CN102952235B - Polymer used in lubricating oil pour point depressing, lubricating oil pour point depressant, and preparation method thereof - Google Patents
Polymer used in lubricating oil pour point depressing, lubricating oil pour point depressant, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polymer used in lubricating oil pour point depressing, a lubricating oil pour point depressant, and a preparation method thereof. The polymer provided by the invention is a random copolymer of fumarate, vinyl acetate and acrylamide. The polymer has a certain dispersion effect, and a good pour point depressing effect.
Description
Technical field
The present invention relates to the polymkeric substance, pour depressant for lubricating oil and preparation method thereof for lubricating oil pour point depression, be specifically related to can be used for the vinyl acetate-fumarate-acrylamide copolymer of lubricating oil pour point depression, the pour depressant for lubricating oil containing this polymkeric substance and preparation method thereof.
Background technology
Pour point depressant is also known as cold flow improver, it is a kind of high molecular polymer of oil-soluble chemosynthesis, appropriate pour point depressant is added in content of wax oil plant, under certain condition can with wax crystalline phase mutual effect in oil plant, reduce the zero pour of content of wax oil plant significantly, improve the low temperature flowability of content of wax oil plant.The kind of pour depressant for lubricating oil is a lot, the multipolymer etc. mainly containing alkylnaphthalene, poly-alpha olefins, polymethacrylate, vinyl acetate and fumarate conventional both at home and abroad at present.Alkylnaphthalene polymkeric substance is pour depressant for lubricating oil the earliest, but in recent years due to the development of multi-stage combustion engine oil and the production of neutral oil, dewaxing depth down, its depression effeCt does not reach the service requirements of some oil product, and alkylnaphthalene is dark oil solid, considerable influence is had to the color and luster adding agent object, and troublesome poeration when adding agent, now exit pour point depressant market gradually.Poly-alpha olefins class pour point depressant is the pour point depressant that current domestic usage quantity is larger, and its depression effeCt is good and of light color, but the investment of its production technique is large, and length consuming time, production cost is higher, and in oil product, add dosage larger.Polymethacrylate has the double effects of pour point depression and thickening, and be used as viscosity index improver and the pour point depressant of oil product for many years, but its raw materials is expensive, product cost is higher always.
Vinyl Acetate Copolymer-fumarate due to its production cost low, product color is shallow, and depression effeCt is good, more and more causes the attention of people.Industrialized product mainly contains T818 series and T882 series product in the market.The external research report comparatively early started it, as US 3765849, JP0181843, AU603180 disclose the preparation process of this type of pour point depressant.
The domestic research to this type of pour point depressant is started late, volume the 3rd phase journal of Zhejiang university (Edition) calendar year 2001 the 28th reports synthesis characterization and the pour-viscosity reduction Effect study thereof of fumaric acid long-chain ester and vinyl acetate copolymer, is preparing the two alcohol mixture of fumaric acid (containing C
22alcohol, C
20alcohol, C
18alcohol, and C
22+ C
20> 80%, C
18< 20%) ester DBF monomer, and with on vinyl acetate copolymer basis, they are characterized, and then investigate the impact of copolymer additives on high wax, highly viscous crude, residual oil, white oil and optical cable oil rheological characteristics.
Apply synthesis and pour-point depressing process thereof that chemical industry the 35th volume the 12nd phase in 2006 reports pour depressant for lubricating oil T818B, adopt C
8-C
26the method of alcohol and fumaric acid esterification has prepared higher alcohols fumarate, be polymerized with vinyl acetate between to for plastic further again and generate dibehenyl fumarate-vinyl acetate copolymer, and investigated its depression effeCt, find that it has good pour-point depressing process to naphthenic base oils, and not obvious to the depression effeCt of paraffin base oil.
As seen through the above analysis, prior art is all with fumarate and vinyl acetate for polymerization single polymerization monomer, and improve depression effeCt by changing alkyl combination of carbon numbers in polymerization single polymerization monomer, effect is not remarkable.So far, there is no the research report improving depression effeCt by introducing the third function monomer.
Summary of the invention
The invention provides a kind of vinyl acetate-fumarate-acrylamide copolymer for lubricating oil pour point depression.Present invention also offers pour depressant for lubricating oil containing above-mentioned polymkeric substance and preparation method thereof, this pour point depressant has certain dissemination, and depression effeCt is excellent.
A kind of polymkeric substance for lubricating oil pour point depression, this polymkeric substance is the random copolymers be made up of following three kinds of structural units, with the quality of polymkeric substance for benchmark, formula I structural unit accounts for 10 ~ 90%, formula II structural unit accounts for 2 ~ 89%, formula III structural unit accounts for 1 ~ 50%, and the number-average molecular weight of polymkeric substance is 2000 ~ 1000000;
Wherein, R
1and R
2be respectively the alkyl of C1 ~ C30.
