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WO2021226845A1 - 螯合剂、清洗剂及螯合剂的制备方法 - Google Patents

螯合剂、清洗剂及螯合剂的制备方法 Download PDF

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WO2021226845A1
WO2021226845A1 PCT/CN2020/089864 CN2020089864W WO2021226845A1 WO 2021226845 A1 WO2021226845 A1 WO 2021226845A1 CN 2020089864 W CN2020089864 W CN 2020089864W WO 2021226845 A1 WO2021226845 A1 WO 2021226845A1
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salt
acid
compound
chelating agent
temperature
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French (fr)
Inventor
欧敏
梅龙毅
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Nanjing All PlusChemical Co ltd
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Nanjing All PlusChemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen

Definitions

  • This application relates to the technical field of organic chemistry synthesis, in particular to the preparation methods of chelating agents, cleaning agents and chelating agents.
  • common chelating agents mainly include phosphate, hydroxycarboxylic acid, aminocarboxylic acid, and carboxylic acid-containing polymers.
  • Phosphate has a better chelating effect, but the phosphorus content causes great pollution to the environment.
  • Sodium tripolyphosphate (STPP) is mainly used more frequently, but it has gradually faded out of the market in the global call for phosphorus restriction and prohibition.
  • Hydroxy carboxylic acids mainly include sodium gluconate, sodium citrate, etc.
  • the chelating performance of metal ions is poor and the cost performance is not high.
  • Acrylic polymer is a polymer chelating agent. In addition to its chelating ability, it also has thickening and flocculation effects.
  • Aminocarboxylic acids mainly include ethylenediaminetetraacetic acid (EDTA), Hydroxyethylethylenediaminetriacetic acid (HEDTA), Diethylenetriaminepentaacetic acid (DTPA), Nitrotriacetic acid (NTA), Iminodisuccinic acid (IDS), Glutamate diacetic acid (GLDA) ), methylglycine diacetic acid (MGDA) and so on.
  • EDTA ethylenediaminetetraacetic acid
  • HEDTA Hydroxyethylethylenediaminetriacetic acid
  • DTPA Diethylenetriaminepentaacetic acid
  • NDA Nitrotriacetic acid
  • GLDA Glutamate diacetic acid
  • MGDA methylglycine diacetic acid
  • EDTA is not easily biodegradable (OECD)
  • NTA has potential carcinogenicity
  • IDS has low performance in chelating metals
  • GLDA and MGDA have high raw material toxicity, high equipment requirements, industrialization difficulties, high production costs, and product prices. It is expensive and often limits its widespread use in real life.
  • This application provides a chelating agent, a cleaning agent, and a preparation method of a chelating agent, which can provide a chelating agent with no phosphorus and strong chelating performance.
  • this application provides a chelating agent, the general formula of the chelating agent is as follows:
  • R 1 , R 2 , R 3 and R 4 are alkyl groups
  • M 1 , M 2 , M 3 and M 4 are hydrogen atoms, metal atoms, ammonium groups or organic amine groups;
  • A is a hydroxyl group or an amino group.
  • the alkyl group is -(CH 2 ) n -, and 0 ⁇ n ⁇ 6.
  • R 1 and R 4 are -(CH 2 ) 0 -, and R 2 and R 3 are -CH 2 -.
  • the metal atom is Na.
  • this application provides a method for preparing the above chelating agent, the method comprising:
  • R is R 2 or R 3 as defined in claim 1
  • M is M 2 or M 3 as defined in claim 1
  • M 1 and M 2 have the same meaning as in claim 1
  • L is a leaving group group.
  • this application provides another method for preparing the above chelating agent, which method includes:
  • compound D is R 2 and R 3 have the same meanings as in claim 1, and M 5 and M 6 are hydrogen atoms, metal atoms, ammonium groups, or organic amine groups.
  • the addition reaction of epoxysuccinic acid (salt) and compound D to obtain the chelating agent includes:
  • the second temperature is 60-100°C; the fourth time is 0.5-2h; the fifth time is 2-24h.
  • said providing epoxysuccinic acid (salt) includes: providing maleic acid (salt) and/or fumaric acid (salt), and cyclizing maleic acid (salt) and/or fumaric acid (salt) Oxidation reaction to obtain epoxysuccinic acid (salt).
  • the epoxidation reaction of maleic acid (salt) and/or fumaric acid (salt) to obtain epoxysuccinic acid (salt) includes: making maleic acid (salt) and/or fumaric acid (salt) Acid (salt) undergoes epoxidation reaction under oxidant, catalyst and weakly alkaline or weakly acidic environment;
  • the catalyst is at least one of sodium tungstate, sodium molybdate, and ammonium vanadate;
  • the weakly alkaline or weakly acidic environment refers to an environment with a pH of 3-8.
  • the epoxidation reaction of maleic acid (salt) and/or fumaric acid (salt) in an oxidant, a catalyst and a weakly alkaline or weakly acidic environment includes:
  • the oxidant solution is added dropwise to maleic acid (salt) and/or fumaric acid (salt), while adjusting the maleic acid (salt) and/or fumaric acid (salt) by adding lye PH of the solution;
  • maleic acid (salt) and/or fumaric acid (salt) includes:
  • the maleic anhydride undergoes a hydrolysis reaction at the hydrolysis temperature to obtain maleic acid (salt) and/or fumaric acid (salt);
  • maleic acid (salt) and/or fumaric acid (salt) then includes:
  • the first time is 30-60min; the second time is 40-120min; the third time is 2-10h; the first temperature is 45-80°C; the third temperature is 40-60°C; The hydrolysis temperature is 0-75°C; the first pH is 4-8.
  • this application provides a method for preparing the above chelating agent, the method comprising:
  • compound C is L is a leaving group
  • R is R 2 or R 3 as defined in claim 1
  • M is M 2 or M 3 as defined in claim 1.
  • this application provides a method for preparing the above chelating agent, the method comprising:
  • L is a leaving group, and R is R 2 or R 3 as defined in claim 1.
  • the present application provides a cleaning agent, which includes the above-mentioned chelating agent.
  • the chelating agent disclosed in the present application has high chelating performance to calcium, magnesium and copper, and the chelating agent disclosed in the present application also has good chelating performance to iron ions.
  • the chelating agent disclosed in the application shows particularly good chelating properties for calcium, magnesium, iron, copper or other metals, and has a strong chelating ability.
  • this application is non-toxic and non-phosphorus, biodegradable, and can replace traditional chelating agents such as EDTA, DPTA, NTA, which are difficult to biodegrade or expensive.
  • it in addition to high solubility in high-concentration aqueous alkali and acid solutions, it also has excellent storage stability.
  • Figure 1 is a schematic diagram of a mass spectrum of an embodiment of the chelating agent of the present application.
  • Fig. 2 is a schematic diagram of the hydrogen nuclear magnetic spectrum of an embodiment of the chelating agent of the present application.
  • this application provides an embodiment of the chelating agent of Formula I:
  • R 1 , R 2 , R 3 and R 4 are alkyl groups.
  • M 1 , M 2 , M 3 and M 4 are hydrogen atoms, metal atoms, ammonium groups or organic amine groups.
  • A is a hydroxyl group or an amino group.
