CN105646187A - Preparation method of super-basic-value alkyl aryl salicylic acid calcium salt - Google Patents
Preparation method of super-basic-value alkyl aryl salicylic acid calcium salt Download PDFInfo
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- CN105646187A CN105646187A CN201610119411.1A CN201610119411A CN105646187A CN 105646187 A CN105646187 A CN 105646187A CN 201610119411 A CN201610119411 A CN 201610119411A CN 105646187 A CN105646187 A CN 105646187A
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- Prior art keywords
- salicylic acid
- super
- calcium salt
- alkyl aryl
- alkylaryl
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- -1 alkyl aryl salicylic acid calcium salt Chemical compound 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 52
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000003921 oil Substances 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 16
- 230000007935 neutral effect Effects 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000002199 base oil Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 46
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 13
- 150000001721 carbon Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 235000012255 calcium oxide Nutrition 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 239000002585 base Substances 0.000 abstract description 45
- 238000001816 cooling Methods 0.000 abstract description 10
- 239000004032 superbase Substances 0.000 abstract description 9
- 150000007525 superbases Chemical class 0.000 abstract description 9
- 239000003599 detergent Substances 0.000 abstract description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 1
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 1
- 239000004571 lime Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 22
- 150000003440 styrenes Chemical class 0.000 description 20
- 238000010792 warming Methods 0.000 description 18
- 229960001860 salicylate Drugs 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- 238000007259 addition reaction Methods 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 230000003068 static effect Effects 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- GTRHHOMIEMLBPC-UHFFFAOYSA-N 2-dodecoxybenzoic acid Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1C(O)=O GTRHHOMIEMLBPC-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JNGQJCLPTALFGM-UHFFFAOYSA-M C(C=1C(O)=CC=CC1)(=O)[O-].C(CCCCCCCCCCC)[Ca+] Chemical compound C(C=1C(O)=CC=CC1)(=O)[O-].C(CCCCCCCCCCC)[Ca+] JNGQJCLPTALFGM-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229960004025 sodium salicylate Drugs 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical class NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 1
- 206010070863 Toxicity to various agents Diseases 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- 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
- C10N2030/04—Detergent property or dispersant property
-
- 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
- C10N2030/52—Base number [TBN]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a super-basic alkyl aryl salicylic acid calcium salt, which comprises the following steps: (1) mixing solvent oil, base oil, lime and auxiliary accelerator to obtain a mixture, adding surfactant and alkyl aryl salicylic acid, stirring at 85-88 deg.C, and reacting for 50-60min to obtain neutral alkyl aryl salicylic acid calcium salt; (2) cooling, adding an accelerant and calcium hydroxide into the neutral alkyl aryl calcium salicylate, and introducing carbon dioxide to obtain the superbase number alkyl aryl calcium salicylate. The super-base-value alkyl aryl salicylic acid calcium salt provided by the embodiment of the invention has good oil solubility and good thermal stability, the base value can reach 400-450mgKOH/g, belongs to a super-base-value product, and makes up for the technical blank of the super-base-value product in the field of preparation of super-base-value oil-soluble salicylic acid detergent in the prior art.
Description
Technical field
The present invention relates to Speciality Petrochemicals category lube oil additive preparation field, in particular to the preparation method of a kind of super basicity alkyl aryl salicylic acid calcium salt.
Background technology
Calcium alkyl salicylate with high base number is one of conventional detergent for lubricating oil, and alkyl salicylate salt compounds, owing to having good high temperature detergency and certain antioxygen, resistance to corrosion, is widely used in lube oil additive field. The long-chain olefin offer that alkyl is generally provided by benzene or is made up of 15-30 carbon atom, also has both at home and abroad in the recent period and introduces the relevant report adopting styrene derivative to prepare.
One of most important index of Calcium Alkylsalicylate is the total base number of product, and conventional TBN represents (abbreviation of TotalBaseNumber). Total base number is made up of deposit base number RBN (abbreviation of ReserveBaseNumber) and direct base number DBN (abbreviation of DirectBaseNumber) in product. Base number unit mgKOH/g represents, namely containing the milligram number being equivalent to potassium hydroxide in every gram of product.
