CN106084094A - A kind of preparation method of polyisobutene succinimide - Google Patents
A kind of preparation method of polyisobutene succinimide Download PDFInfo
- Publication number
- CN106084094A CN106084094A CN201610390969.3A CN201610390969A CN106084094A CN 106084094 A CN106084094 A CN 106084094A CN 201610390969 A CN201610390969 A CN 201610390969A CN 106084094 A CN106084094 A CN 106084094A
- Authority
- CN
- China
- Prior art keywords
- base oil
- polyisobutylene
- anhydride
- preparation
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Landscapes
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides the preparation method of a kind of polyisobutene succinimide, including: A) it is added drop-wise to respectively polyisobutylene reacts by mixture, the maleic anhydride of radical initiator with base oil, obtains the mixture of polyisobutylene butanedioic anhydride and base oil；B) by step A) polyisobutylene butanedioic anhydride that obtains mixes with polyethylene polyamine, the second base oil with the mixture of base oil, carries out aminating reaction, obtain polyisobutene succinimide.The present invention reduces the generation of the by-products such as maleic anhydride autopolymer, polyisobutylene and maleic anhydride polymer, reduce the viscosity of polyisobutylene butanedioic anhydride intermediate, improve effective rate of utilization and the saponification number of polyisobutylene butanedioic anhydride intermediate of maleic anhydride.And the dispersibility of the polyisobutene succinimide prepared has obtained certain improvement.
Description
Technical field
The present invention relates to technology chemical field, particularly relate to the preparation method of a kind of polyisobutene succinimide.
Background technology
Polyisobutene succinimide is a kind of broad-spectrum chemical products, is applied to profit mainly as ashless dispersant
Oil additive field, it is also possible to be used as to manufacture the emulsifying agent of water-in-oil emulsion explosive.
Its preparation method mainly uses polyisobutylene and maleic anhydride to prepare presoma polyisobutylene fourth two
Anhydride, and then polyisobutylene fourth two is synthesized with polyethylene polyamine (diethylenetriamine, triethylene tetramine, TEPA etc.)
Acid imide.
Produce the presoma of polyisobutene succinimide, i.e. polyisobutylene butanedioic anhydride at present, mainly have three kinds of techniques,
Being respectively chloridising, heat adds legal and radical initiator method.
Wherein, when chloridising produces polyisobutylene butanedioic anhydride, post processing can be needed with generating substantial amounts of hydrogen chloride,
Synthesis device and separation equipment need to be made with special substance, and product is chloride, does not meets environmental requirement.
Heat adds legal production polyisobutylene butanedioic anhydride to be needed to carry out at a higher temperature, and energy consumption is higher, course of reaction
Middle coking is more, and product colourity is relatively deep, and the reaction later stage need to blast nitrogen in a large number and take unreacted maleic anhydride out of, maleic anhydride
Separating cumbersome, easily block pipeline, the free acid value content of polyisobutylene butanedioic anhydride product is difficult to reduce.
The temperature that radical initiator method produces polyisobutylene butanedioic anhydride needs is relatively low, is difficult to coking in course of reaction,
Product colour is shallower, and maleic anhydride conversion more thoroughly, is presently the most conventional method.But except life in the method course of reaction
Become outside polyisobutylene butanedioic anhydride, also can generate other products similar with polyisobutylene butanedioic anhydride structure (as along fourth
The autopolymer of enedioic acid acid anhydride, polyisobutylene and the polymer etc. of maleic anhydride), product composition is complicated, it is more difficult to control, these
By-product cannot separate with polyisobutylene butanedioic anhydride, thus these by-products of amination stage also with polyethylene polyamine reaction,
The amine product generated is not to play synergism completely to the use of polyisobutene succinimide, part amine by-product
Even influence whether the application performance of polyisobutene succinimide product.And these byproduct molecules amount wider distribution, lead
Causing polyisobutylene butanedioic anhydride viscosity high, higher viscosity makes the conveying of material bother very much.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the preparation side of a kind of polyisobutene succinimide
Method, by-product is less.
The invention provides the preparation method of a kind of polyisobutene succinimide, including:
A) it is added drop-wise to respectively in polyisobutylene carry out by mixture, the maleic anhydride of radical initiator with base oil
Reaction, obtains the mixture of polyisobutylene butanedioic anhydride and base oil；
B) by step A) mixture of the polyisobutylene butanedioic anhydride that obtains and base oil and polyethylene polyamine, the second basis
Oil mixing, carries out aminating reaction, obtains polyisobutene succinimide.
Preferably, described step A) in, radical initiator is 1:(0.01～100 with the mass ratio of base oil).
Preferably, described step A) in, polyisobutylene is 1:(0.5～2 with the mol ratio of maleic anhydride).
Preferably, described polyisobutylene is 1:(0.1～2 with the mol ratio of polyethylene polyamine).