  • the chelating agent provided in this application can be synthesized by any kind of raw materials and methods by those skilled in the art according to its general structural formula.
  • R 1, R 2 , R 3 and R 4 are preferably -(CH 2 ) n -, 0 ⁇ n ⁇ 6, that is, n can be equal to 1, 2, 3, 4, 5 or 6. .
  • R 1 and R 4 are the same, and at least one of R 2 and R 3 is different from R 1.
  • R 1 and R 4 are -(CH 2 ) 0 -, and R 2 and R 3 are -CH 2 -.
  • the metal atom may be an alkali metal atom, a transition metal atom, a heavy metal atom, or a rare earth metal atom.
  • M 1 , M 2 , M 3 and M 4 are preferably H and alkali metal cations. More preferably, M 1 , M 2 , M 3 and M 4 are H and Na. In addition, M 1 , M 2 , M 3 and M 4 may be different from each other. Alternatively, M 1 , M 2 , M 3 and M 4 are all the same. Alternatively, M 1 and M 4 are the same, and at least one of M 2 and M 3 is different from M 1 .
  • the chelating agent of the present application is preferably Formula Ia, Formula Ib and Formula Ic.
  • the chelating agent represented by formula I can form a coordination geometric structure with the metal cation.
  • the coordination geometric structure formed by the chelating agent and iron ions is as follows:
  • This application takes the chelating agents represented by formulas Ia and Ib as representatives, and analyzes the chelating ability of the chelating agents disclosed in this application.
  • the chelating performance of the chelating agent disclosed in this application on calcium, magnesium, and copper has greatly exceeded that of EDTA and other similar biodegradable chelating agents, and the chelating agent disclosed in this application has a chelating effect on iron ions.
  • the chelating performance is also very good, that is, the chelating agent disclosed in the present application shows particularly good chelating performance for calcium, magnesium, iron, copper or other metals, and has a strong chelating ability.
  • the chelating agent disclosed in the present application has higher dispersibility, and may be more effective when used in conjunction with other chelating dispersing agents.
  • the chelating agent disclosed in the present application can be used as a cleaning agent, and the cleaning agent may include a household detergent, an industrial cleaning agent, a water softener, and an extractant of heavy metal contaminants.
  • the cleaning agent is widely used in printing and dyeing auxiliaries, dyeing and finishing processes, textile industry, paper industry, photosensitive materials, ceramic industry, electroplating industry and other industries.
  • the chelating agent disclosed in the present application can also be used as a scale inhibitor and dispersant in the field of traditional industrial circulating water.
  • the non-toxic, non-phosphorus, biodegradable, and expensive traditional chelating agents such as EDTA, DPTA, NTA, etc., disclosed in this application.
  • the chelating agent disclosed in the present application is a colorless or light yellow transparent liquid at room temperature. It is not easy to crystallize at -25°C and below for a long time. It has high solubility in both high-concentration aqueous alkali and acid solutions. It has excellent storage stability.
  • the present application provides a method for preparing the above-mentioned chelating agent according to the first embodiment.
  • the method for preparing a chelating agent in this embodiment includes the following steps.
  • Step 11 Provide epoxysuccinic acid (salt).
  • epoxysuccinic acid refers to epoxysuccinic acid and/or epoxysuccinate (including a form in which two carboxyl groups are a salt and a form in which only one carboxyl group is a salt).
  • epoxysuccinic acid (salt) can be self-made or commercially available.
  • epoxysuccinic acid (salt) may be cis-epoxysuccinic acid (salt) and/or trans-epoxysuccinic acid (salt).
  • cis-epoxysuccinic acid can be prepared by subjecting maleic acid (salt) to epoxidation reaction.
  • maleic acid (salt) refers to maleic acid and/or maleic acid salt (including two carboxyl groups as a salt form and only one carboxyl group as a salt form).
  • the maleic acid (salt) is subjected to the epoxidation reaction in an oxidizing agent and a catalyst, and a weakly acidic or weakly basic environment.
  • the oxidant may be hydrogen peroxide, but of course it is not limited to this.
  • sodium hypochlorite may also be used as the oxidant.
  • the oxidant solution added to the maleic acid (salt) can be a hydrogen peroxide solution with a mass fraction of 25%-40%.
  • the catalyst may include at least one of sodium tungstate, sodium molybdate, or sodium vanadate, but of course it is not limited thereto.
  • the molar ratio of maleic acid (salt) to the catalyst is greater than or equal to 1:0.005.
  • the molar ratio of maleic acid (salt) to catalyst is 1:0.015-1:0.4.
  • a weakly acidic or weakly alkaline environment refers to an environment with a pH of 3-8.
  • the weakly acidic or weakly alkaline environment refers to an environment with a pH of 6.0-7.5.
  • the weakly alkaline environment can be provided by LiOH, NaOH or KOH.
  • the weakly alkaline environment for the maleic acid (salt) reaction can be constructed by adding lye to the maleic acid (salt).
  • the lye is a solution of LiOH, NaOH and/or KOH with a mass fraction of 25%-60%.
  • the temperature environment for the epoxidation reaction of maleic acid (salt) may not be higher than 100°C.
  • the temperature environment for the epoxidation reaction of maleic acid (salt) may not be higher than 75°C.
  • the temperature environment for the epoxidation reaction of maleic acid (salt) may be 60-70°C.
  • the catalyst can be added to the maleic acid (salt) first, and stirred for the first time, and then the oxidant solution is added dropwise to the maleic acid (salt) during the second time, while adjusting the maleic acid (salt) by adding lye.
  • the pH of the acid (salt) solution After the addition of hydrogen peroxide is completed, the temperature is raised to the first temperature, and the mixture is stirred for the third time. It can be understood that the second time is the time taken to add the oxidant solvent dropwise to the maleic acid (salt).
  • the first time is 30-60 minutes.
  • the first time is 40-50 min. More preferably, the first time is 45 minutes.
  • the second time is 40-120 min. Preferably, the second time is 60-90 min.
  • the first temperature is 45-80°C.
  • the first temperature is 60-65°C.
  • the third time is 2-10h. Preferably, the third time is 3h.
  • maleic acid (salt) can be self-made or commercially available.
  • the present application can obtain maleic acid (salt) through the hydrolysis of maleic anhydride.
  • the pH of the maleic anhydride solution can be adjusted to a suitable range to accelerate the hydrolysis rate of maleic anhydride.
  • the pH of the maleic anhydride solution can be adjusted by NaOH, KOH, or LiOH.
  • the hydrolysis rate can also be adjusted by adjusting the hydrolysis temperature of maleic anhydride.
  • the hydrolysis temperature of maleic anhydride is 0-75°C, such as 20°C, 25°C, or 30°C.
  • the pH and temperature of the solution of the hydrolysate can also be adjusted to enable faster epoxidation.
  • the third temperature of the solution of the hydrolysate is adjusted to 40-60°C
  • the first pH of the solution of the hydrolysate is adjusted to 4-8.
  • trans-epoxysuccinic acid (salt) can be prepared by subjecting fumaric acid (salt) to epoxidation reaction.
  • maleic acid (salt) refers to maleic acid and/or maleic acid salt (including two carboxyl groups as a salt form and only one carboxyl group as a salt form).
