CN107935821A - A kind of preparation method of tert amyl methyl ether(TAME) and a kind of method for modifying of light petrol - Google Patents
A kind of preparation method of tert amyl methyl ether(TAME) and a kind of method for modifying of light petrol Download PDFInfo
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- CN107935821A CN107935821A CN201610889293.2A CN201610889293A CN107935821A CN 107935821 A CN107935821 A CN 107935821A CN 201610889293 A CN201610889293 A CN 201610889293A CN 107935821 A CN107935821 A CN 107935821A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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Abstract
Preparation method and a kind of method for modifying of light petrol, the preparation method the invention discloses a kind of tert amyl methyl ether(TAME) include：Under the conditions of etherification reaction, methanol and iso-amylene are contacted with catalyst for etherification to obtain the reaction product containing tert amyl methyl ether(TAME)；The catalyst for etherification is Polymer-supported ionic-liquid catalyst, which has formula (I) or the structure shown in formula (П),The method of the present invention can make the reaction for preparing tert amyl methyl ether(TAME) to keep higher reactivity.
Description
Technical field
The present invention relates to a kind of etherification reaction, and in particular, in a kind of catalyst etherifying light petrol alkene important composition into
Divide iso-amylene, prepare the method for tert amyl methyl ether(TAME) and a kind of method for modifying of light petrol.
Background technology
Tert amyl methyl ether(TAME) is the oxygen-containing ether compound of a kind of high-octane rating, low-steam pressure.With methyl tertbutyl ethers
Seemingly, tert amyl methyl ether(TAME) (TAME) can be effectively improved gasoline quality as gasoline additive, and gasoline is uprising and the feature of environmental protection for improvement
Can, it is to produce unleaded, oxygen-containing, high-knock rating gasoline, produces the preferable blend component of following clean gasoline.In methyl tertiary butyl ether(MTBE)
Because under the factor confined condition such as environmental protection, raw material, the market demand of tert amyl methyl ether(TAME) increases sharply.In addition, production methyl- tert
The raw material iso-amylene of amyl ether is the important composition component of alkene in light petrol.Catalyst etherifying iso-amylene, etherified benzine can be more
Content of olefin in gasoline is directly effectively reduced, improves gasoline quality from source.Thus, fail the methyl- tert mass produced at this stage
The preparation method research of amyl ether is of great significance.
Researcher in 1977 uses A-15 to make catalyst to cause isobutene and alcohol to react generation ether, be resin catalyst first
Utilization in etherificate field are laid a good foundation.The prior art uses resin cation and is etherified preparation as catalyst
TAME, as made catalyst using sulfonic acid ion exchange resin in US 4193770, makees raw material, one with methanol and iso-amylene
Etherification reaction is carried out under the conditions of constant-pressure and 66-116 DEG C, under industrial suitable space velocities, the conversion ratio of iso-amylene is 35%
Left and right, compared with low-speed, the conversion ratio of iso-amylene is up to 50%-60%.However, cation exchange resin has as catalyst
Following shortcoming：One side catalyst heat endurance is low, and catalyst sulfonic acid group is easy to fall off thus causes catalyst activity relatively low.Separately
On the one hand, H in cation exchange resin active group+Easily exchanged by metal cation in raw material and cause catalyst poisoning.
Also there is molecular sieve catalyst in the prior art as catalyst for etherification.As described in US 4605787 with ZSM-5,
The gas phase reaction of the catalyst such as ZSM-11, ZSM-12 methanol and isobutene.And for example EP 309177 then compares β type molecules
Sieve the catalytic activity for synthesizing sec-amyl methyl ether with 2- amylenes for methanol with A-15.Existing catalyst for etherification species further includes miscellaneous
More acid catalyst and solid super strong acids catalyst etc., such as the heteropolyacid catalyst disclosed in JP 81135439
H4SiMo12O40/SiO2, and the solid super-strong acid SO disclosed in EP 2591054 2-/ZrO2.This three classes catalyst respectively has advantage, but
All there are catalytic activity it is relatively low the problem of.
The content of the invention
Preparation method and a kind of method for modifying of light petrol the object of the present invention is to provide a kind of tert amyl methyl ether(TAME),
The reaction that etherificate catalysis of the present invention prepares tert amyl methyl ether(TAME) can keep higher reactivity.Applied to light petrol
The octane number of gasoline can be improved in method for modifying, is effectively improved the oil product of gasoline.
To achieve these goals, the present invention provides a kind of preparation method of tert amyl methyl ether(TAME), wherein, this method bag
Include：
Under the conditions of etherification reaction, methanol and iso-amylene are contacted to obtain containing tert amyl methyl ether(TAME) with catalyst for etherification
Reaction product；
The catalyst for etherification is Polymer-supported ionic-liquid catalyst, which has formula (I) or formula (П) institute
The structure shown：
In formula (I), m is the integer of 50-200, and preferably m is the integer of 50-150；N1 and n2 are each independently 30-100
Integer, preferably n1 and n2 are each independently the integer of 30-70；X-Selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-
CH3C6H4SO3 -In one or more, preferably X-For HSO4 -Or CF3SO3 -；
In formula (П), m ' is the integer of 50-200, and preferably m ' is the integer of 50-150；N1 ' and n2 ' are each independently
The integer of 30-100, preferably n1 ' and n2 ' are each independently the integer of 30-70；X-Selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-
CH3C6H4SO3 -In one or more, preferably X-For CF3SO3 -。
Present invention also offers a kind of method for modifying of light petrol, contain active olefin in the light petrol, wherein, the party
Method includes：
Under the conditions of etherification reaction, methanol and light petrol are contacted with catalyst for etherification, obtain the ether containing active olefin
Change the reaction product of product；
The catalyst for etherification is Polymer-supported ionic-liquid catalyst, which has formula (I) or formula (П) institute
The structure shown：
In formula (I), m is the integer of 50-200, and preferably m is the integer of 50-150；N1 and n2 are each independently 30-100
Integer, preferably n1 and n2 are each independently the integer of 30-70；X-Selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-
CH3C6H4SO3 -In one or more, preferably X-For HSO4 -Or CF3SO3 -；
In formula (П), m ' is the integer of 50-200, and preferably m ' is the integer of 50-150；N1 ' and n2 ' are each independently
The integer of 30-100, preferably n1 ' and n2 ' are each independently the integer of 30-70；X-Selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-
CH3C6H4SO3 -In one or more, preferably X-For CF3SO3 -。
The method of the present invention enables to the reaction for preparing tert amyl methyl ether(TAME) to keep higher reactivity.Example
Such as, it can be seen that by the data of EXPERIMENTAL EXAMPLE 1-6 and carried out using Polymer-supported ionic-liquid catalyst of the present invention
Etherificate catalysis prepares methyl amylether, and after circular response 9 times, the conversion ratio of iso-amylene is still more stable.Furtherly, adopt
With currently preferred catalyst for etherification, higher reactivity can be kept by not only preparing the reaction of tert amyl methyl ether(TAME), and
And the conversion ratio of iso-amylene can reach 50-60%, this has the research and development for mass producing tert amyl methyl ether(TAME) important
Meaning.Also, the octane number of gasoline can be improved in being modified applied to light petrol and is effectively improved gasoline quality, to non-next life
Production clean gasoline is of great significance.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the test chart of the heat endurance of catalyst for etherification used in embodiment of the invention；
Fig. 2 is catalyst for etherification used in the embodiment of the present invention in 1ug/mL sodium chloride methanol solution environment
In, the test chart of cyclical stability；
Fig. 3 is catalyst for etherification used in the embodiment of the present invention in 100ug/mL potassium chloride methanol solution environment
In, the test chart of cyclical stability.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
According to the present invention, the preparation method of the tert amyl methyl ether(TAME) includes：
Under the conditions of etherification reaction, methanol and iso-amylene are contacted to obtain containing tert amyl methyl ether(TAME) with catalyst for etherification
Reaction product；
The catalyst for etherification is Polymer-supported ionic-liquid catalyst, which has formula (I) or formula (П) institute
The structure shown：
In formula (I), m is the integer of 50-200, and n1 and n2 are each independently the integer of 30-100, X-Selected from HSO4 -、
CF3SO3 -、CH3SO3 -And p-CH3C6H4SO3 -In one or more；
Under preferable case, in formula (I), m is the integer of 50-150, and n1 and n2 are each independently the integer of 30-70, X-For
HSO4 -Or CF3SO3 -；
Under preferable case, in formula (I), n1:N2 is 1:0.9-1.1.
