CN114181254A - Preparation method of quaternary phosphine borane cluster compound and application of quaternary phosphine borane cluster compound as alcohol amine color reducing agent - Google Patents
Preparation method of quaternary phosphine borane cluster compound and application of quaternary phosphine borane cluster compound as alcohol amine color reducing agent Download PDFInfo
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- CN114181254A CN114181254A CN202111624850.5A CN202111624850A CN114181254A CN 114181254 A CN114181254 A CN 114181254A CN 202111624850 A CN202111624850 A CN 202111624850A CN 114181254 A CN114181254 A CN 114181254A
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- borane cluster
- cluster compound
- quaternary phosphine
- alcohol amine
- borohydride
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 66
- -1 alcohol amine Chemical class 0.000 title claims abstract description 57
- BWJRMVLPCQPWGR-UHFFFAOYSA-N boron;phosphane Chemical group [B].P BWJRMVLPCQPWGR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 229910000085 borane Inorganic materials 0.000 claims abstract description 36
- 239000012043 crude product Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011630 iodine Substances 0.000 claims description 21
- 229910052740 iodine Inorganic materials 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 19
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 19
- 239000012279 sodium borohydride Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 150000004714 phosphonium salts Chemical group 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- PKPBCVSCCPTDIU-UHFFFAOYSA-N B.P Chemical group B.P PKPBCVSCCPTDIU-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 15
- 238000000746 purification Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- 238000002407 reforming Methods 0.000 abstract description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 4
- VEWFZHAHZPVQES-UHFFFAOYSA-N boron;n,n-diethylethanamine Chemical compound [B].CCN(CC)CC VEWFZHAHZPVQES-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 241001061264 Astragalus Species 0.000 description 1
- 235000010110 Astragalus glycyphyllos Nutrition 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- KVMLCSKFXCFVGX-UHFFFAOYSA-N C(CC)P(CCC)(CCC)(CCC)Cl Chemical compound C(CC)P(CCC)(CCC)(CCC)Cl KVMLCSKFXCFVGX-UHFFFAOYSA-N 0.000 description 1
- 235000013175 Crataegus laevigata Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 235000006533 astragalus Nutrition 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- GXNZYSLECJVTFK-UHFFFAOYSA-N chloro(tetramethyl)-lambda5-phosphane Chemical compound CP(C)(C)(C)Cl GXNZYSLECJVTFK-UHFFFAOYSA-N 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BAXUMOMSDRKPLK-UHFFFAOYSA-N n,n-dimethylformamide;2-(2-hydroxyethoxy)ethanol Chemical compound CN(C)C=O.OCCOCCO BAXUMOMSDRKPLK-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- 229940126585 therapeutic drug Drugs 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a preparation method of a quaternary phosphine borane cluster compound and application of the quaternary phosphine borane cluster compound as an alcohol amine color reducing agent, wherein borohydride is used as an initial raw material, a borane cluster compound which is a crude product obtained after pyrolysis and reforming of the borohydride is obtained by optimizing the reaction charge ratio and controlling the reaction pyrolysis temperature, and quaternary phosphine organic cations are further introduced to realize rapid separation and purification of the borane cluster compound, so that the quaternary phosphine borane cluster compound is obtained, and the yield can reach more than 90%. The color of the discolored alcohol amine can be reduced by mixing the easily discolored alcohol amine with the quaternary phosphine borane cluster compound, and the chromaticity of Pt-Co is kept below 40, so that the process is simple, convenient and environment-friendly.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a preparation method of a quaternary phosphine borane cluster compound and application of the quaternary phosphine borane cluster compound in the field of alcohol amine color reduction.
Background
The alcohol amine has very important application value in modern industry, and is particularly reflected in the fields of organic synthesis, biological pharmacy, metal processing, coating, desulfurization and purification, tail gas absorption and the like. Taking metal processing as an example, alcohol amine is often used as an antirust component of a metal surface and is one of important components participating in forming metal processing liquid (slow congratulation, sunming, xuxia nan. organic alcohol amine in the metal processing liquid has influence on the service performance of a product [ J ]. lubrication and sealing, 2019, 44 (08): 147-. Furthermore, the alcohol amine can also react with other compounds such as carboxylic acids, boric acids, phosphoric acids and the like to generate functional additives with high-efficiency antirust and anticorrosion functions, and the functional additives are applied to the field of metal processing (Wangyuy\29764, Wangshun, Yaman Zhu, Liyanhui. development and application of nontoxic environment-friendly water-based antirust agent [ J ] automobile technology and materials, 2013 (11): 60-65). However, the problem of darkening in color (colorless to pale yellow to brown) often occurs in the course of practical application of alcohol amines, which greatly affects the later use of alcohol amines. Generally, the lighter the color of the alcohol amine, the higher its practical use value. Discoloration of alcohol amines is generally caused by the decomposition of alcohol amine into amine and aldehyde by oxygen oxidation, and further Schiff base Reaction (Schiffbase Reaction) to form colored substances.
