CN113856752B - Pyridine polymer ionic liquid solid acid catalyst and preparation method and application thereof - Google Patents
Pyridine polymer ionic liquid solid acid catalyst and preparation method and application thereof Download PDFInfo
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- CN113856752B CN113856752B CN202111084375.7A CN202111084375A CN113856752B CN 113856752 B CN113856752 B CN 113856752B CN 202111084375 A CN202111084375 A CN 202111084375A CN 113856752 B CN113856752 B CN 113856752B
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- neopentyl glycol
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000011973 solid acid Substances 0.000 title claims abstract description 40
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 23
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 20
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005642 Oleic acid Substances 0.000 claims abstract description 20
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 20
- VVEKMBGQZPFARL-QXMHVHEDSA-N (3-hydroxy-2,2-dimethylpropyl) (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(C)(C)CO VVEKMBGQZPFARL-QXMHVHEDSA-N 0.000 claims abstract description 16
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- -1 4-butanesulfonic acid lactone Chemical class 0.000 claims description 16
- 238000005886 esterification reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011831 acidic ionic liquid Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 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 9
- 230000032050 esterification Effects 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 10
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 1
- 238000007867 post-reaction treatment Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 7
- 239000010689 synthetic lubricating oil Substances 0.000 description 5
- YTZPOZMREXHDFV-UHFFFAOYSA-N 4-(2-ethenyl-2H-pyridin-1-yl)butane-1-sulfonic acid Chemical compound C=CC1C=CC=CN1CCCCS(=O)(=O)O YTZPOZMREXHDFV-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMTDFMMXJHYDDE-UHFFFAOYSA-N 2-prop-1-enylpyridine Chemical compound CC=CC1=CC=CC=N1 SMTDFMMXJHYDDE-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 description 1
- 229940031016 ethyl linoleate Drugs 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the biological lubricating oil preparation technology, and in particular relates to a pyridine polymer ionic liquid solid acid catalyst, a preparation method and application thereof. In the reaction of synthesizing neopentyl glycol oleate, the catalyst is added in an amount of 0.1-0.6 wt.% of the total amount of neopentyl glycol and oleic acid, the water-carrying agent toluene is added in an amount of 5-15 wt.% of the total amount of neopentyl glycol and oleic acid, reflux dehydration is carried out for 2-5 h, and the crude product obtained by the reaction is washed, steamed and adsorbed by rotation to obtain the final product. The polymerized ionic solid acid catalyst in the reaction is prepared by synthesizing ionic monomers and polymerizing ionic liquid, and has the advantages of mild generating conditions, easy preparation, good catalytic activity, no corrosion to equipment, simple post-reaction treatment and repeatable use of products.
Description
Technical Field
The invention belongs to the biological lubricating oil preparation technology, and in particular relates to a pyridine polymer ionic liquid solid acid catalyst, a preparation method and application thereof.
Background
Synthetic lubricating oils have good thermal stability, a wide liquid range, a high viscosity index, and good friction lubrication characteristics. Among all synthetic lubricating oils, polyol esters are represented (Zhang Wei, liu Dongzhi. Development and status of synthetic ester lubricating oils [ J ]. Chemical propellants and polymeric materials, 1998 (05): 8-10.). The neopentyl glycol oleate not only meets the above aspects, but also has good oxidation resistance, no toxicity, no peculiar smell, good biodegradability and no influence on the environment. Is suitable for the fields of high-speed spinning oil, aeroengine lubricating oil, metal high-temperature processing oil and the like.
In the esterification reaction for synthesizing neopentyl glycol oleate, the catalyst plays an important role, and influences the conversion rate of the product. Currently, industrially employed transmissionThe conventional catalyst such as p-toluenesulfonic acid has high catalytic activity, but has many problems such as serious waste acid pollution, complex post-treatment process and high corrosion of the p-toluenesulfonic acid to equipment. Chinese patent literature (publication No. CN 102826999A) discloses a method for preparing a metal-based solid acid S 2 O/TiO e -La 2 O 3 Or solid acid ZnO/SiO 2 The method for preparing neopentyl glycol oleate by esterification reaction of the catalyst has 92 percent of yield, but the catalyst is added in an amount of 4 weight percent, and the synthesis condition of the metal solid acid catalyst is high, so that the high temperature of 300-700 ℃ is needed. SO for Chinese patent document (publication No. CN 101139288A) 4 2- /TiO 2 -SiO 2 The esterification rate of the method for preparing ethyl linoleate by catalyzing linoleic acid and absolute ethyl alcohol with composite solid superacid can reach more than 95%, but the preparation process of the metal solid acid catalyst is complex, for example, the preparation of metal oxide only needs more than four times by washing and suction filtration, and the generated oxide particles are very fine, so that suction filtration is slow, and a large amount of water resources are wasted.
