CN113896663A - Heat-sensitive acid generator and preparation method and application thereof - Google Patents
Heat-sensitive acid generator and preparation method and application thereof Download PDFInfo
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- CN113896663A CN113896663A CN202111271725.0A CN202111271725A CN113896663A CN 113896663 A CN113896663 A CN 113896663A CN 202111271725 A CN202111271725 A CN 202111271725A CN 113896663 A CN113896663 A CN 113896663A
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- acid generator
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- sensitive acid
- ketone
- temperature
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- 239000002253 acid Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims abstract description 61
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 30
- 150000002576 ketones Chemical class 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 23
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000376 reactant Substances 0.000 claims description 17
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 25
- 239000003513 alkali Substances 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 35
- 230000008569 process Effects 0.000 description 34
- -1 carboxaldehyde hydrazine hydrazone Chemical class 0.000 description 19
- 238000002329 infrared spectrum Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000012452 mother liquor Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 235000013373 food additive Nutrition 0.000 description 6
- 239000002778 food additive Substances 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- 229940124530 sulfonamide Drugs 0.000 description 6
- 150000003456 sulfonamides Chemical class 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 150000007857 hydrazones Chemical class 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 150000004010 onium ions Chemical class 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- VDQKXPPTYHGNGW-UHFFFAOYSA-N butylidenehydrazine Chemical compound CCCC=NN VDQKXPPTYHGNGW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- BLWBNXFYLCDSDB-UHFFFAOYSA-N hexylidenehydrazine Chemical compound CCCCCC=NN BLWBNXFYLCDSDB-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- KSLPENWRZCGAPV-UHFFFAOYSA-N pentylidenehydrazine Chemical compound CCCCC=NN KSLPENWRZCGAPV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- RGALEZGQSYLWSN-UHFFFAOYSA-N 1-(3-aminophenyl)-2h-tetrazole-5-thione Chemical compound NC1=CC=CC(N2C(N=NN2)=S)=C1 RGALEZGQSYLWSN-UHFFFAOYSA-N 0.000 description 1
- IXAUCVOJRVFRBJ-UHFFFAOYSA-N 4-(trichloromethyl)triazine Chemical class ClC(Cl)(Cl)C1=CC=NN=N1 IXAUCVOJRVFRBJ-UHFFFAOYSA-N 0.000 description 1
- ZBXNFTFKKOSPLD-UHFFFAOYSA-N 5-methylsulfanyl-2h-tetrazole Chemical group CSC1=NN=NN1 ZBXNFTFKKOSPLD-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GPSFNVDSNQXPTF-UHFFFAOYSA-N N,N-diphenylaniline sulfane Chemical compound S.C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 GPSFNVDSNQXPTF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 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
- 238000005352 clarification Methods 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RGZRSLKIOCHTSI-UHFFFAOYSA-N hydron;n-methylhydroxylamine;chloride Chemical compound Cl.CNO RGZRSLKIOCHTSI-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- IDBOAVAEGRJRIZ-UHFFFAOYSA-N methylidenehydrazine Chemical compound NN=C IDBOAVAEGRJRIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
-
- 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
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
- C07C311/49—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom to nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a thermosensitive acid generator and a preparation method and application thereof, belonging to the technical field of thermosensitive printing materials. The preparation method of the heat-sensitive acid generator comprises the following steps: dissolving tosyl hydrazide in a solvent, heating to a preset temperature to prepare a clear solution from the system, and dropwise adding liquid aldehyde or ketone into the clear solution to react to obtain the heat-sensitive acid generator. The raw materials used in the preparation method of the invention are common aldehydes or ketones and p-toluenesulfonyl hydrazide, the cost is low, and the pollution to the environment is reduced. In addition, the thermosensitive acid generator obtained by the invention can be used as an additive of a printing thermosensitive CTP printing plate coating, the coating under infrared laser scanning presents good alkali solubility, the sensitivity of the printing plate coating is effectively improved, the contrast of a printing plate image is further improved, meanwhile, the alkali resistance of a non-image area of the printing plate is maintained, and the developing solution is not polluted.
Description
Technical Field
The invention belongs to the technical field of thermosensitive printing materials, and particularly relates to a thermosensitive acid generator and a preparation method and application thereof.
