CN110981906B - Synthetic method of isomeric dodecyl alcohol polyoxyethylene ether phosphate ester - Google Patents
Synthetic method of isomeric dodecyl alcohol polyoxyethylene ether phosphate ester Download PDFInfo
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- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229920000056 polyoxyethylene ether Polymers 0.000 title claims abstract description 46
- 229940051841 polyoxyethylene ether Drugs 0.000 title claims abstract description 46
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 35
- 239000010452 phosphate Substances 0.000 title claims abstract description 35
- -1 phosphate ester Chemical class 0.000 title claims abstract description 20
- 238000010189 synthetic method Methods 0.000 title claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 26
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 230000032050 esterification Effects 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 3
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 230000006698 induction Effects 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002736 nonionic surfactant Substances 0.000 abstract description 3
- 229920000570 polyether Polymers 0.000 description 22
- 239000004721 Polyphenylene oxide Substances 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 18
- 238000001816 cooling Methods 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 10
- 229940087291 tridecyl alcohol Drugs 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- LZLOFGMGFADIKQ-UHFFFAOYSA-N benzene;1,4-dioxane Chemical compound C1COCCO1.C1=CC=CC=C1 LZLOFGMGFADIKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
- C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Wood Science & Technology (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a method for synthesizing isomeric dodecyl alcohol polyoxyethylene ether phosphate ester. Belongs to the technical field of synthesis of anionization of nonionic surfactants in organic chemistry. The invention relates to a method for synthesizing isomeric dodecyl alcohol polyoxyethylene ether phosphate ester, which comprises the following steps: (1) n-hexanol is taken as an initiator, and a catalyst is added under the protection of nitrogen to carry out aldol condensation reaction per se, so as to prepare isomeric dodecanol; (2) under the action of a catalyst, firstly carrying out induction reaction on the isomeric dodecanol prepared in the step (1) and part of ethylene oxide, and then carrying out polymerization reaction on the rest of ethylene oxide to obtain isomeric dodecanol polyoxyethylene ether; (3) adding isomeric dodecyl alcohol polyoxyethylene ether and phosphorus pentoxide to carry out esterification reaction, and adding deionized water into the product obtained by esterification to carry out hydrolysis, thereby finally obtaining isomeric dodecyl alcohol polyoxyethylene ether phosphate.
Description
Technical Field
The invention relates to a method for synthesizing isomeric dodecyl alcohol polyoxyethylene ether phosphate ester. Belongs to the technical field of synthesis of anionization of nonionic surfactants in organic chemistry.
Background
The alkylphenol polyoxyethylene has stable property, good acid and alkali resistance, lower cost and good emulsification, wetting, dispersion and other functions, and is an important nonionic surfactant. However, phenolic polyethers are toxic to organisms, possibly carcinogenic during synthesis, and not easy to be degraded biologically, and are not in accordance with the era trend of green chemistry, and new substitutes are urgently needed to be developed.
The isomeric tridecanol polyoxyethylene ether is a green biodegradable surfactant, and is the best substitute for an anylphenol surfactant in the field of industrial cleaning.
CN 101225161B discloses a synthesis method for preparing isotridecanol polyoxyethylene ether by taking boron trifluoride as a catalyst, the product has good service performance and narrow molecular weight distribution, but the boron trifluoride is toxic and corrosive and does not belong to a green catalyst.
CN 104974339B discloses a synthesis method for preparing isotridecanol polyoxyethylene ether by dissolving an alkaline catalyst in a dispersant for activation, the product has light color, narrow cloud point variation range and narrow molecular weight distribution, and is particularly suitable for industrial cleaning industry, but the permeability, the emulsifying property and the like of the product are obviously reduced under the high-concentration alkaline condition.
Phosphate ester surfactants are surfactants containing phosphate ester groups or phosphate ester salts in a molecule. The phosphate ester surfactant has the characteristics of good emulsibility, corrosion resistance, rust resistance, solubility enhancement, antistatic property, acid and alkali resistance and the like. The research report of isomeric tridecanol polyoxyethylene ether phosphate ester is about, and the synthesis process is explored. However, the raw material isomeric tridecanol is used as a petrochemical product, is mainly imported at home at present, and is expensive.
