CN110343132B - Preparation method and application of branched alkyl phosphonic acid dialkyl ester - Google Patents
Preparation method and application of branched alkyl phosphonic acid dialkyl ester Download PDFInfo
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- CN110343132B CN110343132B CN201910593217.0A CN201910593217A CN110343132B CN 110343132 B CN110343132 B CN 110343132B CN 201910593217 A CN201910593217 A CN 201910593217A CN 110343132 B CN110343132 B CN 110343132B
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- -1 alkyl phosphonic acid Chemical compound 0.000 title claims abstract description 40
- 150000002148 esters Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 35
- 238000007259 addition reaction Methods 0.000 claims abstract description 27
- 239000004711 α-olefin Substances 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000011949 solid catalyst Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000010687 lubricating oil Substances 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 14
- 239000002243 precursor Substances 0.000 description 14
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 13
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 7
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 7
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000004949 mass spectrometry Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 5
- 239000007866 anti-wear additive Substances 0.000 description 5
- QBCOASQOMILNBN-UHFFFAOYSA-N didodecoxy(oxo)phosphanium Chemical compound CCCCCCCCCCCCO[P+](=O)OCCCCCCCCCCCC QBCOASQOMILNBN-UHFFFAOYSA-N 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical class CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 3
- 101150116295 CAT2 gene Proteins 0.000 description 3
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 3
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 3
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940069096 dodecene Drugs 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical group C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 238000007342 radical addition reaction Methods 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical compound CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 description 2
- POWRQOUEUWZUNQ-UHFFFAOYSA-N didecyl phosphite Chemical compound CCCCCCCCCCOP([O-])OCCCCCCCCCC POWRQOUEUWZUNQ-UHFFFAOYSA-N 0.000 description 2
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229960001777 castor oil Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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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
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- 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
- C07F9/4084—Esters with hydroxyaryl compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
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Abstract
The invention discloses a preparation method and application of branched alkyl phosphonic acid dialkyl ester. The invention takes alpha-olefin dimerization product vinylidene olefin and dialkyl phosphite as raw materials to prepare branched alkyl phosphonic acid dialkyl ester by the reverse Ma's addition reaction in the presence of a solid catalyst. The solid catalyst is prepared by using soluble manganese salt as a manganese source and diammonium hydrogen phosphate as a phosphorus source through a hydrothermal method and high-temperature roasting. The catalyst has good catalytic activity for synthesizing the branched alkyl phosphonic acid dialkyl ester by the reverse Markov addition reaction, the yield of the branched alkyl phosphonic acid dialkyl ester can reach more than 90 percent, and the purity can reach more than 95 percent. The catalyst used in the method has simple preparation process, is easy to separate and recycle and implement industrially, and the obtained product of the dialkyl branched alkyl phosphonate has excellent extreme pressure antiwear property as the extreme pressure antiwear agent of the lubricating oil.
Description
Technical Field
The invention belongs to the technical field of preparation of lubricating oil extreme pressure antiwear agents, and particularly relates to synthesis of branched alkyl phosphonic acid dialkyl ester and application of the branched alkyl phosphonic acid dialkyl ester as a lubricating oil extreme pressure antiwear agent.
Background
The phosphorus element is a commonly used active element in the lubricating oil, and the phosphorus-containing compound is used as an extreme pressure antiwear additive, so that the extreme pressure antiwear performance of the lubricating oil can be effectively improved. Phosphoric acid esters or phosphorous acid esters are commonly used phosphorus-containing extreme pressure antiwear additives. Among them, dialkyl phosphites, such as di-n-butyl phosphite (T304), have been widely noticed as a common antiwear additive in practical application research. The short-chain dialkyl phosphite has certain extreme pressure antiwear performance, but is easy to hydrolyze due to active chemical properties, so that the application of the dialkyl phosphite as an extreme pressure antiwear agent is limited. In view of the above, it is necessary to develop a phosphorus-containing extreme pressure anti-wear agent which is synthesized from a short-chain dialkyl phosphite as a raw material by a transesterification reaction, a radical addition reaction, or the like and has excellent stability.
