CN112898335A - Preparation method of low-odor phosphate ester TCPP - Google Patents
Preparation method of low-odor phosphate ester TCPP Download PDFInfo
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- CN112898335A CN112898335A CN202110085850.6A CN202110085850A CN112898335A CN 112898335 A CN112898335 A CN 112898335A CN 202110085850 A CN202110085850 A CN 202110085850A CN 112898335 A CN112898335 A CN 112898335A
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- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 36
- 239000010452 phosphate Substances 0.000 title claims abstract description 36
- 150000002148 esters Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000012043 crude product Substances 0.000 claims abstract description 46
- 238000005406 washing Methods 0.000 claims abstract description 43
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003513 alkali Substances 0.000 claims abstract description 28
- 239000010410 layer Substances 0.000 claims abstract description 25
- 239000012044 organic layer Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- IDEYZABHVQLHAF-GQCTYLIASA-N (e)-2-methylpent-2-enal Chemical compound CC\C=C(/C)C=O IDEYZABHVQLHAF-GQCTYLIASA-N 0.000 claims description 16
- IDEYZABHVQLHAF-UHFFFAOYSA-N 2-Methyl-2-pentenal Natural products CCC=C(C)C=O IDEYZABHVQLHAF-UHFFFAOYSA-N 0.000 claims description 16
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 15
- -1 organic base compound Chemical class 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 28
- 239000000047 product Substances 0.000 abstract description 24
- 238000011161 development Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002466 imines Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CNGPUXZHOOHVHJ-UHFFFAOYSA-N 4-methylhept-4-en-1-yn-3-ol Chemical compound CCC=C(C)C(O)C#C CNGPUXZHOOHVHJ-UHFFFAOYSA-N 0.000 description 1
- ORAAZVDXWSKZHK-UHFFFAOYSA-N Bis-(1-chloro-2-propyl) phosphate Chemical compound CC(CCl)OP(O)(=O)OC(C)CCl ORAAZVDXWSKZHK-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of low-odor phosphate ester TCPP, which comprises the following steps: 1) treating the crude product of the phosphoric ester TCPP by using an aqueous alkali compound, layering after treatment, and respectively collecting a water layer and an organic layer containing the organic alkali compound, wherein the water layer containing the organic alkali compound is used indiscriminately; 2) washing the organic layer with water, layering, collecting the organic layer and the water layer, distilling under reduced pressure, and detecting that the water content is less than or equal to 0.1%. The ammonia water is used for washing to replace other alkali, the layered ammonia water solution can be recycled, the concentration can be adjusted according to the requirement and the product index after the layering can meet the requirement, the energy consumption is greatly reduced, the energy is saved, the environmental pollution is reduced, and the development trend of green environmental protection and green chemistry is compounded.
Description
Technical Field
The invention relates to the technical field of fine chemical production, in particular to a preparation method of low-odor phosphate ester TCPP.
Background
Phosphate flame retardant TCPP, chemical name: tris (1-chloro-2-propyl) phosphate, the english name tris (1-chloro-2-propyl) phosphate, of the formula C9H18Cl3O4P, molecular weight 327.5696, the product is colorless or light yellow transparent liquid, has good hydrolytic stability, is soluble in organic solvents such as alcohol, benzene, ester, carbon tetrachloride and the like, is insoluble in water and aliphatic hydrocarbon, and is phosphate ester TCPP which is an ester derivative of phosphoric acid. Mainly used for polystyreneAlkene, polyurethane foam, polyester, polycarbonate and liquid crystal polymer material's fire-retardant, its low cost of production, the low price, advantages such as fire behaviour are wide above-mentioned field, though receive the restriction in toy application field by the European Union, but have irreplaceable fire-retardant effect in some fields.