Preferably, described second base oil accounts for described base oil and the 0～99% of the second base oil total amount.
Preferably, described step A) temperature that drips is 100～240 DEG C, the time of dropping is 0.5～15h.
Preferably, described step A) reaction temperature be 100～240 DEG C, the response time is 2～4h.
Preferably, described step B) particularly as follows: first react 1～10h at 100～140 DEG C, then at 140～180 DEG C
Lower reaction 0.5～15h.
Preferably, described step B) in, polyethylene polyamine for dropping addition, the time that described polyethylene polyamine drips is
0.1～4h.
Preferably, during described radical initiator is peroxide type free-radical initiator and azo type free radical initiator
Any one or more；Described polyethylene polyamine is any one in diethylenetriamine, triethylene tetramine and TEPA
Plant or multiple.
Compared with prior art, the invention provides the preparation method of a kind of polyisobutene succinimide, including: A) will
Radical initiator is added drop-wise to react in polyisobutylene with mixture, the maleic anhydride of base oil respectively, is gathered
Isobutene. succinic anhydride and the mixture of base oil；B) by step A) mixing of the polyisobutylene butanedioic anhydride that obtains and base oil
Thing mixes with polyethylene polyamine, the second base oil, carries out aminating reaction, obtains polyisobutene succinimide.The present invention reduces
The generation of the by-products such as maleic anhydride autopolymer, polyisobutylene and maleic anhydride polymer, reduces poly-isobutyl
The viscosity of alkene succinic anhydride intermediate, improves effective rate of utilization and the soap of polyisobutylene butanedioic anhydride intermediate of maleic anhydride
Change value.And the dispersibility of the polyisobutene succinimide prepared has obtained certain improvement.
Accompanying drawing explanation
Fig. 1 is the polyisobutylene butanedioic anhydride infrared spectrum with the mixture of base oil of the embodiment of the present invention 1 preparation.
Detailed description of the invention
The invention provides the preparation method of a kind of polyisobutene succinimide, including:
A) it is added drop-wise to respectively in polyisobutylene carry out by mixture, the maleic anhydride of radical initiator with base oil
Reaction, obtains the mixture of polyisobutylene butanedioic anhydride and base oil；
B) by step A) mixture of the polyisobutylene butanedioic anhydride that obtains and base oil and polyethylene polyamine, the second basis
Oil mixing, carries out aminating reaction, obtains polyisobutene succinimide.
It is many with maleic anhydride that the preparation method that the present invention provides decreases maleic anhydride autopolymer, polyisobutylene
The generation of the by-products such as polymers, reduces the viscosity of polyisobutylene butanedioic anhydride intermediate, improves effective profit of maleic anhydride
By rate and the saponification number of polyisobutylene butanedioic anhydride intermediate.And the dispersibility of the polyisobutene succinimide prepared obtains
Certain improvement.
The amination stage is needed the base oil added by the present invention, partly or entirely shifts to an earlier date and oleosoluble radical initiators
Mix homogeneously, is then added drop-wise to maleic anhydride react in polyisobutylene the most respectively.
Concrete, in reaction unit, first add polyisobutylene, stir and heat；The amination stage is needed the basis added
Oil, partly or entirely mixs homogeneously with oleosoluble radical initiators in advance, obtains the mixed of radical initiator and base oil
Compound, is added drop-wise to equipped with in the reaction unit of polyisobutylene the most respectively with maleic anhydride.
The present invention there is no particular determination to described polyisobutylene, can be the polyisobutylene of this area routine, it is preferred that institute
The number-average molecular weight stating polyisobutylene is 700～3000, alhpa olefin content > 75wt%.
The present invention there is no particular determination to described base oil, and the synthesis that is applicable to that can be known to the skilled person gathers
The base oil of isobutene. succimide, the present invention is preferably 150SN not hydrogenated base oil, 150N hydrogenated base oil, and 500SN is not
Any one or a few in hydrogenated base oil and 500N hydrogenated base oil.
Described radical initiator is preferably in peroxide type free-radical initiator and azo type free radical initiator
Any one or more；Described peroxide type free-radical initiator is preferably di-tert-butyl peroxide, two t-amyl peroxy
Compound, cumyl peroxide, benzoyl peroxide, any one or a few in methyl ethyl ketone peroxide；Described azo is certainly
It is preferably azodiisobutyronitrile and/or 2,2'-Azobis(2,4-dimethylvaleronitrile) by base initiator.
The present invention there is no particular determination to the source of described maleic anhydride, can be the most commercially available.Described maleic
Dicarboxylic anhydride is melted maleic anhydride.