Under the conditions that the raw materials of the prior surfactant are in shortage, the price is increased and the environmental protection requirement tends to be strict. The invention adopts n-hexanol as the starting material to synthesize isomeric dodecyl polyoxyethylene ether, can reduce the dependence on isomeric tridecanol of petrochemical products, and has the advantages of easily obtained raw materials, low price and green and environment-friendly synthesis process.
Disclosure of Invention
The invention aims to provide a synthesis method of isomeric dodecyl alcohol polyoxyethylene ether phosphate ester, which has the advantages of reasonable process, environmental protection, low cost and excellent service performance, and the specific method is as follows:
a synthetic method of isomeric dodecyl alcohol polyoxyethylene ether phosphate ester comprises the following steps:
(1) n-hexanol is taken as an initiator, and a catalyst is added under the protection of nitrogen to carry out aldol condensation reaction per se, so as to prepare isomeric dodecanol;
(2) under the action of a catalyst, firstly carrying out induction reaction on the isomeric dodecanol prepared in the step (1) and part of ethylene oxide, and then carrying out polymerization reaction on the rest of ethylene oxide to obtain isomeric dodecanol polyoxyethylene ether;
(3) adding isomeric dodecyl alcohol polyoxyethylene ether and phosphorus pentoxide to carry out esterification reaction, and adding deionized water into the product obtained by esterification to carry out hydrolysis, thereby finally obtaining isomeric dodecyl alcohol polyoxyethylene ether phosphate.
The catalyst in the step (1) is a catalyst mixed by sodium hydroxide and zinc oxide.
The mass of the added sodium hydroxide is 5% of that of the n-hexanol, and the mass ratio of the zinc oxide to the sodium hydroxide is 1: 9;
the reaction temperature of the step (1) is 210-230 ℃, and the reaction time is more than two hours.
And (3) adding ethylene oxide in the step (2) in a dropwise manner.
The total molar ratio of the isomeric dodecanol and the ethylene oxide in the step (2) is 1: 2-10.
The induced reaction in the step (2) has the mol ratio of isomeric dodecanol to ethylene oxide of 1:1 and the reaction temperature of 130 ℃.
The polymerization temperature in the step (2) is 130 ℃.
The catalyst is KOH, and the mass of the catalyst added is 0.1-0.15% of the sum of the mass of the isomeric dodecyl alcohol and the mass of the ethylene oxide.
In the step (3), the molar ratio of isomeric dodecyl alcohol polyoxyethylene ether to phosphorus pentoxide is (2-3) to 1; the esterification temperature is 60-80 ℃, and the reaction time is 3-6 hours.
The reaction equation of the present invention is as follows:
the phosphorus pentoxide is high-purity white amorphous powder, and compared with common alcohol ether surfactants, the phosphate prepared by adding the phosphorus pentoxide has the characteristics of good emulsibility, acid and alkali resistance, corrosion resistance, rust resistance and the like.
The isomeric dodecyl polyether phosphate synthesized by the method has certain performance superior to that of isomeric tridecanol polyoxyethylene ether phosphate, can be used as a complementary product of isomeric tridecanol polyoxyethylene ether phosphate to replace alkylphenol polyether, has the characteristics of good emulsibility, acid and alkali resistance and the like, and has good application in antirust coating.
Detailed description of the invention
Example 1
(1) 204g of n-hexanol, 10.2g of sodium hydroxide and 1.13g of zinc oxide are added into a reaction kettle connected with a water separator, nitrogen is replaced in the reaction kettle, the temperature is slowly raised to 220 ℃ under the protection of nitrogen, the reaction is carried out for 2 hours, and 157g of isomeric dodecanol is obtained after filtration and distillation.
