CN110698406B - Perfluoropolyether imidazoline compound and preparation method and application thereof - Google Patents
Perfluoropolyether imidazoline compound and preparation method and application thereof Download PDFInfo
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- CN110698406B CN110698406B CN201810744077.8A CN201810744077A CN110698406B CN 110698406 B CN110698406 B CN 110698406B CN 201810744077 A CN201810744077 A CN 201810744077A CN 110698406 B CN110698406 B CN 110698406B
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 83
- -1 imidazoline compound Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 230000007797 corrosion Effects 0.000 claims abstract description 80
- 238000005260 corrosion Methods 0.000 claims abstract description 80
- 239000003112 inhibitor Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 19
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 229940078552 o-xylene Drugs 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 18
- 239000000758 substrate Substances 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000003921 oil Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 229910000975 Carbon steel Inorganic materials 0.000 description 9
- 239000010962 carbon steel Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- 150000001265 acyl fluorides Chemical class 0.000 description 5
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BHFJBHMTEDLICO-UHFFFAOYSA-N Perfluorooctylsulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O BHFJBHMTEDLICO-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D233/22—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of metal corrosion inhibitors, and discloses a perfluoropolyether imidazoline compound and a preparation method and application thereof. The perfluoropolyether imidazoline compound is prepared from perfluoropolyether carboxylic acid, diethylenetriamine and perfluoropolyether acyl halide serving as raw materials, and is simple in preparation method and high in yield. When the prepared perfluoropolyether imidazoline compound is used as a metal corrosion inhibitor to treat a metal substrate, the perfluoropolyether imidazoline compound has the characteristics of strong adsorption force, high temperature resistance, high corrosion inhibition rate and the like, can endow the surface of the substrate with the characteristics of water resistance, oil resistance, pollution prevention, corrosion resistance and the like, has no biological accumulated toxicity, has little environmental pollution, and meets the requirements of environmental protection.
Description
Technical Field
The invention relates to the technical field of metal corrosion inhibitors, in particular to a perfluoropolyether imidazoline compound and a preparation method and application thereof.
Background
With the development of the global industry, the problem of corrosion is becoming more and more severe. Although corrosion protection technology is continuously developed to alleviate the corrosion problem, the corrosion of metals is still very serious in general. In metal corrosion, steel corrosion is predominant, while in steel corrosion, marine conditions, humid atmospheres, and atmospheric corrosion in industrially dense areas are of major importance. Compared with many strong medium corrosions, the corrosion strength of the weak medium corrosions is relatively low, but the corrosion strength is large, so that the loss and the influence are more prominent.
The imidazoline corrosion inhibitor has no toxicity, no pungent smell and no harm to human body and surrounding environment, and belongs to an environment-friendly corrosion inhibitor. Moreover, the imidazoline corrosion inhibitor has better corrosion inhibition performance in various acidic media, can prevent the corrosion of oxygen and carbon dioxide to metal equipment by covering effect and improving the activation energy of corrosion reaction, is an effective anticorrosive product, and is widely applied to industrial production of petroleum, natural gas and the like. However, the general hydrocarbon imidazoline corrosion inhibitor cannot resist high temperature, and the application range is greatly limited, so that the introduction of a fluorine-containing group into the corrosion inhibitor is considered to improve the high-temperature resistance of the corrosion inhibitor. Patent CN 102021583A discloses an oil well corrosion inhibitor using N-alkylamino-2-perfluoroalkyl imidazoline quaternary ammonium salt compound as main agent and its preparation method, the compound improves the thermal stability of the corrosion inhibitor by introducing perfluoroalkyl group into the hydrophobic end. Patent CN 102277577A discloses a fluorine-containing cation imidazoline corrosion inhibitor and a preparation method thereof, wherein perfluoroalkyl sulfonyl fluoride is introduced into a hydrophilic end of the compound to reduce the surface tension of an aqueous solution. Patent CN 104513205a discloses a preparation method of a high temperature resistant corrosion inhibitor using bifluorocarbon imidazoline as a main agent, which introduces a diperfluoroalkyl chain to improve the high temperature resistance. Patent CN 106435598A discloses a formula of a metal corrosion inhibitor added with a fluorine-containing surfactant and a production process thereof, wherein perfluorooctyl sulfonyl fluoride is introduced into the metal corrosion inhibitor to improve the high temperature resistance. The fluorine-containing groups introduced in the above patents are all perfluoroalkyl groups, are difficult to degrade in nature, and have potential hazards to living organisms and human bodies, and in order to introduce the perfluoroalkyl groups, perfluorooctylsulfonyl fluoride and perfluorooctanoic acid in the raw materials used have been defined as substances which persist in the environment, have bioaccumulation properties, and are harmful to human bodies, and have been banned from use in many countries. Perfluoroether chains are of interest in the context of the banning of perfluoroalkyl long-chain compounds, which are similar to perfluoroalkanes but are not bioaccumulating.