In the preparation method of the phosphate TCPP, phosphorus oxychloride and an epoxy compound are mostly used as raw materials, Lewis acid is used as a catalyst, the reaction is carried out, then low-boiling-point substances are removed by reduced pressure distillation, and then alkali washing and water washing are carried out, and the finished product is obtained by reduced pressure distillation and water removal.
In the process of synthesizing the phosphate TCPP, phosphorus oxychloride and propylene oxide generate the phosphate TCPP, and aldehyde compounds such as 2-methyl-2-pentenal as a byproduct are generated, the compounds have obvious special odor, even if the compound contains 100ppm, the odor of the product is unpleasant, and the products sold in the market require to control the content of the aldehyde compounds and the odor of the product.
Oxidation is often used in the treatment of aldehydes to oxidize the aldehyde to acids, thereby reducing the level of aldehyde-containing compounds, such as:
200910264987.7 (publication No. CN101775031A), adopts potassium perchlorate to oxidize aldehyde compounds, so as to reduce the content of aldehyde to 10PPM, and uses alkali washing and water washing to carry out post-treatment to obtain stable product. This washing method requires a large amount of water consumption, which cannot be used. The wastewater not only increases the labor cost of production and has high energy consumption, but also has great pollution to the environment and great waste to water resources, and does not accord with the development trend of green chemistry in the future.
201010562551.9 (publication No. CN102002068A) directly uses ozone to oxidize the crude product, so as to reduce the aldehyde content of the product to the minimum, then the treatment operations such as alkali washing, water washing and the like are carried out, the process needs to increase an ozone device, increase the equipment investment, and reduce the aldehyde content of the product to 100ppm, and the effect is common.
200610038132.9(CN101007952A) relates to a purification method of a crude product of phosphoric ester TCPP, which is to add dilute hydrochloric acid into the crude product to wash away the catalyst in the reactant, to separate out an acid water layer, to add dilute alkali to neutralize excessive acid, to separate out an alkali water layer, to add hydroxylamine hydrochloride solution equivalent to aldehyde compounds to react, to add deionized water, to wash to neutrality, to separate out the water layer, to carry out vacuum distillation and dehydration to obtain the phosphoric ester TCPP. After the crude product is washed by alkali, the crude product is washed by hydroxylamine hydrochloride alcohol, and after the crude product is washed, the crude product is washed twice by water, and the product is obtained by treatment, wherein the aldehyde content of the product is reduced to 10-20ppm from 100ppm, and the washing method has obvious high cost. The introduction of alcohol inside is clearly undesirable.
201910282036.6(CN109912644A) discloses a post-treatment purification process for a crude product in the production of phosphate TCPP, which comprises the following steps: standing, settling the alumina catalyst, adding water, stirring and washing, standing for layering, and performing reduced pressure distillation and dehydration to obtain the phosphate TCPP.
201910690591.2 (publication number CN110294773A) relates to a purification method of a crude product of the phosphate ester TCPP, which comprises the following steps: and adding the crude product into an acidic aqueous solution for hydrolysis, washing, removing a water layer, then distilling and dehydrating under reduced pressure, adding the obtained product into a stain oxidant microcapsule solution for reaction, standing and separating the solution, and then performing alkali washing, water washing and distillation to obtain the phosphate TCPP. The method has the advantages that the propylene oxide is excessive in synthesis, the propylene oxide is not treated cleanly after reaction, the excessive propylene oxide is removed by the hydrolysis of acid washing aqueous solution, the bis (1-chloro-2-propyl) phosphate is generated in the synthesis process, the compound needs to be removed under the condition of acid aqueous solution, the method has obvious multiple steps of reaction, a large amount of alkali is consumed in the alkali washing process, odor-containing aldehyde is removed through calcium oxide, and the condition is difficult to treat cleanly.
The invention provides a method for refining phosphate TCPP with high purity by ammonia water again, which can further refine the phosphate TCPP and remove aldehyde odor.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a method for preparing low-odor phosphoric ester TCPP.
