CN117126109A - Formaldehyde remover, and preparation method and application thereof - Google Patents
Formaldehyde remover, and preparation method and application thereof Download PDFInfo
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- CN117126109A CN117126109A CN202311400821.XA CN202311400821A CN117126109A CN 117126109 A CN117126109 A CN 117126109A CN 202311400821 A CN202311400821 A CN 202311400821A CN 117126109 A CN117126109 A CN 117126109A
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- formaldehyde
- diamine
- compound
- treatment
- urea
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 304
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 diamine compounds Chemical class 0.000 claims abstract description 88
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003672 ureas Chemical class 0.000 claims abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 29
- 239000004202 carbamide Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 150000003335 secondary amines Chemical group 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 11
- 150000003141 primary amines Chemical group 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 3
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 claims description 2
- JVQUBHIPPUVHCN-UHFFFAOYSA-N hexane-1,2-diamine Chemical compound CCCCC(N)CN JVQUBHIPPUVHCN-UHFFFAOYSA-N 0.000 claims 1
- LPGZAWSMGCIBOF-UHFFFAOYSA-N pentane-1,2-diamine Chemical compound CCCC(N)CN LPGZAWSMGCIBOF-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 27
- 235000013877 carbamide Nutrition 0.000 description 24
- 239000000463 material Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000004982 aromatic amines Chemical class 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- ZMGMDXCADSRNCX-UHFFFAOYSA-N 5,6-dihydroxy-1,3-diazepan-2-one Chemical class OC1CNC(=O)NCC1O ZMGMDXCADSRNCX-UHFFFAOYSA-N 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012048 reactive intermediate Substances 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-OUBTZVSYSA-N aminoformaldehyde Chemical compound N[13CH]=O ZHNUHDYFZUAESO-OUBTZVSYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000007966 viscous suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
- C07D243/04—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 3
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application provides a formaldehyde remover, a preparation method and application thereof; the preparation method of the formaldehyde remover comprises the following steps: dispersing urea compounds in diamine compounds, and then sequentially performing a first cyclization treatment and a second cyclization treatment; wherein the diamine compound is straight-chain aliphatic amine, and has a carbon chain framework and two primary amine groups; the carbon atoms of the carbon chain skeleton are 3-7, and the two primary amine groups are respectively connected to two adjacent carbon atoms of the carbon chain skeleton. The formaldehyde remover provided by the application has higher formaldehyde adsorption capacity, and can realize effective removal of formaldehyde.
Description
Technical Field
The application relates to formaldehyde removal, in particular to a formaldehyde remover, a preparation method and application thereof.
Background
Formaldehyde is an important chemical raw material and is widely used for manufacturing building materials, interior decoration materials or furniture boards and the like. In the production process of these materials, a large amount of urea-formaldehyde resin (urea-formaldehyde glue) or melamine-formaldehyde resin (triamine glue) is generally used as a binder, and formaldehyde is one of the main raw materials for preparing urea-formaldehyde glue or triamine glue, which usually contains unreacted and completely free formaldehyde due to the limitation of the production process. Therefore, the unreacted and complete free formaldehyde is also remained in the building material, the decorative material or the furniture, and is gradually released into the surrounding environment in the form of vapor, and the release period can reach more than ten years.
Chinese patent application publication No. CN109925852a describes a formaldehyde removal composition and a method for removing formaldehyde comprising by weight: 3-20 parts of formaldehyde scavenger, 0.1-0.5 part of adhesive, 0.2-1 part of stabilizer, 10-30 parts of cosolvent and 80-120 parts of solvent; it also describes that the formaldehyde scavenger is one or more selected from ethylene urea, hydrazide compound, ammonia water, glycine, ammonium chloride and chitosan.
Although the ethylene urea employed in this patent application belongs to the class of cyclic ureas, and this patent application enables formaldehyde removal; however, according to the description of examples, when ethylene urea is used as the formaldehyde scavenger, other substances are also incorporated to jointly act as the formaldehyde scavenger; thus, the patent application does not use cyclic ureas alone as formaldehyde scavengers. Moreover, according to the actual research of the applicant, ethylene urea has good solubility, low biotoxicity and better process applicability compared with linear aliphatic amine compounds such as hexamethylenediamine, diethylenediamine and triethylenediamine, but the adsorption amount of formaldehyde is remarkably reduced.
In addition, when preparing cyclic urea compounds such as ethylene urea, alcohol substances are generally required to be used as solvents, and industrial products can be obtained through the steps of evaporation, recrystallization, extraction, washing and the like in the follow-up process; therefore, not only is the solvent difficult to recover, but also the preparation of the formaldehyde remover is too complicated, which is unfavorable for the industrial application in the field of formaldehyde removal.
