CN115368280A - Preparation method and application of novel thermosensitive color developing agent - Google Patents
Preparation method and application of novel thermosensitive color developing agent Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- -1 diamine compounds Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 150000003461 sulfonyl halides Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- 239000013067 intermediate product Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 11
- 239000012044 organic layer Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 10
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 10
- 150000008041 alkali metal carbonates Chemical class 0.000 description 10
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 10
- 238000011161 development Methods 0.000 description 10
- 230000018109 developmental process Effects 0.000 description 10
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- RUZVAAMFWWVKGG-UHFFFAOYSA-N (3-aminophenyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CC(N)=C1 RUZVAAMFWWVKGG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- IXHBSOXJLNEOPY-UHFFFAOYSA-N 2'-anilino-6'-(n-ethyl-4-methylanilino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C=C(C2(C3=CC=CC=C3C(=O)O2)C2=CC(NC=3C=CC=CC=3)=C(C)C=C2O2)C2=CC=1N(CC)C1=CC=C(C)C=C1 IXHBSOXJLNEOPY-UHFFFAOYSA-N 0.000 description 1
- KNHJIEOCVVIBIV-UHFFFAOYSA-N 2,3-dimethylphenyl isocyanate Chemical compound CC1=CC=CC(N=C=O)=C1C KNHJIEOCVVIBIV-UHFFFAOYSA-N 0.000 description 1
- WHJAQKAAIOHCGN-UHFFFAOYSA-N 2,4,6-trichlorobenzenesulfonyl chloride Chemical compound ClC1=CC(Cl)=C(S(Cl)(=O)=O)C(Cl)=C1 WHJAQKAAIOHCGN-UHFFFAOYSA-N 0.000 description 1
- PVJZBZSCGJAWNG-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonyl chloride Chemical compound CC1=CC(C)=C(S(Cl)(=O)=O)C(C)=C1 PVJZBZSCGJAWNG-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QEJDLQGIDJNJTI-UHFFFAOYSA-N C=1C=CC=CC=1N(S(=O)=O)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1N(S(=O)=O)C1=CC=CC=C1 QEJDLQGIDJNJTI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- ATFKBWNEVZUSKC-UHFFFAOYSA-N methyl 2-isocyanatobenzoate Chemical compound COC(=O)C1=CC=CC=C1N=C=O ATFKBWNEVZUSKC-UHFFFAOYSA-N 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- UJYAZVSPFMJCLW-UHFFFAOYSA-N n-(oxomethylidene)benzenesulfonamide Chemical compound O=C=NS(=O)(=O)C1=CC=CC=C1 UJYAZVSPFMJCLW-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical group OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of IPC 07C311/60, in particular to a preparation method and application of a novel thermosensitive color developing agent. The preparation method of the novel thermosensitive color developing agent comprises the steps of mixing diamine compounds and sulfonyl halides for reaction, and then reacting with a compound containing-NCO to obtain the novel thermosensitive color developing agent product. The novel thermosensitive color developing agent provided by the invention has the following advantages: the ternary benzene ring non-phenol type thermal sensitive color developing agent with a novel structure improves the separation effect of a target product and impurities, remarkably improves the yield and purity of the thermal sensitive color developing agent and provides a feasible scheme for the subsequent preparation of thermal sensitive paper while optimizing the production process efficiency and safety of the color developing agent; the obtained thermosensitive color developing agent has wide adaptability to base materials, can be applied to various thermosensitive paper, and has the characteristics of high color developing sensitivity, high color developing density, strong image stability and strong environmental tolerance, and has wide application prospect.
Description
Technical Field
The invention relates to the field of IPC 07C311/60, in particular to a preparation method and application of a novel thermosensitive color developing agent.
Background
Thermal paper, as an information carrier capable of presenting different patterns on paper, has been rapidly applied to various working scenes such as facsimile communication, securities, labels, ticketing, instrument recording terminals and the like since the development, and is a novel information recording material. The color development principle of the thermal paper is that the base paper is combined with a reagent with a specific color development function, so that the property of the developer directly influences the color development performance of the thermal paper. The traditional phenol color developing agent has poor color developing sensitivity, and is difficult to meet the high requirements of thermal paper on image quality and image stabilization when being applied to the thermal paper; meanwhile, the phenol color developing agent has strong volatility, has negative influence on human health in both the preparation process and the use process, and is gradually eliminated in the field of color developing agents for thermal paper.
