CN112876341B - Preparation method of nonionic-anionic composite bisphenol A ether carboxylic acid - Google Patents
Preparation method of nonionic-anionic composite bisphenol A ether carboxylic acid Download PDFInfo
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- CN112876341B CN112876341B CN202110032886.8A CN202110032886A CN112876341B CN 112876341 B CN112876341 B CN 112876341B CN 202110032886 A CN202110032886 A CN 202110032886A CN 112876341 B CN112876341 B CN 112876341B
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- carboxylic acid
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- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 112
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 79
- -1 bisphenol A ether carboxylic acid Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims description 25
- 238000000926 separation method Methods 0.000 claims abstract description 103
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000945 filler Substances 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 10
- 238000007670 refining Methods 0.000 claims abstract description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 239000003463 adsorbent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005192 partition Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000012856 packing Methods 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 8
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 8
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 3
- 229940106681 chloroacetic acid Drugs 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 abstract description 13
- 239000004094 surface-active agent Substances 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000000746 purification Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 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 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 241001247821 Ziziphus Species 0.000 description 4
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 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
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The invention provides a preparation method of nonionic-anionic compound bisphenol A ether carboxylic acid, belonging to the field of surfactants. The preparation method comprises the following steps: synthesizing non-ionic-anionic compound bisphenol A ether carboxylic acid by a carboxymethyl method, and then introducing the bisphenol A ether carboxylic acid into a tubular separation device filled with separation filler for refining to obtain bisphenol A ether carboxylic acid; the separation filler is composed of 100-300 meshes of zirconium oxide and silicon oxide. The nonionic-anionic compound bisphenol A ether carboxylic acid prepared by the method has low salt residue.
Description
Technical Field
The invention relates to a preparation method of nonionic-anionic compound bisphenol A ether carboxylic acid, belonging to the field of surfactants.
Background
A surfactant refers to a compound that contains at least one group having affinity for a significantly polar surface and one non-polar group having little affinity for water in its molecular structure. After different surfactants are dissolved in water for ionization, the generated hydrophilic ions or hydrophilic functional groups are different, so that the surfactant has different characteristics and is applied to different fields.
If one surfactant contains a group with temperature resistance and salt resistance on the molecular structure, the aims of temperature resistance and salt resistance can be fulfilled. The surfactant is completely different from conventional nonionic and anionic surfactants, has high surface activity, good thermal stability and salt resistance, and has the characteristics of good compatibility, good biodegradability and the like.
At present, the production of alcohol ether carboxylate mainly adopts a carboxymethyl method. The carboxymethyl method raw materials are nontoxic and easy to obtain, the preparation process is simple and feasible, the production cost is lower, and the like, and the carboxymethyl method is a main method for industrial production at home and abroad at present, namely fatty alcohol-polyoxyethylene ether, fatty alcohol-polyoxypropylene-polyoxyethylene ether and other isomeric alcohol ethers are adopted as raw materials, chloroacetic acid (and other alkyl carboxylic acids) and salts thereof are adopted as carboxylation reagents, and carboxymethylation reaction is carried out on alcohol ether under certain temperature and alkaline conditions, but the conventional post-treatment method is adopted, so that the salt residue in the obtained alcohol ether carboxylic acid is higher, the problem of byproduct residue which has adverse effect on human bodies is difficult to fundamentally solve, and the application field of products is restricted.
Disclosure of Invention
The invention aims to provide a preparation method of nonionic-anionic compound bisphenol A ether carboxylic acid, and the product obtained by the method has low salt residue.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of nonionic-anionic composite bisphenol A ether carboxylic acid is disclosed, wherein the chemical molecular formula of the nonionic-anionic composite bisphenol A ether carboxylic acid is as follows:
in the formula: n is the addition number of ethylene oxide EO, and is any integer from 2 to 20; m is H; the preparation method comprises the following steps: synthesizing non-ionic-anionic compound bisphenol A ether carboxylic acid by a carboxymethyl method, and then introducing the bisphenol A ether carboxylic acid into a tubular separation device filled with separation filler for refining to obtain bisphenol A ether carboxylic acid; the separation filler is composed of 100-300 meshes of zirconium oxide and silicon oxide.
