CN116444702A - Preparation method of polyisobutene oil for viscosity standard substance - Google Patents
Preparation method of polyisobutene oil for viscosity standard substance Download PDFInfo
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- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 149
- 239000000126 substance Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 22
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 244000028419 Styrax benzoin Species 0.000 claims description 11
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 11
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 11
- 229960002130 benzoin Drugs 0.000 claims description 11
- 235000019382 gum benzoic Nutrition 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- PVQATPQSBYNMGE-UHFFFAOYSA-N [benzhydryloxy(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)OC(C=1C=CC=CC=1)C1=CC=CC=C1 PVQATPQSBYNMGE-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 31
- 238000012650 click reaction Methods 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- 125000003396 thiol group Chemical class [H]S* 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- -1 mercapto alkane Chemical class 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 3
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VPIAKHNXCOTPAY-UHFFFAOYSA-N Heptane-1-thiol Chemical compound CCCCCCCS VPIAKHNXCOTPAY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005315 distribution function Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000000528 statistical test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of viscosity standard substances, and particularly relates to a preparation method of polyisobutene oil for a viscosity standard substance, which comprises the following steps: the low molecular weight polyisobutene, alkane mercaptan and the catalyst react under the protection of nitrogen to obtain colorless transparent liquid, namely polyisobutene oil. The preparation method is modified by low molecular weight polyisobutene, reduces the content of double bonds in the structure, improves the stability of the polyisobutene, and is beneficial to the application of the polyisobutene in the field of viscosity standard substances.
Description
Technical Field
The invention belongs to the technical field of viscosity standard substances, and particularly relates to a preparation method of polyisobutene oil for a viscosity standard substance.
Background
The standard substance is a substance or material which has been determined to have one or more sufficiently uniform characteristic values, has accuracy, uniformity and stability of the characteristic values, and plays an important role in the fields of calibrating measuring instruments and devices, evaluating measuring and analyzing methods, measuring the characteristic values of the substance or material, and examining the operating technical level of an analyzer. Viscosity is a measure of the viscosity of a fluid and is an indication of the fluid flow force versus its internal friction phenomena. The larger the viscosity, the larger the internal friction, the larger the molecular weight, and the more hydrocarbon is combined, and the larger the force is. The viscosity has decisive significance for various lubricating oils, quality identification and determination purposes, combustion performance and utilization degree of various fuel oils and the like. Therefore, the development of the viscosity standard substance has important significance in the fields of national defense and military industry, industrial production and aerospace.
The viscosity standard substance has three characteristics of Newtonian, stability and viscosity-temperature, wherein Newtonian refers to that the stress of a fluid is in direct proportion to the shear rate, and the viscosity of the fluid is only related to the temperature and is not related to the shear rate. Stability refers to the unchanged viscosity of the fluid over a period of storage. Temperature-sticking means that the viscosity is less variable with temperature. With the continuous and intensive research, mineral oil, silicone oil, polyisobutylene and the like are used as viscosity standard substances for development and production at present. Compared with silicone oil, mineral oil and the like, the low molecular weight polyisobutene (LMPIB) serving as saturated alkane is nontoxic, colorless, odorless, has more excellent heat stability, chemical resistance, weather resistance and the like, and is free of carbon residue after cracking, so that the low molecular weight polyisobutene (LMPIB) is widely applied to the fields of lubricating oil additives, electric insulating materials, fuel additives, adhesives, putty glue, blending modification of other polymers and the like. However, the polyisobutene chain ends available on the market generally contain unsaturated double bonds, owing to chain transfer reactions and chain termination reactions. Polyisobutenes can be classified into conventional polyisobutenes and reactive polyisobutenes according to the chemical structure of the terminal double bond. The tail end alpha-olefin content of the common polyisobutene is less than 15%, and other structures are mainly beta-olefin and internal olefin; reactive polyisobutenes are polyisobutenes having a terminal alpha-olefin structure content of more than 70%, with the alpha-olefin structure content of commercially available reactive polyisobutenes generally being more than 80%.