Background
The structure of the heat-sensitive acid generator is methyl mercapto tetrazole, disulfone compound, sulfonium salt, iodonium salt, etc., and the synthesis process has high cost of raw materials and processing, complex post-treatment process and serious production pollution. For example, mercapto group, sulfone group, sulfonium ion and iodonium ion have high activity, but the synthesis process is complicated. The specific reasons are as follows: the mercapto group is also called mercapto group or thiol group, and is a negative monovalent functional group formed by connecting a sulfur atom and a hydrogen atom, the chemical formula is-SH, the mercapto end is connected with different groups, and the organic matters belong to different categories, such as thiol (R-SH) and thiophenol (Ar-SH). Wherein, regarding 1- [3- (1-hydroxy-1-methyl-phenylureido)]The synthesis method of the-5-mercaptotetrazole comprises the following two steps: dispersing 1- (3-aminophenyl) -5-mercaptotetrazole and triethylamine into a N, N-Dimethylformamide (DMF) solution, slowly dropwise adding phenyl chloroformate into the suspension in ice bath, adding isopropanol and water into the reaction solution, dropwise adding concentrated hydrochloric acid into the reaction solution after complete dissolution, stirring, filtering and washing to obtain light yellow powder. And dispersing 1- (3-aminobenzoate) -5-mercaptotetrazole and methyl hydroxylamine hydrochloride in methanol, slowly dropwise adding sodium methoxide in an ice bath, and slowly dropwise adding the reaction solution in concentrated hydrochloric acid and water in the ice bath to obtain light yellow powder. The synthesis process has high raw material cost, complex process, more waste liquid and environmental pollution. Second, sulfone group (-SO)2-) is typically attached to a benzene ring, and a class of organic compounds characterized by having a sulfonyl group and being linked to two carbon atoms by sulfur (e.g., to two hydrocarbyl groups or a simple divalent group), are typically crystalline stable compounds, and can be prepared by oxidation or other methods of organic sulfides. However, the substance used for heat-sensitive acid production is a disulfone compound, the synthesis cost is higher, the process is more complicated, and the synthesis process is as follows: adding concentrated sulfuric acid into phenol slowly, and reacting at 100 ℃ under stirring to generate phenolsulfonic acid. The temperature is increased to 145-150 ℃, the reaction is vacuumized for 1 hour, and a proper amount of phenol is added after the vacuumization is finished each time. The reaction was taken out and recrystallized with distilled water to obtain white bis sulfone S crystals ". Further, the onium ion is a non-metal ion having a positive charge in addition to carbon atoms, and the onium ion has a positive chargeThe non-metallic atom has the electronic structure of an inert gas with a coordination number higher than or equal to that of a normal covalent compound, and the non-metallic elements oxygen, bromine, sulfur, nitrogen, phosphorus, iodine, etc. can all generate onium ions. However, the raw material cost of the sulfur-containing element or iodine-containing organic compound is relatively high, and the sulfur-containing organic compound and iodine-containing organic compound cause certain environmental pollution.
Secondly, the acid-generating efficiency of the current heat-sensitive acid generator is not high in the using process, and the environment is polluted in the using process. The method comprises the following specific steps: most of heat-sensitive acid generators are replaced by ultraviolet photosensitive acid generators, the photoacid generating efficiency of the original ultraviolet photosensitive acid generators is not high, and the stimulation of acid generation by heat radiation with lower frequency can lead to lower photoacid generating efficiency. For example, trichloromethyl triazine compounds have better photo-generated acid quantum efficiency at 405nm in acetonitrile; the triphenylamine sulfonium salt photo-acid generator has the highest acid generation efficiency at 415nm in dichloromethane; sulfonium salts containing no benzene ring are excellent in transparency and sensitivity at 193 nm; the benzene sulfonate acid generator has the highest acid generating efficiency at 248 nm. In addition, the sulfydryl acid generators release hydrogen sulfide gas after decomposition, and sulfonium salts and sulfonyl groups release sulfonic acid and the like after decomposition, which pollute the environment.
Therefore, in view of the above technical problems, it is necessary to develop a novel heat-sensitive acid generator and a method for preparing the same.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a heat-sensitive acid generator, a preparation method of the heat-sensitive acid generator and application of the heat-sensitive acid generator.
In one aspect of the present invention, there is provided a method for preparing a heat-sensitive acid generator, comprising:
dissolving tosyl hydrazide in a solvent, and heating to a preset temperature to prepare a clear solution from the system;
and dropwise adding liquid aldehyde or ketone into the clear solution to react to obtain the heat-sensitive acid generator.
Optionally, the aldehyde is any one of formaldehyde, acetaldehyde, butyraldehyde, benzaldehyde, salicylaldehyde, n-valeraldehyde and n-hexanal; and/or the presence of a gas in the gas,
the ketone is any one of propionaldehyde, butanone and cyclohexanone.
Optionally, the preset temperature is an inflection point temperature at which the solubility of the tosylhydrazide in the solvent changes.
Optionally, the solvent is any one of absolute methanol, absolute ethanol and 95% ethanol.
Optionally, dropping liquid aldehyde or ketone into the clear solution to perform a reaction, so as to obtain the heat-sensitive acid generator, including:
dropwise adding liquid aldehyde or ketone into the clear solution, heating to reflux temperature after dropwise adding, preserving heat for a period of time, and cooling to obtain white crystals;
carrying out primary dispersion treatment on the white crystals in a sodium bicarbonate solution, and carrying out solid-liquid separation on a dispersion system;
and carrying out secondary dispersion treatment on the separated solid by using deionized water, and filtering and drying to obtain the heat-sensitive acid generator.
Optionally, the mass ratio of the tosylhydrazide to the aldehyde or ketone of the liquid is (0.8-1.3): (1-1.6).
Optionally, the concentration range of the reactant of the tosyl hydrazide and the liquid aldehyde or ketone in the solvent is 35% to 45%.
In another aspect of the present invention, a heat-sensitive acid generator is provided, which is prepared by the preparation method described above.
Optionally, the structural formula of the heat-sensitive acid generator is as follows:
in another aspect of the present invention, there is provided a use of the heat-sensitive acid generator, as described above, in a heat-sensitive CTP printing plate.
The invention provides a preparation method of a thermosensitive acid generator, which comprises the following steps: dissolving tosyl hydrazide in a solvent, heating to a preset temperature to prepare a clear solution from the system, and dropwise adding liquid aldehyde or ketone into the clear solution to react to obtain the heat-sensitive acid generator. The raw materials used in the preparation method of the invention are common aldehydes or ketones and p-toluenesulfonyl hydrazide, which has low cost and reduces the pollution to the environment.
