CN102690705A - Synthesis process of novel lubricant pour point depressant - Google Patents
Synthesis process of novel lubricant pour point depressant Download PDFInfo
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- CN102690705A CN102690705A CN2012101229165A CN201210122916A CN102690705A CN 102690705 A CN102690705 A CN 102690705A CN 2012101229165 A CN2012101229165 A CN 2012101229165A CN 201210122916 A CN201210122916 A CN 201210122916A CN 102690705 A CN102690705 A CN 102690705A
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- pour point
- vinylformic acid
- alcohol ester
- carbon alcohol
- point depressant
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Abstract
The invention provides a synthesis process of a novel lubricant pour point depressant, specifically comprising the following steps: synthetizing high alcohols, polymerization inhibitor, crylic acid and catalyst to obtain white waxy solid acrylic high alcohols ester, and then synthetizing the acrylic high alcohols ester and biopolymer of cetene to obtain biopolymer of acrylic high alcohols ester and cetene. A synthetic ratio of synthetic technologies provided by the invention is high; biopolymer of acrylic high alcohols ester and cetene synthetized by the technology is used as lubricant and pour point depressant, is featured with high purity, and is capable of helping to reduce pour points under the condition that pour point depressants have bad use effects when saled pour point depressants are used singly, so that application prospect is better.
Description
Technical field
The present invention relates to the synthetic field of chemical industry, be specifically related to a kind of synthesis technique of novel lubricant pour point depressant.
Background technology
The distribution of oil product normal paraffin is the principal element that influences the pour point depression effect, and the length of distribution of normal alkanes and pour point depressant ester chain has certain corresponding relation.There is an optimum value in the lateral chain of ester group carbon number of single kind pour point depressant, simultaneously different oil products is had the pour point depression selectivity, has limited the scope of application of single composition pour point depressant.The pour point depressant that different chemical is formed carries out composite, improves the pour point depression effect through coordinating effect, can expand the use range of pour point depressant.
Summary of the invention
The present invention provides a kind of synthesis technique of novel lubricant pour point depressant, and the pour point depressant that makes can rise and assist pour-point depressing process when the independent result of use of commercially available pour point depressant be not good.
For realizing the foregoing invention purpose, the technical scheme that the present invention adopted is:
A kind of synthesis technique of novel lubricant pour point depressant, concrete steps are following:
1) vinylformic acid high-carbon alcohol ester is synthetic: in the there-necked flask that reflux condensing tube, TM and whisking appliance are housed, add the higher alcohols and the stopper of metering, be heated to certain temperature higher alcohols are melted fully, add vinylformic acid and catalyzer more successively; At 110～120 ℃ of about 2.5h of following reflux, progressively be warming up to 135～145 ℃ then, wherein, be warming up to 140 ℃, need 6h approximately, get the thick ester of product for best; Remove intact unsaturated acid and the residual water of unreacted in the thick ester through underpressure distillation; The use temperature is that 40～60 ℃ x is 0.2% weak lye washing an acidic catalyst and stopper; Be neutral with distilled water wash until ester again; With cryodrying 8h under the products therefrom vacuum, obtain white waxy solid vinylformic acid high-carbon alcohol ester;
2) copolymer of vinylformic acid high-carbon alcohol ester and hexadecylene is synthetic: in the four-hole boiling flask of 250mL, add a certain amount of vinylformic acid high-carbon alcohol ester, hexadecylene and toluene solvant; Under the protection of N2; Be heated to temperature of reaction; Slowly drip initiator B PO, stop behind the isothermal reaction number hour under the continuously stirring; Toluene is removed in underpressure distillation, uses absolute ethanol washing, and cooling treats that product solidifies the back suction filtration at low temperatures, obtains the copolymer of pour point depressant vinylformic acid high-carbon alcohol ester and hexadecylene.
Preferably, the reaction molar weight ratio of said vinylformic acid and higher alcohols is 1.25: 1; In the total inventory that adds, said catalyst levels is 1.0%, and the consumption of stopper is 0.5%, and the copolymer consumption of vinylformic acid high-carbon alcohol ester and hexadecylene is 0.5%, and the consumption of initiator is 1%.
