CN105238466A - Gasoline surfactant named as Yixiangjing and preparation method thereof - Google Patents
Gasoline surfactant named as Yixiangjing and preparation method thereof Download PDFInfo
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- CN105238466A CN105238466A CN201510704824.1A CN201510704824A CN105238466A CN 105238466 A CN105238466 A CN 105238466A CN 201510704824 A CN201510704824 A CN 201510704824A CN 105238466 A CN105238466 A CN 105238466A
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- case
- gasoline
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- cyclodextrin
- polyetheramine
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Abstract
The invention discloses a gasoline surfactant named as Yixiangjing and a preparation method thereof. The gasoline surfactant named as Yixiangjing is composed of cyclodextrin-modified polyetheramine, an antioxidant, an antirust agent, an antiseptic and a cosolvent. The gasoline surfactant named as Yixiangjing is capable of effectively cleaning accumulated carbon in an automobile engine atomizer, an intake valve and a combustion chamber, and also is capable of obviously inhibiting formation of carbon deposit in the atomizer, the intake valve and the combustion chamber, thereby improving fuel economy, improving the cold start-up difficult status and reducing harmful gas discharge.
Description
Technical field
The present invention relates to the clean technical field of a kind of gasoline one case, more specifically, the present invention relates to a kind of gasoline one case clean and preparation method thereof.
Background technology
At present, be subject to the impact of oil refining process, alkene in China's gasoline, aromaticity content are higher, olefin component is extremely unstable, under engine high-temperature working conditions, very easily there is oxidation and polymerization in it, and with other impurity acting in conjunction in gasoline, produce settling at positions such as the nozzle burner of engine, intake valve and combustion chambers, thus affect the use properties of engine, cause gasoline combustion process deterioration, oil consumption increase, exhaust pollutant discharge to increase.This just necessarily requires the prime the fuel system long-lasting cleanliness of motor car engine, therefore, must add gasoline one case clean in rear motor spirit on sale.
Gasoline one case is a kind of surfactant only, it can by be oxidized in gasoline formation potential deposit breakup, be solubilized in gasoline, stop them to be deposited on engine key position.Sedimental part has been formed for these, purification agent has very strong adsorption to settling, settling can be made slowly loose and split away off from metallic surface, and be surrounded by detergent-dispersant additive molecule together with some colloids being insoluble to fuel oil, form the micella of surface band positive charge, finally be entrained into combustion chambers burn to fall, play dispersion and clean effect, thus make engine recover normal operating conditions, gasoline is fully burned, significantly reduce the discharge of vehicle exhaust, decrease atmospheric pollution, also reach the effect of saving gasoline simultaneously.
The composition normally organic polymer aminated compounds played a major role during gasoline one case is clean, conventional is PIBA and polyetheramine etc.Although PIBA can solve nozzle burner and inlet valve deposits problem well, stability is higher under the high temperature conditions for it, incomplete combustion in a combustion chamber, and the settling of combustion chamber can be caused obviously to increase.Compare PIBA, there is in polyetheramine C-O-C key, be easy to cracking in high temperature, can effectively control nozzle burner and inlet valve deposits, effectively can also suppress the sedimental generation of engine cylinder simultaneously.Therefore, clean the sending out of polyether monoamine gasoline one case is in recent years opened and applies the attention being subject to domestic and international investigator, is the focus of the clean new product development of gasoline one case.
Summary of the invention
In order to solve the problem, the invention provides a kind of gasoline one case only with and preparation method thereof and purposes.
In order to realize foregoing invention object, this invention takes following technical scheme:
A kind of gasoline one case is clean, the described component only comprising following weight percent for a case:
Cyclo-dextrin-modified polyetheramine 55 ~ 80%
Oxidation inhibitor 1 ~ 4.0%
Rust-preventive agent 1.5 ~ 3.0%
Sanitas 0.5 ~ 1.0%
Solubility promoter 17 ~ 40%
Described cyclo-dextrin-modified polyetheramine is prepared by cyclodextrin, polyetheramine, maleic anhydride and obtained; The structural formula of described polyetheramine can be represented by general formula (1):
（1）
Wherein, R
1for C
5~ C
20alkyl, nonyl phenyl, dodecylphenyl or pentadecylphenyl; R
2for methyl or methoxy; R
3for
,
or
; N is 10 ~ 20; M is 1 ~ 2.