Drawings
FIG. 1 is a block flow diagram of a method of preparing a thermally sensitive acid generator according to an embodiment of the present invention;
FIG. 2 is an infrared spectrum of a N- (4-tosyl) benzaldehyde aldehyde hydrazine hydrazone thermal acid generator according to another embodiment of the present invention;
FIG. 3 is a DSC chart of N- (4-tosyl) benzaldehyde aldehyde hydrazine hydrazone thermal acid generator in another embodiment of the present invention;
FIG. 4 is an infrared spectrum of a N- (4-tosyl) salicylaldehyde hydrazine hydrazone thermal acid generator according to another embodiment of the present invention;
FIG. 5 is a DSC chart of N- (4-tosyl) salicylaldehyde hydrazine hydrazone thermal acid generator in another embodiment of the present invention;
FIG. 6 is an infrared spectrum of a N- (4-tosyl) carboxaldehyde hydrazine hydrazone thermal acid generator according to another embodiment of the present invention;
FIG. 7 is a DSC chart of N- (4-tosyl) formaldehyde hydrazine hydrazone thermal acid generator in another embodiment of the present invention;
FIG. 8 is an infrared spectrum of a N- (4-tosyl) butyraldehyde hydrazinehydrazone heat-sensitive acid generator according to another embodiment of the present invention;
FIG. 9 is a DSC chart of N- (4-tosyl) butyraldehyde hydrazine hydrazone thermal acid generator in another embodiment of the present invention;
FIG. 10 is an infrared spectrum of a N- (4-tosyl) valeraldehyde hydrazine hydrazone thermal acid generator according to another embodiment of the present invention;
FIG. 11 is a DSC of N- (4-tosyl) valeraldehyde hydrazine hydrazone thermal acid generator in another embodiment of the present invention;
FIG. 12 is an infrared spectrum of a N- (4-tosyl) hexanal hydrazine hydrazone thermal acid generator according to another embodiment of the present invention;
FIG. 13 is a DSC chart of N- (4-tosyl) hexanal hydrazine hydrazone thermal acid generator in another embodiment of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
As shown in fig. 1, in one aspect of the present invention, a method S100 for preparing a heat-sensitive acid generator is provided, which specifically includes the following steps S110 to S120:
s110, dissolving the tosyl hydrazide in a solvent, and heating to a preset temperature to prepare a clear solution of the system.
The raw materials selected based on the current acid generators are sulfydryl, sulfuryl, sulfonium ions and iodonium ions, and the acid generators have the advantages of high activity, complex synthesis process, high cost and easy environmental pollution. Therefore, the method for synthesizing the thermosensitive acid generator selects low-cost raw materials, for example, p-toluenesulfonyl hydrazide and common aldehyde or ketone react, and the p-toluenesulfonyl hydrazide and the common aldehyde or ketone react to form a hydrazone compound, that is, the method for forming the thermosensitive acid generator with the new structure of the hydrazine hydrazone compound has the advantages of low raw material cost and no generation of harmful pollutants.
Specifically, p-toluenesulfonyl hydrazide is easily soluble in alkali, soluble in methanol, ethanol and butanone, slightly soluble in water and aldehydes, and insoluble in benzene and toluene. The p-toluenesulfonyl hydrazide is heated to a temperature of more than 105 ℃ and gradually decomposed from a molten state, nitrogen is discharged, sulfonic acid is generated by hydrolysis in hot water, nitrogen is decomposed, the phenomenon of moisture absorption and deliquescence is avoided at normal temperature, and the chemical property is stable. The generated gas and the decomposed residue are nontoxic, odorless and pollution-free. Further, hydrazone is a compound obtained by condensing a carbonyl group with hydrazine, and hydrazone is a kind of organic compound in nature and is a compound obtained by condensing a carbonyl group with a primary amine. Hydrazinohydrazones are compounds containing a C ═ NNHR group formed by the action of hydrazine or substituted hydrazines on carbonyl-containing compounds such as aldehydes or ketones. Aldehyde and ketone compounds are reacted with hydrazine in an equimolar amount. Wherein R is a hydrocarbyl group and R' is a hydrocarbyl group or hydrogen.
It should be noted that any one of formaldehyde, acetaldehyde, butyraldehyde, benzaldehyde, salicylaldehyde, n-valeraldehyde, and n-hexanal, and any one of propionaldehyde, butanone, and cyclohexanone may be used as the aldehyde in this example, and it is needless to say that other aldehydes and ketones such as aliphatic aldehydes and aromatic aldehydes may be selected by those skilled in the art, and this is not particularly limited.
It should be further noted that, from the viewpoint of environmental protection and cost, the solvent in this example is any one of anhydrous methanol, anhydrous ethanol, and 95% ethanol with low boiling points, and the comparison is not particularly limited.
It should be noted that the preset temperature in this example is an inflection point temperature at which the solubility of the tosyl hydrazide in the solvent changes, that is, the solubility of the tosyl hydrazide in the corresponding solvent changes with the change of the temperature.
Illustratively, the solvent of the reaction system is absolute ethyl alcohol, when the tosyl hydrazide is dissolved in the absolute ethyl alcohol, the inflection point of the change of the solubility along with the temperature is 60 ℃, and when the temperature is lower than 60 ℃, the system presents a white suspension; when the temperature is not lower than 60 ℃, the system presents a homogeneous clear solution.
In other embodiments, when the solvent anhydrous methanol with low price is selected, the tosyl hydrazide is dissolved in the anhydrous methanol, the inflection point of the solubility along with the temperature change is 55 ℃, and the system presents a white suspension when the temperature is lower than 55 ℃; when the temperature is not lower than 55 ℃, the system presents a homogeneous clear solution.