Calcium Alkylsalicylate product classification is pressed the height of total base number (TBN) and is distinguished; In general TBN is that about 150mgKOH/g is called middle base number product, about TBN300mgKOH/g is called high base number product, TBN is called super base number product more than 400mgKOH/g, the base number of product is more high, the acidity in oil product (in oil product use procedure can oxidized, condensation, become sour) material can be neutralized more many, neutralising capacity and peace and quiet effect will be more good, therefore the alkyl salicylate calcium product that base number is high is more popular with users, but the base number of corresponding product is more high, its production technology difficulty is more big.
In prior art, the preparation method of publication number a kind of calcium alkyl salicylate with high base number that has been the patent disclosure of CN1144216A, it is with dodecyl salicylic acid and calcium oxide for raw material, charging sequence with certain material proportion and regulation, synthesize the dodecyl calcium salicylate of total base number about 250mgKOH/g, a kind of alkyl salicylate as additive of lubricant oil disclosed in CN1199086A patent, utilize the consumption adjusting surfactant, synthesize, with calcium sulfonate with high base number, there is the dodecyl calcium salicylate of favorable compatibility.
With dodecyl salicylic acid and Calx for raw material in CN1202479A patent, with different charge ratios, by controlling the pH value of the reactant liquor of carbonating, the dodecyl calcium salicylate of different base number can be respectively synthesized out.
With dodecyl salicylic acid and Calx for raw material in CN1504451A patent, can being respectively synthesized out different base number alkyl sodium salicylate, the pH value of the reaction end reactant liquor of carbonating controls.
It is a kind of disclosed in CN1708471A patent that to utilize alkyl side chain be raw material more than the alkyl salicylate of 14 carbon, under the accelerator such as methanol and surfactant exist, generating alkaline alkyl sodium salicylate by carbon dioxide and Calx generation carbonation reaction, this patent further simultaneously discloses and utilizes alkyl salicylate and sulfonate with high base number reactant salt to generate alkaline alkyl Salicylate.
Patent US20040138076, it was recently reported that a kind of machine oil containing the salicylic high alkaline salicylate of styrene-based base. Wherein, styryl salicylic acid is prepared by >=8:1 molar ratio reaction by styrene and salicylic acid, and obtained high alkaline salicylate has the spatter property and non-oxidizability that are better than conventional salicylate detergent. But due to styrene and salicylism reaction feed intake mole relatively larger, obtained alkyl salicylate molecular weight is big, product acid number is low, it is difficult to synthesize more high base number product, simultaneously because styrene polymerization segment polarity contained in product is bigger, thus causing product oil soluble poor, therefore limiting it and using.
The general technological deficiency of prior art is in that to adopt numerous and diverse traditional mode of production dodecyl salicylic acid technique, namely prepare dodecylphenol for raw material by being alkylated reaction with laurylene with phenol, carry out carboxylation reaction again through Koble-Schmitt reaction and obtain dodecyl salicylic acid. Environment and water quality are had severe contamination by the raw material phenol used in such technique, and there is also the ortho position dodecylphenol that 10-25% activity is relatively low in product, and residual can not be degraded in the product, and environmental and biological materials is all had harmful effect by this.
Additionally, the carbon myristyl salicylic acid technique of external recent development and polystyrene-based salicylic acid technique, although there being bigger improvement in environmental protection and energy saving, but product stability and oil-soluble are poor, and the product base number of carbonating technique synthesis is generally relatively low, total base number is many at below 200mgKOH/g, even if the metathesis process product base number adopting cost high also surpasses only 300mgKOH/g.
In view of this, the special proposition present invention.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of super basicity alkyl aryl salicylic acid calcium salt, described method can overcome all defect of existing synthetic technology, easy and simple to handle, step is clear and definite, favorable reproducibility, by with alkylaryl salicylic acid for raw material, the alkylaryl salicylic acid calcium salt oil-soluble obtained is good, thermal stability is good, base number can reach 400-450mgKOH/g, belong to overbased product, compensate for the technological gap of the super base number oil-soluble super base number product of salicylic acid detersive preparation field in prior art.