Preferably, the copolymer of said vinylformic acid high-carbon alcohol ester and hexadecylene synthetic, isothermal reaction 4～6h wherein reacts 5h for best.
The advantage of the inventive method is:
Synthesis technique synthetic ratio of the present invention is high, through the copolymer of this technology synthetic vinylformic acid high-carbon alcohol ester and hexadecylene, as lubricant and pour point depressant pour point depressant; Purity is high; And can when the independent result of use of commercially available pour point depressant be not good, rise and assist pour-point depressing process, application promise in clinical practice is arranged.
Embodiment
A kind of synthesis technique of novel lubricant pour point depressant,
1. vinylformic acid high-carbon alcohol ester is synthetic
Reagent and specification: higher alcohols, Calcium Chloride Powder Anhydrous is analyzed alcohol; Vinylformic acid, CP; Methyl alcohol, analytical pure.
Concrete steps: in the there-necked flask that reflux condensing tube, TM and whisking appliance are housed, add the higher alcohols and the stopper of metering, be heated to certain temperature higher alcohols are melted fully, add vinylformic acid and catalyzer more successively.Mixture progressively is warming up to 140 ℃ then earlier at 110～120 ℃ of about 2.5h of following reflux, needs 6h approximately, gets the thick ester of product.Remove intact unsaturated acid and the residual water of unreacted in the thick ester through underpressure distillation, the use temperature is that 40～60 ℃ x is 0.2% weak lye washing an acidic catalyst and stopper, is neutral with distilled water wash until ester again.With cryodrying 8h under the products therefrom vacuum, obtain white waxy solid vinylformic acid high-carbon alcohol ester.
Test is adopted the U.S. Perkin Elmer Nicolet460 of company type Fourier transformation infrared spectrometer, wave-number range 11000～400cm-1, highest resolution 0.4cm-1 with sign: FT-IR; Chromatograph-mass spectrometer coupling adopts day island proper Tianjin GCMS-QP2010 type GC-MS to analyze.
Interpretation of result:
1) building-up reactions influence factor
The factor that influences product yield and quality is more, mainly investigates the influence to reaction of amount of substance ratio, temperature of reaction, catalyst levels and the stopper consumption of vinylformic acid and higher alcohols, and tabulation is analyzed.
2) reactant ratio
Reactant ratio can be known by mapping and analysis the influence of Zhi Huadu: during the reaction beginning, Zhi Huadu is fast rise along with the increase of vinylformic acid consumption, and when n (acid): n (alcohol) was 1.25: 1, Zhi Huadu was 93.8%; Improve the vinylformic acid consumption again, the variation of Zhi Huadu tends towards stability.N (acid): n (alcohol) is the principal element that influences esterification, and stoichiometric is 1: 1, for guarantee system carries out under slightly acidic condition, generally adopts vinylformic acid excessive, and experimental result conforms to theory.
3) temperature of reaction
Temperature of reaction can be known by mapping and analysis the influence of Zhi Huadu: when temperature of reaction was lower than 110 ℃, molecule was difficult to activate, and reacts hardly.When temperature was higher than 110 ℃, Zhi Huadu improved very fast, and Zhi Huadu reached 93.8% when temperature of reaction was 140 ℃, improved temperature again, and amplification tends towards stability, and explains that optimal reaction temperature is 140 ℃.
4) catalyst levels
Catalyst levels can be known by mapping and analysis the influence of reaction yield: when catalyst levels was low, speed of response was accelerated along with the increasing of catalyst levels.Catalyst levels increases catalyst consumption after surpassing 1.0% (in the total inventory that adds) again, and is not obvious to the influence of Zhi Huadu, confirms that therefore the catalyzer optimum amount is 1.0%.
5) stopper consumption
Vinylformic acid in the esterification is unsaturated carboxylic acid, in reaction process, is prone between the Acrylic Acid Monomer thermopolymerization takes place, so need use stopper in the reaction process.The stopper consumption is to the influence of esterification; By mapping and analyze and can know: when the stopper consumption more after a little while; Increase its consumption and help improving Zhi Huadu, and when its consumption was too much, it might generate ester with vinylformic acid again; Cause Zhi Huadu to reduce, experiment confirms that the stopper optimum amount was 0.5% (having added total material note).
