CN103159966B - Cross-linking formulations for forming quaternary ammonium salts - Google Patents

Abstract

The present invention provides a quaternary ammonium salt-forming cross-linked formulation comprising: a swellable polymer having an amino group; a crosslinker, wherein the crosslinker has at least two halogen substituents, and the halogen substituents are not the same; and a solution, wherein the solution includes a solvent dissolving the swellable polymer having the amino group.

Description

Formation of crosslinked quaternary ammonium salts

【Technical field】

The present invention relates to a crosslinking formulation, and in particular to a crosslinking formulation forming a quaternary ammonium salt.

【current technology】

Major factories in the world are actively developing various desalination filter materials used in seawater, industrial water and wastewater. In addition to being able to efficiently treat salts in water, desalination filter materials also hope to reduce operating pressure, so that due to low energy consumption Reduce water treatment costs.

Some studies have used ionic polymers as desalination filter materials. This material can still have high flux under low pressure. However, in order to strengthen the mechanical strength of desalination filter materials, cross-linking agents are usually added to cross-link with ionic polymers. However, the type of cross-linking agent and the speed of the cross-linking reaction will affect the stability and quality of the desalination filter material.

In order to further improve the quality of the desalination filter material, the present invention proposes a cross-linking preparation, which includes a swellable polymer with amino groups, a cross-linking agent and a solution, and is obtained through a cross-linking reaction of the cross-linking preparation The quaternary ammonium salt can be used as a desalination filter material.

【Content of invention】

The invention provides a cross-linking preparation for forming a quaternary ammonium salt, comprising: a swellable polymer with an amino group; a cross-linking agent, wherein the cross-linking agent has at least two halogen substituents, and these halogen substituents are different; and a solution, wherein the solution includes a solvent for dissolving the amino group-bearing swellable polymer.

In order to make the above-mentioned and other purposes, features and advantages of the present invention more obvious and understandable, the preferred embodiments are specially cited below, and in conjunction with the accompanying drawings, the detailed description is as follows:

【Description of drawings】

1A-1D are a series of Fourier transform infrared spectra (FT-IR) to illustrate the degree of cross-linking of the embodiments of the present invention.

【Detailed ways】

The invention provides a cross-linking preparation for forming a quaternary ammonium salt, comprising: a swellable polymer with an amino group; a cross-linking agent, wherein the cross-linking agent has at least two halogen substituents, and these halogen substituents are different; and A solution, wherein the solution includes a solvent for dissolving the swellable polymer with amino groups, a protic solvent, a non-solvent or a combination of the above. The so-called "water-swellable polymer" here means that the polymer itself can swell by absorbing water, and the polymer can absorb a large amount of water without causing it to dissolve in water.

The above-mentioned swellable polymers with amino groups are polymerized from monomers of the following chemical formula (I-1), chemical formula (I-2) and chemical formula (I-3):

Wherein R ₁ is selected from phenylsulfonic acid group or alkanesulfonic acid group;

wherein _R2 is selected from

Wherein _R3 is selected from And the molar ratio of chemical formula (I-1), chemical formula (I-2) and chemical formula (I-3) is about 0.1-50:1-99:0.1-50.

The above-mentioned crosslinking agent is selected from polyhalogenated alkanes, polyhalogenated benzenes, polyhalogenated heterocycles or polyhalogenated macromolecules, such as compounds of chemical formula (II), chemical formula (III) or chemical formula (IV),

Wherein A is selected from C ₁ -C ₂₅ alkylene (alkylene), C ₆ -C ₂₅ arylene (arylene) or C ₇ -C ₂₅ aralkylene (aralkylene); R ₁ and R ₂ are each independently selected from from Cl, Br or I, and R ₁ ≠ R ₂ .