Disclosure of Invention
As described above, in view of the problems of high temperature resistance, corrosion resistance, environmental friendliness and the like of the metal corrosion inhibitor in the prior art, the present invention aims to provide a perfluoropolyether imidazoline compound that has high temperature resistance, high corrosion inhibition rate, no biological accumulated toxicity, little environmental pollution, and meets the requirements of environmental protection.
In order to achieve the above object, one aspect of the present invention provides a perfluoropolyether imidazoline compound, the structure of which is shown in formula (1):
wherein, Rf1Is composed of
Rf2Is composed of
a and b are integers of 1-60, and a and b are the same or different.
Preferably, a and b are both integers of 2-10, and a and b are the same or different.
In another aspect, the present invention provides a method for preparing a perfluoropolyether imidazoline compound, including the steps of:
mixing perfluoropolyether carboxylic acid, diethylenetriamine and a water carrying agent, and reacting to obtain a first intermediate;
continuing to heat the first intermediate, reacting and purifying to obtain a second intermediate;
and mixing the second intermediate with an acid-binding agent, dropwise adding perfluoropolyether acyl halide, and reacting to obtain the perfluoropolyether imidazoline compound.
Preferably, the structure of the perfluoropolyether carboxylic acid is represented by formula (2):
m is an integer of 1 to 60.
Preferably, the water carrying agent is one or a combination of at least two selected from toluene, o-xylene, m-xylene and p-xylene.
Preferably, the molar ratio of the perfluoropolyether carboxylic acid to the diethylenetriamine to the water carrying agent is 1: 1-2: 0.5-10.
Preferably, the acid-binding agent is one or a combination of at least two selected from triethylamine, potassium carbonate, sodium hydroxide and pyridine.
Preferably, the structure of the perfluoropolyether acyl halide is as shown in formula (3):
n is an integer of 1 to 60.
Preferably, the molar ratio of the second intermediate to the perfluoropolyether acyl halide is 1: 0.1-2.
The invention also provides application of the perfluoropolyether imidazoline compound serving as the metal corrosion inhibitor.
Advantageous effects
The invention utilizes the characteristics of easy degradation of a perfluoroether chain molecular chain, no biological accumulation and the like, and takes perfluoropolyether carboxylic acid, diethylenetriamine and perfluoropolyether acyl halide as raw materials to prepare the perfluoropolyether imidazoline compound. Compared with the prior art, when the perfluoropolyether imidazoline compound provided by the invention is used as a metal corrosion inhibitor to treat a metal substrate, the perfluoropolyether imidazoline compound has the characteristics of strong adsorption force, high temperature resistance, high corrosion inhibition rate and the like, can endow the surface of the substrate with the characteristics of water resistance, oil resistance, pollution resistance, corrosion resistance and the like, has no biological accumulated toxicity, causes little pollution to the environment, and meets the requirements of environmental protection. Meanwhile, the invention also provides a preparation method of the compound, and the preparation method is simple, high in yield and beneficial to industrial popularization and application.