In order to realize the above-mentioned purpose of the present invention, spy by the following technical solutions:
The preparation method that the present invention relates to a kind of super basicity alkyl aryl salicylic acid calcium salt, described method comprises the steps:
(1) mixture solvent naphtha, base oil, Calx, kicker being mixed, adds surfactant and alkylaryl salicylic acid, stirring reaction 50-60min at 85-88 DEG C, generates neutral alkylaryl salicylic acid calcium salt;
(2) lower the temperature and add accelerator and calcium hydroxide in described neutral alkylaryl salicylic acid calcium salt, and passing into carbon dioxide, obtaining super basicity alkyl aryl salicylic acid calcium salt;
Wherein, the salicylic chemical structural formula of described alkylaryl is:
R1��R2��R3��X1��X2��X3��X4It is separately hydrogen atom, alkoxyl or the straight or branched alkyl containing 1 to 10 carbon atom, R4��R5It is separately hydrogen atom or straight chained alkyl or the branched alkyl containing 1 to 30 carbon atom, and R4And R5Carbon number sum be not less than 4.
Raw material alkylaryl salicylic acid used by the present invention belongs to and itself belongs to a kind of new compound, prior art not yet finds relevant record, do not find to adopt it to prepare any record of super basicity alkyl aryl salicylic acid calcium salt as raw material, inventor has finally synthesized this material by a large amount of practices, and has prepared the super basicity alkyl aryl calcium salicylate product salt of good quality in strict accordance with the solution of the present invention enforcement as primary raw material with it.
Wherein, the salicylic preparation method of alkylaryl is as follows: in the presence of a catalyst, salicylic acid or derivatives thereof, styrene or derivatives thereof and alpha-olefin derived thing is made to react, raw material and catalyst are all that this area is common and be readily obtained, and the long-chain aralkyl that styrene derivative and alpha-olefin derived thing are collectively forming is that product provides necessary oil-soluble. Compared with being used alone the alkylated salicylamide acid derivative that aromatic olefin is alkylating reagent, oil-soluble is better, and acid number is higher, it is easier to synthesize the product of more high-alkali value.
Shown in the structural formula such as formula (1) of described salicylic acid or derivatives thereof:
X1��X2Being separately hydrogen atom or the direct-connected or branched paraffin containing 1 to 10 carbon atom, M is hydrogen atom or the straight or branched alkyl containing 1 to 10 carbon atom; It is highly preferred that X1��X2It is separately hydrogen atom or the direct-connected or branched paraffin containing 1 to 4 carbon atom.
Shown in the structural formula such as formula (2) of described styrene or derivatives thereof:
Wherein R1��R2��R3��X3��X4It is separately hydrogen atom or the direct-connected or branched paraffin containing 1 to 10 carbon atom, it is preferred to R1��R2��R3��X3��X4It is separately hydrogen atom or the direct-connected or branched paraffin containing 1 to 4 carbon atom, and meets R2And R3Carbon number sum be not more than 4, it is particularly preferred to ground, R1��R2��R3��X3��X4It is H atom.
Two kinds of raw materials of above formula (1) and formula (2), the optional scope of its substituent group is very extensive, and in theory, any substituent group that reaction does not produce impact is optionally substituted base.
Shown in the structural formula such as formula (3) of described alpha-olefin derived thing:
Wherein, R4��R5It is separately hydrogen atom or straight chained alkyl or the branched alkyl containing 1 to 28 carbon atom, and R4And R5Carbon number sum be not less than 4, it is more preferred to, R4��R5It is separately hydrogen atom or straight chained alkyl or the branched alkyl containing 1 to 28 carbon atom, and R4And R5Carbon number sum be not less than 12.
R4��R5Selection be directly connected to the character of product, it so that product has relatively large acid number, can be conducive to improving the content of product neutral salt containing carbon number time less; More Speleothem can be formed alkalescence and relatively roll into a ball by the neutral salt of high-load, thus being beneficial to the product preparing high base number, and correspondingly, its oil-soluble can be under some influence. Additionally the colloid in carbochain too short sawn timber is not easily stable, reserve alkali CaCO3Easily being precipitated out, therefore selecting suitable carbochain and structure is one of key technology preparing high-quality product. The synthesis route such as following chemical equation that concrete alkylaryl salicylic acid is total:
The alkylaryl salicylic acid being synthetically derived prepares super basicity alkyl aryl salicylic acid calcium salt by a series of step, in step (1), alkylaryl salicylic acid is neutralized reaction with Calx under the effect of kicker and solvent naphtha, base oil and surfactant, generating neutral alkylaryl Salicylate, Calx therein is the mixture of quick lime and Calx.Preferably, in Calx, quick lime is 1:(0.5-4 with the mol ratio of Calx), more preferably 1:(1-3), because needing strictly to control the water content of system in the process, therefore too many Calx can not be added, it is necessary to control suitable dosage.