Based on the color change principle of alcohol amine, the introduction of antioxidant can slow down or prevent the color change process of alcohol amine. The various methods for color reduction with alcohol amines often yield little, due to a number of factors. For example, a trace amount of alkali metal borohydride (sodium borohydride, potassium borohydride), ethylenediamine, hydrazine, olefin, sulfurous acid, or the like is added for the color reduction treatment of alcohol amine, but these methods have the following drawbacks: 1) The discolored alcohol amine cannot be processed into a colorless product; 2) the product with reduced color after the treatment can not maintain the expected time; 3) some color-reducing additives cannot meet the requirements of environmental protection regulations at the present stage. With sodium borohydride (NaBH)4) For example, it has strong reducibility, and when it is used as a color reducing agent for alcohol amine, it can effectively consume oxygen present in the system, but sodium borohydride has poor stability and is easily decomposed after being left for a long time to be inactivated, so that the color reduced alcohol amine cannot be maintained for a desired time.
On the basis of the background, the borane cluster compound provided by the invention can effectively solve the problems. On one hand, the reducibility (-4.1eV) of the borane cluster compound is slightly weaker than that of sodium borohydride (-4.4eV), so that the consumption of oxygen in an alcohol amine system can be effectively ensured; on the other hand, the borane cluster has excellent stability performance and thermal decomposition temperatureThe degree is up to 810 ℃ (Sivaev I B, Bregadze V I,
S.Chemistry of closo-dodecaborate anion[B12H12]2-:a review[J]collection of Czechloroslavak Chemical Communications,2002,67(6): 679-727), commonly used in rocket propellants; in addition, borane cluster compounds, as boron neutron carriers in Boron Neutron Capture Therapy (BNCT), are non-toxic to humans and can selectively kill cancer cells without adverse effects on normal cells (legislation, hominis. boron neutron capture therapy for treating tumors and related technological advances [ J]Radiation protection communication, 2010(02) 26-29; research progress of boron neutron capture therapeutic drugs for Yuanjiao Mei (Japanese milkvetch root and Indian flowering cherry seed) [ J]The Chinese New medicine journal 2010(04): 296-300). Due to the unique properties, the borane cluster compound has application advantages in the field of alcohol amine color reduction, and has the characteristics of high efficiency, sustainability, environmental protection and no toxicity.
Borane clusters have the property of being electron rich, often having two negative charges, wherein hydrogen exhibits electronegativity, which is also responsible for the reducibility of the borane clusters. The traditional borane cluster preparation method has the problems of complex process, low yield, difficult purification and the like. For example: prepared by Hawthorne et al report12H12]2-The yield is less than 4% (Hawthorne M F, PitochelliAR. the isolation of the icosahedral [ B ]12H12]2-ion[J]Journal of the American Chemical Society,1960,82: 3228); makhlouf Et al (Et)4N)BH4Pyrolysis reforming can give higher yields of borane cluster compounds, but the product needs to be isolated by chromatographic purification (Makhlouf J M, Hough W V, Hefferan G T.practical synthesis for decahydro decarates [ J]Inorganic Chemistry,1967,6(6): 1196-1198). Therefore, the synthesis path of the borane cluster compound is optimized, the purification and separation steps of the product are simplified, and the prospect of the borane cluster compound is greatly improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a quaternary phosphine borane cluster compound with simplified process, high yield and simple and convenient purification treatment and application thereof in the field of color reduction of alcohol amine. According to the invention, by controlling the feeding ratio of the reaction and the reaction temperature of pyrolysis reforming, a borane cluster crude product can be obtained with high yield. And the quaternary phosphonium salt is further introduced as a purification substance, so that the target product can be rapidly precipitated and separated out. The obtained quaternary phosphine borane cluster product is applied to color reduction of alcohol amine, and compared with the traditional process, the method has the characteristics of obvious color reduction effect, long color reduction time, environmental protection and no toxicity.