In view of the foregoing, there is a need for a catalyst that has high performance, is simple to operate, and is gentle to react to solve these problems.
Disclosure of Invention
The purpose of the invention is that: in order to overcome the defects in the prior art, the invention provides a pyridine polymer ionic liquid solid acid catalyst, a preparation method and application thereof, and the catalyst is particularly used as an esterification catalyst, particularly used as a catalyst for the esterification reaction of neopentyl glycol and oleic acid, so as to prepare neopentyl glycol oleate.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows: the pyridine polymer ionic liquid solid acid catalyst is characterized in that: has the general formula of [ PyR ] n Im][HSO 4 ]The catalyst is prepared by polymerizing an acidic ionic liquid monomer, and the structural formula of the acidic ionic liquid monomer is as follows:wherein R is a group containing a polymerizable olefinic bond.
Further, n=4;
and/or the polymeric ionic liquid contains 50-100 units derived from acidic ionic liquid monomers.
The preparation method of the pyridine polymer ionic liquid solid acid catalyst comprises the following steps:
(1) Under the condition of heating and stirring (the temperature is preferably 25-40 ℃), adding 1, 4-butanesulfonic acid lactone and pyridine compound (preferably heated in equimolar quantity, wherein the pyridine compound has a general formula of PyR, R is a group containing a polymerizable double bond, preferably any one of vinyl, propenyl and butenyl), and washing with ethyl acetate (generally for 2-3 times) after the reaction is finished (the reaction time is preferably 4-6 h), so as to obtain an ionic liquid intermediate;
(2) Adding distilled water into the ionic liquid intermediate prepared in the step (1) for dissolution, adding concentrated sulfuric acid (preferably, the sulfuric acid and the ionic liquid intermediate are in equimolar quantity), heating and stirring for reaction (the reaction temperature is preferably 40-60 ℃, the reaction time is preferably 3-5 h), and carrying out rotary evaporation for water removal to obtain an acidic ionic liquid monomer;
(3) Adding an ethanol solvent into the acidic ionic liquid monomer prepared in the step (2), stirring to completely dissolve the acidic ionic liquid monomer, adding an initiator azodiisobutyronitrile (preferably 0.1-0.3 wt.% of azodiisobutyronitrile) under the heating condition, promoting the ionic liquid monomer to polymerize through double bonds in R (the polymerization reaction time is preferably 3-6 h), adding ethyl acetate to wash for 2-3 times, standing and drying in vacuum to obtain the pyridine polymerized ionic liquid solid acid catalyst.
Further, in the step (3), the adding amount of the initiator azodiisobutyronitrile is 0.1-0.3 wt% of the mass of the added ionic liquid monomer, the heating temperature is 65-80 ℃, and the reaction time is 3-6 h.
Specifically, the structural formula of the polymeric 1- (4-sulfobutyl) -2-vinylpyridine ionic liquid is as follows:
the structural formula of the polymerized 1- (4-sulfopropyl) -2-propenyl pyridine ionic liquid is as follows:
the structural formula of the polymerized 1- (4-sulfopropyl) -2-butenyl pyridine ionic liquid is as follows:
the pyridine polymer ionic liquid solid acid catalyst is used as an esterification catalyst.
The invention also provides a method for synthesizing the neopentyl glycol oleate, which comprises the following specific steps:
neopentyl glycol and oleic acid are used as raw materials, toluene is used as a water-carrying agent, the dosage of toluene is 5-15 wt.% of the total mass of the added neopentyl glycol and oleic acid, the pyridine polymer ionic liquid solid acid catalyst is added for esterification reaction, and then the neopentyl glycol oleate is prepared through water washing, rotary evaporation and adsorption processes.
Wherein the weight ratio of the catalytic neopentyl glycol to the oleic acid is 1:5.3-6; the catalyst is used in an amount of 0.1 to 0.6wt.% based on the total amount of neopentyl glycol and oleic acid, and the reflux dehydration is carried out for 2 to 5 hours. The rotary steaming adopts a vacuum pump combined with an oil bath pot, the vacuum degree is-0.10 Mpa to-0.095 Mpa, the temperature is 200-300 ℃ and the time is 2-4 hours, and the final product is used for adsorbing odor and color by using activated carbon.