In the present invention, described radical initiator is preferably 1:(0.01～100 with the mass ratio of base oil), more preferably
1:(20～100).The mol ratio of described polyisobutylene and maleic anhydride is preferably 1:(0.5～2), more preferably 1:(1～
1.5).Radical initiator is preferably (0.005～2) with the mol ratio of polyisobutylene: 1, more preferably (0.05～1): 1.Institute
State the mixture of radical initiator and base oil, be preferably 100～240 DEG C with the temperature of maleic anhydride dropping, more excellent
Elect 120～200 DEG C as；The time of dropping is preferably 0.5～15h, more preferably 2～10h.
The present invention preferably controls the mixture of radical initiator and base oil, and the rate of addition of maleic anhydride,
Make the two complete in same time period dropping.
Currently preferred, above-mentioned dropping is carried out in the atmosphere of protective gas, and described protective gas is preferably nitrogen
Gas.
After dropping, system at such a temperature, i.e. under dropping temperature, continue reaction 2～4h, more preferably reaction 2.5～
3h。
After reaction terminates, it is preferred that being adjusted by temperature of reaction system to 170～200 DEG C, negative pressure steams light component, obtains
Polyisobutylene butanedioic anhydride and the mixture of base oil.
Then, by mixture and polyethylene polyamine, second base of polyisobutylene butanedioic anhydride obtained above and base oil
Plinth oil mixes, and carries out aminating reaction, obtains polyisobutene succinimide.
Concrete, the mixture of polyisobutylene butanedioic anhydride Yu base oil is adjusted to target temperature, preferably 100～140
DEG C, in material, add the base oil of residue requirement, the i.e. second base oil, then carry out aminating reaction with polyethylene polyamine.
The present invention there is no particular determination to described polyethylene polyamine, and can be known to the skilled person is applicable to conjunction
Becoming the polyethylene polyamine of polyisobutene succinimide, the present invention is preferably diethylenetriamine, triethylene tetramine and four ethylene five
Any one or more in amine.
In the present invention, described polyisobutylene is preferably 1:(0.1～2 with the mol ratio of polyethylene polyamine), more preferably 1:
(0.5～1.5).
Described second base oil preferably comprises described base oil and the 0～99% of the second base oil total amount, more preferably accounts for described
Base oil and the 0～70% of the second base oil total amount.When described second base oil accounts for described base oil and the second base oil total amount
0 time, refer to that the second base oil is 0, i.e. reaction needed for whole base oils all in step A) in add.
Currently preferred, described aminating reaction, particularly as follows: first react 1～10h at 100～140 DEG C, then exists
0.5～15h is reacted at 140～180 DEG C.
Currently preferred, described polyethylene polyamine adds for dropping, and the time of described dropping is preferably 0.1～4h.
After aminating reaction terminates, the moisture preferably reaction system elimination reaction under negative pressure generated, can prepare
Polyisobutene succinimide.
In the present invention, after polyisobutylene butanedioic anhydride preparation process, the base oil in reaction mass need not separate, will
After the polyisobutylene butanedioic anhydride generated and the mixture temperature of base oil are reduced to desired value, only need to add residue in material
The base oil of requirement, can drip polyethylene polyamine and carry out next step aminating reaction, prepares polyisobutene succinimide
Product.The method optimizes hydrocarbonylation stage process, easy and simple to handle, shortens amination stages operating time, beneficially industrial applications.
The addition in advance of base oil is not only advantageous to reduce the viscosity of reactant mixture, makes polyisobutylene butanedioic anhydride be prone to
Conveying, is also beneficial to save or eliminate the operation of amination stage addition base oil, improves the operating efficiency in amination stage.Exist simultaneously
Ensure polyisobutylene butanedioic anhydride color shallower and without coking on the premise of, the generation of by-product is greatly decreased, makes product more
As clear as crystal, saponification number is high and viscosity is low.By contrast experiment, find macromolecule by-product in the product that the present invention obtains
The content of thing significantly reduces, and makes the quality of product polyisobutene succinimide be improved.
In order to further illustrate the present invention, below in conjunction with embodiment to the polyisobutene succinimide that the present invention provides
Preparation method is described in detail.
Embodiment 1
150 grams of high-activity polyisobutenes (number-average molecular weight 1000, alhpa olefin content are added in 500ml four-hole bottle
84.65wt%), logical nitrogen protection, stir and be warming up to 150 DEG C；Weigh 2.0g di-tert-butyl peroxide in 150ml beaker
In, it is subsequently poured into 100g 150SN not hydrogenated base oil, adds in the burette being fixed on four-hole bottle after being uniformly mixed,
And start dropping；Meanwhile, another mouthful at four-hole bottle starts the maleic anhydride that dropping is melted, maleic anhydride
Dripping quantity be 20.6g.The rate of addition of the mixture of di-tert-butyl peroxide and base oil should be with maleic anhydride
Rate of addition is suitable, and time for adding is 2h.After two kinds of materials are all added dropwise to complete, continue at 150 DEG C of constant temperature 2h, then by temperature
Adjust to 190 DEG C, under negative pressure, isolate light component, go out material after light component adds 70g 150SN to be not added with to separated
Hydrogen base oil, obtains the mixture of polyisobutylene butanedioic anhydride and base oil.Sample is light yellow, generates without coking.Through analyzing,
Sample motion viscosity (100 DEG C) is 57.3mm2/ s, saponification number is 60.1mmgKOH/g, and free acid value amount is 0.12wt%.
