CN1279247A - Poly-alpha-olefin pour depressant and its preparing process - Google Patents
Poly-alpha-olefin pour depressant and its preparing process Download PDFInfo
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- CN1279247A CN1279247A CN 99109415 CN99109415A CN1279247A CN 1279247 A CN1279247 A CN 1279247A CN 99109415 CN99109415 CN 99109415 CN 99109415 A CN99109415 A CN 99109415A CN 1279247 A CN1279247 A CN 1279247A
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Abstract
A poly-alpha-olefin pour-depressant containing C6-C16 alkyl side chains and C18-C22 alkyl side chains (1-20 mol%) with the average number of carbonatoms for side chain: 11-15.5 and mass average molecular weight: 50000-300000 is prepared through mixing the C8-C18 alpha-olefine obtained by cracking wax oil with C20-C24 olefine obtained by oligomerizing ethylene and polymerization under Ziegler-Natta catalyst. Its advantages include high pour-depressing effect, high shear stability and no obvious increasement in viscosity.
Description
The present invention relates to lubricating oil additive and preparation method thereof, exactly, is a kind of poly-α-alkene pour point depressant and preparation method thereof.
Poly-α-the alkene pour point depressant is an important kind of pour depressant for lubricating oil, and prior art is used following three kinds of feedstock production: the α-alkene of (1) ethylene oligomerization, and α-olefin(e) centent is more than 90%; (2) hard wax (oleaginousness is below 3%) cracking olefin, α-olefin(e) centent is in 80～90%:(3) soap waxes (oleaginousness 5～10%) cracking olefin, and α-olefin(e) centent is 60～80%.
DE.2,316,730 disclose the method for the poly-α of a kind of preparation-alkene pour point depressant, polymer raw is made up of two sections alkene, wherein α-alkene of C5～C10 accounts for 70～96mol% of total raw material, and C16～24 α-alkene accounts for 4～30mol%, and the polymkeric substance weight-average molecular weight is 50,000 to 1,000,000.
US3,151,181 disclose the C10 that ethylene oligomerization obtains～C18 α-olefin copolymer, and it is the alkyl of C10～C14 that substituting group is arranged on the main chain, and polymericular weight is 650～1, and 000,000.
US5,188,724 disclose a kind of poly-α-alkene pour point depressant, and by C10, C14, three kinds of α-olefin-copolymerizations of C16, every kind of monomer is no less than 10 heavy %, and average side chain carbon number is 10.5～12.0, and molecular weight 15～540,000 solve light oil condensation point problem.
FR 1564812 disclosed pour point depressants are that the C7～C20 alkene that obtains with the hard wax cracking is material copolymerization, and make solvent with hexane.
α-the alkene of above-mentioned ethylene oligomerization and hard wax cracking olefin need to add solvent, and molecular weight are restive when carrying out polymerization with the ziegler-natta catalyzer, cause molecular weight bigger, the tackify problem is outstanding, and (SSI) is poor for shear stability, thereby uses unsatisfactory as pour point depressant.
The commercially available industrial trade mark is to be feedstock production with C7～C20 alkene (olefin(e) centent is more than 60%) that the soap wax destructive distillation obtains for the T803 pour point depressant, during polymerization without solvent, compare with the preceding two kinds of raw materials of use, molecular weight is easy to control comparatively speaking slightly, but relatively more difficult, need higher hydrogen pressure to regulate molecular weight.Because molecular weight is still very high, aftertreatment is difficulty, and the catalyzer in the product difficulty is removed.In addition, though soap wax destructive distillation alkene cost will be lower than ethylene oligomerization alkene and hard wax cracking alkene,, still can't resolve the demand of market to cheap pour point depressant because soap wax source is inadequate.
The object of the present invention is to provide a kind of pour point depression effective, shear stability is good, poly-α-alkene pour point depressant that the tackify problem is not outstanding.
It is raw material with cheap alkene mainly that another object of the present invention provides a kind of, prepares the method for above-mentioned poly-α-alkene pour point depressant, and prepared pour point depressant molecular weight is little, and viscosity is low, and aftertreatment is easy.
Poly-α provided by the invention-alkene pour point depressant has following feature, the alkyl group side chain that contains the continuous carbon number of C6～C16 in the polymkeric substance, and the alkyl group side chain of C18～C22 even number carbon number, wherein the latter accounts for 1～20mol% of side chain sum, preferred 3～15mol%, more preferably 5～12mol%.The polymer lateral chain average carbon number is 11～15.5, preferred 12.5～14.The polymkeric substance weight-average molecular weight is 5～300,000, and is preferred 10～250,000, more preferably 10～200,000.