6) reaction times
Except that above-mentioned principal element, also investigated the influence of reaction times to Zhi Huadu, can know by mapping and analysis: during the reaction beginning; Zhi Huadu improves along with the prolongation in reaction times fast; After the reaction times surpassed 8h, esterification was accomplished basically, and reaction yield no longer increases.
Product characterizes: the ir spectra of higher alcohols, by mapping and analyze and can know: wave number is the O-H stretching vibration peak near 3328.0cm-1.In acrylic acid ir spectra, its wave number is the stretching vibration peak of COO-near 1701.3cm.
The ir spectra of vinylformic acid high-carbon alcohol ester; Can be known by mapping and analysis: about 1728cm-1, locating all has the strong absorption peak that characterizes the C||O key; And at 1260～1275cm-1 place the absorption peak that characterizes C-O-C is arranged, explain that product is the ester class, the vibration peak of about 1635cm-1, locating the C||C key simultaneously exists; Locate alkene hydrogen stretching vibration about 2916cm-1 into CH2||CH-COOR; In addition, the absorption peak of CH2n chain link (n >=4) occurred at the 721.7cm-1 place, proved that products therefrom is a vinylformic acid high-carbon alcohol ester.At the no strong absorption peak of 3400cm-1 and 3600～3300cm-1 place, showing does not have residual long-chain alcohol and acid in the product.It is thus clear that can make the higher vinylformic acid high-carbon alcohol ester of purity with this method.
The chromatogram of product and mass spectrum; By mapping and analyze and can know: it is 324 molecular ion peak that the high quality end demonstrates total mass number (m/z); And near this molecular ion peak; The molecular weight of having confirmed product is exactly 324, and this molecular weight with the synthetic target product is identical, explains that the synthetic product is vinylformic acid high-carbon alcohol ester really.
2. the copolymer of vinylformic acid high-carbon alcohol ester and hexadecylene is synthetic
In the four-hole boiling flask of 250mL, add a certain amount of monomer vinylformic acid high-carbon alcohol ester and hexadecylene and a certain amount of toluene solvant, under N2 protects, be heated to temperature of reaction, slowly drip initiator B PO, stop behind the isothermal reaction number hour under the continuously stirring.Toluene is removed in underpressure distillation, uses absolute ethanol washing, and cooling treats that product solidifies the back suction filtration at low temperatures, obtains the copolymer of pour point depressant vinylformic acid high-carbon alcohol ester and hexadecylene.
Interpretation of result: polymerizing condition is to the influence of the copolymer pour point depression effect of vinylformic acid high-carbon alcohol ester and hexadecylene
1) B PO consumption is to the influence of pour point depression effect
B PO consumption is to the influence of pour point depression effect, and by mapping and analyze and can know: with the increase of B PO consumption, Δ SP increases afterwards earlier and reduces, and when B PO consumption (with respect to the massfraction of monomer TDMA and HE) when being 1.0%, Δ SP reaches maximum, pour point depression best results.This is that monomeric transformation efficiency is very low because cross when hanging down when B PO consumption; Increase B PO consumption, the radical rate of rise is accelerated, and reaction rate accelerates helps hexadecylene and participates in copolyreaction; But B PO consumption too much can cause in the reaction system the brilliant particle of instantaneous wax too concentrated, thereby causes and gather, and bad stability stops speed and also accelerates, and makes hexadecylene can not participate in copolymerization effectively.Therefore, it is 1% comparatively suitable selecting initiator amount.
2) influence of polymerization time
Polymerization time is to the influence of pour point depression effect, and by mapping and analyze and can know: when polymerization time during at 2～3h, extent of polymerization is not high, so the pour point depression effect is relatively poor; When polymerization time extended to 4～6h, the pour point depression effect obviously improved; Continue to prolong polymerization time, the pour point depression effect does not almost change, and explains that polyreaction accomplishes.Therefore, the selective polymerization time is that 5h is more suitable.
