CN1045107C - Polyolefine butanedioic acid polyhydroxy alkyl ester non-ash dispersant - Google Patents
Polyolefine butanedioic acid polyhydroxy alkyl ester non-ash dispersant Download PDFInfo
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- CN1045107C CN1045107C CN96114272A CN96114272A CN1045107C CN 1045107 C CN1045107 C CN 1045107C CN 96114272 A CN96114272 A CN 96114272A CN 96114272 A CN96114272 A CN 96114272A CN 1045107 C CN1045107 C CN 1045107C
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- Prior art keywords
- oil
- polyolefine
- product
- metal salt
- polyhydroxy
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to a lubricating oil additive, particularly to an ester non-ash dispersant with excellent performance, which is prepared by the reaction of succinic acid substituted by polyolefine and polyhydroxy alcohol. The present invention also relates to a synthesis technology of the ester non-ash dispersant. In the technological process, alkali metal salt is used as a catalyst, a gelatine compound which is not dissolved in oil and is contained in a product can be obviously reduced, and the filtration velocity of the product is improved.
Description
The present invention relates to the polyolefine butanedioic acid polyhydroxy alkyl ester non-ash dispersant that a kind of lubricating oil is used, belong to the lubricating oil additive field, oil-soluble polyolefine butanedioic acid polyhydroxy alkyl ester non-ash dispersant has the peace and quiet and low temperature dispersity of good high-temperature, is widely used in lubricating oil and the fuel.The invention still further relates to a kind of new preparation process of polyolefine butanedioic acid polyhydroxy alkyl ester non-ash dispersant; Under alkaline metal salt catalysis, this method can obviously reduce gum level in the product, improves filtration velocity.
As everyone knows, ester type ashless dispersant is existing many pieces of patents (US3381022, US4199553 etc.) report such as polyisobutene Succinic Acid pentaerythritol ester for example, its synthetic method is all used an acidic catalyst such as Phenylsulfonic acid, phosphoric acid, sulfuric acid etc. and need at high temperature be reacted, can make product contain the gelatinize compound of the insoluble oil of 2-6% thus, influence product appearance and strainability.
Order of the present invention provides a kind of synthetic ester type ashless dispersant and novel preparation method thereof.This method is used the basic metal salt catalyst that is dissolved in oil, can reduce gum level in the product, improves product appearance and strainability.The polyolefinic succinimide acid pentaerythritol ester ashless dispersant appearance transparent of using this method to produce, thick product filter scooter 50Kg/m
2.h; The needs of large-scale commercial production have been satisfied.
The object of the present invention is achieved like this: 1000 parts rare dicarboxylic anhydrides of poly-isobutyl and mineral oil (as 1 50SN) are dropped in the reactor, stir and be warming up to 150～300 ℃; Be generally 220 ℃; The polyhydroxy-alcohol and the alkaline metal salt that in 1 hour, add 150 parts; Then 6～50 hours (being generally 10 hours) of 150～300 ℃ (the best is 190 ℃) reaction; Be cooled to 140 ℃, filtration gets product.
Improving one's methods of a kind of synthetic oil dissolubility polyolefinic succinimide acid polyhydroxy-alcohol is characterized in that: with containing C
6～C
500Polyolefinic succinimide acid with contain C
2～C
40Polyhydroxy-alcohol under the basic metal salt catalyst in 150～300 ℃ down reaction 6～50h generate oil-soluble ester type ashless dispersant.Contained colloid can significantly reduce in the product, the filtration velocity of product when having improved aftertreatment.
The basic metal salt catalyst, its add-on is 0.1～5%, is preferably 3%.
Alkaline metal salt is meant the peace and quiet dispersing additive of alkaline oil that is dissolved in lubricating oil; Comprise high, medium and low oil or synthesising sulfonate commonly used in this area, high, medium and low alkyl monosulfide phenates and analogue thereof, high, medium and low salicylate and analogue; The calcium sulfenyl phenolates of producing as T109, T102, Lanzhou oil-refining chemical head factory etc., total basicnumber should be between 60～400mKOH/g.
Polyolefinic succinimide acid is characterized in that containing the polyolefine side chain of 1～500 carbon atom, and polyolefine can be used C
2～C
18Any monomer alkene or mixed olefins are synthetic as ethene-copolymerization of propylene, polyisobutene, poly-alpha olefins etc.
The synthetic method of ester type ashless dispersant is characterized in that temperature of reaction is 150 ℃～300 ℃, and the reaction times is 10h～50h.
Can use solvent or N in the reaction process
2Purge and remove generation water.
Reacting employed solvent is benzene, dimethylbenzene and sherwood oil etc., comprises not using solvent and using N
2Purge to remove and anhydrate.
The product gum level that generates is few, the obvious raising of filtration velocity during aftertreatment.