In one embodiment, the weight-average molecular weight of described cyclo-dextrin-modified polyetheramine is 1800 ~ 4000.
In one embodiment, described cyclodextrin is selected from one or more in hydroxyl cyclodextrin and Tanabe Seiyoku.
In one embodiment, described cyclodextrin is Tanabe Seiyoku.
In one embodiment, described oxidation inhibitor is selected from the mixture of one or more compositions in T501, T502, T531.
In one embodiment, described rust-preventive agent is selected from the mixture of one or more compositions in T703, T706, SP-80, SP-85.
In one embodiment, described sanitas is selected from T551 or T561.
In one embodiment, described solubility promoter is selected from the mixture of one or more compositions in aromatic hydrocarbon oil, dimethylbenzene, alkylbenzene, toluene.
The preparation method that another aspect of the present invention provides gasoline one case clean, weighs by required component ratio, room temperature or not higher than 30 DEG C of conditions under mix.
The purposes that a third aspect of the present invention provides gasoline one case clean, joins in motor spirit by 300 ~ 600ppm dosage.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
Unless otherwise defined, all technology used herein and scientific terminology have the identical implication usually understood with one skilled in the art of the present invention.When there is contradiction, be as the criterion with the definition in this specification sheets.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " comprising ", " having ", " containing " or its other distortion any, be intended to cover the comprising of non-exclusionism.Such as, comprise the composition of listed elements, step, method, goods or device and need not be only limitted to those key elements, but other key element of clearly not listing or the intrinsic key element of this kind of composition, step, method, goods or device can be comprised.
Conjunction " by ... composition " get rid of any key element, step or the component do not pointed out.If in claim, this phrase will make claim be closed, make it not comprise material except those materials described, but except relative customary impurities.When phrase " by ... composition " to appear in the clause of claim main body instead of immediately preceding after theme time, it is only limited to the key element described in this clause; Other key element is not excluded outside described claim as a whole.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc.When numerical range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers within the scope of this and mark.
In addition, the indefinite article " one " before key element of the present invention or component and " one " are to quantitative requirement (i.e. occurrence number) unrestriction of key element or component.Therefore " one " or " one " should be read as and comprise one or at least one, and the key element of singulative or component also comprise plural form, unless the obvious purport of described quantity refers to singulative.
In order to solve the problem, the invention provides a kind of gasoline one case clean, the described component only comprising following weight percent for a case:
Cyclo-dextrin-modified polyetheramine 55 ~ 80%
Oxidation inhibitor 1 ~ 4.0%
Rust-preventive agent 1.5 ~ 3.0%
Sanitas 0.5 ~ 1.0%
Solubility promoter 17 ~ 40%
Described cyclo-dextrin-modified polyetheramine is prepared by cyclodextrin, polyetheramine, maleic anhydride and obtained; The structural formula of described polyetheramine can be represented by general formula (1):
（1）
Wherein, R
1for C
5~ C
20alkyl, nonyl phenyl, dodecylphenyl or pentadecylphenyl; R
2for methyl or methoxy; R
3for
,
or
; N is 10 ~ 20; M is 1 ~ 2.
Term of the present invention " cyclo-dextrin-modified polyetheramine " is prepared through a step amidate action and a step esterification by polyetheramine, maleic anhydride, cyclodextrin.Not poisoning and do not increase new pollutent in order to ensure automotive exhaust catalysis transforming agent, gasoline one case is clean usually only elementary composition by C, H, O, N etc.At present, the gasoline one case of use is the organic amine material with certain special construction only, and its molecule two ends are respectively the non-polar group of polar group and long-chain.Non-polar group can be given gasoline one case and only have good oil soluble, can make only well to be dissolved in gasoline for one case.Polar group then has stronger adsorption to metallic surface and established settling.One case clean in polar group can be adsorbed on metallic surface and form layer protecting film, make the colloid in fuel oil to be deposited on metallic surface; After polar group is adsorbed on established deposit surface, settling can be made slowly loose and split away off from metallic surface, and be surrounded by one case clean molecule together with some colloids being insoluble to fuel oil, form the micella of surface band positive charge, finally be entrained into combustion chambers burn to fall, play the effect suppressing and clean.The present invention's cyclo-dextrin-modified polyetheramine; polyetheramine one end is made to have a large amount of polar groups; layer protecting film can be formed fast on the metallic surface of engine; suppress sedimental formation; simultaneously; it can have stronger adsorption to the established settling in metallic surface; the settling that makes quickly loosens and splits away off from metallic surface; and be surrounded by purification agent molecule together with some colloids being insoluble to fuel oil; form the micella of surface band positive charge; finally be entrained into combustion chambers burn to fall, play the effect suppressing and clean.In addition, cyclodextrin is easy to cracking in high temperature, in a combustion chamber Thorough combustion, can not cause sedimental increase in combustion chamber.