In view of the foregoing, it is necessary to provide a formaldehyde remover, and a preparation method and application thereof, so as to solve or at least alleviate the technical defects of poor formaldehyde removal performance and solvent introduction in the preparation process of the existing cyclic urea compounds.
Disclosure of Invention
The application mainly aims to provide a formaldehyde remover, a preparation method and application thereof, and aims to solve the technical problems that the existing cyclic urea compound is poor in formaldehyde removing performance and a solvent is introduced in the preparation process.
In order to achieve the above object, the present application provides a preparation method of a formaldehyde remover, comprising the steps of:
s1, dispersing urea compounds in diamine compounds to obtain a pretreatment substance; the molar ratio of the urea compound to the diamine compound is 0.8-3:1;
the diamine compound is straight-chain aliphatic amine, and has a carbon chain framework and two primary amine groups; the number of carbon atoms of the carbon chain skeleton is 3-7, and the two primary amine groups are respectively connected to two adjacent carbon atoms of the carbon chain skeleton;
s2, performing first cyclization treatment on the pretreated object to obtain a first treatment liquid; the first cyclization treatment includes: mixing the pretreated matter for 1.5-4 hours at 145-165 ℃;
s3, performing second cyclization treatment on the first treatment liquid to obtain a second treatment liquid; the second cyclization treatment includes: mixing the first treatment liquid for 1.5-4 hours at 175-200 ℃;
and S4, cooling the second treatment liquid to obtain the solid formaldehyde remover.
Further, the diamine compound comprises at least one of 1, 2-propylene diamine, 1, 2-butylene diamine, 1, 2-pentylene diamine and 1, 2-hexylene diamine.
Further, the urea compound comprises at least one of urea, thiourea, semicarbazide and dimethylurea.
Further, in the step S1, the process of dispersing the urea compound in the diamine compound includes the sub-steps of:
s11, adding the urea compound into the diamine compound to obtain a to-be-treated substance;
s12, mixing the to-be-treated object at the temperature of 60-100 ℃ for 20-50 min to obtain the pretreatment object.
Further, the step S2 further includes; activating the pretreatment before subjecting the pretreatment to the first cyclization treatment;
the activation treatment includes: and mixing the pretreated matter for 0.5-1.5 h at the temperature of 110-130 ℃ to obtain the pretreated matter subjected to the activation treatment.
Further, the step S4 further includes: grinding and drying the cooled product in turn to enable the formaldehyde remover to be powdery and remove unreacted raw materials and ammonia byproducts.
The application also provides a formaldehyde remover which is prepared by adopting the preparation method described in any of the above.
Further, the formaldehyde remover comprises a cyclic urea compound, wherein the cyclic urea compound is provided with an azacyclic ring, a branched chain and a secondary amine group are connected to the azacyclic ring, and the carbon number of the branched chain is 1-3.
The application also provides an application of the formaldehyde remover in removing formaldehyde.
The application also provides a formaldehyde-removing product, which comprises the formaldehyde remover.
Compared with the prior art, the application has at least the following advantages:
the application can improve the aldehyde removal performance of the cyclic urea compound, and a solvent can not be introduced in the preparation process. Specifically, the existing cyclic urea formaldehyde remover such as ethylene urea and the like needs to introduce a solvent to control the reaction degree in the preparation process, so that the material preparation cost is increased, and the final product can be obtained only by carrying out separation and purification operations in the follow-up process; moreover, ethylene urea alone has not high formaldehyde removal performance as a formaldehyde remover.
Under the condition of omitting the solvent, the urea compound is dispersed in the diamine compound, and then the first cyclization treatment and the second cyclization treatment are controlled, so that various side reactions can be reduced, the material synthesis yield is improved, the material preparation cost is reduced, the synthetic reaction process can be effectively controlled, and the problem of excessively severe reaction is avoided.
The diamine compound adopted by the application has a carbon chain skeleton with a linear structure, and two primary amine groups are respectively connected to two adjacent carbon atoms of the carbon chain skeleton by controlling the number of carbon atoms of the carbon chain skeleton to be 3-7, so that the diamine compound and the urea compound can be further ensured to generate a milder cyclization reaction under a solvent-free system, and a branched chain structure is generated on a cyclic structure.
