CN108587473A - The synthetic method of modified chlorofluorination lithium base disproportionated rosin and its application in metal working fluid - Google Patents
The synthetic method of modified chlorofluorination lithium base disproportionated rosin and its application in metal working fluid Download PDFInfo
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- CN108587473A CN108587473A CN201810328591.3A CN201810328591A CN108587473A CN 108587473 A CN108587473 A CN 108587473A CN 201810328591 A CN201810328591 A CN 201810328591A CN 108587473 A CN108587473 A CN 108587473A
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- disproportionated rosin
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 192
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 190
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 190
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 100
- 239000012530 fluid Substances 0.000 title claims abstract description 17
- 238000005555 metalworking Methods 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 117
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 238000005660 chlorination reaction Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- -1 alkyl phenol Chemical compound 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- 230000008859 change Effects 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- MFPGZXKGOYXUEV-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;hydrofluoride Chemical compound F.OCCN(CCO)CCO MFPGZXKGOYXUEV-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000001119 stannous chloride Substances 0.000 claims description 7
- 235000011150 stannous chloride Nutrition 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000007323 disproportionation reaction Methods 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000001954 sterilising effect Effects 0.000 abstract description 7
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 5
- 238000005461 lubrication Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000003754 machining Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 1
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 1
- 229940118781 dehydroabietic acid Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- 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
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
-
- 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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- 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
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- 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
- C10N2030/16—Antiseptic; (micro) biocidal or bactericidal
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
Abstract
The invention belongs to rosin processing technique field, the synthetic method of specifically a kind of modified chlorofluorination lithium base disproportionated rosin and its application in metal working fluid.Preparation method is that chlorine and fluorine element are introduced into the conjugated double bond of disproportionated rosin, the conjugated double bond of disproportionated rosin is chemically modified, lithium base is introduced into the carboxyl of disproportionated rosin, then to the methyl of the disproportionated rosin of gained aoxidize then carry out esterification and it is hyperbranched reaction modified chlorofluorination lithium base disproportionated rosin is prepared.The modification chlorofluorination lithium base disproportionated rosin that the present invention is prepared has lubrication, antirust, cleaning, sterilization, desinsection multi-efficiency, and compatibility is good, and function and effect are good, can be widely applied for the machinery manufacturing industry such as automobile, space flight, has a extensive future.
Description
Technical field
The invention belongs to rosin processing technique field, specifically a kind of synthesis of modified chlorofluorination lithium base disproportionated rosin
Method and its application in metal working fluid.
Background technology
Rosin is the mixture of various kinds of resin acid and a small amount of aliphatic acid, neutral substance, wherein main composition is resin acid, about
Account for the 90% of its total amount.Disproportionated rosin is important one of the modified product of rosin.Disproportionated rosin is in the presence of a catalyst, to borrow nothing
The effect of machine acid and heat, makes a part for rosin be aoxidized, another part is reduced, that is, the production obtained by disproportionated reaction has occurred
Object.Disproportionated rosin is dehydroabietic acid (C19H27COOH), dihydro rosin acid (C19H31COOH) and tetrahydrogenated rosin acid
(C19H33COOH) mixture, average molecular weight are about 304.Rosin forms disproportionated rosin, color after disproportionated reaction
It shoals, component changes, and property is also more stablized.Disproportionated rosin lighter color, good in oxidation resistance, brittleness are small, thermal stability is high.
Disproportionated rosin is mainly used for rubber industry at present, the emulsifier as butadiene and styrene synthesizing butadiene styrene rubber.Rosin is certainly
A kind of renewable resource on right boundary, cheap, abundance.By being modified to rosin, applied to synthesis lubrication
Agent, antirust agent etc., it is nontoxic with its, lubricating and antirust effect is good, easily biological-degradable, advantages of environment protection, adapt to modern hair
The requirement of exhibition, has broad application prospects.
Metal working fluid is mainly the liquid of intermetallic composite coating, main to play lubrication and cooling effect, has antirust cleaning etc. concurrently
Effect, be mainly used for metal and its alloy the various process such as cutting, punching press, rolling and drawing lubricant.Metal adds
Work liquid includes cutting fluid, cutting oil, emulsion, antirust oil, cleaning agent etc..It can be selected in metal cutting process correct
Machining of metals liquid, advantageously reduce cutting temperature improve cutting force, reduce tool wear, improve the surface of converted products
Quality ensures the machining accuracy of product and improves production efficiency.With the development of China's economy science and technology, to the city of metal working fluid
Field needs to be getting faster, and there is metal working fluid advantages, the development of metal working fluid such as added value of product is high, profit is big to obtain
Domestic and international many companies highest attention.Metal working fluid can also there are problems that in use, such as stability
Poor, lubricating and antirust poor performance is easy cooperating microorganisms, and easily smelly, service life is short, causes serious pollution to the environment, containing to human body
The problems such as healthy harmful substance, the presence of these problems defines the application of metal working fluid.