In the invention, the synthesis of the nonionic-anionic compound bisphenol A ether carboxylic acid by adopting a carboxymethyl method comprises the following steps:
(1) Mixing bisphenol A and a catalyst, heating, introducing ethylene oxide, and reacting at 105-115 ℃ to obtain bisphenol A polyoxyethylene ether;
(2) Mixing the bisphenol A polyoxyethylene ether obtained in the step (1) with an alkaline compound, adding chloroacetic acid or sodium chloroacetate, and reacting at 95-105 ℃ for 4-7 hours to obtain bisphenol A polyoxyethylene ether carboxylate;
(3) Acidifying the bisphenol A polyoxyethylene ether carboxylate obtained in the step (2) with an acid compound, heating to 100-140 ℃, vacuumizing, and finally filtering to obtain filtrate to obtain crude bisphenol A ether carboxylic acid;
in the invention, the separation filler is prepared by adopting the following method: uniformly mixing zirconium oxide, silicon oxide, water and acid, treating at 40-50 ℃ for 28-38 hours, drying at 110-130 ℃, roasting at 400-800 ℃ for 1-2 hours in air atmosphere, and finally screening to obtain the 100-300-mesh separation filler.
In the preferable technical scheme, the mass ratio of the zirconia to the silica is 75-85-15, the addition amount of the acid is 3-5% of the total mass of the zirconia and the silica, the addition amount of the water is 30-50%, and the acid is one or a mixture of more than two of sulfuric acid, hydrochloric acid, acetic acid and citric acid.
In a preferred technical scheme, the tubular separation device comprises a Z-shaped pipe, the Z-shaped pipe consists of two vertical end parts and a horizontal pipe connected with the two vertical end parts, the two vertical end parts are respectively a first separation pipe and a third separation pipe, the horizontal pipe is a second separation pipe, a first partition plate 1 and a second partition plate 3 with holes are vertically arranged in the first separation pipe, and a filler is arranged between the first partition plate and the second partition plate; a third clapboard and a fourth clapboard with holes are vertically arranged in the second separation pipe, and a filler is arranged between the third clapboard and the fourth clapboard; the second separation pipe is provided with an upper discharge hole, and the end part of the third separation pipe is provided with a lower discharge hole; the upper discharge hole is positioned above the lower discharge hole.
In the invention, the outer side of the Z-shaped pipe is provided with a jacket for introducing steam or cooling water to heat or cool the Z-shaped pipe.
In the present invention, the tubular separation apparatus is set at 70 to 100 ℃ during the refining.
In the invention, nonionic-anionic compound bisphenol A ether carboxylic acid synthesized by a carboxymethyl method is introduced into a tubular separation device filled with separation filler for refining to obtain primarily purified crude ether; heating the primarily purified crude ether to 70-85 ℃, adding sodium dihydrogen phosphate and distilled water, uniformly stirring, adding a composite adsorbent, stirring, vacuumizing for dehydration, filtering, and taking a filtrate to obtain nonionic-anionic composite bisphenol A ether carboxylic acid; the using amount of the sodium dihydrogen phosphate is 1-5 per mill of the primarily purified crude ether, the using amount of the distilled water is 2% -5% of the primarily purified crude ether, and the using amount of the composite adsorbent is 1-5 per mill of the primarily purified crude ether.
In the present invention, the composite adsorbent is a mixture of a polyether purification adsorbent and clay.
The nonionic-anionic compound bisphenol A ether carboxylic acid prepared by the method avoids the problems of catalyst residue and recycling in a catalyst method. The operation cost is low, the salt residue is low, the process is safe and reliable, the resource utilization is high, the energy consumption is low, and the method is a clean production process which meets the development requirements of green chemical industry.
The nonionic-anionic compound bisphenol A ether carboxylic acid prepared by the method disclosed by the invention is added with a carboxylic acid functional group in a polyoxyethylene group, so that the salt resistance of the surfactant is further improved, the used concentration is obviously reduced, and the phenomena of liquid crystal and gelation can be effectively avoided. The surfactant is completely different from conventional nonionic and anionic surfactants, has high surface activity, good thermal stability and salt resistance, and has the characteristics of good compatibility, good biodegradability and the like. By adopting the preparation method, the product has high purity and low salt residue content because the better separation filler is selected.
Drawings
FIG. 1 is a schematic diagram of an apparatus for purification.
