CN111039828A - Production method of organic guanidine bactericide - Google Patents
Production method of organic guanidine bactericide Download PDFInfo
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- CN111039828A CN111039828A CN201911126391.0A CN201911126391A CN111039828A CN 111039828 A CN111039828 A CN 111039828A CN 201911126391 A CN201911126391 A CN 201911126391A CN 111039828 A CN111039828 A CN 111039828A
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- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 title claims abstract description 87
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 42
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006467 substitution reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 114
- 239000007788 liquid Substances 0.000 claims description 45
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 31
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- 238000005086 pumping Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 239000002351 wastewater Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 10
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical group [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000413 hydrolysate Substances 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- -1 aminomethyl ethyl Chemical group 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims description 4
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011265 semifinished product Substances 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000005057 refrigeration Methods 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 abstract description 6
- 239000012071 phase Substances 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 150000002357 guanidines Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 241000233866 Fungi Species 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- AUBSVTJUXWCYLJ-UHFFFAOYSA-N C(=O)OC.N#CN Chemical compound C(=O)OC.N#CN AUBSVTJUXWCYLJ-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- DGQBFOGDBFMMTN-UHFFFAOYSA-N ethyl n-(n,n-dimethylcarbamimidoyl)-n-methylcarbamate Chemical compound CCOC(=O)N(C)C(=N)N(C)C DGQBFOGDBFMMTN-UHFFFAOYSA-N 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- GFIGYOBTFCXFHZ-UHFFFAOYSA-N CNC#N.OC=O Chemical compound CNC#N.OC=O GFIGYOBTFCXFHZ-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 102000016943 Muramidase Human genes 0.000 description 1
- 108010014251 Muramidase Proteins 0.000 description 1
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000004756 Respiratory Insufficiency Diseases 0.000 description 1
- 206010038678 Respiratory depression Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000037149 energy metabolism Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004325 lysozyme Substances 0.000 description 1
- 229960000274 lysozyme Drugs 0.000 description 1
- 235000010335 lysozyme Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000008558 metabolic pathway by substance Effects 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- ZSYJMXLJNPEAGP-UHFFFAOYSA-N methyl n-cyanocarbamate Chemical compound COC(=O)NC#N ZSYJMXLJNPEAGP-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004763 spore germination Effects 0.000 description 1
- 229960005322 streptomycin Drugs 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/02—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of guanidine from cyanamide, calcium cyanamide or dicyandiamides
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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 production method of an organic guanidine bactericide, belonging to the technical field of bactericide production. The organic guanidine bactericide is prepared by using cyanamide, ethyl chloroformate, dimethyl sulfate and dimethylamine as main raw materials through the steps of blending, substitution, one-step synthesis, dissolution, two-step synthesis and blending. According to the invention, the catalyst is added for blending before the substitution reaction, and the substitution reaction is carried out after the blending, so that the substitution reaction can be rapidly carried out due to the existence of the catalyst even if a water phase and an organic phase exist in the system at the same time, and the industrial production efficiency is ensured.
Description
Technical Field
The invention relates to the technical field of bactericide production, in particular to a production method of an organic guanidine bactericide.
Background
Guanidine exists in natural products such as protein, nucleic acid and streptomycin, and various plants such as beet, rice husk, mushroom and bean, and contains a trace amount of guanidine in human and animal bodies, but free guanidine is very unstable and easily absorbs carbon dioxide in the air to generate guanidine carbonate, so guanidine usually exists stably in the form of guanidine salt. Guanidine salts are an important component of guanidine compounds and can be derived into a wide variety of guanidine derivatives, which have good antibacterial properties. Guanidine antibacterial agents refer to antibacterial compounds containing guanidine groups in the structure, and are mainly used in the fields of medicines and pesticides.
The organic guanidine compound is also widely used as a bactericide, has various effects on fungi, and usually achieves the aim of inhibiting or killing organisms by influencing abnormal phenomena such as growth and division of the fungi, spore germination, respiratory depression, cell expansion, disruption of cytoplast, cell wall damage and the like. The guanidyl compound has high activity and is positively charged after being dissolved in water, so that the guanidyl compound is easily adsorbed on the surface of negatively charged microorganisms, the action of lysozyme of cells is blocked, and the structure of the cell surface layer is denatured and damaged, thereby inhibiting the propagation of bacteria.