Invention content
The present invention provides a kind of synthetic method of modified chlorofluorination lithium base disproportionated rosin and its answering in metal working fluid
With, it can be effectively improved that metal working fluid lubricity is undesirable, and service life is short, easy smelly problem, while what is be prepared changes
Property chlorofluorination lithium base disproportionated rosin have lubrication, antirust, cleaning, sterilization, desinsection multi-efficiency, compatibility is good, and function and effect are good,
It is environmentally friendly, the machinery manufacturing industry such as automobile, space flight are can be widely applied for, are had a extensive future.
The scheme of the invention is realize in this way：A kind of synthetic method of modified chlorofluorination lithium base disproportionated rosin, institute
The synthesis step stated includes：
(1) preparation of chlorination disproportionated rosin：It takes 50 ~ 60 parts of disproportionated rosin to be placed in reaction kettle A, 30 ~ 45 parts of absolute ethyl alcohol is added
10 ~ 12min of heating makes disproportionated rosin be completely dissolved afterwards, and 5 ~ 8 parts of catalyst stannous chloride is added, fully stirs under nitrogen protection
Mix, hydrogen chloride gas be passed through in reaction kettle A and is stirred reaction, reaction temperature be 20 ~ 25 DEG C, mixing speed be 550 ~
560r/min, reaction time are 2 ~ 4h, and decompression, which filters, after reaction removes ethyl alcohol and extra hydrogen chloride, obtains chlorination disproportionation
Rosin；
(2) preparation of chlorofluorination disproportionated rosin：The chlorination disproportionated rosin that (1) obtains is placed in reaction kettle B, absolute ethyl alcohol is added
40 ~ 55 parts are dissolved, and 50 ~ 60 parts of hydrogen fluoride triethanolamine is then added, and it is that 20 ~ 30 DEG C of stirrings are reacted to keep temperature
Product is separated obtain chlorofluorination disproportionated rosin after reaction by 1.5 ~ 2h；
(3) preparation of chlorofluorination lithium base disproportionated rosin：50 ~ 60 parts of lithium hydroxide, 80 ~ 100 parts of distilled water are put into reaction kettle C
In, 8 ~ 12 parts of composite assistant, the chlorofluorination discrimination for taking (2) to be prepared are added dropwise when temperature reaches 70 ~ 80 DEG C for heating stirring heating
Change rosin to put into 5min in reaction kettle C, being stirred makes chlorofluorination disproportionated rosin be completely dissolved, and then rises to temperature
85 DEG C make it be reacted, and mixing speed is 120 ~ 150r/min in reaction kettle C at this time, and reaction stops reaction after carrying out 2 ~ 3h,
Separation product and reagent obtain chlorofluorination lithium base disproportionated rosin；
(4) preparation of modified chlorofluorination lithium base disproportionated rosin:The chlorofluorination lithium base disproportionated rosin that (3) are prepared is placed in reaction
In kettle D, 90 ~ 120 parts of 0.2mol/L NaOH aqueous solutions are added, stirs while adding, is then slow added into liquor potassic permanganate
It 40 ~ 60 parts, is warming up to 80 DEG C and carries out 0.5 ~ 1h of reaction, the chlorofluorination lithium base disproportionated rosin after being aoxidized, by the chlorine after oxidation
Lithium fluoride base disproportionated rosin is placed in reaction kettle E, is vacuumized, is then passed to nitrogen, is heated to 70 ~ 85 DEG C, and catalyst A10 is added
~ 12 parts, 50 ~ 60 parts of progress esterifications of polyethylene glycol are added dropwise, reaction carries out 12 ~ 18h and opens vacuum pump, and decompression filters, cooling
Discharging, obtains hyperbranched chlorofluorination lithium base disproportionated rosin ester, toward the hyperbranched chlorofluorination lithium base disproportionated rosin ester drop being prepared
Add 50 ~ 60 parts of morpholine, add catalyst B10 ~ 12 part, 3 ~ 4h is reacted in 80 ~ 90 DEG C, obtained product is cooled to 60 DEG C, drop
80 ~ 120 parts of 0.2mol/L NaOH aqueous solutions, 40 ~ 50 parts of benzene is added to react 2 ~ 3h at 20 ~ 40 DEG C, obtained product saturation chlorine
Change sodium solution and be washed till neutrality, vacuum distillation removes extra benzene, obtains modified chlorofluorination lithium base disproportionated rosin.