The starting material that the present invention uses mainly contain three kinds, comprise Succinic anhydried, the polyhydroxy-alcohol that polyolefine replaces, basic metal salt compound and the mineral oil that is dissolved in oil, and first kind is the Succinic anhydried that polyolefine replaces, and its structural representation is as follows:
Wherein R can be-H or contain the polyolefine side chain of 1～500 carbon atom; The polyolefine that preferably contains 60～300 carbon atoms.Polyolefine can be used C
2～C
18Any monomer alkene or mixed alkene are synthetic, generally use iso-butylene (C
4Component) comes synthesis of polyolefins.Other is as Ethylene propylene copolymer, polyethylene, polyethylene, poly-alpha-olefin etc.
Second kind is polyhydroxy-alcohol, satisfies following structure
Wherein a can be the alkyl that replaces of H, alkyl, hydroxyl ,-OCH
2C (CH
2OH)
3,-(CH
2)
nOH or-(CH
2OCH
2CH
2O)
nH (n is 1～3); A and a ', a " can be identical also can be different.The most frequently used is tetramethylolmethane.Other also just like:
The third is the basic metal salt compound that is dissolved in oil, comprise various alkaline petroleum additives, as sulfonated petro-leum, synthesising sulfonate, alkyl monosulfide phenates and salicylate, the T102 that T109 that produces as Lanzhou oil-refining chemical head factory and calcium sulfenyl phenolate, shanghai refinery's chemical general factory are produced etc., base number should be between 50～400.The alkaline metal salt addition is 0.1～5% (m) of polyolefinic succinimide acid anhydrides add-on, is generally about 3%.
Ester type ashless dispersant can use solvent such as benzene kind solvent and sherwood oil to wait to remove to anhydrate, and also can directly use N without solvent
2Purge the water that generates.The ashless powder of ester type contains ester carbonyl group, infrared going up at 1780cm
-1Near strong absorption is arranged; Admittedly contain-the OH group, at 3300-3400cm
-1Between Bao Feng is arranged.More than can be used as the qualitative analysis of product.
In the present invention if no special instructions, all percentage ratios and umber all refer to weight percentage or parts by weight.
The following examples and comparative example are to further specify of the present invention, rather than limit the invention, and spirit of the present invention and protection domain are listed in claims.
Embodiment 1: drop into 1000 parts of polyisobutylene butanedioic anhydrides (polyisobutene Mn ≈ 1000) and 1000 parts of mineral oil in there-necked flask, be warming up to 170 ℃, added 85 parts of tetramethylolmethanes in 1 hour; Added 30 parts of high base number calcium mahogany sulfonates subsequently in 2 hours, its base number is 400mgKOH/g; 190 ℃ of following stirring reactions 10 hours; Being cooled to 140 ℃ then filters.Contain 0.1% colloid in the product, filtration velocity is 40Kg/m
2.h (industrial filter paper).
Comparative example 1: in there-necked flask, drop into 1000 parts of polyisobutylene butanedioic anhydrides (P2B Mn ≈ 1000) and 1000 parts of mineral oil, be warming up to 170 ℃, in 1 hour, add 85 parts of tetramethylolmethanes; Subsequently 190 ℃ of stirring reactions 10 hours; Being cooled to 140 ℃ then filters.Contain 3.0% colloid in the product, filtration velocity is 0.2Kg/m
2.h (same model industrial filter paper).
Embodiment 2: press embodiment 1 operation, change the high base number calcium mahogany sulfonate into the high base number calcium salicylate, its base number is 280mgKOH/g.Contain 0.12% colloid in the product; Filtration velocity is 38Kg/m
2.h (industrial filter paper).
Embodiment 3: press embodiment 1 operation, change the high base number calcium mahogany sulfonate into high base number sulfenyl phenolate magnesium, its base number is 255mgKOH/g.Contain 0.06% colloid in the product, filtration velocity is 50Kg/m
2.h (industrial filter paper).
Embodiment 4: press embodiment 1 operation, and base number calcium mahogany sulfonate during the high base number calcium mahogany sulfonate is changed into, its base number is 170mgKOH/g.Contain 0.1% colloid in the product, filtering velocity is 41Kg/m
2.h (industrial filter paper).
The analyzing evaluation data of relevant product see Table-1.From table-1, use basic catalyst (metal-salt) that the high temperature detergency and the thermostability of ester type ashless dispersant are improved.