Compared with the prior art, the invention has the following beneficial effects:
the invention innovatively provides a method for synthesizing a high-performance pyridine polymer ionic liquid solid acid catalyst and a type of catalyst used for synthesizing a neopentyl glycol oleate system. The pyridine polymer ionic liquid solid acid catalyst can be used as a catalyst for preparing synthetic lubricating oil, has great application potential in the field of synthetic lubricating oil production, and lays a foundation for promoting the popularization of green high-performance synthetic lubricating oil in China. The method has the specific advantages that:
1. the catalyst has relatively mild synthesis condition, convenient operation and large scale production.
2. The problems of large catalyst dosage and difficult separation of the catalyst and the product in the background technology are overcome.
3. The neopentyl glycol oleate synthesized by the selected polymeric ionic liquid solid acid catalyst has high product yield and good product color.
4. The preparation process has no wastewater discharge, and the redundant unreacted raw materials can be recycled, thus being a green process.
Drawings
FIG. 1 is a FI-IR spectrum of neopentyl glycol oleate as an esterification product in the examples of the invention.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
example 1:
the embodiment is a prepared polymerized 1- (4-sulfobutyl) -2-vinyl pyridine ionic liquid solid acid, which comprises the following specific synthetic steps:
adding equimolar 1, 4-butyl sultone and vinyl pyridine under the condition of stirring at 30 ℃, finishing the reaction for 4 hours, and washing with ethyl acetate for 2 times to prepare the ionic liquid intermediate. Adding a proper amount of distilled water into the prepared ionic liquid intermediate for dissolution, adding equimolar concentrated sulfuric acid, heating to 40 ℃ and stirring for reaction, and performing rotary evaporation to remove water after the reaction is finished for 3 hours to prepare the ionic liquid monomer. The addition amount of the initiator azodiisobutyronitrile is 0.1wt.% of the mass of the monomer of the added ionic liquid, the heating temperature is 65 ℃, the reaction time is 3h, the vinyl polymerization ionic liquid is prepared by rotary evaporation for water removal, and the yield of the polymerization ionic liquid is 96.7%.
The structural formula of the polymerized 1- (4-sulfobutyl) -2-vinyl pyridine ionic liquid is as follows:
example 2:
the embodiment is a prepared polymerized 1- (4-sulfobutyl) -2-propenyl pyridine ionic liquid solid acid, which comprises the following specific synthetic steps:
adding equimolar 1, 4-butyl sultone and propenyl pyridine under the condition of stirring at 30 ℃, finishing the reaction for 5 hours, and washing with ethyl acetate for 2 times to prepare the ionic liquid intermediate. Adding a proper amount of distilled water into the prepared ionic liquid intermediate for dissolution, adding equimolar concentrated sulfuric acid, heating to 40 ℃ and stirring for reaction, and performing rotary evaporation to remove water after the reaction is finished for 3 hours to prepare the ionic liquid monomer. The addition amount of the initiator azodiisobutyronitrile is 0.2wt.% of the mass of the added ionic liquid monomer, the heating temperature is 65 ℃, the reaction time is 3h, the dehydration is carried out by rotary evaporation, and the allyl polymerized ionic liquid is prepared, and the yield of the polymerized ionic liquid is 97.2%.
The structural formula of the polymerized 1- (4-sulfopropyl) -2-propenyl pyridine ionic liquid is as follows:
example 3:
the embodiment is a prepared polymerized 1- (4-sulfobutyl) -2-butenyl pyridine ionic liquid solid acid, which comprises the following specific synthesis steps:
adding equimolar 1, 4-butanesultone and butenyl pyridine under the condition of stirring at 30 ℃, finishing the reaction for 6 hours, and washing with ethyl acetate for 3 times to prepare the ionic liquid intermediate. Adding a proper amount of distilled water into the prepared ionic liquid intermediate for dissolution, adding equimolar concentrated sulfuric acid, heating to 60 ℃ and stirring for reaction, and performing rotary evaporation to remove water after the reaction is finished for 5 hours to prepare the ionic liquid monomer. The addition amount of the initiator azodiisobutyronitrile is 0.3wt.% of the mass of the added ionic liquid monomer, the heating temperature is 65 ℃, the reaction time is 3h, the rotary evaporation is carried out to remove water, and the butene-based polymerized ionic liquid is prepared, and the yield of the polymerized ionic liquid is 95.4%.