In formula (П), m ' is the integer of 50-200, and n1 ' and n2 ' are each independently the integer of 30-100, X-It is selected from
HSO4 -、CF3SO3 -、CH3SO3 -And p-CH3C6H4SO3 -In one or more；
Under preferable case, in formula (П), m ' is the integer of 50-150, and n1 ' and n2 ' are each independently the integer of 30-70,
X-For CF3SO3 -；
Under preferable case, in formula (П), n1 ':N2 ' is 1:0.9-1.1.
Acidic ion liquid is widely used to all kinds of organic synthesis as the acid catalyzed potentiality material of substitution industry,
Such as diene synthesis, friedel-craft reaction catalyst system and catalyzing.Acidic ion liquid shows clear superiority, such as low volatility, reaction product
High selectivity, easy recycling etc..The catalyst for etherification applied in the method for the present invention is to bear acidic ion liquid
It is downloaded on polymer so that supported ionic liquids, ionic liquid and the advantages of solid carrier material are combined together, and are being protected
While holding ionic liquid excellent physical and chemical characteristic, be more conducive to catalytic reaction after reaction solution and catalyst separation and urge
The recycling of agent.
According to the present invention, the specific preparation method of the Polymer-supported ionic-liquid catalyst includes：
Step 1: the preparation of protective shell
Preparing macromolecular protective shell chain polymerization thing styrene by RFAT bulk polymerizations, (specific synthetic route is for example following
Shown in reaction equation (a)), or polymer butyl methacrylate (shown in for example following reaction equations (b) of specific synthetic route).
Under nitrogen protection, by styrene or butyl methacrylate and chain transfer agents 2-cyanopropan-2yl
Benzodithioate (CPBD) and azodiisobutyronitrile (AIBN) mixing, and polymer reaction is carried out, obtain macromolecular protection
Shell chain polystyrene or polybutyl methacrylate.Reaction product is further purified it is preferred that further including, reaction product will be contained
Reaction solution dilutes, in methyl alcohol reprecipitation, filters drying, obtains polymer powder.
Wherein, the molar ratio of chain transfer agents CPBD and AIBN can be 1:0.1-0.4, under preferable case, CPBD and
The molar ratio of AIBN is 1:1/3.According to gained polystyrene and the difference of the chain length of polybutyl methacrylate, styrene or first
The selectable range of the dosage of base butyl acrylate is wider, such as：The molar ratio of styrene and chain transfer agents CPBD can be
100-400:1, m can be selected from the integer of 50-200.The molar ratio of butyl methacrylate and chain transfer agents CPBD can be
100-400:1, m' can be selected from the integer of 50-200.
The condition of polymerisation includes the temperature and time of polymerisation, and the temperature of polymerisation can be 70-100 DEG C,
Preferably 75-85 DEG C.The time of polymerisation can be according to the chain length of gained polystyrene and polybutyl methacrylate not
With selecting, when the time of general polymerization reaction can be 6-40 small.
Step 2: the preparation of block polymer
Using macromolecular protective shell chain as macromole evocating agent, AIBN is initiator, and 4-vinylpridine after purification is single
Body prepares-block- poly- (4-vinylpridine) (for example following reaction equations of specific synthetic route of block polymer polystyrene
(c) shown in), or polybutyl methacrylate-block- poly- (4-vinylpridine) (for example following reaction equations of specific synthetic route
(d) shown in).
Under nitrogen protection, polystyrene or polybutyl methacrylate are dissolved in anhydrous dimethyl formamide (DMF)
In, and mixed with 4-vinylpridine and azodiisobutyronitrile (AIBN), and polymer reaction is carried out, obtain block polymer and gather
- the block- of styrene poly- (4-vinylpridine) or polybutyl methacrylate-block- poly- (4-vinylpridine).It is excellent
Choosing, which further includes, is further purified reaction product, and the reaction solution containing reaction product is diluted, molten in the mixing of petroleum ether and ether
Reprecipitation in liquid, filters drying, obtains block polymer powder.
Wherein, the molar ratio of polystyrene or polybutyl methacrylate and AIBN can be 1:0.2-0.4, preferable case
Under, polystyrene or the molar ratio of polybutyl methacrylate and AIBN are 1:1/3.According to block list in gained block polymer
The difference of the chain length of member, the selectable range of the dosage of 4-vinylpridine monomer is wider, such as：4-vinylpridine and polyphenyl
The molar ratio of ethene can be 100-200:1, m can be selected from the integer of 50-200, and n can be selected from the integer of 50-200.4- second
The molar ratio of alkenyl pyridine and polybutyl methacrylate can be 100-200:1, m' can be selected from the integer of 50-200, and n' can
With the integer selected from 50-200.As long as DMF is enough dissolved polystyrene or polybutyl methacrylate as solvent and meets anti-
The requirement of the amount of medium is answered, for example, relative to 1 mole of polystyrene or polybutyl methacrylate, the volume of DMF can be with
For 5-30mL.
The condition of polymerisation includes the temperature and time of polymerisation, and the temperature of polymerisation can be 70-100 DEG C,
Preferably 75-85 DEG C.The time of polymerisation can be according to the chain length of gained polystyrene and polybutyl methacrylate not
With selecting, when the time of general polymerization reaction can be 2-20 small.
Step 3: the preparation of micelle forma-tion and catalyst precarsor
The specific synthetic route of poly- (4-vinylpridine) catalyst precarsors of block polymer polystyrene-block- is such as
Shown in following reaction equations (e), before poly- (4-vinylpridine) catalyst of block polymer polybutyl methacrylate-block-
Shown in for example following reaction equations (f) of specific synthetic route of body.
Under nitrogen protection, by-the block- of block polymer polystyrene poly- (4-vinylpridine) or poly- methyl-prop
Olefin(e) acid butyl ester-block- poly- (4-vinylpridine) is dissolved in hot toluene, is stirred at reflux, and is formed with poly- (4-vinylpridine)
For core, polystyrene or the nanometer spherical micella that polybutyl methacrylate is shell.1,4- dibromos are added dropwise into above-mentioned solution
Butane, back flow reaction crosslink part pyridine unit, fixed spherical micelle, forms stable spherical structure.Then 1,3- third is added
Sultones, continues to flow back, catalyst precarsor is prepared.Reaction product is further purified it is preferred that further including, reaction will be contained
The reaction solution dilution of product, in petroleum ether and the in the mixed solvent reprecipitation of ether, filters drying, obtains spherical micelle load
Amphoteric catalyst precursor.
Wherein, when the time being stirred at reflux after being mixed with hot toluene can be 1-5 small.Flow back after adding 1,4- dibromobutanes
When the time of reaction can be 35-55 small, the time for continuing back flow reaction after addition 1,3-propane sultone can be that 35-55 is small
When.The temperature of reflux can be 100-130 DEG C.
With-the block- of 1g polystyrene poly- (4-vinylpridine) or poly- (4- of polybutyl methacrylate-block-
Vinylpyridine) on the basis of, the dosage of Isosorbide-5-Nitrae-dibromobutane can be 120mg-350mg, and the dosage of 1,3-propane sultone can
Think 200-500mg.N=n1+n2, n can be the integer of 50-200.The molar ratio of n1 and n2 can be 1:0.9-1.1, it is more excellent
The molar ratio of choosing, n1 and n2 are 1.N'=n1'+n2', n' can be the integer of 50-200.The molar ratio of n1' and n2' can be
1:0.9-1.1, it is further preferred that the molar ratio of n1' and n2' is 1.
