CN111454291B - Preparation method of sulfur-phosphorus-nitrogen type extreme pressure antiwear agent - Google Patents
Preparation method of sulfur-phosphorus-nitrogen type extreme pressure antiwear agent Download PDFInfo
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- CN111454291B CN111454291B CN202010397292.2A CN202010397292A CN111454291B CN 111454291 B CN111454291 B CN 111454291B CN 202010397292 A CN202010397292 A CN 202010397292A CN 111454291 B CN111454291 B CN 111454291B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 45
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000005886 esterification reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000006683 Mannich reaction Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000006467 substitution reaction Methods 0.000 claims abstract description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims abstract description 6
- KRIFIIWBVJKVST-UHFFFAOYSA-N chloro(chloromethylsulfanyl)methane Chemical compound ClCSCCl KRIFIIWBVJKVST-UHFFFAOYSA-N 0.000 claims abstract description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052802 copper Inorganic materials 0.000 abstract description 15
- 239000010949 copper Substances 0.000 abstract description 15
- 239000012208 gear oil Substances 0.000 abstract description 9
- 239000008139 complexing agent Substances 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- -1 thiophosphate amine salt Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000764238 Isis Species 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- PZFYOFFTIYJCEW-UHFFFAOYSA-N n-tridecyltridecan-1-amine Chemical compound CCCCCCCCCCCCCNCCCCCCCCCCCCC PZFYOFFTIYJCEW-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
- C10M137/14—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent, which comprises the following steps: dripping propylene oxide into dialkyl dithiophosphate to perform a first esterification reaction to obtain a first product; dropwise adding phosphorus chloride into the reaction system of the first product to perform a second esterification reaction to obtain a second product; adding monochloro-methyl sulfide into a reaction system of the second product to carry out substitution reaction to obtain a third product; adding m-CPBA into the reaction system of the third product to carry out oxidation reaction to obtain a fourth product; and adding polyformaldehyde and fatty amine into a reaction system of the fourth product to carry out Mannich reaction to obtain the sulfur-nitrogen-phosphorus extreme pressure antiwear agent. The synthesis method is stable, the corrosion of acid gas to equipment is effectively reduced in the synthesis process, the environment is protected, and the corrosion condition of a copper sheet of a system and the liquid-phase corrosion condition can be effectively improved when the extreme pressure antiwear agent is added into the gear oil complexing agent.
Description
Technical Field
The invention relates to the technical field of antiwear agents, in particular to a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent.
Background
The extreme pressure antiwear property is an important use property of industrial gear oil, and the requirement on the extreme pressure antiwear property is usually realized by introducing an extreme pressure antiwear agent into the gear oil; according to the current research situation, the sulfur-containing phosphorus-nitrogen extreme pressure agent is widely applied to various gear oil complexing agent formulas due to excellent high-temperature stability, high-efficiency anti-abrasion property, anti-corrosion property, anti-oxidation stability, additive compatibility and multiple-effect property.
The research on the thiophosphornitrogen extreme pressure antiwear agent in foreign countries starts in the 60 s, and China also researches on the thiophosphornitrogen extreme pressure antiwear agent in nearly thirty years and develops the agent types with excellent extreme pressure antiwear performance such as T305, T307, T310 and the like, and the agent types are widely applied to the formulas of various gear oil complexing agents; the sulfur-phosphorus-nitrogen extreme pressure antiwear agent is mainly divided into thiophosphate amine salt, thiophosphoric acid complex ester and the like on the whole, and agents with different structures are respectively applied to different formulas.
For thiophosphoric acid complex ester type extreme pressure antiwear agent, CN1033811A reports an extreme pressure antiwear agent, and the synthetic method comprises the following steps: thiophosphoric acid reacts with propylene oxide to generate complex ester, and then Mannich reaction is carried out, so that nitrogen is introduced into the structure to obtain better anti-oxidation stability and corrosion resistance; however, due to the structural particularity, when the Mannich reaction occurs, a higher reaction temperature is often needed, which causes that part of the structure-P = S-is changed into-P = O-, on one hand, the sulfur element in the structure is reduced, and on the other hand, the decomposed sulfur element not only corrodes equipment but also causes pollution. In addition, the corrosion of copper sheets is serious when the agent is applied to a gear oil formula, and the agent cannot be used for the formula with special requirements in the aspect.