The formaldehyde remover comprises the cyclic urea compound, wherein a branched chain is connected to the nitrogen heterocycle of the cyclic urea compound, and the cyclic structure connected with the branched chain improves the affinity of amino to formaldehyde, so that the product synthesized by the formaldehyde remover has higher formaldehyde removal performance (compared with ethylene urea); in the application, secondary amine groups are also connected to the nitrogen heterocycle of the cyclic urea compound, the amino groups contain active hydrogen atoms, and after being combined with formaldehyde, a hydrogen transfer process occurs, so that the formaldehyde structure is changed, and the formaldehyde is adsorbed and fixed in a synthetic product in a covalent bond mode; based on the selection principle of the diamine compound, one secondary amino group on the cyclic urea compound is adjacent to the branched chain on the nitrogen heterocycle, so that the affinity of the secondary amino group to formaldehyde can be further enhanced.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an apparent diagram of cyclic ureas in example 1 of the present application;
FIG. 2 is a FTIR spectrum (infrared spectrum) of cyclic urea compound in example 1 of the present application;
FIG. 3 is an H-NMR spectrum (hydrogen nuclear magnetic resonance spectrum) of a cyclic urea compound in example 1 of the present application.
The achievement of the object, functional features and advantages of the present application will be further described with reference to the drawings in connection with the embodiments.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application.
Moreover, the technical solutions of the embodiments of the present application may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present application.
The adsorption method is the method with the most extensive application range in the indoor formaldehyde pollution treatment method, and has the remarkable advantages of simple operation, obvious effect, low cost, low energy consumption and high efficiency; the chemical adsorption utilizes the strong chemical bond effect between the functional group and formaldehyde, can realize the effective fixation of formaldehyde on the surface of the adsorbent, and has higher selectivity. The amino functional group can chemically react with formaldehyde at room temperature, the amino is one of the most effective formaldehyde capturing groups, and the amino functional group on the surface of the material and formaldehyde molecules undergo Schiff base reaction and Mannich reaction, so that adsorption and degradation of formaldehyde are realized. The amino formaldehyde remover has good solubility, is often used as an aldehyde removing additive for aldehyde-containing resins and coatings, and can obviously reduce the formaldehyde release amount of the resins and the coatings by controlling the proper addition amount.
However, although aromatic amine, straight-chain aliphatic amine and nitrogen heterocycle have good formaldehyde adsorption effect, the aromatic amine, straight-chain aliphatic amine and nitrogen heterocycle have certain volatility and toxicity, and serious environmental pollution is caused when the aromatic amine, the straight-chain aliphatic amine and the nitrogen heterocycle are directly used, wherein the solubility of part of aromatic amine and nitrogen heterocycle compounds is poor, and the aromatic amine, the straight-chain aliphatic amine and the nitrogen heterocycle are not beneficial to being used in resin adhesives.
The ureido compound has better crystal property and good solubility, is harmless to human body, wherein ethylene urea is the most commonly used formaldehyde remover at present, but has low molecular nucleophilicity and limited formaldehyde removal performance, and the ethylene diamine tube product is used as a raw material in the production process, so that the synthesis cost and the danger are increased. In order to reduce the intensity of the reaction, a large amount of solvent is introduced in the preparation process of the ethylene urea, so that the occurrence probability of side reaction is greatly increased, the product separation process is complicated, and the material preparation cost is increased. The existing preparation process of ethylene urea comprises the following steps: the catalyst is prepared by condensing and ring-closing ethanolamine, ethylenediamine or ethylene glycol methyl ether and urea in water or alcohol solution.
Therefore, the application provides a preparation method of the formaldehyde remover, which comprises the following steps:
s1, dispersing urea compounds in diamine compounds to obtain a pretreatment substance; the pretreatment is a mixture, typically in a liquid state; the molar ratio of the urea compound to the diamine compound is 0.8-3:1.
In the present application, the diamine compound may be in a liquid or solid state; the diamine compound is straight-chain aliphatic amine, and has a carbon chain framework and two primary amine groups; the carbon chain skeleton can be of a linear structure generally, the carbon number of the carbon chain skeleton is 3-7, and the two primary amine groups are respectively connected to two adjacent carbon atoms of the carbon chain skeleton.
Because the diamine compound adopted by the application belongs to linear aliphatic amine, and the two amino groups are primary amino groups and are connected to two adjacent carbon atoms, the final product contains a branched chain structure adjacent to secondary amino groups, and the aldehyde removal performance can be improved. And the two primary amine groups are connected to two adjacent carbon atoms, so that the solubility of the final product can be ensured, the final product can be effectively dissolved in industrial products such as resin glue, and the industrial applicability of the final product is ensured.
Specifically, the diamine compound comprises at least one of 1, 2-propylene diamine, 1, 2-butylene diamine, 1, 2-pentylene diamine and 1, 2-hexylene diamine; the urea compound comprises at least one of urea, thiourea, semicarbazide and dimethylurea.