The analyzing evaluation data of table 1 ester type ashless dispersant
Acid number hydroxy radical content differential thermal analysis greasy filth spot lacquering plate
(mgKOH/g) (324 ℃ * 6h) (%) level embodiment 1 5.0 1.50 451 59.0 2.5 comparative examples 1 12.0 1.23 417 57.0 3.5 embodiment 2 6.0 1.40 441 59.9 2.5 embodiment 3 4.5 1.80 461 59.1 2.0 embodiment 4 5.5 1.73 451 59.5 2.5 of (m%) Tm ℃ of distributed tests
Claims (9)
1. improving one's methods of a synthetic oil dissolubility polyolefinic succinimide acid polyhydroxy-alcohol is characterized in that: with containing C
5～C
500Polyolefinic succinimide acid with contain C
2～C
40Polyhydroxy-alcohol under the basic metal salt catalyst in 150～300 ℃ down reaction 6～50h generate oil-soluble ester type ashless dispersant, contained colloid can significantly reduce in the product, the filtration velocity of product when having improved aftertreatment.
2. method according to claim 1 is characterized in that having used the basic metal salt catalyst, and its add-on is 0.1～5% weight, is preferably 3% weight.
3. method according to claim 1 is characterized in that alkaline metal salt is meant the peace and quiet dispersing additive of alkaline oil that is dissolved in lubricating oil; Comprise high, medium and low oil or synthesising sulfonate, high, medium and low alkyl monosulfide phenates and analogue thereof, high, medium and low salicylate and analogue; Total basicnumber should be between 60～400mKOH/g.
4. method according to claim 1 is characterized in that: polyolefinic succinimide acid contains the polyolefine side chain of 1～500 carbon atom, and polyolefine can be used C
12～C
18Any monomer alkene or mixed olefins are synthetic.
5. method according to claim 1 is characterized in that: the polyhydroxy-alcohol of use satisfies the following formula structure:
Wherein X, X ' and X " be the alkyl that replaces of H, alkyl, hydroxyl ,-OCH
2C (CH
2OH)
3,-(CH
2)
NOH or-(CH
2OCH
2CH
2O)
nH (n is 1～3), X, X ' and X " can be the same or different.
6. method according to claim 1 is characterized in that: the synthesis reaction temperature of ester type ashless dispersant is 150 ℃～300 ℃, and the reaction times is 10h～50h.
7. method according to claim 1 is characterized in that can using solvent or N in the reaction process
2Purge and remove generation water.
8. method according to claim 1, it is characterized in that reacting employed solvent is benzene, dimethylbenzene and sherwood oil, comprises not using solvent and using N
2Purge to remove and anhydrate.
9. method according to claim 1 is characterized in that the product gum level that generates is few, the obvious raising of filtration velocity during aftertreatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114272A CN1045107C (en) | 1996-12-25 | 1996-12-25 | Polyolefine butanedioic acid polyhydroxy alkyl ester non-ash dispersant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114272A CN1045107C (en) | 1996-12-25 | 1996-12-25 | Polyolefine butanedioic acid polyhydroxy alkyl ester non-ash dispersant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1186078A CN1186078A (en) | 1998-07-01 |
| CN1045107C true CN1045107C (en) | 1999-09-15 |
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ID=5122039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96114272A Expired - Lifetime CN1045107C (en) | 1996-12-25 | 1996-12-25 | Polyolefine butanedioic acid polyhydroxy alkyl ester non-ash dispersant |
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| CN (1) | CN1045107C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794192A (en) * | 2012-08-05 | 2012-11-28 | 湖北同一石油化工有限公司 | Preparation and application method of supported catalyst for synthetic reaction of polyisobutylene succinate |
| CN103601845B (en) * | 2013-11-04 | 2015-11-11 | 上海金兆节能科技有限公司 | Polyisobutene butene dioic acid ester and preparation method thereof and by this polyester for micro lubricating oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5055523A (en) * | 1989-03-20 | 1991-10-08 | Ce Plastics Japan Limited | Aromatic polycarbonate resin composition |
| US5112917A (en) * | 1989-08-18 | 1992-05-12 | E. I. Du Pont De Nemours & Co. | Block copolymer of perfluoroether and hydrocarbon monomers |
| US5171463A (en) * | 1989-07-14 | 1992-12-15 | Ciba-Geigy Corporation | N-substituted triazole compounds |
-
1996
- 1996-12-25 CN CN96114272A patent/CN1045107C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5055523A (en) * | 1989-03-20 | 1991-10-08 | Ce Plastics Japan Limited | Aromatic polycarbonate resin composition |
| US5171463A (en) * | 1989-07-14 | 1992-12-15 | Ciba-Geigy Corporation | N-substituted triazole compounds |
| US5112917A (en) * | 1989-08-18 | 1992-05-12 | E. I. Du Pont De Nemours & Co. | Block copolymer of perfluoroether and hydrocarbon monomers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1186078A (en) | 1998-07-01 |
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Granted publication date: 19990915 |
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| DD01 | Delivery of document by public notice |
Addressee: Lanzhou Oil Refining Chemical Genernal Plant, Chinese Petro-Chemical Corp. Document name: Notification of Expiration of Patent Right Duration |