阅读说明：本技术 一种去除水垢的季铵型树脂及其合成方法与应用 (Scale-removing quaternary ammonium resin and synthesis method and application thereof ) 是由 李爱民 张怀成 施鹏 双陈冬 季荣 丁新春 曹勋 于 2020-05-08 设计创作，主要内容包括：本发明公开了一种去除水垢的季铵型树脂及其合成方法与应用,属于树脂技术领域。本发明以苯乙烯树脂或丙烯酸或氯乙烯树脂或其共聚骨架树脂白球为树脂基体,采用先胺化、再烷基化反应或者采用季铵化反应,接枝合适的季铵基团,得到新型季铵盐改性强碱阴离子交换树脂；本发明的树脂直接以结合的氯离子优先、高效地交换去除水体中的碳酸氢根和碳酸根,从而减少碳酸钙、镁沉淀的生成,减少水垢,同时保留水体中人体必需的钙、镁离子等健康元素。(The invention discloses a quaternary ammonium type resin for removing water scale, a synthetic method and application thereof, and belongs to the technical field of resins. The invention takes styrene resin or acrylic acid or vinyl chloride resin or copolymerization skeleton resin white balls thereof as a resin matrix, adopts amination and alkylation reaction or quaternization reaction, and grafts proper quaternary ammonium groups to obtain novel quaternary ammonium salt modified strong base anion exchange resin; the resin directly and efficiently exchanges and removes bicarbonate radical and carbonate radical in the water body by the combined chloride ions, thereby reducing the generation of calcium carbonate and magnesium precipitate, reducing water scale, and simultaneously retaining health elements such as calcium ions, magnesium ions and the like necessary for human bodies in the water body.)

1. A quaternary ammonium type resin for removing scale, characterized in that: the basic structure of the resin is a formula (I) or a formula (II),

wherein, the Y is₁And Y₂Is a resin matrix, and A_XQuaternary ammonium group with main carbon chain containing 5-15 carbon atoms.

2. The scale-removing quaternary ammonium resin according to claim 1, wherein: said Y is₁The structural formula (b) includes one or both of formula (101) and formula (102):

Y₂the structural formula (b) includes one or both of formula (103) and formula (104):

wherein, R is₀、R₁、R₂And R₃Are respectively one of H or alkyl, and R₀、R₁、R₂And R₃The number of carbon atoms is 0-30; m, n, g and k are the number of the repeating units, and the numerical value ranges from 500 to 5000; the number of carbon atoms of t, p, q and w is 1-30.

3. The scale-removing quaternary ammonium resin according to claim 1, wherein: a is described_XIs one or two of formula (201) and formula (202):

4. the quaternary ammonium type resin for removing scale according to claim 3, wherein: the R is₄、R₅、R₆、R₇And R₈Are respectively one of H or alkyl, and R₄、R₅、R₆、R₇And R₈The number of carbon atoms is 0-20; x^-Is Cl^-、Br^-、I^-、I₃ ^-、I₅ ^-、I₇ ^-、OH^-、SO₄ ^2-、HCO₃ ^-、CO₃ ^2-、PO₄ ^3-Any one of the above; the value range of h is 1-30.

5. A preparation method of quaternary ammonium resin with a formula (I) comprises the steps of adding resin white balls and an amination reagent, stirring, and carrying out amination reaction to obtain aminated resin; then adding the aminated resin and an alkylating reagent, stirring, and carrying out quaternization reaction to obtain quaternary ammonium resin; wherein the mass ratio of the resin white balls to the amination reagent is 0.2: 1-4: 1, the mass ratio of the amination resin to the alkylation reagent is 0.2: 1-6: 1, and the basic structure of the resin white balls is one or two of formula (301) or formula (302):

wherein, R is₀、R₁And R₁₁Are respectively one of H or alkyl, and R₀、R₁And R₁₁The number of carbon atoms is 0-30; m and n are the number of the repeating units, and the numerical value ranges from 500 to 5000.