Wherein R ₃ , R ₄ , and R ₅ are each independently selected from substituted or unsubstituted aryl (aryl) or acrylic series (acrylic) structures, such as R ₆ , R ₉ are each independently selected from H or CH ₃ ; R ₇ , R ₈ are each independently selected from CH ₂ Cl, CH ₂ Br, CH ₂ I; R ₁₀ , R ₁₁ are each independently selected from H, CH _3. CH ₂ Cl, CH ₂ Br, CH ₂ I, wherein R ₇ ≠ R ₁₀ , R ₈ ≠ R ₁₁ , wherein a, b, and c are the number of repeating units, and a, b, and c are each independently 1 An integer of ~1000.

Wherein R ₁₂ and R ₁₃ are each independently selected from Cl, Br or I, and R ₁₂ ≠ R ₁₃ , wherein d, e are the number of repeating units, and d, e are each independently an integer ranging from 1 to 1000.

The weight ratio between the cross-linking agent and the swellable polymer with amino groups is 0.01-10, however, the ratio of the cross-linking agent is not limited thereto, and those skilled in the art can adjust it according to the requirements of practical applications. When the proportion of cross-linking agent is higher, the quaternary ammonium salt with denser structure can be obtained; when the proportion of cross-linking agent is lower, the quaternary ammonium salt with looser structure can be obtained.

It should be noted that the quaternary ammonium salt prepared by the cross-linking preparation of the present invention can be further formed into fibers through the spinning step. Since the spinning time may take several hours, if the cross-linking speed is too fast, it will cause viscosity. (Viscosity) rises rapidly, making the quaternary ammonium salt unable to carry out the spinning step. Therefore, the present invention slows down the speed of the crosslinking reaction by having different halogen substituents in the crosslinking agent.

In addition, the quaternary ammonium salt prepared by the cross-linking preparation of the present invention can be further formed on the carrier layer through a coating step to make a desalination filter material. However, if the cross-linking speed is too fast, it will cause viscosity ( viscosity) rises rapidly, which will make the thickness of the coating too thick or difficult to control the thickness. Therefore, the present invention regulates the speed of the crosslinking reaction through the different halogen substituents in the crosslinking agent.

In one embodiment, using the same polymer with different cross-linking agents, the experimental results found that at room temperature, the cross-linking agent using 1-bromo-6-chloro-hexane (1-bromo-6-chloro-hexane, BCH) The linking speed is slower than that of 1,6-dibromohexane (DBH), because bromine atoms are more likely to react with polymers than chlorine atoms to form bonds when bromine atoms and chlorine atoms undergo cross-linking reactions , Therefore, the crosslinking speed of the crosslinking agent with bromine atoms on both sides will be faster than that of bromine and chlorine on one side. It can be seen that the use of crosslinking agents with different halogens on both sides can indeed slow down the speed of the crosslinking reaction, so Those skilled in the art can add different types of cross-linking agents according to the needs of the actual process (spinning process or coating process) to regulate the speed of the cross-linking reaction.

The above-mentioned solvents for dissolving the swellable polymers with amino groups are highly polar solvents, such as N,N-dimethylacetamide (DMAc), dimethylformamide (Dimethylformamide, DMF), dimethyl sulfoxide (Dimethylsulfoxide , DMSO), alcohols, N-methylpyrrolidinone (N-methylpyrrolidinone, NMP), etc.

The aforementioned protic solvents include water, acids or alcohols. Acids include formic acid, acetic acid, citric acid, succinic acid, hydrochloric acid, or combinations thereof.

Alcohols can be monohydric alcohols or polyhydric alcohols, monohydric alcohols such as methanol (methanol), ethanol (ethanol), n-propanol (n-propanol), isopropanol (isopropanol), n-butanol (n-butanol) or n-pentanol Alcohol (n-pentanol).

Polyols include diols, polyols, ether diols, or combinations thereof. Glycols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexanediol, cyclohexanediol, cyclohexyldimethanol (Cyclohexyldimethanol, CHDM), octane glycol, neopentyl glycol (Neopentyl glycol, NPG ), trimethylpentanediol (Trimethylpentanediol, TMPD), benzenedimethanol, hydroquinone, cresylenol or bisphenol A (Bisphenol-A), polybutylene adipate [Poly(butanediol-co- adipate) glycol, PBA], polytetramethylene glycol (PTMEG), polypropylene glycol (Polypropylene glycol, PPG), polyethylene glycol (Polyethylene glycol, PEG).