In this step, solvent naphtha may be selected to be: any one or the multiple mixing in Petroleum, light aromatic hydrocarbons and pseudocumene, addition is the 210-250% of alkylaryl salicylic acid quality, and dosage is salicylic about 2 times of alkylaryl.
Preferably, any one or more mixing in low-viscosity mineral oil neutral oil, low-viscosity II class oil, III class oil, its addition is the 35-45% of described alkylaryl salicylic acid quality.
Preferably, surfactant is the mixture of any one or two kinds in stearic acid, aphthenic acids, and its addition is the 5-10% of described alkylaryl salicylic acid quality.
Preferably, kicker is C1-C4Organic carboxyl acid or binary acid, its addition is the 5-6% of described alkylaryl salicylic acid addition.
The present invention selects above-mentioned efficient kicker, it is possible to simplifies control process, accelerate height alkalization reaction process, improve the quality of product.
In step (2), after lowering the temperature, the described neutral alkylaryl salicylic acid calcium salt generated adds accelerator and calcium hydroxide, pass into carbon dioxide, form stable colloidal dispersion system, thus obtaining purpose product super basicity alkyl aryl salicylic acid calcium salt, in this step, the carbon dioxide passed into carries out carbonation reaction together with the calcium hydroxide added in remaining Calx in step (1) or step (2), obtain basic carbonate calcium salt, it is noted herein that what add is calcium hydroxide, rather than calcium oxide, because calcium hydroxide is more conducive to the carrying out of carbonation reaction, and certain micro-moisture is provided. it is dissolved in the colloid micelle of oil by newborn calcium carbonate parcel, form water-in-oil system, in system, calcium carbonate more many products total base number (TBN) of parcel is more high, in carbonation, major part calcium carbonate is wrapped up by micelle, wherein having a small amount of calcium carbonate and calcium hydroxide not to be wrapped up by micelle but remain stuck to colloid surface nor can be filtered, the base number that this moieties provides is called direct base number (DBN). product total base number (TBN) means the summation laying in base number and direct base number in product.
Preferably, in step (2), accelerator is the mixture of ammonia and ethyleneamines, addition is the 1-10% of described alkylaryl salicylic acid quality, the mol ratio of ammonia and ethyleneamines is preferably controlled in 1:(0.1-0.8) between, more excellent in 1:(0.1-0.3) between, ethyleneamines refers to the acyclic polymer series products of ethylenediamine, its carbon number can not be too high, otherwise can affect the activity of accelerator, the mixture of one or more being therefore preferably selected as in ethylenediamine, diethylenetriamine, triethylene tetramine.
In step (2), it is desirable to be cooled to less than 45 DEG C and add accelerator in described neutral alkylaryl salicylic acid calcium salt again or add accelerator and calcium hydroxide, it is preferable that be cooled between 35-39 DEG C.
Preferably, carbon dioxide intake is the 40-55% of the Calx gross mass added, and the speed that passes into of described carbon dioxide is 145-150mL/min. More excellent, described carbon dioxide intake is the 50-55% of the gross mass of the Calx wherein added.
Preferably, passing in the process of carbon dioxide, reaction temperature controls at 35-39 DEG C, and the response time controls at 2-3h.Reaction temperature and response time are preferably controlled in suitable scope, and the calcium salt properties of product so enabling to prepare are more excellent, obtain meeting the product of base number requirement.
Finally, the super basicity alkyl aryl salicylic acid calcium salt obtained passes through distillation, centrifugal step with purification. Wherein, in still-process, eliminating the solvent in system, accelerator and water, obtain the thick product of the alkylaryl calcium salicylate of super base number containing unreacted Calx, crystal form calcium carbonate and polarity thing impurity, the temperature of distillation is preferably controlled in 160-170 DEG C. Rotary process adopts high temperature and high speed centrifugation technique, obtains the super basicity alkyl aryl calcium salicylate product salt refined after centrifugal.
It is emphasized that if not otherwise indicated, the present invention is the numerical value of total base number (TBN) about the data of base number.
