CN116814090A - Water-soluble diacryloyl amino C acid dye and synthesis method and application thereof - Google Patents
Water-soluble diacryloyl amino C acid dye and synthesis method and application thereof Download PDFInfo
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- CN116814090A CN116814090A CN202310684113.7A CN202310684113A CN116814090A CN 116814090 A CN116814090 A CN 116814090A CN 202310684113 A CN202310684113 A CN 202310684113A CN 116814090 A CN116814090 A CN 116814090A
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- -1 amino C acid Chemical compound 0.000 title claims abstract description 41
- 239000000980 acid dye Substances 0.000 title claims abstract description 22
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 239000000975 dye Substances 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002250 absorbent Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000003112 inhibitor Substances 0.000 claims description 28
- 238000009833 condensation Methods 0.000 claims description 25
- 230000005494 condensation Effects 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012954 diazonium Substances 0.000 claims description 17
- 150000001989 diazonium salts Chemical class 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 11
- 235000010288 sodium nitrite Nutrition 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical group CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000005185 salting out Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000006193 diazotization reaction Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000037048 polymerization activity Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 14
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/40—Preparation of azo dyes from other azo compounds by substituting hetero atoms by radicals containing other hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
- C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0014—Monoazo dyes prepared by diazotising and coupling from diazotized aminonaphthalene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a water-soluble diacryloyl amino C acid dye, a synthesis method thereof and application thereof in colored water-absorbent resin. The dye obtained by the invention has simple synthesis process and high yield and purity; the diacryloyl containing unsaturated C=C bond is introduced into dye molecules, so that the dye has extremely high polymerization activity, the dye can be copolymerized with acrylic acid according to different proportions to obtain the colored water-absorbent resin, the obtained resin is uniform in coloring and difficult to fade, and the application of the amino C acid series dye is widened.
Description
Technical Field
The invention relates to a water-soluble dye, in particular to a synthesis method of a diacryloyl amino C acid dye and application of the diacryloyl amino C acid dye in colored water-absorbent resin.
Background
The water-absorbing resin can absorb water of tens or hundreds or thousands of times of the weight of the water-absorbing resin, and is widely used as a water-retaining material for agriculture, forestry and gardening. The new matrix crystal mud (namely water-absorbing resin) for flower cultivation, which is present on the market, can play a role in beautifying the environment and reducing the labor intensity of flower cultivation, and the new matrix for flower cultivation is becoming popular. In order to improve the commodity value, pigment is added into the crystal mud, so that the ornamental value is improved. However, most of the pigments used in the crystal mud at present are water-soluble pigments, and crystal mud with different colors cannot be mixed, otherwise, the colors are mutually penetrated and easy to change color, or the water-insoluble pigments are accumulated in the water-absorbent resin to form clusters although the water-insoluble pigments are adopted, so that the water-absorbent resin is not uniformly dispersed, and the value of the commodity is reduced.
Amino C acid is often used for synthesizing reactive dye, the amino C acid series dye has bright color and stable property, and the bisacryl is introduced into the dye through hydroxyethyl acrylate, so that the dye has extremely high polymerization activity while retaining the original advantages, and the dye is copolymerized with acrylic acid to obtain the colored water-absorbent resin which is uniform in coloring and not easy to fade.
Disclosure of Invention
The invention aims to provide a synthesis method of a water-soluble diacryl amino C acid dye, a synthesis method of application of the water-soluble diacryl amino C acid dye in color water-absorbent resin and application of the water-soluble diacryl amino C acid dye, wherein diacryl is introduced on the premise of not damaging bright color of the dye, so that the dye has extremely high polymerization capacity, and the dye is copolymerized with acrylic acid to prepare the color water-absorbent resin, so that the application of amino C acid series dyes is widened.
In order to achieve the aim, the invention adopts the following technical scheme that the water-soluble diacryloyl amino C acid dye has the following structure:
。
the invention also provides a preparation method of the water-soluble diacryloyl amino C acid dye, which comprises the following steps:
preparing a bis-acryl-chlornitrile intermediate by condensing cyanuric chloride with hydroxyethyl acrylate;
diazotization of (di) amino C acid to obtain diazonium salt system;
coupling diazonium salt and m-methylaniline to prepare a dye chromophore system;
(IV) condensing the diacryloyl chlornitrile intermediate with a chromophore to prepare a condensation system;
and fifthly, salting out the condensation system, and then carrying out suction filtration, washing and drying.