Chinese patent CN202010157164.0 discloses a novel non-phenolic thermosensitive color developing agent, a preparation method and application thereof in thermosensitive recording materials, wherein benzenesulfonyl isocyanate and m-phenylenediamine are adopted to react to obtain N, N ' - ((1,3-phenylenebis (azepindiyl)) bis (carbonyl))) diphenylsulfonamide, but the m-phenylenediamine in the synthetic raw materials is an accepted ' tri-cause ' substance in the industry, and can cause mutagenic action, carcinogenic action and teratogenic action in the use process, and thermosensitive paper is used by human bodies in direct contact in daily life, and the method has greater potential safety hazard.
Chinese patent CN201710175990.6 discloses a preparation method of a thermosensitive color developing agent containing a sulfonylurea structure, which adopts m-aminophenol and p-toluenesulfonyl chloride to esterify under an alkaline condition to obtain 3-aminophenyl p-toluenesulfonate, then reacts with p-toluenesulfonyl isocyanate, and is further acidified and refined to obtain a finished product of the thermosensitive color developing agent. The color developing agent obtained by the method has excellent performance, but has higher requirements on process operation, and can not meet the requirements of large-batch thermal sensitive paper.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a method for preparing a novel heat-sensitive color developing agent, which comprises the steps of mixing a diamine compound with a sulfonyl halide, and then reacting with a compound containing-NCO to obtain a novel heat-sensitive color developing agent product.
In some preferred embodiments, at least 2 of the diamine-based compound, the sulfonyl halide, and the-NCO containing compound contain a benzene ring structure.
In some preferred embodiments, the diamine compound is an aromatic diamine compound, and the number of primary amines in the aromatic diamine compound is greater than or equal to 1.
Further preferably, the aromatic diamine compound contains a primary amine in an amount of 2, preferably at least one of 1,2-phenylenediamine, 1,3-phenylenediamine and 1,4-phenylenediamine.
Still more preferably, the aromatic diamine compound is 1,2-phenylenediamine.
In some preferred embodiments, the sulfonyl halide is specifically a benzenesulfonyl halide, and the number of electron layers of the halogen element in the benzenesulfonyl halide is 2 to 5; namely, the halogen element is selected from any one of chlorine, bromine, iodine and fluorine.
Further preferably, the halogen element in the sulfonyl halide is chlorine; the sulfonyl halide comprises one or more of benzene sulfonyl chloride, 2,4,6-trichlorobenzene sulfonyl chloride, 4 methyl sulfonyl chloride, 4-chlorine-2,5-dimethyl benzene sulfonyl chloride and 2,4,6-trimethyl benzene sulfonyl chloride.
Still more preferably, the sulfonyl halide is benzenesulfonyl chloride.
In some preferred embodiments, the-NCO containing compound contains a benzene ring structure including a combination of one or more of phenyl isocyanate, butyl 4-isocyanate benzoate, p-phenylene diisocyanate, 1-isocyanate-4-pentylbenzene, methyl-benzene diisocyanate, 2,3-dimethylphenyl isocyanate, 2- (methoxycarbonyl) phenyl isocyanate.
More preferably, the melting point of the-NCO containing compound is-15 to-45 ℃ and the surface tension is 30-50dyne/cm.
More preferably, the-NCO containing compound is phenyl isocyanate having a melting point of-31. + -. 1 ℃ and a surface tension of 38.6dyne/cm.
In order to balance the color developing properties and safety of the developer, the present applicant has aimed at exploring a novel color developing material capable of effectively substituting a phenolic developer. In the process of researching the technology of the thermal paper, NH is found 2 -C(＝O)-NH-R-S(＝O) 2 The material with the structure has the characteristics of high sensitivity and high color development density when being applied to paper base materials, and the preparation of the novel thermosensitive color developing agent can be realized by adopting a polyfunctional amine compound as an initial synthetic raw material to react with sulfonyl halide and a compound containing-NCO. However, the starting materials used in this synthetic route are allThe method has the characteristic of high reaction activity, the reaction process is difficult to control in the actual synthesis process, the yield and the purity of the synthesized product are low, and the subsequent color development imaging definition is low. The applicant has studied a lot of attempts, and finds that a high-yield and high-purity ternary benzene ring chromogenic structure can be obtained under mild process conditions by adopting diamine compounds containing a benzene ring structure, sulfonyl halides to react with compounds containing-NCO, particularly by selecting 1,2-phenylenediamine to react with benzenesulfonyl chloride and phenyl isocyanate; the reason is probably that under the condition, each reactant has both reactivity and proper steric hindrance, and the interaction between each reaction group is promoted, so that the yield and the purity of the synthesized product are improved.
