CN102952232A - 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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- CN102952232A CN102952232A CN2011102370137A CN201110237013A CN102952232A CN 102952232 A CN102952232 A CN 102952232A CN 2011102370137 A CN2011102370137 A CN 2011102370137A CN 201110237013 A CN201110237013 A CN 201110237013A CN 102952232 A CN102952232 A CN 102952232A
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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 allyl carbamate. The polymer has a certain dispersion effect, and a good pour point depressing effect.
Description
Technical field
The present invention relates to polymkeric substance, pour depressant for lubricating oil for the lubricating oil pour point depression and preparation method thereof, be specifically related to can be used for the vinyl acetate between to for plastic-fumarate of lubricating oil pour point depression-allyl carbamate multipolymer, contain pour depressant for lubricating oil of this polymkeric substance and preparation method thereof.
Background technology
Pour point depressant claims again cold flow improver, it is a kind of high molecular polymer of oil-soluble chemosynthesis, in content of wax oil plant, add an amount of pour point depressant, under certain condition can with wax crystalline phase mutual effect in the oil plant, reduce significantly the zero pour of content of wax oil plant, improve the low temperature flowability of content of wax oil plant.The kind of pour depressant for lubricating oil is a lot, the multipolymer that mainly contains alkylnaphthalene, poly-alpha olefins, polymethacrylate, vinyl acetate and fumarate of commonly using both at home and abroad at present etc.The alkylnaphthalene polymkeric substance is pour depressant for lubricating oil the earliest, but in recent years because the development of multi-stage combustion engine oil and the production of neutral oil, the dewaxing degree of depth is deepened, the service requirements that its pour point depression effect does not reach some oil product, and alkylnaphthalene is the dark oil solid, the color and luster that adds the agent object there is considerable influence, and troublesome poeration when adding agent, the existing pour point depressant market of withdrawing from gradually.Poly-alpha olefins class pour point depressant is the larger pour point depressant of present domestic usage quantity, and its pour point depression is effective and of light color, but its production technique investment is large, length consuming time, and production cost is higher, and it is larger to add dosage in oil product.Polymethacrylate has the double effects of pour point depression and tackify, be used as for many years viscosity index improver and the pour point depressant of oil product, but its raw materials is expensive always, and product cost is higher.
Vinyl Acetate Copolymer-fumarate is because its production cost is low, and product color is shallow, and pour point depression is respond well, more and more causes people's attention.Industrialized product mainly contains T818 series and T882 series product in the market.External early the beginning reported its research, discloses the preparation process of this type of pour point depressant such as US3765849, JP0181843, AU603180.
Domestic research to this type of pour point depressant is started late, journal of Zhejiang university (Edition) the 3rd phase of the 28th volume calendar year 2001 has been reported synthesis characterization and the pour-viscosity reduction effect research thereof of fumaric acid long-chain ester and vinyl acetate copolymer, (contains C at the two alcohol mixtures of preparation fumaric acid
22Alcohol, C
20Alcohol, C
18Alcohol, and C
22+ C
20＞80%, C
18＜20%) ester DBF monomer, and with the vinyl acetate copolymer basis on, they are characterized, and then investigate copolymer additives to the impact of high wax, highly viscous crude, residual oil, white oil and optical cable oil rheological characteristics.
Use chemical industry the 12nd phase of the 35th volume in 2006 and reported synthesizing and pour-point depressing process of pour depressant for lubricating oil T818B, adopt C
8-C
26The method of pure and mild fumaric acid esterification has prepared the higher alcohols fumarate, further generate dibehenyl fumarate-vinyl acetate copolymer with the vinyl acetate between to for plastic polymerization again, and investigated its pour point depression effect, find that it has good pour-point depressing process to naphthenic base oils, and to the pour point depression DeGrain of paraffin base oil.
As seen through the above analysis, prior art all is take fumarate and vinyl acetate as polymerization single polymerization monomer, and the alkyl carbon number makes up to improve the pour point depression effect in the polymerization single polymerization monomer by changing, and effect is not remarkable.So far, there is no the research report that improves the pour point depression effect by introducing the third function monomer.
Summary of the invention
The invention provides a kind of Vinyl Acetate Copolymer-fumarate for the lubricating oil pour point depression-allyl carbamate multipolymer.The present invention also provides and has contained pour depressant for lubricating oil of above-mentioned polymkeric substance and preparation method thereof, and this pour point depressant has certain dissemination, and the pour point depression effect is good.