Further, the step (one) is as follows: dissolving cyanuric chloride in hydroxyethyl acrylate, adding a polymerization inhibitor, dropwise adding an organic amine acid-making agent under ice water bath, maintaining low temperature for reaction for 0.5 hour after dropwise adding, then adding the organic amine acid-making agent again, slowly heating to 40 ℃ for reaction for 2 hours, adding ethyl acetate into a system for dilution, water system for 10 times, drying by anhydrous sodium sulfate, and removing ethyl acetate by rotary evaporation to obtain a diacryloyl chlornitrile intermediate; preferably, the polymerization inhibitor is a polymerization inhibitor 701 or a polymerization inhibitor 705, and the dosage is 1-5% of the mass of the hydroxyethyl acrylate; the organic amine acid-binding agent is diisopropylethylamine or triethylamine, and the molar quantity of the organic amine acid-binding agent added for two times is 1.05-1.2 times of that of the trichloronitrile.
Further, the step (two) is as follows: dispersing amino C acid in water under stirring, adding concentrated hydrochloric acid (10 mol/L) under ice water bath, rapidly adding aqueous solution of sodium nitrite, and maintaining low temperature for reaction for 1 hour to obtain diazonium salt system; preferably, the molar ratio of the amino C acid to the concentrated hydrochloric acid is 1:2 to 1:3.5, the molar ratio of the amino C acid to the sodium nitrite is 1:1.04, and the concentration of the sodium nitrite aqueous solution is 30-35 wt%.
Further, the step (III) is as follows: injecting m-methylaniline into a diazonium salt system, regulating the pH value of a saturated sodium carbonate solution to be 4-5, and heating the system to 75 ℃ within 3 hours; preferably, the molar ratio of m-methylaniline to amino C acid is 1.05:1.
Further, the step (four) is as follows: heating the dye chromophore system to 50 ℃, dispersing the diacryloyl chloronitrile intermediate in a solvent, adding the dye chromophore system, adding a polymerization inhibitor, reacting for 1 hour, and controlling the pH value to be 6-7 to obtain a condensation system; preferably, the solvent is one or more of ethanol, acetone, acetonitrile and water; the polymerization inhibitor is a polymerization inhibitor 701 or a polymerization inhibitor 705, and the dosage is 0.1% -1% of the mass of the diacryloyl chlornitrile intermediate.
Further, the step (five) is as follows: adding sodium chloride into the condensation system under slow stirring, stirring for 5 hours, uniformly precipitating the dye, performing vacuum filtration on the system under reduced pressure, washing a filter cake with ethanol, and performing vacuum drying to obtain the water-soluble diacryloyl amino C acid dye; preferably, the mass of sodium chloride used is 15-25% of the volume of the condensation system.