Compared with viscosity standard substances such as silicone oil and mineral oil, the low molecular weight polyisobutene (LMPIB) is used as saturated alkane, and has more excellent heat stability, chemical resistance, weather resistance and the like. However, the currently commercially available LMPIB contains active ingredients such as alpha-olefin, beta-olefin and the like, and is extremely easy to generate oxidation, crosslinking and other reactions in the storage process, so that the viscosity change is large, the characteristics of uniformity and stability of a viscosity standard substance are violated, the application of the polyisobutene in the field of the viscosity standard substance is greatly limited, and the existence of alpha-olefin and beta-olefin structures becomes a problem to be solved in the application of the polyisobutene in the viscosity standard substance.
Disclosure of Invention
Aiming at the existing problems, the invention provides a preparation method of polyisobutene oil for viscosity standard substances, which is beneficial to the application of polyisobutene in the field of viscosity standard substances by modifying LMPIB (low molecular weight polyisobutene), reducing the content of double bonds in the structure, improving the stability of the polyisobutene.
The technical scheme of the invention is as follows:
a preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: the low molecular weight polyisobutene, alkane mercaptan and the catalyst react under the protection of nitrogen to obtain colorless transparent liquid.
Preferably, the molar ratio of the low molecular weight polyisobutene to the alkanethiol is from 100:1 to 100.
Preferably, the amount of material of the catalyst is 0-0.1 times the amount of material of the alkanethiol.
Preferably, the solvent selected in the reaction system is one of tetrahydrofuran, chloroform, N, N-dimethylformamide and N, N-dimethylacetamide. It is further preferred that the solvent is used in an amount of 30 to 80% by weight of the entire reaction system.
Preferably, the catalyst is one of benzoin dimethyl ether, azodiisobutyronitrile and benzhydryl ether, wherein the benzoin dimethyl ether and the benzhydryl ether are used under the irradiation of ultraviolet light, the azodiisobutyronitrile is used under the heating condition, and the heating temperature is 60-90 ℃.
Preferably, the colorless transparent liquid is washed with absolute ethanol or methanol, the lower polyisobutylene phase is collected and dried to finally obtain the polyisobutylene oil. Further preferably, the drying is carried out under vacuum at 50-90℃for 10-20 hours.
Preferably, the low molecular weight polyisobutene has an average molecular weight of from 200 to 1500g/mol.
Preferably, the reaction is carried out for 10 to 24 hours.
Since LMPIB contains active ingredients such as α -olefin and β -olefin, the problems of oxidation, crosslinking, and other reactions easily occur during storage, and the inventors found that during the exploration: because the mercapto has higher activity, the mercapto is extremely easy to react with double bonds under the action of a catalyst, and after the reaction is finished, the post-treatment is simple and convenient, and a product with stable performance can be obtained; in the reaction process, a photo/thermal initiation system is adopted, so that the pollution is avoided, the operability is strong, and the production cost is greatly reduced; the sulfhydryl group and olefin in the polyisobutene structure perform click reaction, the viscosity of the polyisobutene is kept stable in the storage process by reducing the double bond content of the polyisobutene, the requirement of developing the polyisobutene for standard substances is met, and the sulfhydryl group click reaction has the advantages of high efficiency, less side reaction, mild reaction conditions and the like. According to the invention, the mercapto alkane and the polyisobutene characteristic are combined to implement mercapto alkene click reaction, so that the modified low molecular weight polyisobutene of saturated alkane is synthesized, and is successfully used for viscosity standard substances.
The modification process of the polyisobutene oil for the viscosity standard substance comprises the following steps:
where r=saturated alkanes (methane, ethane, butane, etc.), n=y+z.