As a further improvement on the present invention, the composite assistant is organosilicon, aliphatic acid, alkyl phenol polyoxyethylene ether
Mixing.
As a further improvement on the present invention, the catalyst A is Zn (CH3COO)2、Ca(CH3COO)2, ZnO it is a kind of
Or two or more combination.
As a further improvement on the present invention, the catalyst B be quaternary ammonium salt, alkyl tin acid, butyl stannonic acid it is a kind of or
Two or more combinations.
As a further improvement on the present invention, the modification chlorofluorination lithium base disproportionated rosin being prepared is applied to intermetallic composite coating
In liquid.
The technical principle that the present invention realizes is：
Chlorine and fluorine element are introduced into the conjugated double bond of disproportionated rosin by the present invention, and the addition of chlorine element makes disproportionated rosin have suppression
Bacterium insecticidal effect.The fluorine element of introducing can form the stronger carbon-fluorine bond of bond energy so that the heat resistance of disproportionated rosin, weatherability,
Chemical resistance enhances, and can reduce the frictional property of disproportionated rosin, improve lubricity, the corrosion resistance of metal working fluid.
Lithium base is introduced, lithium base and carboxylic acid form carboxylic acid lithium salt, enable to the anticorrosive property of disproportionated rosin and oxidation to pacify after introducing lithium base
Qualitative enhancing, while but also the greasy property of disproportionated rosin improves.Chlorofluorination lithium base disproportionated rosin is modified, using height
Potassium manganate carries out the methyl of chlorofluorination lithium base disproportionated rosin to be oxidized to carboxyl, then allows chlorofluorination lithium base to be disproportionated by esterification
The carboxyl of rosin carries out esterification with polyethylene glycol, and lithium base and polyethylene glycol synergistic effect can further increase disproportionated rosin
Greasy property, additionally it is possible to so that the dispersion performance of disproportionated rosin is improved so that disproportionated rosin can have good with many components
Compatibility.Morpholine, which is added, makes disproportionated rosin have corrosion-resistant and rustless property, and disproportionated rosin is applied to process of metal working
In metal can be effectively relieved be corroded problem, the rust-preventing characteristic of metal product is improved, to improve the use of intermetallic composite coating product
Service life.By introducing chlorine fluorine element, lithium base to disproportionated rosin and being modified chlorofluorination lithium base disproportionated rosin, can make to change
Property chlorofluorination lithium base disproportionated rosin there are the multi-efficiencies such as lubrication, cleaning, sterilization and disinsection, antirust.
The present invention has following good result：
1. the modification chlorofluorination lithium base disproportionated rosin that the present invention is prepared has lubrication, antirust, cleaning, sterilization, desinsection multiple
Effect, and property is stablized, and is not easy cooperating microorganisms, service life is long.
2. the modification chlorofluorination lithium base disproportionated rosin that the present invention is prepared is used in metal working fluid, function and effect are good,
The precision and abrasion resistance for effectively improving intermetallic composite coating object, improve the degree of wear of process apparatus, to improve process apparatus
Service life improves working efficiency, reduces cost.
3. the modification chlorofluorination lithium base disproportionated rosin that the present invention is prepared can be widely applied to the machinery system such as automobile, space flight
It makes in industry, application prospect is extensive, and the development of economy and society to Guangxi has certain facilitation.
Specific implementation mode
A kind of synthetic method of modified chlorofluorination lithium base disproportionated rosin of the present invention is described with reference to embodiments and its in gold
Belong to the application of working fluid, these descriptions are not to be further limited to the content of present invention.