The preparation method of the water-soluble diacryloyl amino C acid dye comprises the following steps:
preparation of bis-acryl-chlornitrile intermediate by condensation of cyanuric chloride and hydroxyethyl acrylate
Dissolving cyanuric chloride in hydroxyethyl acrylate, adding a polymerization inhibitor, dropwise adding an organic amine acid-making agent under ice water bath, maintaining low temperature for reaction for 0.5 hour after dropwise adding, then adding the organic amine acid-making agent again, slowly heating to 40 ℃ for reaction for 2 hours, adding ethyl acetate into a system for dilution, water system for 10 times, drying by anhydrous sodium sulfate, and removing ethyl acetate by rotary evaporation to obtain a diacryloyl chlornitrile intermediate; the polymerization inhibitor is a polymerization inhibitor 701 or a polymerization inhibitor 705, and the dosage is 1-5% of the mass of the hydroxyethyl acrylate; the organic amine acid-binding agent is diisopropylethylamine or triethylamine, and the molar quantity of the organic amine acid-binding agent added for two times is 1.05-1.2 times of that of the trichloronitrile;
diazotisation of (di) amino C acids
Adding amino C acid into ice water bath, adding concentrated hydrochloric acid (10 mol/L), quickly adding aqueous solution of sodium nitrite, and maintaining low-temperature reaction for 1 hour to obtain a diazonium salt system, wherein the molar ratio of the amino C acid to the concentrated hydrochloric acid is 1:2-1:3.5; the molar ratio of the amino C acid to the concentrated hydrochloric acid is 1:2-1:3.5, the molar ratio of the amino C acid to the sodium nitrite is 1:1.04, and the concentration of the sodium nitrite aqueous solution is 30-35 wt%;
coupling of diazonium salts with meta-methylanilines
Injecting m-methylaniline into a diazonium salt system, regulating the pH value of a saturated sodium carbonate solution to be 4-5, and heating the system to 75 ℃ within 3 hours to prepare a dye chromophore system; the molar ratio of m-methylaniline to amino C acid is 1.05:1;
(IV) Diacryl chloronitrile intermediate and chromophore condensation
Stirring a dye chromophore system at 50 ℃, adding sodium carbonate for neutralization, dispersing a bisacryloyl chloride nitrile intermediate in a solvent, adding a dye system, adding a polymerization inhibitor, reacting for 4 hours, and controlling the pH value to be 6-7 during the reaction to prepare a condensation system; the solvent is one or more of ethanol, acetone, acetonitrile and water, the polymerization inhibitor is a polymerization inhibitor 701 or a polymerization inhibitor 705, and the amount of the polymerization inhibitor is 0.1-1% of the mass of the diacryloyl chloronitrile intermediate. The method comprises the steps of carrying out a first treatment on the surface of the
And (V) salting out, suction filtering, washing and drying the condensation system, wherein the specific operation is as follows:
adding sodium chloride into the condensation system under slow stirring, stirring for 5 hours, uniformly precipitating the dye, performing vacuum filtration on the system under reduced pressure, washing a filter cake with ethanol, and performing vacuum drying to obtain the water-soluble diacryloyl amino C acid dye; the mass of sodium chloride is 15-25% of the volume of the condensation system.
The invention further provides application of the water-soluble diacryloyl amino C acid dye in preparing colored water-absorbent resin.
The invention has the advantages that: the dye molecule synthesis process is simple, and the prepared dye has high yield and purity; the introduction of the acryloyl group containing unsaturated C=C bond makes the compound have extremely high polymerization activity, can be copolymerized with acrylic acid to prepare the color water-absorbent resin, and widens the application of the C acid series dye.
Detailed Description
The invention is further illustrated by the following examples.
Example 1: synthesis of water-soluble diacryloylamino C acid dye
(1) Preparation of bis-acryl-chlornitrile intermediate by condensing cyanuric chloride with hydroxyethyl acrylate
18.4 Dissolving g cyanuric chloride in 150 ml hydroxyethyl acrylate, adding 2.7g of polymerization inhibitor 701, dropwise adding 18.5 ml diisopropylethylamine in ice water bath, maintaining low temperature for reaction for 0.5 hour after the dropwise addition, then adding 18.5 ml diisopropylethylamine again, slowly heating to 40 ℃ for reaction for 2 hours, adding 200 ml ethyl acetate into the system, diluting, washing with water for 10 times, drying with anhydrous sodium sulfate, and removing ethyl acetate by rotary evaporation to obtain a diacryloyl chloronitrile intermediate;
(2) Diazotisation of amino C acids
Taking 30.3 g of amino C acid in 300 ml water, uniformly stirring in an ice water bath, adding 10.6 g of sodium carbonate for neutralization, then adding 30 ml (10 mol/L) of concentrated hydrochloric acid, rapidly adding a 30% aqueous solution prepared by 7.2 g of sodium nitrite, and maintaining the temperature at 10-15 ℃ for diazotization reaction for 0.5 hour to prepare a diazonium salt system;
(3) Coupling of diazonium salts with meta-methylanilines
Injecting 11.3-ml m-methylaniline into a diazonium salt system, adding a saturated sodium carbonate solution to adjust the pH value to be 4-5, and heating the system to 75 ℃ within 3 hours to prepare a dye chromophore system;
(4) Bis-acryl chloronitriles intermediates and chromophore condensation
Stirring a dye chromophore system at 50 ℃, adding sodium carbonate for neutralization, dispersing 38. 38 g bis-acrylonitrile intermediate in 300 ml ethanol, adding the system, adding a polymerization inhibitor 701 in 0.2. 0.2 g, reacting for 4 hours, and controlling the pH value to be 6-7 during the reaction to prepare a condensation system;
(5) Salting out, suction filtering, washing and drying of condensation system
Adding sodium chloride with the total volume of 15% by mass ratio into the condensation system in batches under slow stirring, stirring for 5 hours, uniformly precipitating the dye, decompressing and filtering the system, washing a filter cake by using ethanol, and then drying in vacuum to obtain the water-soluble diacryloyl amino C acid dye.