  • the process of preparing trans-epoxysuccinic acid (salt) with fumaric acid (salt) can refer to the process of preparing cis-epoxysuccinic acid (salt) with maleic acid (salt), which will not be repeated here.
  • Step 12 Addition reaction of epoxysuccinic acid (salt) and compound A to obtain compound B.
  • M is M 2 and M 3 as defined in the first aspect
  • R is R 2 and R 3 as defined in the first aspect
  • M 1 and M 2 are as defined for formula I in the first aspect.
  • R in compound A is -CH 2 -, that is, compound A is aminoacetic acid.
  • Step 13 Substituting compound B and compound C to obtain the chelating agent represented by formula (I).
  • L is a leaving group.
  • L is Cl, I, or Br, etc., of course, it is not limited thereto.
  • M is the same as M 2 and M 3 defined in the first aspect.
  • M is Na or H.
  • R is as defined in the first aspect as R 2 and R 3 .
  • R is -CH 2 -.
  • compound C is chloroacetic acid.
  • the chelate compound represented by formula Ia of the first aspect can be obtained by reacting the addition product of aminoacetic acid and epoxysuccinic acid with chloroacetic acid.
  • this application provides a second method for preparing the above-mentioned chelating agent.
  • the method for preparing a chelating agent in this embodiment includes the following steps.
  • Step 21 Provide epoxysuccinic acid (salt) and compound D.
  • R 2 and R 3 are as defined for formula I in the first aspect.
  • M 5 and M 6 are hydrogen atoms, metal atoms, ammonium groups, or organic amine groups.
  • M 5 and M 6 are hydrogen atoms, and R 2 and R 3 are -CH 2 -, that is, compound D is iminodiacetic acid.
  • Step 22 Perform an addition reaction between epoxysuccinic acid (salt) and compound D to obtain the chelating agent.
  • epoxysuccinic acid (salt) and compound D can be mixed first, and then stirred for the fourth time, and then the hydroxide containing M 7 is added, the temperature is raised to the second temperature, and the reaction is performed for the fifth time to obtain the formula I
  • M 7 is the same as M 1 and M 4 defined in the first aspect.
  • the fourth time is 0.5-2h. Preferably, the fourth time is 1-1.5h.
  • the second temperature is 60-100°C. Preferably, the second temperature is 80-95°C.
  • the fifth time is 2-24h. Preferably, the fifth time is 3-15h.
  • the molar ratio of epoxysuccinic acid (salt), compound D and M 7 atoms is about 1:1:1 to 1:5.
  • the molar ratio of epoxysuccinic acid (salt), compound D and M 7 atoms is about 1:1:1.5-1:1:2.
  • compound D is iminodiacetic acid, so that the compound represented by formula Ia of the first aspect can be obtained by reacting epoxysuccinic acid (salt) with compound D.
  • the present application provides a method for preparing the above-mentioned chelating agent according to the third embodiment.
  • the method for preparing a chelating agent in this embodiment includes the following steps.
  • Step 31 Provide 3-hydroxyaspartic acid and compound C.
  • L is a leaving group.
  • L is Cl, I, or Br, etc., of course, it is not limited thereto.
  • M is the same as M 2 and M 3 defined in the first aspect.
  • M is Na or H.
  • R is the same as R 2 and R 3 defined in the first aspect.
  • R is -CH 2 -.
  • compound C is chloroacetic acid, iodoacetic acid, bromoacetic acid, or the like.
  • Step 32 Substituting 3-hydroxyaspartic acid and compound C to obtain the chelating agent represented by formula I.
  • 3-hydroxyaspartic acid and compound C can undergo a substitution reaction in an alkaline environment.
  • the alkaline environment can be provided by many alkaline substances.
  • the alkaline environment includes NaOH or KOH.
  • the chelating agent represented by formula Ia can be produced by the substitution reaction of 3-hydroxyaspartic acid and compound C.
  • this application provides a method for preparing the chelating agent represented by Formula I according to the fourth embodiment.
  • the method for preparing the chelating agent represented by Formula I in this embodiment includes the following steps.
  • Step 41 Provide 3-hydroxyaspartic acid and compound E.
  • R is as defined in the first aspect as R 2 and R 3 .
  • R is -CH 2 -.
  • L is a leaving group.
  • L is Cl, I, or Br, etc., of course, it is not limited thereto.
  • the compound E is chloroacetonitrile, iodoacetonitrile, bromoacetonitrile or the like.
  • Step 42 Substituting 3-hydroxyaspartic acid and compound E to obtain compound F.
  • this application can make 3-hydroxyaspartic acid and compound E undergo a substitution reaction under the action of the second catalyst.
  • the second catalyst is inorganic ammonium salt, organic amine or amide, etc.
  • the second catalyst is triethylamine.
  • Step 43 Make compound F undergo a hydrolysis reaction to obtain a chelating agent represented by formula I.
  • compound F By hydrolyzing the cyano group of compound F to produce carboxylic acid or carboxylate, compound F is converted into a chelating agent represented by formula I.
  • the compound F may undergo a hydrolysis reaction in an acidic environment or an alkaline environment.
  • the acid-base requirement for the hydrolysis reaction of compound F can be: the pH of the reaction solution of compound F is less than or equal to 3, or greater than or equal to 10.
  • Various bases can provide an alkaline environment, as long as the pH of the compound F reaction solution meets the above-mentioned acid-base requirements by adding a base.
  • NaOH provides an alkaline environment.
  • various acids can provide an acidic environment, as long as the pH of the compound F reaction solution meets the above-mentioned acid-base requirements by adding an acid.
  • the acidic environment is provided by hydrochloric acid.
  • the above method for preparing the chelating agent represented by formula I has a wide range of raw materials, low price, simple production equipment, chemical reactions in the reaction process can be synthesized in a one-pot method, high safety, no highly toxic substances involved, and product collection High rate, good performance and no negative impact on the environment. It is a green and environmentally friendly process that is easy for large-scale industrial production.
  • the chelating agent shown in Formula Ib can be obtained.
  • the mass spectrum of the obtained product is shown in Figure 1, the measured value is 266.1, and the measured value is consistent with the theoretical value of the chelating agent shown in formula Ib, which proves that the obtained product includes the chelating agent shown in formula Ib.
  • the purity of the chelating agent represented by formula Ib in the obtained product is greater than or equal to 99%.
  • this application uses the following test methods to determine the chelating performance of the chelating agent to various metal ions.
  • V 0 -Blank solution consumes 0.25mol/L MgCl 2 standard solution volume, ml;
  • the number of milligrams of complexed copper ions per gram of copolymer is the number of milligrams consumed during the titration of the standard solution.