Compared with the toxic and side effects (which can cause skin diseases, are harmful to human bodies and even cause cancers) of aldehyde, phenol, alcohol, peroxide and ether antibacterial agents, the defects of poor heat resistance, easiness in decomposition, odor and short service life, the guanidine antibacterial agent is not toxic (does not have carcinogenicity, denaturation and teratogenicity to human bodies), is tasteless, nonirritating, high-temperature resistant and antibacterial to the human bodies, and has good washing fastness and lasting antibacterial effect after being treated on textiles. The guanidine group in guanidino compounds is an effective active group that can interact with groups or elements in the organism, disrupting its normal substance and energy metabolism. Therefore, the guanidino compound with biological activity is commonly used as an antimicrobial agent in agricultural bactericides, disinfectants and industrial biocides, etc. The long-chain alkyl mono-guanidine and poly-guanidine, aryl guanidine, phthalylguanidine and the like have killing or inhibiting effects on a plurality of microorganisms (including bacteria, fungi, viruses and the like) and have certain biological activity.
The organic guanidine compounds are mainly synthesized by the action of amine (ammonia) and guanylated reagents such as cyanamide, isothiourea, isourea, hydrazine, isothiocyanate and the like, and in addition, the guanylated compounds can also be prepared by the condensation polymerization of guanidyl and amine. Butanamine (fine chemical raw material and intermediate, 2008, 9 th: 36-39) discloses a synthetic process of methyl N-methyl-N (N ', N' -dimethylamido) carbamate, which is synthesized as a synthetic cyclic keton preparation intermediate by the following steps: reacting lime nitrogen with water to prepare cyanamide, and reacting the cyanamide with methyl chloroformate to prepare methyl cyanamide formate; adjusting methyl cyanocarbamate to be neutral by using alkali, adding excessive 10% dimethyl sulfate, and controlling the reaction temperature to be 25 ℃ for esterification reaction to obtain a toluene solution of N-methyl cyanocarbamate; and finally, adding the toluene solution of the methyl N-methyl cyanocarbamate into the sulfate solution of dimethylamine under stirring, heating for azeotropic distillation, removing the toluene in vacuum, reacting at 90 ℃ for 5 hours, and cooling to obtain the methyl N-methyl-N-N (N ', N' -dimethyl amidino) carbamate.
The preparation process is simple in flow and uncomplicated in experimental conditions, but in practice, in the reaction process for preparing the cyanamide methyl formate, because a water phase and an organic phase exist in a system at the same time, the preparation reaction is slow, and the industrial production of the cyanamide methyl formate is influenced.
Disclosure of Invention
The invention aims to provide a method for producing an organic guanidine bactericide on the basis of the prior art, wherein a catalyst is added for blending before a substitution reaction, and the substitution reaction is carried out after the blending, so that the substitution reaction can be rapidly carried out due to the existence of the catalyst even if a water phase and an organic phase exist in a system at the same time, and the industrial production efficiency is ensured.
The production method of the organic guanidine bactericide provided by the invention comprises the following steps:
(1) blending: adding water, a catalyst and cyanamide into a liquid caustic soda blending kettle, and starting a kettle lower pump to circulate the materials;
(2) and (3) substitution: pumping the liquid caustic soda into an elevated tank, and pumping ethyl chloroformate into the elevated tank by using a vacuum pump; starting the chilled water of the liquid caustic soda blending kettle to keep the temperature of materials in the kettle below 15 ℃, dropwise adding the liquid caustic soda and ethyl chloroformate to react, keeping the reaction temperature at 15-25 ℃, stopping dropwise adding when the pH of the system is 6-7, and continuously stirring at 15-25 ℃ for 1-2 hours; transferring the material to a hydrolysate blending kettle, and starting a pump to circulate the material;