The embodiment supports a simple production process, improves the production efficiency and ensures the purity of the product based on the existence of the inflection point of the solubility of the tosylhydrazide in the corresponding solvent along with the temperature.
And S120, dripping liquid aldehyde or ketone into the clear solution prepared in the step S110 for reaction to obtain the heat-sensitive acid generator.
Specifically, liquid aldehyde or ketone is dripped into the clear solution, after the dripping is finished, the temperature is raised to the reflux temperature, the temperature is kept for a period of time, and then white crystals are obtained after cooling; carrying out primary dispersion treatment on the white crystals in a sodium bicarbonate solution, and carrying out solid-liquid separation on a dispersion system; and carrying out secondary dispersion treatment on the separated solid by using deionized water, and filtering and drying to obtain the heat-sensitive acid generator.
Further, the mass ratio of the tosylhydrazide to the liquid aldehyde or ketone is (0.8-1.3): (1-1.6). And the concentration range of the reactant of the tosylhydrazide and the liquid aldehyde or ketone in the solvent is 35 to 45 percent.
In the synthesis of the hydrazinehydrazone compound of the present example, the concentration of the dispersion system can be designed to be as high as possible by utilizing the inflection point of the change in solubility with temperature, thereby improving the production efficiency. Namely, liquid aldehyde or ketone can be dripped at the turning point of the clarification of the system, so that an obvious exothermic phenomenon occurs, and the temperature of the system rises. It is worth noting that the temperature of the system can not reach the boiling point of the solvent due to heat release, when the aldehyde or ketone is added and the temperature of the system is stable, the reaction system is heated to the reflux temperature, and the temperature is kept until the reaction is finished.
It should be further noted that, for the purification of the heat-sensitive acid generator, there are inflection points in the solubility of p-toluenesulfonyl hydrazide with certain polarity in ethanol or methanol with respect to the temperature, and then there are inflection points in the solubility of the corresponding hydrazones with weakened polarity formed in this example with respect to the temperature, and the latter is higher than the former. Therefore, after the reaction is finished, the reaction solution is poured into a wide-mouth container with a cover while the reaction solution is hot (notably, the step needs ventilation and explosion prevention), and after the cover is closed, the reaction solution is naturally cooled to room temperature, and a large amount of white crystals are separated out in the process.
It is also noted that the discharged system feed solution is injected into a vessel for facilitating the removal of solids, such as the wide-mouth vessel described above. Then, the cooling time during the natural cooling to room temperature depends on the total mass of the reaction system, and the larger the total mass of the reaction system in the same vessel, the longer the cooling time. After complete crystallization at room temperature, crude product and reaction mother liquor are obtained by filtration. The mother liquor is stored for the next use. The crude product needs to be subjected to two dispersing washes.
It should be noted that no reaction is completely completed, and although the reaction of this example is relatively rapid and the reactants are heated more vigorously during the dropwise addition, unreacted p-toluenesulfonyl hydrazide still exists. Therefore, the white crystals obtained in the above process contain a certain amount of p-toluenesulfonyl hydrazide. For this reason, the white crystals are sufficiently dispersed in water containing a small amount of sodium hydrogencarbonate by a high-speed disperser to dissolve p-toluenesulfonylhydrazide in a dispersion medium, and after a certain period of time, the dispersion is subjected to solid-liquid separation. And the mother liquor generated after the separation can be used as a solvent for the next synthesis, although the solubility of the mother liquor is changed and slightly reduced compared with the previous synthesis, the solubility of the p-toluenesulfonyl hydrazide in the selected solvent in the application is not hindered, because the p-toluenesulfonyl hydrazide has better solubility in hot water, and the solid-liquid separation degree of the product and the mother liquor is further improved. In addition, after the process is repeated three times, the methanol or the ethanol is recovered, and the solvent is recycled, so that the cost is saved.
In this example, based on the solubility of p-toluenesulfonyl hydrazide as a raw material to methanol and ethanol, there is an inflection point below the boiling point with the temperature rise, and a certain mass of p-toluenesulfonyl hydrazide is dispersed in a certain mass of methanol or ethanol, and the system is a white suspension. The color of the suspension does not change with the increase of the temperature of the system until the temperature of the system goes beyond the inflection point and the system suddenly becomes clear. That is, in this example, it is necessary to grasp the solubility of the inflection point, and it is possible to properly grasp the concentration of the reaction system and the concentration of the product in the solvent, and it is estimated that the solubility of the product in methanol or ethanol at room temperature is limited based on the characteristic that the inflection point exists in the solubility, so that the product exhibits a crystallization phenomenon in the solvent at room temperature, and solid-liquid separation is realized.
Specifically, the synthesis process of the heat-sensitive acid generator of this embodiment is as follows:
in the synthesis process of the embodiment, inflection points of solubility generated by reactants and products in the same solvent along with the change of temperature are fully utilized, so that the processes of dissolution and crystallization are realized respectively, and the purposes of simple operation and green and environment-friendly process are achieved.
In addition, the synthesis process of the embodiment has the characteristics of low raw material cost, simple formula process and environmental friendliness. And the acid generator prepared by the embodiment can better improve the alkali solubility effect of the film-forming resin with the help of the thermosensitive sensitizer.
In another aspect of the present invention, a heat-sensitive acid generator is provided, wherein the heat-sensitive acid generator is prepared by the preparation method described above, and the specific preparation process is referred to the above description and is not described herein again.