The long-chain dialkyl phosphite has better hydrolytic stability, and can be prepared by ester exchange reaction of long-chain fatty alcohol and short-chain dialkyl phosphite. Li Sonlin et al synthesized didodecyl phosphite (Li Sonlin, bin, Wahua ying. synthesis and friction performance research of didodecyl phosphite [ J ]. lubrication and sealing, 2017, 42 (01): 137-140.) by using di-n-butyl phosphite and dodecanol as raw materials through transesterification. The synthesized didodecyl phosphite ester has good extreme pressure wear resistance as a water-based lubricating extreme pressure additive. The dialkyl phosphites can also be reacted with compounds containing carbon-carbon double bonds by free-radical addition to give organic compounds containing carbon-phosphorus bonds. BiresawG et al synthesized phosphorus-containing extreme pressure antiwear agents from methyl oleate and dialkyl phosphite esters as raw materials under the action of a free radical initiator, lauroyl peroxide, and tested and studied the lubricating Properties (Biresawg, Bantchev GB. tribological Properties of biological esters J Am Oil Chem Soc 2013,90(6): 891-902.). Tayama O et al catalyzed the synthesis of organic compounds containing carbon-phosphorus bonds by free radical addition of linear alpha-olefins and dialkyl phosphites over manganese acetate as a catalyst (Tayama O, Nakano A, Iwahama T, Sakaguchi S, Ishii Y. phosphorylation of olefins with dialkyl phosphates catalyzed by Mn (III) under air. J Org Chem 2004,69(16): 5494-5496.).
Vinylidene olefins are olefinic compounds containing branched structures which can be prepared by dimerization of alpha-olefins (Janiak C. metallocene and related catalysts for olephin, alkyl and silane polymerization and oligomerization. code Chem Rev 2006,250(1-2): 66-94.). Due to the branched chain structure and unsaturated double bonds, the double bond functionalization reaction of the vinylidene olefin can synthesize various special chemicals with potential application, such as binders, flavors, synthetic lubricants, fuel additives and the like. The research on the preparation of dialkyl branched alkylphosphonate by the reverse mahalanobis addition reaction of vinylidene olefin, which is a dimerization product of alpha-olefin, and dialkyl phosphite, and the application of the dialkyl branched alkylphosphonate as an extreme pressure antiwear additive of lubricating oil, is rarely reported through reference to the literature.
Disclosure of Invention
The invention aims to provide a preparation method and application of branched alkyl dialkyl phosphonate.
The invention is realized by the following technical scheme:
the invention provides a method for synthesizing branched alkyl dialkyl phosphonate by inverse Ma addition reaction, which is characterized in that alpha-olefin dimerization products of vinylidene olefin and dialkyl phosphite are taken as raw materials, the inverse Ma addition reaction is carried out in the presence of a solid catalyst to prepare branched alkyl dialkyl phosphonate, the alpha-olefin dimerization product of vinylidene olefin: the molar ratio of the dialkyl phosphite is 1: 1-6, the dosage of the catalyst is 0.5% -20% of the total mass of the raw materials, the reaction temperature is controlled at 50-120 ℃, and the reaction time is 1-10 h. After the reaction is finished, the catalyst is collected by centrifugation, and the dialkyl phosphite is removed by reduced pressure distillation to obtain the target product of the dialkyl branched alkyl phosphonate.
α -olefin dimerization equation:
the inverse mahalanobis addition reaction equation of vinylidene olefin and dialkyl phosphite, which are the dimerization products of alpha-olefin:
in the formula, R1Is C1～C15A saturated hydrocarbon group of (a); r2Is phenyl or C1～C12A saturated hydrocarbon group of (2).
In the above scheme, the vinylidene olefin used in the anti-Ma addition reaction is a dimerization product of alpha-olefin, wherein the alpha-olefin is C4～C16Any of the linear alpha olefins.
In the above scheme, the dialkyl phosphite used in the anti-mahalanobis addition reaction, wherein the alkyl is phenyl or C1～C12And saturated hydrocarbon groups such as diphenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, and the like.