R
1and R
2preferably be respectively the alkyl of C8 ~ C24.
In polymkeric substance, the mass content sum of three kinds of structural units is 100%.
With the quality of polymkeric substance for benchmark, formula I structural unit preferably accounts for 20 ~ 90%, more preferably accounts for 50 ~ 90%.
With the quality of polymkeric substance for benchmark, formula II structural unit preferably accounts for 10 ~ 80%, more preferably accounts for 10 ~ 60%, and more preferably 20 ~ 50%.
With the quality of polymkeric substance for benchmark, formula III structural unit preferably accounts for 2 ~ 10%.
The number-average molecular weight of polymkeric substance is preferably 5000 ~ 350000, is more preferably 10000 ~ 200000.
Present invention also offers a kind of pour depressant for lubricating oil, comprise above-mentioned polymkeric substance and lubricant base, with the quality of pour depressant for lubricating oil for benchmark, polymkeric substance accounts for 15 ~ 85%, and lubricant base accounts for 10 ~ 80%.
With the quality of pour point depressant for benchmark, polymkeric substance preferably accounts for 35 ~ 60%, and lubricant base preferably accounts for 35 ~ 60%.
The preparation method of above-mentioned pour depressant for lubricating oil, comprising: mixed with lubricant base by polymerization single polymerization monomer, with the total mass of polymerization single polymerization monomer for benchmark, adds the polymerization starter of 0.01 ~ 10%, reacts 2 ~ 20 hours, obtain product at 50 ~ 150 DEG C.
According to polymkeric substance disclosed by the invention, know polymerization single polymerization monomer used in the present invention with those skilled in the art know that.Wherein, a kind of polymerization single polymerization monomer, fumaric acid C
1-30alkyl ester is obtained through esterification by the straight-chain alkyl alcohol of fumaric acid and C1-C30; Another kind of monomer is vinyl acetate; A kind of monomer is also had to be acrylamide.
In the present invention, polymeric reaction temperature is preferably 60 ~ 100 DEG C, and the reaction times is preferably 6 ~ 10 hours.
The kinematic viscosity of described base oil at 100 DEG C is 1 ~ 30mm
2/ s, it can be mineral oil, isomerization dewaxing oil, hydrofined oil or polyalphaolefin synthetic oil (PAO), as 150SN, 6# hydrogenated oil, 4#PAO etc.
Described polymerization starter can be peralcohol, and as dicumyl peroxide, benzoyl peroxide etc. can be also azo-compounds, as Diisopropyl azodicarboxylate etc.With the total mass of polymerization single polymerization monomer for benchmark, the consumption of polymerization starter is preferably 0.05 ~ 3%, is more preferably 0.1 ~ 2%.
The present invention is that above-mentioned polymkeric substance prepared by solvent with lubricant base, and product, without the need to being separated, can directly use as pour depressant for lubricating oil.Base oil in pour point depressant is separated, polymkeric substance of the present invention can be obtained.The present invention also can select other solvent to prepare polymkeric substance of the present invention.
Present invention also offers a kind of lubricating oil, with the total mass of lubricating oil for benchmark, containing the above-mentioned polymkeric substance of 0.005% ~ 5%, preferably contain the above-mentioned polymkeric substance of 0.02% ~ 2%.
The present invention has following Advantageous Effects:
The present invention is by preparing fumarate-vinyl acetate-acrylamide copolymer, nitrogen-containing group is introduced in pour point depressant, make pour point depressant product have certain dispersing property, effectively can improve shape and the size of wax crystal in lubricating oil, thus there is better depression effeCt.
Embodiment
Further illustrate the present invention by the following examples.
Example 1:
Under nitrogen protection in the 500ml there-necked flask with electric mixer and reflux condensing tube, (Sinopec Shanghai Gaoqiao petro-chemical corporation produces, 100 DEG C of kinematic viscosity 5.92mm to add 42g 6# hydrogenated oil
2s
-1), 30.0g fumaric acid octadecyl (laboratory synthesis), 10.0g vinyl acetate (Chemical Reagent Co., Ltd., Sinopharm Group), 2.0g acrylamide (Chemical Reagent Co., Ltd., Sinopharm Group), 0.2g Diisopropyl azodicarboxylate (production of Sinopec Yanshan Petrochemical), opens and stirs and be warmed up to 70 DEG C, now observing response thing has obvious exothermic phenomenon, controlling temperature of reaction is 75 DEG C, reacts 2 hours, the now obvious retrogradation of material.And then add 0.1g Diisopropyl azodicarboxylate to reaction system; continue reaction 5 hours; now material becomes lurid thick liquid, finally under nitrogen protection material is down to room temperature, obtains the terpolymer of fumaric acid octadecyl, vinyl acetate and acrylamide.Wherein fumaric acid octadecyl accounts for 71.4% of monomer total amount, and vinyl acetate is 23.8%, acrylamide be 4.8%, 6# hydrogenated oil account for that polymkeric substance always feeds intake 50%.
