CN104892671A - Organic phosphorus compound and preparation method thereof - Google Patents
Organic phosphorus compound and preparation method thereof Download PDFInfo
- Publication number
- CN104892671A CN104892671A CN201510365836.6A CN201510365836A CN104892671A CN 104892671 A CN104892671 A CN 104892671A CN 201510365836 A CN201510365836 A CN 201510365836A CN 104892671 A CN104892671 A CN 104892671A
- Authority
- CN
- China
- Prior art keywords
- nitrae
- isosorbide
- alkyl
- phosphorous compounds
- organo phosphorous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002903 organophosphorus compounds Chemical class 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 13
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 35
- -1 sodium alkoxide Chemical class 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- 125000005340 bisphosphate group Chemical group 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 238000000605 extraction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 150000002910 rare earth metals Chemical class 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000009434 installation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000005826 halohydrocarbons Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 150000001455 metallic ions Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical class ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 2
- ZRAWJEGJNRTLOE-UHFFFAOYSA-N 2-ethylhexylphosphonous acid Chemical compound CCCCC(CC)CP(O)O ZRAWJEGJNRTLOE-UHFFFAOYSA-N 0.000 description 2
- RPAHVZMBEOTVNE-UHFFFAOYSA-N CCCCC(CC)CO[PH2]=O Chemical compound CCCCC(CC)CO[PH2]=O RPAHVZMBEOTVNE-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- YJBMMHPCGWCCOH-UHFFFAOYSA-N octan-3-yl dihydrogen phosphate Chemical compound CCCCCC(CC)OP(O)(O)=O YJBMMHPCGWCCOH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001012 protector Effects 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BUNRQCDZZLYGHM-UHFFFAOYSA-N 2,4,4-trimethylpentyl dihydrogen phosphate Chemical compound CC(COP(O)(O)=O)CC(C)(C)C BUNRQCDZZLYGHM-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- WLVCBAMXYMWGLJ-UHFFFAOYSA-N 3-(chloromethyl)heptane Chemical compound CCCCC(CC)CCl WLVCBAMXYMWGLJ-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
An organic phosphorus compound includes two phosphate groups, a rigid structure and a plurality of alkyl groups. The rigid structure is located between the two phosphate groups and is of a benzene ring or composite of the benzene ring with the plurality of alkyl groups. The alkyl groups include alkyl containing 1 to 20 carbon atoms. The invention further relates to a preparation method of the organic phosphorus compound.
Description
Technical field
The invention belongs to organo phosphorous compounds field, be specifically related to a kind of bifunctional organo phosphorous compounds with rigid structure and preparation method thereof.
Background technology
Because the chemical property of rare earth element is extremely similar, their separation is very difficult.In recent years, organic phosphoric acid compound has been widely used in rare earth extraction separation industries.
The organic phosphoric acid compound be separated for rare earth extraction at present mainly contains di-(2-ethylhexyl)phosphoric acid (P204), 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene (P507) and two (2,4,4-tri-methyl-amyl phosphoric acid (Cyanex 272).Wherein, P204 is water-soluble little and stable, and is extracted the extracted species that rare earth generates in organic phase, has larger solubleness, be thus used widely in Rare Earth Separation, but P204 has the shortcomings such as separation factor is little, back extraction is difficult, strip liquor spent acid is high.P507 all shows better separating power than P204 in the extracting and separating of nickel/cobalt rare earth, but P507 has counterweight Rare Earth Separation coefficient is lower, back extraction acidity is high shortcoming.Cyanex272 has good selectivity, has larger separation factor, can realize under mildly acidic conditions to effective separation of rare earth, but Cyanex 272 exists in the application, and loading capacity is lower, the shortcoming of the easy emulsification of separation system.
Summary of the invention
In view of this, necessaryly provide that a kind of selectivity is good, loading capacity is high and back extraction is easy to organo phosphorous compounds and preparation method thereof.
A kind of organo phosphorous compounds, this organo phosphorous compounds comprises two bound phosphate groups, a rigid structure and multiple alkyl, described rigid structure is between two bound phosphate groups, described rigid structure is the combination of a phenyl ring or phenyl ring and multiple alkyl, and described multiple alkyl is the alkyl containing 1 ~ 20 carbon atom.