The structural formula of the polymerized 1- (4-sulfopropyl) -2-butenyl pyridine ionic liquid is as follows:
example 4:
100 parts of neopentyl glycol, 600 parts of oleic acid and 90 parts of toluene are added into a reactor as a water carrying agent, 2 parts of solid acid catalyst 1- (4-sulfobutyl) -2-vinyl pyridine ionic liquid solid acid catalyst are added under stirring, the temperature is raised to 70-115 ℃, and reflux is carried out for 2-4 hours. And after the reaction is finished, standing and settling are carried out, and the catalyst is separated. Adopting a vacuum pump and an oil bath pot to perform rotary steaming, wherein the vacuum degree is-0.10 mMpa to-0.095 mMpa, the temperature is 200-300 ℃, the time is 2-4 h, and toluene, oleic acid and water are removed. The end product neopentyl glycol oleate is adsorbed with activated carbon for odor and color.
The esterification rate of the embodiment is 99.1%, the yield is 94.3%, the catalyst dosage is 0.3wt.%, which is obviously higher than that of the prior art, and the product has good color and light yellow.
Example 5:
100 parts of neopentyl glycol, 600 parts of oleic acid and 90 parts of toluene are added into a reactor as a water carrying agent, 3 parts of solid acid catalyst 1- (4-sulfobutyl) -2-propenyl pyridine ionic liquid solid acid catalyst are added under stirring, the temperature is raised to 70-115 ℃, and reflux dehydration is carried out for 3-5 hours. And after the reaction is finished, standing and settling are carried out, and the catalyst is separated. Adopting a vacuum pump and an oil bath pot to perform rotary steaming, wherein the vacuum degree is-0.10 Mpa to-0.095 Mpa, the temperature is 200-300 ℃, the time is 2-4 hours, and toluene, oleic acid and water are removed. The end product neopentyl glycol oleate is adsorbed with activated carbon for odor and color.
The esterification rate of the embodiment is 99.4%, the yield is 95.5%, the catalyst dosage is 0.4wt.%, which is obviously higher than that of the prior art, and the product has good color and light yellow.
Example 6:
100 parts of neopentyl glycol, 600 parts of oleic acid and 90 parts of toluene are added into a reactor as a water carrying agent, 4 parts of solid acid catalyst 1- (4-sulfobutyl) -2-propenyl pyridine ionic liquid solid acid catalyst are added under stirring, the temperature is raised to 70-115 ℃, and reflux dehydration is carried out for 3-5 hours. And after the reaction is finished, standing and settling are carried out, and the catalyst is separated. Adopting a vacuum pump and an oil bath pot to perform rotary steaming, wherein the vacuum degree is-0.10 Mpa to-0.095 Mpa, the temperature is 200-300 ℃, the time is 2-4 hours, and toluene, oleic acid and water are removed. The end product neopentyl glycol oleate is adsorbed with activated carbon for odor and color.
The esterification rate of the embodiment is 99.5%, the yield is 96%, the catalyst consumption is 0.6% by weight, which is obviously higher than that of the prior art, and the product has good color and pale yellow.
Example 7:
100 parts of neopentyl glycol, 600 parts of oleic acid and 90 parts of toluene are added into a reactor as a water carrying agent, 4 parts of solid acid catalyst 1- (4-sulfobutyl) -2-butenyl pyridine ionic liquid solid acid catalyst are added under stirring, the temperature is raised to 70-115 ℃, and reflux dehydration is carried out for 3-5 hours. And after the reaction is finished, standing and settling are carried out, and the catalyst is separated. Adopting a vacuum pump and an oil bath pot to perform rotary steaming, wherein the vacuum degree is-0.10 Mpa to-0.095 Mpa, the temperature is 200-300 ℃, the time is 2-4 hours, and toluene, oleic acid and water are removed. The end product neopentyl glycol oleate is adsorbed with activated carbon for odor and color.
The esterification rate of the embodiment is 99.6%, the yield is 96.1%, the catalyst dosage is 0.3wt.%, which is obviously higher than that of the prior art, and the product has good color and light yellow.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (9)
1. PyridineThe polymeric ionic liquid solid acid catalyst is characterized in that: has the general formula of [ PyR ] n Im][HSO 4 ]The catalyst is prepared by polymerizing an acidic ionic liquid monomer, and the structural formula of the acidic ionic liquid monomer is as follows:
wherein R is a group containing a polymerizable olefinic bond, said n=4;
the polymeric ionic liquid contains 50-100 units derived from acidic ionic liquid monomers.