Poly-α provided by the invention-alkene pour point depressant prepares by following method: with sweat oil cracked C8～C18 α-alkene and the C20～C24 ethylene oligomerization olefin that accounts for alkene sum 1～20mol%, making the alkene average carbon number is 13～17.5, above-mentioned mixed olefins is carried out polymerization under the ziegler-natta catalyst action, products obtained therefrom is poly-α of the present invention-alkene pour point depressant.
Specifically, preparation method of the present invention can implement as follows, sweat oil cracked C8～C18 α-alkene is made with extra care earlier, and to remove desulfuration, nitrogen, oxygen etc. to the deleterious component of catalyzer, finishing agent can adopt carclazyte, gac, diatomite or AlCl
3Deng, preferred AlCl
3, with AlCl
3For the process for purification of finishing agent is well known to those skilled in the art, generally be AlCl with 0.5～2 heavy %
3Join in the cracking olefin, stirred 20～120 minutes down at 30～80 ℃, the disacidify slag also neutralizes with alkali, be washed to neutrality, distillation then, C8～C18 alkene is cut into 1～3 cut, is 13～17.5 requirement according to the alkene average carbon number, with the different fractions of cracking alkene and C20～C24 ethylene oligomerization alkene by required mixed, mixing raw material is under the effect of ziegler-natta catalyzer, regulating molecular weight with molecular weight regulator or hydrogen, is 0～300KPa in gauge pressure, under the pressure of preferred 0～200KPa, at 80～150 ℃, react 1～10h under preferred 80～120 ℃ temperature, best 3～6h is after reaction finishes, add pure termination reaction, product is washed with water to neutrality, and unreacted monomer is removed in distillation, and the product that obtains is poly-α-alkene pour point depressant.
The present invention has selected two kinds of raw materials for use, and a kind of is the alkene of the continuous carbon number of C8～C18 that obtains of sweat oil cracking.Said sweat oil is the oil that gatch is deviate from the lubricating oil processing process, and oleaginousness is generally 10～30%.In the alkene fraction that is obtained by the sweat oil thermo-cracking, olefin(e) centent generally is no more than 60%, and because the foreign matter content height, the component complexity is further utilized relatively difficulty.
Another raw material that the present invention selects for use is the mixed olefins that the ethylene oligomerization of C20～C24 obtains, and ethylene oligomerization alkene accounts for 1～20mol% of raw material alkene sum, preferred 3～15mol%, more preferably 5～12mol%.
To carry out poly-α-alkene that polymerization obtains according to aforementioned proportion raw materials mixed alkene, contain the alkyl group side chain of the continuous carbon number of C6～C16, and the alkyl group side chain of C18～C22 even number carbon number.According to the kind of employed lubricating oil, adjustable side chain average carbon number is 11～15.5, preferred 12.5～14.
Said ziegler-natta catalyzer catalyzer commonly used during for olefinic polymerization, it is complex compound by I～III family metal alkyl compound and IV～VIII group 4 transition metal derivative interaction (as aluminum alkyls or alkyl aluminum halide and halogenated titanium effect) generation, available solid-state system (powder, particle) also can be liquid state or the colloidal dispersion that is dissolved in organic solvent.
The poly-α provided by the invention-addition of alkene pour point depressant in lubricating oil can be 0.1～2.0 heavy %, preferred 0.2～1.0 heavy %.
Poly-α provided by the invention-alkene pour point depressant contains the side chain carbon number distribution of C6～C22 broad in the structure, pour point depression effect and T803 are suitable in light oil, but for the high heavy grease of wax content better pour point depression effect are arranged.In addition, compare with T803, pour point depressant molecular weight of the present invention is little, shear stability good (SSI is less than 50), and the tackify problem is little, and with the OCP of higher ethylene content (60～65%) compatibleness is preferably arranged.
Poly-α provided by the invention-alkene pour point depressant is because selected raw material is the by product-sweat oil cracking alkene in the lubricating oil processing process, therefore lower than the T803 cost that with soap wax destructive distillation alkene is raw material production.Compare with the preparation method of T803, equally without solvent, but prepared polymericular weight is littler under same reaction conditions when polymerization for preparation method provided by the invention, and viscosity is lower, thereby aftertreatment is more easy.
The invention will be further described below by example.