Detailed Description
Example 1 preparation of separation Filler
1. Preparation of separation Filler 1
Weighing 750g of zirconia and 250g of silica, adding 500g of water and 50g of acetic acid, uniformly stirring, treating at 40 ℃ for 36h, drying at 120 ℃, roasting at 500 ℃ for 2h in an air atmosphere, and finally screening to obtain a separation filler with 100-200 meshes, wherein the separation filler is marked as separation filler 1.
2. Preparation of separation Filler 2
850g of zirconia and 150g of silica are weighed, 300g of water and 30g of acetic acid are added, the mixture is uniformly stirred, the mixture is placed at 50 ℃ for treatment for 30 hours, then the mixture is dried at 130 ℃, then the mixture is roasted for 1 hour at 520 ℃ in air atmosphere, and finally the separation filler with 200-300 meshes is obtained by screening, and is marked as separation filler 2.
3. Preparation of control separation Filler 1
Weighing 1000g of zirconia, adding 300g of water and 50g of acetic acid, uniformly stirring, heating and soaking at 40 ℃ for 36h, drying at 120 ℃, roasting at 500 ℃ for 2h in an air atmosphere, and finally screening to obtain 100-200-mesh separation filler, which is marked as reference separation filler 1.
4. Preparation of control separation Filler 2
Weighing 750g of zirconia and 250g of alumina, adding 300g of water and 50g of acetic acid, uniformly stirring, heating and soaking at 40 ℃ for 36h, drying at 120 ℃, roasting at 500 ℃ in an air atmosphere for 2h, and finally screening to obtain 100-200-mesh separation filler, which is recorded as control separation filler 2.
EXAMPLE 2 tubular separation device
The tubular separation device (fig. 1) comprises a Z-shaped tube and a jacket arranged outside the Z-shaped tube. The Z-shaped pipe consists of two vertical end parts and a horizontal pipe connecting the two vertical end parts, the two vertical end parts are respectively a first separation pipe 2 and a third separation pipe 6, the horizontal pipe is a second separation pipe 4, a first partition board 1 and a second partition board 3 with holes are vertically arranged in the first separation pipe, and a filler is arranged between the first partition board and the second partition board; a third clapboard 5 and a fourth clapboard 7 with holes are vertically arranged in the second separation pipe, and a filler is arranged between the third clapboard and the fourth clapboard; the second separator tube is provided with an upper discharge hole, and the end part of the third separator tube is a lower discharge hole. The upper discharge hole is positioned above the lower discharge hole. The jacket is arranged on the outer side of the Z-shaped pipe and used for introducing steam or cooling water to heat or cool the Z-shaped pipe, and the jacket is provided with a thermometer and a pressure gauge.
Example 3
1. Preparation of bisphenol A Ether Carboxylic acid BPA-5H
Weighing 228g (1 mol) of bisphenol A and 0.5g of sodium methoxide, adding the mixture into a reaction kettle, replacing with nitrogen, heating to 105 ℃, keeping the temperature at 105 ℃, introducing 220g of ethylene oxide (the pressure is controlled to be 0.2MPa in the process of introducing the ethylene oxide) until the ethylene oxide completely reacts (the pressure in the reaction kettle is reduced to 0 or negative pressure), and obtaining bisphenol A polyoxyethylene ether BPA-5. Adding 448g of bisphenol A polyoxyethylene ether BPA-5 into a 2000ml four-neck flask provided with a stirrer and a thermometer, heating to 50 ℃, adding 44g of sodium hydroxide, vacuumizing for 1 hour by blowing nitrogen, slowly adding 122g of sodium chloroacetate, stirring for 0.5 hour, heating to 100 ℃, and reacting for 5 hours at 100 ℃ to obtain bisphenol A polyoxyethylene ether carboxylate BPA-5Na. And cooling to 45 ℃, slowly adding 66g of acetic acid, neutralizing for 1H, heating to 110 ℃, vacuumizing for 2H, filtering, and taking filtrate to obtain crude bisphenol A ether carboxylic acid BPA-5H. The conversion of bisphenol a ethercarboxylic acid was determined to be 95.1%. Wherein the structural formula of bisphenol A ether carboxylic acid BPA-5H is as follows:
n =5,M is H.