Polyols include polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyacrylate polyols, such as glycerin, trimethylolpropane (Trimethylolpropane), pentaerythritol (Pentaerythritol ), glucinol.

Ether glycols include, for example, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.

The above-mentioned non-solvent refers to a solvent immiscible with the swellable macromolecule with an amino group. Since the swellable macromolecule with an amino group is an ionic polymer, the non-solvent is a low-polarity solvent, and the non-solvent includes tetrahydrofuran ( Tetrahydrofuran, THF), dichloromethane (dichloromethane, DCM), chloroform (chloroform), straight chain or branched chain alkanes (pentane, hexane (hexane), heptane (heptane)), benzene (benzene), Toluene or acetone, etc.

The weight ratio of the solvent for dissolving the swellable polymer with amino groups: protic solvent or non-solvent is about 9/1-5/5.

In one embodiment, the solvent for dissolving the swellable polymer with amino groups is N, N-dimethylacetamide (DMAc), and the protic solvent is ethanol (ethanol), and the mixing weight ratio of the former to the latter is 9 : 1.

In another embodiment, the solvent for dissolving the swellable polymer with amino groups is N, N-dimethylacetamide (DMAc), and the non-solvent is tetrahydrofuran (Tetrahydrofuran, THF), the mixing weight of the former and the latter The ratio is 5:5.

It should be noted that hydrogen bonds will be formed between the protic solvent and the swellable polymer with amino groups, which can slow down the crosslinking reaction. In addition, since the non-solvent is not compatible with the swellable polymer, the presence of the non-solvent will reduce the chance of collision between the cross-linking agent and the swellable polymer, thereby reducing the speed of the cross-linking reaction. It can be seen that those skilled in the art can mix one or more protic solvents or non-solvents according to the needs of the actual process, so as to control the required cross-linking reaction speed.

Furthermore, in one embodiment, the cross-linking preparation provided by the present invention begins to undergo a partial cross-linking reaction at room temperature (20-25° C.), and a heating step can be used to help the cross-linking reaction proceed. In another embodiment, the cross-linking preparation provided by the present invention requires a heating step to carry out the cross-linking reaction.

In summary, the cross-linking preparation provided by the present invention can be used to control the speed of the cross-linking reaction, so as to facilitate the subsequent processing of ionic polymers (such as spinning to form fibers, or coating on the carrier layer to form a coating layer), The fiber or coating layer obtained in the subsequent process can be heated again to completely cross-link the polymer and the cross-linking agent, and the resulting material can be used as a desalination filter material.

【Example】

Example 1 Synthetic Crosslinking Agent Chemical Structure (III): Poly(styrene-co-vinylbenzylhalide)copolymer

Take 2g/1g/1g of styrene (Styrene)/chloromethylstyrene (vinylbenzylchloride)/bromomethylstyrene (vinylbenzylbromide) respectively (the ratio of each monomer can be determined according to demand), and add 20ml tetrahydrofuran (THF), The reaction was carried out under nitrogen, and then the temperature was raised to 70° C., followed by the addition of the initiator benzoyl peroxide (benzoyl peroxide, BPO) solution (BPO solution: 0.04 g/5 ml THF), and the reaction was carried out at 70° C. for 3 hours. Then the product was settled with methanol, filtered and dried to obtain Poly(styrene-co-vinylbenzylhalide)copolymer.

Example 2 Synthetic Crosslinking Agent Chemical Structure (IV): Halide-methylatedPolysulfone (PSF-X)

3 g of polysulfone (molecular weight: 35,000) was mixed with 80 ml of chloroform, and heated to 50° C. under nitrogen to completely dissolve to form a mixed solution.