In order to sufficiently disperse and dissolve the urea-based material in the solid state in the diamine-based compound, the process of dispersing the urea-based compound in the diamine-based compound includes the sub-steps of:
s11, adding the urea compound into the diamine compound to obtain a to-be-treated substance;
and S12, mixing the to-be-treated object at 60-100 ℃ (preferably 75-90 ℃) for 20-50 min to obtain the pretreatment object.
In the application, the to-be-treated substances generally react in a reaction container, the reaction container adopted in the application is a three-necked flask, the reaction container is connected with a condensation reflux device, and the tail end of the condensation reflux device is connected with a tail gas absorption mechanism; in the reaction process, the main bottle mouth of the three-neck flask is communicated with the condensation reflux device, and other bottle mouths are in a blocking state.
S2, performing activation treatment on the pretreated matter; the activation treatment includes: and mixing the pretreated matter for 0.5-1.5 h at the temperature of 110-130 ℃ to obtain the pretreated matter subjected to the activation treatment.
Then, performing first cyclization treatment on the pretreated object to obtain a first treatment liquid; the first cyclization treatment includes: and mixing the pretreated substance at 145-165 ℃ for 1.5-4 hours (preferably 2-4 hours).
The activation treatment may partially decompose the urea compound, release a portion of ammonia, and produce a quantity of reactive intermediates; and the activation treatment can remove air in the reaction system while generating ammonia gas, so that oxidation of the product at high temperature is prevented, yellow byproducts are formed, and the property of the formaldehyde remover is influenced.
The first cyclization treatment may substantially decompose the remaining urea compound while the resulting reactive intermediate begins to bind with the diamine species and cyclize to form the final product.
S3, performing second cyclization treatment on the first treatment liquid to obtain a second treatment liquid; the second cyclization treatment includes: and mixing the first treatment liquid for 1.5-4 hours (preferably 2-4 hours) at 175-200 ℃.
The second cyclization treatment can further improve the reaction efficiency of the reactive intermediate and the diamine substance, and a large amount of final products are formed.
And S4, cooling the second treatment liquid to obtain the solid formaldehyde remover.
By cooling the second treatment liquid to room temperature, the product is completely converted from a liquid state to a solid substance, and the cyclic urea compound for formaldehyde removal can be obtained without further separation and purification processes (e.g., evaporation, recrystallization, extraction, washing, etc.).
In the application, the product of the cooling treatment can be sequentially ground and dried to enable the formaldehyde remover to be powdery and remove unreacted raw materials and ammonia byproducts. The formaldehyde remover in a solid state can be converted into white powder in the grinding process, and unreacted raw materials and ammonia byproducts can be volatilized and removed in the drying process; the drying temperature can be 50-70 ℃ and the drying time can be 10-24 hours.
It should be noted that in the prior art, when preparing cyclic urea compounds such as ethylene urea, a solvent is generally required; the aim is to avoid the reaction between pure substances being too severe, and to control the reaction degree conveniently, thereby obtaining the required cyclic urea compound. However, the presence of a large amount of solvent not only causes difficult recovery of the solvent, but also increases the occurrence probability of side reactions, and finally causes impure products, which require further separation and purification, causes solvent waste, and increases the preparation cost of materials. Therefore, the solvent-free preparation mode adopted in the application can avoid various side reactions, improve the synthesis yield of the material and reduce the preparation cost of the material. In addition, the application uses a multi-stage heating mode at the same time, so that the synthetic reaction rate can be effectively controlled, and the problem of excessively severe reaction is avoided.
The application ensures that the reaction process is more stable and controllable, and the product with better solubility and crystallinity can be obtained by the reaction at a higher temperature. Compared with the preparation of ethylene urea, the preparation method has the advantages that the two primary amine groups in the diamine compound are adjacently arranged, the carbon chain of the diamine compound is extended, the branched chain compound can be formed to strengthen the formaldehyde removal performance, meanwhile, the reaction rate can be slowed down to a certain extent by utilizing the steric effect, but the number of carbon atoms of the carbon chain is controlled within 7, so that the problem that the reaction cannot be normally carried out due to the excessively low reaction activity is avoided.
The application also provides a formaldehyde remover which is prepared by adopting the preparation method described in any of the above.
The formaldehyde remover provided by the application has a specific annular structure, and the nucleophilicity of amino groups is improved, so that the formaldehyde remover is more beneficial to adsorption of formaldehyde. The formaldehyde remover prepared by the application comprises a cyclic urea compound, wherein the cyclic urea compound is provided with an nitrogen heterocycle, a branched chain and a secondary amine group are connected to the nitrogen heterocycle, the number of carbon atoms of the branched chain can be 1-3, and the branched chain can comprise one of methyl, ethyl, propyl and methylene; based on the principle of choice of the reactants in the present application, the nitrogen heterocycle may have attached thereto two of the secondary amine groups, the branch and one of the secondary amine groups being attached to two adjacent carbon atoms of the nitrogen heterocycle.