As long as the requirement for the amount that toluene is enough to dissolve the block polymer and meet reaction medium as solvent, example
Such as, with-the block- of 1mmol polystyrene poly- (4-vinylpridine) or poly- (the 4- second of polybutyl methacrylate-block-
Alkenyl pyridine) on the basis of, the volume of toluene is 150-300mL.
Step 4: the preparation of catalyst
By amphoteric catalyst precursor supported acidic activated centre, for example following reaction equations (g) of specific synthetic route or (h)
It is shown.
By amphoteric catalyst precursor supported acidic activated centre, it is ionic liquid-catalyzed that Polymer-supported is prepared
Agent.The method and condition in specific supported acidic activated centre are known to those skilled in the art, and details are not described herein.It is described
Acid activated centre can be selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-CH3C6H4SO3 -In one kind, be preferably HSO4 -Or
CF3SO3 -。
Technique according to the invention scheme understands that the present invention is essentially consisted in be answered in the preparation method to tert amyl methyl ether(TAME)
The improvement of catalyst for etherification.To ether when the foregoing catalyst for etherification of the present invention is applied to the preparation of tert amyl methyl ether(TAME)
Changing reaction has higher reactivity, and repeatedly the conversion ratio of the iso-amylene after catalyst etherifying reaction is able to maintain that higher
Level, illustrate that the stability of the catalyst for etherification is good, service life length, therefore, to large-scale production tert amyl methyl ether(TAME)
Preparation method research is of great significance.
According to the present invention, in order to ensure the etherification reaction of the high reaction activity of methanol and iso-amylene, with the quality of iso-amylene
On the basis of, the dosage of the catalyst for etherification can be 1-80 mass %, it is further preferred that the dosage of the catalyst for etherification is 1-50
Quality %.
Although in the present invention, as long as can realize the invention mesh of the present invention using catalyst for etherification of the present invention
And the etherification reaction condition is selected in a wider scope, for example, the specific side for being referred to the prior art
Method carries out the etherification conditions that etherificate prepares tert amyl methyl ether(TAME) in methyltertiarvbutyl ether reactor.But in order to which the present invention is better achieved
Goal of the invention, and can application catalyst for etherification of the present invention after ensure etherification reaction high reaction activity, iso-amylene
Conversion ratio and etherification reaction stability, the condition of the etherification reaction is preferably：Temperature is 55-95 DEG C, methanol and isoamyl
The molar ratio of alkene is 1-4:1.In the case of more preferably, in an exemplary embodiment of the present invention, the temperature of the etherification reaction is
75 DEG C, the molar ratio of methanol and iso-amylene is 1-2:1, on the basis of the quality of iso-amylene, the dosage of the catalyst for etherification is
40 mass %.
According to the present invention, this method is further included reaction product separation of solid and liquid, obtains liquid phase tert amyl methyl ether(TAME) and recycling
Obtain solid phase catalyst for etherification.The solid catalyst of recycling may be reused.
In the present invention, the acidic ionic liquid catalysts of the Polymer-supported are powder solid, insoluble in general common
Organic solvent.Through TG-DT A spectrum, catalyst thermostabilization is high, and less than 300 DEG C catalyst are without decomposition.Transmitted by Flied emission
Electronic Speculum and scanning electron microscope analysis, catalyst are scattered very homogeneous spherical structure, size between 40-50nm, kernel be with
P4VP is the acidic ion liquid of carrier, and shell is hydrophobic chain protective shell.During catalyst etherifying iso-amylene, reactant passes through
Protective shell reaches acidic site, carries out etherification reaction.After reaction, because catalyst does not dissolve in organic solvent, by simple
Separation of solid and liquid, the catalyst of recycling are recycled catalytic reaction.
According to the present invention, a kind of method for modifying of light petrol is additionally provided, contains active olefin in the light petrol, its
In, this method includes：
Under the conditions of etherification reaction, methanol and light petrol are contacted with catalyst for etherification, obtain the ether containing active olefin
Change the reaction product of product；
The catalyst for etherification is Polymer-supported ionic-liquid catalyst, which has formula (I) or formula (П) institute
The structure shown：
In formula (I), m is the integer of 50-200, and n1 and n2 are each independently the integer of 30-100, X-Selected from HSO4 -、
CF3SO3 -、CH3SO3 -And p-CH3C6H4SO3 -In one or more；
Under preferable case, in formula (I), m is the integer of 50-150, and n1 and n2 are each independently the integer of 30-70, X-For
HSO4 -Or CF3SO3 -；
Under preferable case, in formula (I), n1:N2 is 1:0.9-1.1.
In formula (П), m ' is the integer of 50-200, and n1 ' and n2 ' are each independently the integer of 30-100, X-It is selected from
HSO4 -、CF3SO3 -、CH3SO3 -And p-CH3C6H4SO3 -In one or more；
Under preferable case, in formula (П), m ' is the integer of 50-150, and n1 ' and n2 ' are each independently the integer of 30-70,
X-For CF3SO3 -；
Under preferable case, in formula (П), n1 ':N2 ' is 1:0.9-1.1.
According to the present invention, in order to which the goal of the invention of the present invention is better achieved, and etherificate of the present invention can applied
Ensure high reaction activity, the conversion ratio of etherification product and the stabilization of etherification reaction of active olefin of etherification reaction after catalyst
Property, the condition of the etherification reaction is preferably：Temperature is 55-95 DEG C, and the molar ratio of methanol and active olefin in light petrol is 1-
4:1.On the basis of the quality of active olefin, the dosage of the catalyst for etherification is 1-80 mass %, is preferably 1-50 mass %.
Wherein, the light petrol can be selected from catalytic cracking (FCC) light petrol, catalytic pyrolysis (DCC) light petrol, the light vapour of steam cracking
One or more in oil, light coker naphtha, methanol-to-olefins (MTO) light petrol and preparing gasoline by methanol (MTG) light petrol；It is described
The content of active olefin is 5-50 mass % in light petrol, and the active olefin is in isobutene, iso-amylene and dissident's alkene
It is one or more.
According to the present invention, catalyst for etherification of the present invention is applied to the modification of light petrol, modification can be effectively improved
The octane number of light petrol afterwards, improves gasoline quality.In an exemplary embodiment of the present invention embodiment, the etherificate production containing active olefin
The octane number of the reaction product of thing is than being etherified the high at least two unit of premise.The octane number refers to RON octane numbers.
In the present invention, reaction product composition is measured using gas chromatography, mol%.
In the present invention, the conversion ratio of iso-amylene calculates according to the following equation.The conversion ratio calculation formula of dissident's alkene with etc
Seemingly.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
The present invention will be described in detail by way of examples below.