Embodiment 1
The preparation of chlorination disproportionated rosin：It takes 58 parts of disproportionated rosin to be placed in reaction kettle A, is heated after 33 parts of absolute ethyl alcohol is added
10.5min makes disproportionated rosin be completely dissolved, and 8 parts of catalyst stannous chloride is added, is sufficiently stirred under nitrogen protection, by hydrogen chloride
Gas, which is passed through in reaction kettle A, is stirred reaction, and reaction temperature is 20 DEG C, mixing speed 552r/min, reaction time 3h,
Decompression, which filters, after reaction removes ethyl alcohol and extra hydrogen chloride, obtains chlorination disproportionated rosin；
The preparation of chlorofluorination disproportionated rosin：Obtained chlorination disproportionated rosin is placed in reaction kettle B, be added 55 parts of absolute ethyl alcohol into
Row dissolving, is then added 55 parts of hydrogen fluoride triethanolamine, and it is that 25 DEG C of stirrings carry out reaction 1.5h to keep temperature, after reaction will
Product, which is separated, obtains chlorofluorination disproportionated rosin；
The preparation of chlorofluorination lithium base disproportionated rosin：52 parts of lithium hydroxide, 100 parts of distilled water are put into reaction kettle C, heating stirring
Organosilicon, aliphatic acid, totally 8 parts of alkyl phenol polyoxyethylene ether composite assistant are added dropwise when temperature reaches 80 DEG C, takes chlorofluorination for heating
Disproportionated rosin is put into 5min in reaction kettle C, and being stirred makes chlorofluorination disproportionated rosin be completely dissolved, then by temperature liter
It is set to be reacted to 85 DEG C, mixing speed is 120r/min in reaction kettle C at this time, and reaction stops reaction after carrying out 2.5h, point
From product and reagent, chlorofluorination lithium base disproportionated rosin is obtained；
The preparation of modified chlorofluorination lithium base disproportionated rosin:Chlorofluorination lithium base disproportionated rosin is placed in reaction kettle D, is added
90 parts of 0.2mol/L NaOH aqueous solutions, stir while adding, and are then slow added into 50 parts of liquor potassic permanganate, are warming up to 80
DEG C reaction 0.5h is carried out, the chlorofluorination lithium base disproportionated rosin after being aoxidized sets the chlorofluorination lithium base disproportionated rosin after oxidation
It in reaction kettle E, vacuumizes, then passes to nitrogen, be heated to 73 DEG C, 210.5 parts of catalyst AZn (CH3COO) is added, be added dropwise
60 parts of progress esterifications of polyethylene glycol, reaction carry out 14h and open vacuum pump, and decompression filters, and cooling discharge obtains hyperbranched chlorine
Lithium fluoride base disproportionated rosin ester is added dropwise 52 parts of morpholine toward the hyperbranched chlorofluorination lithium base disproportionated rosin ester being prepared, adds
11 parts of catalyst B quaternary ammonium salts react 3.2h in 80 DEG C, and obtained product is cooled to 60 DEG C, and 0.2mol/L NaOH aqueous solutions are added dropwise
120 parts, 42 parts of benzene react 2h at 30 DEG C, obtained product is washed till neutrality with saturated nacl aqueous solution, and vacuum distillation removes more
Remaining benzene obtains modified chlorofluorination lithium base disproportionated rosin.
Embodiment 2
The preparation of chlorination disproportionated rosin：It takes 50 parts of disproportionated rosin to be placed in reaction kettle A, is heated after 37 parts of absolute ethyl alcohol is added
12min makes disproportionated rosin be completely dissolved, and 5 parts of catalyst stannous chloride is added, is sufficiently stirred under nitrogen protection, by hydrogen chloride gas
Body, which is passed through in reaction kettle A, is stirred reaction, and reaction temperature is 23 DEG C, mixing speed 550r/min, reaction time 2h, instead
Decompression, which filters, after answering removes ethyl alcohol and extra hydrogen chloride, obtains chlorination disproportionated rosin；
The preparation of chlorofluorination disproportionated rosin：The chlorination disproportionated rosin that step 1) obtains is placed in reaction kettle B, absolute ethyl alcohol is added
44 parts are dissolved, and 60 parts of hydrogen fluoride triethanolamine is then added, and it is that 20 DEG C of stirrings carry out reaction 1.8h, reaction knot to keep temperature
Product is separated after beam and obtains chlorofluorination disproportionated rosin；
The preparation of chlorofluorination lithium base disproportionated rosin：55 parts of lithium hydroxide, 90 parts of distilled water are put into reaction kettle C, heating stirring
Organosilicon, aliphatic acid, totally 11 parts of alkyl phenol polyoxyethylene ether composite assistant are added dropwise when temperature reaches 75 DEG C, takes chlorine fluorine for heating
Change disproportionated rosin to put into 5min in reaction kettle C, being stirred makes chlorofluorination disproportionated rosin be completely dissolved, then by temperature
Rising to 85 DEG C makes it be reacted, and mixing speed is 130r/min in reaction kettle C at this time, and reaction stops reaction after carrying out 2h, point
From product and reagent, chlorofluorination lithium base disproportionated rosin is obtained；
The preparation of modified chlorofluorination lithium base disproportionated rosin：Chlorofluorination lithium base disproportionated rosin is placed in reaction kettle D, is added
120 parts of 0.2mol/L NaOH aqueous solutions, stir while adding, and are then slow added into 45 parts of liquor potassic permanganate, are warming up to 80
DEG C reaction 0.8h is carried out, the chlorofluorination lithium base disproportionated rosin after being aoxidized sets the chlorofluorination lithium base disproportionated rosin after oxidation
It in reaction kettle E, vacuumizes, then passes to nitrogen, be heated to 76 DEG C, 211.5 parts of catalyst ACa (CH3COO) is added, be added dropwise
50 parts of progress esterifications of polyethylene glycol, reaction carry out 15h and open vacuum pump, and decompression filters, and cooling discharge obtains hyperbranched chlorine
Lithium fluoride base disproportionated rosin ester is added dropwise 58 parts of morpholine toward the hyperbranched chlorofluorination lithium base disproportionated rosin ester being prepared, adds
10.5 parts of catalyst B alkyl tin acids react 3.5h in 82 DEG C, and obtained product is cooled to 60 DEG C, and 0.2mol/L NaOH water is added dropwise
90 parts of solution, 50 parts of benzene react 2.5h at 40 DEG C, and obtained product is washed till neutrality with saturated nacl aqueous solution, and vacuum distillation removes
Extra benzene is removed, modified chlorofluorination lithium base disproportionated rosin is obtained.