2. Purification of crude bisphenol A Ether Carboxylic acid BPA-5H
(1) Refining with separating Filler 1
In the tubular separation apparatus (example 2), 0.5kg of separation packing 1 was charged between the two separators of the first separation tube and 1kg of separation packing was charged between the two separators of the second separation tube. 20kg of crude bisphenol A ethercarboxylic acid BPA-5H was charged into a high-pressure reactor, and 1kg of water was added thereto, followed by stirring at room temperature. After the nitrogen substitution, the temperature was raised to 115 ℃ under nitrogen protection, and the mixture was stirred for 1 hour. Meanwhile, an upper discharge port of the tubular separation device is opened, a lower discharge port of the tubular separation device is closed, steam is introduced into the jacket for heating, when the temperature of the tubular separation device is 90 ℃, stirring is stopped in the high-pressure reaction kettle, the high-pressure reaction kettle is connected with a first separation pipe of the tubular separation device through a hose, materials in the high-pressure reaction kettle are pressed into a Z-shaped pipe of the tubular separation device through nitrogen, and the materials are kept stand after being adsorbed by the separation filler 1, so that ether water is layered, and ether water is separated. And in the separation process, the temperature of the tubular separation device is kept at 90 ℃, when the product flows out from the upper discharge hole, the lower discharge hole is opened to discharge the water phase, and the material at the upper discharge hole is collected to obtain the primarily purified crude ether. Putting 1kg of the primarily purified crude ether separated from the upper discharge port into a 2000ml three-necked flask with a thermometer and a stirrer, adding 2g of sodium dihydrogen phosphate and 25g of distilled water at the temperature of 80 ℃, stirring for 1 hour, adding 2g of a composite adsorbent, stirring for 1 hour, vacuumizing and dehydrating at the temperature of 130 ℃ until the water content (percentage content of water in the substance) is less than or equal to 0.08%, filtering, taking the filtrate to obtain bisphenol A ether carboxylic acid BPA-5H, and analyzing the quality index. The composite adsorbent is a mixture of polyether refined adsorbent of Yonghua silicon magnesium materials Limited company in the market of jujube Yang and argil (Oreoclay mining Limited company in Asia east of Nanjing) according to the mass ratio of 1:1.
(2) The crude bisphenol A ethercarboxylic acid BPA-5H was purified by the method (1) in title 2 of this example, except that 0.5kg of separation filler 2 was charged in each of the first and second separation tubes of the tubular separation apparatus, and the total amount was 1kg.
(3) Comparative purification method 1: the crude bisphenol A ether carboxylic acid BPA-5H was purified by the method (1) in the title 2 of this example, except that 0.5kg of the control separation packing 1 was charged in each of the first and second separation tubes of the tubular separation apparatus, and that 1kg of the control separation packing was charged in total.
(4) Comparative purification method 2: the crude bisphenol A ether carboxylic acid BPA-5H was purified by the method (1) in the title 2 of this example, except that 0.5kg of the control separation packing 2 was charged in the first and second separation tubes of the tubular separation apparatus, respectively, and that 1kg of the control separation packing was charged in total.
(5) Comparative purification method 3: putting 1kg of crude bisphenol A ether carboxylic acid BPA-5H into a 2000ml three-necked flask with a thermometer and a stirrer, adding 2g of sodium dihydrogen phosphate and 25g of distilled water at the temperature of 80 ℃, stirring for 1 hour, adding 2g of a composite adsorbent, stirring for 1 hour, vacuumizing and dehydrating at the temperature of 130 ℃ until the water content (percentage content of water in the substance) is less than or equal to 0.08%, filtering, taking filtrate to obtain bisphenol A ether carboxylic acid BPA-5H, and analyzing the quality index of the bisphenol A ether carboxylic acid BPA-5H. The composite adsorbent is a mixture of polyether refined adsorbent of Yonghua silicon magnesium materials Limited company in the market of jujube Yang and argil (Oreoclay mining Limited company in Asia east of Nanjing) according to the mass ratio of 1:1.
The appearance of bisphenol A ethercarboxylic acid obtained by purification according to the method of title 2 of this example was observed to detect the potassium and sodium content in crude bisphenol A ethercarboxylic acid BPA-5H before purification and the potassium and sodium content in bisphenol A ethercarboxylic acid BPA-5H after treatment according to the purification method. Specific results are shown in table 1.