Detailed Description
The invention provides a perfluoropolyether imidazoline compound which has high corrosion inhibition rate, high temperature resistance, no biological accumulated toxicity, small environmental pollution and accordance with the requirements of environmental protection.
The structure of the perfluoropolyether imidazoline compound provided by the invention is shown as the formula (1):
wherein, Rf1Is composed of
Rf2Is composed of
a and b are both 1-60, preferably integers of 2-10, and a and b are the same or different.
The perfluoropolyether imidazoline compound is prepared by taking perfluoropolyether carboxylic acid, diethylenetriamine and perfluoropolyether acyl halide as raw materials. The specific preparation method can comprise the following steps: mixing perfluoropolyether carboxylic acid, diethylenetriamine and a water carrying agent, stirring and heating to 140-160 ℃, and maintaining the reaction temperature for 0.5-5 h to obtain a first intermediate; then continuously stirring and heating to 180-210 ℃, and maintaining the reaction temperature for 0.5-5 h; cooling and purifying to obtain a second intermediate; and continuously mixing the obtained second intermediate with an acid-binding agent, dropwise adding perfluoropolyether acyl halide in a protective gas atmosphere, heating to 40-80 ℃ after dropwise adding, and maintaining the reaction temperature for 20-30 h to obtain the perfluoropolyether imidazoline compound.
The perfluoropolyether carboxylic acids used in some embodiments of the invention have the structure shown in formula (2):
wherein m is an integer of 1 to 60, preferably 2 to 10. The m value reflects the polymerization degree of the perfluoropolyether carboxylic acid molecules, and when the m value is too large, the steric hindrance between perfluorocarbon chain molecules is correspondingly increased, which is unfavorable for the arrangement of the perfluorocarbon chain molecules on the surface of the metal substrate, influences the adsorption effect of the metal substrate, further influences the corrosion inhibition effect of the metal substrate when the metal substrate is used as a corrosion inhibitor, and increases the cost.
According to some embodiments of the invention, the water-carrying agent is one or a combination of at least two selected from toluene, o-xylene, m-xylene, p-xylene. The perfluoropolyether carboxylic acid and the diethylenetriamine react at high temperature to generate water, and the water carrying agent and the water form an azeotropic system to carry the water out of the reaction system, so that the reaction is carried out smoothly. Meanwhile, in order to avoid the generation of diamide in the reaction process, according to some embodiments of the present invention, the molar ratio of the perfluoropolyether carboxylic acid, the diethylenetriamine and the water-carrying agent may be 1: 1-2: 0.5-10, preferably 1: 1-1.5: 0.5-5.
In order to fully react the perfluoropolyether carboxylic acid with diethylenetriamine, when the temperature is raised to 140-160 ℃, the reaction temperature is maintained for 0.5-5 h, according to some embodiments of the present invention, the reaction temperature is preferably maintained for 2-4 h, and stirring is not stopped during the period, so as to obtain the first intermediate.
According to some embodiments of the invention, the first intermediate has the structure according to formula (4):
wherein m is an integer of 1 to 60, preferably 2 to 10.
And (2) continuously stirring the obtained first intermediate, heating to 180-210 ℃, carrying out cyclization reaction, maintaining the reaction temperature for 0.5-5 h, preferably maintaining the reaction temperature for 2-4 h according to some embodiments of the invention, and then purifying after cooling. The purification method may be any suitable method known in the art, such as distillation under reduced pressure, to remove unreacted diethylenetriamine and excess water-carrying agent, and obtain the second intermediate.
According to some embodiments of the invention, the second intermediate has the structure according to formula (5):
wherein m is an integer of 1 to 60, preferably 2 to 10.