  • V 1 The volume of the trivalent iron standard solution consumed by the sample solution (ml);
  • V 0 The volume of the trivalent iron standard solution consumed by the blank solution (ml);

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Abstract

本申请提供螯合剂、清洗剂及螯合剂的制备方法。该螯合剂的结构通式如（I）所示，其中：R1、R2、R3和R4为烷基；M1、M2、M3和M4为氢原子、金属原子、铵基或有机胺基；A为羟基或氨基。本申请可以提供无磷且螯合性能强的螯合剂。

Description

螯合剂、清洗剂及螯合剂的制备方法 技术领域
本申请涉及有机化学合成技术领域，特别是涉及螯合剂、清洗剂及螯合剂的制备方法。
背景技术
目前常见的螯合剂主要有磷酸盐、羟基羧酸、氨基羧酸以及含羧酸类聚合物。磷酸盐的螯合效果较佳，但含磷对环境造成极大污染，使用比较多的主要有三聚磷酸钠(STPP)，但是在全球限磷、禁磷的呼声中逐渐淡出市场。羟基羧酸主要有葡萄糖酸钠、柠檬酸钠等，一般金属离子的螯合性能较差，性价比不高。丙烯酸类聚合物属于高分子螯合剂，除具有螯合能力外，兼具增稠和絮凝作用，一般螯合后会沉降在水中同时也难生物降解，氨基羧酸类主要有乙二胺四乙酸(EDTA)、羟乙基乙二胺三乙酸(HEDTA)、二乙烯三胺五乙酸(DTPA)、氮川三乙酸(NTA)、亚氨基二琥珀酸(IDS)、谷氨酸二乙酸(GLDA)、甲基甘氨酸二乙酸(MGDA)等。其中，EDTA不易生物降解(OECD)，NTA具有潜在的致癌性，IDS螯合金属的性能较低，GLDA、MGDA制作过程中原料毒性高、设备要求高，工业化难度大，生产成本高，产品价格昂贵，往往限制其在实际生活中的广泛使用。
发明内容
本申请提供螯合剂、清洗剂及螯合剂的制备方法，可以提供无磷且螯合性能强的螯合剂。
为达到上述目的，本申请提供一种螯合剂，该螯合剂的通式如下所示：
Figure PCTCN2020089864-appb-000001
其中：
R 1、R 2、R 3和R 4为烷基；
M 1、M 2、M 3和M 4为氢原子、金属原子、铵基或有机胺基；
A为羟基或氨基。
其中，所述烷基为-(CH 2) n-，且0≤n≤6。
其中，R 1和R 4为-(CH 2) 0-，R 2和R 3为-CH 2-。
其中，所述金属原子为Na。
为达到上述目的，本申请提供一种制备上述螯合剂的方法，该方法包括：
提供环氧琥珀酸(盐)，
使环氧琥珀酸(盐)和化合物A进行加成反应，以得到化合物B；
使化合物B和化合物C进行取代反应，以得到所述螯合剂；
其中，化合物A、化合物B和化合物C的结构通式如下，
化合物A：
Figure PCTCN2020089864-appb-000002
化合物B：
Figure PCTCN2020089864-appb-000003
化合物C：
Figure PCTCN2020089864-appb-000004
其中，R为如权利要求1定义的R 2或R 3，M为如权利要求1定义的M 2或M 3，M 1和M 2具有与权利要求1相同的含义，且L为离去基团。
为达到上述目的，本申请提供另一种制备上述螯合剂的方法，该方法包括：
提供环氧琥珀酸(盐)和化合物D；
使环氧琥珀酸(盐)和化合物D进行加成反应，以得到所述的螯合剂；
其中，化合物D为
Figure PCTCN2020089864-appb-000005
R 2和R 3具有与权利要求1相同的含义，M 5和M 6为氢原子、金属原子、铵基或有机胺基。
其中，所述使环氧琥珀酸(盐)和化合物D进行加成反应，以得到所述的螯合剂，包括：
将环氧琥珀酸(盐)和化合物D混合，搅拌第四时间，添加包含M 7的氢氧化物，升温至第二温度，并反应第五时间，以得到所述螯合剂，其中，M 7为如权利要求1定义的M 1和M 4。
其中，所述第二温度为60-100℃；所述第四时间为0.5-2h；所述第五时间为2-24h。
其中，所述提供环氧琥珀酸(盐)，包括：提供马来酸(盐)和/或富马 酸(盐)，使马来酸(盐)和/或富马酸(盐)进行环氧化反应，以得到环氧琥珀酸(盐)。
其中，所述使马来酸(盐)和/或富马酸(盐)进行环氧化反应，以得环氧琥珀酸(盐)，包括：使马来酸(盐)和/或富马酸(盐)在氧化剂、催化剂和弱碱性或弱酸性环境下进行环氧化反应；
其中，所述催化剂为钨酸钠、钼酸钠、钒酸铵中的至少一种；
所述弱碱性或弱酸性环境是指pH为3-8的环境。
其中，所述使马来酸(盐)和/或富马酸(盐)在氧化剂、催化剂和弱碱性或弱酸性环境下进行环氧化反应，包括：
将催化剂添加到马来酸(盐)和/或富马酸(盐)中，搅拌第一时间；
再在第二时间内将氧化剂溶液滴加到马来酸(盐)和/或富马酸(盐)中，同时通过添加碱液调节马来酸(盐)和/或富马酸(盐)溶液的pH；
在第一温度下，反应第三时间，以得到环氧琥珀酸(盐)。
其中，所述提供马来酸(盐)和/或富马酸(盐)，包括：
使马来酸酐在水解温度下进行水解反应，以得到马来酸(盐)和/或富马酸(盐)；
所述提供马来酸(盐)和/或富马酸(盐)，之后包括：
将马来酸(盐)和/或富马酸(盐)的溶液的pH调节至第一pH，将马来酸(盐)和/或富马酸(盐)的溶液的温度调节至第三温度。
其中，所述第一时间为30-60min；第二时间为40-120min；第三时间为2-10h；所述第一温度为45-80℃；所述第三温度为40-60℃；所述水解温度为0-75℃；所述第一pH为4-8。
为达到上述目的，本申请提供一种制备上述螯合剂的方法，该方法包括：
提供3-羟基天冬氨酸和化合物C；
使3-羟基天冬氨酸和化合物C进行取代反应，以得到所述螯合剂；
其中，化合物C为
Figure PCTCN2020089864-appb-000006
L为离去基团，R为如权利要 求1定义的R 2或R 3，M为如权利要求1定义的M 2或M 3。
为达到上述目的，本申请提供一种制备上述螯合剂的方法，该方法包括：
提供3-羟基天冬氨酸和化合物E；
使3-羟基天冬氨酸和化合物E进行取代反应，以得到化合物F，
使化合物F进行水解反应，以得到所述螯合剂；
所述化合物E和化合物F的结构通式如下所示：
化合物E：
Figure PCTCN2020089864-appb-000007
化合物F：
Figure PCTCN2020089864-appb-000008
L为离去基团，R为如权利要求1定义的R 2或R 3。
为达到上述目的，本申请提供一种清洗剂，所述清洗剂包括上述的螯合剂。