In the scheme, the solid catalyst is prepared by taking soluble manganese salt as a manganese source and diammonium hydrogen phosphate as a phosphorus source through a hydrothermal method and high-temperature roasting, and the preparation steps of the catalyst are as follows:
(1) adding the required raw materials into a hydrothermal reaction kettle according to a ratio, fully stirring and uniformly mixing;
(2) reacting the hydrothermal reaction kettle (1) at 80-200 ℃ for 12-72 h;
(3) fully washing the obtained solid with deionized water, and drying to obtain a catalyst precursor;
(4) roasting the obtained catalyst precursor for 2-10 h at the temperature of 200-600 ℃;
(5) grinding the obtained product to obtain the solid catalyst.
The soluble manganese salt used by the hydrothermal synthesis method is any one of manganese nitrate, manganese acetate, manganese chloride, manganese bromide and manganese sulfate, and the molar ratio of the components in the catalyst is as follows: mn, P is 1: 2-10, Mn is H2O＝1:20～200。
The invention provides the branched alkyl phosphonic acid dialkyl ester prepared by the synthesis method.
The invention provides an application of the branched alkyl phosphonic acid dialkyl ester as an extreme pressure antiwear additive of lubricating oil.
The invention has the beneficial effects that:
1) the synthetic method has simple operation process, high atom utilization rate of raw materials and easy industrial implementation;
2) the solid catalyst used in the invention has simple preparation process, has good catalytic activity for catalyzing the reverse Ma addition reaction of alpha-olefin dimerization products, namely vinylidene olefin and dialkyl phosphite, and can be recycled for many times;
3) the branched alkyl phosphonic acid dialkyl ester synthesized by the invention is used as an extreme pressure antiwear agent of lubricating oil, and has excellent extreme pressure antiwear performance.
Drawings
FIG. 1 is an XRD pattern of Cat-1, a catalyst prepared in example 1.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
and (3) dimerization reaction: in a three-necked flask equipped with a magnetic stirrer, 15.429g (137.5mmol) of n-octene was added as follows: methylaluminoxane: the molar ratio of alpha-olefin was 1:10:275, and 0.146g (0.5mmol) of zirconocene dichloride and 2.901g (5mmol) of methylaluminoxane were sequentially added to the glove box. Stirring and reacting for 12h at 25 ℃, adding water to quench the reaction after the reaction is finished, washing with water, extracting with petroleum ether, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain 14.972g of octene dimerization product, wherein the purity of the product is 95.26% by gas chromatography.
N-octene dimerization equation:
preparing a catalyst: taking MnSO4·H2O 8.451g(0.05mol)，(NH4)2HPO419.809g (0.15mol) and 90.000g (5mol) of deionized water are added into a hydrothermal reaction kettle, fully stirred and mixed evenly; and (3) placing the prepared reaction kettle in a drying oven at 100 ℃ for reaction for 24 hours, washing and drying to obtain a precursor, roasting the obtained precursor in a muffle furnace at 400 ℃ for 4 hours, and grinding to obtain the required catalyst Cat-1. FIG. 1 is an XRD pattern of the Cat-1 catalyst. By Jade5.0X-ray analysis software combines with standard PDF card library to search phase of sample, find XRD atlas and manganese pyrophosphate (Mn) of Cat-12P2O7) The peak position and the peak intensity are basically consistent, and the Cat-1 is determined to be manganese pyrophosphate (Mn)2P2O7)。
Anti-mahalanobis addition reaction: 6.733g (0.03mol) of branched vinylidene olefin serving as an octene dimerization product, 20.715g (0.15mol) of diethyl phosphite and 0.274g (1 percent of Cat-1 catalyst relative to the total mass of reactants) of Cat-1 catalyst are taken and placed in a three-neck flask provided with a magnetic stirrer, the temperature is increased to 90 ℃ for reaction for 10 hours, the Cat-1 catalyst is removed by washing and filtering after the reaction is finished, and the obtained liquid is subjected to reduced pressure distillation to remove the diethyl phosphite to obtain oily liquid branched alkyl diethyl phosphonate (AW-1). The yield of the target product is 93 percent and the purity of the product is 98.68 percent after the analysis of a gas chromatographic analyzer. The molecular weight of the product was 326 as determined by mass spectrometry.