The nuclear magnetic detection results are as follows:
1 H NMR (400 MHz, DMSO-d6) δ 10.49 (s, 1H), 9.56 (d, J = 2.0 Hz, 1H), 8.93 (d, J = 8.4 Hz, 1H), 8.47 (d, J = 2.0 Hz, 1H), 8.06 (dd, J = 7.2, 1.3 Hz, 1H), 7.86 – 7.72 (m, 3H), 7.57 (t, J = 7.2 Hz, 1H), 6.36 (dd, J = 17.2, 1.6 Hz, 2H), 6.19 – 6.26 (m, 2H), 5.98 (dd, J = 10.0, 1.6 Hz, 2H), 4.62 (m, 4H), 4.54 – 4.43 (m, 4H), 2.75 (s, 3H)。
example 2: preparation of colored water-absorbent resin
Dissolving the water-soluble diacryloyl amino C acid dye obtained in the example 1 of 5 g and 95 g acrylic acid in 100 ml water, introducing nitrogen for protection, stirring at 70 ℃, adding 0.5 g potassium persulfate and 0.5 g sodium bisulphite, reacting for 5 hours, and drying to obtain the colored water absorbent resin.
Comparative example: to illustrate the superiority of the samples made in this experiment, the following are samples that were not made according to the conditions set forth in the examples.
Comparative example 1: the dye chromophore reacts with the trichloronitrile and then reacts with the hydroxyethyl acrylate, and the rest steps are the same as the original method
(1) Diazotisation of amino C acids
Taking 30.2 g of amino C acid in 300 ml water, uniformly stirring in an ice water bath, adding 10.6 g of sodium carbonate for neutralization, then adding 30 ml g of concentrated hydrochloric acid, rapidly adding a 30% aqueous solution prepared from 7.2 g of sodium nitrite, and maintaining the temperature at 10-15 ℃ for diazotization reaction for 0.5 hour to prepare a diazonium salt system;
(2) Coupling of diazonium salts with meta-methylanilines
Injecting 11.3-ml m-methylaniline into a diazonium salt system, adding a saturated sodium carbonate solution to adjust the pH value to be 4-5, and heating the system to 75 ℃ within 3 hours to prepare a dye chromophore system;
(3) Preparation of condensation systems
Stirring a dye chromophore system in an ice water bath, adding sodium carbonate for neutralization, adding 18.4 g cyanuric chloride into the ice water bath, maintaining pH=6-7 for reaction for 3 hours, taking hydroxyethyl acrylate 25 g, adding the system, adding 1.2 g polymerization inhibitor 701, heating to 40 ℃ for reaction for 4 hours, and then continuously heating to 80 ℃ for reaction for 8 hours to prepare a condensation system;
(4) Salting out, suction filtering, washing and drying of condensation system
Adding sodium chloride with the mass ratio of 15% of the volume of the condensation system into the condensation system in batches under slow stirring, stirring for 5 hours, uniformly precipitating the dye, decompressing and filtering the system, washing a filter cake by using ethanol, and then drying in vacuum to obtain the water-soluble diacryloyl amino C acid dye.
Table 1 shows the yields and purities of the dyes obtained in example 1 and comparative example 1.