(2) And (3) cleaning the epoxy polyether in a self-made epoxy polyether reaction kettle by using deionized water, and drying. 157g of the produced isomeric dodecanol and 0.5g of a catalyst were added, nitrogen gas was used for substitution 3 times, and the mixture was dehydrated for one hour by raising the temperature to 110 ℃. After dehydration, the temperature is continuously raised to 130 ℃, meanwhile, 37g of ethylene oxide is dripped, and after dripping is finished, curing is carried out for 0.5h at the temperature of 130 ℃. 223g of ethylene oxide is continuously dripped, the temperature is controlled at 130-140 ℃, and the pressure is 0.2 MPa. Curing for 0.5h at 130 ℃ after the epoxy is dripped. Cooling to below 100 deg.C, degassing with vacuum pump, cooling to below 70 deg.C, and neutralizing with acetic acid. Discharging to obtain isomeric dodecyl alcohol polyoxyVinyl ether (C) 12 H 25 O(CH 2 CH 2 O) 7 H）。
(3) Adding isomeric dodecyl alcohol polyoxyethylene ether (approximatively 417 g) into a reaction kettle, introducing nitrogen, raising the temperature to 70 ℃, and adding 52gP 2 O 5 (molar ratio of isomeric polyetherol to phosphorus pentoxide 2.3: 1) was added in 10 portions over 2 h. And continuously keeping the temperature of 70 ℃ for reaction for 3h, adding 20g of deionized water for hydrolysis reaction, and finishing the reaction after 1 h. Cooling to below 50 ℃, adding ammonia water to neutralize until PH =7 to obtain the product isomeric dodecyl polyether phosphate with monoester content of 85.3%.
Example 2
(1) 255g of n-hexanol, 12.75g of sodium hydroxide and 1.41g of zinc oxide are added into a reaction kettle connected with a water separator, nitrogen is replaced in the reaction kettle, the temperature is slowly raised to 220 ℃ under the protection of nitrogen, the reaction is carried out for 2 hours, and 193g of isomeric dodecanol is obtained after filtration and distillation.
(2) And (3) cleaning the epoxy polyether in a self-made epoxy polyether reaction kettle by using deionized water, and drying. 193g of the produced isomeric dodecanol and 0.91g of the catalyst were charged, and the mixture was purged with nitrogen 3 times, and dehydrated for one hour by raising the temperature to 110 ℃. After dehydration, the temperature is continuously raised to 130 ℃, 46g of ethylene oxide is added dropwise at the same time, and after the addition, the mixture is cured for 0.5h at the temperature of 130 ℃. 365g of ethylene oxide is continuously dripped, the temperature is controlled at 130-140 ℃, and the pressure is 0.2 MPa. Curing for 0.5h at 130 ℃ after the epoxy is dripped. Cooling to below 100 deg.C, degassing with vacuum pump, cooling to below 70 deg.C, and neutralizing with acetic acid. Discharging to obtain isomeric dodecyl alcohol polyoxyethylene ether (C) 12 H 25 O(CH 2 CH 2 O) 9 H）。
(3) Adding isomeric dodecyl alcohol polyoxyethylene ether (about 604 g) into a reaction kettle, introducing nitrogen, raising the temperature to 60 ℃, and adding 59gP 2 O 5 (molar ratio of isomeric polyetherol to phosphorus pentoxide 2.5: 1) was added in 10 portions over 2 h. And continuously keeping the temperature of 60 ℃ for reacting for 4 hours, adding 22g of deionized water for hydrolysis reaction, and finishing the reaction after 1 hour. Cooling to below 50 ℃, adding ammonia water to neutralize until PH =7 to obtain the product isomeric dodecyl polyether phosphate with monoester content of 81.4%.
Example 3
(1) 204g of n-hexanol, 10.2g of sodium hydroxide and 1.13g of zinc oxide are added into a reaction kettle connected with a water separator, nitrogen is replaced in the reaction kettle, the temperature is slowly raised to 210 ℃ under the protection of nitrogen, the reaction is carried out for 3 hours, and 160g of isomeric dodecanol is obtained after filtration and distillation.