The polyisobutylene butanedioic anhydride prepared and base oil mixture have carried out infrared detection, and infrared spectrum is with poly-
The standard spectrogram of isobutene. succinic anhydride is consistent, illustrates that the product obtained in this step is polyisobutylene butanedioic anhydride.
Reaction mass is cooled to 120 DEG C, in four-hole bottle, in 1.5h, drips triethylene tetramine 11g (polyisobutylene fourth two
Anhydride and triethylene tetramine mol ratio are 1:0.5), after completion of dropwise addition, reaction unit, in 120 DEG C of constant temperature 4h, then heats to 160
DEG C, constant temperature 3h, the moisture that under negative pressure, elimination reaction generates, obtain polyisobutene succinimide product.Through check analysis, product
Kinematic viscosity (100 DEG C) is 165mm2/ s, base number is 21.6mmgKOH/g, and nitrogen content is 1.17wt%.
Embodiment 2
150 grams of high-activity polyisobutenes (number-average molecular weight 1000, alhpa olefin content are added in 500ml four-hole bottle
84.65wt%), logical nitrogen protection, stir and be warming up to 150 DEG C；Weigh 2.0g cumyl peroxide in 150ml beaker,
It is subsequently poured into 100g 150SN not hydrogenated base oil, adds in the burette being fixed on four-hole bottle after being uniformly mixed, and
Start dropping；Meanwhile, another mouthful at four-hole bottle starts the maleic anhydride that dropping is melted, maleic anhydride
Dripping quantity is 20.6g.The rate of addition of the mixture of cumyl peroxide and base oil should be with the dropping of maleic anhydride
Speed is suitable, and time for adding is 2h.After two kinds of materials are all added dropwise to complete, continue at 150 DEG C of constant temperature 2h, then temperature is adjusted
To 190 DEG C, under negative pressure, isolate light component, go out material after light component adds 70g 150SN to be not added with hydrogen-based to separated
Plinth oil, obtains the mixture of polyisobutylene butanedioic anhydride and base oil.Sample is light yellow, generates without coking.Through analyzing, sample
Kinematic viscosity (100 DEG C) is 59.4mm2/ s, saponification number is 61.4mmgKOH/g, and free acid value amount is 0.19wt%.
The polyisobutylene butanedioic anhydride prepared and base oil mixture have carried out infrared detection, and infrared spectrum is with poly-
The standard spectrogram of isobutene. succinic anhydride is consistent, illustrates that the product obtained in this step is polyisobutylene butanedioic anhydride.
Reaction mass is cooled to 120 DEG C, in four-hole bottle, in 1.5h, drips triethylene tetramine 11g (polyisobutylene fourth two
Anhydride and triethylene tetramine mol ratio are 1:0.5), after completion of dropwise addition, reaction unit, in 120 DEG C of constant temperature 4h, then heats to 160
DEG C, constant temperature 3h, the moisture that under negative pressure, elimination reaction generates, obtain polyisobutene succinimide product.Through check analysis, product
Kinematic viscosity (100 DEG C) is 174mm2/ s, base number is 22.3mmgKOH/g, and nitrogen content is 1.21wt%.
Embodiment 3
150 grams of high-activity polyisobutenes (number-average molecular weight 1000, alhpa olefin content are added in 500ml four-hole bottle
84.65wt%), logical nitrogen protection, stir and be warming up to 150 DEG C；Weigh 2.0g bis-t-amyl peroxy compound in 150ml beaker
In, it is subsequently poured into 100g 150SN not hydrogenated base oil, adds in the burette being fixed on four-hole bottle after being uniformly mixed,
And start dropping；Meanwhile, another mouthful at four-hole bottle starts the maleic anhydride that dropping is melted, maleic anhydride
Dripping quantity be 20.6g.The rate of addition of the mixture of two t-amyl peroxy compounds and base oil should be with maleic anhydride
Rate of addition is suitable, and time for adding is 2h.After two kinds of materials are all added dropwise to complete, continue at 150 DEG C of constant temperature 2h, then by temperature
Adjust to 190 DEG C, under negative pressure, isolate light component, go out material after light component adds 70g 150SN to be not added with to separated
Hydrogen base oil, obtains the mixture of polyisobutylene butanedioic anhydride and base oil.Sample is light yellow, generates without coking.Through analyzing,
Sample motion viscosity (100 DEG C) is 61.5mm2/ s, saponification number is 59.2mmgKOH/g, and free acid value amount is 0.14wt%.