According to the preparation method of the polyisobutene oil for the viscosity standard substance, disclosed by the invention, the double bond content in the polyisobutene structure for the viscosity standard substance is reduced through the mercapto click reaction, and the double bond structure is prevented from reacting again in the use process of the modified polyisobutene, so that the viscosity of the polyisobutene oil is kept stable in the storage process, and the polyisobutene oil is more beneficial to the application of the polyisobutene as the viscosity standard substance.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of PIB 400;
FIG. 2 is a nuclear magnetic resonance spectrum of the polyisobutene prepared in example 1;
FIG. 3 is an infrared spectrum of the polyisobutene prepared in example 1;
FIG. 4 is a nuclear magnetic resonance spectrum of the polyisobutene prepared in example 2;
FIG. 5 is an infrared spectrum of the polyisobutene prepared in examples 3-5.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The following polyisobutene 400 (PIB 400) represents a polyisobutene having an average molecular mass of 400g/mol, polyisobutene 800 represents a polyisobutene having an average molecular mass of 800g/mol, and polyisobutene 1300 represents a polyisobutene having an average molecular mass of 1300g/mol. The polyisobutene is commercially available, and specifically selected from the Korean forest.
Example 1
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 400 (PIB 400,0.01 mol), mercaptooctane (0.01 mol), a photocatalyst benzoin dimethyl ether (0.001 mol) and a solvent tetrahydrofuran (10 mL) are added into a 50mL single-neck flask, vacuum pumping is carried out, ultraviolet light irradiation is carried out under the protection of nitrogen, colorless transparent liquid is obtained after reaction for 18 hours at room temperature, absolute ethyl alcohol is used for washing reaction products for many times after the reaction is finished, solution layering is carried out after standing, a lower polyisobutylene phase is collected, and hollow drying is carried out at 50 ℃ for 10 hours, so that the modified polyisobutylene oil for a viscosity standard substance is finally obtained.
Example 2
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 400 (0.15 mol), mercaptopropane (0.15 mol), benzoin dimethyl ether (0.0015 mol) serving as a photocatalyst and tetrahydrofuran (80 mL) serving as a solvent are added into a 250mL single-neck flask, vacuum pumping is carried out, ultraviolet light irradiation is carried out under the protection of nitrogen, colorless transparent liquid is obtained after room temperature reaction for 18 hours, colorless transparent liquid is obtained after reaction is finished, pale yellow transparent liquid is obtained after rotary evaporation, a reaction product is washed by absolute ethyl alcohol for multiple times, a solution is layered after standing, a lower polyisobutylene phase is collected, and hollow drying is carried out for 10 hours at 50 ℃ to finally obtain the modified polyisobutylene oil for the viscosity standard substance.
Example 3
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 400 (0.15 mol), mercaptobutane (0.15 mol), benzoin dimethyl ether (0.0015 mol) as a photocatalyst and tetrahydrofuran (80 mL) as a solvent are added into a 250mL single-neck flask, vacuum pumping is carried out, colorless transparent liquid is obtained after the reaction is carried out for 18 hours at room temperature under the irradiation of nitrogen and ultraviolet light, colorless transparent liquid is obtained after the reaction is finished, pale yellow transparent liquid is obtained after rotary evaporation, a reaction product is washed by absolute ethyl alcohol for multiple times, a solution is layered after standing, a lower polyisobutylene phase is collected, and the lower polyisobutylene phase is dried in a hollow mode for 10 hours at 50 ℃ to finally obtain the modified polyisobutylene oil for the viscosity standard substance.
Example 4
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 400 (0.15 mol), mercaptohexane (0.15 mol), benzoin dimethyl ether (0.0015 mol) as a photocatalyst and tetrahydrofuran (80 mL) as a solvent are added into a 250mL single-neck flask, vacuum pumping is carried out, the colorless and transparent liquid is obtained after the reaction is carried out for 18 hours at room temperature under the irradiation of nitrogen and ultraviolet light, the colorless and transparent liquid is obtained after the reaction is finished, light yellow and transparent liquid is obtained after rotary evaporation, a reaction product is washed by absolute ethyl alcohol for multiple times, a solution is layered after standing, a lower polyisobutylene phase is collected, and the lower polyisobutylene phase is dried in a hollow mode for 15 hours at 50 ℃ to finally obtain the modified polyisobutylene oil for the viscosity standard substance.