3) influence of pour point depressant consumption
The copolymer consumption of vinylformic acid high-carbon alcohol ester and hexadecylene is to the influence of pour point depression effect; By mapping and analyze and can know: when the copolymer consumption of vinylformic acid high-carbon alcohol ester and hexadecylene more after a little while, the pour point depression effect improves with the increase of the copolymer consumption of vinylformic acid high-carbon alcohol ester and hexadecylene; When the copolymer consumption (with respect to the massfraction of base oil) of vinylformic acid high-carbon alcohol ester and hexadecylene when reaching 0.5%, it is best that the pour point depression effect reaches, and Δ SP is 29 ℃; Continue to increase the copolymer consumption of vinylformic acid high-carbon alcohol ester and hexadecylene, considerable change no longer takes place in the pour point depression effect, even descends to some extent.This is because after adding the copolymer of a certain amount of vinylformic acid high-carbon alcohol ester and hexadecylene; The copolymer molecule of vinylformic acid high-carbon alcohol ester and hexadecylene is when wax precipitation; Generate the eutectic crystal with most of wax molecule or be adsorbed in the brilliant surface of wax; Form metastable crystalline structure, with the increase of the copolymer consumption of vinylformic acid high-carbon alcohol ester and hexadecylene, the pour point depression effect improves.But when the copolymer consumption of vinylformic acid high-carbon alcohol ester and hexadecylene reaches certain value; The pour point depression effect no longer improves; Because the cost of the copolymer of vinylformic acid high-carbon alcohol ester and hexadecylene is higher, the copolymer of excessive interpolation vinylformic acid high-carbon alcohol ester and hexadecylene is unreasonable economically simultaneously.Therefore, it is 0.5% more suitable selecting the copolymer consumption of vinylformic acid high-carbon alcohol ester and hexadecylene.
The copolymer of vinylformic acid high-carbon alcohol ester of the present invention and hexadecylene and the performance of commercially available pour point depressant compare:
Homemade vinylformic acid high-carbon alcohol ester is mixed by mass ratio with two kinds of commercially available pour point depressant T8088 and T602 respectively with the copolymer of hexadecylene at 1: 1; Obtain compound I and II; Investigate the pour point depression effect of different pour point depressants; Tabulation is also analyzed and can be known: for Yanshan Mountain 500SN, Yanshan Mountain 200SN and Hunan base oil, the pour point depression effect of compound I is better than pour point depressant T8088, and the pour point depression effect of compound II is better than pour point depressant T602; For the Henan base oil, the pour point depression effect of compound I is better than pour point depressant T8088; For the grand celebration base oil, the pour point depression effect of compound II is better than pour point depressant T602.No matter this explanation is compound I or compound II; Certain synergistic effect has all taken place between two kinds of pour point depressants; Therefore the copolymer of this vinylformic acid high-carbon alcohol ester and hexadecylene can be used as the auxiliary agent of some commercially available pour point depressant; When the independent result of use of commercially available pour point depressant is not good, rises and assist pour-point depressing process.This shows that the copolymer of this vinylformic acid high-carbon alcohol ester and hexadecylene has certain prospects for commercial application.
The foregoing description just is to let the one of ordinary skilled in the art can understand content of the present invention and enforcement according to this in order technical conceive of the present invention and characteristics to be described, to be its objective is, can not limit protection scope of the present invention with this.The variation or the modification of every equivalence that the essence of content has been done according to the present invention all should be encompassed in protection scope of the present invention.