The polyisobutylene butanedioic anhydride prepared and base oil mixture have carried out infrared detection, and infrared spectrum is with poly-
The standard spectrogram of isobutene. succinic anhydride is consistent, illustrates that the product obtained in this step is polyisobutylene butanedioic anhydride.
Reaction mass is cooled to 120 DEG C, in four-hole bottle, in 1.5h, drips TEPA 14g (polyisobutylene fourth two
Anhydride and TEPA mol ratio are 1:0.5), after completion of dropwise addition, reaction unit, in 120 DEG C of constant temperature 4h, then heats to 160
DEG C, constant temperature 3h, the moisture that under negative pressure, elimination reaction generates, obtain polyisobutene succinimide product.Through check analysis, product
Kinematic viscosity (100 DEG C) is 184mm2/ s, base number is 33.5mmgKOH/g, and nitrogen content is 1.47wt%.
Comparative example 1
150 grams of high-activity polyisobutenes (number-average molecular weight 1000, alhpa olefin content are added in 500ml four-hole bottle
84.65wt%) with 100g 150SN not hydrogenated base oil, logical nitrogen protection, stir and be warming up to 150 DEG C；Weigh 2.0g bis-uncle
Butylperoxide is in the micro type buret being fixed on four-hole bottle, and starts dropping；Meanwhile, at another of four-hole bottle
Individual mouth starts the maleic anhydride that dropping is melted, and the dripping quantity of maleic anhydride is 20.6g.Di-tert-butyl peroxide with
The rate of addition of the mixture of base oil should be suitable with the rate of addition of maleic anhydride, and time for adding is 2h.Two kinds of things
After material is all added dropwise to complete, continues at 150 DEG C of constant temperature 2h, then temperature is adjusted to 190 DEG C, under negative pressure, isolate light component, to
Separated go out material after light component adds 70g 150SN not hydrogenated base oil, obtain polyisobutylene butanedioic anhydride and base
The mixture of plinth oil.Sample is light yellow, generates without coking.Through analyzing, sample motion viscosity (100 DEG C) is 69.7mm2/ s, soap
Change value is 54.1mmgKOH/g, and free acid value amount is 0.14wt%.
Reaction mass is cooled to 120 DEG C, in four-hole bottle, in 1.5h, drips triethylene tetramine 11g (polyisobutylene fourth two
Anhydride and triethylene tetramine mol ratio are 1:0.5), after completion of dropwise addition, reaction unit, in 120 DEG C of constant temperature 4h, then heats to 160
DEG C, constant temperature 3h, the moisture that under negative pressure, elimination reaction generates, obtain polyisobutene succinimide product.Through check analysis, product
Kinematic viscosity (100 DEG C) is 187mm2/ s, base number is 22.4mmgKOH/g, and nitrogen content is 1.11wt%.
Comparative example 2
150 grams of high-activity polyisobutenes (number-average molecular weight 1000, alhpa olefin content are added in 500ml four-hole bottle
84.65wt%) with 70g 150SN not hydrogenated base oil, logical nitrogen protection, stir and be warming up to 150 DEG C；Weigh the tertiary fourth of 2.0g bis-
Base peroxide, in 150ml beaker, is subsequently poured into 100g 150SN not hydrogenated base oil, adds fixing after being uniformly mixed
In burette on four-hole bottle, and start dropping；Meanwhile, another mouthful at four-hole bottle starts the suitable fourth that dropping is melted
Enedioic acid acid anhydride, the dripping quantity of maleic anhydride is 20.6g.Di-tert-butyl peroxide is fast with the dropping of the mixture of base oil
Degree should be suitable with the rate of addition of maleic anhydride, and time for adding is 2h.After two kinds of materials are all added dropwise to complete, continue
150 DEG C of constant temperature 2h, then adjust temperature to 190 DEG C, isolate light component, obtain polyisobutylene butanedioic anhydride and base under negative pressure
The mixture of plinth oil.Sample is light yellow, generates without coking.Through analyzing, sample motion viscosity (100 DEG C) is 49.7mm2/ s, soap
Change value is 55.1mmgKOH/g, and free acid value amount is 0.37wt%.
Reaction mass is cooled to 120 DEG C, in four-hole bottle, in 1.5h, drips triethylene tetramine 11g (polyisobutylene fourth two
Anhydride and triethylene tetramine mol ratio are 1:0.5), after completion of dropwise addition, reaction unit, in 120 DEG C of constant temperature 4h, then heats to 160
DEG C, constant temperature 3h, the moisture that under negative pressure, elimination reaction generates, obtain polyisobutene succinimide product.Through check analysis, product
Kinematic viscosity (100 DEG C) is 161mm2/ s, base number is 24.8mmgKOH/g, and nitrogen content is 1.12wt%.