Embodiment 3
The preparation of chlorination disproportionated rosin：It takes 60 parts of disproportionated rosin to be placed in reaction kettle A, is heated after 40 parts of absolute ethyl alcohol is added
11min makes disproportionated rosin be completely dissolved, and 6 parts of catalyst stannous chloride is added, is sufficiently stirred under nitrogen protection, by hydrogen chloride gas
Body, which is passed through in reaction kettle A, is stirred reaction, and reaction temperature is 25 DEG C, mixing speed 555r/min, reaction time 2.5h,
Decompression, which filters, after reaction removes ethyl alcohol and extra hydrogen chloride, obtains chlorination disproportionated rosin；
The preparation of chlorofluorination disproportionated rosin：Obtained chlorination disproportionated rosin is placed in reaction kettle B, be added 47 parts of absolute ethyl alcohol into
Row dissolving, is then added 52 parts of hydrogen fluoride triethanolamine, and it is that 28 DEG C of stirrings carry out reaction 1.6h to keep temperature, after reaction will
Product, which is separated, obtains chlorofluorination disproportionated rosin；
The preparation of chlorofluorination lithium base disproportionated rosin：50 parts of lithium hydroxide, 95 parts of distilled water are put into reaction kettle C, heating stirring
Organosilicon, aliphatic acid, totally 12 parts of alkyl phenol polyoxyethylene ether composite assistant are added dropwise when temperature reaches 72 DEG C, takes chlorine fluorine for heating
Change disproportionated rosin to put into 5min in reaction kettle C, being stirred makes chlorofluorination disproportionated rosin be completely dissolved, then by temperature
Rising to 85 DEG C makes it be reacted, and mixing speed is 140r/min in reaction kettle C at this time, and reaction stops reaction after carrying out 2.2h,
Separation product and reagent obtain chlorofluorination lithium base disproportionated rosin；
The preparation of modified chlorofluorination lithium base disproportionated rosin:Chlorofluorination lithium base disproportionated rosin is placed in reaction kettle D, is added
100 parts of 0.2mol/L NaOH aqueous solutions, stir while adding, and are then slow added into 40 parts of liquor potassic permanganate, are warming up to 80
DEG C reaction 1h is carried out, the chlorofluorination lithium base disproportionated rosin after oxidation is placed in by the chlorofluorination lithium base disproportionated rosin after being aoxidized
It in reaction kettle E, vacuumizes, then passes to nitrogen, be heated to 70 DEG C, AZnO10 parts of catalyst is added, 58 parts of polyethylene glycol is added dropwise
Esterification is carried out, reaction carries out 12h and opens vacuum pump, and decompression filters, cooling discharge, obtains hyperbranched chlorofluorination lithium base disproportionation
Rosin ester is added dropwise 60 parts of morpholine toward the hyperbranched chlorofluorination lithium base disproportionated rosin ester being prepared, adds catalyst B butyl tins
10 parts of acid reacts 3h in 85 DEG C, and obtained product is cooled to 60 DEG C, 80 parts of 0.2mol/L NaOH aqueous solutions is added dropwise, 48 parts of benzene exists
3h is reacted at 20 DEG C, obtained product is washed till neutrality with saturated nacl aqueous solution, and vacuum distillation removes extra benzene, is modified
Chlorofluorination lithium base disproportionated rosin.