The invention adopts the following technical scheme for realizing the purpose:
a preparation method of a quaternary phosphine borane cluster compound is characterized by comprising the following steps:
Further, in step 1, the solvent is at least one of N, N-dimethylformamide, dimethyl sulfoxide, cyclohexanone, diethylene glycol dimethyl ether and ethylene glycol.
Further, in step 1, the borohydride is at least one of potassium borohydride, sodium borohydride, triethylamine borohydride and trimethylamine borohydride.
Further, in step 1, the borane cluster is [ B7H7]2-、[B8H8]2-、[B9H9]2-、[B10H10]2-、[B11H11]2-And [ B12H12]2-One kind of (1).
Further, in step 2, the structure of the quaternary phosphonium salt is shown as follows:
the structure of the quaternary phosphine borane cluster compound obtained by the invention is shown as follows:
the quaternary phosphine borane cluster compound obtained by the invention can be used as an alcohol amine color reducing agent, and the method for reducing the color of the alcohol amine comprises the following steps: the quaternary phosphine borane cluster compound is mixed with alcohol amine to contact, and the color reduction of the alcohol amine can be realized.
Further, the alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, N-dimethylethanolamine, N-diethylethanolamine, isopropanolamine and diglycolamine.
Further, the quaternary phosphine borane cluster compound and the alcohol amine are mixed according to the mass ratio of 10-6～10-2:1, the discolored alcohol amine can be discolored, and the Pt-Co chroma of the obtained mixed system can be kept below 40.
The method for using the quaternary phosphine borane cluster compound in alcohol amine color reduction is suitable for the fields of metal processing, coating, tail gas treatment, organic synthesis, biological pharmacy and the like.
Compared with the traditional alcohol amine color reduction method, the method has the beneficial effects that:
1. the invention realizes the high-efficiency and rapid preparation of the target product, namely the quaternary phosphine borane cluster compound, by reasonably optimizing the feeding ratio of the reaction, controlling the pyrolysis reforming temperature of the reaction and introducing the purification treatment factor, and has the advantages of simplified preparation process, high reaction yield and simple product purification treatment.
2. The quaternary phosphine borane cluster compound obtained by the invention has the characteristics of good reducibility, high stability, environmental protection and no toxicity.
3. The invention has simple and convenient process, and the color reduction of the alcohol amine can be realized only by simply mixing and contacting the quaternary phosphine borane cluster compound with the alcohol amine for a period of time.
4. The principle of the invention applied to color reduction of alcohol amine is that quaternary phosphine borane cluster compounds are used as antioxidants for color reduction of alcohol amine, so that color reduction of alcohol amine is effectively realized, and meanwhile, due to the high stability of borane clusters, the duration of color reduction alcohol amine can be greatly prolonged, and the color reduction effect is obvious and long.
5. The quaternary phosphine cations in the quaternary phosphine borane cluster color reducing agent prepared by the invention are high-efficiency broad-spectrum sterilization components, and are beneficial to the subsequent mildew-proof sterilization application of color-reducing alcohol amine.
Drawings
FIG. 1 is an IR spectrum of a borane cluster quaternary phosphine compound obtained in example 2;
FIG. 2 is the nuclear magnetic hydrogen spectrum of the quaternary phosphine borane cluster compound obtained in example 4 with the solvent d6-DMSO；
FIG. 3 is the nuclear magnetic boron spectrum of the quaternary phosphine borane cluster compound obtained in example 4 with the solvent d6-DMSO；
FIG. 4 is a graph comparing the effect of the quaternary phosphine borane clusters of example 8 before and after color reduction with alcohol amine.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Preparation of quaternary phosphine borane cluster color reducing agent
The preparation method of the quaternary phosphine borane cluster compound comprises the following steps:
Example 1
This example prepares a quaternary phosphine borane cluster compound as follows:
And 2, dissolving 1 part by mass of borane cluster crude product with 10 parts by mass of deionized water, adding 4 parts by mass of tetrabutyl phosphonium chloride, and stirring for half an hour until precipitation is complete. Filtering and collecting solid precipitate, washing the solid precipitate for 3 times by using deionized water, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain a pure product of the quaternary phosphine borane cluster compound, wherein the yield is 91%.
Example 2
This example prepares a quaternary phosphine borane cluster compound as follows:
And 2, dissolving 1 part by mass of borane cluster crude product by using 40 parts by mass of deionized water, adding 6 parts by mass of tetrapropyl phosphorus chloride, and stirring for half an hour until precipitation is completely separated out. Filtering and collecting solid precipitate, washing the solid precipitate for 3 times by using deionized water, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain a pure product of the quaternary phosphine borane cluster compound, wherein the yield is 93%.