6. The method of claim 5, wherein said amination reagent is selected from one or more of the following: n, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N-dimethylbutylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ' -tetramethylpropylenediamine, N, N, N ', N ' -tetramethylbutylenediamine, N, N, N ', N ' -tetramethylpentylenediamine, N, N, N ', N ' -tetramethylhexamethylenediamine, N, N, N ', N ' -tetraethylethylenediamine, N, N ', N ' -tetraethylpropylenediamine, N, N, N ', N ' -tetraethylbutylenediamine, N, N ', n ' -tetramethylpentanediamine or N, N, N ', N ' -tetramethylhexanediamine.

7. The method for preparing the quaternary ammonium resin having the formula (I) according to claim 5, wherein the alkylating agent is a monohaloalkane or a dihaloalkane, and the basic structure of the alkylating agent is one or both of the formula (303) or the formula (304):

wherein, R is₉And R₁₀Are respectively one of H or alkyl, and R₉And R₁₀The number of carbon atoms is 1-20; x is Cl, Br or I.

8. A preparation method of quaternary ammonium resin with formula (II) comprises adding resin white ball and tertiary amine hydrochloride, stirring, and performing quaternization reaction to obtain quaternary ammonium resin; wherein the mass ratio of the resin white balls to the tertiary amine hydrochloride is 0.2: 1-6: 1, and the basic structure of the resin white balls is one or two of formula (401) or formula (402):

wherein, R is₂And R₃Are respectively one of H or alkyl, and R₂And R₃The number of carbon atoms is 0-30; g and k are the number of the repeating units, and the numerical value ranges from 500 to 5000; the numerical ranges of q and w are 1-30.

9. The method for preparing the quaternary ammonium resin having the formula (II) according to claim 8, wherein the basic structure of the tertiary amine hydrochloride is one or both of the formula (403) or the formula (404):

wherein, R is₄、R₅、R₆And R₇Are respectively one of H or alkyl, and R₄、R₅、R₆And R₇The number of carbon atoms is 0-20; x is Cl, Br, I; the value range of h is 1-30.

10. The application of quaternary ammonium resin in water treatment is characterized in that: removing bicarbonate and carbonate in a water body by adsorption by using the quaternary ammonium resin for removing scale according to any one of claims 1 to 4, or the quaternary ammonium resin prepared by the method for preparing quaternary ammonium resin according to any one of claims 5 to 7, or the quaternary ammonium resin prepared by the method for preparing quaternary ammonium resin according to any one of claims 8 to 9, thereby removing scale.

Technical Field

The invention belongs to the technical field of resin, and particularly relates to scale-removing quaternary ammonium resin and a synthesis method and application thereof.

Background

Natural bodies of water or tap water contain large amounts of dissolved electrolytes in ionic form, e.g. Ca²⁺、Mg²⁺、Fe³⁺Isocation, and F^-、Cl^-、Br^-、I^-、NO₃ ^-、HCO₃ ^-、SO₄ ^2-、CO₃ ^2-And (4) plasma. Ca being among these ions²⁺、Mg²⁺、HCO₃ ^-、CO₃ ^2-The water is an important component forming a water quality detection index of "hardness", and is also the largest source of scale generation, and water having a hardness of 8 or more is generally called hard water (1 ═ 10mg/L in terms of calcium oxide). If the hardness of the water is too high, white surface froth or kettle bottom precipitation can occur after boiling, people feel uncomfortable, gastrointestinal dysfunction is easy to cause after drinking, and the water is not suitable for cooking, tea making, washing, bean curd making and the like. In addition, hard water is prone to form scale in water heaters, hot water kettles or boilers, which not only reduces heat transfer efficiency and wavesThe fuel is consumed, and the generated water scale easily blocks the pipeline to form potential safety hazard.

However, the recommended hardness of drinking water is 8-16 degrees, and moderately hard water has a protective effect on some diseases, mainly due to the presence of calcium and magnesium ions. Studies by the National institute of Research Council of the united kingdom have shown that calcium dissolved in water is most readily absorbed by the human body. And soft water when used for cooking removes a significant proportion of the various "protective" nutrients in food, compared to hard water (macroscopia, joker, water hardness and health, beverage industry, 520 (1999): 7-9). In conclusion, compared with "hard water" or "soft water", drinking water with proper hardness is the most healthy, and calcium, magnesium ions and the like contained in the drinking water are indispensable nutrient elements for human bodies.

