO, was added to the reaction mixture. The resulting polymeric mixture was cast on a PP cloth and sandwiched with a polyester film and a glass plate, followed by curing in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours.

Experiments 19-24, Table 2

MeHQ was dissolved in a solvent mixture of PG/DMF. DMAPMA was dissolved in the solvent mixture, DBH was added to the solvent mixture, and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. DVB80, then TPO, was added to the reaction mixture. The resulting polymerization mixture was cast on PAN, PP or polyester cloth and sandwiched with polyester film and glass plate, followed by curing in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours.

Comparative example 1, Table 3

DMAPMA was dissolved in a solvent mixture of DMF/NMP, CHDMDGE was added to the solvent mixture, and the temperature was raised to 76 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. V-Cap, then TPO, was added to the reaction mixture. The resulting polymerization mixture was cast on PAN. The resulting film was very soft.

Comparative example 2, Table 3

DMAPMA was dissolved in NMP and 33% HCl was added to the mixture at a rate such that the mixing temperature did not exceed 40 ℃, followed by CHDMDGE. Thereafter, the mixture was heated and polymerization was found to occur at about 45 ℃ prior to the addition of V-Cap and V601.

Comparative example 3, Table 3

DMAPMA was dissolved in PG and 33% HCl was added to the mixture at a rate such that the mixing temperature did not exceed 40 ℃, followed by CHDMDGE. Thereafter, the mixture was heated and polymerization was found to occur at about 70 ℃ prior to the addition of V-Cap and V601.

Comparative example 4, Table 3

DMAPMA was dissolved in DMF and 33% HCl was added to the mixture at a rate such that the mixing temperature did not exceed 40 ℃, followed by addition of CHDMDGE to the mixture. The reaction mixture was stirred for 1 hour and then cooled to room temperature. V-Cap, then V-601, was added to the reaction mixture. The resulting polymeric mixture was cast on PAN and PP cloth and sandwiched with mylar and glass plates, followed by curing in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours. The resulting film was soft.

Comparative experiment 5, Table 3

DMAPMA was dissolved in DMF and MSA was added slowly enough that the temperature did not exceed 60 ℃. After addition of MSA, the temperature of the reaction mixture was raised to 70 ℃ for 30 minutes. CHDMDGE was added to the solvent mixture and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. V-Cap, then V-601, was added to the reaction mixture. The resulting polymeric mixture was cast on PAN and PP cloth and sandwiched with mylar and glass plates, followed by curing in an oven at 90 ℃ for 1 hour. No polymerization was found.

Comparative experiment 6, Table 3

DMAPMA was dissolved in PG and MSA was added slowly enough that the temperature did not exceed 60 ℃. After addition of MSA, the temperature of the reaction mixture was raised to 70 ℃ for 30 minutes. CHDMDGE was added to the solvent mixture and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. V-Cap, then TPO, was added to the reaction mixture. The resulting polymeric mixture was cast on PAN and PP cloth and sandwiched with mylar and glass plates, followed by curing in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours. The resulting film was soft.

Comparative experiment 7, Table 3

DMAPMA was dissolved in a solvent mixture of PG and DMF, DBH was added to the solvent mixture, and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. Methacrylamide (MAA), then TPO, was added to the reaction mixture. The resulting polymeric mixture was cast on PP and polyester cloth, sandwiched with polyester film and glass plates, and then cured in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours. The resulting film was severely peeled off.

Comparative experiment 8, Table 3

DMAPMA was dissolved in a solvent mixture of PG and DMF, DBH was added to the solvent mixture, and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. V-Cap, then TPO, was added to the reaction mixture. The resulting polymeric mixture was cast on PP and polyester cloth, sandwiched with polyester film and glass plates, and then cured in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours. The resulting film was soft.

Comparative experiment 9, Table 3

DMAPMA was dissolved in a solvent mixture of PG and NMP, DBH was added to the solvent mixture, and the temperature was raised to 76 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. The monomer precipitated out at room temperature.

Comparative experiment 10, Table 3

DMAPMA was dissolved in a solvent mixture of PG and DMF, DBH and VBC were added to the solvent mixture, and the temperature was raised to 76 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. TPO was added to the reaction mixture. The resulting polymeric mixture was cast on a PP cloth, sandwiched with a polyester film and a glass plate, and then cured in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours. The resulting film was soft.

Comparative experiment 11, Table 3

DMAPMA was dissolved in DMF, DBH was added to the solvent mixture, and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. MAA, then TPO was added to the reaction mixture. The resulting polymerization mixture was cast on PAN, PP and polyester cloth, sandwiched with polyester film and glass plate, and subsequently cured in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours. The resulting film was severely peeled off and soft.

Comparative experiment 12, Table 3

DMAPMA was dissolved in PG, DBH and DVB80 were added to the solvent mixture, and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour, and the mixture was found to be cloudy.

Comparative experiment 13, Table 3

DMAPMA was dissolved in NMP and DBH and DVB80 were added to the solvent mixture. When the temperature rose to about 40 ℃, the reaction mixture solidified.

Comparative experiment 14, Table 3

DMAPMA was dissolved in DMF, DBH and DVB80 were added to the solvent mixture, and the temperature was raised to 78 ℃. The reaction mixture was stirred for 1 hour and then cooled to room temperature. TPO was added to the reaction mixture. The resulting polymeric mixture was cast on a PP cloth, sandwiched with a polyester film and a glass plate, and then cured in an oven at 90 ℃ for 1 hour. The solidified membrane was conditioned in a 1N NaCl solution for 24 hours. The resulting film had cracks.

In the previous description, for purposes of explanation, numerous details were set forth in order to provide a thorough understanding of the embodiments. However, it will be apparent to one skilled in the art that these specific details are not required. Thus, what has been described is merely illustrative of the application of the described embodiments and many modifications and variations are possible in light of the above teaching.

Since the above description provides embodiments, it will be appreciated that modifications and variations to the specific embodiments may be practiced by those skilled in the art. Accordingly, the scope of the claims should not be limited by the particular embodiments set forth herein but should be construed in a manner consistent with the specification as a whole.