A kind of polymkeric substance for the lubricating oil pour point depression, this polymkeric substance is by following three kinds of random copolymerss that structural unit consists of, take the quality of polymkeric substance as benchmark, formula I structural unit accounts for 10～90%, formula II structural unit accounts for 2～89%, the 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 the polymkeric substance, the mass content sum of three kinds of structural units is 100%.
Take the quality of polymkeric substance as benchmark, formula I structural unit preferably accounts for 20～90%, more preferably accounts for 50～90%.
Take the quality of polymkeric substance as benchmark, formula II structural unit preferably accounts for 10～80%, more preferably accounts for 10～60%, and more preferably 20～50%.
Take the quality of polymkeric substance as benchmark, the formula III structural unit preferably accounts for 2～10%.
The number-average molecular weight of polymkeric substance is preferably 5000～350000, and more preferably 10000～200000.
The present invention also provides a kind of pour depressant for lubricating oil, comprises above-mentioned polymkeric substance and lubricant base, and take the quality of pour depressant for lubricating oil as benchmark, polymkeric substance accounts for 15～85%, and lubricant base accounts for 10～80%.
Take the quality of pour depressant for lubricating oil as 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 comprises: polymerization single polymerization monomer is mixed with lubricant base, take the total mass of polymerization single polymerization monomer as benchmark, add 0.01～10% polymerization starter, 50～150 ℃ of lower reactions 2～20 hours, obtain product.
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 to be obtained through esterification by the straight-chain alkyl alcohol of fumaric acid and C1-C30; Another kind of monomer is vinyl acetate; Also having a kind of monomer is allyl carbamate.
Among the present invention, polymeric reaction temperature is preferably 60～100 ℃, and the reaction times is preferably 6～10 hours.
The kinematic viscosity of described base oil under 100 ℃ is 1～30mm
2/ s, it can be mineral oil, isomerization dewaxing oil, hydrofined oil or polyalphaolefin synthetic oil (PAO), such as 150SN, 6# hydrogenated oil, 4#PAO etc.
Described polymerization starter can be peralcohol, and such as dicumyl peroxide, benzoyl peroxide etc. also can be azo-compounds, such as Diisopropyl azodicarboxylate etc.Take the total mass of polymerization single polymerization monomer as benchmark, the consumption of polymerization starter is preferably 0.05～3%, and more preferably 0.1～2%.
The present invention is take the lubricant base polymkeric substance above-mentioned as solvent prepares, and product need not to separate, and can directly use as pour depressant for lubricating oil.Base oil in the pour point depressant is separated, can obtain polymkeric substance of the present invention.The present invention also can select other solvent to prepare polymkeric substance of the present invention.
The present invention also provides a kind of lubricating oil, take the total mass of lubricating oil as benchmark, contains 0.005%～5% above-mentioned polymkeric substance, preferably contains 0.02%～2% above-mentioned polymkeric substance.
The present invention has following useful technique effect:
The present invention is by preparation fumarate-vinyl acetate-allyl carbamate multipolymer, in pour point depressant, introduced nitrogen-containing group, so that the pour point depressant product has certain dispersing property, can effectively improve shape and the size of wax crystal in the lubricating oil, thereby have better pour point depression effect.
Embodiment
Further specify by the following examples the present invention.
Example 1
In the 500ml there-necked flask with electric mixer and reflux condensing tube, (Sinopec Shanghai Gaoqiao petro-chemical corporation produces, 100 ℃ of kinematic viscosity 5.92mm to add 42g 6# hydrogenated oil under nitrogen protection
2S
-1), 30.0g fumaric acid stearyl alcohol ester (laboratory is synthetic), 10.0g vinyl acetate (Chemical Reagent Co., Ltd., Sinopharm Group), 2.0g allyl carbamate (laboratory is synthetic), 0.2g Diisopropyl azodicarboxylate (production of Sinopec Yanshan Petrochemical) is opened stirring and is warmed up to 70 ℃, this moment, the observing response thing had obvious exothermic phenomenon, the control temperature of reaction is 75 ℃, reacts the obvious retrogradation of material this moment 2 hours.And then to reaction system adding 0.1g Diisopropyl azodicarboxylate; continue reaction 5 hours; this moment, material became lurid thick liquid, under nitrogen protection material was down to room temperature at last, obtained the terpolymer of fumaric acid stearyl alcohol ester, vinyl acetate and allyl carbamate.Wherein fumaric acid stearyl alcohol ester accounts for 71.4% of monomer total amount, and vinyl acetate is 23.8%, allyl carbamate be 4.8%, 6# hydrogenated oil account for that polymkeric substance always feeds intake 50%.