Embodiment 4
The preparation of chlorination disproportionated rosin：It takes 55 parts of disproportionated rosin to be placed in reaction kettle A, is heated after 30 parts of absolute ethyl alcohol is added
10min makes disproportionated rosin be completely dissolved, and 7 parts of catalyst stannous chloride is added, is sufficiently stirred under nitrogen protection, by hydrogen chloride gas
Body, which is passed through in reaction kettle A, is stirred reaction, and reaction temperature is 24 DEG C, mixing speed 558r/min, reaction time 4h, instead
Decompression, which filters, after answering removes ethyl alcohol and extra hydrogen chloride, obtains chlorination disproportionated rosin；
The preparation of chlorofluorination disproportionated rosin：Obtained chlorination disproportionated rosin is placed in reaction kettle B, be added 40 parts of absolute ethyl alcohol into
Row dissolving, is then added 50 parts of hydrogen fluoride triethanolamine, and it is that 30 DEG C of stirrings carry out reaction 2h to keep temperature, after reaction will production
Object, which is separated, obtains chlorofluorination disproportionated rosin；
The preparation of chlorofluorination lithium base disproportionated rosin：58 parts of lithium hydroxide, 85 parts of distilled water are put into reaction kettle C, heating stirring
Organosilicon, aliphatic acid, totally 10 parts of alkyl phenol polyoxyethylene ether composite assistant are added dropwise when temperature reaches 72 DEG C, takes chlorine fluorine for heating
Change disproportionated rosin to put into 5min in reaction kettle C, being stirred makes chlorofluorination disproportionated rosin be completely dissolved, then by temperature
Rising to 85 DEG C makes it be reacted, and mixing speed is 150r/min in reaction kettle C at this time, and reaction stops reaction after carrying out 3h, point
From product and reagent, chlorofluorination lithium base disproportionated rosin is obtained；
The preparation of modified chlorofluorination lithium base disproportionated rosin:Chlorofluorination lithium base disproportionated rosin is placed in reaction kettle D, is added
110 parts of 0.2mol/L NaOH aqueous solutions, stir while adding, and are then slow added into 55 parts of liquor potassic permanganate, are warming up to 80
DEG C reaction 0.6h is carried out, the chlorofluorination lithium base disproportionated rosin after being aoxidized sets the chlorofluorination lithium base disproportionated rosin after oxidation
It in reaction kettle E, vacuumizes, then passes to nitrogen, be heated to 85 DEG C, catalyst AZn (CH3COO) 2 and Ca (CH3COO) is added
2 totally 12 parts, 55 parts of progress esterifications of polyethylene glycol are added dropwise, reaction carries out 16h and opens vacuum pump, and decompression filters, cooling discharge,
Hyperbranched chlorofluorination lithium base disproportionated rosin ester is obtained, morpholine is added dropwise toward the hyperbranched chlorofluorination lithium base disproportionated rosin ester being prepared
50 parts, totally 11.5 parts of catalyst B alkyl tin acids and butyl stannonic acid are added, reacts 4h in 88 DEG C, obtained product is cooled to 60
DEG C, 100 parts of 0.2mol/L NaOH aqueous solutions are added dropwise, 40 parts of benzene reacts 2.8h at 25 DEG C, obtained product saturated sodium-chloride
Solution is washed till neutrality, and vacuum distillation removes extra benzene, obtains modified chlorofluorination lithium base disproportionated rosin.