In some preferred embodiments, the preparation steps of the novel heat-sensitive color developer are specifically as follows:
s1, putting diamine compounds into a reaction vessel containing a mixed solvent, setting the temperature to be 10-16 ℃ under nitrogen atmosphere, then adding sulfonyl halide, heating to 50-60 ℃, reacting for 1-2h, and collecting intermediate products;
s2, cooling the intermediate product to 30-37 ℃, adding a compound containing-NCO, carrying out heat preservation reaction for 1-2h, and carrying out purification treatment to obtain the novel thermosensitive color developing agent product.
In some preferred embodiments, the operation of collecting the intermediate product is specifically, after the reaction in step S1 is finished, adding the second solvent into the reaction vessel, raising the temperature to 55-65 ℃, dissolving all the materials, standing, separating the materials into an organic layer and a water layer, removing the water layer, and performing azeotropic dehydration on the organic layer to obtain the intermediate product.
In some preferred embodiments, the mixed solvent includes a combination of an organic solvent and an inorganic solvent; the inorganic solvent is water, and the organic solvent comprises at least one of ethyl acetate, methanol, acetonitrile, acetone, cyclohexane, N-dimethylformamide and toluene.
More preferably, the mixed solvent is water and toluene, and the volume ratio of the toluene to the water is (2-5): 1.
in some preferred embodiments, in the step S1, when the diamine compound is fed into the reaction vessel, the alkali metal carbonate is added at the same time; the molar ratio of the diamine compound to the alkali metal carbonate is 2: (1-1.5).
In some preferred embodiments, the alkali metal carbonates include, but are not limited to, sodium carbonate, potassium carbonate.
The applicant finds that in the experimental operation process, organic-inorganic mixed solvent is adopted in the reaction process of 1,2-phenylenediamine and benzene sulfonyl chloride, and a specific amount of alkali metal carbonate is added, so that the formation of-NHSO (N-NHSO) between a primary amine molecule and a sulfonyl group can be effectively promoted 2 -a structure; the normal step S1 needs more than 2 hours for reaction from normal temperature to 50 ℃, and the invention unexpectedly discovers that when the volume ratio of the mixed solvent is (2-5): 1, controlling the initial temperature to be 10-16 ℃, then heating to react, and obviously improving the reaction activity of the aromatic diamine and the benzene sulfonyl chloride, so that the reaction in the step S1 can be completed within 1.5 hours, the obtained intermediate product is easy to separate from impurities, and the yield of the finished product of the color developing agent is improved while the process efficiency is improved.
In some preferred embodiments, the purification treatment is specifically, after the reaction in step S2 is finished, the temperature of the reaction vessel is reduced to below 10 ℃, the solid product is collected by suction filtration, and dried under a negative pressure condition, so as to obtain the novel heat-sensitive color developing agent product.
The applicant also finds that the moisture content of the intermediate product is easy to interfere with the subsequent reaction process, the generated by-products influence the smooth reaction, and reactants are consumed to reduce the yield of the final product. After the organic layer and the water layer are separated and separated, the organic layer is further subjected to azeotropic dehydration before the step S2 begins, so that the occurrence of side reaction can be obviously inhibited, the step S2 can be stably carried out at a lower temperature, and after the reaction is finished, a novel color developing agent with the yield of 95 percent and the purity of more than 98 percent can be obtained through simple suction filtration and drying operations.
In some preferred embodiments, the sulfonyl halide is added at a rate of 0.05 to 1mol/min.
In some preferred embodiments, the addition rate of the-NCO containing compound is from 0.1 to 0.2mol/min.
In some preferred embodiments, the addition rate of the sulfonyl halide is 0.5 to 3 times the addition rate of the-NCO containing compound.