(2) And (3) cleaning the epoxy polyether in a self-made epoxy polyether reaction kettle by using deionized water, and drying. 160g of the prepared isomeric dodecanol and 0.35g of the catalyst are added, nitrogen is replaced for 3 times, and the temperature is raised to 110 ℃ for dehydration for one hour. After dehydration, the temperature is continuously raised to 130 ℃, meanwhile, 38g of ethylene oxide is dripped, and after dripping is finished, curing is carried out for 0.5h at 130 ℃. And continuously dripping 151g of ethylene oxide, controlling the temperature at 130-140 ℃ and the pressure at 0.2 MPa. Curing for 0.5h at 130 ℃ after the epoxy is dripped. Cooling to below 100 deg.C, degassing with vacuum pump, cooling to below 70 deg.C, and neutralizing with acetic acid. Discharging to obtain isomeric dodecyl alcohol polyoxyethylene ether (C) 12 H 25 O(CH 2 CH 2 O) 5 H）。
(3) Adding isomeric dodecyl alcohol polyoxyethylene ether (about 349 g) into a reaction kettle, introducing nitrogen, raising the temperature to 80 ℃, and adding 58gP 2 O 5 (molar ratio of isomeric polyetherol to phosphorus pentoxide 2.1: 1) was added in 10 portions over 2 h. And continuously keeping the temperature of 80 ℃ for reaction for 3h, adding 22g of deionized water for hydrolysis reaction, and finishing the reaction after 1 h. Cooling to below 50 ℃, adding ammonia water to neutralize until PH =7 to obtain the product isomeric dodecyl polyether phosphate with monoester content of 83.8%.
Example 4
(1) Adding 306g of n-hexanol, 15.3g of sodium hydroxide and 1.7g of zinc oxide into a reaction kettle connected with a water separator, replacing nitrogen in the reaction kettle, slowly heating to 230 ℃ under the protection of nitrogen, reacting for 2 hours, and filtering and distilling to obtain 230g of isomeric dodecanol.
(2) And (3) cleaning the epoxy polyether in a self-made epoxy polyether reaction kettle by using deionized water, and drying. 230g of the prepared isomeric dodecanol and 0.47g of the catalyst are added, nitrogen is replaced for 3 times, and the temperature is raised to 110 ℃ for dehydration for one hour. After dehydration, the temperature is continuously raised to 130 ℃, 54g of ethylene oxide is dripped at the same time, and after dripping is finished, the ethylene oxide is drippedAging at 130 deg.C for 0.5 h. 109g of ethylene oxide is continuously added dropwise, the temperature is controlled at 130-140 ℃, and the pressure is 0.2 MPa. Curing for 0.5h at 130 ℃ after the epoxy is dripped. Cooling to below 100 deg.C, degassing with vacuum pump, cooling to below 70 deg.C, and neutralizing with acetic acid. Discharging to obtain isomeric dodecyl alcohol polyoxyethylene ether (C) 12 H 25 O(CH 2 CH 2 O) 3 H）。
(3) Adding isomeric dodecyl alcohol polyoxyethylene ether (approximatively 393 g) into a reaction kettle, introducing nitrogen, raising the temperature to 70 ℃, and adding 63gP 2 O 5 (molar ratio of isomeric polyetherol to phosphorus pentoxide 2.8: 1) was added in 10 portions over 2 h. And continuously keeping the temperature of 70 ℃ for reaction for 3h, adding 24g of deionized water for hydrolysis reaction, and finishing the reaction after 1 h. Cooling to below 50 ℃, adding ammonia water to neutralize until PH =7 to obtain the product isomeric dodecyl polyether phosphate with monoester content of 82.1%.
Example 5
(1) 204g of n-hexanol, 10.2g of sodium hydroxide and 1.13g of zinc oxide are added into a reaction kettle connected with a water separator, nitrogen is replaced in the reaction kettle, the temperature is slowly raised to 220 ℃ under the protection of nitrogen, the reaction is carried out for 2 hours, and 157g of isomeric dodecanol is obtained after filtration and distillation.