The invention provides a preparation method of low-odor phosphate ester TCPP, which comprises the following steps:
1) treating the crude product of the phosphoric ester TCPP by using an aqueous alkali compound, layering after treatment, and respectively collecting a water layer and an organic layer containing the organic alkali compound, wherein the water layer containing the organic alkali compound is used indiscriminately;
2) washing the organic layer with water, layering, collecting the organic layer and the water layer, distilling under reduced pressure, and detecting that the water content is less than or equal to 0.1%.
The method comprises the following steps:
in step 1)
The content of the phosphate TCPP crude product is 99.1 percent, and the content of 2-methyl-2-pentenal is not higher than 1000ppm, preferably not higher than 800 ppm; when 2-methyl-2-pentenal is detected to be within the above range, the operation may be repeated until the content thereof is not higher than 10 ppm;
the aqueous organic alkali compound is ammonia water, the concentration of the ammonia water is 2-5%, the dosage of the ammonia water is 20-40% of the crude product, and the optimal dosage is 25-35%;
the treatment is carried out by washing at a temperature of 25-40 ℃ for 1-3 hours, preferably, at a temperature of 35-40 ℃, for a washing time: 1-2 hours;
in step 2):
the weight of the water is 10-30% of the weight of the crude product, preferably 15-25%;
during the reduced pressure distillation, the vacuum degree is kept between-0.09 MPa and-0.10 MPa, and the distillation temperature is 110-115 ℃.
The preparation method provided by the invention has the following advantages:
1. compared with the conventional method (200910264987.7 (publication No. CN101775031A), hereinafter referred to as 2009 patent):
1) the method is different in the objects, the 2009 patent is based on refining of a crude product obtained after preparation by a phosphate ester TCPP method, and the method is based on treatment of purified phosphate ester TCPP, so the objects are distinguished;
2) excess oxidant: in 2009, after a crude phosphate ester TCPP product is obtained, an oxidant solution which is excessive compared with aldehyde compounds, such as acidified potassium perchlorate aqueous solution, potassium chlorate aqueous solution, sodium hypochlorite aqueous solution or hydrogen peroxide, is added, and the aim of removing excessive aldehydes of reaction species is achieved. The color number of the product can not meet the requirement.
3) Alkali washing: in 2009, alkali washing, water washing and the like are carried out by adopting a conventional method. The invention carries out subsequent treatment by using a method of water washing and reduced pressure distillation.
Generally speaking, the inventor uses 3-5% ammonia water solution to replace liquid alkali for washing, during the washing process, the compound containing aldehyde in the crude product and ammonia water carry out addition reaction to produce the compound with imine structure, during the washing process, the crude product is 600ppm, 5000kg of the crude product contains about 3kg of aldehyde, the amount of the added ammonia water is 45kg, and the molar ratio of the aldehyde compound to the ammonia water is 1:85, so that the aldehyde compound is promoted to go towards the direction of generating the compound with imine structure, the compound with imine structure has no odor, thereby achieving the purposes of eliminating the aldehyde compound in the product, eliminating the odor of the product, reducing the aldehyde compound from 100-200ppm to 1-10ppm, having obvious reducing effect, and the product index is less than 10 ppm.
2. Prior document 201410269580.4 (publication No. CN104030887A, hereinafter referred to as 2014 patent) relates to a method for preparing 2-methyl-1-ethynyl-2-penten-1-ol, and it is mentioned in the background art that 2-methyl-2-pentenal is reacted with liquid ammonia, and compared with the document, the differences are as follows:
1) the reaction is different in alkali, liquid ammonia is NH and is colorless liquid, and the chemical formula of ammonia water NH & H0 is an aqueous solution of ammonia, is colorless and transparent and has pungent smell; liquid ammonia is gas at room temperature, liquid ammonia is used for reaction equivalent to gas-liquid, and the reaction is difficult to carry out, while liquid-liquid reaction carried out by ammonia water is easy to carry out.