For thiophosphate amine salt type extreme pressure antiwear agent, a synthetic method thereof is reported in US5573696A, and the preparation method is as follows: reaction of thiophosphoric acid with propylene oxide followed by reaction with P 2 O 5 Carrying out acidification reaction, and finally carrying out salt forming reaction with fatty amine; the agent has good extreme pressure abrasion resistance, but because nitrogen element is introduced into the structure through salt forming reaction, the corrosion result of the agent on copper sheets is obviously inferior to that of the thiophosphoric acid complex ester type extreme pressure abrasion resistant agent, the reason may be that the content of active sulfur in the structure of the agent is increased due to the existence of amine salt, when the agent is applied to a gear oil formula, the obtained structure is just opposite to the corrosion result, namely the copper sheet corrosion condition of the complexing agent is obviously superior to that of the complexing agent, and the reason may be that the content of the active sulfur in the system is effectively reduced due to the existence of the amine salt in the structure.
The sulfur-phosphorus-nitrogen extreme pressure antiwear agent reported in patent CN1033811A, US5573696A and the synthetic method thereof are the current classical methods for synthesizing the compound, but the structural characteristics thereof cause that the compound has obvious defects in certain characteristics; the method specifically comprises the following steps:
1. when the thiophosphoryl-nitrogen type compound ester extreme pressure antiwear agent is added into the gear oil complexing agent, the copper sheet of the system is seriously corroded, and the copper sheet often reaches the 2d-3a grade;
2. when the extreme pressure antiwear agent disclosed in patent CN1033811a is synthesized, in order to obtain a better copper sheet corrosion effect, synthesis is often required to be performed at a higher temperature, which may result in conversion from-P = S-to-P = O-and generation of a certain amount of acid gas; on one hand, the corrosion to equipment can be caused, and on the other hand, the damage to the environment can be caused;
3. when the sulfuric phosphoric acid complex ester amine salt extreme pressure antiwear agent disclosed in the patent US5573696A is synthesized, the copper sheet corrosion effect is poor and the copper sheet corrosion effect is often up to the 2d-2e grade.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent.
The invention discloses a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent, which comprises the following steps:
dripping propylene oxide into dialkyl dithiophosphate to perform a first esterification reaction to obtain a first product;
dropwise adding phosphorus chloride into the reaction system of the first product to perform a second esterification reaction to obtain a second product;
adding monochloro-methyl sulfide into the reaction system of the second product to carry out substitution reaction to obtain a third product;
adding m-CPBA into the reaction system of the third product to carry out oxidation reaction to obtain a fourth product;
and adding polyformaldehyde and fatty amine into a reaction system of the fourth product to carry out a Mannich reaction to obtain the sulfur-nitrogen-phosphorus extreme pressure antiwear agent.
As a further improvement of the invention, the synthetic route of the preparation method is as follows:
the first esterification reaction is:
the second esterification reaction is as follows:
the substitution reaction is as follows:
the oxidation reaction is as follows:
the mannich reaction is:
wherein R is 1 And R 2 Is C 4 ～C 12 Alkyl radical, R 3 Is C 8 ～C 18 An alkyl group.
As a further improvement of the invention, the reaction temperature of the first esterification reaction is 70-85 ℃, and the reaction time is 1-2h;
the acid value of the system is detected during the reaction, and when the acid value is not more than 10KOHmg/g, the second esterification reaction can be carried out.
As a further improvement of the invention, the reaction temperature of the second esterification reaction is-5-0 ℃, and the reaction time is 1-3h.
As a further improvement of the invention, the reaction temperature of the substitution reaction is 80-110 ℃, and the reaction time is 4-6h.
As a further improvement of the invention, the reaction temperature of the oxidation reaction is not more than 0 ℃, and the reaction time is 1-2h.