Anti-mahalanobis addition reaction equation:
example 2:
and (3) dimerization reaction: in a three-necked flask equipped with a magnetic stirrer were added 11.572g of n-hexene (137.5mmol), as per zirconocene dichloride: methylaluminoxane: the molar ratio of alpha-olefin was 1:10:275, and 0.146g (0.5mmol) of zirconocene dichloride and 2.901g (5mmol) of methylaluminoxane were sequentially added to the glove box. Stirring and reacting for 12h at 25 ℃, adding water to quench the reaction after the reaction is finished, washing with water, extracting with petroleum ether, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain 11.036g of hexene dimer product, wherein the purity of the product is 96.37% by gas chromatography.
N-hexene dimerization equation:
preparing a catalyst: taking Mn (NO)3)2 8.948g(0.05mol)，(NH4)2HPO433.015g (0.25mol) and 72.000g (4mol) of deionized water are added into the hydrothermal reaction kettle, fully stirred and mixed evenly; and (3) placing the prepared reaction kettle in a drying oven at 150 ℃ for reacting for 36h, washing and drying to obtain a precursor, roasting the obtained precursor in a muffle furnace at 500 ℃ for 5h, and grinding to obtain the required catalyst Cat-2.
Anti-mahalanobis addition reaction: 6.733g (0.04mol) of branched vinylidene olefin serving as a hexene dimerization product, 23.293g (0.12mol) of dibutyl phosphite and 1.501g (5 percent of catalyst of Cat-2 relative to the total mass of reactants) of catalyst are placed in a three-neck flask provided with a magnetic stirrer, the temperature is increased to 70 ℃ for reaction for 6 hours, the catalyst of Cat-2 is removed by washing and filtering after the reaction is finished, and the dibutyl phosphite is removed from the obtained liquid through reduced pressure distillation to obtain oily liquid branched alkyl dibutyl phosphonate (AW-2). The yield of the target product is 95 percent and the purity of the product is 98.23 percent after the analysis of a gas chromatographic analyzer. The molecular weight of the product was 362 by mass spectrometry.
Anti-mahalanobis addition reaction equation:
example 3:
and (3) dimerization reaction: in a three-necked flask equipped with a magnetic stirrer were added 19.287g (137.5mmol) of n-decene as the molar ratio of zirconocene dichloride: methylaluminoxane: the molar ratio of alpha-olefin was 1:10:275, and 0.146g (0.5mmol) of zirconocene dichloride and 2.901g (5mmol) of methylaluminoxane were sequentially added to the glove box. Stirring and reacting for 12h at 25 ℃, adding water to quench the reaction after the reaction is finished, washing with water, extracting with petroleum ether, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain 18.919g of a decene dimerization product, wherein the purity of the product is 97.10% as measured by gas chromatography.
N-decene dimerization equation:
preparing a catalyst:taking MnCl2 6.292g(0.05mol)，(NH4)2HPO452.824g (0.40mol) and 45.000g (2.5mol) of deionized water are added into the hydrothermal reaction kettle, fully stirred and mixed evenly; and (3) placing the prepared reaction kettle in an oven at 170 ℃ for reaction for 72h, washing and drying to obtain a precursor, roasting the obtained precursor in a muffle furnace at 200 ℃ for 6h, and grinding to obtain the required catalyst Cat-3.
Anti-mahalanobis addition reaction: 8.416g (0.03mol) of branched vinylidene olefin serving as a decene dimerization product, 28.085g (0.12mol) of diphenyl phosphite and 3.650g (10 percent of catalyst, relative to the total mass of reactants) of Cat-3 are taken and placed in a three-neck flask provided with a magnetic stirrer, the temperature is increased to 110 ℃ for reaction for 8 hours, the Cat-3 catalyst is removed by washing and filtering after the reaction is finished, and the diphenyl phosphite is removed from the obtained liquid through reduced pressure distillation to obtain oily liquid branched alkyl diphenyl phosphonate (AW-3). The yield of the target product is 94 percent and the purity of the product is 97.64 percent after the analysis of a gas chromatographic analyzer. The molecular weight of the product was 514 as determined by mass spectrometry.