Term of the present invention " cyclodextrin " is hydroxyl cyclodextrin and Tanabe Seiyoku.Herein, term " hydroxyl cyclodextrin " refers to that the group in cyclodextrin is all hydroxyl, can be alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin, preferred beta-cyclodextrin.Term " Tanabe Seiyoku " is 3A-amino-3A-deoxidation-(2AS, 3AS)-alpha-cylodextrin, 3A-amino-3A-deoxidation-(2AS, 3AS)-beta-cyclodextrin, 3A-amino-3A-deoxidation-(2AS, 3AS)-γ-cyclodextrin, preferred 3A-amino-3A-deoxidation-(2AS, 3AS)-beta-cyclodextrin.
Term of the present invention " polyetheramine " be by, propylene oxide, Acetolon or acetylacetic ester, organic amine, maleic anhydride prepare and obtain.Herein, described term " " refers to R
1for the alkyl of C5 ~ C20, nonyl phenyl, dodecylphenyl or pentadecylphenyl, preferred dodecylphenyl or pentadecylphenyl.Described term " Acetolon " is methyl ethyl diketone.Described " acetylacetic ester " is methyl acetoacetate.Described term " organic amine " is quadrol, piperazine, diethylenetriamine, preferred diethylenetriamine.
The preparation method of cyclo-dextrin-modified polyetheramine is as follows:
(1) preparation of polyethers
To add in reactor, after nitrogen replacement twice, intensification limit, limit vacuumizes, and when temperature is raised to 120 DEG C, closes vacuum valve, and slowly adds propylene oxide, and at 130 ~ 150 DEG C, reaction, to after completely, is cooled to 80 DEG C of dischargings; : the molar ratio of propylene oxide is 1.01:1.
(2) polyethers and Acetolon or acetoacetic ester condensation
Polyethers, Acetolon or acetylacetic ester, DMAP, toluene are added in the reactor that water trap and condenser are housed, stir 4 hours at 25 DEG C, then 120 ~ 130 DEG C of backflows are slowly heated to, the water that reaction generates is by discharging through water trap with methylbenzene azeotropic, terminate when anhydrous generation, be cooled to 70 DEG C; Polyethers: the molar ratio of Acetolon or acetylacetic ester: DMAP is 1:1:0.005.
(3) preparation of polyetheramine
The organic amine with polyethers equivalent is added in step (2), under agitation slowly be heated to 120 ~ 130 DEG C of backflows, the water generated is by discharging through water trap with methylbenzene azeotropic, and when anhydrous generation, underpressure distillation desolventizes and namely other low-boiling-point substances obtain product polyether amine.
(4) preparation of cyclo-dextrin-modified polyetheramine
Be dissolved in toluene by polyetheramine, maleic anhydride, react 24h at 90 DEG C after, separating-purifying obtains maleic anhydride modified polyetheramine; The molar ratio of polyetheramine, maleic anhydride is 1.01 ~ 1.05:1;
Be dissolved in toluene by maleic anhydride modified polyetheramine, cyclodextrin, tosic acid, react 36h at 130 DEG C after, separating-purifying obtains cyclo-dextrin-modified polyetheramine; The molar ratio of maleic anhydride modified polyetheramine, cyclodextrin is 1:1.2 ~ 1.6, and tosic acid feeds intake and accounts for 0.01 ~ 1% of maleic anhydride modified polyetheramine and cyclodextrin total mass.