Continuing to mix the obtained second intermediate with the acid-binding agent, the perfluoropolyether acid halide is added dropwise under a protective gas, such as nitrogen or an inert gas atmosphere, preferably under an anhydrous oxygen-free nitrogen-protected atmosphere established by repeated evacuation and nitrogen charging operations, according to some embodiments of the present invention. In some embodiments of the present invention, the perfluoropolyether acid halide has the structure shown in formula (3):
wherein n is an integer of 1 to 60, preferably 2 to 10. Similarly, the too large value of n is not favorable for the arrangement of the n on the surface of the metal substrate, thereby affecting the adsorption effect and the corrosion inhibition effect and increasing the cost. According to some embodiments of the invention, the molar ratio of the second intermediate to the perfluoropolyether acid halide is set to 1:0.1 to 2, preferably 1:0.5 to 1.5. The perfluoropolyether imidazoline compound and the hydrogen halide are obtained after the reaction of the perfluoropolyether imidazoline compound and the hydrogen halide, and the acid-binding agent can absorb the hydrogen halide generated in the reaction, so that the reaction is more smooth. According to some embodiments of the invention, the acid scavenger is one or a combination of at least two selected from the group consisting of triethylamine, potassium carbonate, sodium hydroxide, pyridine. The acid-binding agent may be added in excess so that it sufficiently absorbs hydrogen halide generated in the reaction.
After the perfluoropolyether acyl halide is dripped, heating to 40-80 ℃, preferably to 50-60 ℃, and maintaining the reaction temperature for 20-30 hours to obtain the perfluoropolyether imidazoline compound.
The preparation method is simple, has high yield and is beneficial to industrial popularization and application; and the obtained product has strong adsorption capacity, high temperature resistance and high corrosion inhibition rate.
The invention also provides application of the perfluoropolyether imidazoline compound serving as the metal corrosion inhibitor. When the metal corrosion inhibitor is used for treating a metal substrate, the metal corrosion inhibitor has the characteristics of strong adsorption force, high temperature resistance, high corrosion inhibition rate and the like, and can endow the surface of the substrate with the characteristics of water resistance, oil resistance, pollution resistance, corrosion resistance and the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
mixing 50g of perfluoropolyether carboxylic acid (994g/mol, m is 5), 6.23g of diethylenetriamine and 11g of xylene, stirring and heating to 160 ℃, and maintaining the temperature to react for 2.5 hours to obtain a first intermediate; then the reaction was further heated to 200 ℃ and maintained at this reaction temperature for 2.5h, after cooling, purified by distillation under reduced pressure to obtain 51.28g of a second intermediate with a yield of 96.08%.
And (2) mixing 50g of the second intermediate and 3ml of triethylamine, dropwise adding 50g of perfluoropolyether acyl fluoride (996g/mol, n is 5) in an anhydrous oxygen-free nitrogen atmosphere, heating to 55 ℃ after dropwise adding, and reacting for 25 hours to obtain 92.80g of perfluoropolyether imidazoline compound with the yield of 96.68%. The perfluoropolyether imidazoline compound obtained here was labeled as corrosion inhibitor a.
Example 2:
mixing 100g of perfluoropolyether carboxylic acid (828g/mol, m is 4), 13.71g of diethylenetriamine and 40g of xylene, stirring and heating to 155 ℃, and maintaining the temperature to react for 2 hours to obtain a first intermediate; then the reaction was further heated to 190 ℃ and maintained at this reaction temperature for 2h, after cooling, purified by distillation under reduced pressure to obtain 104.56g of a second intermediate with a yield of 96.73%.
100g of the second intermediate and 3ml of triethylamine are mixed, 125g of perfluoropolyether acyl fluoride (996g/mol, n is 5) is dripped in under the atmosphere of anhydrous oxygen-free nitrogen, after the dripping is finished, the temperature is raised to 50 ℃, and after the reaction is carried out for 24 hours, 195.45g of perfluoropolyether imidazoline compound is obtained, and the yield is 93.49%. The perfluoropolyether imidazoline compound obtained here was labeled as corrosion inhibitor B.