与EDTA、GLDA、MGDA和IDS等相比，本申请公开的螯合剂对钙、镁和铜的螯合性能高，并且本申请公开的螯合剂对铁离子的螯合性能也很好，即本申请公开的螯合剂对钙、镁、铁、铜或其他金属显示综合性能特别好的螯合性能，螯合能力强。并且本申请无毒无磷，可生物降解、可取代EDTA、DPTA、NTA等难生物降解或者成本昂贵的传统螯合剂。此外，在高浓度的碱水溶液与酸水溶液中都具有很高的溶解度以外，还有具有很优越的保存稳定性。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描 述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请螯合剂一实施例的质谱示意图；
图2为本申请螯合剂一实施例的核磁氢谱示意图。
具体实施方式
为使本领域的技术人员更好地理解本申请的技术方案，下面结合附图和具体实施方式对本申请所提供的螯合剂及其制备方法做进一步详细描述。
在一方面，本申请提供一实施方式式Ι的螯合剂：
Figure PCTCN2020089864-appb-000009
其中，R 1、R 2、R 3和R 4为烷基。
M 1、M 2、M 3和M 4为氢原子、金属原子、铵基或有机胺基。
A为羟基或氨基。
本申请提供的螯合剂，本领域技术人员根据其结构通式，可采用任意种原料、方法合成。
在式Ι的螯合剂中，R 1、R 2、R 3和R 4优选为-(CH 2) n-，0≤n≤6，即n可以等于1、2、3、4、5或6。另外，R 1和R 4相同，R 2和R 3的至少一者与R 1不同。最优选地，R 1和R 4为-(CH 2) 0-，R 2和R 3为-CH 2-。
其中，金属原子可以是碱金属原子、过渡金属原子、重金属原子或稀土金属原子等。
M 1、M 2、M 3和M 4优选为H和碱金属阳离子。更为优选地，M 1、M 2、M 3和M 4为H和Na。另外，M 1、M 2、M 3和M 4可以互不相同。或者，M 1、M 2、M 3和M 4均相同。或者，M 1和M 4相同，M 2和M 3中的至少一者与M 1不相同。
本申请的螯合剂优选为式Ia、式Ib和式Ic。
Figure PCTCN2020089864-appb-000010
式I所示的螯合剂可以和金属阳离子形成配位几何结构。
以铁离子为例，螯合剂和铁离子形成的配位几何结构如下所示：
Figure PCTCN2020089864-appb-000011
本申请以式Ia和Ib所示的螯合剂为代表，分析本申请公开的螯合剂的螯合能力。
Figure PCTCN2020089864-appb-000012
具体如表1所示，本申请公开的螯合剂对钙、镁和铜的螯合性能已经很大程度超过EDTA和其他同类型生物降解螯合剂，并且本申请公开的螯合剂对铁离子的螯合性能也很好，即本申请公开的螯合剂对钙、镁、铁、铜或其他金属显示综合性能特别好的螯合性能，螯合能力强。另外，本申请公开的螯合剂分散能力较高，与其他螯合分散剂配合使用可能效果更好。本申请公开的螯合剂可用做清洗剂，该清洗剂可以包括民用洗涤剂、工业清洗剂、软水剂和重金属污染物的萃取剂。该清洗剂广泛应用于印染助剂、染整工艺、纺织工业、造纸工业、感光材料、陶瓷工业、电镀工业等行业。另外，本申请公开的螯合剂在传统的工业循环水领域也可以阻垢分散剂。并且本申请公开的无毒无磷，可生物降解、可取代EDTA、DPTA、NTA等难生物降解或者成本昂贵的传统螯合剂。此外，本申请公开的螯合剂在常温下是无色或浅黄色透明液体，长期处于-25℃及以下不容易结晶，在高浓度的碱水溶液与酸水溶液中都具有很高的溶 解度以外，还有具有很优越的保存稳定性。
在第二方面，本申请提供第一实施方式制备上述螯合剂的方法。本实施方式制备螯合剂的方法包括以下步骤。
步骤11：提供环氧琥珀酸(盐)。
其中，环氧琥珀酸(盐)是指环氧琥珀酸和/或环氧琥珀酸盐(包括两个羧基为盐的形态和仅一个羧基为盐的形态)。
其中，环氧琥珀酸(盐)可以是自制的，或者市购得到的。
另外，环氧琥珀酸(盐)可以是顺式环氧琥珀酸(盐)和/或反式环氧琥珀酸(盐)。
在一实现方式中，可以通过让马来酸(盐)进行环氧化反应来制得顺式环氧琥珀酸(盐)。其中，马来酸(盐)是指马来酸和/或马来酸盐(包括两个羧基为盐的形态和仅一个羧基为盐的形态)。
具体地，使马来酸(盐)在氧化剂和催化剂、弱酸性或弱碱性环境下进行环氧化反应。
其中，氧化剂可为双氧水，当然不限于此，例如还可以使用次氯酸钠作为氧化剂。另外，添加到马来酸(盐)中的氧化剂溶液可为质量分数为25％-40％的双氧水溶液。
催化剂可以包括钨酸钠、钼酸钠或钒酸钠中的至少一种，当然不限于此。可选地，马来酸(盐)与催化剂的摩尔比大于或等于1:0.005。优选地，马来酸(盐)与催化剂的摩尔比为1:0.015-1:0.4。
弱酸性或弱碱性环境是指pH为3-8的环境。优选地，弱酸性或弱碱性环境是指pH为6.0-7.5的环境。其中，弱碱性环境可以由LiOH，NaOH或KOH来提供。具体地，可以通过向马来酸(盐)添加碱液来构造马来酸(盐)反应的弱碱性环境。碱液为质量分数为25％-60％的LiOH，NaOH和/或KOH的溶液。
进一步地，马来酸(盐)进行环氧化反应的温度环境可以不高于100℃。优选地，马来酸(盐)进行环氧化反应的温度环境可以不高于75℃。优选地，马来酸(盐)进行环氧化反应的温度环境可以为60-70℃。
进一步地，可以先将催化剂添加到马来酸(盐)中，并搅拌第一时间， 继而在第二时间内将氧化剂溶液滴加到马来酸(盐)中，同时通过添加碱液调节马来酸(盐)溶液的pH。滴加双氧水完毕后，升温至第一温度，搅拌第三时间。可以理解的是，第二时间为将氧化剂溶剂滴加到马来酸(盐)所消耗的时间。
可选地，第一时间为30-60min。优选地，第一时间为40-50min。更为优选地，第一时间为45min。
可选地，第二时间为40-120min。优选地，第二时间为60-90min。
可选地，第一温度为45-80℃。优选地，第一温度为60-65℃。
可选地，第三时间为2-10h。优选地，第三时间为3h。
可以理解的是，马来酸(盐)可以自制或市购得到。示例性地，本申请可以通过马来酸酐水解得到马来酸(盐)。优选地，可以将马来酸酐溶液的pH调节至合适范围内，以加快马来酸酐的水解速度。例如，可通过NaOH、KOH或LiOH调节马来酸酐溶液的pH。并且还可以通过调节马来酸酐的水解温度来调节水解速率。可选地，马来酸酐的水解温度为0-75℃，例如为20℃、25℃或30℃等。
另外，在水解之后，还可以调节水解产物的溶液的pH和温度，使其能够更快地进行环氧化。具体地，将水解产物的溶液的第三温度调节至40-60℃，将水解产物的溶液的第一pH调节至4-8。