Example 3
This example prepares a quaternary phosphine borane cluster compound as follows:
And 2, dissolving 1 part by mass of borane cluster crude product by using 30 parts by mass of deionized water, adding 1 part by mass of tetramethyl phosphorus chloride, and stirring for half an hour until precipitation is completely separated out. Filtering and collecting solid precipitate, washing the solid precipitate for 3 times by using deionized water, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain a pure product of the quaternary phosphine borane cluster compound, wherein the yield is 90%.
Example 4
This example prepares a quaternary phosphine borane cluster compound as follows:
And 2, dissolving 1 part by mass of borane cluster crude product with 20 parts by mass of deionized water, adding 8 parts by mass of tetrabutyl phosphonium bromide, and stirring for half an hour until precipitation is complete. Filtering and collecting solid precipitate, washing the solid precipitate for 3 times by using deionized water, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain a pure product of the quaternary phosphine borane cluster compound, wherein the yield is 92.5%.
Example 5
This example prepares a quaternary phosphine borane cluster compound as follows:
And 2, dissolving 1 part by mass of borane cluster crude product with 40 parts by mass of deionized water, adding 5 parts by mass of tetrabutyl phosphonium bromide, and stirring for half an hour until precipitation is complete. Filtering and collecting solid precipitate, washing the solid precipitate for 3 times by using deionized water, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain a pure product of the quaternary phosphine borane cluster compound, wherein the yield is 90%.
Example 6
This example prepares a quaternary phosphine borane cluster compound as follows:
And 2, dissolving 1 part by mass of borane cluster crude product with 8 parts by mass of deionized water, adding 3 parts by mass of tetraethyl phosphonium bromide, and stirring for half an hour until precipitation is complete. Filtering and collecting solid precipitate, washing the solid precipitate for 3 times by using deionized water, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain a pure product of the quaternary phosphine borane cluster compound, wherein the yield is 94%.
Di-quaternary phosphine borane cluster compound used for alcohol amine color reduction
Mixing alcohol amine (monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine or diglycolamine) and quaternary phosphine borane cluster compound according to the mass ratio of 1: 10-6～10-2And mixing to realize color reduction of the alcohol amine. The mixing time is 10 minutes to 12 hours, and preferably the platinum-cobalt color (measured according to ASTM D1209-2000) of the mixed system of the alcohol amine and the quaternary phosphine borane cluster compound is less than 40, and more preferably the platinum-cobalt color of the mixed system is less than 20.
In some embodiments, it is preferred that the platinum-cobalt color of the mixed system does not increase by 30%, and more preferably that the platinum-cobalt color of the mixed system does not increase by 10%, after storage for 1-6 years at room temperature (20-25 ℃).
In some embodiments, it is preferred that the platinum-cobalt color of the mixed system does not increase by 30%, and more preferably the platinum-cobalt color of the mixed system does not increase by 10%, after 0.5-3 years of storage at 45 ℃. As can be seen from the Van't Hoff equation, a change in temperature results in a change in the rate of chemical reaction, generally by a factor of about 2 to 4 per liter of 10℃. From this, the time for which the alcohol amine can be stored at room temperature can be roughly estimated.
Example 7
Monoethanolamine with a platinum-cobalt color of 35 and the quaternary phosphine borane cluster compound prepared in example 2 are mixed according to a mass ratio of 1: 10-4And (4) mixing. The sample was stirred for 2 hours and stored in a 25 ℃ incubator for 2 years, and the platinum-cobalt color of monoethanolamine after two years of storage was 12 by color value test.
Example 8
Triethanolamine with a platinum-cobalt color number of 30 and the quaternary phosphine borane cluster compound prepared in example 3 are mixed according to a mass ratio of 1: 10-2And (4) mixing. After stirring for 2 hours, a sample is taken and placed in a thermostat at 25 ℃ for 2 years, and the platinum-cobalt chroma of the triethanolamine after two years of storage is 10 through color value test.
Example 9
Diethanolamine with platinum-cobalt color of 32 and the quaternary phosphine borane cluster compound prepared in example 4 are mixed according to the mass ratio of 1: 10-3And (4) mixing. After stirring for 2 hours, the sample was placed in a 25 ℃ incubator for 2 years, and the platinum-cobalt color of diethanolamine after two years of storage was 11 by color value test.