Example 2
In the 500ml there-necked flask with electric mixer and reflux condensing tube, (Sinopec Shanghai Gaoqiao petro-chemical corporation produces, 100 ℃ of kinematic viscosity 3.8mm to add 46.0g 100N hydrogenated oil under nitrogen protection
2/ s), 15.0g fumaric acid lauryl alcohol ester (laboratory is synthetic), 18.0g fumaric acid hexadecanol ester (laboratory is synthetic), 8.6g vinyl acetate, 4.0g allyl carbamate (laboratory is synthetic), 0.15g Diisopropyl azodicarboxylate, open stirring and be warmed up to 70 ℃, this moment, the observing response thing had obvious exothermic phenomenon, and the control temperature of reaction is 75 ℃, reacted the obvious retrogradation of material this moment 2 hours.And then to reaction system adding 0.15g Diisopropyl azodicarboxylate; continue reaction 5 hours; this moment, material became lurid thick liquid; under nitrogen protection, material is down to room temperature at last, obtains the tetrapolymer of fumaric acid lauryl alcohol ester, fumaric acid stearyl alcohol ester, vinyl acetate and allyl carbamate.Wherein fumaric acid lauryl alcohol ester accounts for 32.9% of monomer total amount, and fumaric acid stearyl alcohol ester is 39.5%, and vinyl acetate is 18.9%, allyl carbamate be 8.8%, 100SN oil account for that polymkeric substance always feeds intake 50%.
Example 3
Under nitrogen protection, in the 500m1 there-necked flask with electric mixer and reflux condensing tube, add 45.0gPAO4 base oil (Petrochina Lanzhou Petrochemical Company production, 100 ℃ of kinematic viscosity 3.9mm
2/ s), 5.0g fumaric acid ester in the last of the ten Heavenly stems (laboratory is synthetic), 12.0g fumaric acid tetradecyl alcohol ester (laboratory is synthetic), 15.0g fumaric acid stearyl alcohol ester, 10.0g vinyl acetate, 3.0g allyl carbamate (laboratory is synthetic), the 0.15g Diisopropyl azodicarboxylate is opened stirring and is warmed up to 70 ℃, this moment, the observing response thing had obvious exothermic phenomenon, the control temperature of reaction is 75 ℃, reacts the obvious retrogradation of material this moment 2 hours.And then to reaction system adding 0.1g Diisopropyl azodicarboxylate; continue reaction 5 hours; this moment, material became lurid thick liquid; under nitrogen protection, material is down to room temperature at last, obtains the five-membered copolymer of fumaric acid ester in the last of the ten Heavenly stems, fumaric acid tetradecyl alcohol ester, fumaric acid stearyl alcohol ester, vinyl acetate and allyl carbamate.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 stearyl alcohol ester is 33.3%, and vinyl acetate is 22.2%, allyl carbamate be 6.7%, PAO4 base oil account for that polymkeric substance always feeds intake 50%.
Example 4
This example is used for pour point depressant that illustrated example 1～3 synthesized in the result of use of lubricating oil.
Prepared fumarate-the vinyl acetate of the present invention-allyl carbamate multiple copolymer analog pour point depressant, because it has introduced nitrogen-containing group in preparation process, so that the pour point depressant product has certain dispersing property, can effectively improve shape and the size of wax crystal in the lubricating oil, thereby have better pour point depression effect.At first investigate the dispersing property of the synthetic product of this patent, and with market on like product T818B, T818C and T882 pour point depressant compared, spotting method is adopted in the test of dispersing property, method is the mixture with the sample of specified amount, carbon black and base oil, after evenly mixing in specified temperature with in the time, to mix oil sample and drop on the filter paper, it is spread under prescribed condition, according to the carbon black on filter paper and the carbon black spot dispersion value of oil stain loop diameter calculation sample after the diffusion.Test-results sees Table 1
The dispersing property evaluation of table 1 pour point depressant
Test-results by table 1 can find out, with respect to like product, the pour point depressant that the present invention synthesizes has certain dissemination.
Respectively the base oil of different fractions is carried out the pour point depression effect assessment with like product T818B, T818C and T882 pour point depressant on pour point depressant that above-described embodiment synthesized and the market, the pour point drop-out value (being the pour point depression degree) of test oil product, pour point is tested according to GB/T3535, the add-on of pour point depressant is w (pour point depressant) %=0.5% in the formation testing, and test-results sees Table 2.