As a further improvement of the invention, the reaction temperature of the Mannich reaction is 80-100 ℃ and the reaction time is 8-10h.
Compared with the prior art, the invention has the beneficial effects that:
the synthesis method is stable, the corrosion of acid gas to equipment is effectively reduced in the synthesis process, the environment is protected, and the corrosion condition of a copper sheet of a system and the liquid-phase corrosion condition can be effectively improved when the extreme pressure antiwear agent is added into the gear oil complexing agent.
Drawings
FIG. 1 is a flow chart of a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent disclosed by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention is described in further detail below with reference to the attached drawing figures:
as shown in figure 1, the invention provides a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent, which comprises the following steps:
step 1, dripping propylene oxide into dialkyl dithiophosphate to perform a first esterification reaction to obtain a first product; wherein the content of the first and second substances,
the first esterification reaction is:
in the formula, R 1 And R 2 Is C 4 ～C 12 An alkyl group; the reaction temperature of the first esterification reaction is 70-85 ℃, and the reaction time is 1-2h; the acid value of the system is detected during the reaction, and when the acid value is not more than 10KOHmg/g, the second esterification reaction can be carried out.
The method comprises the following specific steps:
adding 0.32mol of dialkyl dithiophosphate into a four-mouth bottle provided with a thermometer, a reflux condenser tube, a dropping funnel and a stirrer, and slowly dropping 0.33mol of propylene oxide into a reaction system under the stirring condition; controlling the temperature of the system to be not more than 30 ℃ in the dripping process, preferably controlling the dripping time to be 45min, raising the temperature to 70-85 ℃ after finishing dripping, and carrying out heat preservation reaction for 1-2h; in the process, the acid value of the system is detected, and when the acid value is not more than 10KOHmg/g, the next reaction can be carried out.
Step 2, dropwise adding phosphorus chloride into the reaction system of the first product to perform a second esterification reaction to obtain a second product; wherein the content of the first and second substances,
the second esterification reaction is:
in the formula, R 1 And R 2 Is C 4 ～C 12 An alkyl group; the reaction temperature of the second esterification reaction is-5-0 ℃, and the reaction time is 1-3h;
the method comprises the following specific steps:
slowly dripping PCl into the reaction system through a dripping funnel 3 The dripping time is preferably 45min, the reaction temperature is controlled between minus 5 ℃ and 0 ℃ in the dripping process, and the reaction is continued for 1 to 3 hours after the dripping is finished; it should be noted that the nitrogen purge is performed throughout the reaction process to allow the HCl formed to be removed as quickly as possible to minimize side reactions.
Step 3, adding monochloromethyl sulfide into a reaction system of the second product to carry out substitution reaction to obtain a third product; wherein the content of the first and second substances,
the substitution reaction is:
in the formula, R 1 And R 2 Is C 4 ～C 12 An alkyl group; the reaction temperature of the substitution reaction is 80-110 ℃, and the reaction time isIs 4-6h;
the method comprises the following specific steps:
adding 0.31mol of monochloromethyl sulfide into the reaction system, raising the temperature to 80-100 ℃, and continuing to react for 4-6h to obtain the target product.
Step 4, adding m-CPBA into a reaction system of the third product to carry out oxidation reaction to obtain a fourth product; wherein the content of the first and second substances,
the oxidation reaction is as follows:
in the formula, R 1 And R 2 Is C 4 ～C 12 An alkyl group; the reaction temperature of the oxidation reaction is not more than 0 ℃, and the reaction time is 1-2h;
the method comprises the following specific steps:
slowly adding 0.35mol of m-CPBA into the reaction system, controlling the temperature of the system not to exceed 0 ℃ in the process, and continuing to react for 1-2 hours after the oxidant is added, thus obtaining the target product.
Step 5, adding polyformaldehyde and fatty amine into a reaction system of the fourth product to perform a Mannich reaction to obtain a sulfur-phosphorus-nitrogen extreme pressure antiwear agent; wherein the content of the first and second substances,
the mannich reaction is:
in the formula, R 1 And R 2 Is C 4 ～C 12 Alkyl radical, R 3 Is C 8 ～C 18 An alkyl group; the reaction temperature of the Mannich reaction is 80-100 ℃, and the reaction time is 8-10h.