Optionally, the structural formula of the heat-sensitive acid generator is as follows:
as can be seen from the above structural formula, the left side of the structure of the heat-sensitive acid generator of this example maintains the structure of hydrazinehydrazone, and has the property of releasing nitrogen gas by thermal decomposition, and the right side of the structure maintains the structure of p-toluenesulfonyl hydrazide, and has the properties of releasing nitrogen gas by heating and generating sulfonyl acid, and this structure increases the range of pH value change before and after thermal decomposition, that is, the heat-sensitive acid generator of this embodiment has the properties of thermally decomposing acid and releasing nitrogen gas.
Furthermore, the thermal acid generator of the present embodiment has good thermal stability at room temperature, and the thermal decomposition temperature range of the thermal acid generator in the present embodiment is 120 ℃ to 220 ℃ through detection and analysis of differential thermal analyzer (DSC), and such temperature range satisfies the requirement of instantly decomposing the acid generator at an instant temperature of 400 ℃ in application, and shortens the response speed of decomposition, and improves the sensitivity. Meanwhile, the release of nitrogen in the heat-sensitive acid generator based on the present example makes the region of heat radiation more convenient for the developer penetration development.
In another aspect of the present invention, there is provided a use of the heat-sensitive acid generator as described above in a heat-sensitive CTP printing plate.
It should be understood that the structure of the heat-sensitive acid generator according to the present embodiment, which retains the hydrazinehydrazone structure on the left, has the property of releasing nitrogen gas by thermal decomposition, and the structure of p-toluenesulfonyl hydrazide on the right, has the property of releasing nitrogen gas by heating and generating sulfonyl acid, and the release of nitrogen gas makes the region of heat radiation more convenient for the developer penetration development.
Specifically, the application of the heat-sensitive acid generator of the present embodiment depends on the cleavage of C ═ N bonds and N — S bonds, as shown below:
the imaging mechanism of the thermosensitive acid generator in the thermosensitive CTP printing plate is that the infrared laser is utilized to excite corresponding infrared dye to release heat, the original association state of a polymer chain is destroyed, and the alkali solubility of a coating in an exposure area is improved. And then, the exposed area is washed away through the developing process of the alkaline developing solution, and an image is displayed on the printing plate. In the process, the polymer has a large molecular weight, and the dissociation of molecular chains is difficult to achieve, so that the alkali solubility of exposed molecular chains is difficult to achieve the expected effect. For this reason, the following two effects are achieved by adding a proper amount of heat-sensitive acid generator: firstly, nitrogen is released after heating, sulfonic acid is generated, and the alkali solubility of the coating is improved. And secondly, the heat-sensitive acid generator is associated with the coating polymer, so that the alkali solubility of the coating is improved.
The preparation of the heat-sensitive acid generator and its specific properties are further illustrated below with reference to several specific examples:
example 1
The ratio of reactants in this example is p-toluenesulfonyl hydrazide: benzaldehyde is 1: 1.1 (amount of substance), the concentration of reactant in ethanol is 40%, and the formula of each raw material is shown in the following table 1:
table 1 raw materials each component and ratio
| Medicine and food additive | Dosage (parts) |
| P- |
0～186 |
| Benzaldehyde | 0～116.6 |
| |
0～454 |
| |
0～5 |
| |
0～1000 |
The preparation method of the heat-sensitive acid generator in the embodiment comprises the following steps:
stirring at room temperature to disperse p-toluenesulfonyl hydrazide in absolute ethanol, starting heating, clarifying the system when the temperature of the system reaches 60 ℃, and keeping the temperature. Beginning to add benzaldehyde, and finishing the dropwise adding of the benzaldehyde at a constant speed for 2 hours. The system has obvious heat release during the dripping process, and the system keeps a clear state or generates slight turbidity. Then the temperature is increased until the reaction system refluxes, and the reaction system is kept for 6 hours in a refluxing state, and then the reaction system is cooled and discharged. After complete crystallization at room temperature, crude product and reaction mother liquor are obtained by filtration. The mother liquor is stored for the next use, and the crude product is subjected to two dispersing washes.
Further, sodium bicarbonate and 1/2 dosage of deionized water are mixed to prepare a solution, the sodium bicarbonate solution pours the crude product into the solution under the high speed action of a high speed dispersion machine, the crude product is dispersed for 2 hours, the solid is filtered again and taken out, the solid is mixed with 1/2 dosage of deionized water, the mixture is dispersed again for 1 hour under the high speed dispersion machine, the solid is filtered and taken out, and the mixture is dried, so that the N- (4-tosyl) benzaldehyde hydrazine hydrazone heat-sensitive acid generator is obtained.
As shown in the attached figure 2, an infrared spectrum of the N- (4-tosyl) benzaldehyde hydrazine hydrazone of the embodiment is shown, and the results of various characteristic peaks of the product in the graph are shown in the following table 2:
TABLE 2 characteristic absorption results of N- (4-tosyl) benzaldehyde hydrazones
| Chemical bond(s) | Form of vibration | Wave number (cm)-1) |
| C＝N | Telescopic vibration | 1670～1600 |
| S＝O | Symmetric telescopic vibration | 1180～1140 |
| N-H (sulfonamides, secondary amines) | Telescopic vibration | 3280～3250 |
Based on the above infrared spectrum, it was identified as N- (4-tosyl) benzaldehyde hydrazine hydrazone, and further thermal properties thereof were developed by DSC on the basis of the above structure, as shown in FIG. 3, wherein the N- (4-tosyl) benzaldehyde hydrazine hydrazone C ═ N shows a cleavage temperature of 120 ℃ and the thermal decomposition of the whole molecule is 204.26 ℃.