在另一实现方式中，可以通过让富马酸(盐)进行环氧化反应来制得反式环氧琥珀酸(盐)。其中，马来酸(盐)是指马来酸和/或马来酸盐(包括两个羧基为盐的形态和仅一个羧基为盐的形态)。其中，以富马酸(盐)制备反式环氧琥珀酸(盐)的过程，可以参照以马来酸(盐)制备顺式环氧琥珀酸(盐)的过程，在此不做赘述。
步骤12：使环氧琥珀酸(盐)和化合物A进行加成反应，以得到化合物B。
其中，化合物A的结构通式为
Figure PCTCN2020089864-appb-000013
化合物B的结构通式为
Figure PCTCN2020089864-appb-000014
其中，M如第一方面定义的M 2和M 3，R如第一方面定义的R 2和R 3。M 1和M 2如在第一方面中对式I所定义。
优选地，化合物A中的R为-CH 2-，即化合物A为氨基乙酸。
这样以氨基乙酸和环氧琥珀酸制得的化合物B的结构通式为
Figure PCTCN2020089864-appb-000015
步骤13：使化合物B和化合物C进行取代反应，以得到式(I)所示的螯合剂。
其中，化合物C的结构通式为
Figure PCTCN2020089864-appb-000016
其中，L为离去基团。可选地，L为Cl、I或Br等，当然不限于此。
并且，M如第一方面定义的M 2和M 3。优选地，M为Na或H。
R如第一方面定义的R 2和R 3。优选地，R为-CH 2-。
优选地，化合物C为氯乙酸。通过氨基乙酸和环氧琥珀酸的加成产物，和氯乙酸反应可以得到第一方面的式Ia所示的螯合物。
在第三方面，本申请提供第二种制备上述螯合剂的方法。本实施方式制备螯合剂的方法包括以下步骤。
步骤21：提供环氧琥珀酸(盐)和化合物D。
其中，化合物D为
Figure PCTCN2020089864-appb-000017
R 2和R 3如在第一方面中对式I所定义。
M 5和M 6为氢原子、金属原子、铵基或有机胺基。
示例性地，M 5和M 6为氢原子，R 2和R 3为-CH 2-，即化合物D为亚氨基二乙酸。
步骤22：使环氧琥珀酸(盐)和化合物D进行加成反应，以得到所述的螯合剂。
可以理解的是，环氧琥珀酸(盐)的获取方法可以如制备螯合剂的方法第一实施方式所述，在此不做赘述。
具体地，可以先将环氧琥珀酸(盐)和化合物D混合，然后搅拌第四时间，继而添加包含M 7的氢氧化物，升温至第二温度，反应第五时间，以得到式I所示的螯合剂。其中，M 7如第一方面定义的M 1和M 4。
可选地，第四时间为0.5-2h。优选地，第四时间为1-1.5h。
可选地，第二温度为60-100℃。优选地，第二温度为80-95℃。
可选地，第五时间为2-24h。优选地，第五时间为3-15h。
另外，环氧琥珀酸(盐)、化合物D和M 7原子的摩尔比约为1:1:1-1:1:5。优选地，环氧琥珀酸(盐)、化合物D和M 7原子的摩尔比约为1:1:1.5-1:1:2。
在一应用场景中，化合物D为亚氨基二乙酸，这样通过环氧琥珀酸(盐)和化合物D进行反应可以得到第一方面的式Ia所示的化合物。
在第四方面，本申请提供第三实施方式制备上述螯合剂的方法。本实施方式制备螯合剂的方法包括以下步骤。
步骤31：提供3-羟基天冬氨酸和化合物C。
其中，化合物C为
Figure PCTCN2020089864-appb-000018
L为离去基团。可选地，L为Cl、I或Br等，当然不限于此。
M如第一方面定义的M 2和M 3。优选地，M为Na或H。
并且，R如第一方面定义的R 2和R 3。优选地，R为-CH 2-。
优选地，化合物C为氯乙酸、碘乙酸或溴乙酸等。
步骤32：使3-羟基天冬氨酸和化合物C进行取代反应，以得到式I所示的螯合剂。
其中，3-羟基天冬氨酸和化合物C可以在碱性环境下发生取代反应。
其中，该碱性环境可以由诸多碱性物质来提供，例如，碱性环境包括NaOH或KOH等。
以化合物C为氯乙酸为例，可以通过3-羟基天冬氨酸和化合物C的取代反应生成式Ia所示的螯合剂。
在第五方面，本申请提供第四种实施方式的制备式I所示的螯合剂的方法。本实施方式制备式I所示的螯合剂的方法包括以下步骤。
步骤41：提供3-羟基天冬氨酸和化合物E。
其中，化合物E：
Figure PCTCN2020089864-appb-000019
R如第一方面定义的R 2和R 3。优选地，R为-CH 2-。
L为离去基团。可选地，L为Cl、I或Br等，当然不限于此。
优选地，化合物E为氯乙腈、碘乙腈或溴乙腈等。
步骤42：使3-羟基天冬氨酸和化合物E进行取代反应，以得到化合物F。
化合物F：
Figure PCTCN2020089864-appb-000020
优选地，本申请可以在第二催化剂的作用下使3-羟基天冬氨酸和化 合物E进行取代反应。第二催化剂为无机铵盐、有机胺或酰胺等。例如，第二催化剂为三乙胺。
例如，3-羟基天冬氨酸和氯乙腈在三乙胺的催化作用下生成的化合物F的结构通式为
Figure PCTCN2020089864-appb-000021
步骤43：使化合物F发生水解反应，以得到式I所示螯合剂。
通过使化合物F的氰基水解生成羧酸或羧酸盐，让化合物F转变为式I所示的螯合剂。
具体地，化合物F可以在酸性环境下或碱性环境下发生水解反应。化合物F发生水解反应的酸碱要求可以是：化合物F反应溶液的pH小于或等于3，或者大于或等于10。
可以由各种碱提供碱性环境，只要通过添加碱使化合物F反应溶液的pH满足上述酸碱要求即可。例如，通过NaOH提供碱性环境。
同样地，可以由各种酸提供酸性环境，只要通过添加酸使化合物F反应溶液的pH满足上述酸碱要求即可。例如，通过盐酸提供酸性环境。
上述制备式I所示的螯合剂的方法，原料来源广泛，价格低廉，生产设备简单，反应过程中的化学反应可以一锅法进行合成，安全性高、没有涉及剧毒类物质，同时产品收率高，性能好，对环境无负面影响，是绿色环保且易于大工业生产的工艺。
具体通过下述实施例来说明本申请。
实施例1：
向2000mL四口瓶中加入196g马来酸酐，然后加入200g去离子水，25℃水解1h。再用50％(质量分数)的NaOH溶液调节反应体系的pH 为6.0-6.5，保持温度不超过45℃。滴加完毕后，升温至55℃，搅拌15min。在反应体系中加入14g钨酸钠，搅拌45min。再在90min内滴加完30％双氧水溶液，同时向体系加50％NaOH调节pH。反应过程中，pH＝6.0-7.5，温度不超过75℃。滴加双氧水完毕后，升温至65℃，搅拌3h，然后加入亚氨基二乙酸266g，搅拌1h，加入160g固体氢氧化钠，然后升温到80℃，反应5h，降温得到N，N-二乙羧酸基-3-羟基二琥珀酸四钠盐的溶液，即式Ia所示的螯合剂的溶液，收率：95.33％。
实施例2：