Example 5
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 400 (0.15 mol), mercaptoheptane (0.15 mol), benzoin dimethyl ether (0.0015 mol) as a photocatalyst and tetrahydrofuran (80 mL) as a solvent are added into a 250mL single-neck flask, vacuum pumping is carried out, colorless transparent liquid is obtained after the reaction is carried out for 18 hours at room temperature under the irradiation of nitrogen and ultraviolet light, colorless transparent liquid is obtained after the reaction is finished, pale yellow transparent liquid is obtained after rotary evaporation, a reaction product is washed by absolute ethyl alcohol for multiple times, a solution is layered after standing, a lower polyisobutylene phase is collected, and the lower polyisobutylene phase is dried in a hollow mode for 10 hours at 50 ℃ to finally obtain the modified polyisobutylene oil for the viscosity standard substance.
Example 6
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 400 (0.15 mol), mercaptooctane (0.15 mol), benzoin dimethyl ether (0.0015 mol) serving as a photocatalyst and tetrahydrofuran (80 mL) serving as a solvent are added into a 250mL single-neck flask, vacuum pumping is carried out, colorless and transparent liquid is obtained after the reaction is carried out for 18 hours at room temperature under the irradiation of nitrogen and ultraviolet light, colorless and transparent liquid is obtained after the reaction is finished, pale yellow and transparent liquid is obtained after rotary evaporation, a reaction product is washed with absolute ethyl alcohol for multiple times, a solution is layered after standing, a lower polyisobutylene phase is collected, and hollow drying is carried out for 10 hours at 50 ℃ to finally obtain the modified polyisobutylene oil for the viscosity standard substance.
Example 7
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 400 (0.2 mol), mercaptopropane (0.2 mol), benzoin dimethyl ether (0.01 mol) serving as a photocatalyst and tetrahydrofuran (150 mL) serving as a solvent are added into a 500mL single-neck flask, vacuum pumping is carried out, the colorless and transparent liquid is obtained after the reaction is carried out for 24 hours at room temperature under the irradiation of nitrogen and ultraviolet light, the colorless and transparent liquid is obtained after the reaction is finished, light yellow and transparent liquid is obtained after spin evaporation, a reaction product is washed by absolute ethyl alcohol for multiple times, a solution is layered after standing, a lower polyisobutylene phase is collected, and the lower polyisobutylene phase is dried in a hollow mode for 10 hours at 55 ℃ to finally obtain the modified polyisobutylene for the viscosity standard substance.
Example 8
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 800 (0.15 mol), mercaptohexane (0.15 mol), azodiisobutyronitrile (0.015 mol) as a catalyst and chloroform (80 mL) as a solvent are added into a 250mL single-neck flask, the mixture is vacuumized, and the mixture is reacted for 20 hours under the conditions of nitrogen and heating to 60 ℃ to obtain colorless and transparent liquid, the colorless and transparent liquid is obtained after the reaction is finished, the pale yellow and transparent liquid is obtained after the rotary evaporation, the reaction product is washed by absolute ethyl alcohol for multiple times, the solution is layered after standing, a lower polyisobutylene phase is collected, and the mixture is dried for 10 hours in a hollow mode at 50 ℃ to finally obtain the modified polyisobutylene for the viscosity standard substance.
Example 9
A preparation method of polyisobutene oil for viscosity standard substances comprises the following steps: polyisobutylene 1300 (0.4 mol), mercaptohexane (0.15 mol), photocatalyst benzil ether (0.015 mol) and solvent chloroform (80 mL) are added into a 1L single-neck flask, vacuum pumping is carried out, colorless transparent liquid is obtained after room temperature reaction is carried out for 20 hours under nitrogen and ultraviolet irradiation, colorless transparent liquid is obtained after the reaction is finished, pale yellow transparent liquid is obtained after rotary evaporation, a reaction product is washed by absolute ethyl alcohol for multiple times, a solution is layered after standing, a lower layer polyisobutylene phase is collected, and hollow drying is carried out for 10 hours at 50 ℃ to finally obtain the modified polyisobutylene for the viscosity standard substance.