The structural formula of the novel thermosensitive color developing agent provided by the invention is as follows:
the invention provides an application of a preparation method of a novel thermosensitive color developing agent in the field of thermosensitive materials.
The applicant finds that the thermosensitive color developing agent with the structure obtained by the preparation method has the characteristics of high sensitivity, high color development density and high image stability, can exert excellent color development effect when being combined with various paper materials, can be used for thermosensitive paper with various color development requirements such as thermosensitive fax paper, thermosensitive films, boarding cards, thermosensitive label paper, lottery tickets, tickets and the like in the practical application process, has clear color development and long aging period, is not easy to lose even in the severe environments such as moist environment, muggy environment and the like, and has the advantages that the pattern is not easy to deform and migrate after the thermosensitive paper is folded.
Has the advantages that:
the novel thermosensitive color developing agent provided by the invention has the following advantages:
(1) 1,2-phenylenediamine is adopted to react with benzenesulfonyl chloride and phenyl isocyanate to obtain the non-phenolic heat-sensitive color developing agent with the active color developing group under mild reaction conditions, so that the production process efficiency and safety of the color developing agent are optimized, and the ternary benzene ring non-phenolic heat-sensitive color developing agent with a novel structure is provided;
(2) By controlling the dosage of each raw material and matching with a specific temperature rise program and impurity removal steps, the occurrence of side reactions in the reaction process is inhibited, the separation effect of a target product and impurities is improved, the yield and the purity of the thermosensitive color developing agent are obviously improved, and a feasible scheme is provided for the subsequent preparation of thermosensitive paper;
(3) The obtained thermosensitive color developing agent has wide adaptability to base materials, can be applied to various thermosensitive paper, and has the characteristics of high color developing sensitivity, high color developing density, strong image stability and strong environmental tolerance, and has wide application prospect.
Detailed Description
Example 1.
The embodiment provides a preparation method of a novel thermosensitive color developing agent, which specifically comprises the following steps:
s1, putting 2mol of diamine compound into a reaction vessel containing 1500mL of mixed solvent, setting the temperature to be 14 ℃ under nitrogen atmosphere, then adding 1.8mol of sulfonyl halide, heating to 53 ℃, reacting for 1.5h, and collecting an intermediate product;
s2, cooling the intermediate product to 35 ℃, adding 1.9mol of compound containing-NCO, carrying out heat preservation reaction for 1.5h, and carrying out purification treatment to obtain the novel thermosensitive color developing agent product.
The aromatic diamine compound is 1,2-phenylenediamine with CAS number 95-54-5.
The sulfonyl halide is benzene sulfonyl chloride, and the CAS number is 98-09-9.
The compound containing-NCO is phenyl isocyanate, and the CAS number is 103-71-9; the melting point is-31 +/-1 ℃ and the surface tension is 38.6dyne/cm.
And specifically, after the reaction in the step S1 is finished, adding 700mL of a second solvent into the reaction container, heating to 62 ℃, dissolving the materials completely, standing, separating into an organic layer and a water layer, removing the water layer, and performing azeotropic dehydration on the organic layer to obtain the intermediate product.
The mixed solvent is water and toluene, and the volume ratio of the toluene to the water is 0.3:1.
in the step S1, when the diamine compound is put into a reaction container, alkali metal carbonate is added at the same time; the molar ratio of the diamine compound to the alkali metal carbonate is 2:1.4.
the alkali metal carbonate is sodium carbonate.
The second solvent is toluene.
And specifically, after the reaction in the step S2 is finished, cooling the reaction container to 5 ℃, performing suction filtration to collect a solid product, and performing vacuum drying for 12 hours to obtain a novel thermosensitive color developing agent product.
The addition rate of the sulfonyl halide is 0.2mol/min.
The addition rate of the-NCO-containing compound was 0.1mol/min.
The structural formula of the novel thermosensitive color developing agent provided by the embodiment is as follows:
in a second aspect, this embodiment provides an application of a method for preparing a novel heat-sensitive color developing agent, and the method for preparing the novel heat-sensitive color developing agent is applied to the field of heat-sensitive materials.
Example 2.