向2000mL四口瓶中加入232g顺丁烯二酸，然后加入200g去离子水，45℃搅拌1h。再用50％(质量分数)的NaOH溶液调节反应体系的pH为5.0-6.5，保持温度不超过55℃。滴加完毕后，升温至55℃，搅拌15min。在反应体系中加入16g钨酸钠，搅拌45min。再在90min内滴加完30％双氧水溶液，同时向体系加50％NaOH调节pH。反应过程中，pH＝6.0-7.0，温度不超过75℃。滴加双氧水完毕后，升温至60-65℃，搅拌3h，然后加入亚氨基二乙酸266g，搅拌1h，加入160g固体氢氧化钠，然后升温到90℃，反应8h，降温得到N，N-二乙羧酸基-3-羟基二琥珀酸四钠盐的溶液，即式Ia所示的螯合剂的溶液，收率：96.12％。
实施例3：
向2000mL四口瓶中加入232g富马酸，然后加入200g去离子水，45℃搅拌1h。再用50％(质量分数)的NaOH溶液调节反应体系的pH为5.0-6.5，保持温度不超过55℃。滴加完毕后，升温至55℃，搅拌15min。在反应体系中加入20g钨酸钠，搅拌45min。再在90min内滴加完30％双氧水溶液，同时向体系加50％NaOH调节pH。反应过程中，pH＝6.0-7.0，温度不超过75℃。滴加双氧水完毕后，升温至60-65℃，搅拌3h，然后加入亚氨基二乙酸266g，搅拌1h，加入160g固体氢氧化钠，然后升温到90℃，反应8h，降温得到N，N-二乙羧酸基-3-羟基二琥珀酸四钠盐的溶液，即式Ia所示的螯合剂的溶液，收率：85.12％。
实施例4：
向2000mL四口瓶中加入196g马来酸酐，然后加入200g去离子水， 25℃水解1h。再用30％(质量分数)的KOH溶液调节反应体系的pH为6.0-6.5，保持温度不超过45℃。滴加完毕后，升温至55℃，搅拌15min。在反应体系中加入10g钨酸钠，搅拌45min。再在90min内滴加完30％双氧水溶液，同时向体系加30％KOH调节pH。反应过程中，pH＝6.0-7.5，温度不超过75℃。滴加双氧水完毕后，升温至60-65℃，搅拌3h，然后加入亚氨基二乙酸266g，搅拌1h，加入224g固体氢氧化钾，然后升温到95℃，反应15h，降温得到N，N-二乙羧酸基-3-羟基二琥珀酸四钠盐的溶液，即式Ia所示的螯合剂的溶液，收率：96.23％。
实施例5：
向2000mL四口瓶中加入232g顺丁烯二酸，然后加入200g去离子水，45℃搅拌1h。再用30％(质量分数)的KOH溶液调节反应体系的pH为6.0-6.5，保持温度不超过45℃。滴加完毕后，升温至55℃，搅拌15min。在反应体系中加入15g钨酸钠，搅拌45min。再在60min内滴加完30％双氧水溶液，同时向体系加30％KOH调节pH。反应过程中，pH＝6.0-7.5，温度不超过75℃。滴加双氧水完毕后，升温至60-65℃，搅拌3h，然后加入亚氨基二乙酸266g，搅拌1h，加入224g固体氢氧化钾，然后升温到80℃，反应15h，降温得到N，N-二乙羧酸基-3-羟基二琥珀酸四钠盐的溶液，即式Ia所示的螯合剂的溶液，收率：91.23％。
实施例6：
向2000mL四口瓶中加入196g马来酸酐，然后加入150g去离子水，甲醇50g，25℃水解1h。再用50％(质量分数)的NaOH溶液调节反应体系的pH为6.0-6.5，保持温度不超过45℃。滴加完毕后，升温至55℃，搅拌15min。在反应体系中加入14g按质量比1:1混合的钼酸钠和钨酸钠，搅拌45min。再在90min内滴加完30％双氧水溶液，同时向体系加50％NaOH调节pH。反应过程中，pH＝6.0-7.5，温度不超过65℃。滴加双氧水完毕后，升温至65℃，搅拌2h，然后加入亚氨基二乙酸266g，搅拌1h，加入160g固体氢氧化钠，然后升温到80℃，反应15h，降温得到N，N-二乙羧酸基-3-羟基二琥珀酸四钠盐的溶液，即式Ia所示的螯合剂的溶液，收率：94.23％。
另外，将实施例1至实施例6任一实施例得到的Ia所示的螯合剂进行酸化，可以得到式Ib所示的螯合剂。其中，所得产物的质谱图如图1所示，测量值为266.1，测量值与式Ib所示的螯合剂的理论值相吻合，证明所得的产物包括式Ib所示的螯合剂。结合如图2所示的所得产物的核磁氢谱图，能够证明所得的产物中式Ib所示的螯合剂的纯度大于或等于99％。
并且，本申请通过下述测试方法确定螯合剂对各种金属离子的螯合性能。
(1)镁离子螯合值测定方法
称取试样1g，加80ml蒸馏水溶解或分散，再加入10％Na 2CO 3溶液15ml，并用2mol/L的NaOH标准溶液调节pH在10.5，将上述配制好的试样溶液，放置在磁力搅拌器上，放入搅拌棒，开启搅拌器，再用0.25mol/L的MgCl 2标准溶液滴定，滴定至试样溶液成微浑时为终点。记录消耗0.25mol/L MgCl 2标准溶液体积为V，同时做空白对照实验，记录消耗MgCl 2体积V 0。
W＝(V-V 0)*6.0775/m
V 0-空白溶液消耗0.25mol/L MgCl 2标准溶液体积，ml；
V-消耗0.25mol/L MgCl 2标准溶液体积，ml；
m-试样质量，g；
6.0775-Mg 2+摩尔质量和MgCl 2摩尔浓度的积。
(2)铁离子螯合值—磺基水杨酸显色测定
准确称取待测样品1.0000g，加去离子水溶解，移至100ml容量瓶中定容至刻度，摇匀备用待测。移取配制好的样品溶液2ml于50ml锥形瓶中，加30ml水和5滴2％磺基水杨酸，用0.01mol/L硫酸铁铵标准溶液滴定至溶液由无色变为微红色为终点。计算公式如下：
X＝V*C*159.6*50/m
V-样品消耗硫酸铁铵溶液的体积，ml；
C-硫酸铁铵标准溶液的浓度，mol/L；
M-样品质量，g。
(3)铜离子螯合值测定方法
首先准确称取1g样品(精确至0.0001g)，配成100ml溶液。然后移取10ml样品溶液加入至锥形瓶中，加入40ml去离子水，用30％NaOH溶液调节pH为12，最后用1g/L的Cu 2+标准溶液滴定，直至产生永久性浑浊为终点(滴定过程中保持溶液pH为12)。
按上述步骤进行空白试验。每克共聚物络合铜离子的毫克数即为标准溶液滴定时所消耗的毫克数。
A＝(V 1-V 0)*C*10/G
V 1-样品溶液消耗三价铁标准溶液的体积(ml)；
V 0-空白溶液消耗三价铁标准溶液的体积(ml)；
C-Cu 2+标准溶液的质量浓度(1g/L)；
G-样品的质量(1g)；
A-样品螯合Cu 2+的值，mg/g。
(4)钙离子螯合值测定方法
称取2g样品于250ml广口锥形瓶中，加入约100ml去离子水，再加入20g/L Na 2CO 3溶液10ml，加水至150ml刻度。调节pH在11，磁力搅拌条件下用10mg/ml CaCl 2标准溶液滴定至产生微浑浊永久性沉淀，滴定过程中保持pH在11左右。消耗氯化钙溶液的体积V，以碳酸钙mg/g表示钙螯合值X。