Anti-mahalanobis addition reaction equation:
example 4:
and (3) dimerization reaction: in a three-necked flask equipped with a magnetic stirrer were added 23.126g of n-dodecene (137.5mmol) as a solution of zirconocene dichloride: methylaluminoxane: the molar ratio of alpha-olefin was 1:10:275, and 0.146g (0.5mmol) of zirconocene dichloride and 2.901g (5mmol) of methylaluminoxane were sequentially added to the glove box. Stirring and reacting for 12h at 25 ℃, adding water to quench the reaction after the reaction is finished, washing with water, extracting with petroleum ether, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain 22.829g of dodecene dimer product, wherein the purity of the product is 96.11% as measured by gas chromatography.
N-dodecene dimerization equation:
preparing a catalyst: taking Mn (OAc)2 8.650g(0.05mol)，(NH4)2HPO466.030g (0.50mol) and 81.000g (4.50mol) of deionized water are added into the hydrothermal reaction kettle, fully stirred and mixed evenly; and (3) placing the prepared reaction kettle in an oven at 80 ℃ for reaction for 48h, washing and drying to obtain a precursor, roasting the obtained precursor in a muffle furnace at 600 ℃ for 8h, and grinding to obtain the required catalyst Cat-4.
Anti-mahalanobis addition reaction: 13.455g (0.04mol) of branched vinylidene olefin serving as a dodecene dimerization product, 22.002g (0.20mol) of dimethyl phosphite and 0.177g (0.5 percent relative to the total mass of reactants) of Cat-4 catalyst are taken and placed in a three-neck flask provided with a magnetic stirrer to be heated to 60 ℃ for reaction for 10 hours, after the reaction is finished, the Cat-4 catalyst is removed by washing and filtering, and the dimethyl phosphite is removed from the obtained liquid through reduced pressure distillation to obtain oily liquid branched chain alkyl dimethyl phosphonate (AW-4). The yield of the target product is 96 percent and the purity of the product is 96.74 percent after the analysis of a gas chromatographic analyzer. The molecular weight of the product was 446 as determined by mass spectrometry.
Anti-mahalanobis addition reaction equation:
example 5:
and (3) dimerization reaction: in a three-necked flask equipped with a magnetic stirrer were added 12.334g (55mmol) of n-hexadecene as follows zirconocene dichloride: methylaluminoxane: the molar ratio of alpha-olefin was 1:10:275, and 0.058g (0.2mmol) of zirconocene dichloride and 1.160g (2mmol) of methylaluminoxane were sequentially added to the glove box. Stirring and reacting for 12h at 25 ℃, adding water to quench the reaction after the reaction is finished, washing with water, extracting with petroleum ether, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain 11.867g of hexadecene dimerization product, wherein the purity of the product is 96.95% by gas chromatography.
N-hexadecene dimerization equation:
preparing a catalyst: taking MnBr2 8.590g(0.04mol)，(NH4)2HPO410.565g (0.08mol) and 21.600g (1.20mol) of deionized water are added into the hydrothermal reaction kettle, fully stirred and mixed evenly; and (3) placing the prepared reaction kettle in a 200 ℃ drying oven for reaction for 12h, washing and drying to obtain a precursor, roasting the obtained precursor in a 300 ℃ muffle furnace for 10h, and grinding to obtain the required catalyst Cat-5.
Anti-mahalanobis addition reaction: 8.970g (0.02mol) of branched vinylidene olefin which is a product of dimerization of hexadecene, 6.125g (0.02mol) of dioctyl phosphite and 3.019g (20 percent of catalyst, relative to the total mass of reactants) of Cat-5 are taken and placed in a three-neck flask which is provided with a magnetic stirrer, the temperature is increased to 120 ℃ for reaction for 3h, after the reaction is finished, the Cat-5 catalyst is removed by washing and filtering, and the obtained liquid is subjected to reduced pressure distillation to remove the dioctyl phosphite to obtain oily liquid branched chain alkyl dioctyl phosphonate (AW-5). The yield of the target product is 96.38 percent and the purity of the product is 97.41 percent after the analysis of a gas chromatographic analyzer. The molecular weight of the product was 754 as determined by mass spectrometry.