TABLE 1
Example 4
1. Preparation of bisphenol A Ether Carboxylic acid BPA-10H
Weighing 228g (1 mol) of bisphenol A and 0.7g of sodium methoxide, adding into a reaction kettle, replacing with nitrogen, heating to 110 ℃, keeping the temperature at 110 ℃, and introducing 440g of ethylene oxide (the pressure is controlled to be 0.4MPa in the process of introducing the ethylene oxide) until the ethylene oxide completely reacts to obtain bisphenol A polyoxyethylene ether BPA-10. 668g of bisphenol A polyoxyethylene ether BPA-10 is added into a 2000ml four-neck flask provided with a stirrer and a thermometer, the temperature is raised to 70 ℃, 44g of sodium hydroxide is gradually added, nitrogen is blown for 2 hours in vacuum, 122g of sodium chloroacetate is slowly added, the stirring is carried out for 1 hour, the temperature is raised to 105 ℃, and the reaction is carried out for 7 hours at 105 ℃, so as to obtain bisphenol A polyoxyethylene ether carboxylate BPA-10Na. Cooling to 50 ℃, slowly adding 66g of acetic acid, neutralizing for 1H, heating to 115 ℃, vacuumizing for 2H, filtering, and taking filtrate to obtain crude bisphenol A ether carboxylic acid BPA-10H. Wherein the structural formula of bisphenol A ether carboxylic acid BPA-10H is as follows:
n =10, m is H.
2. Purification of crude bisphenol A Ether Carboxylic acid BPA-10H:
(1) Refining with separating Filler 1
1kg of separation packing 1, 2kg in total, was placed between the two baffles of the first separation tube and between the two baffles of the second separation tube of the tubular separation apparatus, respectively. 20kg of crude bisphenol A ethercarboxylic acid BPA-10H was added to a high-pressure reactor, and 1kg of water was added thereto and stirred at room temperature. After the nitrogen substitution, the temperature was raised to 125 ℃ under nitrogen protection, and the mixture was stirred for 1 hour. Meanwhile, an upper discharge port of the tubular separation device is opened, a lower discharge port of the tubular separation device is closed, steam is introduced into the jacket for heating, when the temperature of the tubular separation device is 80 ℃, stirring is stopped in the high-pressure reaction kettle, the high-pressure reaction kettle is connected with a first separation pipe of the tubular separation device through a hose, materials in the high-pressure reaction kettle are pressed into a Z-shaped pipe of the tubular separation device through nitrogen, the materials are kept stand after being adsorbed by the separation filler 1, ether water is layered, when a product flows out from the upper discharge port, the lower discharge port is opened to discharge a water phase, and the materials at the upper discharge port are collected, so that the primarily purified crude ether is obtained. Putting 1kg of the primarily purified crude ether into a 2000ml three-necked flask with a thermometer and a stirrer, adding 3g of sodium dihydrogen phosphate and 30g of distilled water at 70 ℃, stirring for 1.5 hours, adding 2.5g of a composite adsorbent, stirring for one hour, vacuumizing and dehydrating at 110 ℃ until the water content is less than or equal to 0.08%, filtering, taking the filtrate to obtain bisphenol A ether carboxylic acid BPA-10H, and analyzing the quality index. The composite adsorbent is a mixture of polyether refined adsorbent of Yonghua silicon magnesium materials Limited company in the market of jujube Yang and argil (south Jing Asia Toyobo Ore mining Limited company) according to the mass ratio of 1.
(2) The crude bisphenol A ether carboxylic acid BPA-10H was purified by the method (1) in the title 2 of this example, except that 1kg of separation filler 2 was contained in each of the first and second separation tubes of the tubular separation apparatus, i.e., 2kg in total.
(3) Comparative purification method 1: the crude bisphenol A ether carboxylic acid BPA-10H was purified by the method (1) in the title 2 of this example, except that 1kg of the control separation packing 1 was contained in each of the first and second separation tubes of the tubular separation apparatus, i.e., 2kg in total.
(4) Comparative purification method 2: the crude bisphenol A ether carboxylic acid BPA-10H was purified according to the method (1) in the title 2 of this example, except that the first and second separation tubes of the tubular separation apparatus were filled with 2kg of the control separation packing 2 in total.