It should be noted that, according to the application, through optimization of diamine raw materials and optimization of synthesis process, branched chains are also connected to the cyclic structure of the obtained product, which is essentially different from the product structure reported in the prior literature; however, it is the branched cyclic structure that promotes the affinity of amino groups for formaldehyde, so the product synthesized in this patent has higher formaldehyde removal performance (compared to ethylene urea).
In some existing documents, amino belongs to tertiary amine, active hydrogen atoms do not exist on nitrogen atoms of the amino, and products with the structures do not have formaldehyde adsorption capacity and cannot be used for adsorption removal of formaldehyde from the reaction principle of the amino and formaldehyde. In addition, in the application, one secondary amine group is adjacent to the branched chain, so that the electron cloud density around the secondary amine group can be improved, the affinity of the secondary amine group to formaldehyde is enhanced, and finally the formaldehyde removal efficiency is improved. In the present application, although two of the secondary amine groups are attached to the nitrogen heterocycle of the cyclic urea compound, the two secondary amine groups are generally arranged meta to the nitrogen heterocycle; however, since the cyclic urea compound of the present application is a small molecular compound, the branched chain can also enhance the aldehyde removal efficiency of the other secondary amine group.
It should be noted that the formaldehyde remover (cyclic urea compound) provided in each embodiment of the application is a solid substance with high crystallinity, has no pungent smell, has no volatility, does not generate biotoxicity, has good solubility, and is beneficial to application in practical scenes.
The application also provides an application of the formaldehyde remover in removing formaldehyde.
As one of the modes of use, the present application also provides a formaldehyde-removing article comprising therein a formaldehyde-removing agent as described in any of the above; the formaldehyde-removing product may comprise or be any form of formaldehyde-removing product such as a building decorative material.
In the application, the formaldehyde adsorption performance is measured by the following method:
and (3) weighing a material to be measured, loading the material into a reaction tube, introducing formaldehyde gas with a certain concentration into the reaction tube from a climatic chamber, and enabling the formaldehyde gas which is not adsorbed to flow back into the climatic chamber from the reaction tube, wherein after the formaldehyde concentration is stable, the reaction is stopped, and the formaldehyde concentration at the moment is the concentration after adsorption.
The formaldehyde adsorption capacity of the adsorption material is calculated as follows:
in the method, in the process of the application,Qthe adsorption capacity of the material to be tested is mg/g;C 0 the initial concentration of formaldehyde gas in the climatic chamber is ppm;C t the concentration of formaldehyde gas in the climatic chamber is real-time and ppm;1.25 is the mass concentration of formaldehyde gas of 1 ppm at room temperature, mg/cm 3 ；VFor the volume of the climatic chamber, m 3 ；mAnd g is the dosage of the material to be measured.
The following are specific examples of the present application:
example 1
1. 100g of 1, 2-propanediamine and 80g of urea were successively introduced into a three-necked flask equipped with a condensing reflux device; stirring at 80deg.C for 30min to obtain pretreated product.
And (3) heating to 120 ℃, and then continuing stirring for 1h to perform activation treatment on the pretreated matter to obtain the activated pretreated matter.
The temperature was raised to 160℃and stirring was continued for 2 hours to conduct the first cyclization treatment of the pretreated product to obtain a first treatment liquid.
Heating to 180 ℃, and then continuously stirring for 2 hours to perform second cyclization treatment on the first treatment liquid to obtain a second treatment liquid; and cooling the second treatment liquid to room temperature to obtain a white solid substance.
And sequentially grinding and drying the white solid matters obtained by cooling (the drying temperature is 60 ℃ and the duration is 12 h) to obtain the cyclic urea compound.
In this example, the reaction process was mild, and the yield of the cyclic urea compound was 92%.
Referring to FIG. 1, the cyclic urea compound in this example is white powder; the cyclic urea compound in the embodiment is non-sticky and has no pungent smell; the solution was completely dissolved in pure water or ethanol at a solid-to-liquid ratio of 0.5 g/mL.
As will be appreciated with reference to FIG. 2, the cyclic ureas in this example contain methyl branches and secondary amine groups.
As will be understood with reference to fig. 3, the cyclic urea compound in this embodiment belongs to a cyclic structure and is an azacyclic ring.
The cyclic urea compound is used as a material to be measured for measuring formaldehyde adsorption performance:
in the measurement of the formaldehyde adsorption performance in this example, the initial concentration of formaldehyde gas in the climatic chamber was 40ppm, and the volume of the climatic chamber was 0.02m 3 The amount of the material to be measured is 0.1g, and the measurement time is 6h. As a result of measurement, in this example, the formaldehyde adsorption capacity of the cyclic urea compound was 4.1mg/g.