2) Reaction conditions are as follows: the reaction with liquid ammonia needs to be carried out at minus 34 ℃ to minus 50 ℃ under harsh conditions, the reaction with ammonia water needs to be carried out at 25 ℃ to 40 ℃, and the reaction conditions are mild.
3. The ammonia water is used for washing to replace other alkali, the layered ammonia water solution can be recycled, the concentration can be adjusted according to the requirement and the product index after the layering can meet the requirement, the energy consumption is greatly reduced, the energy is saved, the environmental pollution is reduced, and the development trend of green environmental protection and green chemistry is compounded.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1: preparation method of low-odor phosphate ester TCPP
1. Adding 5000kg (content 99.1% of 2-methyl-2-pentenal 600ppm) of the produced phosphate TCPP crude product into 1500kg of 3% ammonia water solution (30% of the crude product), washing at 35-40 ℃ for 1 hour, layering, and respectively collecting an organic layer and an ammonia water layer, wherein the ammonia water layer is indiscriminately used;
2. adding 1000kg of water (20 percent of the crude product) into the organic layer, washing at the temperature of 75-80 ℃, layering, collecting the organic layer and the water layer respectively, wherein the water layer is used indiscriminately, distilling the organic layer under reduced pressure to remove water, controlling the distillation temperature at 110-115 ℃, and keeping the vacuum at-0.098 MPa until no water is evaporated, detecting that the water content is less than or equal to 0.1 percent, and obtaining 4965 kg of phosphate TCPP, the yield: 99.3%, purity: 99.6 percent.
Example 2: preparation method of low-odor phosphate ester TCPP
1. Adding 5000kg (content 99.1% of 2-methyl-2-pentenal 600ppm) of the produced phosphate TCPP crude product into 1500kg of recovered 3% ammonia water solution (30% of the crude product), washing at 35-40 ℃ for 1 hour, layering, and respectively collecting an organic layer and an ammonia water layer, wherein the ammonia water layer is reused;
2. and continuously adding 1000kg of recovered water (20 percent of the crude product) into the organic layer, washing at the temperature of 75-80 ℃, layering, collecting the organic layer and the water layer respectively, wherein the water layer is used indiscriminately, continuously distilling the organic layer under reduced pressure to remove water, controlling the distillation temperature to be 110-115 ℃, and keeping the vacuum at-0.098 MPa until no water is evaporated, and detecting that the water content is less than or equal to 0.1 percent to be qualified to obtain 4960kg of the yield: 99.2%, purity: 99.5 percent.
Example 3: preparation method of low-odor phosphate ester TCPP
The crude product was mixed with aqueous ammonia and water at a weight ratio of crude product to aqueous ammonia of 3.5:1 as in example 1. Yield: 99.1%, purity: 99.5 percent.
Example 4: preparation method of low-odor phosphate ester TCPP
As in example 1, the crude product was synthesized using titanium tetrachloride as a catalyst, and the phosphate ester TCPP crude product (2-methyl-2-pentenal having a content of 99.35% 700PPm, yield: 99%, purity: 99.5%.
Example 5: preparation method of low-odor phosphate ester TCPP
As in example 1, the crude synthesis used magnesium chloride as the catalyst crude (TCPP, content 99.1%, 2-methyl-2-pentenal 800ppm, synthesized with different catalysts: 98.9% yield: 99.4% purity).
Comparative example 1: preparation method of low-odor phosphate ester TCPP
5000kg (the content is 99.1 percent, wherein the content is 600PPm of 2-methyl-2-pentenal) of the produced crude phosphate TCPP is added with 1500kg of 2wt percent sodium hydroxide solution, the mixture is washed for 1 hour at the temperature of 35 to 40 ℃, layered, 1000kg of water is added, the mixture is washed at the temperature of 75 to 80 ℃, layered and water layers are applied, the organic layer is subjected to reduced pressure distillation for removing water, the highest distillation temperature is controlled at 110-115 ℃, the vacuum is kept at-0.098 MPa until no water is evaporated, and the water content is detected to be less than or equal to 0.1 percent and qualified. 4925kg, yield: 98.5%, purity: 99.4 percent.