(3) one-step synthesis: pumping liquid caustic soda into a head tank, and pumping dimethyl sulfate into the head tank from a tank area; heating the materials in the hydrolysate blending kettle to 35-40 ℃, dropwise adding liquid caustic soda and dimethyl sulfate to react, controlling the pH = 7.0-7.2, and controlling the temperature at 35-40 ℃ after dropwise adding to react for 2-3 h; standing and layering after the reaction is finished, transferring the lower layer to a 15% hydrolysis kettle by a pump, and obtaining a one-step finished product of N-methyl cyanoethyl carbamate at the upper layer; extracting the lower layer liquid with organic solvent, merging the desolventizing product into one-step finished product after the organic solvent is extracted, pumping the raffinate into a liquid caustic soda dehydration kettle, raising the temperature with steam, cooling the residual organic solvent to a liquid caustic soda dehydration recovery tank through a condenser, and sending the raffinate to sewage treatment;
(4) dissolving: adding dimethylamine into a 50% dissolving kettle, and adding hydrochloric acid into an elevated tank; starting a 50% dissolving kettle for freezing, starting a kettle lower pump to circulate the materials at the temperature of below 15 ℃, dropwise adding hydrochloric acid, and dissolving to obtain dimethylamine hydrochloride;
(5) two-step synthesis: injecting hydrochloride of dimethylamine into a head tank, and pumping N-methyl cyanoethyl carbamate into a 15% dissolving kettle; starting 15% of dissolving kettle steam, heating to 75-85 ℃, starting a kettle lower pump, dropwise adding dimethylamine hydrochloride, and transferring the materials to a wastewater neutralization kettle through a pump after the reaction is finished; pumping the liquid caustic soda into a head tank; starting a wastewater neutralization kettle for refrigeration, starting a kettle lower pump to enable materials to be internally circulated, dropwise adding liquid caustic soda until the pH of the system is 7-8, pumping an organic solvent after the reaction is finished, standing for layering, transferring a lower layer to a scraper evaporator through a pump and a preheater, and transferring an upper layer to an acidified wastewater for transferring to a tank; preheating materials in a scraper evaporator by a preheater, cooling an organic solvent to a scraper water recovery tank by a condenser, cooling a second-step finished product N-ethoxy-carbonyl-N, N ', N' -trimethylguanidine by the condenser, transferring the cooled second-step finished product to a storage tank, and pumping a semi-finished product into the top of the scraper evaporator again by a wastewater circulating transfer tank for circulation;
(6) blending: pumping the second-step finished product into a finished product preparation kettle, pumping a blending solvent for blending to obtain a finished product, namely the organic guanidine bactericide, wherein the structural formula of the organic guanidine bactericide is as follows:
the production method of the organic guanidine bactericide further comprises the following steps: (7) recovering dimethylamine: pumping the liquid caustic soda into a high-level tank, transferring materials in a rotary tank in the acidified wastewater into a 50% hydrolysis kettle through a pump, dropwise adding the liquid caustic soda, adjusting the pH value to 7.0-7.2, starting steam, and cooling dimethylamine to a 50% hydrolysis recovery water tank through a condenser.
In the production method of the organic guanidine bactericide, in the step (1), the catalyst is benzyltriethylammonium chloride, and the adding amount of the catalyst is 3.0-4.5% of the feeding amount of ethyl chloroformate.
In the above method for producing an organic guanidine bactericide, further, in the production method, the organic solvent is chloroform (i.e., chloroform); the blending solvent is chloroform or toluene.
In the production method of the organic guanidine bactericide, the feeding molar ratio of the production raw materials of aminomethyl ethyl ester, cyanamide, dimethyl sulfate and dimethylamine is 1: 0.9-1.1: 0.9-1.1: 2.1 to 2.2.
The production method of the organic guanidine bactericide further comprises the step of controlling the content of the organic guanidine bactericide to be 80-82%.
The production method of the invention is adopted to produce the organic guanidine bactericide, and has at least the following beneficial effects: the catalyst is added for blending before the substitution reaction, and the substitution reaction is carried out after the blending, so that the substitution reaction can be rapidly carried out due to the existence of the catalyst even if a water phase and an organic phase exist in the system at the same time, and the industrial production efficiency is ensured.
Detailed Description
The present invention is further described below with reference to examples. It should be noted that the present invention is not limited to the following embodiments.