TABLE 1 dye yield and purity
| Yield (%) | Purity (%) | |
| Example 1 | 94 | 97% |
| Comparative example 1 | 70 | 66% |
。
Those skilled in the art will further recognize that the invention may be embodied in other specific forms without departing from the spirit or central characteristics thereof. Since the foregoing description of the invention discloses only exemplary embodiments thereof, it should be understood that other variations are considered to be within the scope of the invention. Therefore, the present invention is not limited to the specific embodiments described in detail herein. Rather, reference should be made to the appended claims for indicating the scope and content of the invention.
Claims (13)
1. A water-soluble bisacryloylamino C acid dye, characterized by having the following structure:
。
2. the method for preparing a water-soluble diacryloylamino C acid dye according to claim 1, comprising the steps of:
preparing a bis-acryl-chlornitrile intermediate by condensing cyanuric chloride with hydroxyethyl acrylate;
diazotization of (di) amino C acid to obtain diazonium salt system;
coupling diazonium salt and m-methylaniline to prepare a dye chromophore system;
(IV) condensing the diacryloyl chlornitrile intermediate with a chromophore to prepare a condensation system;
and fifthly, salting out the condensation system, and then carrying out suction filtration, washing and drying.
3. The method of claim 2, wherein the step (one) is: the cyanuric chloride is dissolved in hydroxyethyl acrylate, a polymerization inhibitor is added, an organic amine acid-making agent is dropwise added under ice water bath, the low temperature reaction is maintained for 0.5 hour after the dropwise addition is finished, then the organic amine acid-making agent is added again, the temperature is slowly increased to 40 ℃ for 2 hours, the system is diluted by ethyl acetate and then washed for 10 times, and the ethyl acetate is removed by rotary evaporation after anhydrous sodium sulfate is dried, so that the diacryloyl chlornitrile intermediate is obtained.
4. The preparation method according to claim 3, wherein the polymerization inhibitor is a polymerization inhibitor 701 or a polymerization inhibitor 705, and the amount is 1% -5% of the mass of the hydroxyethyl acrylate; the organic amine acid-binding agent is diisopropylethylamine or triethylamine, and the amount of the organic amine acid-binding agent added each time is 1.05-1.2 times of the mole amount of the trichloronitrile.
5. The method of claim 2, wherein the step (two) is: dispersing amino C acid in water under stirring, adding concentrated hydrochloric acid (10 mol/L) under ice water bath, rapidly adding aqueous solution of sodium nitrite, and maintaining low temperature for reaction for 1 hr to obtain diazonium salt system.
6. The method according to claim 5, wherein the molar ratio of the amino C acid to the concentrated hydrochloric acid is 1:2 to 1:3.5, the molar ratio of the amino C acid to the sodium nitrite is 1:1.04, and the concentration of the sodium nitrite aqueous solution is 30-35 wt%.
7. The method according to claim 2, wherein the step (iii) is: m-methylaniline was injected into the diazonium salt system and the saturated sodium carbonate solution was adjusted to ph=4-5, after which the system was warmed to 75 ℃ over 3 hours.
8. The method of claim 7, wherein the molar ratio of m-methylaniline to amino C acid is 1.05:1.
9. The method according to claim 2, wherein the step (four) is: and (3) heating the dye chromophore system to 50 ℃, dispersing the diacryloyl chloronitrile intermediate in a solvent, adding the dye chromophore system, adding a polymerization inhibitor, reacting for 1 hour, and controlling the pH value to be 6-7 during the reaction to obtain a condensation system.
10. The method of claim 9, wherein the solvent is one or more of ethanol, acetone, acetonitrile, and water; the polymerization inhibitor is a polymerization inhibitor 701 or a polymerization inhibitor 705, and the dosage is 0.1% -1% of the mass of the diacryloyl chlornitrile intermediate. .
11. The method according to claim 2, wherein the step (five) is: and adding sodium chloride into the condensation system in batches under slow stirring, stirring for 5 hours, uniformly precipitating the dye, decompressing and filtering the system, washing a filter cake by using ethanol, and then drying in vacuum to obtain the water-soluble diacryloyl amino C acid dye.
12. The process according to claim 11, wherein the mass of sodium chloride used is 15-25% of the volume of the condensation system.
13. The use of the water-soluble bisacryloyl amino C acid dye according to claim 1 in preparing colored water-absorbent resin.
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