After the sodium hydroxide solution is adopted for alkaline washing, the yield is slightly low, the purity is not much different from that of the invention, and mainly the sodium hydroxide can not reduce the 2-methyl-2-pentenal.
Comparative example 2
5000kg (the content is 99.1 percent, wherein the content is 600ppm of 2-methyl-2-pentenal) of the produced crude product of the phosphate TCPP, 50kg of liquid ammonia (1 percent of the crude product) is introduced, the reaction is carried out for 1 hour at the temperature of-35 to-40 ℃, the liquid ammonia is removed, 1000kg of recovered water is continuously added into an organic layer, the washing and the layering are carried out at the temperature of 75 to 80 ℃, an organic layer and a water layer are respectively collected, wherein the water layer is indiscriminately used, the organic layer is continuously subjected to reduced pressure distillation and water removal, the distillation temperature is controlled at 105 ℃ and 110 ℃, the vacuum is kept at-0.098 MPa until no water is distilled out, the qualified product with the water content less than or equal to: 98%, purity: 99.1 percent.
The ammonia water of the example 1 is replaced by the liquid ammonia, and the purity of the final product is the same as that of the original product.
Comparative example 3: (carried out in example 3 using 200910264987.7 (publication No. CN 101775031A))
Adding 600g of prepared phosphate TCPP crude product into a 1000ml four-neck flask provided with a thermometer and a stirrer (the specific method is that phosphorus oxychloride and an aluminum trichloride catalyst are added into a reaction device, then heating to 60-70 ℃, starting to drip propylene oxide, keeping the temperature unchanged, keeping the dripping time for 6-9 hours, continuing to keep the temperature at 80 ℃ for reacting for 1-2 hours after dripping to obtain the TCPP crude product), stirring and heating to 70 ℃, adding 290g of sodium chlorate solution which is acidified by sulfuric acid and has the concentration of 0.05 percent, stirring and reacting for 30 minutes at 70 ℃, carrying out alkali washing for 1 time after liquid separation, carrying out water washing for 2 times, removing a water layer, and carrying out vacuum pumping to remove water to obtain the finished product TCPP. 570g were obtained, yield: 95%, purity: 99.3 percent.
It should be noted that, in comparative example 3, the reaction is performed under laboratory conditions, the examples provided by the present invention are mass production, and compared with the above two, the laboratory conditions are easier to control, and after mass production, the conditions need to be adjusted.
Experimental example 1: index detection
1. The investigation method comprises the following steps:
1) the color number determination method comprises the following steps: GB-3143
2) The acid value measurement method comprises the following steps: GB-264-1983;
3) the detection method of aldehyde comprises the following steps: external standard method
Gas phase analysis method: sample introduction temperature: 170 ℃, detector: column temperature 180 ℃: raising the temperature to 280 ℃ at 70 ℃ and 15 ℃/min, and carrying out gas chromatographic column: SE-3025 × 0.2 × 0.25.
The impurity control requirement of TCPP-LO (short for low odor phosphate ester TCPP) is less than 10 ppm;
4) the purity detection method comprises the following steps:
gas phase analysis method: sample introduction temperature: 280 ℃, detector: column temperature at 280 ℃: raising the temperature to 280 ℃ at 70 ℃ and 15 ℃/min, and carrying out gas chromatographic column: SE 25 × 0.2 × 0.25.
Sample preparation: 1g of sample is weighed, dissolved and diluted to 10ml by trichloromethane, and 0.2ul of sample is injected.
5) And (3) detecting metal residues of the sample: mainly measures the residual metal, and the specific method comprises the following steps:
a: firstly, a hollow cathode lamp with the element is needed,
b: it is secondary to making a suitable standard working curve with a standard solution of the element:
before the measurement of the sample, a standard working curve is firstly made, and 10ppm, 20ppm, 50ppm and 100ppm can be prepared.
The standard solution was measured for absorbance against a blank/background of the solvent (0ppm) and a standard working curve of absorbance vs concentration was prepared.
C: detecting the concentration of the element in the sample: and calculating the metal content in the sample according to the standard curve.
2. The experimental results are as follows:
1) the results of the tests of the examples and comparative examples are shown in tables 1-1 and 1-2
Tables 1 to 1: the result of the detection
| The crude product used in the present invention | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Color number (platinum-cobalt) | 60 | 20 | 25 | 25 | 25 | 25 |
| Acid value (mgKOH/g) | 0.2 | 0.03 | 0.04 | 0.03 | 0.05 | 0.06 |
| 2-chloropropanol | 0.01 | Not detected out | Not detected out | Not detected out | Not detected out | Not detected out |
| Propylene oxide | 0.01 | Not detected out | Not detected out | Not detected out | Not detected out | Not detected out |
| 2-methyl-2-pentenal (ppm) | 600 | 4 | 6 | 7 | 5 | 8 |
| Residual amount of catalyst (ppm) | 1500 | 1 | 1 | 2 | 2 | 3 |
| Catalyst and process for preparing same | -- | Aluminium chloride | Aluminium chloride | Aluminium chloride | Titanium chloride | Magnesium chloride |
| Yield% | -- | 99.3 | 99.2 | 99.1 | 99 | 98.9. |
| Purity% | 99.1 | 99.6 | 99.5 | 99.5 | 99.5 | 99.4 |
Tables 1 to 2: the result of the detection
| The crude product used in the present invention | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Color number (platinum-cobalt) | 60 | 30 | 30 | 60 |
| Acid value (mgKOH/g) | 0.2 | 0.08 | 0.1 | 0.1 |
| 2-chloropropanol | 0.01 | Not detected out | Not detected out | Not detected out |
| Propylene oxide | 0.01 | Not detected out | Not detected out | Not detected out |
| 2-methyl-2-pentenal (ppm) | 600 | 500 | 580 | 20 |
| Residual amount of catalyst (ppm) | 1500 | 6 | 100 | 80 |
| Catalyst and process for preparing same | -- | Aluminium chloride | Aluminium chloride | Aluminium chloride |
| Yield% | -- | 98.5 | 98 | 95 |
| Purity% | 99.1 | 99.4 | 99.1 | 99.3 |
Note: the detection limit of the invention is 1ppm, and the undetected value is less than 1 ppm.
2) Mechanically applying:
the crude product of the same batch as in example 1 was continuously washed with aluminum trichloride as a catalyst, and the number of applications of ammonia was examined.
The concentration of the ammonia water is kept at 3% in the process of applying mechanically, and if the concentration of the ammonia water cannot reach the concentration, the high-concentration ammonia water is supplemented to be diluted to the specified concentration, so that the best washing effect is ensured. The water in the water washing process is used mechanically, and the water is recovered by a triple-effect membrane water distillation recovery device after the water is used mechanically, so that 50 kilograms of water is consumed for each ton of finished products, and half ton of water is consumed for each ton of finished products in the previous process, so that the process is greatly technically innovative compared with the previous process.
The results of the application are shown in tables 2-1 and 2-2
TABLE 2-1 application frequency detection results
| Crude product | Apply it for 1 time | Apply it for 2 times | Apply it 3 times | Apply it 4 times | Sleeve for use 5Next time | |
| Color number (platinum-cobalt) | 60 | 20 | 25 | 25 | 25 | 25 |
| Acid value (mgKOH/g) | 0.2 | 0.03 | 0.04 | 0.04 | 0.03 | 0.05 |
| 2-chloropropanol | 0.01 | Not detected out | Not detected out | Not detected out | Not detected out | Not detected out |
| Propylene oxide | 0.01 | Not detected out | Not detected out | Not detected out | Not detected out | Not detected out |
| 2-methyl-2-pentenal (ppm) | 600 | 4 | 5 | 6 | 7 | 5 |
| Residual amount of catalyst (ppm) | 1500 | 1 | 2 | 1 | 2 | 2 |
TABLE 2-2 application frequency detection results
| Crude product | Apply it for 6 times | Apply it for 7 times | Apply it for 8 times | Apply it for 9 times | Apply it 10 times | |
| Color number (platinum-cobalt) | 60 | 25 | 25 | 30 | 30 | 30 |
| Acid value (mgKOH/g) | 0.2 | 0.06 | 0.04 | 0.05 | 0.06 | 0.07 |
| 2-chloropropanol | 0.01 | Not detected out | Not detected out | Not detected out | Not detected out | Not detected out |
| Propylene oxide | 0.01 | Not detected out | Not detected out | Not detected out | Not detected out | Not detected out |
| 2-methyl-2-pentenal (ppm) | 600 | 8 | 7 | 6 | 8 | 8 |
| Residual amount of catalyst (ppm) | 1500 | 3 | 2 | 2 | 3 | 3 |
Tables 2-1, 2-2 the results show: alkali washing is not mentioned in the aftertreatment of a plurality of phosphoric ester TCPP crude products, the phosphoric ester TCPP crude products are used indiscriminately after being washed with water, and the applicant washes the phosphoric ester TCPP crude products by using alkali washing and water washing solutions, so that the cost of wastewater treatment is greatly saved, resources are greatly saved, the environment is protected, and great difference is realized between the phosphoric ester TCPP crude products and other patents through indiscriminate use.
The comparative example No. 3 is high in color number because sodium chlorate is very oxidative under acidic conditions so that the product appears pink with a trace amount of light to a sample irradiated by the light
In a word, compared with the prior art, the method provided by the invention can well remove aldehyde chemical combination, and meanwhile, the aqueous solution of ammonia water can be well recycled, so that the energy consumption is greatly reduced, the environmental pollution is reduced, and the development trend of green environmental protection and compound green chemistry is achieved.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of low-odor phosphate ester TCPP comprises the following steps:
1) treating the crude product of the phosphoric ester TCPP by using an aqueous alkali compound, layering after treatment, and respectively collecting a water layer and an organic layer containing the organic alkali compound, wherein the water layer containing the organic alkali compound is used indiscriminately;
2) washing the organic layer with water, layering, collecting the organic layer and the water layer, distilling under reduced pressure, and detecting that the water content is less than or equal to 0.1%.
2. The preparation method according to claim 1, wherein in the step 1), the content of the crude phosphate ester TCPP is 99.1%, and the content of 2-methyl-2-pentenal is not higher than 1000 ppm.
3. The process according to claim 1, wherein in step 1), the aqueous organic base compound is aqueous ammonia.
4. The method according to claim 3, wherein the concentration of the aqueous ammonia is 2 to 5%.
5. The method according to claim 3, wherein the amount of ammonia is 20-40% of the crude product.
6. The method according to claim 5, wherein the amount of ammonia is 25-35% of the crude product.
7. The method according to claim 1, wherein in the step 1), the treatment is washing at a temperature of 25 to 40 ℃ for 1 to 3 hours.
8. The method according to claim 1, wherein in the step 1), the treatment is washing at a temperature of 35 to 40 ℃ for 1 to 2 hours.
9. The method of claim 1, wherein in step 2), the weight of water is 10-30%, preferably 15-25% of the weight of the crude product.
10. The method as claimed in claim 1, wherein in the step 2), the vacuum degree is maintained at-0.09 MPa to-0.10 MPa and the distillation temperature is at 110 ℃ to 115 ℃.
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