Example 1
The production process of organic guanidine bactericide includes the following steps:
(1) blending: adding 350Kg of water, 22Kg of 98% benzyltriethylammonium chloride and 800Kg of 30% cyanamide into a liquid caustic soda blending kettle, and starting a pump under the kettle to circulate the materials;
(2) and (3) substitution: 1670Kg of 30% caustic soda liquid is pumped into a head tank, and 665Kg of 98% ethyl chloroformate is pumped into the head tank by a vacuum pump; starting a liquid caustic soda blending kettle, freezing and keeping the temperature below 15 ℃, dropwise adding liquid caustic soda and ethyl chloroformate to react, keeping the reaction temperature at about 20 ℃, stopping dropwise adding when the pH =7 is the end point, and continuously stirring at about 20 ℃ for 1 h; after the reaction is finished, transferring the materials to a hydrolysate blending kettle, and starting a pump to make the materials internally circulate; the substitution reaction process is shown as the following formula:
(3) one-step synthesis: 30 Kg of 30% liquid caustic soda is thrown into a head tank, and 1065 Kg of 98% dimethyl sulfate is thrown into the head tank from a tank area; heating the materials in the hydrolysate blending kettle to 40 ℃, dropwise adding liquid caustic soda and dimethyl sulfate to react, controlling the pH to be =7.0, and controlling the temperature to be 40 ℃ for heat preservation reaction for 3 hours after dropwise adding; standing and layering after the reaction is finished, transferring the lower layer to a 15% hydrolysis kettle by a pump, and obtaining a one-step finished product of N-methyl cyanoethyl carbamate at the upper layer; extracting the lower layer liquid by using chloroform of 200L, and merging the desolventizing product after chloroform extraction into a finished product in one step; pumping the materials in the transfer tank into a liquid caustic soda dehydration kettle, heating the steam to about 40 ℃, cooling the residual chloroform to a liquid caustic soda dehydration recovery tank by a condenser, and sending the residual liquid to sewage treatment; the synthesis process is shown as the following formula;
(4) dissolving: 1440Kg of 40% dimethylamine was put into a 50% dissolution vessel, and 1556Kg of 30% hydrochloric acid was put into an overhead tank. Starting a dissolving kettle for freezing, starting a kettle lower pump to make the material internally circulate at 10 ℃, and dropwise adding hydrochloric acid to obtain the hydrochloride of dimethylamine;
(5) two-step synthesis: the hydrochloride of dimethylamine is pumped into a head tank, and the N-methyl cyanoethyl carbamate is pumped into a 15 percent dissolving kettle. Starting steam of the dissolution kettle, raising the temperature to 80 ℃, starting a kettle lower pump, dropwise adding hydrochloride of dimethylamine, and transferring the materials to a wastewater neutralization kettle through a pump after the reaction is finished; pumping the liquid caustic soda into a head tank; freezing a wastewater neutralization kettle, starting a kettle lower pump to circulate materials internally, dripping liquid alkali, pumping chloroform after the reaction is finished, standing for layering, enabling the lower layer to pass through a pump and a preheater to reach a scraper evaporator, and placing the upper layer into acidified wastewater for transferring to a tank; in the scraper evaporator, materials are preheated by a preheater (the heat source is from a hot water tank and is circulated by a pump), chloroform is cooled to a scraper water recovery tank by a condenser, a two-step finished product N-ethoxy-carbonyl-N, N ', N' -trimethylguanidine is cooled to a residual liquid storage tank by the condenser, and a semi-finished product is pumped to the top of the scraper evaporator again by a wastewater circulation transfer tank for circulation; the synthesis process is shown as the following formula, and the two-step finished product, namely the organic guanidine bactericide, is generated:
(6) blending: pumping the second-step finished product into a finished product preparation kettle, pumping chloroform for blending to obtain a finished product, namely the organic guanidine bactericide;
(7) recovering dimethylamine: pumping the liquid caustic soda into a head tank, transferring materials in a rotary tank in the acidified wastewater to a 50% hydrolysis kettle through a pump, dropwise adding the liquid caustic soda, adjusting the pH value to 7.0, starting steam, and cooling dimethylamine to a 50% hydrolysis recovery water tank through a condenser.
In the method, when the method is specifically implemented, the feeding molar ratio of the production raw materials of aminomethyl ethyl ester, cyanamide, dimethyl sulfate and dimethylamine is 1: 0.9-1.1: 0.9-1.1: 2.1-2.2, when the adding amount of the catalyst is 3.0-4.5% of the feeding amount of ethyl chloroformate, the substitution and synthesis reaction can be smoothly completed, and the production of the organic guanidine bactericide is realized; the dimethylamine is fed in excess, and can be used as reaction raw material, and can also be used as acid-binding agent by utilizing the alkalescence of the dimethylamine to absorb acidic substances in the reaction system, so that the acid does not influence the two-step synthesis reaction. In specific implementation, the organic solvent toluene can also be adopted to carry out two-step finished product blending to obtain the finished product of the organic guanidine bactericide.