The embodiment provides a preparation method of a novel thermosensitive color developing agent, which specifically comprises the following steps:
s1, putting 2mol of diamine compound into a reaction vessel containing 1500mL of mixed solvent, setting the temperature to 10 ℃ under nitrogen atmosphere, then adding 1.8mol of sulfonyl halide, heating to 53 ℃ for reaction for 1.5h, and collecting an intermediate product;
s2, cooling the intermediate product to 35 ℃, adding 1.9mol of compound containing-NCO, carrying out heat preservation reaction for 1.5h, and carrying out purification treatment to obtain the novel thermosensitive color developing agent product.
The aromatic diamine compound is 1,2-phenylenediamine with a CAS number of 95-54-5.
The sulfonyl halide is benzene sulfonyl chloride, and the CAS number is 98-09-9.
The compound containing-NCO is phenyl isocyanate, and the CAS number is 103-71-9; the melting point is-31 + -1 deg.C, and the surface tension is 38.6dyne/cm.
And specifically, after the reaction in the step S1 is finished, adding 700mL of a second solvent into the reaction container, heating to 62 ℃, completely dissolving the materials, standing, separating the solution into an organic layer and a water layer, removing the water layer, and performing azeotropic dehydration on the organic layer to obtain the intermediate product.
The mixed solvent is water and toluene, and the volume ratio of the toluene to the water is 0.4:1.
in the step S1, when the diamine compound is put into a reaction vessel, alkali metal carbonate is added at the same time; the molar ratio of the diamine compound to the alkali metal carbonate is 2:1.2.
the alkali metal carbonate is sodium carbonate.
The second solvent is toluene.
And the purification treatment is specifically that after the reaction in the step S2 is finished, the temperature of the reaction container is reduced to 5 ℃, a solid product is collected by suction filtration, and the solid product is dried in vacuum for 12 hours to obtain a novel thermosensitive color developing agent product.
The addition rate of the sulfonyl halide is 0.2mol/min.
The addition rate of the-NCO-containing compound was 0.15mol/min.
The structural formula of the novel thermosensitive color developing agent provided by the embodiment is as follows:
in a second aspect, this embodiment provides an application of a method for preparing a novel heat-sensitive color developing agent, and the method for preparing the novel heat-sensitive color developing agent is applied to the field of heat-sensitive materials.
Comparative example 1.
The comparative example provides a preparation method of a novel thermosensitive color developing agent, and the specific implementation mode is the same as that of example 1; the difference is that in the step S1, 2mol of diamine compound is put into a reaction vessel containing 1500mL of mixed solvent, the temperature is set to 24 ℃ under nitrogen atmosphere, then 1.8mol of sulfonyl halide is added, the temperature is raised to 50 ℃ for reaction for 1.5h, and intermediate product is collected; .
Comparative example 2.
The comparative example provides a preparation method of a novel heat-sensitive color developing agent, and the specific implementation mode is the same as that of example 1; the difference lies in that the mixed solvent is water and ethyl acetate, the volume ratio of ethyl acetate to water is 0.5:1.
performance test method
1. Target product Properties
(1) Yield: weighing the products of the thermosensitive color developing agents obtained in the examples and the comparative examples, and calculating the yield of the thermosensitive color developing agent according to the following formula;
yield = (theoretical amount of produced-actual amount of produced)/theoretical amount of produced × 100%
(2) Purity: the purity of the heat-sensitive color developing agents obtained in examples and comparative examples was analyzed by HPLC (Agilent 1260).
The results are reported in table 1.
2. Color rendering Properties
The rest is made up of 4% thermosensitive color developing agent, 3% coupler, 8% sensitizer, 5% adhesive and water according to the formula amount, and the coating dry weight is 4g/m 2 The color developing agent is coated on heat-sensitive base paper, and then the heat-sensitive base paper is placed in a heat-sensitive color developing instrument to develop color under the conditions of 15V voltage and 2ms pulse width, so that a heat-sensitive paper sample is obtained.
Wherein the heat-sensitive developer was the heat-sensitive developer provided in examples 1-2 and comparative examples 1-2, the color former was 3- (N-ethyl-4-toluidino) -6-methyl-7-anilinofluoran (ETAC), the sensitizer was 1,2-Diphenoxyethane (DPE), and the binder was polyvinyl alcohol (brand JVP VP-18).
The thermal paper sample was immersed in water at 30 ℃ for 48 hours, and the optical concentrations before and after immersion were measured using a densitometer (LS 117 on forest) to calculate the loss δ.