2. The method for preparing the pyridine polymer ionic liquid solid acid catalyst according to claim 1, which is characterized in that: the method comprises the following steps:
(1) Adding 1, 4-butanesulfonic acid lactone and pyridine compounds under the condition of heating and stirring, and washing with ethyl acetate after the reaction is finished to prepare an ionic liquid intermediate; wherein the pyridine compound has a general formula of PyR, wherein R is a group containing a polymerizable double bond;
(2) Adding distilled water into the ionic liquid intermediate prepared in the step (1) for dissolution, adding concentrated sulfuric acid, heating and stirring for reaction, and performing rotary evaporation for water removal after the reaction is finished to prepare an acidic ionic liquid monomer;
(3) Adding ethanol solvent into the acidic ionic liquid monomer prepared in the step (2), stirring to completely dissolve the acidic ionic liquid monomer, adding azo-bis-isobutyronitrile initiator under the heating condition to promote the ionic liquid monomer to polymerize through double bonds in R, adding ethyl acetate to wash after the reaction is finished, and standing for vacuum drying to obtain the pyridine polymer ionic liquid solid acid catalyst.
3. The method for preparing the pyridine polymer ionic liquid solid acid catalyst according to claim 2, which is characterized in that: in the step (1), the addition amount of the 1, 4-butanesulfonic acid lactone and the pyridine compound is equimolar, the heating temperature is 25-40 ℃, and the reaction time is 4-6 hours;
and/or R is vinyl, allyl or butenyl.
4. The method for preparing the pyridine polymer ionic liquid solid acid catalyst according to claim 2, which is characterized in that: in the step (2), the addition amount of the ionic liquid intermediate and the concentrated sulfuric acid is equimolar, the reaction temperature is 40-60 ℃, and the reaction time is 3-5 hours.
5. The method for preparing the pyridine polymer ionic liquid solid acid catalyst according to claim 2, which is characterized in that: in the step (3), the addition amount of the initiator azodiisobutyronitrile is 0.1-0.3 wt.% of the mass of the added ionic liquid monomer, the heating temperature is 65-80 ℃, and the reaction time is 3-6 h.
6. The use of the pyridine polymer ionic liquid solid acid catalyst according to claim 1, wherein: used as an esterification catalyst.
7. The use of the pyridine polymer ionic liquid solid acid catalyst according to claim 6, wherein: used as a catalyst for the esterification reaction of neopentyl glycol and oleic acid, thereby producing neopentyl glycol oleate.
8. The use of the pyridine polymer ionic liquid solid acid catalyst according to claim 7, wherein: the method comprises the following steps: neopentyl glycol and oleic acid are used as raw materials, toluene is used as a water-carrying agent, the dosage of toluene is 5-15 wt.% of the total mass of the added neopentyl glycol and oleic acid, the pyridine polymer ionic liquid solid acid catalyst is added for esterification reaction, and then the neopentyl glycol oleate is prepared through water washing, rotary evaporation and adsorption processes.
9. The use of the pyridine polymer ionic liquid solid acid catalyst according to claim 8, wherein: the weight ratio of the catalytic neopentyl glycol to the oleic acid is 1:5.3-6; the dosage of the catalyst is 0.1-wt wt.% to 0.6wt.% of the total amount of neopentyl glycol and oleic acid, and the reflux dehydration is carried out for 2-5 h; the rotary steaming after the esterification reaction adopts a vacuum pump and an oil bath pot, the vacuum degree is-0.10 Mpa to-0.095 Mpa, the temperature is 200-300 ℃, and the time is 2-4 h.
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| CN101456813A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing polyatomic alcohol fatty acid ester |
| KR20200095188A (en) * | 2019-01-31 | 2020-08-10 | 주식회사 엘지화학 | Composite for solid polymer electrolytes and all solid polymer electrolytes comprising the same |
| CN112174876A (en) * | 2020-10-14 | 2021-01-05 | 江苏高科石化股份有限公司 | Preparation method and application of pyridine ionic liquid acidic catalyst |
| CN112264095A (en) * | 2020-11-05 | 2021-01-26 | 常州大学 | Polymeric ionic liquid solid acid catalyst for catalyzing esterification reaction of pentaerythritol and oleic acid and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456813A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing polyatomic alcohol fatty acid ester |
| KR20200095188A (en) * | 2019-01-31 | 2020-08-10 | 주식회사 엘지화학 | Composite for solid polymer electrolytes and all solid polymer electrolytes comprising the same |
| CN112174876A (en) * | 2020-10-14 | 2021-01-05 | 江苏高科石化股份有限公司 | Preparation method and application of pyridine ionic liquid acidic catalyst |
| CN112264095A (en) * | 2020-11-05 | 2021-01-26 | 常州大学 | Polymeric ionic liquid solid acid catalyst for catalyzing esterification reaction of pentaerythritol and oleic acid and preparation method thereof |
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