In following embodiments：
The preparation method of chain transfer agents 2-cyanopropan-2yl benzodithioate (CPBD) is as follows：
1.83g magnesium chips (76.25mmol) is added in the three-necked flask of 250mL, is loaded on reflux condensing tube and 100mL
Constant pressure funnel, closed system, substitutes gas three times, takes out 10min every time.Under nitrogen protection, the bromobenzene (1.496g/ of 8mL
ML, 76.22mmol) and the THF of anhydrous and oxygen-free of 30mL be added in constant pressure funnel, the THF of 20mL anhydrous and oxygen-frees and three
Grain iodine is added in three-necked flask.A few drop bromobenzenes are added dropwise, stir, hair-dryer auxiliary heating, after initiation, 30 DEG C are placed in by reaction bulb
Water-bath in, be slowly added dropwise bromobenzene, maintain temperature of reaction system to be less than 40 DEG C.After being added dropwise, 75 DEG C are warming up to, back flow reaction
3h.Then reaction bulb is placed in 0 DEG C of ice-water bath, under nitrogen protection, 4.6mLCS2(1.26g/mL, 76.12mmol) and
The anhydrous and oxygen-free THF of 20mL is added in constant pressure funnel, is added dropwise at 0 DEG C, after being added dropwise, ice-water bath is removed, in room temperature
Under continue stirring reaction 3h.Under nitrogen protection, the saturated ammonium chloride solution of 100mL is added in constant pressure funnel, at room temperature
It is added dropwise, after dripping off, continues stirring reaction 1h.Then reaction solution is filtered through sand core funnel, with washed with ether filter residue, removed not anti-
The magnesium chips answered.Then extracted in three times with 500mL separatory funnels, ether is extractant.Combined ether layer, is spin-dried for, and will obtain
Product be transferred to the single-necked flask of 1000mL, the anhydrous ether dissolving of 200mL is added, then by the NaOH of 250mL
(3.234g, 80.85mmol) solution instills, and drips off, is stirred overnight.500mL separatory funnels extract in three times, and extractant is water,
Combining water layer.Then water layer is transferred in the single-necked flask of 1000mL, the 210mL potassium ferricyanides (K3[Fe(CN)6])
The aqueous solution of (25.818g, 78.42mmol) instills, and stirring reaction, has red precipitate generation, after dripping off, continue to stir at room temperature
4h is reacted, filters, obtains aubergine solid；Double thio benzoyl hydroperoxide acid anhydride 10.508g, yield 90%.
Double thio over cure benzoyl oxides (4mmol) of 1.235g and the AIBN (6mmol) of 1.002g are added to the three of 100mL
In mouth flask, on device on reflux condensing tube, closed system, substitutes gas three times, is evacuated 10min every time.Then add 30mL's
The ethyl acetate of anhydrous and oxygen-free, back flow reaction 18h.After stopping reaction, directly it is spin-dried for, then crosses pillar separation, solvent is stone
Oily ether and ethyl acetate (volume ratio) 50:1 mixed solvent.Product point is collected, is spin-dried for, vacuum is drained, and it is dark red to obtain 1.504g
Color solid (CPBD), yield 85%.
Agents useful for same is that analysis is pure in following embodiments.
Capital equipment and model used in the present embodiment is as follows：
Bruker-300 and Bruker-400 Nuclear Magnetic Resonance, with CDCl3For solvent, TMS is internal standard；
Size exclusion chromatography Agilent1200seriesGPC【Detector：G1362 type differential refraction detectors】；Elution
Agent：Tetrahydrofuran；Flow velocity：1mL/min；Column temperature：35 DEG C, standard curve is done with monodispersed polystyrene standard sample；
Flied emission transmission electron microscope (TEM) model：The chloroform that Tecnai G2F20 (FEI Co.) sample is made into 1mg/mL is molten
Liquid, the carbon that solution is dropped in 0.45 μ support on film that naturally dry, is then tested；
Dynamic laser light scattering experimental (DLS) model：Malvern Zeta Sizer Nano-90, it is molten to be made into a certain concentration chloroform
Liquid, filters before determination sample by 800nm Millipore filters, is operated at 25 DEG C；
Ion chromatography (IC) model：DX-120 (DIONEX, the U.S.), sample fully burns in oxygen atmosphere, absorbs, is made into
F and S contents in solution, with standard specimen comparing calculation sample, eluant, eluent：Water containing 0.35% sodium carbonate and 0.1% sodium acid carbonate；
Thermogravimetric analysis (TGA) instrument model：Rigaku PTC-10A TG-DTA analyzers, air atmosphere, heating rate
For 10 DEG C/min；
Infrared (FT-IR) model：Bruker Tensor 27；
Centrifugal precipitation mechanism model：80-2, Ying Yu Yu Hua instrument plants of Gongyi City.
Prepare embodiment 1
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
The Schlenk bottles of 100mL first add 527mg chain transfer agents CPBD (2.385mmol) and 130mg AIBN
(0.795mmol), then adds 39.7g styrene, closed system, is evacuated 10min after liquid nitrogen frozen, logical nitrogen is placed in cold water
Thaw, repeated freezing substitutes gas three times, the Schlenk bottles after defrosting are put into and are preheated in advance in 80 DEG C of oil bath pan, polymerize
React 11h.Reaction is quenched in liquid nitrogen, makees crude product nmr analysis after thaw at RT, and it is 56.7% to calculate styrene conversion rate.THF is dilute
Reaction solution is released, reprecipitation obtains pink powder polystyrene PS three times in absolute methanol91 18.483g。
The PS of 10g is added in the Schlenk pipes of 100mL91(1.032mmol), 56mg AIBN (0.344mmol) and
The 4-vinylpridine (123.84mmol) of 13.087g, rear to add 15mLDMF stirring and dissolvings, closed system, freezes and substitutes gas three
It is secondary, Schlenk pipes are put into after defrosting and are preheated in advance in 80 DEG C of oil bath pans, react 7.5h.Reaction is quenched in liquid nitrogen, is taken after defrosting
Sample makees nuclear-magnetism, calculates monomer conversion 75.9%, chloroform dilute reaction solution, in ether：Petroleum ether (volume ratio)=1:1 mixing
Three times, cleared unreacted monomer, obtains the poly- (4- of-block- of pink powder block polymer polystyrene to reprecipitation in solvent
Vinylpyridine) PS91-b-P4VP93 16.569g。
The PS of 8.761g (0.45mmol) is added in the there-necked flask of 250mL91-b-P4VP93, load onto the constant pressure addition of 50mL
Funnel and reflux condensate device, closed system, substitutes gas three times, and nitrogen protection is lower to add 120mL dry toluenes, and reaction is heated to
120 DEG C, back flow reaction 2h, form micellar solution.Nitrogen protection under, add 2.235g (10.35mmol) Isosorbide-5-Nitrae-dibromobutane and
10mL toluene is to constant pressure funnel, the reaction was continued after being slowly added dropwise 24h.Nitrogen protection is lower to add 3.099g
The propane sultone of (25.38mmol) and the toluene of 10mL are slowly added dropwise into constant pressure funnel, the reaction was continued 24h.Reaction
Liquid reprecipitation in a large amount of anhydrous ethers, filters, dry yellowish-brown catalyst precarsor PS91-b-(P4VP46)-b-(P4VP47)
(hereinafter abbreviated as PS 91-46-47) 13.576g.