Boiling, the simplest method for removing hardness, produces precipitates that remove most of the healthy elements such as calcium and magnesium ions. The distillation method can also be adopted to soften water, but the distillation method has high energy consumption and low efficiency; in addition, the hardness can be removed by RO membrane, electrodialysis, electrode method, etc., but these methods involve complicated equipment, inconvenient use, high electricity and water consumption, and high cost, such as patent application publication No. CN206872580U, patent application publication nos. CN104291451A, CN107840487A, and CN 101353191A.

A common ion exchange process for softening water features that the H-type cation exchange resin is used to exchange the cations in water to release H⁺With HCO in water₃ ^-Or CO₃ ^2-Formation of CO₂(ii) a Blowing CO with a blower₂Blowing off; then the obtained product is connected into OH type anion exchange resin, and the released OH^-With surplus H⁺Are combined into H₂And O. This process requires the regeneration of the resin with acid and alkali consumption, is complicated and has a certain safety risk, and also removes the healthy elements such as calcium and magnesium ions, as described in patent application publication No. CN 109264896A. The other scheme is that the negative and positive exchange resins are reversely connected: weak base anion resin releasing OH^-With HCO₃ ^-Formation of CO₃ ^2-With Ca in the raw water²⁺、Mg²⁺Formation of CaCO₃Or MgCO₃Precipitating; removing the precipitate by filtration; followed by cationic resin, liberating H⁺Neutralizing excess OH^-As described in patent application publication No. CN 101979329A. The scheme reduces the consumption of alkali in the regeneration process; the carbon removing process can be selectively adopted, the process is simplified, but OH of the process is^-Exchange with a large amount of anions such as chloride ions, nitrate radicals and the like in the water body, and HCO in the water body₃ ^-The molar quantity of the catalyst is far more than that of calcium and magnesium ions, and the practical effect and cost of the method are to be examined. In addition, water softening is also carried out by exchanging with Na type cation resin, which releases sodium ions to exchange and remove calcium and magnesium ions, such as patent application publication No. CN205398302U and patent application publication No. CN 96113019A. In the process, the introduction of sodium ions can increase the burden of blood pressure and easily cause cerebrovascular diseases, cardiovascular diseases, hypertension and the like; on the other hand, the positive resin takes sodium chloride as a regenerant, so that the positive resin is easily polluted by iron, so that the iron of the resin is poisoned, an exchange pore channel is blocked, the exchange capacity and the regeneration capacity are reduced, and the consumption of the regenerant and cleaning water is increased.

In conclusion, the existing method for softening water by adopting anion and cation exchange resins has the disadvantages of complex process and high cost, the regenerant is acid and alkali, the safety risk exists, the disposal and discharge difficulty of the regenerated waste liquid is high, particularly, sodium ions are introduced into the sodium cation resin method, the burden of blood pressure and the health risk are increased, iron poisoning is easy to occur, and the service life is shortened. In addition, the existing water softening treatment methods can remove healthy elements such as calcium ions and magnesium ions in water bodies, and cannot meet the current health requirements of drinking water.

Disclosure of Invention

1. Problems to be solved

Aiming at the problems of complex process, poor treatment effect, high cost and the like of softened water treatment by adopting resin in the prior art, the invention provides scale-removing quaternary ammonium resin and a synthesis method and application thereof. The invention takes styrene resin or acrylic acid or vinyl chloride resin or copolymerization skeleton resin white balls thereof as a resin matrix, adopts amination and alkylation reaction or quaternization reaction, and grafts proper quaternary ammonium groups to obtain novel quaternary ammonium salt modified strong base anion exchange resin; the resin directly and efficiently exchanges and removes bicarbonate radical and carbonate radical in the water body by the combined chloride ions, reduces the generation of calcium carbonate and magnesium precipitate, thereby reducing scale and simultaneously retaining the health elements such as calcium ions, magnesium ions and the like necessary for human bodies in the water body.