The method comprises the following specific steps:
adding 0.36mol of paraformaldehyde and 0.33mol of aliphatic amine into the system, controlling the reaction temperature at 80-100 ℃, reacting for 8-10h, cooling and filtering after the reaction is finished, and obtaining the target product.
The preparation method adopts the following mechanism:
1. according to the invention, the phosphate complex ester and sulfoalkyl structure are introduced into the structure, so that the structure can improve the stability of-P = S-in the structure on one hand, and effectively improve the reaction activity of Mannich reaction of the substrate on the other hand; the synthesis method can effectively reduce the reaction temperature and shorten the reaction time, and can reduce the occurrence of side reactions based on the reasons, thereby effectively reducing the generation of acid gas and the equipment corrosion caused by the acid gas, and having better environmental benefit;
2. according to the method, nitrogen is introduced into the product through a Mannich reaction, but not through a salt forming reaction, so that the existence proportion of free amine in the product is effectively reduced (through repeated research and reference of documents, the content of active sulfur in a system is increased due to the existence of the free amine, and the active sulfur is the most main factor causing serious corrosion of a copper sheet), and therefore, the product has certain advantages in the detection of the corrosion of the copper sheet;
3. the synthetic method of the invention well ensures the element content of sulfur (the content is not less than 12%) and phosphorus (the content is not less than 8%) in the product, so the product has good performance on extreme pressure abrasion resistance.
Example 1:
the invention provides a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent, which comprises the following steps:
step 1, a first esterification reaction: adding 0.32mol of O-n-butyl-O' -2-ethylhexyl dialkyl dithiophosphate into a four-mouth bottle provided with a thermometer, a reflux condenser tube, a dropping funnel and a stirrer, slowly dropping 0.33mol of propylene oxide into a reaction system under the stirring condition, controlling the temperature of the system to be not more than 30 ℃ in the dropping process, preferably controlling the dropping time to be 45min, raising the temperature to 75 ℃ after the dropping is finished, carrying out heat preservation reaction for 1-2h, detecting the acid value of the system in the process, and carrying out the next reaction when the acid value is not more than 10 KOHmg/g.
Step 2, carrying out a second esterification reaction: slowly dripping PCl into the reaction system through a dripping funnel 3 The dropping time is preferably 45min, and the reaction temperature is controlled between-5 ℃ and 0 ℃ during the dropping processAnd continuously reacting for 1.5 hours after the dropwise adding is finished, wherein nitrogen purging is required in the whole reaction process so that the generated HCl is discharged as soon as possible to reduce the occurrence of side reactions.
And 3, substitution reaction: adding 0.31mol of monochloromethyl sulfide into the reaction system, then raising the temperature to 100 ℃, and continuing to react for 5 hours to obtain the target product.
And 4, oxidation reaction: slowly adding 0.35mol of m-CPBA into the reaction system, controlling the temperature of the system not to exceed 0 ℃ in the process, and continuing to react for 2 hours after the oxidant is added, thus obtaining the target product.
And step 5, mannich reaction: adding 0.36mol of paraformaldehyde and 0.33mol of dodecylamine into the system, controlling the reaction temperature at 90 ℃, reacting for 90 hours, cooling and filtering after the reaction is finished, and obtaining the target product.
Example 2:
the invention provides a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent, which comprises the following steps:
the O-n-butyl-O '-2-ethylhexyl dialkyldithiophosphate is replaced by O-sec-butyl-O' -2-ethylhexyl dialkyldithiophosphate and the other operations are in accordance with those described in example 1.
Example 3:
the invention provides a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent, which comprises the following steps:
the O-n-butyl-O '-2-ethylhexyl dialkyldithiophosphate is replaced by O, O' -di-2-ethylhexyl dialkyldithiophosphate and the other operations are in accordance with those described in example 1.
Example 4:
the invention provides a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent, which comprises the following steps:
the dodecylamine is exchanged for the isomeric ditridecylamine, the rest remaining the same as in example 1.