Comparative example 3
150 grams of high-activity polyisobutenes (number-average molecular weight 1000, alhpa olefin content are added in 500ml four-hole bottle
84.65wt%), logical nitrogen protection, stir and be warming up to 150 DEG C；Weigh 2.0g di-tert-butyl peroxide in being fixed on four mouthfuls
In micro type buret on bottle, and start dropping；Meanwhile, another mouthful at four-hole bottle starts the maleic that dropping is melted
Dicarboxylic anhydride, the dripping quantity of maleic anhydride is 20.6g.The rate of addition of the mixture of di-tert-butyl peroxide and base oil
Should be suitable with the rate of addition of maleic anhydride, time for adding is 2h.After two kinds of materials are all added dropwise to complete, continue 150
DEG C constant temperature 2h, then adjusts temperature to 190 DEG C, isolates light component under negative pressure, and adds 170g 150SN and be not added with hydrogen-based plinth
Oil, obtains the mixture of polyisobutylene butanedioic anhydride and base oil.Sample is light yellow, but the most muddy.Through analyzing, sample is transported
Kinetic viscosity (100 DEG C) is 97.3mm2/ s, saponification number is 53.4mmgKOH/g, and free acid value amount is 0.12wt%.
Reaction mass is cooled to 120 DEG C, in four-hole bottle, in 1.5h, drips triethylene tetramine 11g (polyisobutylene fourth two
Anhydride and triethylene tetramine mol ratio are 1:0.5), after completion of dropwise addition, reaction unit, in 120 DEG C of constant temperature 4h, then heats to 160
DEG C, constant temperature 3h, the moisture that under negative pressure, elimination reaction generates, obtain polyisobutene succinimide product.Through check analysis, product
Kinematic viscosity (100 DEG C) is 253mm2/ s, base number is 23.6mmgKOH/g, and nitrogen content is 1.17wt%.
By the polyisobutylene butanedioic anhydride obtained in above-described embodiment and comparative example and polyisobutene succinimide
Analysis result list is analyzed, and by industry standard (SH0623 appendix A ashless dispersant low temperature dispersity rating method) to gained
Polyisobutene succinimide sample is evaluated as the dispersive property of ashless dispersant, the results are shown in Table 1, and table 1 is this
Bright Product checking the results list
Table 1 Product checking of the present invention the results list
From above-described embodiment and comparative example, the polyisobutylene butanedioic anhydride base oil that the present invention obtains is diluted to phase
After in proportion, it can be seen that at the synthesis phase of polyisobutylene butanedioic anhydride, radical initiator is entered with a certain amount of base oil
Row dilution, can reduce the viscosity of final base oil and polyisobutylene butanedioic anhydride mixture significantly, and keep it to have relatively
High saponification number.
Wherein, in comparative example 1, radical initiator molecule not diluted and be directly added drop-wise to the technical side in reaction system
Case, in comparative example 2, the technical scheme that base oil mixes with polyisobutylene, the viscosity of the polyisobutylene butanedioic anhydride prepared
With saponification number compared with Example 1, reduce a lot.
Thus it can also be seen that the step that mixes with base oil of radical initiator, it is to affect polyisobutylene butanedioic anhydride
The key factor of quality.
Polyisobutylene butanedioic anhydride is carried out amination, the testing result table of the polyisobutene succinimide sample obtained
Bright, the viscosity of polyisobutene succinimide product has dropped along with the reduction of polyisobutylene butanedioic anhydride intermediate viscosity
Low, and the polyisobutene succinimide sample of embodiment 1 is as the dispersive property adduction hotter than conventional catalyst of ashless dispersant
The polyisobutene succinimide effect that method obtains is the best.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. the preparation method of a polyisobutene succinimide, it is characterised in that including:
A) it is added drop-wise to respectively in polyisobutylene carry out instead by radical initiator and the mixture of base oil, maleic anhydride
Should, obtain the mixture of polyisobutylene butanedioic anhydride and base oil；
B) by step A) polyisobutylene butanedioic anhydride that obtains mixes with polyethylene polyamine, the second base oil with the mixture of base oil
Close, carry out aminating reaction, obtain polyisobutene succinimide.
Preparation method the most according to claim 1, it is characterised in that described step A) in, radical initiator and basis
The mass ratio of oil is 1:(0.01～100).
Preparation method the most according to claim 1, it is characterised in that described step A) in, polyisobutylene and maleic two
The mol ratio of anhydride is 1:(0.5～2).
Preparation method the most according to claim 1, it is characterised in that described polyisobutylene and the mol ratio of polyethylene polyamine
For 1:(0.1～2).
Preparation method the most according to claim 1, it is characterised in that described second base oil accounts for described base oil and second
The 0～99% of base oil total amount.