Example 3:
mixing 50g of perfluoropolyether carboxylic acid (1160g/mol, m is 6), 6.67g of diethylenetriamine and 10g of xylene, stirring and heating to 160 ℃, and maintaining the temperature to react for 3 hours to obtain a first intermediate; then the reaction was further heated to 210 ℃ and maintained at this reaction temperature for 3 hours, after cooling, the reaction was purified by distillation under reduced pressure to give 48.34g of a second intermediate in 91.40% yield.
And (3) mixing 40g of the second intermediate and 3ml of triethylamine, dropwise adding 33g of perfluoropolyether acyl fluoride (830g/mol, n is 4) in an anhydrous oxygen-free nitrogen atmosphere, heating to 55 ℃ after dropwise adding, and reacting for 30 hours to obtain 61.74g of perfluoropolyether imidazoline compound with the yield of 92.97%. The perfluoropolyether imidazoline compound obtained here was labeled as corrosion inhibitor C.
Example 4:
mixing 100g of perfluoropolyether carboxylic acid (828g/mol, m is 4), 13.71g of diethylenetriamine and 40g of xylene, stirring and heating to 155 ℃, and maintaining the temperature to react for 2 hours to obtain a first intermediate; then the reaction was further warmed to 190 ℃ and maintained at this reaction temperature for 2h, cooled and then purified by distillation under reduced pressure to obtain 102.83g of a second intermediate with a yield of 95.13%.
And (3) mixing 100g of the second intermediate and 3ml of triethylamine, dropwise adding 130g of perfluoropolyether acyl fluoride (1162g/mol, n is 6) in an anhydrous oxygen-free nitrogen atmosphere, heating to 60 ℃ after dropwise adding, and reacting for 30 hours to obtain 210.79g of perfluoropolyether imidazoline compound with the yield of 92.62%. The perfluoropolyether imidazoline compound obtained here was labeled as corrosion inhibitor D.
Example 5:
mixing 50g of perfluoropolyether carboxylic acid (662g/mol, m is 3), 9.40g of diethylenetriamine and 24g of xylene, stirring and heating to 140 ℃, and maintaining the temperature to react for 2 hours to obtain a first intermediate; then the reaction was further heated to 180 ℃ and maintained at this reaction temperature for 2h, after cooling, purified by distillation under reduced pressure to obtain 50.29g of a second intermediate with a yield of 91.34%.
And mixing 50g of the second intermediate and 3ml of triethylamine, dropwise adding 91g of perfluoropolyether acyl fluoride (1328g/mol, n is 7) in an anhydrous oxygen-free nitrogen atmosphere, heating to 60 ℃ after dropwise adding, and reacting for 30 hours to obtain 133.16g of perfluoropolyether imidazoline compound with the yield of 95.40%. The perfluoropolyether imidazoline compound obtained here was labeled as corrosion inhibitor E.
The corrosion inhibitors prepared in examples 1 to 5 were subjected to corrosion inhibition tests at 25 c, 80 c and 200 c, respectively, and water and n-hexadecane were tested for contact angles on the corrosion inhibitor-treated carbon steel sheet, respectively, with the results shown in table 1.
(Performance test)
Pretreatment: the material is Q235 carbon steel, and before testing, the test piece is ground and polished by metallographic abrasive paper, washed by deionized water, degreased by absolute ethyl alcohol and acetone, and dried at room temperature for later use.
And (3) testing the corrosion inhibition rate: taking two parts of the pretreated carbon steel by a weight loss method, respectively suspending and immersing the two parts of the pretreated carbon steel in a 10% hydrochloric acid solution without adding a corrosion inhibitor and a 10% hydrochloric acid solution with the mass fraction of the corrosion inhibitor being 0.08% at 25 ℃ and 80 ℃, taking out after 24 hours, respectively wiping off surface corrosion products by absorbent cotton, and cleaning and drying the products to constant weight by deionized water and acetone.
Eta represents the corrosion inhibition rate, and is expressed in a "%";
Δ m1 represents the mass loss in g of test pieces in a 10% hydrochloric acid solution without corrosion inhibitor;
Δ m2 represents the mass loss in g of the test piece in a 10% hydrochloric acid solution to which the corrosion inhibitor is added.