2g of formaldehyde (P-formaldehyde), 0.35g of tin tetrachloride (SnCl ₄ ), 4.3g of trimethylsilylchloride (SiMe ₃ Cl) and 5.9g of trimethylsilylbromide (SiMe ₃ Br) ( The proportion of SiMe ₃ Cl and SiMe ₃ Br (adjusted according to actual needs) was dissolved together in 30 ml of chloroform (chloroform), and then the above solution was added into the polysulfone solution and mixed together, and heated to reflux at 50° C. for 48 hours. After the reaction, methanol was added to precipitate the product, and finally a white solid Halide-methylated Polysulfone (PSF-X) was obtained.

Example 3 Synthesis of swellable polymer Poly(sodium styrenesulfate-co-4-vinylpyridine-co-styrene)

Take 230g sodium styrene sulfonate (sodium styrene sulfate), 460g 4-vinylpyridine (4-vinylpyridine), 230g styrene (styrene) (the ratio of each monomer can be adjusted according to the situation), 1150ml deionized water, 1150ml isopropanol (IPA) was stirred and dissolved, nitrogen gas was introduced, and the reaction was carried out at a constant temperature of 70° C. for 30 minutes to form a mixed solution.

Take 9.2g of potassium persulfate (potassium persulfate, KPS) and dissolve it in 230ml of deionized water, then slowly drop it into the above mixed solution, and the reaction is completed in 3 hours. The reacted polymer solution was settled with brine, dried, washed and purified to obtain milky white solid Poly(sodium styrenesulfate-co-4-vinylpyridine-co-styrene).

Embodiment 4 synthetic quaternary ammonium salt

The macromolecule of embodiment 3 is formulated in N, N-dimethylacetamide (DMAc) solvent, solid content is 20wt%, is added in proportion to 0.3 times (0.3 equiv. ) of the cross-linking agent 1-bromo-6 chlorohexane (1-bromo-6-chloro-hexane, BCH).

The above-mentioned appropriate amount of samples were taken for viscosity monitoring on a viscometer. The viscosity measurement and reaction temperature were both carried out at room temperature, and the changes in viscosity values were recorded at regular intervals. The experimental results are shown in Table 1.

Table 1

Comparative example 1

Experimental procedure, material, measuring method and implementation condition are the same as embodiment 4, only crosslinking agent is changed into 1,6-dibromohexane (1,6-dibromohexane, DBH) by BCH, and crosslinking agent equivalent number still maintains 0.3 equivalent. The experimental results are shown in Table 2.

From the experimental results in Table 1 and Table 2, it can be seen that compared with DBH, the viscosity of BCH rises much slower under the same experimental conditions.

Table 2

Embodiment 5 utilizes protic solvent or non-solvent to control cross-linking reaction speed

The polymers of Example 3 were prepared in the solvents shown in Table 3 (respectively N,N-dimethylacetamide (DMAc), N,N-dimethylacetamide and tetrahydrofuran (THF) mixed solvent , and a mixed solvent of N,N-dimethylacetamide and alcohol), wherein the solid content of the solution is fixed at 23.5wt%.

Add 1-bromo-6-chloro-hexane (1-bromo-6-chloro-hexane, BCH) cross-linking agent corresponding to 0.3 equivalents of polymer chain pyridine (pyridine) in proportion to the above-mentioned batches of solutions, and take an appropriate amount of samples in On-line viscosity monitoring was carried out on the viscometer, the temperature was set at 25°C, and the change of viscosity value was recorded every 0.5 hours. The experimental results are shown in Table 3.

It can be seen from the data in Table 3 that adding a protic solvent (such as alcohol) or a non-solvent (such as tetrahydrofuran) can indeed slow down the crosslinking reaction speed.

table 3

Example 6

Mix the swellable molecules of Example 3 with the polymers of Example 1 (crosslinking agent) in weight ratio (75:25, 60:40, 50:50 and 40:60), and prepare in N, N-di In the methylacetamide solvent, the polymer solid content is 20wt%.