2. Technical scheme

In order to solve the problems, the technical scheme adopted by the invention is as follows:

the invention relates to a quaternary ammonium resin (namely quaternary ammonium salt modified resin) for removing scale, wherein the basic structure of the resin is shown in formula (I) or formula (II),

wherein, the Y is₁And Y₂Is a resin matrix, generally a resin white sphere; and A is_XQuaternary ammonium group with main carbon chain containing 5-15 carbon atoms,

further, A is_XThe main carbon chain is a quaternary ammonium group having 5 to 15 carbon atoms, preferably 5 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and most preferably 8 to 10 carbon atoms.

Further, said Y is₁The structural formula (b) includes one or both of formula (101) and formula (102):

Y₂the structural formula (b) includes one or both of formula (103) and formula (104):

wherein, in the structural formulaRepresents and the structure and A_XConnecting;

and wherein R is₀、R₁、R₂And R₃Are respectively one of H or alkyl, and R₀、R₁、R₂And R₃The number of carbon atoms is 0-30; m, n, g and k are the number of the repeating units, and the numerical value ranges from 500 to 5000; the number of carbon atoms of t, p, q and w is 1-30.

When R is₀、R₁、R₂And R₃When it is a hydrocarbon group, R₀、R₁、R₂And R₃The number of carbon atoms of (A) is preferably 1 to 20, more preferably 1 to 15, most preferably 1 to 10; m, n, g and k are preferably 500-4000, and more preferably 2000-3000; the number of carbon atoms of t, p, q and w is preferably 1 to 20, more preferably 1 to 10.

Further, the particle size of the scale-removed quaternary ammonium resin is 10-2000 μm, the degree of crosslinking is 1-40%, the exchange capacity of strong base is 0.5-10.0 mmol/g, and the contact angle is 90.0 +/-0.0-180.0 +/-0.0 degrees.

Further, the particle size of the scale-removed quaternary ammonium resin is preferably 30 to 2000 μm, more preferably 30 to 1000 μm, further preferably 30 to 800 μm, and most preferably 50 to 400 μm; the crosslinking degree is preferably 5 to 40%, more preferably 10 to 40%, most preferably 10 to 30%; the exchange capacity of the strong base is preferably 1.0-8.0 mmol/g, more preferably 1.0-6.0 mmol/g, and most preferably 3.0-6.0 mmol/g; the contact angle is preferably 100.0 + -0.0-180.0 + -0.0 deg., more preferably 100.0 + -0.0-160.0 + -0.0 deg., most preferably 120.0 + -0.0-160.0 + -0.0 deg..

Further, the particle size of the scale-removed quaternary ammonium resin is 50-400 μm, the degree of crosslinking is 10-30%, the exchange capacity of strong base is 3.0-6.0 mmol/g, and the contact angle is 120.0 +/-0.0-160.0 +/-0.0 degrees.

Further, A is_XIs one or two of formula (201) and formula (202):

wherein, the above structureIn the formulaDenotes and the structure and Y₁Or Y₂Are connected.

Further, said R₄、R₅、R₆、R₇And R₈Are respectively one of H or alkyl, and R₄、R₅、R₆、R₇And R₈The number of carbon atoms is 0-20; x^-Is Cl^-、Br^-、I^-、I₃ ^-、I₅ ^-、I₇ ^-、OH^-、SO₄ ^2-、HCO₃ ^-、CO₃ ^2-、PO₄ ^3-Any one of the above; the value range of h is 1-30.

The preparation method of the quaternary ammonium resin with the formula (I) comprises the steps of adding resin white balls/chlorine balls and an amination reagent, stirring, and carrying out amination reaction to obtain aminated resin; then adding the aminated resin and an alkylating reagent, stirring, and carrying out quaternization reaction to obtain quaternary ammonium resin; wherein the mass ratio of the resin white balls to the amination reagent is 0.2: 1-4: 1, the mass ratio of the amination resin to the alkylation reagent is 0.2: 1-6: 1, and the basic structure of the resin white balls is one or two of formula (301) or formula (302):

wherein, R is₀、R₁And R₁₁Are respectively one of H or alkyl, and R₀、R₁And R₁₁The number of carbon atoms is 0-30; m and n are the number of the repeating units, and the numerical value ranges from 500 to 5000.