Compared with prior art, the invention have the benefit that
(1) preparation method of the present invention can according to user's request, by adjusting material proportion, produce the alkylaryl calcium salicylate product of different size base number, product total base number can reach 450mgKOH/g, compared to the total base number 250mgKOH/g of alkyl salicylate calcium product of the prior art, there is huge lifting;
(2) method of the present invention is easy and simple to handle, radically simplify processing step, step is clear and definite, favorable reproducibility, and the product alkylaryl salicylic acid calcium salt obtained can realize natural biology degraded, environmental protection, not polluting the environment, during concrete application, its solubility property is good, and purity is high, good stability, quality and yield are all of a relatively high;
(3) the raw material alkylaryl salicylic acid used by the present invention belongs to the chemical substance of a kind of new structure, not yet find relevant record at present, in prior art about the research of alkyl salicylate with report many, but the dissolubility of alkyl salicylate own is bad, acid number is low, it is difficult to synthesize more high base number product, these defects all limit it and further apply, the product of the present invention exactly solves puzzlement those skilled in the art's technical barrier for a long time, meets the urgent need of domestic and international high-end oil product user.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, it will be appreciated by those skilled in the art that the following example is merely to illustrate the present invention, and are not construed as restriction the scope of the present invention. Unreceipted actual conditions person in embodiment, conventionally the condition of condition or manufacturer's suggestion carries out. Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercially available acquisition.
Embodiment 1: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, add the salicyclic acid derivatives 69.1g (0.5mol) shown in pyrovinic acid 9.6g, formula (1), weigh the styrene derivative 67.7g (0.65mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 140 DEG C, dropping styrene derivative, 8h drips off. Weigh the alkene 117.8g (0.6mol) shown in formula (3) containing 14 carbon, disposable addition reaction bulb again, be warming up to 160 DEG C, stirring reaction 12 hours, stopped reaction. Cooling, adds 200ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylic acid product 239.6g, productivity 94.1%.Bromine number: 1.7gBr/100g, acid number: 115.8mgKOH/g. Storage at normal temperature after 30 days acid number do not decline, and without precipitation occur.
In above reaction raw materials, M, X in formula (1)1And X2It is H; R in formula (2)1��R2��R3��X3��X4It is H; R in formula (3)4For H, R5For straight chain C12Alkyl.
Embodiment 2: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, add the salicyclic acid derivatives 83.1g (0.5mol) shown in pyrovinic acid 9.6g, formula (1), weigh the styrene derivative 76.7g (0.65mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 120 DEG C, dropping styrene derivative, 0.5h drips off. Weigh the alkene 67.3g (0.6mol) shown in formula (3), disposable addition reaction bulb again, be warming up to 140 DEG C, stirring reaction 10 hours, stopped reaction. Cooling, adds 200ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylate product 213.7g, productivity 94.1%. Bromine number: 1.7gBr/100g, acid number: 1.3mgKOH/g.
In above reaction raw materials, in formula (1), M is methyl, X1For H, X2For 4-methyl; R in formula (2)1For methyl, R2��R3��X3��X4For H; In formula (3), R4 is H, R5It it is C6 alkyl.
Embodiment 3: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, add the salicyclic acid derivatives 136.1g (0.5mol) shown in pyrovinic acid 9.6g, formula (1), weigh the styrene derivative 76.7g (0.65mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 160 DEG C, dropping styrene derivative, 12h drips off. Weigh the alkene 67.3g (0.6mol) shown in formula (3), disposable addition reaction bulb again, be warming up to 180 DEG C, stirring reaction 24 hours, stopped reaction. Cooling, adds 200ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylic acid product 266.9g, productivity 95.3%. Bromine number: 1.8gBr/100g, acid number: 1.2mgKOH/g.
In above reaction raw materials, in formula (1), M is Na+, X1It is methyl, X2It it is side chain C8 alkyl; R in formula (2)1, R2��R3��X3For H, X4For 4-methyl; R in formula (3)4It is H, R5It it is C6 alkyl.
Embodiment 4: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, add the salicyclic acid derivatives 104.1g (0.5mol) shown in pyrovinic acid 9.6g, formula (1), weigh the styrene derivative 76.7g (0.65mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 140 DEG C, dropping styrene derivative, 12h drips off. Weigh the alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, disposable addition reaction bulb again, be warming up to 180 DEG C, stirring reaction 0.5 hour, stopped reaction. Cooling, adds 200ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylic acid product 396.9g, productivity 91.7%. Bromine number: 1.7gBr/100g, acid number: 70.2mgKOH/g.