(5) Comparative purification method 3: putting 1kg of crude bisphenol A ether carboxylic acid BPA-10H into a 2000ml three-necked flask with a thermometer and a stirrer, adding 3g of sodium dihydrogen phosphate and 30g of distilled water at the temperature of 70 ℃, stirring for 1.5 hours, adding 2g of a composite adsorbent, stirring for 1 hour, vacuumizing and dehydrating at the temperature of 110 ℃ until the water content (percentage content of water in the substance) is less than or equal to 0.08%, filtering, taking the filtrate to obtain the bisphenol A ether carboxylic acid BPA-10H, and analyzing the quality index of the bisphenol A ether carboxylic acid BPA-10H. The composite adsorbent is a mixture of a polyether refined adsorbent of Yonghua silicon magnesium materials Limited company in the city of jujube Yang and argil (Aotu mineral industry Limited company in the east of Nanjing) according to the mass ratio of 1.
The appearance of bisphenol A ether carboxylic acid BPA-10H obtained by purification according to the method of title 2 of this example was observed to detect the potassium and sodium content in crude bisphenol A ether carboxylic acid BPA-10H before purification and the potassium and sodium content in bisphenol A ether carboxylic acid BPA-10H after treatment according to the purification method. Specific results are shown in Table 2.
TABLE 2
From the above examples 3-4, it can be seen that the nonionic-anionic composite bisphenol a ether carboxylic acid refined by the separation fillers 1 and 2 has a significantly reduced potassium and sodium ion content, and when used in the fields of skin care products and the like, the damage to the skin can be significantly reduced, and the problems of catalyst residue and recycling in the catalyst method can be avoided. The refining method has the advantages of low operation cost, low salt residue, safe and reliable process and high resource utilization, and is a clean production process which meets the development requirements of green chemical industry. The prepared bisphenol A alcohol ether carboxylic acid has a nonionic-anionic group at the same time, the surfactant is completely different from conventional nonionic and anionic surfactants, and the bisphenol A alcohol ether carboxylic acid has the characteristics of high surface activity, good thermal stability and salt resistance, good compatibility, good biodegradability and the like.
Claims (7)
1. A preparation method of nonionic-anionic composite bisphenol A ether carboxylic acid is characterized in that the chemical molecular formula of the nonionic-anionic composite bisphenol A ether carboxylic acid is as follows:
in the formula: n is any integer from 2 to 20; m is H; the preparation method comprises the following steps: synthesizing non-ionic-anionic composite bisphenol A ethercarboxylic acid by a carboxymethyl method, and then introducing the bisphenol A ethercarboxylic acid into a tubular separation device filled with separation filler for refining to obtain bisphenol A ethercarboxylic acid; the separation filler consists of 100-300 meshes of zirconium oxide and silicon oxide; the separation filler is prepared by adopting the following method: mixing zirconium oxide, silicon oxide, water and acid uniformly, treating at 40-50 deg.C for 28-38 hr, drying at 110-130 deg.C, 400-800 deg.C o C, roasting for 1-2h in the air atmosphere, and finally screening to obtain 100-300-mesh separation filler; the mass ratio of the zirconia to the silica is 75-85-15, the addition amount of acid is 3-5% of the total mass of the zirconia and the silica, the addition amount of water is 30-50%, and the acid is one or a mixture of more than two of sulfuric acid, hydrochloric acid, acetic acid and citric acid.
2. The preparation method according to claim 1, wherein the synthesis of the nonionic-anionic composite bisphenol A ethercarboxylic acid by the carboxymethyl method comprises the following steps:
(1) Mixing bisphenol A and a catalyst, heating, introducing ethylene oxide, and reacting at 105-115 ℃ to obtain bisphenol A polyoxyethylene ether;
(2) Mixing the bisphenol A polyoxyethylene ether obtained in the step (1) with an alkaline compound, adding chloroacetic acid or sodium chloroacetate, and reacting at 95-105 ℃ for 4-7 hours to obtain bisphenol A polyoxyethylene ether carboxylate;
(3) Acidifying the bisphenol A polyoxyethylene ether carboxylate obtained in the step (2) with an acid compound, heating to 100-140 ℃, vacuumizing, and finally filtering to obtain filtrate to obtain crude bisphenol A ether carboxylic acid;
3. the production method according to claim 2, wherein the tubular separation apparatus comprises a Z-shaped pipe consisting of two vertical ends and a horizontal pipe connecting the two vertical ends, the two vertical ends being a first separation pipe and a third separation pipe, respectively, the horizontal pipe being a second separation pipe, the first separation pipe having a first partition plate 1 and a second partition plate 3 vertically provided therein with holes, and a packing material being provided between the first partition plate and the second partition plate; a third clapboard and a fourth clapboard with holes are vertically arranged in the second separation pipe, and a filler is arranged between the third clapboard and the fourth clapboard; the second separation pipe is provided with an upper discharge hole, and the end part of the third separation pipe is a lower discharge hole; the upper discharge hole is positioned above the lower discharge hole.