Example 10
Triethanolamine with a platinum-cobalt color number of 30 and the quaternary phosphine borane cluster compound prepared in example 1 are mixed according to a mass ratio of 1: 10-2And (4) mixing. After stirring for 2 hours, sampling, placing in a constant temperature box at 45 ℃ for half a year, and testing the color value, wherein the platinum-cobalt chroma of the triethanolamine after half a year storage is 12. The Van't Hoff equation can be used to calculate that the alcohol amine system with the platinum-cobalt chromaticity of 12 at room temperature (25 ℃) can be ensuredFor 4.5 years (calculated as 3-fold increase in reaction rate per 10 ℃ increase in temperature).
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a quaternary phosphine borane cluster compound is characterized by comprising the following steps:
step 1, taking borohydride and iodine simple substance as reaction raw materials, firstly reacting a mixed system of borohydride, iodine simple substance and solvent at 80-120 ℃ to a clear state, then heating to 150 ℃ and 220 ℃, carrying out reflux reaction for 12 hours, and distilling to remove the solvent to obtain a borane cluster crude product; wherein the mass ratio of the borohydride to the iodine to the solvent is 1: 0.1-10: 1-100;
step 2, dissolving the borane cluster crude product with water, adding quaternary phosphonium salt to precipitate a solid product, filtering, washing with deionized water, and drying to obtain a pure product of the quaternary phosphonium borane cluster compound; wherein the mass ratio of the borane cluster crude product to the quaternary phosphonium salt to the water is 1: 0.5-20: 1 to 100.
2. The method of preparing a quaternary phosphine borane cluster compound according to claim 1, wherein: in the step 1, the solvent is at least one of N, N-dimethylformamide, dimethyl sulfoxide, cyclohexanone, diethylene glycol dimethyl ether and ethylene glycol.
3. The method of preparing a quaternary phosphine borane cluster compound according to claim 1, wherein: in step 1, the borohydride is at least one of potassium borohydride, sodium borohydride, triethylamine borohydride and trimethylamine borohydride.
4. The method of preparing a quaternary phosphine borane cluster compound according to claim 1, wherein: in step 1, the borane cluster is [ B7H7]2-、[B8H8]2-、[B9H9]2-、[B10H10]2-、[B11H11]2-And [ B12H12]2-One kind of (1).
5. The method of preparing a quaternary phosphine borane cluster compound according to claim 1, wherein: in the step 2, the structure of the quaternary phosphonium salt is as follows:
6. a quaternary phosphine borane cluster compound obtained by the production method according to any one of claims 1 to 5, characterized in that: the quaternary phosphine borane cluster compound has the following structure:
7. use of the quaternary phosphine borane cluster compound of claim 6 as an alcohol amine color reducing agent.
8. Use according to claim 7, characterized in that: the quaternary phosphine borane cluster compound is mixed with alcohol amine to contact, and the color reduction of the alcohol amine can be realized.
9. Use according to claim 7 or 8, characterized in that: the alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, N-dimethylethanolamine, N-diethylethanolamine, isopropanolamine and diglycolamine.
10. Use according to claim 7 or 8, characterized in that: quaternary phosphine borane cluster compounds10 to alcohol amine according to the mass ratio-6～10-2:1, and the Pt-Co chroma of the obtained mixed system is less than 40.
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| US4871826A (en) * | 1987-06-22 | 1989-10-03 | Massachusetts Institute Of Technology | Lewis base adducts of decaborane for forming new preceramic polymers, using as binders, forming shaped bodies and forming fibers |
| CN102584878A (en) * | 2012-01-17 | 2012-07-18 | 中国科学院过程工程研究所 | Ionic liquid containing divalent boron cluster negative ion and preparation method thereof |
| CN108290825A (en) * | 2015-12-11 | 2018-07-17 | 沙特基础工业全球技术有限公司 | The method to lose lustre in alkanolamine composition and thus obtained composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871826A (en) * | 1987-06-22 | 1989-10-03 | Massachusetts Institute Of Technology | Lewis base adducts of decaborane for forming new preceramic polymers, using as binders, forming shaped bodies and forming fibers |
| CN102584878A (en) * | 2012-01-17 | 2012-07-18 | 中国科学院过程工程研究所 | Ionic liquid containing divalent boron cluster negative ion and preparation method thereof |
| CN108290825A (en) * | 2015-12-11 | 2018-07-17 | 沙特基础工业全球技术有限公司 | The method to lose lustre in alkanolamine composition and thus obtained composition |
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