The examples main equipment and results are as follows:
liquid caustic soda blending kettle, phi 1900 is multiplied by 2100mm, 5000L; a head tank with phi of 800 multiplied by 1000mm and 500L; a vacuum pump made of PP material; hydrolysate blending kettle, phi 1900 × 2100mm, 5000L; 15% hydrolysis kettle, phi 1900 x 2100mm, 5000L; condenser, contact area 30m2Stainless steel tubulation; 15% dissolving kettle, 1HF32-25-125 m; a wastewater neutralization kettle, CQB-50-32-125 combination; preheater, 20m2Stainless steel coil plate; scraper evaporator, 20m2(ii) a A finished product preparing kettle with phi 1900 multiplied by 2100mm and 5000L; a 50% hydrolysis recovery water tank with phi of 800X 2200mm and 1000L;
the raw materials adopted in the embodiment are obtained in a commercially available mode, and the preparation method is common knowledge in the industry; the results were as follows:
appearance: a light yellow oily liquid;
moisture content: 0.15 percent;
content of organic guanidine: 80.47 percent;
chloroform content: 0.72 percent.
In the finished bactericide product, during specific implementation, the content of the organic guanidine is detected by adopting an enterprise standard Q/JH0012-2019 gas chromatography, and a detection instrument of the bactericide product is GC-2010, a color matching spectrum workstation, an FID detector and a 10 mu L chromatography sample injector; the standard substance is purchased from Hubei on a network, and the content is 98.8 percent; the chromatographic conditions are as follows: a chromatographic column: HP-5, 30 m.times.0.32 m.times.0.25 um, column temperature: 145 ℃, vaporizer temperature: 270 ℃, detection chamber temperature: 270 ℃; carrier gas nitrogen gas: 5Mp, tail blown hydrogen: 0.1Mpa, combustion-supporting gas air: 0.08 MPa; feeding amount: 0.2 mu L; retention time: organoguanidine 10min, internal standard 7.231 min. Chloroform adopts GB/T4118-2008 industrial chloroform to detect the content, and the water content adopts a trace moisture tester to detect.
The standard requirement of the water content of the finished product is less than or equal to 0.2 percent, the standard requirement of the organic guanidine content is more than or equal to 80 percent, and the standard requirement of the chloroform content is less than or equal to 4 percent. The implementation result shows that the organic guanidine bactericide product produced by the production method meets the quality requirement.
Comparative example 1
The production method of the organic guanidine bactericide comprises the following production processes:
firstly, 350Kg of water and 22Kg of 98% benzyltriethylammonium chloride are added into a substitution reaction kettle, and a pump under the kettle is started to make the materials internally circulate; 1670Kg of 30% caustic soda liquid is pumped into a head tank, and 665Kg of 98% ethyl chloroformate is pumped into the head tank by a vacuum pump; starting a substitution reaction kettle, keeping the temperature below 15 ℃ for freezing, dropwise adding liquid caustic soda and ethyl chloroformate for reacting, keeping the reaction temperature at about 20 ℃, stopping dropwise adding when the pH =7 is the end point, and continuously stirring at about 20 ℃ for 1h to perform substitution reaction;
the rest of the one-step synthesis, dissolution, two-step synthesis and blending operations were the same as in example 1;
practice shows that in the substitution reaction of the comparative example, a water phase and an organic phase exist in the system at the same time, the substitution reaction is slow to carry out, and the dropwise addition needs 8 hours, so that the production efficiency is influenced; in example 1, after adding the catalyst in the blending step, the catalyst increases the transfer of the aqueous phase and the organic phase, and the dropwise addition of the base and the ethyl chloroformate only needs 2 to 3 hours, so that the substitution reaction can be rapidly carried out.
The present invention is not described in detail in the prior art.
Claims (6)
1. A production method of an organic guanidine bactericide is characterized by comprising the following steps: the production method comprises the following steps:
(1) blending: adding water, a catalyst and cyanamide into a liquid caustic soda blending kettle, and starting a kettle lower pump to circulate the materials;
(2) and (3) substitution: pumping the liquid caustic soda into an elevated tank, and pumping ethyl chloroformate into the elevated tank by using a vacuum pump; starting the chilled water of the liquid caustic soda blending kettle to keep the temperature of materials in the kettle below 15 ℃, dropwise adding the liquid caustic soda and ethyl chloroformate to react, keeping the reaction temperature at 15-25 ℃, stopping dropwise adding when the pH of the system is 6-7, and continuously stirring at 15-25 ℃ for 1-2 hours; transferring the material to a hydrolysate blending kettle, and starting a pump to circulate the material;
(3) one-step synthesis: pumping liquid caustic soda into a head tank, and pumping dimethyl sulfate into the head tank from a tank area; heating the materials in the hydrolysate blending kettle to 35-40 ℃, dropwise adding liquid caustic soda and dimethyl sulfate to react, controlling the pH = 7.0-7.2, and controlling the temperature at 35-40 ℃ after dropwise adding to react for 2-3 h; standing and layering after the reaction is finished, transferring the lower layer to a 15% hydrolysis kettle by a pump, and obtaining a one-step finished product of N-methyl cyanoethyl carbamate at the upper layer; extracting the lower layer liquid with organic solvent, merging the desolventizing product into one-step finished product after the organic solvent is extracted, pumping the raffinate into a liquid caustic soda dehydration kettle, raising the temperature with steam, cooling the residual organic solvent to a liquid caustic soda dehydration recovery tank through a condenser, and sending the raffinate to sewage treatment;
(4) dissolving: adding dimethylamine into a 50% dissolving kettle, and adding hydrochloric acid into an elevated tank; starting a 50% dissolving kettle for freezing, starting a kettle lower pump to circulate the materials at the temperature below 15 ℃, dropwise adding hydrochloric acid, and dissolving to obtain dimethylamine hydrochloride;
(5) two-step synthesis: injecting hydrochloride of dimethylamine into a head tank, and pumping N-methyl cyanoethyl carbamate into a 15% dissolving kettle; starting 15% of dissolving kettle steam, heating to 75-85 ℃, starting a kettle lower pump, dropwise adding dimethylamine hydrochloride, and transferring the materials to a wastewater neutralization kettle through a pump after the reaction is finished; pumping the liquid caustic soda into a head tank; starting a wastewater neutralization kettle for refrigeration, starting a kettle lower pump to enable materials to be internally circulated, dropwise adding liquid caustic soda until the pH of the system is 7-8, pumping an organic solvent after the reaction is finished, standing for layering, transferring a lower layer to a scraper evaporator through a pump and a preheater, and transferring an upper layer to an acidified wastewater for transferring to a tank; preheating materials in a scraper evaporator by a preheater, cooling an organic solvent to a scraper water recovery tank by a condenser, cooling a second-step finished product N-ethoxy-carbonyl-N, N ', N' -trimethylguanidine by the condenser, transferring the cooled second-step finished product to a storage tank, and pumping a semi-finished product into the top of the scraper evaporator again by a wastewater circulating transfer tank for circulation;
(6) blending: pumping the second-step finished product into a finished product preparation kettle, pumping a blending solvent for blending to obtain a finished product, namely the organic guanidine bactericide, wherein the structural formula of the organic guanidine bactericide is as follows:
2. the method for producing an organic guanidine bactericide as claimed in claim 1, wherein: the production method further comprises the following steps: (7) recovering dimethylamine: pumping the liquid caustic soda into a high-level tank, transferring materials in a rotary tank in the acidified wastewater into a 50% hydrolysis kettle through a pump, dropwise adding the liquid caustic soda, adjusting the pH value to 7.0-7.2, starting steam, and cooling dimethylamine to a 50% hydrolysis recovery water tank through a condenser.
3. The method for producing an organic guanidine bactericide as claimed in claim 1, wherein: in the step (1), the catalyst is benzyltriethylammonium chloride, and the adding amount of the catalyst is 4.0-4.5% of the feeding amount of ethyl chloroformate.
4. The method for producing an organic guanidine bactericide as claimed in claim 1, wherein: in the production method, the organic solvent is chloroform; the blending solvent is chloroform or toluene.
5. The method for producing an organic guanidine bactericide as claimed in claim 1, wherein: the production raw materials of aminomethyl ethyl ester, cyanamide, dimethyl sulfate and dimethylamine are fed in a molar ratio of 1: 0.9-1.1: 0.9-1.1: 2.1 to 2.2.
6. The method for producing an organic guanidine bactericide as claimed in claim 1, wherein: the content of the organic guanidine bactericide is 80-82%.
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