In above reaction raw materials, in formula (1), M is normal-butyl, X1For H, X2It it is 4-methyl;R in formula (2)1For methyl, R2��R3��X3��X4For H; R in formula (3)4It is H, R5It it is side chain C28 alkyl.
Embodiment 5: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, add the salicyclic acid derivatives 75.6g (0.5mol) shown in Emathlite 10.0g, formula (1), weigh the styrene derivative 76.7g (0.65mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 140 DEG C, dropping styrene derivative, 12h drips off. Weigh the alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, disposable addition reaction bulb again, be warming up to 180 DEG C, stirring reaction 0.5 hour, stopped reaction. Cooling, adds 200ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylic acid product 376.8g, productivity 93.2%. Bromine number: 1.5gBr/100g. Acid number: 73.8mgKOH/g:
In above reaction raw materials, M, X in formula (1)1For H, X2It it is 4-methyl; R in formula (2)1, R2��R3��X3For H, X4For 4-methyl; R in formula (3)4It is H, R5It it is side chain C28 alkyl.
Embodiment 6: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 5000ml four-hole bottle, add the salicyclic acid derivatives 691.0g (5mol) shown in pyrovinic acid 96.0g, formula (1), weigh the styrene derivative 677.0g (6.5mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 140 DEG C, dropping styrene derivative, 8h drips off. Weigh the alkene 1178.0g (6.0mol) shown in formula (3) containing 14 carbon, disposable addition reaction bulb again, be warming up to 160 DEG C, stirring reaction 12 hours, stopped reaction. Cooling, adds 2000ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylic acid product 2412.0g, productivity 94.7%. Bromine number: 1.8gBr/100g, acid number: 114.3mgKOH/g.
In above reaction raw materials, M, X in formula (1)1And X2It is H; R in formula (2)1��R2��R3��X3��X4It is H; R in formula (3)4For H, R5For straight chain C12Alkyl.
Embodiment 7: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 1000ml four-hole bottle, add the salicyclic acid derivatives 209.2g (0.5mol) shown in Emathlite 10.0g, formula (1), weigh the styrene derivative 158.9g (0.65mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 140 DEG C, dropping styrene derivative, 12h drips off. Weigh the alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, disposable addition reaction bulb again, be warming up to 180 DEG C, stirring reaction 0.5 hour, stopped reaction. Cooling, adds 200ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylic acid product 566.0g, productivity 91.3%. Bromine number: 1.2gBr/100g. Acid number: 49.5mgKOH/g:
In above reaction raw materials, in formula (1), M is H, X1, X2It it is C10 straight chained alkyl; R in formula (2)1, R2��R3��X3For H, X4For C10 branched alkyl; R in formula (3)4It is H, R5It it is side chain C28 alkyl.
Embodiment 8: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 1500ml four-hole bottle, add the salicyclic acid derivatives 209.4g (0.5mol) shown in Emathlite 10.0g, formula (1), weigh the styrene derivative 434.4g (0.65mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 140 DEG C, dropping styrene derivative, 12h drips off. Weigh the alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, disposable addition reaction bulb again, be warming up to 180 DEG C, stirring reaction 0.5 hour, stopped reaction. Cooling, adds 200ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylic acid product 836.7g, productivity 93.4%. Bromine number: 1.3gBr/100g. Acid number: 0.8mgKOH/g. In above reaction raw materials, M, X in formula (1)1For C10 alkyl, X2It is H; R in formula (2)1It is H, R2It is C4 alkyl, R3It is H, X3For C10 alkyl, X4For H; R in formula (3)4It is side chain C28 alkyl, R5It is H.
Embodiment 9: prepare the salicylic method of alkylaryl
Equipped with in condenser, thermometer, constant pressure funnel and churned mechanically 1000ml four-hole bottle, add the salicyclic acid derivatives 279.3g (0.5mol) shown in Emathlite 10.0g, formula (1), weigh the styrene derivative 76.7g (0.65mol) shown in formula (2) and load in constant pressure funnel, it is warming up to 140 DEG C, dropping styrene derivative, 12h drips off. Weigh the alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, disposable addition reaction bulb again, be warming up to 180 DEG C, stirring reaction 0.5 hour, stopped reaction. Cooling, adds 200ml120# solvent naphtha, is poured into by material in separatory funnel, static layering, and separatory removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl salicylic acid product 573.9g, productivity 94.4%. Bromine number: 1.4gBr/100g. Acid number: 0.5mgKOH/g. In above reaction raw materials, M, X in formula (1)1For C10 branched alkyl, X2It it is C10 straight chained alkyl; R in formula (2)1It is C4 alkyl, R2It is ethyl, R3It is ethyl, X3For H, X4For methyl; R in formula (3)4It is H, R5It it is side chain C28 alkyl.