As a kind of preferred implementation of the present invention, the weight-average molecular weight of described cyclo-dextrin-modified polyetheramine is 1800 ~ 4000; Preferably, the weight-average molecular weight of cyclo-dextrin-modified polyetheramine is 2000 ~ 3000.
As a kind of preferred implementation of the present invention, described cyclodextrin be selected from hydroxyl cyclodextrin and Tanabe Seiyoku one or more.
As a kind of preferred implementation of the present invention, described cyclodextrin is Tanabe Seiyoku.
As a kind of preferred implementation of the present invention, described oxidation inhibitor is selected from the mixture of one or more compositions in T501, T502, T531.
As a kind of preferred implementation of the present invention, described rust-preventive agent is selected from the mixture of one or more compositions in T703, T706, SP-80, SP-85.
As a kind of preferred implementation of the present invention, described sanitas is selected from T551 or T561.
As a kind of preferred implementation of the present invention, described solubility promoter is selected from the mixture of one or more compositions in aromatic hydrocarbon oil, dimethylbenzene, alkylbenzene, toluene.
The preparation method that another aspect of the present invention provides gasoline one case clean, weigh by required component ratio, by cyclo-dextrin-modified polyetheramine, oxidation inhibitor, rust-preventive agent, sanitas, solubility promoter room temperature or not higher than 30 DEG C of conditions under mix, stir until solution is transparent.
The purposes that a third aspect of the present invention provides gasoline one case clean, joins in motor spirit by 300 ~ 600ppm dosage.
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of foregoing invention, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, raw materials used is all commercially available, and following material component used is weight percentage.
A1: (cyclodextrin is alpha-cylodextrin to cyclo-dextrin-modified polyetheramine; R in polyetheramine
1for nonyl phenyl, R
2for methyl, R
3for
, n is 15, m is 1)
A2: (cyclodextrin is beta-cyclodextrin to cyclo-dextrin-modified polyetheramine, R in polyetheramine
1for dodecylphenyl, R
2for methyl, R
3for
, n is 15, m is 1)
A3: (cyclodextrin is beta-cyclodextrin to cyclo-dextrin-modified polyetheramine, R in polyetheramine
1for pentadecylphenyl, R
2for methoxyl group, R
3for
, n is 15, m is 2)
A4: (cyclodextrin is 3A-amino-3A-deoxidation-(2AS, 3AS)-beta-cyclodextrin to cyclo-dextrin-modified polyetheramine, R in polyetheramine
1for dodecylphenyl, R
2for methyl, R
3for
, n is 15, m is 2)
A5: polyetheramine (R in polyetheramine
1for dodecylphenyl, R
2for methyl, R
3for
, n is 15, m is 0)
B1：T501
B2：T531
C1：T703
C2：SP-80
D1：T551
D2：T561
E1: dimethylbenzene
E2: toluene
Embodiment 1 ~ 8 and comparative example 1:
Gasoline one case is prepared clean, preparation method's following (consumption of following component is all weight percentage) according to the formula in table 1:
Weigh by required component ratio, by cyclo-dextrin-modified polyetheramine, oxidation inhibitor, rust-preventive agent, sanitas, solubility promoter room temperature or not higher than 30 DEG C of conditions under mix, stir until solution is transparent.
Table 1 is for preparing the clean composition of raw materials of gasoline one case and consumption (weight percent)
Testing method:
Gasoline of the present invention one case is added in 92 commercially available gasoline by the dosage of 300 ~ 600ppm only, and through specialized department's evaluation, the physical and chemical index of oil product all meets the requirement of GB17930-2006.Settling rate of descent is generated, by the change of thermogravimetric analyzer simulated automotive deposition of combustion chamber of engine increment by GB/T19230.4 test method simulated automotive intake valve.Above-mentioned test result is in table 2.
Table 2 is the clean test result of gasoline one case
In sum, 8 Example formulations, according to dosage 300 ~ 600ppm of the present invention, add in current commercially available motor spirit, all has obvious cleaning action to the fuel oil inlet system of engine and combustion chamber.Therefore, can make the automobile state that long-term maintenance is excellent under the operating mode run, fuel oil consumption can not produce too fast growth, reduces the discharge of tail gas nuisance, decreases the maintenance cost of engine, extend automotive service life.