And (3) testing the high-temperature corrosion inhibition rate: taking two parts of the pretreated carbon steel by adopting a weight loss method, putting the two parts into two same high-pressure kettles, respectively adding a 10% hydrochloric acid solution without adding a corrosion inhibitor and a 10% hydrochloric acid solution with the mass fraction of the corrosion inhibitor being 0.08% into the kettles, heating the kettles to 200 ℃ in a closed manner, taking out the kettles after 24 hours, respectively wiping off surface corrosion products by absorbent cotton, and cleaning and drying the kettles by using deionized water and acetone until the weight is constant.
Contact angle test: suspending a pretreated carbon steel sheet in a corrosion inhibitor solution, taking out after 24 hours, wiping surface corrosion products with absorbent cotton, cleaning and drying with deionized water and acetone, controlling the size of liquid drops to be 5 mu L at room temperature, measuring the contact angle of water and n-hexadecane on a contact angle measuring instrument, and taking the average value of ten measurement results.
TABLE 1 results of the corrosion inhibitors prepared in examples 1 to 5 on the corrosion inhibition test and on the contact angle test
As can be seen from Table 1, the corrosion inhibitors prepared in examples 1-5 exhibited corrosion inhibition rates of 90% or more with respect to carbon steel at 25 deg.C, 80 deg.C and 200 deg.C. And the contact angles of water on the carbon steel subjected to corrosion inhibition treatment are both larger than 90 degrees, and the contact angles of n-hexadecane on the carbon steel subjected to corrosion inhibition treatment are both larger than 60 degrees, which shows that when the perfluoropolyether imidazoline compound prepared by the invention is used as a metal corrosion inhibitor to treat a metal substrate, the metal substrate has the characteristics of strong adsorption force, high temperature resistance, high corrosion inhibition rate and the like, and meanwhile, the substrate surface can be endowed with the characteristics of water resistance, oil resistance, pollution resistance, corrosion resistance and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A perfluoropolyether imidazoline compound is disclosed, and the structure of the compound is shown as formula (1):
wherein, Rf1Is composed of
Rf2Is composed of
a and b are integers of 2-10, and a and b are the same or different.
2. A method for producing the perfluoropolyether imidazoline compound of claim 1, comprising the steps of:
mixing perfluoropolyether carboxylic acid, diethylenetriamine and a water carrying agent, and reacting to obtain a first intermediate;
continuing to heat the first intermediate, reacting and purifying to obtain a second intermediate;
and mixing the second intermediate with an acid-binding agent, dropwise adding perfluoropolyether acyl halide, and reacting to obtain the perfluoropolyether imidazoline compound.
3. The process for producing a perfluoropolyether imidazoline compound according to claim 2, wherein the perfluoropolyether carboxylic acid has a structure represented by formula (2):
a is an integer of 2 to 10.
4. The method for producing a perfluoropolyether imidazoline compound according to claim 2, wherein the water-carrying agent is one or a combination of at least two selected from toluene, o-xylene, m-xylene, and p-xylene.
5. The method for producing a perfluoropolyether imidazoline compound according to claim 2, wherein a molar ratio of the perfluoropolyether carboxylic acid, diethylenetriamine, and water-carrying agent is 1:1 to 2:0.5 to 10.
6. The method for producing a perfluoropolyether imidazoline compound according to claim 2, wherein the acid scavenger is one or a combination of at least two selected from triethylamine, potassium carbonate, sodium hydroxide, and pyridine.
7. The process for producing a perfluoropolyether imidazoline compound according to claim 2, wherein the perfluoropolyether acid halide has a structure represented by formula (3):
b is an integer of 2 to 10.
8. The method for producing the perfluoropolyether imidazoline compound according to claim 2, wherein a molar ratio of the second intermediate to the perfluoropolyether acid halide is 1:0.1 to 2.
9. Use of the perfluoropolyether imidazoline compound of claim 1 as a metal corrosion inhibitor.
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