Embodiment 5
The preparation of chlorination disproportionated rosin：It takes 52 parts of disproportionated rosin to be placed in reaction kettle A, is heated after 45 parts of absolute ethyl alcohol is added
11.5min makes disproportionated rosin be completely dissolved, and 6 parts of catalyst stannous chloride is added, is sufficiently stirred under nitrogen protection, by hydrogen chloride
Gas, which is passed through in reaction kettle A, is stirred reaction, and reaction temperature is 21 DEG C, mixing speed 560r/min, and the reaction time is
3.5h, decompression, which filters, after reaction removes ethyl alcohol and extra hydrogen chloride, obtains chlorination disproportionated rosin；
The preparation of chlorofluorination disproportionated rosin：Obtained chlorination disproportionated rosin is placed in reaction kettle B, be added 51 parts of absolute ethyl alcohol into
Row dissolving, is then added 58 parts of hydrogen fluoride triethanolamine, and it is that 22 DEG C of stirrings carry out reaction 1.7h to keep temperature, after reaction will
Product, which is separated, obtains chlorofluorination disproportionated rosin；
The preparation of chlorofluorination lithium base disproportionated rosin：60 parts of lithium hydroxide, 80 parts of distilled water are put into reaction kettle C, heating stirring
Organosilicon, aliphatic acid, totally 9 parts of alkyl phenol polyoxyethylene ether composite assistant are added dropwise when temperature reaches 78 DEG C, takes chlorofluorination for heating
Disproportionated rosin is put into 5min in reaction kettle C, and being stirred makes chlorofluorination disproportionated rosin be completely dissolved, then by temperature liter
It is set to be reacted to 85 DEG C, mixing speed is 135r/min in reaction kettle C at this time, and reaction stops reaction after carrying out 2.8h, point
From product and reagent, chlorofluorination lithium base disproportionated rosin is obtained；
The preparation of modified chlorofluorination lithium base disproportionated rosin:Chlorofluorination lithium base disproportionated rosin is placed in reaction kettle D, is added
105 parts of 0.2mol/L NaOH aqueous solutions, stir while adding, and are then slow added into 60 parts of liquor potassic permanganate, are warming up to 80
DEG C reaction 0.7h is carried out, the chlorofluorination lithium base disproportionated rosin after being aoxidized sets the chlorofluorination lithium base disproportionated rosin after oxidation
It in reaction kettle E, vacuumizes, then passes to nitrogen, be heated to 81 DEG C, catalyst ACa (CH3COO) 2 and totally 11 parts of ZnO is added,
52 parts of progress esterifications of polyethylene glycol are added dropwise, reaction carries out 18h and opens vacuum pump, and decompression filters, and cooling discharge is overspend
Change chlorofluorination lithium base disproportionated rosin ester, 55 parts of morpholine is added dropwise toward the hyperbranched chlorofluorination lithium base disproportionated rosin ester being prepared, then
Totally 12 parts of catalyst B quaternary ammonium salts and alkyl tin acid is added, 3.8h is reacted in 90 DEG C, obtained product is cooled to 60 DEG C, is added dropwise
110 parts of 0.2mol/L NaOH aqueous solutions, 45 parts of benzene react 2.2h at 35 DEG C, and obtained product is washed with saturated nacl aqueous solution
To neutrality, vacuum distillation removes extra benzene, obtains modified chlorofluorination lithium base disproportionated rosin.
In order to verify the performance for the modification chlorofluorination lithium base disproportionated rosin that the present invention is prepared, the present invention is prepared
Modification chlorofluorination lithium base disproportionated rosin product be added in machining of metals liquid, while with commercially available machining of metals liquid
It for comparative example, is tested according to GB/T 6144, obtained detection data is as shown in table 1.
Table 1 contains the test situation of modified chlorofluorination lithium base disproportionated rosin machining of metals liquid
In order to verify the modification chlorofluorination lithium base disproportionated rosin sterilization and disinsection performance that the present invention obtains, by modified chlorofluorination lithium base discrimination
Change rosin for sterilize, insecticidal test.
(1) sterilization experiment
Embodiment is prepared into modified chlorofluorination lithium base disproportionated rosin respectively and is configured to a certain concentration gradient, according to 1:9 volume ratio
It is mixed with preprepared PDA culture medium, pours into and be prepared into tablet in culture dish, Escherichia coli are then inoculated in tablet
In, measure the fungistatic effect of modified chlorofluorination lithium base disproportionated rosin.Each embodiments of 1 ~ 2d are measured using crossing method and are modified chlorine
The colony diameter and thalli growth situation of lithium fluoride base disproportionated rosin processing and blank control.Calculate growth inhibiting rate.
(2) insecticidal test
Using dip method.Modified chlorofluorination lithium base disproportionated rosin uses a concentration of 5.0g.L-11d investigation borer population living, poisoning after medicine
Borer population, dead borer population, calculate the worm death rate and desinsection is efficient.
2 sterilization and disinsection of table is tested
The above embodiment of the present invention scheme is only the description of the invention and cannot limit the present invention, this is indicated in claim
The range of invention product form ingredient, component ratio, preparation method parameter, and above-mentioned explanation does not point out parameter of the present invention
Range, therefore, any change within the meaning and scope equivalent to the claims of the present invention, be all considered to be including
In the range of claims.
The present invention and is created by creative work by multidigit metal working fluid processing staff's long-term work experience accumulation
Make, the modification chlorofluorination lithium base disproportionated rosin that the present invention is prepared has preferable lubricating and antirust performance, additionally it is possible to kill
Worm is sterilized, and has multiple efficacies, has broad application prospects.