Example 2:
Under nitrogen protection in the 500ml there-necked flask with electric mixer and reflux condensing tube, (Sinopec Shanghai Gaoqiao petro-chemical corporation produces, 100 DEG C of kinematic viscosity 3.8mm to add 46.0g 100N hydrogenated oil
2/ s), 15.0g fumaric acid lauryl alcohol ester (laboratory synthesis), 18.0g fumaric acid hexadecanol ester (laboratory synthesis), 8.6g vinyl acetate, 4.0g acrylamide (Chemical Reagent Co., Ltd., Sinopharm Group), 0.15g Diisopropyl azodicarboxylate, open and stir and be warmed up to 70 DEG C, now observing response thing has obvious exothermic phenomenon, and controlling temperature of reaction is 75 DEG C, react 2 hours, the now obvious retrogradation of material.And then add 0.15g Diisopropyl azodicarboxylate to reaction system; continue reaction 5 hours; now material becomes lurid thick liquid; finally under nitrogen protection material is down to room temperature, obtains the tetrapolymer of fumaric acid lauryl alcohol ester, fumaric acid octadecyl, vinyl acetate and acrylamide.Wherein fumaric acid lauryl alcohol ester accounts for 32.9% of monomer total amount, and fumaric acid octadecyl is 39.5%, and vinyl acetate is 18.9%, acrylamide be 8.8%, 100SN oil account for that polymkeric substance always feeds intake 50%.
Example 3:
Under nitrogen protection in the 500ml there-necked flask with electric mixer and reflux condensing tube, (Petrochina Lanzhou Petrochemical Company produces, 100 DEG C of kinematic viscosity 3.9mm to add 45.0gPAO4 base oil
2/ s), 5.0g fumaric acid ester in the last of the ten Heavenly stems (laboratory synthesis), 12.0g fumaric acid tetradecyl alcohol ester (laboratory synthesis), 15.0g fumaric acid octadecyl, 10.0g vinyl acetate, 3.0g acrylamide (Chemical Reagent Co., Ltd., Sinopharm Group), 0.15g Diisopropyl azodicarboxylate, opens and stirs and be warmed up to 70 DEG C, now observing response thing has obvious exothermic phenomenon, controlling temperature of reaction is 75 DEG C, reacts 2 hours, the now obvious retrogradation of material.And then add 0.1g Diisopropyl azodicarboxylate to reaction system; continue reaction 5 hours; now material becomes lurid thick liquid; finally under nitrogen protection material is down to room temperature, obtains the five-membered copolymer of fumaric acid ester in the last of the ten Heavenly stems, fumaric acid tetradecyl alcohol ester, fumaric acid octadecyl, vinyl acetate and acrylamide.Wherein fumaric acid ester in the last of the ten Heavenly stems accounts for 11.1% of monomer total amount, and fumaric acid lauryl alcohol ester is 26.7%, and fumaric acid octadecyl is 33.3%, and vinyl acetate is 22.2%, acrylamide be 6.7%, PAO4 base oil account for that polymkeric substance always feeds intake 50%.
Example 4:
The pour point depressant result of use in lubricating oil of this example synthesized by example 1 ~ 3.
Fumarate prepared by the present invention-vinyl acetate-acrylic acid amides multiple copolymer analog pour point depressant, because it introduces nitrogen-containing group in preparation process, pour point depressant product is made to have certain dispersing property, effectively can improve shape and the size of wax crystal in lubricating oil, thus there is better depression effeCt.First the dispersing property of the product of this patent synthesis is investigated, and compared with like product T818B, T818C and T882 pour point depressant on market, the test of dispersing property adopts spotting method, method is by the mixture of the sample of specified amount, carbon black and base oil, in specified temperature with in the time after Homogeneous phase mixing, mixing oil sample is dropped on filter paper, makes it spread under prescribed conditions, according to the carbon black spot dispersion value of carbon black on filter paper and oil stain loop diameter calculation sample after diffusion.Test-results is in table 1
The dispersing property evaluation of table 1 pour point depressant
Can be had by the test-results of table 1, relative to like product, the pour point depressant of the present invention's synthesis has certain dissemination.