Anti-mahalanobis addition reaction equation:
example 6:
and (3) dimerization reaction: in a three-necked flask equipped with a magnetic stirrer were added 10.792g (55mmol) of n-tetradecene, as described by zirconocene dichloride: methylaluminoxane: the molar ratio of alpha-olefin was 1:10:275, and 0.058g (0.2mmol) of zirconocene dichloride and 1.160g (2mmol) of methylaluminoxane were sequentially added to the glove box. Stirring and reacting for 12h at 25 ℃, adding water to quench the reaction after the reaction is finished, washing with water, extracting with petroleum ether, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain 10.219g of tetradecene dimer product, wherein the purity of the product is 95.37% by gas chromatography.
N-tetradecene dimerization equation:
preparing a catalyst: taking MnCl2 6.292g(0.05mol)，(NH4)2HPO439.618g (0.30mol) and 18.000g (1.0mol) of deionized water are added into the hydrothermal reaction kettle, fully stirred and mixed evenly; and (3) placing the prepared reaction kettle in a 110 ℃ drying oven for reaction for 50h, washing and drying to obtain a precursor, roasting the obtained precursor in a 450 ℃ muffle furnace for 2h, and grinding to obtain the required catalyst Cat-6.
Anti-mahalanobis addition reaction: 7.849g (0.02mol) of branched vinylidene olefin serving as a dimerization product of tetradecene, 43.475g (0.12mol) of didecyl phosphite and 7.699g (15 percent of catalyst relative to the total mass of reactants) are taken and placed in a three-neck flask provided with a magnetic stirrer to be heated to 50 ℃ for reaction for 1h, the Cat-6 catalyst is removed by washing and filtering after the reaction is finished, and the obtained liquid is subjected to reduced pressure distillation to remove the didecyl phosphite to obtain oily liquid branched alkyl phosphonic acid didecyl ester (AW-6). The yield of the target product is 95.11 percent and the purity of the product is 96.31 percent after the analysis of a gas chromatographic analyzer. The molecular weight of the product was 754 as determined by mass spectrometry.
Anti-mahalanobis addition reaction equation:
example 7:
and (3) dimerization reaction: in a three-necked flask equipped with a magnetic stirrer were added 6.172g (55mmol) of n-octene (Invitrogen), as per the molar ratio of zirconocene dichloride: methylaluminoxane: the molar ratio of alpha-olefin was 1:10:275, and 0.058g (0.2mmol) of zirconocene dichloride and 1.160g (2mmol) of methylaluminoxane were sequentially added to the glove box. Stirring and reacting for 12h at 25 ℃, adding water to quench the reaction after the reaction is finished, washing with water, extracting with petroleum ether, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain 5.985g of octene dimerization product, wherein the purity of the product is 98.17% by gas chromatography.
N-octene dimerization equation:
preparing a catalyst: taking Mn (OAc)2 8.650g(0.05mol)，(NH4)2HPO452.824g (0.40mol) and 54.000g (3.0mol) of deionized water are added into the hydrothermal reaction kettle, fully stirred and mixed evenly; and (3) placing the prepared reaction kettle in a drying oven at 100 ℃ for reaction for 30h, washing and drying to obtain a precursor, roasting the obtained precursor in a muffle furnace at 400 ℃ for 6h, and grinding to obtain the required catalyst Cat-7.
Anti-mahalanobis addition reaction: 4.488g (0.02mol) of branched vinylidene olefin serving as an octene dimerization product, 16.734g (0.04mol) of didodecyl phosphite and 2.122g (10 percent of Cat-7 catalyst relative to the total mass of reactants) of catalyst are taken and placed in a three-neck flask provided with a magnetic stirrer, the temperature is increased to 80 ℃ for reaction for 9 hours, the Cat-7 catalyst is removed by washing and filtering after the reaction is finished, and the obtained liquid is subjected to reduced pressure distillation to remove the didodecyl phosphite to obtain oily liquid branched alkyl didodecyl phosphonate (AW-7). The yield of the target product is 95.34 percent and the purity of the product is 95.56 percent after the analysis of a gas chromatographic analyzer. The molecular weight of the product was 642 by mass spectrometry.