As shown in fig. 1, PIB400 was characterized by nuclear magnetic hydrogen spectroscopy using deuterated chloroform as a solvent. Wherein the chemical shift is the absorption peak of the solvent at 7.26ppm, the multiple peaks at 0.5-2.0ppm are the chemical shifts of methyl and methylene groups of saturated alkanes in the polyisobutylene structure, and the chemical shifts are the alpha olefins obtained by directly deprotonating the PIB structure without isomerisation rearrangement at 4.64ppm and 4.85ppm, and the chemical shifts are the beta olefins obtained by directly deprotonating the corresponding polyisobutylene at 5.15ppm and 5.38ppm without isomerisation rearrangement. Because alpha olefin and beta olefin are active groups, polymerization reaction is easy to occur, and the existence of the alpha olefin and the beta olefin becomes an unstable factor in the application of the polyisobutene as a viscosity standard substance, thereby greatly limiting the application of the polyisobutene in the viscosity standard substance.
As shown in FIG. 2, in example 1, mercaptooctane and PIB400 undergo a mercapto-alkene click reaction to obtain a modified PIB400 nuclear magnetic hydrogen spectrum as shown in the figure. In the figure, the chemical shift is the absorption peak of deuterated chloroform at 7.26ppm, and the multiple peaks at 0.5ppm-2.0ppm of chemical shift are the methyl, methylene and alkane chemical shifts of saturated alkane in the polyisobutylene structure. In addition, it can be seen that almost no peak is generated at the positions of 4.4ppm to 5.6ppm in the chemical shift, which indicates that the alpha olefin and the beta olefin in the PIB400 structure successfully undergo a click reaction with mercapto groups, so that the saturated alkane polyisobutene with stable performance is obtained and can be used as a viscosity standard substance.
FIG. 3 is an infrared absorption spectrum of modified polyisobutylene oil obtained after PIB400 click reaction in example 1, as can be seen from the figure, 2965cm -1 The structure is characterized in that the structure is provided with a stretching vibration absorption peak of methyl and methylene, the peak is stronger, and the content of the methyl methylene in the structure is higher and is 1477cm -1 、1372cm -1 The equivalent is the bending vibration peak of methyl and methylene, and in the PIB structure modified by mercaptooctyl, the peak is 728cm -1 The absorption peak of the C-S bond was found, indicating that a saturated polyisobutene with better stability was successfully obtained.
As shown in FIG. 4, in example 2, mercaptopropane and PIB400 were subjected to a mercapto-olefin click reaction to obtain modified PIB400 nuclear magnetism as shown in the figure. In the figure, the chemical shift is the absorption peak of deuterated chloroform at 7.26ppm, and the multiple peaks at 0.5ppm-2.0ppm of chemical shift are the methyl, methylene and alkane chemical shifts of saturated alkane in the polyisobutylene structure. In addition, it can be seen that almost no peak is generated at the positions of 4.4ppm to 5.6ppm in the chemical shift, which indicates that the alpha olefin and the beta olefin in the PIB400 structure successfully undergo a click reaction with mercapto groups, so that the saturated alkane polyisobutene with stable performance is obtained and can be used as a viscosity standard substance.
FIG. 5 is an infrared absorption spectrum of modified polyisobutylene oil obtained after PIB click reaction in examples 3-5, as can be seen from the figure, 2965cm -1 The structure is characterized in that the structure is provided with a stretching vibration absorption peak of methyl and methylene, the peak is stronger, and the content of the methyl methylene in the structure is higher and is 1477cm -1 、1372cm -1 The equivalent is the bending vibration peak of methyl and methylene, and in the PIB structure modified by mercaptooctyl, the peak is 728cm -1 The absorption peak of the C-S bond was found, indicating that a saturated polyisobutene with better stability was successfully obtained.