Respectively depression effeCt evaluation is carried out to the base oil of different fractions with like product T818B, T818C and T882 pour point depressant on the pour point depressant synthesized by above-described embodiment and market, the pour point drop-out value (i.e. pour point depression degree) of test oil product, pour point is tested according to GB/T3535, in formation testing, the add-on of pour point depressant is w (pour point depressant) %=0.5%, and test-results is respectively in table 2.
Table 2 pour point depressant is to the pour point depression degree (Δ SP/ DEG C) of different base oil
As can be seen from the test-results of table 2, the pour point depressant depression effeCt synthesized by the present invention is better than like product in the market, has good application prospect.
Claims (17)
1. the polymkeric substance for lubricating oil pour point depression, this polymkeric substance is the random copolymers be made up of following three kinds of structural units, with the quality of polymkeric substance for benchmark, formula I structural unit accounts for 10 ~ 90%, formula II structural unit accounts for 2 ~ 89%, formula III structural unit accounts for 1 ~ 50%, and the number-average molecular weight of polymkeric substance is 2000 ~ 1000000;
Wherein, R
1and R
2be respectively the alkyl of C1 ~ C30.
2. according to polymkeric substance according to claim 1, it is characterized in that, R
1and R
2be respectively the alkyl of C8 ~ C24.
3. according to polymkeric substance according to claim 1, it is characterized in that, with the quality of polymkeric substance for benchmark, formula I structural unit accounts for 20 ~ 90%.
4. according to polymkeric substance according to claim 3, it is characterized in that, with the quality of polymkeric substance for benchmark, formula I structural unit accounts for 50 ~ 90%.
5. according to polymkeric substance according to claim 1, it is characterized in that, with the quality of polymkeric substance for benchmark, formula II structural unit accounts for 10 ~ 80%.
6. according to polymkeric substance according to claim 5, it is characterized in that, with the quality of polymkeric substance for benchmark, formula II structural unit accounts for 10 ~ 60%.
7. according to polymkeric substance according to claim 1, it is characterized in that, with the quality of polymkeric substance for benchmark, formula III structural unit accounts for 2 ~ 10%.
8. according to polymkeric substance according to claim 1, it is characterized in that, the number-average molecular weight of polymkeric substance is 5000 ~ 350000.
9. according to polymkeric substance according to claim 1, it is characterized in that, the number-average molecular weight of polymkeric substance is 10000 ~ 200000.
10. a pour depressant for lubricating oil, comprise the arbitrary described polymkeric substance of claim 1 ~ 9 and lubricant base, with the quality of pour depressant for lubricating oil for benchmark, polymkeric substance accounts for 15 ~ 85%, and lubricant base accounts for 10 ~ 80%.
11., according to pour point depressant according to claim 10, is characterized in that, with the quality of pour point depressant for benchmark, polymkeric substance accounts for 35 ~ 60%, and lubricant base accounts for 35 ~ 60%.
The preparation method of 12. pour depressant for lubricating oil according to claim 10, comprise: polymerization single polymerization monomer is mixed with lubricant base, with the total mass of polymerization single polymerization monomer for benchmark, add the polymerization starter of 0.01 ~ 10%, react 2 ~ 20 hours at 50 ~ 150 DEG C, obtain product.
13., according to preparation method according to claim 12, is characterized in that, polymeric reaction temperature is 60 ~ 100 DEG C, and the reaction times is 6 ~ 10 hours.
14., according to preparation method according to claim 12, is characterized in that, described base oil is mineral oil, isomerization dewaxing oil, hydrofined oil or polyalphaolefin synthetic oil.
15., according to preparation method according to claim 12, is characterized in that, with the total mass of polymerization single polymerization monomer for benchmark, the consumption of polymerization starter is 0.05 ~ 3%.
16. 1 kinds of lubricating oil, with the total mass of lubricating oil for benchmark, the arbitrary described polymkeric substance of the claim 1 ~ 9 containing 0.005% ~ 5%.
17., according to lubricating oil according to claim 16, is characterized in that, with the total mass of lubricating oil for benchmark, and the arbitrary described polymkeric substance of the claim 1 ~ 9 containing 0.02% ~ 2%.
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| CN101705138A (en) * | 2009-11-18 | 2010-05-12 | 济南开发区星火科学技术研究院 | Pour point depressant of lubricating oil and preparation method thereof |
Non-Patent Citations (2)
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| "柴油低温流动改性剂AMMSV的制备与性能研究";张宏喜等;《应用化工》;20080528;第37卷(第5期);第559-561页 * |
| 邹佩良."两种润滑油降凝剂的合成及降凝机理研究".《中国优秀硕士论文全文数据库(工程科技I辑)》.2008,(第4期),B019-38. * |
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