Anti-mahalanobis addition reaction equation:
the compounds AW-1 to AW-7 prepared in examples 1 to 7 were added to the base oil (liquid paraffin, castor oil, polyethylene glycol 400, PAO8) in an amount of 1.0 wt.% and mixed thoroughly at room temperature to obtain an additive-containing lubricating oil. A four-ball friction wear tester is adopted to respectively test the antifriction and anti-wear performance and the extreme pressure performance of the lubricating oil containing the AW-1-AW-7 additives according to national standards SH/T0189-92 and GB/T12583-1998, and a comparison experiment is carried out with the antiwear agent tricresyl phosphate (TCP) in the prior art.
As can be seen from Table 1, the reaction ofCompared with base oil and tricresyl phosphate (TCP) which is an antiwear agent in the prior art, when the addition amount of the branched alkyl dialkyl phosphonate is 1.0 percent, the average friction coefficient is reduced, and the bearing capacity P is improvedBValue and extreme pressure Property PDThe value is obviously improved, and the abrasion spot diameter (WSD) is obviously reduced, which shows that the branched alkyl phosphonic acid dialkyl ester has excellent extreme pressure antiwear performance as the lubricating oil extreme pressure antiwear agent.
TABLE 1 results of testing antifriction, antiwear and extreme pressure performances of four-ball friction and wear testing machine
Claims (4)
1. A method for preparing branched alkyl phosphonic acid dialkyl ester is characterized in that:
taking vinylidene olefin and dialkyl phosphite ester as raw materials, and carrying out anti-Ma addition reaction in the presence of a solid catalyst to prepare branched alkyl dialkyl phosphonate, vinylidene olefin: the molar ratio of the dialkyl phosphite is 1: 1-6, the dosage of the catalyst is 0.5-20% of the total mass of the raw materials, the reaction temperature is controlled at 50-120 ℃, and the reaction time is 1-10 h; after the reaction is finished, centrifugally collecting the catalyst, and carrying out reduced pressure distillation to remove dialkyl phosphite to obtain a target product, namely the branched alkyl phosphonic acid dialkyl ester;
the vinylidene olefin used in the anti-Markov addition reaction is an alpha-olefin dimerization product, wherein the alpha-olefin is C4 ~ C16Any of linear alpha-olefins;
the solid catalyst used in the anti-Markov addition reaction is prepared by using soluble manganese salt as a manganese source and diammonium hydrogen phosphate as a phosphorus source through a hydrothermal method and high-temperature roasting; the preparation steps of the solid catalyst are as follows:
(1) adding the required raw materials into a hydrothermal reaction kettle according to a ratio, fully stirring and uniformly mixing;
(2) reacting the hydrothermal reaction kettle (1) at 80-200 ℃ for 12-72 h;
(3) fully washing the obtained solid with deionized water, and drying to obtain a catalyst precursor;
(4) roasting the obtained catalyst precursor for 2-10 h at the temperature of 200-600 ℃;
(5) grinding the obtained product to obtain the solid catalyst.
2. The process for preparing dialkyl branched alkylphosphonates according to claim 1, wherein: the dialkyl phosphite used in the anti-Markovnikov addition reaction is one of dimethyl phosphite, diethyl phosphite and dibutyl phosphite.
3. The process for preparing dialkyl branched alkylphosphonates according to claim 1, wherein: the catalyst comprises the following components in molar ratio: mn: P =1: 2-10, Mn: H2O=1:20 ~ 200。
4. The process for preparing dialkyl branched alkylphosphonates according to claim 1, wherein: the soluble manganese salt is any one of manganese nitrate, manganese acetate, manganese chloride, manganese bromide and manganese sulfate.
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