Analytical procedure in the example and method of calculation:
1. condensation point: GB/T 510
2. molecular weight: gel permeation chromatography
3. shear stability (SSI): supersonic method SH/T 0505
4. carbon number distribution: vapor-phase chromatography
5. raw material average carbon number computing method:
6. side chain average carbon number=Cn-2 (in the polymerization process, thinking that the alkene primitive reaction finishes)
Example 1
With oleaginousness is C8-C18 α-alkene (olefin(e) centent is 55.1 heavy %, and swallowization three factories produce) 1000g AlCl that the 20 sweat oil thermo-crackings that weigh % obtain
3Distill after refining, and cut into two components, receive overhead product, first cut is α-alkene of C8～C15, and average carbon number is 12.5, and olefin(e) centent is 61.3 heavy %; Second cut is α-alkene of C15～C18, and average carbon number is 16.1, and olefin(e) centent is 48.8 heavy %.Example 2
C20～24 ethylene oligomerization alkene (average carbon numbers 21 with the first cut 70mol%, the second cut 20mol% and 10mol% in the example 1, Xue Fulong company produces) blending mutually, the raw material average carbon number is 14.5, is put in the there-necked flask of 250ml, with hydrogen pressurize (gauge pressure is 0KPa), at TiCl
3, Al (iC
4H
9)
3Have polymerization down, temperature maintenance is at 100 ℃, and reaction times 3h adds ethanol 7ml termination reaction then, and product is washed with water to neutrality, boils off unreacted reactant, and the 150SN lubricating oil of adding and product equivalent mixes, and getting concentration is the product of 50 heavy %.Product side chain average carbon number is 12.5.The pour point depression effect sees Table 1, and molecular weight and shear stability (SSI) see Table 2.Example 3
With the first cut 50mol%, second cut, 38 mol% of example 1 and C20～C24 α-olefin of 12mol%, use the condition identical to react with example 2, product side chain average carbon number is 13.1, the pour point depression effect sees Table 1.Example 4
With the first cut 40mol%, the second cut 54mol% of example 1 and C20～C24 α-olefin of 6mol%, use the condition identical to react with example 2, product side chain average carbon number is 13.3, the pour point depression effect sees Table 1.Comparative Examples 1
Preparation method according to commercially available T803, with purified soap wax (oleaginousness is 5 heavy %) cracking olefin C7～C20 (α-olefin(e) centent 70%, Lanzhou Oil Refinery is produced), press the mode polymerization of example 2, wherein C7～C12 alkene is 30 heavy %, and C12～C20 alkene is 70 heavy %, the side chain average carbon number is 12.2 product, the pour point depression effect sees Table 1, and molecular weight product and SSI see Table 2.
Table 1
| The pour point depression effect, ℃ | ||||
| Base oil | Dalian 150SN | East refining second line of distillation | Dalian 10# automotive engine oil | 1m%JEX9600+ Dalian 150SN |
| The base oil condensation point, ℃ | —12 | —16 | ?0 | —14 |
| Example 2 | —33 | —34 | —14 | —27 |
| Example 3 | —30 | —33 | —18 | —31 |
| Example 4 | —30 | —31 | —17 | —27 |
| Comparative Examples 1 | —31 | —32 | —12 | —20 |
Annotate: 1 addition is 0.25 heavy % (doing agent)
2 JEX9600 (Exxon, Jinzhou petro-chemical corporation product) are the ethylene-propylene copolymer (OCP) of ethylene content about 63 heavy %
As can be seen from Table 1, pour point depression effect and the T803 in light oil is suitable for poly-α provided by the invention-alkene pour point depressant, but the heavy grease high to wax content has better pour point depression effect as Dalian 10# automotive engine oil, and with the higher OCP of ethylene content better compatibleness arranged.Example 5
In the ratio and the processing condition preparation of example 3, but hydrogen pressure is 150KPa, and molecular weight of product and shear stability see Table 3.Comparative Examples 2
Adopt the raw material and the method polymerization of Comparative Examples 1, but hydrogen pressure is 150KPa, average carbon number is 12.2 product.Molecular weight product and SSI see Table 2.Comparative Examples 3
With reference to US 5,188,724 method is pressed the reaction conditions of example 2, and with 29.1m%C10,37.8m%C14, the copolymerization of 33.1m%C16 alkene, average carbon number is 11.02.Molecular weight product and SSI see Table 2.
Table 2
| Raw material | Weight-average molecular weight Mw | Shear stability index (SSI) * | |
| Example 2 | Sweat oil alkene+C20～24 alkene | 17.6 ten thousand | 45 |
| Example 4 | Sweat oil alkene+C20～24 alkene | 15.1 ten thousand | 39 |
| Example 5 | Sweat oil alkene+C20～24 alkene | 12.6 ten thousand | 32 |
| Comparative Examples 1 | The soap wax olefin cracking | 32.2 ten thousand | 58 |
| Comparative Examples 2 | The soap wax olefin cracking | 16.4 ten thousand | 42 |
| Comparative Examples 3 | Pure alkene | 50.3 ten thousand | 75 |
* in containing the Dalian 150SN base oil of 1% pour point depressant, test
As can be seen from Table 2, the C8 that obtains with the sweat oil cracking provided by the invention～C18 alkene adds the polymkeric substance of the heavy olefin production of small amount of ethylene oligomerisation, the little characteristics of sweat oil cracking alkene polymer molecular weight have been kept, than the polymkeric substance of pure alkene, soap wax destructive distillation alkene polymer etc. littler molecular weight is arranged, better shear stability, and soap cerotene hydrocarbon polymer will obtain the same molecular amount and must improve hydrogen pressure (seeing Comparative Examples 2).