X＝V*2.5*C/m
V-样品消耗氯化钙标准溶液的体积，ml；
C-氯化钙标准溶液的浓度，mg/ml；
M-样品质量，g。
(5)钙离子分散性能测定方法：
称量样品4g于100ml容量瓶内，将样品稀释至100ml定容，移取25ml稀释液置于100ml广口锥形瓶中，加入30ml去离子水，加入10ml的10％Na 2CO 3，磁力搅拌下用0.1mol/L乙酸钙标准溶液滴定，记录消耗乙酸钙标准溶液的体积V，同时做空白对照记录消耗乙酸钙体积V0。
W＝(V-V 0)*C(乙酸钙)*400/m。
以上仅为本申请的实施方式，并非因此限制本申请的专利范围，凡 是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (16)

  1. 一种螯合剂，其特征在于，所述螯合剂的通式如下所示：
    Figure PCTCN2020089864-appb-100001
    其中：
    R 1、R 2、R 3和R 4为烷基；
    M 1、M 2、M 3和M 4为氢原子、金属原子、铵基或有机胺基；
    A为羟基或氨基。
  2. 根据权利要求1所述的螯合剂，其特征在于，所述烷基为-(CH 2) n-，且0≤n≤6。
  3. 根据权利要求2所述的螯合剂，其特征在于，R 1和R 4为-(CH 2) 0-，R 2和R 3为-CH 2-。
  4. 根据权利要求1所述的螯合剂，其特征在于，所述金属原子为Na。
  5. 一种制备权利要求1所述螯合剂的方法，其特征在于，所述方法包括：
    提供环氧琥珀酸(盐)，
    使环氧琥珀酸(盐)和化合物A进行加成反应，以得到化合物B；
    使化合物B和化合物C进行取代反应，以得到所述螯合剂；
    其中，化合物A、化合物B和化合物C的结构通式如下，
    化合物A：
    Figure PCTCN2020089864-appb-100002
    化合物B：
    Figure PCTCN2020089864-appb-100003
    化合物C：
    Figure PCTCN2020089864-appb-100004
    其中，R为如权利要求1定义的R 2或R 3，M为如权利要求1定义的M 2或M 3，M 1和M 2具有与权利要求1相同的含义，且L为离去基团。
  6. 一种制备权利要求1所述螯合剂的方法，其特征在于，所述方法包括：
    提供环氧琥珀酸(盐)和化合物D；
    使环氧琥珀酸(盐)和化合物D进行加成反应，以得到所述的螯合剂；
    其中，化合物D为
    Figure PCTCN2020089864-appb-100005
    R 2和R 3具有与权利要求1相同的含义，M 5和M 6为氢原子、金属原子、铵基或有机胺基。
  7. 根据权利要求6所述的制备螯合剂的方法，其特征在于，所述使环氧琥珀酸(盐)和化合物D进行加成反应，以得到所述的螯合剂，包括：
    将环氧琥珀酸(盐)和化合物D混合，搅拌第四时间，添加包含M 7的氢氧化物，升温至第二温度，并反应第五时间，以得到所述螯合剂，其中，M 7为如权利要求1定义的M 1和M 4。
  8. 根据权利要求7所述的制备螯合剂的方法，其特征在于，
    所述第二温度为60-100℃；所述第四时间为0.5-2h；所述第五时间为2-24h。
  9. 根据权利要求5或6所述的制备螯合剂的方法，其特征在于，
    所述提供环氧琥珀酸(盐)，包括：提供马来酸(盐)和/或富马酸(盐)，使马来酸(盐)和/或富马酸(盐)进行环氧化反应，以得到环氧琥珀酸(盐)。
  10. 根据权利要求9所述的制备螯合剂的方法，其特征在于，
    所述使马来酸(盐)和/或富马酸(盐)进行环氧化反应，以得环氧琥珀酸(盐)，包括：使马来酸(盐)和/或富马酸(盐)在氧化剂、催化剂和弱碱性或弱酸性环境下进行环氧化反应；
    其中，所述催化剂为钨酸钠、钼酸钠、钒酸铵中的至少一种；
    所述弱碱性或弱酸性环境是指pH为3-8的环境。
  11. 根据权利要求10所述的制备螯合剂的方法，其特征在于，所述使马来酸(盐)和/或富马酸(盐)在氧化剂、催化剂和弱碱性或弱酸性环境下进行环氧化反应，包括：
    将催化剂添加到马来酸(盐)和/或富马酸(盐)中，搅拌第一时间；
    再在第二时间内将氧化剂溶液滴加到马来酸(盐)和/或富马酸(盐)中，同时通过添加碱液调节马来酸(盐)和/或富马酸(盐)溶液的pH；
    在第一温度下，反应第三时间，以得到环氧琥珀酸(盐)。
  12. 根据权利要求11所述的制备螯合剂的方法，其特征在于，所述提供马来酸(盐)和/或富马酸(盐)，包括：
    使马来酸酐在水解温度下进行水解反应，以得到马来酸(盐)和/或富马酸(盐)；
    所述提供马来酸(盐)和/或富马酸(盐)，之后包括：
    将马来酸(盐)和/或富马酸(盐)的溶液的pH调节至第一pH，将马来酸(盐)和/或富马酸(盐)的溶液的温度调节至第三温度。
  13. 根据权利要求12所述的制备螯合剂的方法，其特征在于，所述第一时间为30-60min；第二时间为40-120min；第三时间为2-10h；所述第一温度为45-80℃；所述第三温度为40-60℃；所述水解温度为 0-75℃；所述第一pH为4-8。
  14. 一种制备权利要求1-4任一项所述螯合剂的方法，其特征在于，所述方法包括：
    提供3-羟基天冬氨酸和化合物C；
    使3-羟基天冬氨酸和化合物C进行取代反应，以得到所述螯合剂；
    其中，化合物C为
    Figure PCTCN2020089864-appb-100006
    L为离去基团，R为如权利要求1定义的R 2或R 3，M为如权利要求1定义的M 2或M 3。
  15. 一种制备权利要求1-4任一项所述螯合剂的方法，其特征在于，所述方法包括：
    提供3-羟基天冬氨酸和化合物E；
    使3-羟基天冬氨酸和化合物E进行取代反应，以得到化合物F，
    使化合物F进行水解反应，以得到所述螯合剂；
    所述化合物E和化合物F的结构通式如下所示：
    化合物E：
    Figure PCTCN2020089864-appb-100007
    化合物F：
    Figure PCTCN2020089864-appb-100008
    L为离去基团，R为如权利要求1定义的R 2或R 3。
  16. 一种清洗剂，其特征在于，所述清洗剂包括权利要求1-4任一项所述的螯合剂。
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