Claims (5)
1. a kind of synthetic method of modified chlorofluorination lithium base disproportionated rosin, characterized in that include the following steps：
The preparation of step 1) chlorination disproportionated rosin：It takes 50 ~ 60 parts of disproportionated rosin to be placed in reaction kettle A, absolute ethyl alcohol 30 ~ 45 is added
10 ~ 12min of heating makes disproportionated rosin be completely dissolved after part, and 5 ~ 8 parts of catalyst stannous chloride is added, fully stirs under nitrogen protection
Mix, hydrogen chloride gas be passed through in reaction kettle A and is stirred reaction, reaction temperature be 20 ~ 25 DEG C, mixing speed be 550 ~
560r/min, reaction time are 2 ~ 4h, and decompression, which filters, after reaction removes ethyl alcohol and extra hydrogen chloride, obtains chlorination disproportionation
Rosin；
The preparation of step 2) chlorofluorination disproportionated rosin：The chlorination disproportionated rosin that step 1) obtains is placed in reaction kettle B, nothing is added
40 ~ 55 parts of water-ethanol is dissolved, and 50 ~ 60 parts of hydrogen fluoride triethanolamine is then added, and it is that 20 ~ 30 DEG C of stirrings carry out to keep temperature
1.5 ~ 2h is reacted, product is separated obtain chlorofluorination disproportionated rosin after reaction；
The preparation of step 3) chlorofluorination lithium base disproportionated rosin：50 ~ 60 parts of lithium hydroxide, 80 ~ 100 parts of distilled water are put into reaction kettle
In C, 8 ~ 12 parts of composite assistant, the chlorine fluorine for taking step 2) to be prepared are added dropwise when temperature reaches 70 ~ 80 DEG C for heating stirring heating
Change disproportionated rosin to put into 5min in reaction kettle C, being stirred makes chlorofluorination disproportionated rosin be completely dissolved, then by temperature
Rising to 85 DEG C makes it be reacted, and mixing speed is 120 ~ 150r/min in reaction kettle C at this time, and reaction stops instead after carrying out 2 ~ 3h
It answers, separation product and reagent, obtains chlorofluorination lithium base disproportionated rosin；
The preparation of the modified chlorofluorination lithium base disproportionated rosin of step 4):The chlorofluorination lithium base disproportionated rosin that step 3) is prepared is set
In reaction kettle D, 90 ~ 120 parts of 0.2mol/L NaOH aqueous solutions are added, stirs while adding, is then slow added into permanganic acid
40 ~ 60 parts of potassium solution is warming up to 80 DEG C and carries out 0.5 ~ 1h of reaction, and the chlorofluorination lithium base disproportionated rosin after being aoxidized will aoxidize
Chlorofluorination lithium base disproportionated rosin afterwards is placed in reaction kettle E, is vacuumized, is then passed to nitrogen, is heated to 70 ~ 85 DEG C, addition is urged
50 ~ 60 parts of progress esterifications of polyethylene glycol are added dropwise in agent A10 ~ 12 part, and reaction carries out 12 ~ 18h and opens vacuum pump, and decompression is taken out
Filter, cooling discharge obtain hyperbranched chlorofluorination lithium base disproportionated rosin ester, toward the hyperbranched chlorofluorination lithium base disproportionation pine being prepared
50 ~ 60 parts of morpholine is added dropwise in fragrant ester, adds catalyst B10 ~ 12 part, reacts 3 ~ 4h in 80 ~ 90 DEG C, obtained product is cooled to 60
DEG C, 80 ~ 120 parts of 0.2mol/L NaOH aqueous solutions are added dropwise, 40 ~ 50 parts of benzene reacts 2 ~ 3h at 20 ~ 40 DEG C, obtained product use
Saturated nacl aqueous solution is washed till neutrality, and vacuum distillation removes extra benzene, obtains modified chlorofluorination lithium base disproportionated rosin.
2. a kind of synthetic method of modified chlorofluorination lithium base disproportionated rosin according to claim 1, characterized in that described
Composite assistant is the mixing of organosilicon, aliphatic acid, alkyl phenol polyoxyethylene ether.
3. a kind of synthetic method of modified chlorofluorination lithium base disproportionated rosin according to claim 1, characterized in that described
Catalyst A is Zn (CH3COO)2、Ca(CH3COO)2, ZnO a combination of one or more.
4. a kind of synthetic method of modified chlorofluorination lithium base disproportionated rosin according to claim 1, characterized in that described
Catalyst B is quaternary ammonium salt, alkyl tin acid, butyl stannonic acid a combination of one or more.
5. a kind of synthetic method of modified chlorofluorination lithium base disproportionated rosin according to claim 1, characterized in that be prepared into
To chlorofluorination lithium base disproportionated rosin be applied to metal working fluid in.
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Application publication date: 20180928 |