A preparation method for organo phosphorous compounds, comprises the following steps: S1, and make alcohol and phosphorus trichloride reaction, generate dialkyl phosphites, the alkyl in described alcohol and the alkyl in dialkyl phosphites are R
1, R
1for the alkyl containing 1 ~ 20 carbon atom; S2, makes described dialkyl phosphites and sodium alkoxide react, obtains dialkyl group phosphorous acid sodium ester; S3, makes described dialkyl group phosphorous acid sodium ester and Isosorbide-5-Nitrae-xylylene dichlorides solution reaction, obtains an intermediate, and described Isosorbide-5-Nitrae-xylylene dichlorides contains R on phenyl ring
2, R
3, R
4, R
5, wherein, R
2, R
3, R
4, R
5it is separately the alkyl of hydrogen atom or 1 ~ 20 carbon atom; And S4, described intermediate and sodium hydroxide solution are reacted, then washs with sulphuric acid soln, obtain described organo phosphorous compounds.
Compared with prior art, organo phosphorous compounds provided by the invention, it is the bifunctional organic phosphoric acid compound with rigid structure, linker between this biphosphonate functional group has rigid structure, the space structure effect of this rigid structure linker and steric effect to the selectivity improved when described organo phosphorous compounds is used as extraction agent and saturated capacity very favourable, improve the loading capacity of this organo phosphorous compounds.And, because described organo phosphorous compounds contains two phosphate functional groups, therefore can give body and metallic ion coordination with single, also can give body and metallic ion coordination with two or more, thus cause the selective difference to different metal ion.In addition, containing C-P key in the extracted species that described organo phosphorous compounds generates in extraction process, its acidity is more weak, and back extraction is relatively easy.The preparation method of organo phosphorous compounds provided by the invention, can form C-P key at a lower temperature, produce a large amount of impurity under avoiding high temperature, and the reaction times is short, efficiency is higher.
Accompanying drawing explanation
Fig. 1 be organo phosphorous compounds provided by the invention H-nuclear-magnetism (
1h NMR) collection of illustrative plates.
P-nuclear-magnetism that Fig. 2 is organo phosphorous compounds described in Fig. 1 (
31p NMR) collection of illustrative plates.
Fig. 3 is the infrared spectra of organo phosphorous compounds described in Fig. 1.
Fig. 4 be another organo phosphorous compounds provided by the invention H-nuclear-magnetism (
1h NMR) collection of illustrative plates.
P-nuclear-magnetism that Fig. 5 is organo phosphorous compounds described in Fig. 4 (
31p NMR) collection of illustrative plates.
Fig. 6 is the infrared spectra of organo phosphorous compounds described in Fig. 4.
Fig. 7 is the synthetic route chart of organo phosphorous compounds provided by the invention.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments organo phosphorous compounds provided by the invention and preparation method thereof is described in further detail.
The invention provides a kind of organo phosphorous compounds, this organo phosphorous compounds comprises two bound phosphate groups, a rigid structure and multiple alkyl, described rigid structure is between two bound phosphate groups, and described rigid structure is the combination of a phenyl ring or phenyl ring and multiple alkyl.Described multiple alkyl is the alkyl containing 1 ~ 20 carbon atom.The general formula of this organo phosphorous compounds is structural formula A:
structural formula A
Wherein, R
1for the alkyl containing 1 ~ 20 carbon atom.R
2, R
3, R
4, R
5be separately hydrogen atom or the alkyl containing 1 ~ 20 carbon atom.
Chemical formula A is that Isosorbide-5-Nitrae-terephthaldehyde supports bisphosphate dialkyl compounds.Be appreciated that described two bound phosphate groups
also can be ortho position or a position.
In the present embodiment, it is that Isosorbide-5-Nitrae-terephthaldehyde supports di 2 ethylhexyl phosphonic acid diisooctyl ester or Isosorbide-5-Nitrae-terephthaldehyde supports di 2 ethylhexyl phosphonic acid diethyl ester that described Isosorbide-5-Nitrae-terephthaldehyde supports bisphosphate dialkyl compounds.
(1) Isosorbide-5-Nitrae-terephthaldehyde supports di 2 ethylhexyl phosphonic acid diisooctyl ester, and its structural formula is structural formula A1:
structural formula A1
Refer to Fig. 2, this organo phosphorous compounds
1h NMR composes (CDCl
3, 400MHz) and there are 5 groups of peaks. chemical shift is respectively: 0.80 ~ 1.55ppm(-CH (CH
2cH
3) (CH
2)
3cH
3in all H atom, totally 30), 2.55 ~ 2.85ppm(Ar-CH
2h atom on-methylene, totally 4), 3.80 ~ 4.10ppm(O-CH
2h atom on-CH methylene, totally 4), 7.08 ~ 7.19 ppm(Ar-H, the H atom on phenyl ring, totally 4) and, the hydrogen atom on 11.16ppm(-OH, totally 2).Their integral area is respectively: 1.0,1.87,1.81,1.84,14.56.Visible, in the nuclear magnetic spectrum of this organo phosphorous compounds, the chemical shift of all kinds of H atom and integral area all support di 2 ethylhexyl phosphonic acid diisooctyl ester with target compound Isosorbide-5-Nitrae-terephthaldehyde and are consistent.
Refer to Fig. 3, this organo phosphorous compounds
31p NMR composes (CDCl
3, 400MHz) there is a peak at chemical shift 27.99ppm place, illustrate in organo phosphorous compounds do not have other containing phosphorus impurities.Visible, the chemical shift of this organo phosphorous compounds meets the chemical environment that target compound Isosorbide-5-Nitrae-terephthaldehyde supports phosphorus (P) in di 2 ethylhexyl phosphonic acid diisooctyl ester.
Refer to Fig. 4, the position of this organo phosphorous compounds major absorbance peak is in table 1.
Table 1. Isosorbide-5-Nitrae-terephthaldehyde supports the infrared spectra of di 2 ethylhexyl phosphonic acid diisooctyl ester
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
Absorption peak (cm -1) | 3425 | 2873-2960 | 1681 | 152914651423 | 1408 | 1142 | 1063 | 983 |
Of bonding | ν(O-H) | ν(-C-H) | ν(P-C) | ν(C=C) | Symmetrical δ (C-H) | ν(P=O) | ν(P-O-C) | ν(P-O-H) |
Analyze conclusion: the nuclear-magnetism of this organo phosphorous compounds
1h,
31the structure that P spectrum and infrared spectra and target compound Isosorbide-5-Nitrae-terephthaldehyde support di 2 ethylhexyl phosphonic acid diisooctyl ester is identical, and this organo phosphorous compounds is that Isosorbide-5-Nitrae-terephthaldehyde supports di 2 ethylhexyl phosphonic acid diisooctyl ester as seen.
(2) Isosorbide-5-Nitrae-terephthaldehyde supports di 2 ethylhexyl phosphonic acid diethyl ester, and its structural formula is structural formula A2:
structural formula A2
Refer to Fig. 4, this organo phosphorous compounds
1h NMR composes (DMSO-d
6, 400MHz) and there are 5 groups of peaks, chemical shift is respectively: 1.06 ~ 1.19ppm(-CH
2cH
3middle methyl H atom, totally 6), 2.96 ~ 3.03ppm(Ar-CH
2h atom on-methylene, totally 4), 3.82 ~ 3.88ppm(O-CH
2-CH
3h atom on methylene, totally 4), 7.10 ~ 7.16ppm(Ar-H, the H atom on phenyl ring, totally 4) and, the hydrogen atom on 10.66ppm(-OH, totally 2).Their integral area is respectively: 0.55,1.00,0.99,0.97,1.55.Visible, in this organo phosphorous compounds nuclear magnetic spectrum, the chemical shift of all kinds of H atom and integral area all support di 2 ethylhexyl phosphonic acid diethyl ester with target compound Isosorbide-5-Nitrae-terephthaldehyde and are consistent.
Refer to Fig. 5, this organo phosphorous compounds
31p NMR composes (DMSO-d
6, 400MHz) have a peak at chemical shift 23.93ppm place, illustrate in organo phosphorous compounds do not have other containing phosphorus impurities.Visible, the chemical shift of this organo phosphorous compounds meets the chemical environment that target compound Isosorbide-5-Nitrae-terephthaldehyde supports P in di 2 ethylhexyl phosphonic acid diethyl ester.
Refer to Fig. 6, the position of organo phosphorous compounds major absorbance peak is in table 2.
Table 2. Isosorbide-5-Nitrae-terephthaldehyde supports the infrared spectra of di 2 ethylhexyl phosphonic acid diethyl ester
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
Absorption peak (cm -1) | 3446 | 2917-2989 | 1641 | 151314751425 | 1395 | 1128 | 1025 | 960 |
Of bonding | ν(O-H) | ν(-C-H) | ν(P-C) | ν(C=C) | Symmetrical δ (C-H) | ν(P=O) | ν(P-O-C) | ν(P-O-H) |
Analyze conclusion: the nuclear-magnetism of this organo phosphorous compounds
1h,
31the structure that P spectrum and infrared spectra and target compound Isosorbide-5-Nitrae-terephthaldehyde support di 2 ethylhexyl phosphonic acid diethyl ester is identical, and this organo phosphorous compounds is that Isosorbide-5-Nitrae-terephthaldehyde supports di 2 ethylhexyl phosphonic acid diethyl ester as seen.
Organo phosphorous compounds provided by the invention has the following advantages: the first, described organo phosphorous compounds is the bifunctional organic phosphoric acid compound with rigid structure, linker between this biphosphonate functional group has rigid structure, the space structure effect of this rigid structure linker and steric effect to the selectivity improved when described organo phosphorous compounds is used as extraction agent and saturated capacity very favourable; The second, the alkoxyl group in described phosphate functional group is connected with alkyl chain, and this alkyl chain can ensure the solubleness of described organo phosphorous compounds in thinner; Three, because described organo phosphorous compounds contains two phosphate functional groups, therefore can give body and metallic ion coordination with single, also can give body and metallic ion coordination with two or more, thus cause the selective difference to different metal ion; Four, contain C-P key in the extracted species that described organo phosphorous compounds generates in extraction process, its acidity is more weak, and back extraction is relatively easy; 5th, this organo phosphorous compounds also can be used as fire retardant and uses.
Refer to Fig. 7, the present invention further provides a kind of preparation method of described organo phosphorous compounds, comprise the following steps:
S1, makes alcohol and phosphorus trichloride (PCl
3) reaction, generate dialkyl phosphites, the alkyl in described alcohol and the alkyl in dialkyl phosphites are R
1, R
1for the alkyl containing 1 ~ 20 carbon atom;
S2, makes described dialkyl phosphites and sodium alkoxide react, obtains dialkyl group phosphorous acid sodium ester;
S3, makes described dialkyl group phosphorous acid sodium ester and Isosorbide-5-Nitrae-xylylene dichlorides solution reaction, obtains an intermediate, and described Isosorbide-5-Nitrae-xylylene dichlorides contains R on phenyl ring
2, R
3, R
4, R
5, wherein, R
2, R
3, R
4, R
5it is separately the alkyl of hydrogen atom or 1 ~ 20 carbon atom;
S4, makes described intermediate and sodium hydroxide (NaOH) solution reaction, then uses sulfuric acid (H
2sO
4) solution washs, and obtains described organo phosphorous compounds.
In step S1, make alcohol and PCl
3the detailed process of reaction is: by PCl
3be added drop-wise in described alcohol, under certain temperature of reaction and pressure, make described alcohol and PCl
3react, until do not have gas and liquid to steam.After reaction terminates, first use basic solution (such as Na
2cO
3solution) be washed till alkalescence, then use neutral solution (such as the saturated common salt aqueous solution) to be washed till neutrality, finally carry out drying, filtration, obtain described dialkyl phosphites.Described alcohol and PCl
3temperature of reaction be: 0 ~ 40 DEG C, described pressure is 1 × 10
4~ 9 × 10
4pa, total reaction time is 1 ~ 8 hour.Described alcohol and PCl
3mol ratio be 1:1 ~ 8:1, preferably, described alcohol and PCl
3mol ratio be 3.5:1.The general formula of described dialkyl phosphites is structural formula B:
structural formula B
Wherein, R
1for the alkyl containing 1 ~ 20 carbon atom.
In the present embodiment, at described alcohol and PCl
3in reaction process, reaction system is first at pressure 1 × 10
4~ 2 × 10
4react 0.2 ~ 1 hour under Pa, then pressure is increased to 7 × 10 gradually
4~ 9 × 10
4pa, continues reaction 1 ~ 5 hour, and the object done like this is discharged by the HCl gas generated in reaction system, promotes to react completely.
In step S2, described sodium alkoxide can be sodium ethylate, sodium propylate, sodium butylate etc., described dialkyl phosphites can be added drop-wise in described sodium alkoxide and react.The temperature of reaction of described dialkyl phosphites and sodium alkoxide is 50 ~ 110 DEG C, and preferably, described temperature of reaction is 80 DEG C, and the reaction times is 0.5 ~ 5 hour.The mol ratio of described sodium alkoxide and dialkyl phosphites is 3:1 ~ 1:3, and preferably, the mol ratio of this sodium alkoxide and dialkyl phosphites is 1.2:1.The general formula of described dialkyl group phosphorous acid sodium ester is structural formula C:
structural formula C
Wherein, R
1for the alkyl containing 1 ~ 20 carbon atom.
In step S3, described Isosorbide-5-Nitrae-dichloromethyl benzole soln refers to that Isosorbide-5-Nitrae-xylylene dichlorides is dissolved in the solution formed in toluene, dimethylbenzene or Isosorbide-5-Nitrae-dioxane etc.Particularly, at normal temperatures, be added drop-wise in dialkyl group phosphorous acid sodium ester by Isosorbide-5-Nitrae-dichloromethyl benzole soln and react, then react at a certain temperature, dialkyl phosphites base replaces chlorine atom in described Isosorbide-5-Nitrae-xylylene dichlorides, obtains described intermediate.After reaction terminates, be washed till neutrality, vacuum rotary steam at a certain temperature by neutral solution (such as the saturated common salt aqueous solution).The mol ratio of described Isosorbide-5-Nitrae-xylylene dichlorides and dialkyl group phosphorous acid sodium ester is 3:1 ~ 1:3, and preferably, the mol ratio of Isosorbide-5-Nitrae-xylylene dichlorides and dialkyl group phosphorous acid sodium ester is 1:1.The temperature of reaction of Isosorbide-5-Nitrae-xylylene dichlorides and dialkyl group phosphorous acid sodium ester is 50 ~ 110 DEG C, and preferably, this temperature of reaction is 80 DEG C.Reaction times is 1 ~ 4 hour, preferably, and 1.5 hours described reaction times.The temperature of underpressure distillation is 70 ~ 150 DEG C, can steam described toluene, dimethylbenzene or Isosorbide-5-Nitrae-dioxane equal solvent, and preferably, described vacuum rotary steam temperature is 100 DEG C.The vacuum rotary steam time is 2 ~ 4 hours, and preferably, the described vacuum rotary steam time is 2 hours.
The general formula of described Isosorbide-5-Nitrae-xylylene dichlorides is structural formula D:
structural formula D
Wherein, R
2, R
3, R
4, R
5it is separately the alkyl of hydrogen atom or 1 ~ 20 carbon atom.
The general formula of described intermediate is structural formula E:
structural formula E
Wherein, R
1for the alkyl containing 1 ~ 20 carbon atom.R
2, R
3, R
4, R
5it is separately the alkyl of hydrogen atom or 1 ~ 20 carbon atom.
In step S4, the reaction of described intermediate and sodium hydroxide (NaOH) solution can be carried out under certain temperature and underpressure distillation, and object is the alcohol generated to get rid of intermediate and NaOH hydrolysis reaction, promotes that balance moves right, and promotes further to react completely.
After described intermediate and sodium hydroxide (NaOH) solution reaction terminate, with sulfuric acid (H
2sO
4) the solution detailed process of carrying out washing is: use certain density H
2sO
4solution is washed till strongly-acid, then uses neutral solution (such as the saturated common salt aqueous solution) to be washed till neutrality, vacuum rotary steam 2 hours under last fixed temperature.
The mol ratio of described intermediate and NaOH is 1:1 ~ 1:10, and preferably, the mol ratio of described intermediate and NaOH is 1:4.The concentration of NaOH solution is 0.1 ~ 10mol/L, and preferably, the concentration of described NaOH solution is 10mol/L.H
2sO
4the concentration of solution is 1 ~ 10mol/L, preferably, and H
2sO
4the concentration of solution is 2mol/L.The temperature of reaction of intermediate and NaOH is 70 ~ 150 DEG C, and preferably, the temperature of reaction of intermediate and NaOH is 110 DEG C.The reaction times of intermediate and NaOH is 0.5 ~ 3 hour.The temperature of described vacuum rotary steam is 80 DEG C ~ 150 DEG C, and preferably, the temperature of described vacuum rotary steam is 110 DEG C.
Embodiment 1
(1) 18.23g isooctyl alcohol is added with stirring, backflow, drying installation and constant pressure funnel there-necked flask in, then slowly drip 5.50gPCl
3, and keep pressure to be 1.5 × 10
4pa, about 0.5 hour.After dripping, under temperature is 25 DEG C of conditions, keep pressure 7 × 10
4pa, and react 1.5 hours, increase pressure gradually, finally reach 9 × 10
4pa, keeping 2 hours, steaming to not having gas and liquid.Na is used after reaction terminates
2cO
3solution is washed till strong basicity, then is washed to neutrality with saturated common salt, then uses anhydrous Na
2sO
4drying, filters.
(2) 3.00g sodium ethylate is added there is stirring, backflow, N
2in the four-hole boiling flask of protector and drying installation, at ambient temperature, slowly drip the product obtained in (1), after dropwising, under 80 DEG C of conditions, react 2 hours.
(3) at normal temperatures, the Isosorbide-5-Nitrae-xylylene dichlorides of the 3.75g that slow dropping is dissolved with toluene in (2), after dropwising, under 80 DEG C of conditions, reacts 1.5 hours.After reaction terminates, with saturated aqueous common salt, organic phase is washed till neutrality, vacuum rotary steam 2 hours under 100 DEG C of conditions.
(4) by 10.00g(3) in product add have stirring, backflow and drying installation there-necked flask in, then add the NaOH solution of 8.00g10mol/L, under 110 DEG C of conditions, underpressure distillation 2 hours.After reaction terminates, with 2 mol/L H
2sO
4be washed till strongly-acid, then be washed to neutrality with saturated common salt.Vacuum rotary steam 2 hours under 110 DEG C of conditions.
Embodiment 2
(1) 8.41g propyl alcohol is added with stirring, backflow, drying installation and constant pressure funnel there-necked flask in, then slowly drip 5.50gPCl
3, and keep pressure to be 1.5 × 10
4pa, reacts 0.5 hour, after dripping, under temperature is 25 DEG C of conditions, keeps pressure 7 × 10
4pa, and react 1 hour, increase pressure gradually, finally reach to 9 × 10
4pa, keeping 1.5 hours, steaming to not having gas and liquid.Na is used after reaction terminates
2cO
3solution is washed till strong basicity, then is washed to neutrality with saturated common salt, then uses anhydrous Na
2sO
4drying, filters.
(2) 3.00g sodium ethylate is added there is stirring, backflow, N
2in the four-hole boiling flask of protector and drying installation, at ambient temperature, slowly drip the product obtained in (1), after dropwising, under 80 DEG C of conditions, react 1.5 hours.
(3) at normal temperatures, the Isosorbide-5-Nitrae-xylylene dichlorides of the 3.75g that slow dropping is dissolved with toluene in (2), after dropwising, under 80 DEG C of conditions, reacts 1.5 hours.After reaction terminates, with saturated aqueous common salt, organic phase is washed till neutrality, vacuum rotary steam under 100 DEG C of conditions.
(4) by 9.00g(3) in product add have stirring, backflow and drying installation there-necked flask in, then add the NaOH solution of 6.00g10 mol/L, under 110 DEG C of conditions, underpressure distillation 2 hours.After reaction terminates, with 2 mol/L H
2sO
4be washed till strongly-acid, then be washed to neutrality with saturated common salt.Vacuum rotary steam 2 hours under 110 DEG C of conditions.
The preparation method of described organo phosphorous compounds has the following advantages: the first, in prior art, and the structure of C-P key is more difficult.Such as, the synthetic route of the P507 containing single C-P key: the first step 2-Ethylhexyl Alcohol and phosphorus trichloride prepare two (2-ethylhexyl) phosphinate; Second step sodium ethylate process two (2-ethylhexyl) phosphinate, obtains two (2-ethylhexyl) phosphonous acid and receives ester; 3rd step adds 2-ethylhexyl Chloride in two (2-ethylhexyl) phosphonous acid receives ester, obtains O, O-bis-(2-ethylhexyl) ethylhexyl dihydrogen phosphate; 4th step, 20% HCl treatment O, O-bis-(2-ethylhexyl) ethylhexyl dihydrogen phosphate sloughs alkyl hydrocarbon, obtains di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (i.e. P507); But, the method building C-P in preparation method of the present invention is simple, particularly, benzene A type halohydrocarbon (1 is used in step S3 of the present invention, 4-xylylene dichlorides) react with described dialkyl group phosphorous acid sodium ester, because benzene A type halohydrocarbon activity is higher, halogen atom easily departs from, be easy at a lower temperature make described dialkyl group phosphorous acid sodium ester slough sodium, form C-P key; The second, described C-P key can be formed at a lower temperature, produce a large amount of impurity, and the reaction times is short, efficiency is higher under avoiding high temperature; Three, benzene A type halohydrocarbon (1,4-xylylene dichlorides) react with described dialkyl group phosphorous acid sodium ester, thus make described dialkyl group phosphorous acid sodium ester slough sodium, construct two C-P keys simultaneously, rigid structure can be provided for described organo phosphorous compounds, improve the selectivity of described organo phosphorous compounds; Four, by introducing alkyl on the phenyl ring of benzene A type halohydrocarbon, improve the solubleness of described organo phosphorous compounds in organic phase, making this organo phosphorous compounds more be conducive to rare earth extraction; Five, the organo phosphorous compounds prepared by the preparation method of described organo phosphorous compounds is utilized to have flame retardant resistance.
In addition, those skilled in the art also can do other changes in spirit of the present invention, and certainly, these changes done according to the present invention's spirit, all should be included within the present invention's scope required for protection.
Claims (10)
1. an organo phosphorous compounds, this organo phosphorous compounds comprises two bound phosphate groups, a rigid structure and multiple alkyl, it is characterized in that, described rigid structure is between two bound phosphate groups, described rigid structure is the combination of a phenyl ring or phenyl ring and multiple alkyl, and described multiple alkyl is the alkyl containing 1 ~ 20 carbon atom.
2. organo phosphorous compounds as claimed in claim 1, it is characterized in that, described organo phosphorous compounds is that Isosorbide-5-Nitrae-terephthaldehyde supports bisphosphate dialkyl compounds, and the general formula of this organo phosphorous compounds is:
Wherein, R
1for the alkyl containing 1 ~ 20 carbon atom, R
2, R
3, R
4, R
5it is separately the alkyl of hydrogen atom or 1 ~ 20 carbon atom.
3. organo phosphorous compounds as claimed in claim 2, it is characterized in that, it is that Isosorbide-5-Nitrae-terephthaldehyde supports di 2 ethylhexyl phosphonic acid diisooctyl ester or Isosorbide-5-Nitrae-terephthaldehyde supports di 2 ethylhexyl phosphonic acid diethyl ester that described Isosorbide-5-Nitrae-terephthaldehyde supports bisphosphate dialkyl compounds.
4. organo phosphorous compounds as claimed in claim 1, it is characterized in that, described two bound phosphate groups ortho positions or a ground are positioned on described rigid structure.
5. a preparation method for organo phosphorous compounds, comprises the following steps:
S1, make alcohol and phosphorus trichloride reaction, generate dialkyl phosphites, the alkyl in described alcohol and the alkyl in dialkyl phosphites are R
1, R
1for the alkyl containing 1 ~ 20 carbon atom;
S2, makes described dialkyl phosphites and sodium alkoxide react, obtains dialkyl group phosphorous acid sodium ester;
S3, makes described dialkyl group phosphorous acid sodium ester and Isosorbide-5-Nitrae-xylylene dichlorides solution reaction, obtains an intermediate, and described Isosorbide-5-Nitrae-xylylene dichlorides contains R on phenyl ring
2, R
3, R
4, R
5, wherein, R
2, R
3, R
4, R
5it is separately the alkyl of hydrogen atom or 1 ~ 20 carbon atom; And
S4, makes described intermediate and sodium hydroxide solution react, then washs with sulphuric acid soln, obtain described organo phosphorous compounds.
6. preparation method as claimed in claim 5, is characterized in that, in step S1, under a temperature of reaction and a pressure, make described alcohol and PCl
3react, described temperature of reaction is 0 ~ 40 DEG C, and described negative pressure is 1 × 10
4~ 9 × 10
4pa, the mol ratio of described alcohol and phosphorus trichloride is 1:1 ~ 8:1.
7. preparation method as claimed in claim 5, it is characterized in that, in step S2, the temperature of reaction of described dialkyl phosphites and sodium alkoxide is 50 ~ 110 DEG C, and the mol ratio of described sodium alkoxide and dialkyl phosphites is 3:1 ~ 1:3.
8. preparation method as claimed in claim 5, it is characterized in that, described Isosorbide-5-Nitrae-dichloromethyl benzole soln refers to that Isosorbide-5-Nitrae-xylylene dichlorides is dissolved in the solution formed in toluene, dimethylbenzene or Isosorbide-5-Nitrae-dioxane.
9. preparation method as claimed in claim 5, it is characterized in that, the reaction of described intermediate and sodium hydroxide solution is carried out under certain temperature and underpressure distillation, and the temperature of reaction of this intermediate and sodium hydroxide solution is 70 ~ 150 DEG C.
10. preparation method as claimed in claim 5, it is characterized in that, the general formula of described intermediate is:
Wherein, R
1for the alkyl containing 1 ~ 20 carbon atom, R
2, R
3, R
4, R
5it is separately the alkyl of hydrogen atom or 1 ~ 20 carbon atom.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510365836.6A CN104892671A (en) | 2015-06-29 | 2015-06-29 | Organic phosphorus compound and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510365836.6A CN104892671A (en) | 2015-06-29 | 2015-06-29 | Organic phosphorus compound and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN104892671A true CN104892671A (en) | 2015-09-09 |
Family
ID=54025681
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510365836.6A Pending CN104892671A (en) | 2015-06-29 | 2015-06-29 | Organic phosphorus compound and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104892671A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110746454A (en) * | 2019-11-12 | 2020-02-04 | 济南大学 | Dual-phosphoric acid extracting agent for extracting and separating zirconium and hafnium and preparation method thereof |
-
2015
- 2015-06-29 CN CN201510365836.6A patent/CN104892671A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110746454A (en) * | 2019-11-12 | 2020-02-04 | 济南大学 | Dual-phosphoric acid extracting agent for extracting and separating zirconium and hafnium and preparation method thereof |
CN110746454B (en) * | 2019-11-12 | 2021-07-13 | 济南大学 | Dual-phosphoric acid extracting agent for extracting and separating zirconium and hafnium and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zon et al. | Synthesis of phosphonic acids and their esters as possible substrates for reticular chemistry | |
CN101405292A (en) | Method for the purification of triorganophosphites by treatment with a basic additive | |
CN108864183B (en) | Method for synthesizing organophosphorus compound by catalyzing Atherton-Todd reaction through photoinduced iodine | |
CN106832259B (en) | A kind of preparation method for the fire retardant of polyphosphate that branch is double DOPO | |
CN106519297A (en) | Method for synthesizing flame retardant by aminolysis and phosphorous-nitrogen flame retardant | |
CN103374030A (en) | Method for preparing glufosinate-ammonium and preparation method for intermediate thereof | |
Stepinski et al. | Facile high yielding synthesis of symmetric esters of methylenebisphosphonic acid | |
CN104892671A (en) | Organic phosphorus compound and preparation method thereof | |
Dar et al. | Synthetic strategies to achieve further-functionalised monoaryl phosphate primary building units: crystal structures and solid-state aggregation behavior | |
Morohashi et al. | Selective extraction of heavy rare-earth metal ions with a novel calix [4] arene-based diphosphonic acid | |
CN103073747A (en) | Phosphorus-containing fire retardant and its preparation method | |
CN102399243A (en) | Environment-friendly synthesis method for diphenyl phosphine chloride | |
US9035083B2 (en) | Synthesis of H-phosphonate intermediates and their use in preparing the herbicide glyphosate | |
CN109134535B (en) | Preparation method of methyl phosphate | |
CN102796137B (en) | Method for preparing 0,0-di(2-ethylhexyl)-2-ethylhexyl phosphonate | |
JP4536185B2 (en) | Method for producing condensed phosphate ester | |
US20170158719A1 (en) | Process for reducing the chlorine content of organotetraphosphites | |
CN114524843A (en) | Hydroxyl-terminated reactive flame retardant and preparation method thereof | |
CN109134534B (en) | Simple preparation method of 3, 3-dialkoxy propyl methylphosphonate | |
US9701697B2 (en) | Process for reducing the chlorine content of organotetraphosphites | |
US6909010B2 (en) | Facile synthesis of symmetric esters of alkylenebisphosphonic acids | |
CN104004015A (en) | Preparation method of dialkyl phosphinic acid | |
CN102766162A (en) | Synthetic method of p-dibenzyl diphosphonic acid 4-methyl iodide | |
JP2019147747A (en) | Manufacturing method of alkenyl phosphorus compound | |
CN103509056B (en) | A kind of microwave synthesis method of diphosphite three (2,2 '-xenol) ester |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150909 |