Example 2
The ratio of reactants in this example is p-toluenesulfonyl hydrazide: salicylaldehyde 1: 1.1 (amount of substance), concentration of reactant in ethanol is 40%, and formulation of each raw material is shown in table 3 below:
table 3 raw material components and proportions
| Medicine and food additive | Dosage (parts) |
| P- |
0～186 |
| |
0～134.2 |
| |
0～480 |
| |
0～5 |
| |
0～1000 |
Referring to example 1, the thermal acid generator of N- (4' -tosyl) -2-hydroxy salicylaldehyde hydrazinehydrazone was synthesized by the above method, based on the difference in the amount of each raw material used in the reaction.
As shown in the attached figure 4, an infrared spectrum of N- (4-tosyl) salicylaldehyde hydrazine hydrazone of the embodiment is shown, and the results of various characteristic peaks of the product in the graph are shown in a table 4:
TABLE 4 characteristic absorption results of N- (4-tosyl) salicylaldehyde hydrazinehydrazone
| Chemical bond(s) | Form of vibration | Wave number (cm)-1) |
| C＝N | Telescopic vibration | 1670～1600 |
| S＝O | Symmetric telescopic vibration | 1180～1140 |
| N-H (sulfonamides, secondary amines) | Telescopic vibration | 3280～3250 |
| C-OH (phenolic hydroxyl) | Telescopic vibration | 1260～1180 |
Based on the above infrared spectrum, the compound can be determined to be N- (4-tosyl) salicylaldehyde hydrazine hydrazone, and the thermal performance of the compound is further tested by DSC, as shown in figure 5, the breaking temperature of the N- (4-tosyl) salicylaldehyde hydrazine hydrazone structure C-N is 132.07 ℃, and the thermal decomposition temperature of the whole molecule is 199.07 ℃.
Example 3
In this example, the ratio of the reactants is p-toluenesulfonyl hydrazide to formaldehyde is 1: 1.1 (amount of substance), the concentration of the reactants in ethanol is 40%, and the formula of each raw material is shown in table 5 below:
table 5 raw materials each component and ratio
| Medicine and food additive | Dosage (parts) |
| P- |
0～186 |
| Formaldehyde (30 wt%) | 0～116.6 |
| |
0～454 |
| |
0～5 |
| |
0～1000 |
The preparation method of the heat-sensitive acid generator of the present embodiment is as follows: p-toluenesulfonyl hydrazide is dissolved in absolute ethyl alcohol at room temperature to prepare a clear solution (the amount of absolute ethyl alcohol may be insufficient and can be properly adjusted), and the concentration approaches saturation. Then, the formaldehyde solution was added dropwise at room temperature, and the temperature was controlled to 40 ℃ or lower (notably, a tap water bath was added for incubation if necessary). After the dropwise addition, the mixture is kept warm for 6 hours in a water bath at room temperature. In the process, when the absolute ethyl alcohol clear solution and the formaldehyde clear solution of the p-toluenesulfonyl hydrazide are mixed, white solid (p-toluenesulfonyl hydrazide formaldehyde hydrazone is insoluble in water) is separated out, or crystals are generated after cooling. After that, the white precipitate was filtered, washed with water, and dried. The processes of filtering, washing, drying and the like can be referred to in example 1, and the heat-sensitive acid generator of N- (4' -tosyl) formaldehyde hydrazine hydrazone can be synthesized by the method.
As shown in the attached figure 6, an infrared spectrum of the N- (4' -tosyl) formaldehyde hydrazine hydrazone of the embodiment is shown, and the results of various characteristic peaks of the product in the graph are shown in the following table 6:
TABLE 6 characteristic absorption results of N- (4' -tosyl) carboxaldehydrazone
| Chemical bond(s) | Form of vibration | Wave number (cm)-1) |
| C＝N | Telescopic vibration | 1670～1600 |
| S＝O | Symmetric telescopic vibration | 1180～1140 |
| N-H (sulfonamides, secondary amines) | Telescopic vibration | 3280～3250 |
| H2C＝ | Symmetric telescopic vibration | 3025～3012 |
Based on the above infrared spectrum, it was determined that N- (4 '-tosyl) formaldehyde hydrazine hydrazone was further tested for its thermal properties by DSC, as shown in FIG. 7, and the cleavage temperature of N- (4' -tosyl) formaldehyde hydrazine hydrazone structure C ═ N was 139.14 ℃, and it was an exothermic process.
Example 4
In this example, the ratio of the reactants is p-toluenesulfonylhydrazide to butyraldehyde is 1: 1.1 (amount of substance), the concentration of the reactants in ethanol is 40%, and the formula of each raw material is shown in table 7 below:
table 7 raw material components and proportions
| Medicine and food additive | Dosage (parts) |
| P- |
0～186 |
| Butyraldehyde (30 wt%) | 0～116.6 |
| |
0～454 |
| |
0～5 |
| |
0～1000 |
The preparation method of the heat-sensitive acid generator of the present embodiment is as follows: p-toluenesulfonyl hydrazide is dissolved in absolute ethanol at 50 ℃ to prepare a clear solution (the amount of absolute ethanol is possibly insufficient and can be properly adjusted), and the concentration is close to saturation. Then, dripping butyraldehyde at 50 ℃, controlling the temperature to be not higher than 60 ℃, after finishing dripping, keeping the temperature of 60 ℃ in a water bath for 1 hour, and then heating the system to 70 ℃ and keeping the temperature for 6 hours. In the process, when the absolute ethyl alcohol clarified solution of the p-toluenesulfonyl hydrazide is mixed with the butyraldehyde, a white solid (p-toluenesulfonyl hydrazide butyraldehyde hydrazone is insoluble in water) is separated out, or the p-toluenesulfonyl hydrazide butyraldehyde hydrazone is cooled to generate crystals. Finally, more white precipitate is obtained by cooling, and then filtering, washing and drying are carried out. The processes of filtering, washing, drying and the like can be referred to in example 1, and the heat-sensitive acid generator of N- (4' -tosyl) butyraldehyde hydrazinehydrazone is synthesized by the method.