Catalyst precarsor PS 91-46-47 4g are added in 100mL there-necked flasks, load onto reflux condensate device, closed system,
Substitute gas three times, nitrogen protection is lower to add the 40mL concentrated sulfuric acids, stirs, and reaction temperature adds to 60 DEG C, reacts 24h, reaction solution is existed
Reprecipitation in anhydrous ether, filters, and vacuum drying obtains 5.449g catalyst PS 91-46-47HSO4 -。
Prepare embodiment 2
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
Method according to embodiment 1 is prepared prepares catalyst for etherification, unlike：Born by amphoteric catalyst precursor
In the step of carrying acid activated centre, catalyst precarsor PS 91-46-47 2g are added in 100mL there-necked flasks
(0.067mmol), loads onto constant pressure funnel and reflux condensate device, and closed system, substitutes gas three times, and nitrogen protection is lower to be added
40mL dry methylene chlorides, are put into and are preheated in advance in 40 DEG C of oil bath pans, and trifluoromethanesulfonic acid 2.8ml is added dropwise after stirring 1h
(31.47mmol), stirring reaction 24h, by reaction solution, reprecipitation, suction filtration, vacuum drying obtain 1.83g catalysis in anhydrous ether
Agent PS91-46-47CF3SO3 -。
Prepare embodiment 3
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
Method according to embodiment 1 is prepared prepares catalyst for etherification, unlike：Born by amphoteric catalyst precursor
In the step of carrying acid activated centre, catalyst precarsor PS 91-46-47 1g are added in 100mL there-necked flasks
(0.034mmol), loads onto constant pressure funnel and reflux condensate device, and closed system, substitutes gas three times, and nitrogen protection is lower to be added
20mL dry methylene chlorides, are put into and are preheated in advance in 40 DEG C of oil bath pans, and methanesulfonic acid 0.184g is added dropwise after stirring 1h
(1.918mmol), stirring reaction 24h, by reaction solution, reprecipitation, suction filtration, vacuum drying obtain 0.547g and urge in anhydrous ether
Agent PS 91-46-47CH3SO3 -。
Prepare embodiment 4
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
Method according to embodiment 1 is prepared prepares catalyst for etherification, unlike：Born by amphoteric catalyst precursor
In the step of carrying acid activated centre, catalyst precarsor PS 91-46-47 1g are added in 100mL there-necked flasks
(0.034mmol), loads onto constant pressure funnel and reflux condensate device, and closed system, substitutes gas three times, and nitrogen protection is lower to be added
P-methyl benzenesulfonic acid 0.330g (1.918mmol), stirring, reaction temperature add to 40 DEG C, 24h are reacted, by reaction solution in anhydrous ether
Middle reprecipitation, filters, and vacuum drying obtains 0.734g catalyst PS 91-46-47p-CH3C6H4SO3 -。
Prepare embodiment 5
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
The Schlenk bottles of 100mL first add 157.8mg chain transfer agents CPBD (0.714mmol) and 54.7mg AIBN
(0.238mmol), then adds 7.430g styrene, closed system, is evacuated 10min after liquid nitrogen frozen, logical nitrogen is placed in cold water
Middle defrosting, repeated freezing substitute gas three times, and the Schlenk bottles after defrosting are put into and are preheated in advance in 80 DEG C of oil bath pan, gather
Close reaction 11h.Reaction is quenched in liquid nitrogen, makees crude product nmr analysis after thaw at RT, and it is 53.3% to calculate styrene conversion rate.THF
Dilute reaction solution, reprecipitation obtains pink powder polystyrene PS533.552g three times in absolute methanol.
In the Schlenk pipes of 100mL add 3g PS53 (0.523mmol), 28.6mg AIBN (0.174mmol) and
The 4-vinylpridine (52.3mmol) of 5.497g, rear to add 5mLDMF stirring and dissolvings, closed system, freezes and substitutes gas three times,
Schlenk pipes are put into after defrosting and are preheated in advance in 80 DEG C of oil bath pans, react 7.5h.Reaction is quenched in liquid nitrogen, is sampled after defrosting
Make nuclear-magnetism, calculate monomer conversion 80%, chloroform dilute reaction solution, in ether：Petroleum ether (volume ratio)=1:1 mixed solvent
Three times, cleared unreacted monomer, obtains poly- (the 4- vinyl of pink powder block polymer polystyrene-block- to middle reprecipitation
Pyridine) PS53-b-P4VP806.875g.
The PS53-b-P4VP80 of 3g (0.212mmol) is added in the there-necked flask of 100mL, loads onto the constant pressure addition leakage of 20mL
Bucket and reflux condensate device, closed system, substitute gas three times, and nitrogen protection is lower to add 10mL dry toluenes, and reaction is heated to 120
DEG C, back flow reaction 2h, forms micellar solution.Under nitrogen protection, 0.915g (4.240mmol) Isosorbide-5-Nitrae-dibromobutane and 10mL are added
Toluene is to constant pressure funnel, the reaction was continued after being slowly added dropwise 24h.Nitrogen protection is lower to add 1.242g (10.176mmol)
Propane sultone and 10mL toluene into constant pressure funnel, be slowly added dropwise, the reaction was continued 24h.Reaction solution is in a large amount of nothings
Reprecipitation in water ether, filters, dry yellowish-brown catalyst precarsor PS53-40-405.062g.
Catalyst precarsor PS 53-40-40 1.0g (0.043mmol) are added in 100mL there-necked flasks, load onto constant pressure addition
Funnel and reflux condensate device, closed system, substitutes gas three times, and nitrogen protection is lower to add 15mL dry methylene chlorides, is put into thing
First it is preheated in 40 DEG C of oil bath pans, trifluoromethanesulfonic acid 2.582g (17.201mmol), stirring reaction 24h is added dropwise after stirring 1h, will
Reaction solution reprecipitation in anhydrous ether, filters, and vacuum drying obtains 0.975g catalyst PS 53-40-40CF3SO3 -。
Prepare embodiment 6
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
The Schlenk bottles of 100mL first add 149.8mg chain transfer agents CPBD (0.678mmol) and 37.1mg AIBN
(0.226mmol), then adds 14.107g styrene, closed system, is evacuated 10min after liquid nitrogen frozen, logical nitrogen is placed in cold water
Middle defrosting, repeated freezing substitute gas three times, and the Schlenk bottles after defrosting are put into and are preheated in advance in 80 DEG C of oil bath pan, gather
Close reaction 11h.Reaction is quenched in liquid nitrogen, makees crude product nmr analysis after thaw at RT, and it is 49.7% to calculate styrene conversion rate.THF
Dilute reaction solution, reprecipitation obtains pink powder polystyrene PS99 6.282g three times in absolute methanol.
In the Schlenk pipes of 100mL add 3g PS99 (0.285mmol), 15.6mg AIBN (0.095mmol) and
The 4-vinylpridine (28.497mmol) of 2.995g, rear to add 5mLDMF stirring and dissolvings, closed system, freezes and substitutes gas three
It is secondary, Schlenk pipes are put into after defrosting and are preheated in advance in 80 DEG C of oil bath pans, react 7.5h.Reaction is quenched in liquid nitrogen, is taken after defrosting
Sample makees nuclear-magnetism, calculates monomer conversion 73.5%, chloroform dilute reaction solution, in ether：Petroleum ether (volume ratio)=1:1 mixing
Three times, cleared unreacted monomer, obtains pink powder block polymer PS99-b-P4VP745.052g to reprecipitation in solvent.
The PS99-b-P4VP74 of 3g (0.164mmol) is added in the there-necked flask of 100mL, loads onto the constant pressure addition leakage of 20mL
Bucket and reflux condensate device, closed system, substitute gas three times, and nitrogen protection is lower to add 50mL dry toluenes, and reaction is heated to 120
DEG C, back flow reaction 2h, forms micellar solution.Under nitrogen protection, 0.655g (3.034mmol) Isosorbide-5-Nitrae-dibromobutane and 10mL are added
Toluene is to constant pressure funnel, the reaction was continued after being slowly added dropwise 24h.Nitrogen protection is lower to add 0.889g (7.282mmol)
Propane sultone and 10mL toluene into constant pressure funnel, be slowly added dropwise, the reaction was continued 24h.Reaction solution is in a large amount of nothings
Reprecipitation in water ether, filters, dry yellowish-brown catalyst precarsor PS99-37-374.359g.
Catalyst precarsor PS 99-37-37 2.0g (0.034mmol) are added in 100mL there-necked flasks, load onto constant pressure addition
Funnel and reflux condensate device, closed system, substitutes gas three times, and nitrogen protection is lower to add 22mL dry methylene chlorides, is put into thing
First it is preheated in 40 DEG C of oil bath pans, trifluoromethanesulfonic acid 4.165g (27.748mmol), stirring reaction 24h is added dropwise after stirring 1h, will
Reaction solution reprecipitation in anhydrous ether, filters, and vacuum drying obtains 1.552g catalyst PS 99-37-37CF3SO3 -。
Prepare embodiment 7
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
2.806g is added in the Schlenk pipes of 100mL and prepares PS99 (0.267mmol) obtained in embodiment 6,
The 4-vinylpridine (29.37mmol) of 14.6mg AIBN (0.089mmol) and 3.087g, it is rear to add 5mLDMF stirring and dissolvings,
Closed system, freezing substitute gas three times, are put into Schlenk pipes after defrosting and are preheated in advance in 80 DEG C of oil bath pans, react 7.5h.