Test examples
Table 1 shows the viscosity changes of PIB before and after modification at 20 ℃ (examples 3-9).
TABLE 1 viscosity Change before and after PIB modification at 20 ℃
As can be seen from Table 1, the viscosity of the polyisobutene increased after the mercapto-click reaction, due to the addition of sulfur-containing alkanes in the polymer chain, and also indicated that double bonds in the polyisobutene structure did react with mercaptoalkanes.
Stability test
Table 2 shows the viscosity change after half a year of PIB storage at 20 ℃.
TABLE 2 viscosity Change after PIB storage for a certain time before and after modification at 20 ℃
As can be seen from Table 2, the viscosity change rate of unmodified PIB exceeds 2% and does not meet the requirement (GB/T265) of less than 1% of the viscosity standard substance stability, while the viscosity change of modified PIB after one year of storage is only about 0.2% and the stability thereof exceeds ten orders of magnitude, which indicates that the modified PIB is more stable and meets the requirement of the viscosity standard substance.
Uniformity test
The modified polyisobutene oil obtained in example 3 was subjected to split charging, and the sampling amount per bottle was 20mL. And randomly extracting 6 bottles of the samples after sub-packaging, and carrying out uniformity inspection according to the requirement of a constant value experiment. The test temperature was 20 ℃, and the kinematic viscosity was calculated by measuring the outflow time at the measured temperature 2 times per bottle with independent sampling. And judging whether a systematic error exists or not through the comparison of the intra-group variance and the inter-group variance, simultaneously counting the measured data by using an F distribution function, and judging that the sample is uniform if F is less than or equal to F (a critical value of statistical test), or non-uniform if F is less than or equal to F.
TABLE 3 example 3 uniformity test results
As can be seen from Table 3, the modified polyisobutene oil obtained in example 3 was homogeneous and met the requirements of the viscosity standard.
According to the preparation method of the polyisobutene oil for the viscosity standard substance, disclosed by the invention, the double bond content in the polyisobutene structure for the viscosity standard substance is reduced through the mercapto click reaction, and the double bond structure is prevented from reacting again in the use process of the modified polyisobutene, so that the viscosity of the polyisobutene oil is kept stable in the storage process, and the polyisobutene oil is more beneficial to the application of the polyisobutene as the viscosity standard substance.
Claims (10)
1. The preparation method of the polyisobutene oil for the viscosity standard substance is characterized by comprising the following steps of: the low molecular weight polyisobutene, alkane mercaptan and the catalyst react under the protection of nitrogen to obtain colorless transparent liquid.
2. The method for preparing polyisobutylene oil for viscosity standard according to claim 1, wherein the molar ratio of the low molecular weight polyisobutylene to the alkanethiol is 100:1-100.
3. The method for preparing polyisobutylene oil for viscosity standard according to claim 1, wherein the amount of the material of the catalyst is 0-0.1 times the amount of the material of the alkanethiol.
4. The method for preparing polyisobutylene oil for viscosity standard substances according to claim 1, wherein the catalyst is one of benzoin dimethyl ether, azobisisobutyronitrile, and benzhydryl ether; wherein, benzoin dimethyl ether and benzhydryl ether are used under the irradiation of ultraviolet light, and azo-diisobutyronitrile is used under the heating condition, and the heating temperature is 60-90 ℃.
5. The method for preparing a polyisobutene oil for a viscosity standard according to claim 1, wherein the low molecular weight polyisobutene has an average molecular weight of 200-1500g/mol.
6. The method for preparing the polyisobutene oil for the viscosity standard substance according to claim 1, wherein the colorless transparent liquid is washed by absolute ethyl alcohol or methanol, a lower polyisobutene phase is collected, and the polyisobutene oil is finally obtained after drying.