After fully mixing the above solutions, apply the solution on the glass substrate, cross-link and harden at 130°C, and then confirm with FT-IR. The experimental results are shown in Table 5 and Figures 1A-1D ^. The characteristic absorption peak of FT-IR can confirm that the mixed solution has undergone cross-linking reaction.

table 5

Embodiment 3: the weight mixing ratio of embodiment 1 attached 75:25 1A 60:40 1B 50:50 1C 40:60 1D

Example 7

The implementation steps are the same as in Example 6, except that the polymer material is changed to the swellable macromolecule of Example 3 and Example 2 (crosslinking agent), and the mixing ratios are 70:30, 63:37 and 37:63, respectively, by 1638cm ^-1 The characteristic absorption peak of FT-IR can confirm that the mixed solution has undergone cross-linking reaction.

Although the present invention has been disclosed as above with several preferred embodiments, it is not intended to limit the present invention, and any skilled person in the technical field with common knowledge can make arbitrary decisions without departing from the spirit and scope of the present invention. Changes and modifications, so the protection scope of the present invention should be defined by the claims.

Claims (11)

1. a cross-linked formulations that forms quaternary ammonium salt, comprising:

With amino swellable polymer, wherein should be formed with the monomer polymerization of chemical formula (I-3) by following chemical formula (I-1), chemical formula (I-2) with amino swellable polymer:

wherein R ₁be selected from phenylbenzimidazole sulfonic acid base or alkyl group sulfonic group;

wherein R ₂be selected from

wherein R ₃be selected from and chemical formula (I-1), chemical formula (I-2) are 0.1-50: 1-99: 0.1-50 with the mol ratio of chemical formula (I-3);

Linking agent, wherein this linking agent has at least two halogenic substituents, and these halogenic substituents are not identical; And

Solution, wherein this solution comprises that dissolving is with the high molecular solvent of amino swellable.

2. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 1, wherein this linking agent is selected from chemical formula (II), chemical formula (III) or chemical formula (IV),

Wherein A is selected from C ₁-C ₂₅alkylidene group (alkylene), C ₆-C ₂₅arylidene (arylene) or C ₇-C ₂₅sub-aralkyl (aralkylene); R ₁, R ₂be selected from independently of one another Cl, Br or I, and R ₁≠ R ₂;

Wherein R ₃, R ₄, R ₅be selected from independently of one another

R ₆, R ₉be selected from independently of one another H or CH ₃;

R ₇, R ₈be selected from independently of one another CH ₂cl, CH ₂br, CH ₂i;

R ₁₀, R ₁₁be selected from independently of one another H, CH ₃, CH ₂cl, CH ₂br, CH ₂i, wherein R ₇≠ R ₁₀, R ₈≠ R ₁₁, the number that wherein a, b, c are repeating unit, and a, b, c are 1～1000 integer independently of one another;

Wherein R ₁₂, R ₁₃be selected from independently of one another Cl, Br or I, and R ₁₂≠ R ₁₃, the number that wherein d, e are repeating unit, and d, e are 1～1000 integer independently of one another.

3. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 1, wherein this solution also comprises protonic solvent or non-solvent.

4. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 3, wherein this dissolving is with the high molecular solvent of amino swellable: the part by weight of protonic solvent or non-solvent is 9/1-5/5.

5. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 3, wherein this protonic solvent comprises water, acids or alcohols.

6. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 5, wherein this acids comprises formic acid, acetic acid, citric acid, succsinic acid, hydrochloric acid or above-mentioned combination.

7. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 5, wherein this alcohols comprises monohydroxy-alcohol or polyvalent alcohol.

8. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 7, wherein this monohydroxy-alcohol comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohol or above-mentioned combination.

9. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 7, wherein this polyvalent alcohol comprises many alcohols, ether glycols or above-mentioned combination.

10. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 3, wherein this non-solvent comprises tetrahydrofuran (THF), methylene dichloride, trichloromethane, straight or branched alkanes, benzene, toluene, acetone or above-mentioned combination.

The cross-linked formulations of 11. formation quaternary ammonium salts as claimed in claim 1, wherein this linking agent account for this with the high molecular part by weight of amino swellable be 0.01-10 doubly.