Embodiment 10: the synthesis of super basicity alkyl aryl salicylic acid calcium salt detersive
Room temperature adds pseudocumene 210g in 1000mL flask, 2 centistokes(cst) II class hydrogenated oil 45g, calcium hydroxide 4.8g and calcium oxide 6g, succinic acid 6g, aphthenic acids 3g, stearic acid 2g, stir and be warmed up to 60 DEG C, then the alkylaryl salicylic acid 100g in dropping embodiment 1, maintains temperature 85-88 DEG C of reaction 50min. System cools to less than 45 DEG C, adds accelerator (mixture of ammonia and ethylenediamine, according to mol ratio 1:0.1 proportioning) 1g. 24g calcium hydroxide (or neutralizing front addition) is added to system, regulate temperature between 35-39 DEG C, carbon dioxide is passed into 145mL/min speed, carbon dioxide intake is the 40% of the Calx gross mass added, control carbonation temperature at 37-38 DEG C, distillation elimination accelerator, water and solvent. Being centrifuged the super basicity alkyl thick product high speed centrifuge of aryl salicylic acid calcium salt while hot separating, isolate the impurity such as a small amount of unreacted Calx and solid carbonic acid calcium, the base number obtaining product is 450mgKOH/g, viscosity (100 DEG C) 65.04mm2/ s, flash-point opening >=190 DEG C, turbidity 19.2JTU.Crankcase simulation test: 0.5 grade; Plastic weightening finish 12mg.
Embodiment 11: the synthesis of super basicity alkyl aryl salicylic acid calcium salt detersive
Room temperature adds solvent naphtha 250g in 1000mL flask, 5 centistokes(cst) II class hydrogenated oil 35g, calcium hydroxide 4.9g and calcium oxide 6.1g, stearic acid 10g, stir and be warmed up to 60 DEG C, then the alkylaryl salicylic acid 100g in dropping embodiment 2, maintain temperature 85-88 DEG C of reaction 60min. System cools to less than 45 DEG C, adds accelerator (mixture of ammonia and diethylenetriamine, according to mol ratio 1:0.3 proportioning) 10g. 24g calcium hydroxide (or neutralizing front addition) is added to system, regulate temperature between 38-39 DEG C, carbon dioxide is passed into 150mL/min speed, carbon dioxide intake is the 50% of the Calx gross mass added, controlling carbonation temperature at 35-39 DEG C, 160-170 DEG C is distilled methanol removal, water and solvent. Being centrifuged the super basicity alkyl thick product high speed centrifuge of aryl salicylic acid calcium salt while hot separating, isolate the impurity such as a small amount of unreacted Calx and solid carbonic acid calcium, the base number obtaining product is 446mgKOH/g, viscosity (100 DEG C) 125.02mm2/ s, flash-point opening >=195 DEG C, turbidity 23.4JTU. Crankcase simulation test: 1.0 grades; Plastic weightening finish 15mg.
Embodiment 12: the synthesis of super basicity alkyl aryl salicylic acid calcium salt detersive
Room temperature adds light aromatic hydrocarbons 210g, paraffinic base low-viscosity neutral oil 40g in 1000mL flask, calcium hydroxide 5g and calcium oxide 5.8g, formic acid 5.5g, stearic acid 7g, stir and be warmed up to 60 DEG C, then the alkylaryl salicylic acid 100g in dropping embodiment 3, maintains temperature 85-88 DEG C of reaction 55min. System cools to 40 DEG C, adds accelerator (mixture of ammonia and diethylenetriamine, according to mol ratio 1:0.8 proportioning) 8g. 24g calcium hydroxide (or neutralizing front addition) is added to system, regulating temperature between 38-39 DEG C, pass into carbon dioxide with 148mL/min speed, carbon dioxide intake is the 55% of the Calx gross mass added, controlling carbonation temperature at 35-39 DEG C, the response time controls at 2-3h. In 160-170 DEG C of removed under reduced pressure accelerator, water and solvent. It is centrifuged separating by the super basicity alkyl thick product high speed centrifuge of aryl salicylic acid calcium salt at 150-155 DEG C, isolate the impurity such as a small amount of unreacted Calx and solid carbonic acid calcium, the base number obtaining product is 452mgKOH/g, viscosity (100 DEG C) 171.41mm2/ s, flash-point opening >=200 DEG C, turbidity 44.1JTU, crankcase simulation experiment: 1.5 grades; Plastic weightening finish 20mg.