δ = (optical concentration before immersion-optical concentration after immersion)/optical concentration before immersion × 100%
Defining that the color rendering is qualified when the delta is less than or equal to 3 percent, and disqualified when the delta is more than 3 percent; the results are reported in table 1.
Performance test data
TABLE 1 Performance test results
| Yield% | Purity% | Color rendering property | |
| Example 1 | 95.4 | 98.9 | Qualified |
| Example 2 | 94.2 | 97.2 | Qualified |
| Comparative example 1 | 90.5 | 95.4 | Fail to be qualified |
| Comparative example 2 | 92.6 | 94.8 | Fail to be qualified |
Claims (10)
1. The preparation method of the novel thermosensitive color developing agent is characterized in that the preparation method of the novel thermosensitive color developing agent comprises the steps of mixing diamine compounds and sulfonyl halides for reaction, and then reacting with a compound containing-NCO to obtain a novel thermosensitive color developing agent product.
2. The method for preparing a novel heat-sensitive color developing agent according to claim 1, wherein at least 2 of the diamine compound, the sulfonyl halide compound and the-NCO-containing compound contain a benzene ring structure.
3. The preparation method of the novel heat-sensitive color developing agent according to claim 2, wherein the diamine compound is an aromatic diamine compound, and the number of primary amines in the aromatic diamine compound is not less than 1.
4. The method for preparing a novel heat-sensitive color developing agent according to any one of claims 1 to 3, wherein the sulfonyl halide is specifically a benzenesulfonyl halide, and the number of electron layers of a halogen element in the benzenesulfonyl halide is 2 to 5.
5. The preparation method of the novel heat-sensitive color developing agent according to any one of claims 1 to 4, wherein the melting point of the-NCO-containing compound is-15 to-45 ℃ and the surface tension is 30 to 50dyne/cm.
6. The preparation method of the novel heat-sensitive color developing agent according to any one of claims 1 to 5, wherein the preparation steps of the novel heat-sensitive color developing agent are as follows:
s1, putting diamine compounds into a reaction vessel containing a mixed solvent, setting the temperature to 10-16 ℃ under a nitrogen atmosphere, then adding sulfonyl halide, heating to 50-60 ℃, reacting for 1-2h, and collecting intermediate products;
s2, cooling the intermediate product to 30-37 ℃, adding a compound containing-NCO, carrying out heat preservation reaction for 1-2h, and carrying out purification treatment to obtain the novel thermosensitive color developing agent product.
7. The method for preparing a novel thermosensitive color developing agent according to claim 6, wherein the operation of collecting the intermediate product is specifically, after the reaction in step S1 is completed, adding a compound containing-NCO into the reaction vessel, raising the temperature to 55 to 65 ℃ to completely dissolve the material, standing to separate the material into an organic layer and an aqueous layer, removing the aqueous layer, and performing azeotropic dehydration on the organic layer to obtain the intermediate product.
8. The preparation method of the novel heat-sensitive color developing agent according to claim 6 or 7, wherein the purification treatment is specifically that after the reaction in the step S2 is finished, the temperature of the reaction container is reduced to below 10 ℃, the solid product is collected by suction filtration and dried under a negative pressure condition, and the novel heat-sensitive color developing agent product is obtained.
9. The method for preparing a novel heat-sensitive color developing agent according to any one of claims 6 to 8, wherein the addition rate of the sulfonyl halide is 0.5 to 3 times that of the-NCO-containing compound.
10. Use of a process for the preparation of a novel heat-sensitive colour developer according to any one of claims 1 to 9 in the field of heat-sensitive materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104797429A (en) * | 2012-11-21 | 2015-07-22 | 日本曹达株式会社 | Recording material produced using non-phenol compound |
| CN111285787A (en) * | 2020-03-09 | 2020-06-16 | 潍坊大有生物化工有限公司 | Novel non-phenolic thermosensitive color developing agent, preparation method and application thereof in thermosensitive recording material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104797429A (en) * | 2012-11-21 | 2015-07-22 | 日本曹达株式会社 | Recording material produced using non-phenol compound |
| CN111285787A (en) * | 2020-03-09 | 2020-06-16 | 潍坊大有生物化工有限公司 | Novel non-phenolic thermosensitive color developing agent, preparation method and application thereof in thermosensitive recording material |
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