Preparation method the most according to claim 1, it is characterised in that described step A) temperature that drips is 100～240
DEG C, the time of dropping is 0.5～15h.
Preparation method the most according to claim 1, it is characterised in that described step A) reaction temperature be 100～240
DEG C, the response time is 2～4h.
Preparation method the most according to claim 1, it is characterised in that described step B) particularly as follows: first 100～140
React 1～10h at DEG C, at 140～180 DEG C, then react 0.5～15h.
Preparation method the most according to claim 1, it is characterised in that described step B) in, polyethylene polyamine is that dropping adds
Entering, the time of described polyethylene polyamine dropping is 0.1～4h.
Preparation method the most according to claim 1, it is characterised in that described radical initiator be peroxide type from
By any one or more in base initiator and azo type free radical initiator；Described polyethylene polyamine be diethylenetriamine,
Any one or more in triethylene tetramine and TEPA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610390969.3A CN106084094A (en) | 2016-06-02 | 2016-06-02 | A kind of preparation method of polyisobutene succinimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610390969.3A CN106084094A (en) | 2016-06-02 | 2016-06-02 | A kind of preparation method of polyisobutene succinimide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106084094A true CN106084094A (en) | 2016-11-09 |
Family
ID=57447423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610390969.3A Pending CN106084094A (en) | 2016-06-02 | 2016-06-02 | A kind of preparation method of polyisobutene succinimide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106084094A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110494170A (en) * | 2017-04-25 | 2019-11-22 | 波士顿科学国际有限公司 | Biocompatibility polyisobutene-fibrous composite and method |
| CN111676080A (en) * | 2020-06-23 | 2020-09-18 | 新乡市瑞丰新材料股份有限公司 | Preparation method of novel efficient soot dispersant |
| CN111690081A (en) * | 2020-06-23 | 2020-09-22 | 新乡市瑞丰新材料股份有限公司 | Preparation method of boronized high-molecular-weight ashless dispersant |
| CN111690143A (en) * | 2020-06-23 | 2020-09-22 | 新乡市瑞丰新材料股份有限公司 | Preparation method of high molecular weight high-nitrogen ashless dispersant |
| CN112646079A (en) * | 2020-12-22 | 2021-04-13 | 黄山市强力化工有限公司 | High-dispersion lasting carbon deposition resistant synthetic ester base oil and preparation method thereof |
| CN113387760A (en) * | 2021-07-08 | 2021-09-14 | 新乡市瑞丰新材料股份有限公司 | Novel composite emulsifier for emulsion explosive |
| US11304798B2 (en) | 2015-04-09 | 2022-04-19 | Boston Scientific Scimed, Inc. | Prosthetic heart valves having fiber reinforced leaflets |
| CN114507301A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Method and system for producing polyisobutylene succinimide ashless dispersant |
| US11559394B2 (en) | 2016-05-19 | 2023-01-24 | Boston Scientific Scimed, Inc. | Prosthetic valves, valve leaflets and related methods |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0602863A1 (en) * | 1992-12-15 | 1994-06-22 | BP Chemicals Limited | Resin-free succinimides |
| CN1354190A (en) * | 2000-11-16 | 2002-06-19 | 许敬文 | Free radical one-step method for producing polyisobutylene butanedioic anhydride and its ashless dispersing agent |
| CN101284887A (en) * | 2008-05-18 | 2008-10-15 | 锦州康泰润滑油添加剂有限公司 | Process for producing polyisobutene succinimide ashless dispersant by free radical method |
| WO2010002863A2 (en) * | 2008-06-30 | 2010-01-07 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
| CN102482607A (en) * | 2009-07-08 | 2012-05-30 | 卢布里佐尔公司 | Dispersant viscosity modifiers |
| CN105384946A (en) * | 2015-11-03 | 2016-03-09 | 葛洲坝易普力股份有限公司 | Polymer emulsifier for low shear emulsification and preparation method thereof |
-
2016
- 2016-06-02 CN CN201610390969.3A patent/CN106084094A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0602863A1 (en) * | 1992-12-15 | 1994-06-22 | BP Chemicals Limited | Resin-free succinimides |
| CN1354190A (en) * | 2000-11-16 | 2002-06-19 | 许敬文 | Free radical one-step method for producing polyisobutylene butanedioic anhydride and its ashless dispersing agent |
| CN101284887A (en) * | 2008-05-18 | 2008-10-15 | 锦州康泰润滑油添加剂有限公司 | Process for producing polyisobutene succinimide ashless dispersant by free radical method |
| WO2010002863A2 (en) * | 2008-06-30 | 2010-01-07 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
