CN105238466B - A kind of gasoline one case is clean and preparation method thereof - Google Patents
A kind of gasoline one case is clean and preparation method thereof Download PDFInfo
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- CN105238466B CN105238466B CN201510704824.1A CN201510704824A CN105238466B CN 105238466 B CN105238466 B CN 105238466B CN 201510704824 A CN201510704824 A CN 201510704824A CN 105238466 B CN105238466 B CN 105238466B
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Abstract
The invention discloses a kind of gasoline one case clean and preparation method thereof, this gasoline one case is only by including that cyclo-dextrin-modified polyetheramine, antioxidant, antirust agent, preservative, cosolvent form.Described gasoline one case only can not only effectively cleaning vehicle engine nozzle, intake valve and combustion-chamber deposit, can also substantially suppress atomizer, intake valve and the formation of combustion-chamber deposit deposit, thus improve fuel economy, improve the difficult situation of cold start-up and reduce noxious gas emission.
Description
Technical field
The present invention relates to a kind of clean technical field of gasoline one case, more particularly it relates to an gasoline one case is clean and preparation
Method.
Background technology
At present, being affected by oil refining process, alkene in China's gasoline, arene content are higher, and olefin component is the most unstable,
Easily there is oxidation and polymerization in it under engine high-temperature working condition, and jointly acts on, at electromotor with other impurity in gasoline
The position such as fuel nozzle, intake valve and combustor produce deposit, thus affect the serviceability of electromotor, cause gasoline
Combustion process deterioration, oil consumption increase, exhaust pollutant discharge increase.This is necessary for requiring that the fuel system of automobile engine is long-term
Keep cleaning, therefore, rear motor petrol on sale must add gasoline one case clean.
Gasoline one case is a kind of surfactant only, and it can will aoxidize the potential deposit breakup of formation, solubilising in gasoline
In gasoline, them are stoped to be deposited on electromotor key position.These having been formed to the part of deposit, detersive is to deposition
Thing has the strongest adsorption, deposit can be made slowly loose and split away off from metal surface, and and some are insoluble in fuel oil
Colloid be surrounded by detergent-dispersant additive molecule together, form the positively charged micelle in surface, be finally entrained into combustion chambers burn
Falling, play dispersion and the effect of cleaning, so that electromotor recovers normal operating conditions, gasoline is fully burned, effectively
Reduce the discharge of vehicle exhaust, decrease air pollution, the most also reach to save the effect of gasoline.
The composition played a major role during gasoline one case is clean is typically organic polymer aminated compounds, conventional is PIBA and
Polyetheramine etc..Although PIBA can solve fuel nozzle and inlet valve deposits problem well, but it is in hot conditions
Stability inferior is higher, in a combustion chamber incomplete combustion, and the deposit of combustor can be caused substantially to increase.Compare PIBA
For, polyetheramine has C-O-C key, it is easy to crack in high temperature, fuel nozzle and intake valve deposition can be efficiently controlled
Thing, can also suppress the generation of cylinder deposit simultaneously effectively.Therefore, polyether amine gasoline one case is clean in recent years
Send out to open and paid attention to by domestic and international researcher with applying, be the focus of the clean new product development of gasoline one case.
Summary of the invention
In order to solve the problems referred to above, the invention provides a kind of gasoline one case only with and preparation method thereof and purposes.
In order to realize foregoing invention purpose, this invention takes techniques below scheme:
A kind of gasoline one case is clean, only includes following components in percentage by weight for described one case:
Described cyclo-dextrin-modified polyetheramine is to be prepared with maleic anhydride modified polyetheramine by cyclodextrin；Described maleic anhydride modified
The structural formula of polyetheramine is represented by formula (1):
Wherein, R1For C5～C20Alkyl, nonyl phenyl, dodecylphenyl or pentadecylphenyl；R2For methyl or methoxy
Base；R3For-NH-CH2CH2NH-、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, one or more in hydroxyl cyclodextrin and Tanabe Seiyoku of described cyclodextrin.
In one embodiment, described cyclodextrin is Tanabe Seiyoku.
In one embodiment, the mixture of the described antioxidant one or more compositions in T501, T502, T531.
In one embodiment, one or more in T703, T706, SP-80, SP-85 of described antirust agent form
Mixture.
In one embodiment, described preservative is selected from T551 or T561.
In one embodiment, described cosolvent one or more compositions in aromatic naphtha, dimethylbenzene, alkylbenzene, toluene
Mixture.
Another aspect of the present invention provides gasoline one case clean preparation method, weighs by required component ratio, in room temperature or not higher than
Mix homogeneously under the conditions of 30 DEG C.
A third aspect of the present invention provides the purposes that gasoline one case is clean, joins in motor petrol by 300～600ppm dosage.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Detailed description of the invention
Unless otherwise defined, all technology used herein and scientific terminology have and one skilled in the art of the present invention
The identical implication being generally understood that.When there is contradiction, it is as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " including ", " tool
Have ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, comprise listed elements compositions,
Step, method, goods or device are not necessarily solely those key elements, but can include other not expressly listed key element or this kind
The key element that compositions, step, method, goods or device are intrinsic.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If in claim, this is short
Language will make claim be closed so that it is do not comprise the material in addition to the material that those describe, but relative routine is miscellaneous
Except matter.When being rather than immediately following during phrase " Consists of " occurs in the clause of claim main body after theme, it is only
It is limited to the key element described in this clause；Other key element is not excluded outside as overall described claim.
Equivalent, concentration or other value or parameter are with scope, preferred scope or a series of upper limit preferred value and lower preferable values
During the Range Representation limited, this be appreciated that specifically disclose by any range limit or preferred value and any range lower limit or
All scopes that arbitrary pairing of preferred value is formed, regardless of whether whether this scope separately discloses.Such as, when disclosing scope
Time " 1 to 5 ", described scope should be interpreted as including 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 is intended to include its end value
All integers within the range and mark.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to the quantitative requirement of key element or component (i.e.
Occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least one, and odd number shape
The key element of formula or component also include plural form, unless the obvious purport of described quantity refers to singulative.
In order to solve the problems referred to above, the invention provides a kind of gasoline one case clean, only include following percentage by weight described one case
Component:
Described cyclo-dextrin-modified polyetheramine is to be prepared with maleic anhydride modified polyetheramine by cyclodextrin；Described maleic anhydride modified
The structural formula of polyetheramine can be represented by formula (1):
Wherein, R1For C5～C20Alkyl, nonyl phenyl, dodecylphenyl or pentadecylphenyl；R2For methyl or methoxy
Base；R3For-NH-CH2CH2NH-、N is 10～20；M is 1～2.
Term of the present invention " cyclo-dextrin-modified polyetheramine " is through a step amidation process by polyetheramine, maleic anhydride, cyclodextrin
Prepare with a step esterification.It is not poisoned in order to ensure automotive exhaust catalysis transforming agent and do not increase new pollutant,
Gasoline one case is only the most elementary composition by C, H, O, N etc..At present, the gasoline of use one case is to have certain special knot only
The organic amine material of structure, its molecule two ends are respectively the non-polar group of polar group and long-chain.Non-polar group can give
Gasoline one case has good oil-soluble only, can make the most well to be dissolved in gasoline for one case.Polar group then to metal surface with
And established deposit has stronger adsorption.One case clean in polar group can adsorb and form one layer of guarantor in metal surface
Cuticula so that the colloid in fuel oil cannot be deposited on metal surface；Polar group adsorbs after established deposit surface, energy
Make deposit slowly loose and split away off from metal surface, and by one case clean molecule bag together with some colloids insoluble in fuel oil
Fence up, form the micelle that surface is positively charged, be finally entrained into combustion chambers burn and fall, play suppression and the effect cleaned.This
Cyclo-dextrin-modified polyetheramine is used in invention, makes polyetheramine one end have substantial amounts of polar group, can be on the metal surface of electromotor
Quickly forming layer protecting film, the formation of suppression deposit, meanwhile, it can have more by deposit established to metal surface
Strong adsorption, the deposit that makes quickly loosens and splits away off from metal surface, and and some colloids insoluble in fuel oil
It is surrounded by detersive molecule together, forms the micelle that surface is positively charged, be finally entrained into combustion chambers burn and fall, play and press down
System and the effect cleaned.Additionally, cyclodextrin is prone in high temperature cracking, the most fully burns, be not result in combustor
The increase of middle deposit.
Term of the present invention " cyclodextrin " is hydroxyl cyclodextrin and Tanabe Seiyoku.Herein, term " hydroxyl cyclodextrin " refers to
The all hydroxyls of group in cyclodextrin, can be alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, preferably beta-schardinger dextrin-.Term
" Tanabe Seiyoku " is 3A-amino-3A-deoxidation-(2AS, 3AS)-alpha-cyclodextrin, 3A-amino-3A-deoxidation-(2AS, 3AS)
-beta-schardinger dextrin-, 3A-amino-3A-deoxidation-(2AS, 3AS)-gamma-cyclodextrin, preferably 3A-amino-3A-deoxidation-(2AS, 3AS)
-beta-schardinger dextrin-.
Described term " Acetolon " is acetylacetone,2,4-pentanedione.Described " acetoacetic ester " is methyl acetoacetate.Described term " has
Machine amine " it is ethylenediamine, piperazine, diethylenetriamine, preferably diethylenetriamine.
The preparation method of cyclo-dextrin-modified polyetheramine is as follows:
(1) preparation of polyethers
To add in reactor, after nitrogen replaces twice, intensification limit, limit evacuation, when temperature is raised to 120 DEG C, close vacuum
Valve, and be slowly added to expoxy propane, at 130～150 DEG C, reacts to after completely, is cooled to 80 DEG C of dischargings；
(2) polyethers and Acetolon or acetoacetic ester condensation
Polyethers, Acetolon or acetoacetic ester, DMAP, toluene are equipped with in the reactor of water knockout drum and condenser,
Stirring 4 hours at 25 DEG C, be then slowly heated to 120～130 DEG C of backflows, the water that reaction generates is by dividing with toluene azeotropic warp
Hydrophone is discharged, and terminates, be cooled to 70 DEG C when anhydrous generation；Polyethers: feeding intake of Acetolon or acetoacetic ester: DMAP rubs
That ratio is 1:1:0.005.
(3) preparation of polyetheramine
In step (2), add the organic amine with polyethers equivalent, be under agitation slowly heated to 120～130 DEG C of backflows,
The water generated is by discharging through water knockout drum with toluene azeotropic, and when anhydrous generation, decompression distillation except solvent and other low-boiling-point substances and get final product
Product polyether amine.
(4) preparation of cyclo-dextrin-modified polyetheramine
Polyetheramine, maleic anhydride being dissolved in toluene, after reacting 24h at 90 DEG C, separating-purifying obtains maleic anhydride modified poly-
Ether amines；Polyetheramine, the molar ratio of maleic anhydride are 1.01～1.05:1；
Maleic anhydride modified polyetheramine, cyclodextrin, p-methyl benzenesulfonic acid are dissolved in toluene, divide after reacting 36h at 130 DEG C
Cyclo-dextrin-modified polyetheramine is obtained from purification；Maleic anhydride modified polyetheramine, the molar ratio of cyclodextrin are 1:1.2～1.6,
P-methyl benzenesulfonic acid feeds intake and accounts for maleic anhydride modified polyetheramine and the 0.01 of cyclodextrin gross mass～1%.
As a kind of preferred implementation of the present invention, the weight average molecular weight of described cyclo-dextrin-modified polyetheramine is 1800～4000；Excellent
Selection of land, 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 one or many in hydroxyl cyclodextrin and Tanabe Seiyoku
Kind.
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, one or more in T501, T502, T531 of described antioxidant
The mixture of composition.
As a kind of preferred implementation of the present invention, described antirust agent one in T703, T706, SP-80, SP-85
Or the mixture of several composition.
As a kind of preferred implementation of the present invention, described preservative is selected from T551 or T561.
As a kind of preferred implementation of the present invention, described cosolvent is selected from aromatic naphtha, dimethylbenzene, alkylbenzene, toluene
Plant or the mixture of several composition.
Another aspect of the present invention provides the preparation method that gasoline one case is clean, weighs by required component ratio, by cyclo-dextrin-modified polyethers
Amine, antioxidant, antirust agent, preservative, cosolvent be mix homogeneously under the conditions of room temperature or not higher than 30 DEG C, and stirring is until solution
Transparent.
A third aspect of the present invention provides the purposes that gasoline one case is clean, joins in motor petrol by 300～600ppm dosage.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example be served only for this
Invention is described further, it is impossible to be interpreted as limiting the scope of the invention, and professional and technical personnel in the field is according to above-mentioned
Some nonessential improvement and adjustment that the content of invention is made, still fall within protection scope of the present invention.
It addition, illustrate without other, raw materials used is all commercially available, and component used by following material is weight percentage.
(cyclodextrin is alpha-cyclodextrin to A1: cyclo-dextrin-modified polyetheramine；R in polyetheramine1For nonyl phenyl, R2For methyl, R3
For-NH-CH2CH2NH-, n are 15, and m is 1)
(cyclodextrin is beta-schardinger dextrin-to A2: cyclo-dextrin-modified polyetheramine, R in polyetheramine1For dodecylphenyl, R2For methyl,
R3For-NH-CH2CH2NH-, n are 15, and m is 1)
(cyclodextrin is beta-schardinger dextrin-to A3: cyclo-dextrin-modified polyetheramine, R in polyetheramine1For pentadecylphenyl, R2For methoxy
Base, R3ForN is 15, and m is 2)
(cyclodextrin is 3A-amino-3A-deoxidation-(2AS, 3AS)-beta-schardinger dextrin-to A4: cyclo-dextrin-modified polyetheramine, polyetheramine
Middle R1For dodecylphenyl, R2For methyl, R3ForN is 15, and m is 2)
A5: polyetheramine (R in polyetheramine1For dodecylphenyl, R2For methyl, R3ForN 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:
Preparing gasoline one case according to the formula in table 1 clean, preparation method is following (consumption of following component is all weight percentage):
Weigh by required component ratio, by cyclo-dextrin-modified polyetheramine, antioxidant, antirust agent, preservative, cosolvent in room temperature or
Mix homogeneously under the conditions of not higher than 30 DEG C, stirring is until solution is transparent.
Table 1 is to prepare the clean composition of raw materials of gasoline one case and consumption (percentage by weight)
Method of testing:
The gasoline one case of the present invention is added in 92 commercially available gasoline by the dosage of 300～600ppm only, through specialized department
Evaluation, the physical and chemical index of oil product all meets the requirement of GB17930-2006.Vapour is simulated by GB/T19230.4 test method
Car intake valve generates deposit rate of descent, by the change of thermogravimetric analyzer simulated automotive deposition of combustion chamber of engine increment.
Above-mentioned test result is shown in Table 2.
Table 2 is the clean test result of gasoline one case
In sum, 8 Example formulations of the present invention, according to dosage 300～600ppm, add in presently commercially available motor petrol, right
The fuel oil gas handling system of electromotor and combustor all have obvious cleaning action.Therefore, it can make automobile long under the operating mode run
Phase keeps excellent state, and fuel oil consumption will not produce too fast growth, reduces the discharge of tail gas nuisance, decreases electromotor
Maintenance cost, extend automotive service life.
Aforesaid example is merely illustrative, for explaining some features of inventive feature.Appended claim is intended to
Seek the widest scope that it is contemplated that, and embodiments as presented herein is only the combination according to all possible embodiment
The explanation of the embodiment selected.Therefore, the purpose of applicant is appended claim not showing by explanation inventive feature
The selectional restriction of example.And what formation was not presently considered by the progress in science and technology due to the inaccurate reason of language performance
Possible equivalent or son are replaced, and these changes also should be interpreted to be covered by appended claim in the conceived case.
Claims (10)
1. a gasoline one case is clean, it is characterised in that only include following components in percentage by weight for described one case:
Described cyclo-dextrin-modified polyetheramine is to be prepared with maleic anhydride modified polyetheramine by cyclodextrin；Described maleic anhydride modified
The structural formula of polyetheramine is represented by formula (1):
Wherein, R1Alkyl, nonyl phenyl, dodecylphenyl or pentadecylphenyl for C5～C20；R2For methyl or methoxy
Base；R3For-NH-CH2CH2NH-、N is 10～20；M is 1～2.
Gasoline the most according to claim 1 one case is clean, it is characterised in that the Weight-average molecular of described cyclo-dextrin-modified polyetheramine
Amount is 1800～4000.
Gasoline the most according to claim 1 one case is clean, it is characterised in that described cyclodextrin is selected from hydroxyl cyclodextrin and amino
One or more in cyclodextrin.
Gasoline the most according to claim 3 one case is clean, it is characterised in that described cyclodextrin is Tanabe Seiyoku.
Gasoline the most according to claim 1 one case is clean, it is characterised in that described antioxidant is selected from T501, T502, T531
In one or more composition mixture.
Gasoline the most according to claim 1 one case is clean, it is characterised in that described antirust agent selected from T703, T706, SP-80,
The mixture of one or more compositions in SP-85.
Gasoline the most according to claim 1 one case is clean, it is characterised in that described preservative is selected from T551 or T561.
Gasoline the most according to claim 1 one case is clean, it is characterised in that described cosolvent is selected from dimethylbenzene or toluene.
9. the method that preparation gasoline one case described in any one of claim 1～8 is clean, it is characterised in that claim by required component ratio
Amount, mix homogeneously under the conditions of not higher than 30 DEG C.
10. the purposes that gasoline one case described in any one of claim 1～8 is clean, it is characterised in that add by 300～600ppm dosage
Enter in motor petrol.
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| 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 |
| CN106336506B (en) * | 2016-09-13 | 2019-01-15 | 深圳市广昌达石油添加剂有限公司 | A kind of gasoline cleaning agent polyetheramine and its synthetic method |
| 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 |
| CN107881019B (en) * | 2017-11-02 | 2021-01-29 | 上海新阳半导体材料股份有限公司 | Low-alkalinity environment-friendly solution for removing flash through electrolysis, and preparation method and application thereof |
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| JP6254609B2 (en) * | 2012-12-27 | 2017-12-27 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎ Ｖｅｎｎｏｏｔｓｈａｐ | Composition |
| CN104761718B (en) * | 2015-03-09 | 2017-03-15 | 广昌达新材料技术服务（深圳）股份有限公司 | A kind of novel polyether amine and its synthetic method as gasoline cleaning agent |
| CN104789283B (en) * | 2015-03-11 | 2017-03-08 | 吉林化工学院 | The diethylene glycol monomethyl ether preparation method of composition of beta cyclodextrin basic ring alkanoic acid ester |
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Effective date of registration: 20170307 Address after: 511400 Guangzhou, Panyu District, Luopu street, Nanpu, Guangxi Road, No. 3 (A3 plant), ladder 3 B Patentee after: Guangzhou Xin Road Automotive Technology Co., Ltd. Address before: 529300 Guangdong Province, Jiangmen city Kaiping District West Tsui Lake Road No. 16 Patentee before: Guangdong Yue Fu Automobile Products Co., Ltd |