(2) And (3) cleaning the epoxy polyether in a self-made epoxy polyether reaction kettle by using deionized water, and drying. 157g of the obtained isomeric dodecanol and 0.5g of a catalyst were added, nitrogen gas was substituted for 3 times, and the temperature was raised to 110 ℃ to dehydrate for one hour. After dehydration, the temperature is continuously raised to 130 ℃, meanwhile, 37g of ethylene oxide is dripped, and after dripping is finished, curing is carried out for 0.5h at the temperature of 130 ℃. 223g of ethylene oxide is continuously dripped, the temperature is controlled at 130-140 ℃, and the pressure is 0.2 MPa. Curing for 0.5h at 130 ℃ after the epoxy is dripped. Cooling to below 100 deg.C, degassing with vacuum pump, cooling to below 70 deg.C, and neutralizing with acetic acid. Discharging to obtain isomeric dodecyl alcohol polyoxyethylene ether (C) 12 H 25 O(CH 2 CH 2 O) 7 H）。
(3) Adding isomeric dodecyl alcohol polyoxyethylene ether (approximatively 417 g) into a reaction kettle, introducing nitrogen, raising the temperature to 50 ℃, and adding 52gP 2 O 5 (molar ratio of isomeric polyetherol to phosphorus pentoxide 2.3: 1) was added in 10 portions over 2 h. Continue to useAnd (3) reacting for 3h under the condition of keeping the temperature at 50 ℃, adding 20g of deionized water for hydrolysis reaction, and finishing the reaction after 1 h. Cooling to below 50 ℃, adding ammonia water to neutralize until PH =7 to obtain the product of isomeric dodecyl polyether phosphate with monoester content of 60.4%.
Comparative example 1
And (3) cleaning the epoxy polyether in a self-made epoxy polyether reaction kettle by using deionized water, and drying. 200g of isomeric tridecanol and BF as catalyst were charged 3 0.47g, replaced with nitrogen 3 times, and dehydrated by heating to 100 ℃. After the dehydration was completed, the temperature was further raised to 150 ℃ and 176g of ethylene oxide was added dropwise. Curing for 0.5h at 150 ℃ after the epoxy is dripped. Discharging at 80 ℃ after the reaction is completed. To obtain isomeric tridecanol polyoxyethylene ether (C) 13 H 27 O(CH 2 CH 2 O) 4 H）。
Adding isomeric dodecyl alcohol polyoxyethylene ether (approximatively 376 g) into a reaction kettle, introducing nitrogen, raising the temperature to 90 ℃, and adding 47gP 2 O 5 (molar ratio of isomeric alcohol polyether to phosphorus pentoxide 3: 1). After the addition of the water and the reaction are continued for 4 hours, 18g of deionized water is added for hydrolysis reaction, and the reaction is finished after 3 hours. Cooling to below 50 ℃, adding ammonia water for neutralization until PH =7 to obtain the product of isomeric tridecanol polyether phosphate with monoester content of 72.9%.
The indexes of the parameters of the isomeric polyoxyethylene dodecanol phosphate prepared in the above examples 1-5 are shown in Table 1. When the esterification temperature was reduced to 50 ℃ the monoester content was significantly lower and when the temperature was increased to 80 ℃ the monoester content did not change significantly. The esterification temperature of the monoester content is 60-80 ℃ with good effect. The monoester contents of examples 1 to 4 were all 80% or more.
TABLE 1
Performance characterization
And measuring the surface tension and Critical Micelle Concentration (CMC) of the sample by adopting a QBZY series full-automatic surface tension meter.
0.1g of each of the samples of examples 1 to 4 and comparative example 1 was taken, and deionized water was added to prepare an aqueous solution having a mass fraction of 0.1%. According to the volume ratio of 1:1 adding liquid paraffin, taking 80mL, oscillating for about 50 times, and accurately recording the time required for separating 10mL of water. Thereby characterizing the relative emulsifying capacity of the product.
0.5g of each of the samples of examples 1 to 4 and comparative example 1 was taken, and deionized water was added to prepare an aqueous solution having a mass fraction of 0.5%. 20mL of the suspension was taken and shaken vigorously 50 times, the foam height was recorded for the first time, and again after standing for 5 min. The FE (foaming property),. and FVS (foam stability) values were calculated. Thereby characterizing the foam properties of the product.