| CN102482607A (en) * | 2009-07-08 | 2012-05-30 | 卢布里佐尔公司 | Dispersant viscosity modifiers |
| CN105384946A (en) * | 2015-11-03 | 2016-03-09 | 葛洲坝易普力股份有限公司 | Polymer emulsifier for low shear emulsification and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11304798B2 (en) | 2015-04-09 | 2022-04-19 | Boston Scientific Scimed, Inc. | Prosthetic heart valves having fiber reinforced leaflets |
| US11559394B2 (en) | 2016-05-19 | 2023-01-24 | Boston Scientific Scimed, Inc. | Prosthetic valves, valve leaflets and related methods |
| CN110494170A (en) * | 2017-04-25 | 2019-11-22 | 波士顿科学国际有限公司 | Biocompatibility polyisobutene-fibrous composite and method |
| US12115275B2 (en) | 2017-04-25 | 2024-10-15 | Boston Scientific Scimed, Inc. | Biocompatible polyisobutylene-fiber composite materials and methods |
| CN111676080A (en) * | 2020-06-23 | 2020-09-18 | 新乡市瑞丰新材料股份有限公司 | Preparation method of novel efficient soot dispersant |
| CN111690081A (en) * | 2020-06-23 | 2020-09-22 | 新乡市瑞丰新材料股份有限公司 | Preparation method of boronized high-molecular-weight ashless dispersant |
| CN111690143A (en) * | 2020-06-23 | 2020-09-22 | 新乡市瑞丰新材料股份有限公司 | Preparation method of high molecular weight high-nitrogen ashless dispersant |
| CN111690143B (en) * | 2020-06-23 | 2022-08-05 | 新乡市瑞丰新材料股份有限公司 | Preparation method of high molecular weight high-nitrogen ashless dispersant |
| CN114507301A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Method and system for producing polyisobutylene succinimide ashless dispersant |
| CN114507301B (en) * | 2020-10-28 | 2023-12-12 | 中国石油化工股份有限公司 | Method and system for producing polyisobutene succinimide ashless dispersant |
| CN112646079A (en) * | 2020-12-22 | 2021-04-13 | 黄山市强力化工有限公司 | High-dispersion lasting carbon deposition resistant synthetic ester base oil and preparation method thereof |
| CN113387760A (en) * | 2021-07-08 | 2021-09-14 | 新乡市瑞丰新材料股份有限公司 | Novel composite emulsifier for emulsion explosive |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106084094A (en) | A kind of preparation method of polyisobutene succinimide | |
| US9108172B2 (en) | Method and device for the continuous production of polymers by radical polymerization | |
| CN104910299B (en) | A kind of preparation method of polyisobutylene butanedioic anhydride | |
| Rinaldi et al. | RAFT copolymerization of methacrylic acid and poly (ethylene glycol) methyl ether methacrylate in the presence of a hydrophobic chain transfer agent in organic solution and in water | |
| RU2689781C2 (en) | Method of producing butadiene-styrene block-copolymers | |
| JP2011517723A5 (en) | ||
| Vandenbergh et al. | Polymer end group modifications and polymer conjugations via “click” chemistry employing microreactor technology | |
| TW200720294A (en) | Polymerization process | |
| Garg et al. | Effect of glycidyl methacrylate (GMA) content on thermal and mechanical properties of ternary blend systems based on cardanol-based vinyl ester resin, styrene and glycidyl methacrylate | |
| CN101284887A (en) | Process for producing polyisobutene succinimide ashless dispersant by free radical method | |
| JP2002522415A (en) | Open-chain alkoxyamines and their use as polymerization regulators | |
| CN102869691A (en) | Method for producing modified polymer | |
| IN2014DN11138A (en) | ||
| Ma et al. | Synthesis of novel macrophotoinitiator for the photopolymerization of acrylate | |
| CN106832111B (en) | A kind of preparation method of multi-functional slickwater fracturing fluid drag reducer drag reducer | |
| King et al. | Controlled Synthesis and Degradation of Poly (N‐(isobutoxymethyl) acrylamide) Homopolymers and Block Copolymers | |
| CN1688678A (en) | Polymer dispersions with low viscosity and method for production thereof | |
| CN101117363A (en) | Process for producing high-nitrogen dispersion type ethylene-propylene copolymer viscosity index improver | |
| JPS61247712A (en) | Emulsion polymerization method and polymer formed by said method | |
| JP5577407B2 (en) | N-vinyl lactam polymer and process for producing the same | |
| JP5946255B2 (en) | N-vinyl lactam polymer and process for producing the same | |
| JP2021070809A (en) | Method for Producing N-Vinyl Lactam Copolymer | |
| RU2506278C2 (en) | Rubber-reinforced vinyl aromatic (co) | |
| RU2568440C1 (en) | Aqueous styrene-acrylic dispersion and preparation method thereof | |
| Hernández‐Ortiz et al. | The Relevance of Multi‐Injection and Temperature Profiles to Design Multi‐Phase Reactive Processing of Polyolefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |