A temperature-sensitive ion exchange resin based on an interpenetrating network and a preparation method thereof

Abstract

The present invention provides a thermosensitive ion exchange resin based on an interpenetrating network and a preparation method thereof. The thermosensitive polymer is incorporated into a resin structure through secondary interpenetration by utilizing the response of the hydrophilicity of the thermosensitive polymer to temperature, thereby preparing the thermosensitive ion exchange resin. The ion exchange capacity is 1.0 to 4.5 mmol / g, the water content is 30% to 90%, and the water content and expansion rate of the thermosensitive ion exchange resin vary greatly with temperature. At temperatures of 20°C and 50°C, the water content of the resin differs by 2 to 60%, and the expansion rate of the resin in pure water differs by 5 to 70%. The use of organic solvents in the resin regeneration process can be effectively reduced, the desorption rate of hydrophobic adsorbates of the resin can be increased, and thus the water treatment cost can be reduced.

Description

Technical Field

[0001] The invention belongs to the field of resin materials, and in particular relates to a temperature-sensitive ion exchange resin based on an interpenetrating network and a preparation method thereof. Background Art

[0002] In recent years, ion exchange resin materials have been widely used in the field of water treatment due to their advantages such as large adsorption capacity, fast adsorption rate and strong selectivity. However, adsorption saturated resins need to be chemically regenerated to restore the exchange capacity so that they can be used again. The regeneration of ion exchange resins is the reverse process of adsorption. The current regeneration is achieved by using chemical reagents, such as high-concentration salt solutions, inorganic base solutions, inorganic acid solutions, etc., to compete with the adsorbate for adsorption sites, so that the adsorbate on the resin is released. However, this regeneration method is only suitable for adsorbates adsorbed by the resin through electrostatic effects. When the hydrophobicity of the adsorbate is strong, there will be a strong hydrophobic interaction between the adsorbate and the resin. At this time, the regeneration effect of a single acid / base / salt solution is poor, and an organic solvent (such as methanol) needs to be added for regeneration. The use of organic solvents greatly increases the regeneration cost and brings safety management issues.

[0003] Regenerating the resin by changing the environmental conditions (such as increasing the temperature) can reduce the use of chemical reagents. However, current thermal regeneration is only applicable to amphoteric resins and is achieved through the interaction between the charges of the amphoterics. For example, patent CN113209949B discloses a heat-regenerated adsorbent doped with an ion exchange resin and a preparation method thereof, in which anion exchange and cation exchange resin particles are physically coated with a thermosensitive polymer matrix, and the functional reaction of the thermosensitive component to temperature is used to achieve the distance and proximity of the anion and cationic resin groups, thereby achieving the effect of low-temperature adsorption and high-temperature desorption. However, this method cannot promote the desorption of hydrophobic adsorbates on the resin, and the thermosensitive polymer matrix and the anion and cationic resin particles are only physically coated. Summary of the Invention

[0004] The purpose of the present invention is to provide a temperature-sensitive ion exchange resin based on an interpenetrating network on the basis of the existing technology.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned temperature-sensitive ion exchange resin based on the interpenetrating network.

[0006] The technical solutions of the present invention are as follows:

[0007] A temperature-sensitive ion exchange resin based on an interpenetrating network is prepared by the following steps:

[0008] (1) A low-crosslinked strong base anion exchange resin is mixed with reaction phase A, the mixed ion exchange resin is separated, and added to dispersed phase C. A polymerization reaction is carried out under the condition of excluding oxygen. After the reaction is completed, solid-liquid separation is carried out to obtain a "single interpenetrating resin";

[0009] (2) The "primary interpenetrating resin" obtained in step (1) is washed and dried, and then mixed with reaction phase B. The mixed "primary interpenetrating resin" is separated and added to dispersed phase D. The polymerization reaction is carried out again under the condition of excluding oxygen. After the reaction is completed, solid-liquid separation is carried out again to obtain "secondary interpenetrating resin". After washing and drying again, a temperature-sensitive ion exchange resin based on an interpenetrating network is obtained.

[0010] The present invention provides a thermosensitive ion exchange resin based on an interpenetrating network. The thermosensitive polymer is incorporated into the resin structure through secondary interpenetration by utilizing the response of the hydrophilicity of the thermosensitive polymer to temperature. The thermosensitive polymer is prepared by incorporating the thermosensitive polymer into the resin structure through secondary interpenetration. The ion exchange capacity is 1.0 to 4.5 mmol / g, the water content is 30 to 90%, and the water content and expansion rate of the thermosensitive ion exchange resin vary greatly with temperature. At temperatures of 20°C and 50°C, the water content of the resin differs by 2 to 60%, and the expansion rate of the resin in pure water differs by 5 to 70%. This can effectively reduce the use of organic solvents in the resin regeneration process, improve the desorption rate of hydrophobic adsorbates of the resin, and thus reduce water treatment costs.

[0011] The low-crosslinking strong base anion exchange resin used in the present invention has a crosslinking degree of 2% to 6%. For example, the low-crosslinking strong base anion exchange resin is 201×2 ion exchange resin, 201×4 ion exchange resin, 201×6 ion exchange resin, D201×2 ion exchange resin, D201×4 ion exchange resin, and D201×6 ion exchange resin.

[0012] In the present invention, the reaction phase A mentioned in step (1) comprises monomer A, crosslinking agent A and initiator A, wherein monomer A is one or more of acrylamide, acrylic acid, methacrylic acid, butyl methacrylate, N-acryloyloxysuccinimide or N-isopropylacrylamide; crosslinking agent A is one of N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate or divinylbenzene; and initiator A is one of ammonium persulfate, potassium persulfate, dibenzoyl peroxide or lauroyl peroxide.

[0013] Furthermore, the reaction phase A further comprises solvent A, which may be deionized water or ultrapure water. The mass ratio of monomer A to crosslinker A is 100:0.05 to 100:5, the mass ratio of monomer A to initiator A is 100:0.03 to 100:3, and the mass ratio of monomer A to solvent A is 1:0.5 to 1:20.

[0014] In the present invention, the dispersed phase C mentioned in step (1) is composed of solvent C or solvent C and emulsifier C, wherein solvent C is kerosene, liquid paraffin, normal alkane C 12 -C 18 or one of cyclohexane; emulsifier C is one or more of SP60, SP80, Tween60 or Tween80.

[0015] Furthermore, the mass ratio of solvent C to emulsifier C is 100:0 to 100:8.

[0016] In a preferred embodiment, the mass ratio of the low-crosslinked strong base anion exchange resin to the reaction phase A in step (1) is 1:0.5 to 1:15, preferably 1:1 to 1:10, and more preferably 1:1 to 1:8, without affecting the effects of the present invention. The mass ratio of the low-crosslinked strong base anion exchange resin to the dispersed phase C is 1:1 to 1:20, and preferably 1:1.5 to 1:15.

[0017] In one embodiment, in step (1), a low-crosslinking strong base anion exchange resin is mixed with reaction phase A for 0.5 to 12 hours, preferably 0.5 to 6 hours; the mixed exchange resin is separated and added to dispersed phase C, and a polymerization reaction is carried out under conditions of excluding oxygen, the polymerization reaction temperature is 40 to 80° C., and the reaction time is 3 to 12 hours.

[0018] In the present invention, the reaction phase B mentioned in step (1) comprises a monomer B, a crosslinking agent B and an initiator B, wherein the monomer B is one or more of acrylamide, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile or N,N-dimethylacrylamide; the crosslinking agent B is one of tetraethylene glycol dimethacrylate, N,N'-methylenebisacrylamide or ethylene glycol dimethacrylate; and the initiator B is one of ammonium persulfate, potassium persulfate, dibenzoyl peroxide or lauroyl peroxide.

[0019] Furthermore, the reaction phase B further comprises solvent B, which may be deionized water or ultrapure water. The mass ratio of monomer B to crosslinker B is 100:0.05 to 100:10, and the mass ratio of monomer B to initiator B is 100:0.1 to 100:5. The mass ratio of monomer B to solvent B is 1:0.5 to 1:50.

[0020] In the present invention, the dispersed phase D mentioned in step (1) is composed of solvent D or solvent D and emulsifier D, wherein solvent D is one of kerosene, liquid paraffin, dodecane, cyclohexane, n-heptane, n-octane or petroleum ether; and emulsifier D is one or more of SP60, SP80 or Tween80.

[0021] Furthermore, the mass ratio of the solvent D to the emulsifier D is 100:0 to 100:7.

[0022] In a preferred embodiment, in step (2), the mass ratio of the dried "primary interpenetrating resin" to the reaction phase B is 1:0.5 to 1:10, preferably 1:1 to 1:8.5, and more preferably 1:1.5 to 1:5; the mass ratio of the "primary interpenetrating resin" to the dispersed phase D is 1:1 to 1:10, preferably 1:1.5 to 1:8.5.

[0023] In one embodiment, in step (2), the dried "primary interpenetrating resin" is mixed with reaction phase B for a mixing time of 0.5 to 24 hours, preferably 1 to 16 hours; the mixed "primary interpenetrating resin" is separated and added to dispersed phase D, and polymerization is carried out again under the condition of excluding oxygen, the polymerization reaction temperature is 40 to 90°C, preferably 45 to 65°C; and the reaction time is 2 to 24 hours, preferably 4 to 16 hours.

[0024] Furthermore, the mass ratio of monomer A to monomer B in reaction phase A and reaction phase B is 1:0.1 to 1:10, preferably 1:0.5 to 1:5.

[0025] In the present invention, the "primary interpenetrating resin" obtained in step (1) is washed and then dried at 20-80° C. to a constant weight, and then the dried "primary interpenetrating resin" is mixed with reaction phase B.

[0026] Furthermore, the "secondary interpenetrating resin" obtained in step (2) is washed and dried at 20-60° C. to a constant weight, thereby obtaining a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0027] Adopt the technical scheme of the present invention, the advantages are as follows:

[0028] The present invention provides a thermosensitive ion exchange resin based on an interpenetrating network. The thermosensitive polymer is incorporated into a resin structure through secondary interpenetration by utilizing the response of the hydrophilicity and hydrophobicity of the thermosensitive polymer to temperature to prepare the thermosensitive ion exchange resin. The ion exchange capacity is 1.0 to 4.5 mmol / g, the water content is 30% to 90%, and the water content and expansion rate of the thermosensitive ion exchange resin vary greatly with temperature. At temperatures of 20°C and 50°C, the water content of the resin differs by 2 to 60%, and the expansion rate of the resin in pure water differs by 5 to 70%. The thermosensitive ion exchange resin can effectively reduce the use of organic solvents in the resin regeneration process, improve the desorption rate of hydrophobic adsorbates of the resin, and thus reduce water treatment costs. DETAILED DESCRIPTION

[0029] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0030] Example 1

[0031] 5 g of acrylamide, 5 g of acrylic acid, 0.005 g of N,N'-methylenebisacrylamide, and 0.003 g of ammonium persulfate were weighed and dissolved in 10 mL of deionized water as reaction phase A. 10 g of dry 201×4 ion exchange resin was weighed and mixed with reaction phase A for 0.5 h. The mixed ion exchange resin was separated and added to dispersed phase C consisting of 10 mL of n-dodecane and 0.4 g of SP80. The polymerization reaction was carried out at 50°C for 3 h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single interpenetrating resin".

[0032] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 25°C to constant weight; 10g of acrylic acid, 0.005g of N,N'-methylenebisacrylamide, and 0.01g of potassium persulfate were weighed and dissolved in 5mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 2h. The mixed "primary interpenetrating resin" was separated and added to dispersed phase D consisting of 20mL of n-dodecane and 0.05g of SP80. The polymerization reaction was carried out at 50°C for 2h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain a "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 25°C to constant weight to obtain a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0033] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 4.01 mmol / g. At 20°C, the water content of the resin is 47.0%, and the transition expansion rate in pure water is 38.1%; at 50°C, the water content of the resin is 78.9%, and the transition expansion rate in pure water is 89.8%.

[0034] Example 2

[0035] 10 g of acrylamide, 0.5 g of N,N'-methylenebisacrylamide, and 0.3 g of potassium persulfate were weighed and dissolved in 200 mL of deionized water as reaction phase A; 20 g of dry 201×6 ion exchange resin was weighed and mixed with reaction phase A for 1 hour; the mixed ion exchange resin was separated and added to dispersed phase C composed of 30 mL of n-hexadecane, 0.98 g of SP80, and 0.02 g of Tween80, and polymerization was carried out at 40°C for 5 hours under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single interpenetrating resin".

[0036] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 25°C to constant weight; 10 g of acrylic acid, 1 g of N,N'-methylenebisacrylamide and 0.5 g of ammonium persulfate were weighed and dissolved in 100 mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 4 hours. The mixed "primary interpenetrating resin" was separated and added to a dispersed phase D composed of 30 mL of n-hexadecane, 0.78 g of SP80 and 0.22 g of Tween80. The polymerization reaction was carried out at 40°C for 4 hours under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain a "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 25°C to constant weight to obtain a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0037] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 3.09 mmol / g. At 20°C, the water content of the resin is 47.5%, and the transition expansion rate in pure water is 17.8%; at 50°C, the water content of the resin is 66.9%, and the transition expansion rate in pure water is 42.5%.

[0038] Example 3

[0039] 1 g of N-isopropylacrylamide, 0.025 g of ethylene glycol dimethacrylate, and 0.01 g of lauroyl peroxide were weighed and dissolved in 25 mL of deionized water as reaction phase A. 10 g of dry 201×2 ion exchange resin was weighed and mixed with reaction phase A for 2 h. The mixed ion exchange resin was separated and added to dispersed phase C consisting of 30 mL of cyclohexane and 1 g of SP 60. The polymerization reaction was carried out at 50°C for 6 h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single-stage interpenetrating resin."

[0040] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 30°C to constant weight; 1 g of N,N-dimethylacrylamide, 0.05 g of ethylene glycol dimethacrylate, and 0.05 g of lauroyl peroxide were weighed and dissolved in 50 mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 6 hours. The mixed "primary interpenetrating resin" was separated and added to a dispersed phase D consisting of 30 mL of cyclohexane, 1 g of SP60, and 0.04 g of Tween60. The polymerization reaction was carried out at 40°C for 6 hours under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain a "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 30°C to constant weight, thereby obtaining a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0041] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 3.65 mmol / g. At 20°C, the water content of the resin is 48.1%, and the transition expansion rate in pure water is 18.2%; at 50°C, the water content of the resin is 58.5%, and the transition expansion rate in pure water is 24.7%.

[0042] Example 4

[0043] 7.5 g of acrylamide, 7.5 g of butyl methacrylate, 0.15 g of N,N'-methylenebisacrylamide and 0.2 g of ammonium persulfate were weighed and dissolved in 15 mL of deionized water as reaction phase A; 3 g of dry 201×2 ion exchange resin was weighed and mixed with reaction phase A for 3 h; the mixed ion exchange resin was separated and added to dispersed phase C composed of 40 mL of n-hexadecane, and polymerization was carried out at 40°C for 8 h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single interpenetrating resin".

[0044] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 40°C to constant weight; 7.5g of acrylic acid, 0.025g of N,N'-methylenebisacrylamide and 0.03g of ammonium persulfate were weighed and dissolved in 10mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 8h. The mixed "primary interpenetrating resin" was separated and added to dispersed phase D consisting of 40mL of cyclohexane. The polymerization reaction was carried out at 60°C for 8h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 40°C to constant weight to obtain a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0045] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 3.97 mmol / g. At 20°C, the water content of the resin is 39.9%, and the transition expansion rate in pure water is 27.6%; at 50°C, the water content of the resin is 55.4%, and the transition expansion rate in pure water is 33.0%.

[0046] Example 5

[0047] 10 g of N-acryloyloxysuccinimide, 0.05 g of divinylbenzene, and 0.2 g of dibenzoyl peroxide were weighed and dissolved in 100 mL of deionized water as reaction phase A; 10 g of dry 201×2 ion exchange resin was weighed and mixed with reaction phase A for 4 hours; the mixed ion exchange resin was separated and added to dispersed phase C composed of 50 mL of liquid paraffin, and polymerization was carried out at 60°C for 10 hours under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single interpenetrating resin".

[0048] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 50°C to constant weight; 1g of methacrylic acid, 0.01g of N,N'-methylenebisacrylamide and 0.01g of ammonium persulfate were weighed and dissolved in 10mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 10h. The mixed "primary interpenetrating resin" was separated and added to dispersed phase D composed of 50mL of liquid paraffin. The polymerization reaction was carried out at 60°C for 10h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 50°C to constant weight to obtain a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0049] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 2.45 mmol / g. At 20°C, the water content of the resin is 37.8%, and the transition expansion rate in pure water is 32.2%; at 50°C, the water content of the resin is 56.2%, and the transition expansion rate in pure water is 47.9%.

[0050] Example 6

[0051] 5 g of acrylamide, 0.05 g of N,N'-methylenebisacrylamide, and 0.08 g of ammonium persulfate were weighed and dissolved in 75 mL of deionized water as reaction phase A; 10 g of dry 201×2 ion exchange resin was weighed and mixed with reaction phase A for 4 h; the mixed ion exchange resin was separated and added to dispersed phase C composed of 60 mL of n-tetradecane, and polymerization was carried out at 60°C for 12 h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single interpenetrating resin".

[0052] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight; 5g of acrylonitrile, 0.05g of N,N'-methylenebisacrylamide and 0.08g of ammonium persulfate were weighed and dissolved in 75mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 10 hours, and the mixed "primary interpenetrating resin" was separated and added to a dispersed phase D composed of 60mL of liquid paraffin. The polymerization reaction was carried out at 70°C for 10 hours under the condition of excluding oxygen. After the reaction, solid-liquid separation was carried out to obtain a "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight to obtain a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0053] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 2.27 mmol / g. At 20°C, the water content of the resin is 41.1%, and the transition expansion rate in pure water is 21.8%; at 50°C, the water content of the resin is 49.6%, and the transition expansion rate in pure water is 31.9%.

[0054] Example 7

[0055] 1 g of acrylamide, 1 g of methacrylic acid, 0.01 g of N,N'-methylenebisacrylamide, and 0.01 g of ammonium persulfate were weighed and dissolved in 5 mL of deionized water as reaction phase A; 10 g of dry 201×2 ion exchange resin was weighed and mixed with reaction phase A for 5 h; the mixed ion exchange resin was separated and added to dispersed phase C consisting of 70 mL of kerosene, and polymerization was carried out at 70°C for 12 h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single interpenetrating resin".

[0056] The resulting "primary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight. 1g of acrylamide, 1g of methyl methacrylate, 0.02g of N,N'-methylenebisacrylamide, and 0.02g of ammonium persulfate were weighed and dissolved in 5mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 12 hours. The mixed "primary interpenetrating resin" was separated and added to dispersed phase D, consisting of 70mL of kerosene. Polymerization was carried out at 60°C for 14 hours in the absence of oxygen. After completion of the reaction, solid-liquid separation was performed to obtain the "secondary interpenetrating resin." The resulting "secondary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight, thus obtaining a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0057] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 2.69 mmol / g. At 20°C, the water content of the resin is 37.8%, and the transition expansion rate in pure water is 36.3%; at 50°C, the water content of the resin is 47.5%, and the transition expansion rate in pure water is 79.8%.

[0058] Example 8

[0059] 2 g of methacrylic acid, 0.5 g of butyl methacrylate, 0.05 g of N,N'-methylenebisacrylamide and 0.04 g of ammonium persulfate were weighed and dissolved in 15 mL of deionized water as reaction phase A; 10 g of dry D201×2 ion exchange resin was weighed and mixed with reaction phase A for 6 h. The mixed ion exchange resin was separated and added to dispersed phase C composed of 80 mL of kerosene. The polymerization reaction was carried out at 80°C for 6 h under the condition of excluding oxygen. After the reaction, solid-liquid separation was carried out to obtain "single interpenetrating resin".

[0060] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight; 7.5g of acrylamide, 5g of acrylic acid, 0.05g of N,N'-methylenebisacrylamide and 0.03g of ammonium persulfate were weighed and dissolved in 8mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 14h, the mixed "primary interpenetrating resin" was separated and added to a dispersed phase D consisting of 80mL of kerosene, and polymerization was carried out at 70°C for 18h under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain a "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight to obtain a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0061] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 3.76 mmol / g. At 20°C, the water content of the resin is 55.4%, and the transition expansion rate in pure water is 18.5%; at 50°C, the water content of the resin is 69.1%, and the transition expansion rate in pure water is 25.7%.

[0062] Example 9

[0063] 10 g of N-acryloyloxysuccinimide, 0.05 g of butyl methacrylate, 0.05 g of methacrylic acid, 0.05 g of N,N'-methylenebisacrylamide and 0.1 g of ammonium persulfate were weighed and dissolved in 50 mL of deionized water as reaction phase A; 10 g of dry D201×4 ion exchange resin was weighed and mixed with reaction phase A for 8 hours, the mixed ion exchange resin was separated and added to dispersed phase C consisting of 90 mL of petroleum ether, and polymerization was carried out at 40°C for 3 hours under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single interpenetrating resin".

[0064] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight; 1g of acrylic acid, 0.005g of N,N'-methylenebisacrylamide and 0.01g of ammonium persulfate were weighed and dissolved in 25mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 18h, and the mixed "primary interpenetrating resin" was separated and added to a dispersed phase D consisting of 90mL of n-heptane. The polymerization reaction was carried out at 50°C for 24h under the condition of excluding oxygen. After the reaction, solid-liquid separation was carried out to obtain a "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 50°C to constant weight to obtain a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0065] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 3.48 mmol / g. At 20°C, the water content of the resin is 60.7%, and the transition expansion rate in pure water is 46.6%; at 50°C, the water content of the resin is 72.3%, and the transition expansion rate in pure water is 53.5%.

[0066] Example 10

[0067] 10 g of N-acryloyloxysuccinimide, 0.4 g of N,N'-methylenebisacrylamide, and 0.3 g of ammonium persulfate were weighed and dissolved in 130 mL of deionized water as reaction phase A; 10 g of dry D201×6 ion exchange resin was weighed and mixed with reaction phase A for 12 hours; the mixed ion exchange resin was separated and added to dispersed phase C consisting of 100 mL of petroleum ether, and polymerization was carried out at 50°C for 5 hours under oxygen exclusion conditions. After the reaction, solid-liquid separation was performed to obtain "single interpenetrating resin".

[0068] The obtained "primary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight; 5 g of N-acryloyloxysuccinimide, 0.05 g of N,N'-methylenebisacrylamide and 0.05 g of ammonium persulfate were weighed and dissolved in 90 mL of deionized water as reaction phase B. The dried "primary interpenetrating resin" was mixed with reaction phase B for 24 hours. The mixed "primary interpenetrating resin" was separated and added to a dispersed phase D composed of 100 mL of n-octane. The polymerization reaction was carried out at 90°C for 24 hours under the condition of excluding oxygen. After the reaction, solid-liquid separation was carried out to obtain a "secondary interpenetrating resin". The obtained "secondary interpenetrating resin" was washed with deionized water and dried at 60°C to constant weight to obtain a temperature-sensitive ion exchange resin based on an interpenetrating network.

[0069] The obtained thermosensitive ion exchange resin based on the interpenetrating network has an ion exchange capacity of 3.54 mmol / g. At 20°C, the water content of the resin is 58.3%, and the transition expansion rate in pure water is 32.3%; at 50°C, the water content of the resin is 71.5%, and the transition expansion rate in pure water is 80.8%.

[0070] Table 1 Ion exchange capacity of the temperature-sensitive ion exchange resin in the embodiment and the water content and transition expansion ratio at different temperatures

[0071]

[0072] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that it is still possible to modify the technical solutions described in the aforementioned embodiments, or to make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A thermosensitive ion exchange resin based on an interpenetrating network, characterized in that: It is made by the following steps: (1) A low-crosslinked strong base anion exchange resin is mixed with the reaction phase A, the mixed ion exchange resin is separated and added to the dispersed phase C, and a polymerization reaction is carried out under the condition of excluding oxygen. After the reaction is completed, solid-liquid separation is carried out to obtain a "single interpenetrating resin"; The reaction phase A comprises monomer A, crosslinking agent A and initiator A, wherein the monomer A is one or more of acrylamide, acrylic acid, methacrylic acid, butyl methacrylate, N-acryloyloxysuccinimide or N-isopropylacrylamide; the crosslinking agent A is one of N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate or divinylbenzene; and the initiator A is one of ammonium persulfate, potassium persulfate, dibenzoyl peroxide or lauroyl peroxide; (2) The "primary interpenetrating resin" obtained in step (1) is washed and dried, and then mixed with reaction phase B. The mixed "primary interpenetrating resin" is separated and added to dispersed phase D. The polymerization reaction is carried out again under the condition of excluding oxygen. After the reaction is completed, solid-liquid separation is carried out again to obtain "secondary interpenetrating resin". After washing and drying again, a temperature-sensitive ion exchange resin based on an interpenetrating network is obtained; The reaction phase B comprises a monomer B, a crosslinker B and an initiator B, wherein the monomer B is one or more of acrylamide, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile or N,N-dimethylacrylamide; the crosslinker B is one of tetraethylene glycol dimethacrylate, N,N'-methylenebisacrylamide or ethylene glycol dimethacrylate; and the initiator B is one of ammonium persulfate, potassium persulfate, dibenzoyl peroxide or lauroyl peroxide.

2. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that The ion exchange capacity of the thermosensitive ion exchange resin is 1.0~4.5 mmol / g, and the water content is 30%~90%; the water content and expansion rate of the thermosensitive ion exchange resin vary greatly with temperature. At temperatures of 20°C and 50°C, the water content of the thermosensitive ion exchange resin differs by 2~60%, and the expansion rate in pure water differs by 5~70%.

3. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that The mass ratio of the monomer A to the crosslinking agent A is 100:0.05 to 100:5; the mass ratio of the monomer A to the initiator A is 100:0.03 to 100:

3.

4. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that In step (1), the dispersed phase C is composed of solvent C or solvent C and emulsifier C, wherein the solvent C is kerosene, liquid paraffin, normal alkane C 12 -C 18 or one of cyclohexane; the emulsifier C is one or more of SP60, SP80, Tween60 or Tween80; the mass ratio of the solvent C to the emulsifier C is 100:0~100:

8.

5. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that In step (1), the mass ratio of the low-crosslinking strong-base anion exchange resin to the reaction phase A is 1:0.5-1:15; the mass ratio of the low-crosslinking strong-base anion exchange resin to the dispersed phase C is 1:1-1:

20.

6. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 5, characterized in that In step (1), the mass ratio of the low-crosslinking strong-base anion exchange resin to the reaction phase A is 1:1-1:10; the mass ratio of the low-crosslinking strong-base anion exchange resin to the dispersed phase C is 1:1.5-1:

15.

7. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 6, characterized in that In step (1), the mass ratio of the low-crosslinking strong base anion exchange resin to the reaction phase A is 1:1 to 1:

8.

8. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that In step (1), the mixing time is 0.5 to 12 h; the polymerization temperature is 40 to 80° C., and the reaction time is 3 to 12 h.

9. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 8, characterized in that In step (1), the mixing time is 0.5 to 6 hours.

10. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that: The mass ratio of the monomer B to the crosslinking agent B is 100:0.05 to 100:10, and the mass ratio of the monomer B to the initiator B is 100:0.1 to 100:

5.

11. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that: In step (2), the dispersed phase D is composed of a solvent D or a solvent D and an emulsifier D, wherein the solvent D is one of kerosene, liquid paraffin, dodecane, cyclohexane, n-heptane, n-octane or petroleum ether; the emulsifier D is one or more of SP60, SP80 or Tween80; and the mass ratio of the solvent D to the emulsifier D is 100:0 to 100:

7.

12. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that: In step (2), the mass ratio of the dried "primary interpenetrating resin" to the reaction phase B is 1:0.5 to 1:10; the mass ratio of the "primary interpenetrating resin" to the dispersed phase D is 1:1 to 1:

10.

13. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 12, characterized in that: In step (2), the mass ratio of the dried "primary interpenetrating resin" to the reaction phase B is 1:1 to 1:8.5; the mass ratio of the "primary interpenetrating resin" to the dispersed phase D is 1:1.5 to 1:8.

5.

14. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 13, characterized in that: In step (2), the mass ratio of the dried "primary interpenetrating resin" to the reaction phase B is 1:1.5 to 1:

5.

15. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 1, characterized in that: In step (2), the mixing time is 0.5 to 24 h; the polymerization temperature is 40 to 90° C.; and the reaction time is 2 to 24 h.

16. The thermosensitive ion exchange resin based on an interpenetrating network according to claim 15, characterized in that: In step (2), the mixing time is 1 to 16 h; the polymerization temperature is 45 to 65° C.; and the reaction time is 4 to 16 h.

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