7. The method for preparing a polyisobutene oil for a viscosity standard according to claim 6, wherein the polyisobutene oil is dried in vacuum at 50-90 ℃ for 10-20 hours.
8. The method for preparing a polyisobutene oil for a viscosity standard according to claim 1, wherein the reaction is carried out for 10 to 24 hours.
9. The method for preparing polyisobutylene oil for viscosity standard according to claim 1, wherein the solvent selected in the reaction system is one of tetrahydrofuran, chloroform, N-dimethylformamide, N-dimethylacetamide.
10. The method for preparing polyisobutylene oil for viscosity standard according to claim 1, wherein the solvent is used in an amount of 30-80wt% of the whole reaction system.
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3103500A (en) * | 1963-09-10 | Polyolefins heat stabilized with z-alkyl- | ||
US4080364A (en) * | 1976-09-27 | 1978-03-21 | Argus Chemical Corporation | Stabilization of polyolefins against degradative deterioration as a result of exposure to light and air at elevated temperatures |
SU1659424A1 (en) * | 1988-08-28 | 1991-06-30 | Казанский Химико-Технологический Институт Им.С.М.Кирова | Method for obtaining polyisobutylene |
CN101925614A (en) * | 2008-01-29 | 2010-12-22 | 朗盛德国有限责任公司 | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
CN101932611A (en) * | 2008-01-29 | 2010-12-29 | 朗盛德国有限责任公司 | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
US20140087986A1 (en) * | 2012-09-27 | 2014-03-27 | Exxonmobil Research And Engineering Company | High viscosity, functionalized metallocene polyalphaolefin base stocks and processes for preparing same |
CN105873995A (en) * | 2013-12-30 | 2016-08-17 | 阿朗新科德国有限责任公司 | Nitrile-butadiene rubbers that are stable in storage and method for producing same |
WO2019020491A1 (en) * | 2017-07-28 | 2019-01-31 | Basf Se | Lubricant composition containing copolymers of polyisobutylenemethacrylate |
CN109504440A (en) * | 2018-11-15 | 2019-03-22 | 江苏科创石化有限公司 | A kind of slurry fouling inhibitor |
-
2023
- 2023-05-11 CN CN202310538801.2A patent/CN116444702A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3103500A (en) * | 1963-09-10 | Polyolefins heat stabilized with z-alkyl- | ||
US4080364A (en) * | 1976-09-27 | 1978-03-21 | Argus Chemical Corporation | Stabilization of polyolefins against degradative deterioration as a result of exposure to light and air at elevated temperatures |
SU1659424A1 (en) * | 1988-08-28 | 1991-06-30 | Казанский Химико-Технологический Институт Им.С.М.Кирова | Method for obtaining polyisobutylene |
CN101925614A (en) * | 2008-01-29 | 2010-12-22 | 朗盛德国有限责任公司 | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
CN101932611A (en) * | 2008-01-29 | 2010-12-29 | 朗盛德国有限责任公司 | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
US20140087986A1 (en) * | 2012-09-27 | 2014-03-27 | Exxonmobil Research And Engineering Company | High viscosity, functionalized metallocene polyalphaolefin base stocks and processes for preparing same |
CN105873995A (en) * | 2013-12-30 | 2016-08-17 | 阿朗新科德国有限责任公司 | Nitrile-butadiene rubbers that are stable in storage and method for producing same |
WO2019020491A1 (en) * | 2017-07-28 | 2019-01-31 | Basf Se | Lubricant composition containing copolymers of polyisobutylenemethacrylate |
CN109504440A (en) * | 2018-11-15 | 2019-03-22 | 江苏科创石化有限公司 | A kind of slurry fouling inhibitor |
Non-Patent Citations (1)
Title |
---|
张锡鹏;: "苏联聚异丁烯粘度添加剂的化学改质", 润滑油, no. 02, 31 December 1989 (1989-12-31), pages 25 - 28 * |
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