The total base number of the alkylaryl calcium salicylate in the embodiment of the present invention can directly bring up to 450mgKOH/g from about the 250mgKOH/g of prior art, and upgrading for China's lubricating oil and additive integral product level provides high-quality host.
Although illustrate and describing the present invention with specific embodiment, however it will be appreciated that may be made that when without departing substantially from the spirit and scope of the present invention many other change and amendment. It is, therefore, intended that include all such changes and modifications belonging in the scope of the invention in the following claims.
Claims (10)
1. the preparation method of a super basicity alkyl aryl salicylic acid calcium salt, it is characterised in that comprise the steps:
(1) mixture solvent naphtha, base oil, Calx, kicker being mixed, adds surfactant and alkylaryl salicylic acid, stirring reaction 50-60min at 85-88 DEG C, generates neutral alkylaryl salicylic acid calcium salt;
(2) lower the temperature and add accelerator and calcium hydroxide in described neutral alkylaryl salicylic acid calcium salt, passing into carbon dioxide, obtain super basicity alkyl aryl salicylic acid calcium salt;
Wherein, the salicylic chemical structural formula of described alkylaryl is:
R1��R2��R3��X1��X2��X3��X4It is separately hydrogen atom, alkoxyl or the straight or branched alkyl containing 1 to 10 carbon atom, R4��R5It is separately hydrogen atom or straight chained alkyl or the branched alkyl containing 1 to 30 carbon atom, and R4And R5Carbon number sum be not less than 4.
2. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, it is characterized in that, in described step (1), described solvent naphtha is: any one or the multiple mixing in Petroleum, light aromatic hydrocarbons and pseudocumene, and addition is the 210-250% of alkylaryl salicylic acid quality;
Preferably, described base oil is any one or more mixing in low-viscosity mineral oil neutral oil, low-viscosity II class oil and III class oil, and its addition is the 35-45% of described alkylaryl salicylic acid quality;
Preferably, in described Calx, the mol ratio of quick lime and Calx is 1:(0.5-4).
3. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, it is characterized in that, in described step (1), described surfactant is the mixture of any one or two kinds in stearic acid, aphthenic acids, and its addition is the 5-10% of described alkylaryl salicylic acid quality.
4. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, it is characterised in that in described step (1), described kicker is C1-C4Organic carboxyl acid or binary acid, its addition is the 5-6% of described alkylaryl salicylic acid quality.
5. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, it is characterized in that, in described step (2), described accelerator is the mixture of ammonia and ethyleneamines, and addition is the 1-10% of described alkylaryl salicylic acid quality.
6. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 5, it is characterised in that in described accelerator, the mol ratio of ammonia and ethyleneamines controls at 1:(0.1-0.8) between;
Preferably, ethyleneamines includes the mixture of one or more in ethylenediamine, diethylenetriamine, triethylene tetramine.
7. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, it is characterized in that, in described step (2), in described neutral alkylaryl salicylic acid calcium salt, accelerator and calcium hydroxide is added again, it is preferable that be cooled between 35-39 DEG C when being cooled to less than 45 DEG C.
8. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, it is characterised in that in described step (2), the speed that passes into of described carbon dioxide is 145-150mL/min.
9. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, it is characterised in that in described step (2), passing in the process of carbon dioxide, reaction temperature controls at 35-39 DEG C, and the response time controls at 2-3h.
10. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, it is characterised in that in described step (2), the super basicity alkyl aryl salicylic acid calcium salt obtained passes through distillation, centrifugal step with purification.
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| CN113549481A (en) * | 2021-07-29 | 2021-10-26 | 新乡市瑞丰新材料股份有限公司 | Preparation process of ultrahigh-base-number calcium alkyl salicylate |
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| CN105646187B (en) | 2018-12-21 |
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