Further, the amination reagent is selected from one or more of the following: n, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N-dimethylbutylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ' -tetramethylpropylenediamine, N, N, N ', N ' -tetramethylbutylenediamine, N, N, N ', N ' -tetramethylpentylenediamine, N, N, N ', N ' -tetramethylhexamethylenediamine, N, N, N ', N ' -tetraethylethylenediamine, N, N ', N ' -tetraethylpropylenediamine, N, N, N ', N ' -tetraethylbutylenediamine, N, N ', n ' -tetramethylpentanediamine or N, N, N ', N ' -tetramethylhexanediamine.

Further, the alkylating agent is a monohaloalkane or dihaloalkane, and the basic structure of the alkylating agent is one or both of formula (303) or formula (304):

wherein, R is₉And R₁₀Are respectively one of H or alkyl, and R₉And R₁₀The number of carbon atoms is 1-20; x is Cl, Br or I.

The preparation method of the quaternary ammonium resin with the formula (II) comprises the steps of adding resin white balls and tertiary amine hydrochloride, stirring, and carrying out quaternization reaction to obtain the quaternary ammonium resin; wherein the mass ratio of the resin white balls to the tertiary amine hydrochloride is 0.2: 1-6: 1, and the basic structure of the resin white balls is one or two of formula (401) or formula (402):

wherein, R is₂And R₃Are respectively one of H or alkyl, and R₂And R₃The number of carbon atoms is 0-30; g and k are the number of the repeating units, and the numerical value ranges from 500 to 5000; the numerical ranges of q and w are 1-30.

Further, the basic structure of the tertiary amine hydrochloride is one or two of formula (403) or formula (404):

wherein, R is₄、R₅、R₆And R₇Are respectively one of H or alkyl, and R₄、R₅、R₆And R₇The number of carbon atoms is 0-20; x is Cl, Br, I; the value range of h is 1-30.

The quaternary ammonium resin for removing the scale is adopted or the quaternary ammonium resin prepared by the preparation method of the quaternary ammonium resin is used for adsorbing and removing bicarbonate radical and carbonate radical in a water body, so that the scale is removed.

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that:

(1) the quaternary ammonium resin for removing the water scale is different from the traditional anion-cation exchange resin which needs two-step ion exchange, and can directly remove bicarbonate radical and carbonate radical in a water body by the chloride ion exchange combined on the resin by adopting a one-step exchange method, so that the generation of calcium carbonate and magnesium carbonate is reduced, and the generation of the water scale is reduced; and different from the traditional sodium type cation resin, the hardness is removed, and simultaneously, sodium ions are introduced, so that the burden of blood pressure is not increased, and health risks are not introduced;

(2) according to the preparation method of the scale-removing quaternary ammonium resin, the quaternary ammonium salt modified strong base anion exchange resin with proper hydrophobicity (contact angle) is prepared by grafting proper quaternary ammonium groups through amination and alkylation reaction or quaternization reaction, and the resin is adopted for water treatment, so that bicarbonate radicals and carbonate radicals in a water body can be well removed, the generation of precipitates such as calcium carbonate and magnesium carbonate is reduced, the scale is reduced, and healthy elements calcium and magnesium ions required by a human body can be retained;

(3) the process for water treatment by adopting the scale-removing quaternary ammonium resin is simple, the operation is convenient, the operation cost is low, only neutral sodium chloride solution is needed in the regeneration process, strong acid, strong alkali or weak acid and weak alkali liquid in the traditional resin process is not needed as a regenerant, and the process is safer, more economic and more environment-friendly.

Drawings

FIG. 1 is a graph showing the results of measuring the contact angle between the scale-removing quaternary ammonium resin of the present invention and a conventional quaternary ammonium resin;

FIG. 2 is a graph showing the scaling of HCO versus complex multi-ion simulated aqueous environments for the quaternary ammonium-based resins of the invention₃ ^-A graph of effects of preferential removal;

FIG. 3 is a graph showing the effect of the scale-removing quaternary ammonium resin of the present invention on HCO in an actual water body₃ ^-Preferential removal of scale, i.e., dissolved total solids, while retaining Ca²⁺、Mg²⁺A graph of the effect of (c);

FIG. 4 shows a quaternary ammonium-type resin A for scale removal according to the present invention₀-2 with conventional commercial resins A₀-1 comparison of the effect of scale removal in real water bodies.

Detailed Description

The invention is further described with reference to specific examples.