Claims (11)
1. poly-α-alkene pour point depressant is characterized in that, contains the alkyl group side chain of the continuous carbon number of C6～C16 in the polymkeric substance, and the alkyl group side chain of C18～C22 even number carbon number, and wherein the latter accounts for 1～20mol% of side chain sum, and the side chain average carbon number is 11～15.5.
2. according to the described pour point depressant of claim 1, it is characterized in that C18～C22 alkyl group side chain accounts for 3～15mol% of side chain sum.
3. according to the described pour point depressant of claim 1, it is characterized in that the polymkeric substance weight-average molecular weight is 5～300,000.
4. according to the described pour point depressant of claim 3, it is characterized in that the polymkeric substance weight-average molecular weight is 10～250,000.
5. according to the described pour point depressant of claim 1, it is characterized in that the side chain average carbon number is 12.5～14.
6. the preparation method of the described poly-α of claim 1-alkene pour point depressant, be under the Ziegler-Natta catalyst effect, α-alkene is carried out polymerization, it is characterized in that, the mixed olefins of raw material C20～C24 alkene that to be sweat oil cracked C8～C18 α-alkene obtain with the ethylene oligomerization that accounts for alkene sum 1～20mol%, the alkene average carbon number is 13～17.5.
7. according to the described preparation method of claim 6, it is characterized in that ethylene oligomerization alkene accounts for 3～15mol% of raw material alkene sum.
8. according to the described preparation method of claim 6, it is characterized in that, make with extra care with finishing agent before the sweat oil cracking alkene reaction.
9. according to the described preparation method of claim 8, it is characterized in that finishing agent is selected from carclazyte, gac, diatomite or AlCl
3
10. according to the described preparation method of claim 6, it is characterized in that polyreaction is carried out under the hydrogen condition, gauge pressure 0～300KPa, temperature of reaction is 80～150 ℃, the reaction times is 1～10h.
11., it is characterized in that polyreaction is carried out according to the described preparation method of claim 10 under the hydrogen condition, gauge pressure 0～200KPa, temperature of reaction is 80～120 ℃, the reaction times is 3～6h.
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| CN 99109415 CN1122049C (en) | 1999-06-30 | 1999-06-30 | Poly-alpha-olefin pour depressant and its preparing process |
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| CN 99109415 CN1122049C (en) | 1999-06-30 | 1999-06-30 | Poly-alpha-olefin pour depressant and its preparing process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142133A (en) * | 2017-04-12 | 2017-09-08 | 沈阳工业大学 | The preparation method of new lubricant viscosity index improver |
| CN114524889A (en) * | 2022-01-07 | 2022-05-24 | 国家能源集团宁夏煤业有限责任公司 | Method and system for synthesizing T803 pour point depressant from coal-based olefin and T803 pour point depressant |
| CN114605586A (en) * | 2022-02-25 | 2022-06-10 | 中海油(天津)油田化工有限公司 | Polyacrylic acid higher alcohol ester pour point depressant and preparation method thereof |
-
1999
- 1999-06-30 CN CN 99109415 patent/CN1122049C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142133A (en) * | 2017-04-12 | 2017-09-08 | 沈阳工业大学 | The preparation method of new lubricant viscosity index improver |
| CN114524889A (en) * | 2022-01-07 | 2022-05-24 | 国家能源集团宁夏煤业有限责任公司 | Method and system for synthesizing T803 pour point depressant from coal-based olefin and T803 pour point depressant |
| CN114524889B (en) * | 2022-01-07 | 2024-01-09 | 国家能源集团宁夏煤业有限责任公司 | Method and system for synthesizing T803 pour point depressant from coal-based olefin and T803 pour point depressant |
| CN114605586A (en) * | 2022-02-25 | 2022-06-10 | 中海油(天津)油田化工有限公司 | Polyacrylic acid higher alcohol ester pour point depressant and preparation method thereof |
| CN114605586B (en) * | 2022-02-25 | 2023-10-03 | 中海油(天津)油田化工有限公司 | Polyacrylic acid high-carbon alcohol ester pour point depressant and preparation method thereof |
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