Example 2
In this example, the mass of 1, 2-propanediamine was adjusted to 120g and the mass of urea was adjusted to 85g, as compared to example 1, with the other conditions remaining unchanged.
In the embodiment, the reaction process is mild; the cyclic urea compound obtained after grinding and drying is white powder, has no viscosity and no pungent smell; can be completely dissolved in water or ethanol according to the solid-to-liquid ratio of 0.5 g/mL.
In this example, the yield of the cyclic urea compound was 86%, and the formaldehyde adsorption capacity was 4.0mg/g.
Example 3
In this example, the temperature of the activation treatment was adjusted to 110℃as compared with example 1, and other conditions were kept unchanged.
In the embodiment, the reaction process is mild; the cyclic urea compound obtained after grinding and drying is white powder, has no viscosity and no pungent smell; can be completely dissolved in water or ethanol according to the solid-to-liquid ratio of 0.5 g/mL.
In this example, the yield of the cyclic urea compound was 90%, and the formaldehyde adsorption capacity was 3.9mg/g.
Example 4
In this example, the temperature of the second cyclization treatment was adjusted to 190℃as compared with example 1, and other conditions were kept unchanged.
In the embodiment, the reaction process is mild; the cyclic urea compound obtained after grinding and drying is white powder, has no viscosity and no pungent smell; can be completely dissolved in water or ethanol according to the solid-to-liquid ratio of 0.5 g/mL.
In this example, the yield of the cyclic urea compound was 93%, and the formaldehyde adsorption capacity was 4.1mg/g.
Example 5
In this example, 1, 2-propanediamine was adjusted to 1, 2-butanediamine as compared to example 1, and the other conditions were kept unchanged.
In the embodiment, the reaction process is mild; the cyclic urea compound obtained after grinding and drying is white powder, has no viscosity and no pungent smell; can be completely dissolved in water or ethanol according to the solid-to-liquid ratio of 0.5 g/mL.
In this example, the yield of the cyclic urea compound was 90%, and the formaldehyde adsorption capacity was 4.4mg/g.
Comparative example 1
In this comparative example, the temperature of the first cyclization treatment was adjusted to 140℃as compared with example 1, and other conditions were kept unchanged.
The product of this comparative example was a white solid substance having slight tackiness after grinding and drying.
Comparative example 2
In this comparative example, the first cyclizing treatment was omitted and the pretreated product after the activation treatment was directly subjected to the second cyclizing treatment while other conditions were kept unchanged as compared with example 1.
The product of this comparative example was a viscous white thick substance after cooling to room temperature, had a pungent ammonia taste, was not the target product, and could not be converted into a solid product by baking.
Comparative example 3
In this comparative example, the second cyclizing treatment was omitted and the first treatment solution was directly cooled to room temperature, while other conditions were maintained, as compared with example 1.
The product of this comparative example after cooling to room temperature was a white viscous paste-like substance, had a pungent odor, was not the target product, and could not be converted into a solid product by baking.
Comparative example 4
In this comparative example, the pretreatment was directly stirred at 120 ℃ for 5 hours, and then the product was cooled to room temperature, as compared to example 1, with other conditions remaining unchanged.
The product of this comparative example was a colorless transparent viscous liquid after cooling to room temperature, was not the target product, and could not be converted to a solid product by baking.
Comparative example 5
In this comparative example, 100g of 1, 2-propanediamine and 80g of urea were sequentially added to a three-necked flask equipped with a condensing reflux device, and then the mixture was directly stirred at 180℃for 2 hours, and then the product was cooled to room temperature under other conditions, while maintaining the same conditions.
The reaction process of the comparative example is severe, and a sputtering phenomenon occurs, resulting in poor industrial applicability; and, even the reaction system has serious suck-back behavior, a large amount of air is gushed into the reaction device, and the product is oxidized and yellow.
Comparative example 6
In this comparative example, as compared with example 1, the dispersion treatment was omitted, 100g of 1, 2-propanediamine and 80g of urea were sequentially added to a three-necked flask equipped with a condensing reflux device, and then the activation treatment was directly performed, while the other conditions were maintained.
The product of this comparative example was a viscous white solid after cooling to room temperature, which was difficult to grind into a powder.
Comparative example 7
In this comparative example, 1, 2-propanediamine was adjusted to 1, 4-butanediamine, as compared to example 1, with the other conditions remaining unchanged.
The product of the comparative example after cooling to room temperature is white solid matter, and is white powder after grinding and drying; however, it is not soluble in water and ethanol, resulting in not being effectively dissolved in industrial materials such as resin glue.