0.2g of each of the samples in examples 1 to 4 and comparative example 1 was taken, dissolved in a dioxane-benzene solution, and titrated with distilled water, and the volume of distilled water was recorded to calculate the HLB value.
The performance characterization comparison table of the isomeric dodecyl alcohol polyoxyethylene ether phosphate and isomeric tridecyl alcohol ether phosphate prepared in the above examples 1-4 is shown in table 2.
TABLE 2
5g of the product from example 1 and comparative example 1 were each dissolved in 500mL of deionized water. Each of the solutions was divided into 5 parts, and 0g, 5g, 10g, 15g, and 20g of NaOH were added thereto, respectively. Standing for 20h, and observing the solution phenomenon. Thus testing the alkali resistance of the product. As shown in table 3.
TABLE 3
The isomeric dodecyl alcohol polyoxyethylene ether phosphate synthesized by the method has the advantages of cheap and easily-obtained raw materials and catalysts, environmental protection, simple and feasible process, higher monoester content of the obtained product, stable property, good acid and alkali resistance, and good characterization results of foam performance and emulsifying performance through testing. The antirust paint has good use effect when being applied to the preparation of antirust paint and the like.
Claims (7)
1. A synthetic method of isomeric dodecyl alcohol polyoxyethylene ether phosphate ester is characterized by comprising the following steps:
(1) n-hexanol is taken as an initiator, and a catalyst is added under the protection of nitrogen to carry out aldol condensation reaction per se, so as to prepare isomeric dodecanol;
(2) under the action of a catalyst, firstly carrying out induction reaction on the isomeric dodecanol prepared in the step (1) and part of ethylene oxide, and then carrying out polymerization reaction on the rest of ethylene oxide to obtain isomeric dodecanol polyoxyethylene ether;
(3) adding isomeric dodecyl alcohol polyoxyethylene ether and phosphorus pentoxide to carry out esterification reaction, and adding deionized water into a product obtained by esterification to carry out hydrolysis, thereby finally obtaining isomeric dodecyl alcohol polyoxyethylene ether phosphate;
the catalyst in the step (1) is a catalyst mixed by sodium hydroxide and zinc oxide; the mass of the added sodium hydroxide is 5% of that of the n-hexanol, and the mass ratio of the zinc oxide to the sodium hydroxide is 1: 9; the reaction temperature of the step (1) is 210-230 ℃, and the reaction time is more than two hours;
the isomeric dodecyl alcohol polyoxyethylene ether phosphoric acid is applied to the antirust coating.
2. The method for synthesizing the isomeric dodecanol polyoxyethylene ether phosphate ester according to claim 1, wherein the method comprises the following steps: and (3) adding ethylene oxide in the step (2) in a dropwise manner.
3. The method for synthesizing the isomeric dodecanol polyoxyethylene ether phosphate ester according to claim 1, wherein the method comprises the following steps: the total molar ratio of the isomeric dodecanol and the ethylene oxide in the step (2) is 1: 2-10.
4. The method for synthesizing the isomeric dodecanol polyoxyethylene ether phosphate ester according to claim 1, wherein the method comprises the following steps: the induced reaction in the step (2) has the mol ratio of isomeric dodecanol to ethylene oxide of 1:1 and the reaction temperature of 130 ℃.
5. The method for synthesizing the isomeric dodecanol polyoxyethylene ether phosphate ester according to claim 1, wherein the method comprises the following steps: the polymerization temperature in the step (2) is 130 ℃.
6. The method for synthesizing the isomeric dodecanol polyoxyethylene ether phosphate ester according to claim 1, wherein the method comprises the following steps: the catalyst is KOH, and the mass of the catalyst added is 0.1-0.15% of the sum of the mass of the isomeric dodecyl alcohol and the mass of the ethylene oxide.
7. The method for synthesizing the isomeric dodecanol polyoxyethylene ether phosphate ester according to claim 1, wherein the method comprises the following steps: in the step (3), the molar ratio of isomeric dodecyl alcohol polyoxyethylene ether to phosphorus pentoxide is (2-3) to 1; the esterification temperature is 60-80 ℃, and the reaction time is 3-6 hours.
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