Reaction is quenched in liquid nitrogen, is sampled after defrosting and makees nuclear-magnetism, calculates monomer conversion 85%, chloroform dilute reaction solution, in ether：Petroleum ether
(volume ratio)=1:Three times, cleared unreacted monomer, obtains pink powder block polymer to 1 in the mixed solvent reprecipitation
PS99-b-P4VP853.939g。
The PS99-b-P4VP85 of 3.841g (0.197mmol) is added in the there-necked flask of 100mL, loads onto the constant pressure drop of 20mL
Liquid funnel and reflux condensate device, closed system, substitutes gas three times, and nitrogen protection is lower to add 60mL dry toluenes, reaction heating
To 120 DEG C, back flow reaction 2h, micellar solution is formed.Under nitrogen protection, 0.893g (4.137mmol) Isosorbide-5-Nitrae-dibromobutane is added
With 10mL toluene to constant pressure funnel, the reaction was continued after being slowly added dropwise 24h.Nitrogen protection is lower to add 1.241g
The propane sultone of (10.165mmol) and the toluene of 10mL are slowly added dropwise into constant pressure funnel, the reaction was continued 24h.Instead
Liquid reprecipitation in a large amount of anhydrous ethers is answered, is filtered, dry yellowish-brown catalyst precarsor PS91-42-435.084g.
Catalyst precarsor PS 99-42-43 1.0g (0.068mmol) are added in 100mL there-necked flasks, load onto constant pressure addition
Funnel and reflux condensate device, closed system, substitutes gas three times, and nitrogen protection is lower to add the 20mL concentrated sulfuric acids, stirring, reaction temperature
60 DEG C are added to, reacts 24h, reprecipitation, suction filtration, vacuum drying obtain 1.034g catalyst PS in anhydrous ether by reaction solution
99-42-43HSO4 -。
Prepare embodiment 8
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
The Schlenk bottles of 100mL first add 0.117mg chain transfer agents CPBD (0.528mmol) and 8.700mg AIBN
(0.053mmol), then adds 13.958g (98.853mmol) butyl methacrylate, closed system, is evacuated after liquid nitrogen frozen
10min, logical nitrogen, which is placed in cold water, to thaw, and repeated freezing substitutes gas three times, and the Schlenk bottles after defrosting are put into prior preheating
Into 80 DEG C of oil bath pans, polymerisation 11h.Reaction is quenched in liquid nitrogen, makees crude product nmr analysis after thaw at RT, calculates methyl-prop
Olefin(e) acid butyl ester conversion ratio is 66.4%.THF dilute reaction solutions, reprecipitation obtains the poly- methyl of pink powder three times in absolute methanol
Butyl acrylate PBMA124 8.033g.
The PBMA (0.190mmol), 10.300mg AIBN of 3.375g is added in the Schlenk pipes of 100mL
The 4-vinylpridine of (0.063mmol) and 2.995g (28.497mmol), rear addition 5mLDMF stirring and dissolvings, closed system,
Freezing substitutes gas three times, is put into Schlenk pipes after defrosting and is preheated in advance in 80 DEG C of oil bath pans, reacts 7.5h.Liquid nitrogen is quenched
Reaction, samples after defrosting and makees nuclear-magnetism, calculate monomer conversion 96%, chloroform dilute reaction solution, in ether：Petroleum ether (volume ratio)
=1:Three times, cleared unreacted monomer, obtains pink powder block polymer PBMA124-b- to 1 in the mixed solvent reprecipitation
P4VP96 16.569g。
The PBMA124-b-P4VP96 of 3.558g (0.128mmol) is added in the there-necked flask of 100mL, loads onto the constant pressure of 20mL
Dropping funel and reflux condensate device, closed system, substitutes gas three times, and nitrogen protection is lower to add 40mL dry toluenes, and reaction adds
Heat forms micellar solution to 120 DEG C, back flow reaction 2h.Under nitrogen protection, 0.663g (3.071mmol) Isosorbide-5-Nitrae-dibromo fourth is added
Alkane and 10mL toluene are to constant pressure funnel, the reaction was continued after being slowly added dropwise 24h.Nitrogen protection is lower to add 0.900g
The propane sultone of (7.373mmol) and the toluene of 10mL are slowly added dropwise into constant pressure funnel, the reaction was continued 24h.Reaction
Liquid reprecipitation in a large amount of anhydrous ethers, filters, dry yellowish-brown catalyst precarsor PBMA124-48-484.289g.
500mg catalyst precarsor PBMA 124-48-48 are added in Schlenk bottles of 25mL, load onto reflux condensate device, are sealed
Reaction system is closed, takes out ventilation operation three times, the 5mL concentrated sulfuric acids are added under nitrogen protective condition, are stirred evenly, reaction temperature adds to
60 DEG C, when stirring reaction 24 is small, reaction solution reprecipitation in a large amount of n-hexanes after cooling is stood, n-hexane washs during suction filtration, very
Empty drying box it is dry 454mg catalyst PBMA 124-48-48HSO4 -。
Prepare embodiment 9
This preparation embodiment is used for the preparation for illustrating catalyst for etherification.
The Schlenk bottles of 100mL first add 97mg chain transfer agents CPBD (0.439mmol) and 7.2mg AIBN
(0.044mmol), then adds 9.365g butyl methacrylates, and closed system, is evacuated 10min after liquid nitrogen frozen, leads to nitrogen
It is placed in cold water and thaws, repeated freezing substitutes gas three times, and the Schlenk bottles after defrosting are put into the prior oil bath for being preheated to 80 DEG C
In pot, polymerisation 11h.Reaction is quenched in liquid nitrogen, makees crude product nmr analysis after thaw at RT, calculates butyl methacrylate conversion
Rate is 70.4%.THF dilute reaction solutions, reprecipitation obtains pink powder polybutyl methacrylate three times in absolute methanol
PBMA1065.53g。
In the Schlenk pipes of 100mL add 3g PBMA106 (1.032mmol), 10.8mg AIBN (0.066mmol) and
The 4-vinylpridine (23.758mmol) of 2.497g, rear to add 5mLDMF stirring and dissolvings, closed system, freezes and substitutes gas three
It is secondary, Schlenk pipes are put into after defrosting and are preheated in advance in 80 DEG C of oil bath pans, react 7.5h.Reaction is quenched in liquid nitrogen, is taken after defrosting
Sample makees nuclear-magnetism, calculates monomer conversion 58.7%, chloroform dilute reaction solution, in ether：Petroleum ether (volume ratio)=1:1 mixing
Three times, cleared unreacted monomer, obtains pink powder block polymer PBMA106-b-P4VP714.536g to reprecipitation in solvent.
The PBMA106-b-P4VP71 of 1.429g (0.063mmol) is added in the there-necked flask of 100mL, loads onto the constant pressure of 20mL
Dropping funel and reflux condensate device, closed system, substitutes gas three times, and nitrogen protection is lower to add 20mL dry toluenes, and reaction adds
Heat forms micellar solution to 120 DEG C, back flow reaction 2h.Under nitrogen protection, 0.238g (1.102mmol) Isosorbide-5-Nitrae-dibromo fourth is added
Alkane and 10mL toluene are to constant pressure funnel, the reaction was continued after being slowly added dropwise 24h.Nitrogen protection is lower to add 0.332g
The propane sultone of (2.722mmol) and the toluene of 10mL are slowly added dropwise into constant pressure funnel, the reaction was continued 24h.Reaction
Liquid reprecipitation in a large amount of anhydrous ethers, filters, dry yellowish-brown catalyst precarsor PBMA106-35-361.401g.