Comparative example 8
In the comparative example, deionized water was introduced as a solvent, the mass ratio of deionized water to 1, 2-propanediamine was 2:1, and the remaining specific preparation process remained unchanged, as compared to example 1; wherein the mass of the 1, 2-propylene diamine is 100g.
The product of this comparative example was a white, viscous suspension after cooling to room temperature; filtering the suspension, washing with ethanol for 3-5 times, collecting filtrate, performing rotary evaporation at 40 ℃ under vacuum, and finally collecting white solid matters; it is still sticky after drying and grinding, and the yield of the cyclic urea compound is only 65%.
Comparative example 9
In this comparative example, the material to be measured in the process of measuring the formaldehyde adsorption property was adjusted to ethylene urea, and other conditions were kept unchanged as compared with example 1.
In this comparative example, the formaldehyde adsorption capacity was 2.9mg/g.
In the above technical solution of the present application, the above is only a preferred embodiment of the present application, and therefore, the patent scope of the present application is not limited thereto, and all the equivalent structural changes made by the content of the present application under the technical concept of the present application, or the direct/indirect application in other related technical fields are included in the patent protection scope of the present application.
Claims (10)
1. The preparation method of the formaldehyde remover is characterized by comprising the following steps:
s1, dispersing urea compounds in diamine compounds to obtain a pretreatment substance; the molar ratio of the urea compound to the diamine compound is 0.8-3:1;
the diamine compound is straight-chain aliphatic amine, and has a carbon chain framework and two primary amine groups; the number of carbon atoms of the carbon chain skeleton is 3-7, and the two primary amine groups are respectively connected to two adjacent carbon atoms of the carbon chain skeleton;
s2, performing first cyclization treatment on the pretreated object to obtain a first treatment liquid; the first cyclization treatment includes: mixing the pretreated matter for 1.5-4 hours at 145-165 ℃;
s3, performing second cyclization treatment on the first treatment liquid to obtain a second treatment liquid; the second cyclization treatment includes: mixing the first treatment liquid for 1.5-4 hours at 175-200 ℃;
and S4, cooling the second treatment liquid to obtain the solid formaldehyde remover.
2. The method according to claim 1, wherein the diamine compound comprises at least one of 1, 2-propane diamine, 1, 2-butane diamine, 1, 2-pentane diamine, and 1, 2-hexane diamine.
3. The method according to claim 1, wherein the urea compound comprises at least one of urea, thiourea, semicarbazide, dimethylurea.
4. The method according to claim 1, wherein the process of dispersing the urea compound in the diamine compound in the step S1 comprises the sub-steps of:
s11, adding the urea compound into the diamine compound to obtain a to-be-treated substance;
s12, mixing the to-be-treated object at the temperature of 60-100 ℃ for 20-50 min to obtain the pretreatment object.
5. The method according to claim 1, wherein the step S2 further comprises; activating the pretreatment before subjecting the pretreatment to the first cyclization treatment;
the activation treatment includes: and mixing the pretreated matter for 0.5-1.5 h at the temperature of 110-130 ℃ to obtain the pretreated matter subjected to the activation treatment.
6. The method according to claim 1, wherein the step S4 further comprises: grinding and drying the cooled product in turn to enable the formaldehyde remover to be powdery and remove unreacted raw materials and ammonia byproducts.
7. A formaldehyde remover prepared by the method of any one of claims 1-6.
8. The formaldehyde remover according to claim 7, characterized in that it comprises a cyclic urea compound having an azacyclic ring to which a branched chain and a secondary amine group are attached, the branched chain having 1 to 3 carbon atoms.