As shown in the attached figure 8, an infrared spectrum of the hydrazine hydrazone N- (4' -tosyl) butyraldehyde is shown, and the result of each characteristic peak of the product in the spectrum is shown in the following table 8:
TABLE 8 characteristic absorption results of N- (4' -tosyl) butyraldehyde hydrazinehydrazone
| Chemical bond(s) | Form of vibration | Wave number (cm)-1) |
| C＝N | Telescopic vibration | 1670～1600 |
| S＝O | Symmetric telescopic vibration | 1180～1140 |
| N-H (sulfonamides, secondary amines) | Telescopic vibration | 3280～3250 |
| (CH2)2 | Rocking vibration | 750-740 |
Based on the above infrared spectrum, it can be determined as N- (4 '-tosyl) butyraldehyde hydrazine hydrazone, and the thermal performance is further tested by DSC on the basis of the structure, as shown in figure 9, the N- (4' -tosyl) butyraldehyde hydrazine hydrazone structure C ═ N has a breaking temperature of 178 ℃, and is an exothermic process.
Example 5
In this example, the ratio of the reactants is p-toluenesulfonylhydrazide to n-valeraldehyde is 1: 1.1 (amount of substance), the concentration of the reactants in ethanol is 40%, and the formula of each raw material is shown in table 9 below:
table 9 raw materials each component and ratio
| Medicine and food additive | Dosage (parts) |
| P- |
0～186 |
| N- |
0～35 |
| |
0～454 |
| |
0～5 |
| |
0～1000 |
The preparation method of the heat-sensitive acid generator of the embodiment is as follows: p-toluenesulfonyl hydrazide is dissolved in absolute ethyl alcohol at 60 ℃ to prepare a clear solution (the amount of the absolute ethyl alcohol is possibly insufficient and can be properly adjusted), and the concentration is close to saturation. Then, valeraldehyde is dripped at the temperature of 60 ℃, and the temperature is controlled to be not higher than 70 ℃. After the dropwise addition, the system was heated to 70 ℃ and kept warm for 6 hours. In the process, when the absolute ethyl alcohol clarified solution of the p-toluenesulfonylhydrazide is mixed with the valeraldehyde, a white solid (p-toluenesulfonylhydrazide valeraldehyde hydrazone is insoluble in water) is separated out, or crystals are generated after cooling. Finally, more white precipitate is obtained by cooling, filtering, washing and drying. The processes of filtering, washing, drying and the like can be referred to in example 1, and the heat-sensitive acid generator of N- (4' -tosyl) valeraldehyde hydrazine hydrazone can be synthesized by the method.
As shown in the attached FIG. 10, the infrared spectrum of N- (4' -tosyl) valeraldehyde hydrazinehydrazone of this example is shown, and the results of various characteristic peaks of the product in the graph are shown in Table 10:
TABLE 10 characteristic absorption results for N- (4' -tosyl) valeraldehyde hydrazones
| Chemical bond(s) | Form of vibration | Wave number (cm)-1) |
| C＝N | Telescopic vibration | 1670～1600 |
| S＝O | Symmetric telescopic vibration | 1180～1140 |
| N-H (sulfonamides, secondary amines) | Telescopic vibration | 3280～3250 |
| (CH2)n(n＞4) | Horizontal rocking vibration | 720 |
Based on the above infrared spectrum, N- (4 '-tosyl) valeraldehyde hydrazine hydrazone can be determined, and the thermal performance of the structure is further tested by DSC, as shown in figure 11, the breaking temperature of the N- (4' -tosyl) valeraldehyde hydrazine hydrazone structure C ═ N is 183 ℃, and the process is exothermic.
Example 6
In this example, the ratio of the reactants is p-toluenesulfonylhydrazide to n-hexanal is 1: 1.1 (amount of substance), the concentration of the reactants in ethanol is 40%, and the formula of each raw material is shown in table 11 below:
table 11 raw materials each component and ratio
| Medicine and food additive | Dosage (parts) |
| P- |
0～186 |
| N- |
0～40 |
| |
0～454 |
| |
0～5 |
| |
0～1000 |
The preparation method of the heat-sensitive acid generator of the present embodiment is as follows: p-toluenesulfonyl hydrazide is dissolved in absolute ethyl alcohol at 60 ℃ to prepare a clear solution (the amount of the absolute ethyl alcohol is possibly insufficient and can be properly adjusted), and the concentration is close to saturation. Then, hexanal is added dropwise at 60 ℃ and the temperature is controlled to be not higher than 70 ℃. After the dropwise addition, the system was heated to 70 ℃ and kept warm for 6 hours. In the process, when the absolute ethyl alcohol clarified solution of the p-toluenesulfonylhydrazide is mixed with hexanal, a white solid (p-toluenesulfonylhydrazide hexanal hydrazone is insoluble in water) is separated out, or crystals are generated after cooling. Finally, more white precipitate is obtained by cooling, filtering, washing and drying. The processes of filtering, washing, drying and the like can be referred to in example 1, and the heat-sensitive acid generator of N- (4' -tosyl) hexanal hydrazine hydrazone can be synthesized by the method.