Aforesaid example is only illustrative, for explaining some features of feature of the present invention.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. a gasoline one case is clean, it is characterized in that, the described component only comprising following weight percent for a case:
Cyclo-dextrin-modified polyetheramine 55 ~ 80%
Oxidation inhibitor 1 ~ 4.0%
Rust-preventive agent 1.5 ~ 3.0%
Sanitas 0.5 ~ 1.0%
Solubility promoter 17 ~ 40%
Described cyclo-dextrin-modified polyetheramine is prepared by cyclodextrin, polyetheramine, maleic anhydride and obtained; The structural formula of described polyetheramine can be represented by general formula (1):
（1）
Wherein, R
1for the alkyl of C5 ~ C20, nonyl phenyl, dodecylphenyl or pentadecylphenyl; R
2for methyl or methoxy; R
3for
,
or
; N is 10 ~ 20; M is 1 ~ 2.
2. gasoline according to claim 1 one case is clean, and it is characterized in that, the weight-average molecular weight of described cyclo-dextrin-modified polyetheramine is 1800 ~ 4000.
3. gasoline according to claim 1 one case is clean, it is characterized in that, described cyclodextrin be selected from hydroxyl cyclodextrin and Tanabe Seiyoku one or more.
4. gasoline according to claim 3 one case is clean, and it is characterized in that, described cyclodextrin is Tanabe Seiyoku.
5. gasoline according to claim 1 one case is clean, it is characterized in that, described oxidation inhibitor is selected from the mixture of one or more compositions in T501, T502, T531.
6. gasoline according to claim 1 one case is clean, it is characterized in that, described rust-preventive agent is selected from the mixture of one or more compositions in T703, T706, SP-80, SP-85.
7. gasoline according to claim 1 one case is clean, and it is characterized in that, described sanitas is selected from T551 or T561.
8. gasoline according to claim 1 one case is clean, it is characterized in that, described solubility promoter is selected from the mixture of one or more compositions in aromatic hydrocarbon oil, dimethylbenzene, alkylbenzene, toluene.
9. prepare the method that gasoline one case described in any one of claim 1 ~ 8 is clean, it is characterized in that, weigh by required component ratio, room temperature or not higher than 30 DEG C of conditions under mix.
10. the purposes that the gasoline described in any one of claim 1 ~ 8 one case is clean, is characterized in that, joins in motor spirit by 300 ~ 600ppm dosage.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336506A (en) * | 2016-09-13 | 2017-01-18 | 深圳市广昌达石油添加剂有限公司 | Polyether amine used as gasoline deterging and synthesis method thereof |
| CN106336680A (en) * | 2016-09-05 | 2017-01-18 | 台州五麦香生物科技有限公司 | Biomass-containing plastic master batch, as well as preparation method and application thereof |
| CN107011957A (en) * | 2017-04-25 | 2017-08-04 | 南宁市钱隆汽车租赁有限公司 | Gasoline one case is net |
| CN107881019A (en) * | 2017-11-02 | 2018-04-06 | 上海新阳半导体材料股份有限公司 | A kind of low alkalinity Environment-friendlyelectrolytic electrolytic removes solution, its preparation method and its application of flash |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336680A (en) * | 2016-09-05 | 2017-01-18 | 台州五麦香生物科技有限公司 | Biomass-containing plastic master batch, as well as preparation method and application thereof |
| CN106336680B (en) * | 2016-09-05 | 2018-09-14 | 台州五麦香生物科技有限公司 | A kind of plastic master batch containing biomass, preparation method and its application |
| CN106336506A (en) * | 2016-09-13 | 2017-01-18 | 深圳市广昌达石油添加剂有限公司 | Polyether amine used as gasoline deterging and synthesis method thereof |
| CN107011957A (en) * | 2017-04-25 | 2017-08-04 | 南宁市钱隆汽车租赁有限公司 | Gasoline one case is net |
| CN107011957B (en) * | 2017-04-25 | 2018-07-31 | 南宁市钱隆汽车租赁有限公司 | Gasoline one case is net |
| CN107881019A (en) * | 2017-11-02 | 2018-04-06 | 上海新阳半导体材料股份有限公司 | A kind of low alkalinity Environment-friendlyelectrolytic electrolytic removes solution, its preparation method and its application of flash |
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