9. Use of the formaldehyde remover according to claim 7 or 8 for removing formaldehyde.
10. A formaldehyde-removing article comprising the formaldehyde remover of claim 7 or 8.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2874149A (en) * | 1957-03-18 | 1959-02-17 | Monsanto Chemicals | Ureas |
| US2881152A (en) * | 1955-04-26 | 1959-04-07 | American Cyanamid Co | Alkyleneurea-thiourea condensates |
| US3957431A (en) * | 1975-03-28 | 1976-05-18 | Basf Aktiengesellschaft | Process for easy-care finishing cellulosics |
| JPS6399060A (en) * | 1986-06-26 | 1988-04-30 | Mitsui Toatsu Chem Inc | Production of cyclic ureas |
| US4864026A (en) * | 1987-02-05 | 1989-09-05 | Huls Aktiengesellschaft | Method of manufacturing N-alkyl-N'-methyl-alkyleneureas, particularly N,N'-d |
| US4900820A (en) * | 1986-06-12 | 1990-02-13 | Mitsui Toatsu Chemicals, Inc. | Process for producing cyclic ureas |
| US5206362A (en) * | 1992-02-19 | 1993-04-27 | Texaco Chemical Company | Two-step method for preparing cyclic ureas |
| JPH06200234A (en) * | 1992-12-28 | 1994-07-19 | Sumitomo Chem Co Ltd | Formaldehyde acceptor ad its application to textile |
| JPH1029280A (en) * | 1996-07-15 | 1998-02-03 | Kuraray Co Ltd | Deodorizable laminate |
| JP2001019768A (en) * | 1999-07-08 | 2001-01-23 | Rengo Co Ltd | High-molecular weight thiourea polymer and its production |
| CN101195606A (en) * | 2006-12-09 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for synthesizing oxazoline ketone and cyclic urea compounds |
| CN101717367A (en) * | 2009-12-11 | 2010-06-02 | 天津理工大学 | Preparation method of N, N'-dialkyl cyclic urea type derivative |
| CN103732580A (en) * | 2011-07-20 | 2014-04-16 | 湛新美国股份有限公司 | Process for the synthesis of cyclic alkylene ureas |
| CN104645800A (en) * | 2013-11-25 | 2015-05-27 | 北京市理化分析测试中心 | Formaldehyde catching agent and preparation method thereof |
| CN110997622A (en) * | 2017-08-11 | 2020-04-10 | 诺力昂化学品国际有限公司 | Reactive separation process for converting cyclic alkylene ureas to their corresponding alkyleneamines |
| JP2021031462A (en) * | 2019-08-27 | 2021-03-01 | 東ソー株式会社 | 1-acryloylimidazolidine-2-one compound |
| JP2021038373A (en) * | 2019-08-27 | 2021-03-11 | 東ソー株式会社 | Polymer of 1-acryloylimidazolidin-2-one compound, and cell culture material based on the same |
-
2023
- 2023-10-26 CN CN202311400821.XA patent/CN117126109B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2881152A (en) * | 1955-04-26 | 1959-04-07 | American Cyanamid Co | Alkyleneurea-thiourea condensates |
| US2874149A (en) * | 1957-03-18 | 1959-02-17 | Monsanto Chemicals | Ureas |
| US3957431A (en) * | 1975-03-28 | 1976-05-18 | Basf Aktiengesellschaft | Process for easy-care finishing cellulosics |
| US4900820A (en) * | 1986-06-12 | 1990-02-13 | Mitsui Toatsu Chemicals, Inc. | Process for producing cyclic ureas |
| JPS6399060A (en) * | 1986-06-26 | 1988-04-30 | Mitsui Toatsu Chem Inc | Production of cyclic ureas |
| US4864026A (en) * | 1987-02-05 | 1989-09-05 | Huls Aktiengesellschaft | Method of manufacturing N-alkyl-N'-methyl-alkyleneureas, particularly N,N'-d |
| US5206362A (en) * | 1992-02-19 | 1993-04-27 | Texaco Chemical Company | Two-step method for preparing cyclic ureas |
| JPH06200234A (en) * | 1992-12-28 | 1994-07-19 | Sumitomo Chem Co Ltd | Formaldehyde acceptor ad its application to textile |
| JPH1029280A (en) * | 1996-07-15 | 1998-02-03 | Kuraray Co Ltd | Deodorizable laminate |
| JP2001019768A (en) * | 1999-07-08 | 2001-01-23 | Rengo Co Ltd | High-molecular weight thiourea polymer and its production |
| CN101195606A (en) * | 2006-12-09 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for synthesizing oxazoline ketone and cyclic urea compounds |
| CN101717367A (en) * | 2009-12-11 | 2010-06-02 | 天津理工大学 | Preparation method of N, N'-dialkyl cyclic urea type derivative |
| CN103732580A (en) * | 2011-07-20 | 2014-04-16 | 湛新美国股份有限公司 | Process for the synthesis of cyclic alkylene ureas |
| CN104645800A (en) * | 2013-11-25 | 2015-05-27 | 北京市理化分析测试中心 | Formaldehyde catching agent and preparation method thereof |
| CN110997622A (en) * | 2017-08-11 | 2020-04-10 | 诺力昂化学品国际有限公司 | Reactive separation process for converting cyclic alkylene ureas to their corresponding alkyleneamines |
| JP2021031462A (en) * | 2019-08-27 | 2021-03-01 | 東ソー株式会社 | 1-acryloylimidazolidine-2-one compound |
| JP2021038373A (en) * | 2019-08-27 | 2021-03-11 | 東ソー株式会社 | Polymer of 1-acryloylimidazolidin-2-one compound, and cell culture material based on the same |
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