As shown in the attached FIG. 12, the infrared spectrum of N- (4' -tosyl) hexanal hydrazine hydrazone of this example is shown, and the results of the characteristic peaks of the product in the graph are shown in Table 12:
TABLE 12 characteristic absorption results for N- (4' -tosyl) hexanal hydrazones
| Chemical bond(s) | Form of vibration | Wave number (cm)-1) |
| C＝N | Telescopic vibration | 1670～1600 |
| S＝O | Symmetric telescopic vibration | 1180～1140 |
| N-H (sulfonamides, secondary amines) | Telescopic vibration | 3280～3250 |
| (CH2)n(n＞4) | Horizontal rocking vibration | 720 |
Based on the above infrared spectrum, it was determined that N- (4 '-tosyl) hexanal hydrazine hydrazone was further subjected to thermal properties by DSC, and as shown in FIG. 13, the N- (4' -tosyl) hexanal hydrazine hydrazone structure C ═ N had a cleavage temperature of 183 ℃ and was an exothermic process.
The invention provides a heat-sensitive acid generator and a preparation method and application thereof, and compared with the prior art, the heat-sensitive acid generator has the following beneficial effects:
firstly, the raw materials used for preparing the heat-sensitive acid generator are low in cost, and the main raw materials are common aldehydes or ketones and p-toluenesulfonyl hydrazide.
Secondly, the invention can stably synthesize the hydrazine hydrazone at the reflux temperature with low boiling point of the solvent, thereby reducing the energy consumption and the preparation cost.
Thirdly, after the product post-treatment of the invention is carried out with a low-temperature recrystallization step, and the filtered product can be dispersed and washed in water, thereby reducing the pollution to the environment.
Fourthly, the mother liquor of the product formed by the invention after low-temperature recrystallization can be used as the solvent for the next synthesis.
Fifthly, the thermosensitive acid generator obtained by the invention can be used as an additive of a printing thermosensitive CTP printing plate coating, the coating under infrared laser scanning presents good alkali solubility, the sensitivity of the printing plate coating is effectively improved, the contrast of a printing plate image is further improved, meanwhile, the alkali resistance of a non-image area of the printing plate is maintained, and the developing solution is not polluted.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. A method of preparing a heat-sensitive acid generator, comprising:
dissolving tosyl hydrazide in a solvent, and heating to a preset temperature to prepare a clear solution from the system;
and dropwise adding liquid aldehyde or ketone into the clear solution to react to obtain the heat-sensitive acid generator.
2. The production method according to claim 1, wherein the aldehyde is any one of formaldehyde, acetaldehyde, butyraldehyde, benzaldehyde, salicylaldehyde, n-valeraldehyde, and n-hexanal; and/or the presence of a gas in the gas,
the ketone is any one of propionaldehyde, butanone and cyclohexanone.
3. The method according to claim 1, wherein the predetermined temperature is an inflection temperature at which solubility of the tosyl hydrazide in the solvent is changed.
4. The method according to claim 1, wherein the solvent is any one of absolute methanol, absolute ethanol, and 95% ethanol.
5. The preparation method according to any one of claims 1 to 4, wherein the dropwise addition of liquid aldehyde or ketone into the clear solution to perform the reaction to obtain the heat-sensitive acid generator comprises:
dropwise adding liquid aldehyde or ketone into the clear solution, heating to reflux temperature after dropwise adding, preserving heat for a period of time, and cooling to obtain white crystals;
carrying out primary dispersion treatment on the white crystals in a sodium bicarbonate solution, and carrying out solid-liquid separation on a dispersion system;
and carrying out secondary dispersion treatment on the separated solid by using deionized water, and filtering and drying to obtain the heat-sensitive acid generator.
6. The method according to any one of claims 1 to 4, wherein the mass ratio between the tosylhydrazide and the aldehyde or ketone of the liquid is (0.8 to 1.3): (1-1.6).
7. The method according to any one of claims 1 to 4, wherein the concentration of the reactant of tosyl hydrazide and the aldehyde or ketone of the liquid in the solvent is in the range of 35% to 45%.
8. A heat-sensitive acid generator, characterized in that it is produced by the production method according to any one of claims 1 to 7.
9. The heat-sensitive acid generator of claim 8, wherein the structure of the heat-sensitive acid generator is as follows:
10. the use of the heat-sensitive acid generator according to claim 8 or 9 in heat-sensitive CTP printing plates.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960022A (en) * | 2022-05-30 | 2023-04-14 | 北京印刷学院 | Thermosensitive acid-producing type free radical polymerization monomer and preparation method and application thereof |
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| CN102314084A (en) * | 2010-07-09 | 2012-01-11 | 乐凯集团第二胶片厂 | Light sensitization composition using p-toluenesulfonylhydrazide hydrazone compound and application of light sensitization composition |
| CN103885287A (en) * | 2012-12-24 | 2014-06-25 | 乐凯华光印刷科技有限公司 | Photosensitive composition with sulfonyl hydrazone-modified phenolic resin as acid-producing agent and application thereof |
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| CN102314084A (en) * | 2010-07-09 | 2012-01-11 | 乐凯集团第二胶片厂 | Light sensitization composition using p-toluenesulfonylhydrazide hydrazone compound and application of light sensitization composition |
| CN103885287A (en) * | 2012-12-24 | 2014-06-25 | 乐凯华光印刷科技有限公司 | Photosensitive composition with sulfonyl hydrazone-modified phenolic resin as acid-producing agent and application thereof |
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