1.0g (0.032mmol) catalyst precarsor PBMA 106-35-36 are added in 100mL three-necked flasks, load onto 10mL rule
Lattice constant pressure funnel and reflux condensate device, capping system, repetition are substituted gas three times, are added under nitrogen protective condition
20mL dry methylene chlorides, insert and are preheated in advance in 40 DEG C of oil bath pan, stirring 1 it is small when after, micellar solution is added dropwise after being formed
1.0mL trifluoromethanesulfonic acids (11.520mmol), when stirring reaction 24 is small, reaction solution reprecipitation in a large amount of n-hexanes, filters, very
Empty drying box it is dry 781mg catalyst PBMA 106-35-36CF3SO3 -。
Reference preparation example 1
This reference preparation example is used for the preparation for illustrating catalyst for etherification.
102mg chain transfer agents CPBD (0.459mmol), 25mg AIBN are sequentially added in Schlenk bottles of 50mL
(0.153mmol) and 4.824g 4-vinylpridines (45.9mmol), closed system, is evacuated 10min after liquid nitrogen frozen, leads to nitrogen
Gas, which is placed in cold water, to thaw, and repeated freezing substitutes gas three times, and the Schlenk bottles after defrosting are put into the prior oil for being preheated to 70 DEG C
In bath, when polymerisation about 4 is small.Reaction is quenched in liquid nitrogen, makees crude product nmr analysis after thaw at RT, calculates 4-vinylpridine
Conversion ratio is 52.3%.Chloroform dilute reaction solution, in a large amount of anhydrous ethers reprecipitation three times, dry the pink toners of 2.341g
End is poly 4 vinyl pyridine P4VP52。
In 50mL three-necked flasks, 1.0g P4VP are added52After (0.176mmol), constant pressure funnel and reflux condensation mode are loaded onto
Device.Capping system, repetition substitute gas three times, then add 10mL drying DMF stirring and dissolving polymer.Reaction solution heats
627mg (4.576mmol) 1- bromobutane is added to 110 DEG C, under nitrogen protective condition and 10mL drying DMF mixed liquors are dripped in constant pressure
Liquid funnel, when reaction 12 is small after being slowly added dropwise；670mg propane sultones are added into constant pressure funnel again
(5.491mmol) and 10mL drying DMF, the reaction was continued after being added dropwise 24 it is small when.Reaction solution is directly filtered after standing cooling, is used
Ether wash solid, insert rapidly vacuum drying chamber it is dry 2.319g brown solids i.e. catalyst precarsor P4VP 26-26.
500mg catalyst precarsor P4VP 26-26 (0.040mmol), capping body are added in Schlenk bottles of 25mL
System, repetition substitute gas three times, and the 5mL concentrated sulfuric acids are added under nitrogen protective condition, are stirred evenly, and reaction temperature adds to 60 DEG C, reaction
24 it is small when, stand cooling after reaction solution reprecipitation in a large amount of anhydrous ethers, filter, vacuum drying chamber it is dry 368mg catalysis
Agent P4VP 26-26HSO4 -。
Reference preparation example 2
This reference preparation example is used for the preparation for illustrating catalyst for etherification.
Method according to reference preparation example 1 prepares catalyst for etherification, unlike：1.0g is added in 100mL three-necked flasks
Catalyst precarsor P4VP 26-26 (0.080mmol), load onto constant pressure funnel and reflux condensate device, capping system,
Repetition substitutes gas three times, and 40mL dry methylene chlorides are added under nitrogen protective condition, is put into and is preheated in advance in 40 DEG C of oil bath pans,
Stir 1 it is small when after be added dropwise 1.8mL trifluoromethanesulfonic acids (20.80mmol), stirring reaction 24 it is small when, stand cooling after reaction solution big
Measure anhydrous ether in reprecipitation, filter, vacuum drying chamber it is dry 955mg catalyst P4VP 26-26CF3SO3 -。
Embodiment 1-9
The present embodiment is used for the preparation method for illustrating the tert amyl methyl ether(TAME) of the present invention.
Preheated metallic heating module is separately added into real to preparing by preparation embodiment 1 to 75 DEG C in the small-sized reaction bulbs of 4mL
The 40 mass % of catalyst for etherification (mass percent for accounting for iso-amylene) of the preparation of example 9 is applied, then by iso-amylene and methanol molar ratio
According to 1:2 add in reaction bulb, seal a bottle, insert in metal module and start to react.After reacting 4h, reaction bulb is put into rapidly ice
Cooled down in cabinet.Then reaction product is centrifuged 5 minutes, pours out supernatant liquid, carry out gas chromatographic analysis, calculate etherification reaction
The conversion ratio of iso-amylene, shown in table 1 specific as follows.
Comparative example 1-2
This comparative example is used for the reference preparation method for illustrating tert amyl methyl ether(TAME).
Method according to embodiment 1-9 prepares tert amyl methyl ether(TAME), unlike：Catalyst for etherification is respectively by reference system
Catalyst for etherification prepared by standby example 1 and reference preparation example 2.The conversion ratio of iso-amylene is as shown in table 1 below.
Table 1
| Embodiment is numbered | Catalyst type | Iso-amylene conversion ratio (%) |
| Embodiment 1 | PS 91-46-47HSO4 - | 50.7 |
| Embodiment 2 | PS 91-46-47CF3SO3 - | 52.6 |
| Embodiment 3 | PS 91-46-47CH3SO3 - | 30.2 |
| Embodiment 4 | PS 91-46-47p-CH3C6H4SO3 - | 31.9 |
| Embodiment 5 | PS 53-40-40CF3SO3 - | 56.2 |
| Embodiment 6 | PS 99-37-37CF3SO3 - | 52.6 |
| Embodiment 7 | PS 99-42-43HSO4 - | 54.3 |
| Embodiment 8 | PBMA 124-48-48HSO4 - | 32.3 |
| Embodiment 9 | PBMA 106-35-36CF3SO3 - | 55.8 |
| Comparative example 1 | P4VP 26-26HSO4 - | 20.0 |
| Comparative example 2 | P4VP 26-26CF3SO3 - | 49.8 |
Embodiment 10-18
This series embodiment is used for the method for modifying for illustrating the light petrol of the present invention.
500g light petrols are added in the stainless steel cauldron that volume is 1L and (FCC apparatus of certain oil plant are derived from, through rectifying
Component before cutting obtains 75 DEG C, analysis result show that its mass fraction containing iso-amylene is 20.5%, and dissident's alkene mass fraction is
89) 9.8%, RON octane number is, and on the basis of the amount of active olefin (the gross mass percentage for accounting for iso-amylene and dissident's alkene) point
The catalyst for etherification prepared by preparation embodiment 1 to preparation embodiment 9 of 40 mass % is not added, is rubbed by active olefin and methanol
That ratio 1:2 add methanol, capping kettle.After nitrogen displacement air therein, open stirring (800rpm) and heat, 75
DEG C and from pressure reaction 4h after, stop heating and stirring, wait and release reaction mass from reaction kettle after being cooled to less than 40 DEG C,
Solid-liquor separation is carried out with Buchner funnel.Filtrate is extracted 4 times with 50g deionized waters, its unreacted methanol is cleared, is finally obtained
Etherified gasoline product.Its composition is measured with gas chromatography, and its organon (RON) octane number is measured with octane number testing machine.Specifically
Reaction result is shown in Table 2.
Table 2
EXPERIMENTAL EXAMPLE 1-6
This EXPERIMENTAL EXAMPLE is used to illustrate the recovering effect of catalyst for etherification and the reactivity retentivity of etherification reaction
Energy.
After method according to embodiment 1-9 carries out etherification reaction, reaction product is centrifuged 5 minutes, by 1 (91- of embodiment
46-47HSO4 -), 2 (PS91-46-47CF of embodiment3SO3 -), 3 (PS91-46-47CH of embodiment3SO3 -), (the PS 91- of embodiment 4
46-47p-CH3C6H4SO3 -), 8 (BMA126-48-48HSO of embodiment4 -) and (the P4VP 26-26CF of comparative example 23SO3 -) separation
The lower catalyst agent gone out is respectively put into vacuum drying chamber drying recycling (drying temperature is 40 DEG C, drying time 2h), and repeats
Circulation carries out the catalyst etherifying and reacts 9 times, and catalyst recovering effect is as shown in table 3 below.
Table 3
It can be seen from the result of above-mentioned table 3 compared with the conversion ratio of the iso-amylene of comparative example 2, first using the present invention
The preparation method of base tert-amyl ether, after catalyst for etherification is recycled, is etherified under the same conditions, after circular response 9 times
The conversion ratio of iso-amylene is still more stable, unobvious to reduce, and illustrates that the recovering effect of the catalyst for etherification of the present invention is good
It is good.Although the iso-amylene conversion ratio reacted first of the catalyst for etherification for the reference preparation example 2 applied in comparative example 2 is higher,
It is that the conversion ratio of iso-amylene drops down to 17.9% only after catalyst recycling and circular response 3 times.Thus illustrate, the present invention
The catalyst for etherification performance is stablized so that the reaction of tert amyl methyl ether(TAME) can continue to keep having higher reactivity.
Further it can be seen that from the data of embodiment 1 and embodiment 2, embodiment 5-7 and embodiment 9 using currently preferred
Catalyst for etherification, the not only reaction of tert amyl methyl ether(TAME) can continue to keep having higher reactivity, and iso-amylene
Conversion ratio higher, can reach 50-60%.
EXPERIMENTAL EXAMPLE 7-8
This EXPERIMENTAL EXAMPLE is used to illustrate the test to reacting middle catalyst heat endurance.
To the catalyst PS 91-46-47HSO used in embodiment 14 -And the catalyst PS 99-37- used in embodiment 6
37CF3SO3 -Carry out thermogravimetric analysis.
As shown in Figure 1, less than 300 DEG C at the basic free of losses of catalytic component, thus prove used in the method for the present invention
The heat endurance of catalyst for etherification is high.
EXPERIMENTAL EXAMPLE 9-10
This EXPERIMENTAL EXAMPLE is used to illustrate the stability test to catalyst active center.
Preheated metallic heating module adds the etherificate prepared by preparation embodiment 1 in the small-sized reaction bulbs of 4mL and urges to 75 DEG C
40 mass % of agent (mass percent for accounting for iso-amylene) and a certain amount of sodium chloride or potassium chloride, then press iso-amylene and methanol
According to molar ratio 1:1 ratio is added in reaction bulb, is sealed a bottle, is inserted in metal module and start to react.After reacting 4h, reaction bulb
Rapid be put into refrigerator-freezer cools down.Then reaction product is centrifuged 5 minutes, pours out supernatant liquid, carry out gas chromatographic analysis, meter
The conversion ratio of etherification reaction iso-amylene is calculated, the lower catalyst agent isolated is respectively put into vacuum drying chamber drying recycling (dry temperature
Spend for 40 DEG C, drying time 2h), wait to reuse.
As shown in Fig. 2, when the methanol solution of sodium chloride containing 1ug/mL is selected in reaction, catalyst is different after recycling 8 times
Pentene conversion still is able to reach more than 30%, illustrate the catalyst be maintained to after being used for multiple times in the present context compared with
High reaction activity.
As shown in figure 3, when reaction select the methanol solution of potassium chloride containing 100ug/mL when, catalyst recycling 5 times after,
Iso-amylene conversion ratio remains able to reach more than 45%, illustrates that the catalyst remains able to protect after being used for multiple times in the present context
Hold compared with high reaction activity.
Thus illustrate, the hydrophobicity protective shell of catalyst for etherification used in preparation method of the invention is in sodium ion, potassium ion
There is certain protective effect to activated centre in environment, more effectively can prevent catalyst from coming off, prevent activity H+Exchanged.Into
One step illustrates that the stability of the catalyst for etherification is good, and the higher reaction beneficial to the etherification reaction for keeping methanol and iso-amylene is lived
Property and keep higher iso-amylene conversion ratio.
Claims (11)
1. a kind of preparation method of tert amyl methyl ether(TAME), it is characterised in that this method includes：
Under the conditions of etherification reaction, methanol and iso-amylene are contacted with catalyst for etherification to obtain the reaction containing tert amyl methyl ether(TAME)
Product；
The catalyst for etherification is Polymer-supported ionic-liquid catalyst, which has shown in formula (I) or formula (П)
Structure：
In formula (I), m is the integer of 50-200, and preferably m is the integer of 50-150；N1 and n2 is each independently the whole of 30-100
Number, preferably n1 and n2 are each independently the integer of 30-70；X-Selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-CH3C6H4SO3 -In
One or more, preferably X-For HSO4 -Or CF3SO3 -；
In formula (П), m ' is the integer of 50-200, and preferably m ' is the integer of 50-150；N1 ' and n2 ' are each independently 30-100
Integer, preferably n1 ' and n2 ' are each independently the integer of 30-70；X-Selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-
CH3C6H4SO3 -In one or more, preferably X-For CF3SO3 -。
2. according to the method described in claim 1, wherein, in formula (I), n1:N2 is 1:0.9-1.1, in formula (П), n1 ':n2’
For 1:0.9-1.1.
3. preparation method according to claim 1, wherein, on the basis of the quality of iso-amylene, the catalyst for etherification
Dosage is 1-80 mass %, is preferably 1-50 mass %.
4. preparation method according to claim 1, wherein, the condition of the etherification reaction includes：Temperature is 55-95 DEG C,
The molar ratio 1-4 of methanol and iso-amylene:1.
5. preparation method according to claim 1, wherein, this method further includes：By reaction product separation of solid and liquid, liquid is obtained
Phase tert amyl methyl ether(TAME) and recycle obtain solid phase catalyst for etherification.
6. a kind of method for modifying of light petrol, contain active olefin in the light petrol, it is characterised in that this method includes：
Under the conditions of etherification reaction, methanol and light petrol are contacted with catalyst for etherification, obtain the etherificate production containing active olefin
The reaction product of thing；
The catalyst for etherification is Polymer-supported ionic-liquid catalyst, which has shown in formula (I) or formula (П)
Structure：
In formula (I), m is the integer of 50-200, and preferably m is the integer of 50-150；N1 and n2 is each independently the whole of 30-100
Number, preferably n1 and n2 are each independently the integer of 30-70；X-Selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-CH3C6H4SO3 -In
One or more, preferably X-For HSO4 -Or CF3SO3 -；
In formula (П), m ' is the integer of 50-200, and preferably m ' is the integer of 50-150；N1 ' and n2 ' are each independently 30-100
Integer, preferably n1 ' and n2 ' are each independently the integer of 30-70；X-Selected from HSO4 -、CF3SO3 -、CH3SO3 -And p-
CH3C6H4SO3 -In one or more, preferably X-For CF3SO3 -。
7. according to the method described in claim 6, wherein, in formula (I), n1:N2 is 1:0.9-1.1, in formula (П), n1 ':n2’
For 1:0.9-1.1.
8. according to the method described in claim 6, wherein, on the basis of the quality of active olefin, the use of the catalyst for etherification
Measure as 1-80 mass %, preferably 1-50 mass %.
9. according to the method described in claim 6, wherein, the condition of the etherification reaction includes：Temperature is 55-95 DEG C, methanol
Molar ratio with active olefin in light petrol is 1-4:1.
10. according to the method described in claim 6, wherein, the octane number of the reaction product of the etherification product containing active olefin
Than being etherified the high at least two unit of premise.
11. according to the method described in claim 6, wherein, the light petrol is selected from light FCC gasoline, the light vapour of catalytic pyrolysis
Oil, steam cracking light petrol, light coker naphtha, methanol-to-olefins light petrol and one kind or more in preparing gasoline by methanol light petrol
Kind；The content of active olefin is 5-50 mass % in the light petrol, and the active olefin is selected from isobutene, iso-amylene and dissident
One or more in alkene.
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| CN102408316A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Method for preparing tert-amyl methyl ether |
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