4. The production method according to claim 3, wherein the Z-shaped tubes are externally provided with a jacket for introducing steam or cooling water to heat or cool the Z-shaped tubes.
5. The production method according to claim 4, wherein the tubular separation apparatus is 70 to 100 in refining o C。
6. The method according to claim 5, wherein: introducing nonionic-anionic compound bisphenol A ether carboxylic acid synthesized by a carboxymethyl method into a tubular separation device filled with separation filler for refining to obtain primarily purified crude ether; heating the primarily purified crude ether to 70-85 deg.C o C, adding sodium dihydrogen phosphate and distilled water, uniformly stirring, adding the composite adsorbent, stirring, vacuumizing for dehydration, filtering, and taking a filtrate to obtain nonionic-anionic composite bisphenol A ethercarboxylic acid; the using amount of the sodium dihydrogen phosphate is 1-5 per mill of the primarily purified crude ether, the using amount of the distilled water is 2% -5% of the primarily purified crude ether, and the using amount of the composite adsorbent is 1-5 per mill of the primarily purified crude ether.
7. The method of claim 6, wherein the composite adsorbent is a mixture of polyether refined adsorbent and clay.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772698A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Alkyl phenol ether carboxylate and preparation method thereof |
| CN106146822A (en) * | 2016-07-22 | 2016-11-23 | 大庆华营化工有限公司 | A kind of preparation method of crude oil thinner |
| CN107141465A (en) * | 2017-06-05 | 2017-09-08 | 浙江皇马科技股份有限公司 | A kind of styrylphenol polyoxyethylene ether and preparation method thereof |
| CN109265323A (en) * | 2018-08-23 | 2019-01-25 | 浙江三江化工新材料有限公司 | A kind of preparation method of Narrow Molecular Weight Distribution bisphenol A polyethenoxy ether |
| CN110669213A (en) * | 2019-10-22 | 2020-01-10 | 武汉奥克特种化学有限公司 | Preparation method of bisphenol A polyether |
| CN111117587A (en) * | 2019-12-17 | 2020-05-08 | 德仕能源科技集团股份有限公司 | Salt-resistant high-calcium-magnesium-resistant anionic-nonionic surfactant |
| CN111348989A (en) * | 2020-04-24 | 2020-06-30 | 浙江皇马科技股份有限公司 | Bis-hydroxyethyl bisphenol A ether and preparation method thereof |
| CN111499501A (en) * | 2020-04-24 | 2020-08-07 | 浙江皇马科技股份有限公司 | Bisphenol A bis (2, 3-dihydroxypropyl) ether and preparation method thereof |
-
2021
- 2021-01-11 CN CN202110032886.8A patent/CN112876341B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772698A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Alkyl phenol ether carboxylate and preparation method thereof |
| CN106146822A (en) * | 2016-07-22 | 2016-11-23 | 大庆华营化工有限公司 | A kind of preparation method of crude oil thinner |
| CN107141465A (en) * | 2017-06-05 | 2017-09-08 | 浙江皇马科技股份有限公司 | A kind of styrylphenol polyoxyethylene ether and preparation method thereof |
| CN109265323A (en) * | 2018-08-23 | 2019-01-25 | 浙江三江化工新材料有限公司 | A kind of preparation method of Narrow Molecular Weight Distribution bisphenol A polyethenoxy ether |
| CN110669213A (en) * | 2019-10-22 | 2020-01-10 | 武汉奥克特种化学有限公司 | Preparation method of bisphenol A polyether |
| CN111117587A (en) * | 2019-12-17 | 2020-05-08 | 德仕能源科技集团股份有限公司 | Salt-resistant high-calcium-magnesium-resistant anionic-nonionic surfactant |
| CN111348989A (en) * | 2020-04-24 | 2020-06-30 | 浙江皇马科技股份有限公司 | Bis-hydroxyethyl bisphenol A ether and preparation method thereof |
| CN111499501A (en) * | 2020-04-24 | 2020-08-07 | 浙江皇马科技股份有限公司 | Bisphenol A bis (2, 3-dihydroxypropyl) ether and preparation method thereof |
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