Claims (6)
1. the synthesis technique of a novel lubricant pour point depressant is characterized in that, concrete steps are following:
1) vinylformic acid high-carbon alcohol ester is synthetic: in the there-necked flask that reflux condensing tube, TM and whisking appliance are housed, add the higher alcohols and the stopper of metering, be heated to certain temperature higher alcohols are melted fully, add vinylformic acid and catalyzer more successively; At 110～120 ℃ of about 2.5h of following reflux, progressively be warming up to 135～145 ℃ then, need 6h approximately, get the thick ester of product; Remove intact unsaturated acid and the residual water of unreacted in the thick ester through underpressure distillation; The use temperature is that 40～60 ℃ x is 0.2% weak lye washing an acidic catalyst and stopper; Be neutral with distilled water wash until ester again; With cryodrying 8h under the products therefrom vacuum, obtain white waxy solid vinylformic acid high-carbon alcohol ester;
2) copolymer of vinylformic acid high-carbon alcohol ester and hexadecylene is synthetic: in the four-hole boiling flask of 250mL, add a certain amount of vinylformic acid high-carbon alcohol ester, hexadecylene and toluene solvant; Under the protection of N2; Be heated to temperature of reaction; Slowly drip initiator B PO, stop behind the isothermal reaction number hour under the continuously stirring; Toluene is removed in underpressure distillation, uses absolute ethanol washing, and cooling treats that product solidifies the back suction filtration at low temperatures, obtains the copolymer of vinylformic acid high-carbon alcohol ester and hexadecylene.
2. the synthesis technique of novel lubricant pour point depressant according to claim 1 is characterized in that, the reaction molar weight ratio of said vinylformic acid and higher alcohols is 1.25: 1.
3. the synthesis technique of novel lubricant pour point depressant according to claim 1 is characterized in that, in the total inventory that adds, said catalyst consumption is 1.0%, and the consumption of stopper is 0.5%.
4. the synthesis technique of novel lubricant pour point depressant according to claim 1 is characterized in that, in the synthesis step of said vinylformic acid high-carbon alcohol ester, is at 110～120 ℃ of about 2.5h of following reflux, progressively is warming up to 140 ℃ then for best.
5. the synthesis technique of novel lubricant pour point depressant according to claim 1 is characterized in that, in the total inventory that adds, the copolymer consumption of said vinylformic acid high-carbon alcohol ester and hexadecylene is 0.5%, and the consumption of initiator is 1%.
6. the synthesis technique of novel lubricant pour point depressant according to claim 1 is characterized in that, the copolymer of said vinylformic acid high-carbon alcohol ester and hexadecylene synthetic, and isothermal reaction 4～6h wherein reacts 5h for best.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129841A (en) * | 2017-06-21 | 2017-09-05 | 上海应用技术大学 | A kind of aminolysis ter-polymers diesel pour inhibitor and preparation method thereof |
| CN107383268A (en) * | 2017-06-27 | 2017-11-24 | 东北石油大学 | A kind of nanometer Wax coagulation preventing agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619248A (en) * | 2009-05-14 | 2010-01-06 | 上海九元石油化工有限公司 | Method for preparing novel environmental-friendly high-efficiency diesel pour inhibitor |
| CN101845299A (en) * | 2010-05-17 | 2010-09-29 | 湖北大学 | Crude oil pour point depressant and preparation method thereof |
| CN102382695A (en) * | 2011-09-21 | 2012-03-21 | 陕西省石油化工研究设计院 | Novel diesel oil pour point depressant |
-
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- 2012-04-25 CN CN2012101229165A patent/CN102690705A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619248A (en) * | 2009-05-14 | 2010-01-06 | 上海九元石油化工有限公司 | Method for preparing novel environmental-friendly high-efficiency diesel pour inhibitor |
| CN101845299A (en) * | 2010-05-17 | 2010-09-29 | 湖北大学 | Crude oil pour point depressant and preparation method thereof |
| CN102382695A (en) * | 2011-09-21 | 2012-03-21 | 陕西省石油化工研究设计院 | Novel diesel oil pour point depressant |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129841A (en) * | 2017-06-21 | 2017-09-05 | 上海应用技术大学 | A kind of aminolysis ter-polymers diesel pour inhibitor and preparation method thereof |
| CN107383268A (en) * | 2017-06-27 | 2017-11-24 | 东北石油大学 | A kind of nanometer Wax coagulation preventing agent and preparation method thereof |
| CN107383268B (en) * | 2017-06-27 | 2019-06-04 | 东北石油大学 | A kind of nanometer of Wax coagulation preventing agent and preparation method thereof |
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Application publication date: 20120926 |