Table 2 pour point depressant is to the pour point depression degree (Δ SP/ ℃) of different base oils
Test-results by table 2 can find out, the pour point depressant pour point depression effect that the present invention synthesized is better than like product in the market, and good application prospect is arranged.
Claims (17)
1. polymkeric substance that is used for the lubricating oil pour point depression, this polymkeric substance is by following three kinds of random copolymerss that structural unit consists of, take the quality of polymkeric substance as benchmark, formula I structural unit accounts for 10～90%, formula II structural unit accounts for 2～89%, the 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～C 30.
2. in accordance with the method for claim 1, it is characterized in that R
1And R
2Be respectively the alkyl of C8～C24.
3. in accordance with the method for claim 1, it is characterized in that, take the quality of polymkeric substance as benchmark, formula I structural unit accounts for 20～90%.
4. in accordance with the method for claim 3, it is characterized in that, take the quality of polymkeric substance as benchmark, formula I structural unit accounts for 50～90%.
5. in accordance with the method for claim 1, it is characterized in that, take the quality of polymkeric substance as benchmark, formula II structural unit accounts for 10～80%.
6. in accordance with the method for claim 5, it is characterized in that, take the quality of polymkeric substance as benchmark, formula II structural unit accounts for 10～60%.
7. in accordance with the method for claim 1, it is characterized in that, take the quality of polymkeric substance as benchmark, the formula III structural unit accounts for 2～10%.
8. in accordance with the method for claim 1, it is characterized in that, the number-average molecular weight of polymkeric substance is 5000～350000.
9. in accordance with the method for 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 comprises the arbitrary described polymkeric substance of claim 1～9 and lubricant base, and take the quality of pour depressant for lubricating oil as benchmark, polymkeric substance accounts for 15～85%, and lubricant base accounts for 10～80%.
11. according to pour point depressant claimed in claim 10, it is characterized in that, take the quality of pour point depressant as benchmark, polymkeric substance accounts for 35～60%, lubricant base accounts for 35～60%.
12. the preparation method of pour depressant for lubricating oil claimed in claim 10, comprise: polymerization single polymerization monomer is mixed with lubricant base, take the total mass of polymerization single polymerization monomer as benchmark, add 0.01～10% polymerization starter, 50～150 ℃ of lower reactions 2～20 hours, obtain product.
13. according to the described preparation method of claim 12, it is characterized in that, polymeric reaction temperature is 60～100 ℃, the reaction times is 6～10 hours.
14. according to the described preparation method of claim 12, it is characterized in that, described base oil is mineral oil, isomerization dewaxing oil, hydrofined oil or polyalphaolefin synthetic oil.
15. according to the described preparation method of claim 12, it is characterized in that, take the total mass of polymerization single polymerization monomer as benchmark, the consumption of polymerization starter is 0.05～3%.
16. a lubricating oil take the total mass of lubricating oil as benchmark, contains 0.005%～5% the arbitrary described polymkeric substance of claim 1～9.
17. according to the described lubricating oil of claim 16, it is characterized in that, take the total mass of lubricating oil as benchmark, contain 0.02%～2% the arbitrary described polymkeric substance of claim 1～9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084128A (en) * | 2016-06-07 | 2016-11-09 | 江苏金迪润滑油有限公司 | Lubricating oil anti-coagulants and preparation method and application |
| CN106243277A (en) * | 2016-08-23 | 2016-12-21 | 中国石油化工股份有限公司 | For improving the multiple copolymer of High viscosity crude mobile performance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101076578A (en) * | 2004-07-16 | 2007-11-21 | 罗麦斯添加剂有限公司 | Use of graft polymers |
| 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 |
-
2011
- 2011-08-18 CN CN201110237013.7A patent/CN102952232B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101076578A (en) * | 2004-07-16 | 2007-11-21 | 罗麦斯添加剂有限公司 | Use of graft polymers |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084128A (en) * | 2016-06-07 | 2016-11-09 | 江苏金迪润滑油有限公司 | Lubricating oil anti-coagulants and preparation method and application |
| CN106243277A (en) * | 2016-08-23 | 2016-12-21 | 中国石油化工股份有限公司 | For improving the multiple copolymer of High viscosity crude mobile performance |
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| CN102952232B (en) | 2014-10-29 |
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