Example 5:
the invention provides a preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent, which comprises the following steps:
the dodecylamine was changed to octadecylamine, the remainder was in accordance with example 1.
Comparative examples 1 and 2 will be synthesized according to the method described in CN1033811a and US5573696 a.
And (3) testing:
the results of detecting the copper sheet corrosion and the extreme pressure anti-wear property (5 percent is dissolved in 80w/90 thickened oil) of the sulfur-nitrogen-phosphorus extreme pressure anti-wear agent synthesized by the synthesis method are shown in the following table:
from the above results, it can be seen that: when a product is synthesized according to CN1033811A, on one hand, a certain amount of acid gas is generated (analysis shows that part of-P = S-in the structure is converted into-P = O-), so that equipment is corroded and the environment is polluted, and on the other hand, when the acid gas is compatible with a gear oil complexing agent, the copper sheet corrosion effect is poor; when the product is synthesized according to US5573696A, the single agent copper sheet has poor corrosion effect.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a sulfur-phosphorus-nitrogen extreme pressure antiwear agent is characterized by comprising the following steps:
dripping propylene oxide into dialkyl dithiophosphate to perform a first esterification reaction to obtain a first product; wherein the first esterification reaction is:
R 1 and R 2 Is C 4 ～C 12 An alkyl group;
dropwise adding phosphorus chloride into the reaction system of the first product to perform a second esterification reaction to obtain a second product; wherein the second esterification reaction is:
adding monochloro-methyl sulfide into the reaction system of the second product to carry out substitution reaction to obtain a third product; wherein the substitution reaction is:
adding m-CPBA into the reaction system of the third product to carry out oxidation reaction to obtain a fourth product; wherein the oxidation reaction is as follows:
adding polyformaldehyde and fatty amine into a reaction system of the fourth product to carry out a Mannich reaction to obtain a sulfur-phosphorus-nitrogen extreme pressure antiwear agent; wherein the Mannich reaction is:
R 3 is C 8 ～C 18 An alkyl group.
2. The process according to claim 1, wherein the first esterification reaction is carried out at a reaction temperature of 70 to 85 ℃ for a reaction time of 1 to 2 hours;
the acid value of the system is detected during the reaction, and when the acid value is not more than 10KOHmg/g, the second esterification reaction can be carried out.
3. The method of claim 1, wherein the second esterification reaction is carried out at a temperature of-5 to 0 ℃ for a period of 1 to 3 hours.
4. The process according to claim 1, wherein the substitution reaction is carried out at a temperature of 80 to 110 ℃ and for a time of 4 to 6 hours.
5. The method of claim 1, wherein the oxidation reaction is carried out at a temperature of no more than 0 ℃ for a time of 1 to 2 hours.
6. The process according to claim 1, wherein the Mannich reaction is carried out at a reaction temperature of from 80 to 100 ℃ and for a reaction time of from 8 to 10 hours.
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| CN1033811A (en) * | 1987-12-28 | 1989-07-12 | 中国石油化工总公司石油化工科学研究院 | A kind of preparation method of S-P-N type extrme-pressure wearing agent |
| JPH09235578A (en) * | 1996-02-29 | 1997-09-09 | Ethyl Corp | Oil-soluble additive containing phosphorus and nitrogen atoms |
| CN1673322A (en) * | 2004-03-24 | 2005-09-28 | 中国石油天然气股份有限公司 | Prepn of nitrogen sulfate phosphate type phosphorus-containing agent |
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| US7049456B2 (en) * | 2003-03-07 | 2006-05-23 | Bayer Cropscience Lp | Method for preparing O,O-dialkyl S-[2-(alkylthio)alkyl] phosphorodithioates |
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| CN1033811A (en) * | 1987-12-28 | 1989-07-12 | 中国石油化工总公司石油化工科学研究院 | A kind of preparation method of S-P-N type extrme-pressure wearing agent |
| JPH09235578A (en) * | 1996-02-29 | 1997-09-09 | Ethyl Corp | Oil-soluble additive containing phosphorus and nitrogen atoms |
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