CN109762086A - The preparation method and application of alpha-olefin polymers - Google Patents
The preparation method and application of alpha-olefin polymers Download PDFInfo
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- CN109762086A CN109762086A CN201910043268.6A CN201910043268A CN109762086A CN 109762086 A CN109762086 A CN 109762086A CN 201910043268 A CN201910043268 A CN 201910043268A CN 109762086 A CN109762086 A CN 109762086A
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Abstract
The present invention provides a kind of preparation method and applications of alpha-olefin polymers, are related to technical field of polymer.Alpha olefin monomers are mainly carried out polymerization reaction by the preparation method under the action of specific acidic ionic liquid catalysts, obtain alpha-olefin polymers, wherein used acidic ionic liquid catalysts stability is high, it is environmentally friendly, alpha olefin monomers can be promoted to carry out polymerization reaction, and reaction rate is fast, the high income of alpha-olefin polymers in obtained reaction product, in addition, the acidic ionic liquid catalysts are easier to separate with reaction product, be conducive to recycling；The preparation method process flow of the alpha-olefin polymers is simple, stablizes, easily operated, is suitable for industrial volume production；The present invention also provides application of the alpha-olefin polymers in lube base oil made from the preparation method using above-mentioned alpha-olefin polymers.
Description
Technical field
The present invention relates to technical field of polymer preparation, preparation method in particular to alpha-olefin polymers and answer
With.
Background technique
Lubricating oil is one of the grand strategy product to involve the interests of the state and the people.By the development of many years, lube base oil is gone through
The different phases such as mineral oil, vegetable oil, synthetic oil are passed through.Wherein, oligomer (PAO) excellent combination property of Long carbon chain alhpa olefin,
It is important one of base oil.At present synthesis PAO catalyst mainly have Ziegler-Natta catalyst, lewis acid catalyst,
Metal supported catalyst and metallocene catalyst.
Ziegler-Natta catalyst belongs to the catalyst system of more active sites, and the activity of active site is different, causes to gather
The molecular weight for closing object controls deficiency, thus document report is less.Patent CN200510112794 reports the catalysis of carried metal chromium
Agent synthesizes the preparation method of high viscosity index (HVI) polyalphaolefin synthetic oil, although the chrome catalysts are easily prepared or regeneration, chromium are easy
It is oxidized to Cr VI, harm is brought to environment.
Lewis acid catalyst mainly includes boron trifluoride, alchlor.Boron trifluoride catalyst itself and do not have urge
Change activity, need promotor such as water, alcohol, ester, ether etc. can initiated polymerization, patent CN201611238965,
CN200610072874, CN03155992 are all made of boron trifluoride catalyst system preparation PAO, and prepared distribution of polymer is narrow,
React easy to control, the viscosity index (VI) of high income and synthetic oil is higher.But boron trifluoride is toxic, and chance water can discharge hydrogen fluoride gas and make
Forming apparatus corrosion.
Patent CN201210423202, CN201310176482 and CN201710244544 use Aluminium Trichloride as Catalyst body
System, has the characteristics that at low cost, easy to operate, but the PAO molecular weight distribution of preparation is wider, and complex process, corrosivity is strong.For solution
Certainly this problem, method patent CN200310120887, CN201210323278 immobilized using alchlor, can keep three
The excellent characteristic of aluminium chloride, while the pollution to environment is reduced, but the method is complicated for operation, repeatability is not high.
The catalyst system with single-activity position that metallocene catalyst is made of metallocene compound and co-catalyst,
Thus there is the characteristics of catalytic activity height, obtained oligomer viscosity height and narrow molecular weight distribution, but its preparation condition is harsh,
Experimental implementation is complicated, and higher cost.
In view of this, the present invention is specifically proposed at least one of to solve the above technical problems.
Summary of the invention
The first purpose of this invention is to provide a kind of preparation method of alpha-olefin polymers, and the preparation method is using steady
Qualitative high and environment amenable acidic ion liquid is as catalyst, so that polymerization rate is fast, final product high income,
And post catalyst reaction is easily isolated, it being capable of recycling.
Second object of the present invention is to provide a kind of application of the preparation method of alpha-olefin polymers.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention provides a kind of preparation methods of alpha-olefin polymers, comprising the following steps:
Alpha olefin monomers are subjected to polymerization reaction under the action of acidic ionic liquid catalysts, obtain alpha-olefin polymers；
Wherein, the alpha olefin monomers include in C8-C14 alkene any one or at least two combination；
The raw material of the acidic ionic liquid catalysts includes alchlor, organohalogen compounds and solvent, organic halogen
Compound includes any one in pyridine halogen class, imidazoles halogen class or quaternary ammonium halogen class.
Further, on the basis of technical solution of the present invention, the organohalogen compounds include trimethylamine hydrochloride, three
Ethylamine hydrochloride, 1- ethyl pyridinium chloride, 1- ethyl pyridinium bromide, 1- butyl pyridinium chloride, 1- butyl pyridinium bromide, dodecane
Base pyridinium bromide, dodecyl pyridinium chloride, cetyl pyridinium bromide, hexadecylpyridinium chloride, 1- ethyl -3- methyl miaow
Azoles bromide, 1- ethyl-3-methylimidazole villaumite, 1- vinyl -3- butyl imidazole bromide, 1- vinyl -3- butyl imidazole villaumite,
Any one in 1- butyl -3- methylimidazole bromide or 1- butyl -3- methylimidazole villaumite, preferably includes trimethylamine hydrochloride
Or triethylamine hydrochloride.
Further, on the basis of technical solution of the present invention, the organohalogen compounds rub with the alchlor
You are than being (0.2-0.8): 1, preferably (0.3-0.7): 1.
Further, on the basis of technical solution of the present invention, the acidic ionic liquid catalysts account for the alhpa olefin
The 5-20% of monomer and acidic ionic liquid catalysts gross mass, preferably 10-18%.
Further, on the basis of technical solution of the present invention, the solvent is saturated alkane, preferably includes positive heptan
In alkane, n-hexane or hexamethylene any one or at least two combination.
Further, on the basis of technical solution of the present invention, the polymeric reaction temperature is 25-75 DEG C, preferably
30-70℃；
And/or the polymerization reaction time is 1-6h, preferably 1.5-5h.
Further, on the basis of technical solution of the present invention, the preparation method of the alpha-olefin polymers includes following
Step:
By alpha olefin monomers under the catalytic action of acidic ionic liquid catalysts, in 25-75 DEG C of progress polymerization reaction 1-
6h refines the reaction product that polymerization obtains, and separates, obtains alpha-olefin polymers.
Further, on the basis of technical solution of the present invention, the preparation method of the acidic ion liquid includes such as
Lower step:
By organohalogen compounds, alchlor and solvent formed mixed liquor once stirred, then heating and while into
Row secondary agitation, obtains acidic ionic liquid catalysts.
Further, on the basis of technical solution of the present invention, the time once stirred is 20-40min；
And/or the time of the secondary agitation is 3-8h；
And/or the temperature of the heating is 40-90 DEG C.
The present invention also provides alpha-olefin polymers made from a kind of preparation method using above-mentioned alpha-olefin polymers to moisten
Application in lubricant base oil.
Compared with prior art, the preparation method of alpha-olefin polymers provided by the invention has the advantage that
(1) the present invention provides a kind of preparation methods of alpha-olefin polymers, by alpha olefin monomers in specific acid ion
Polymerization reaction is carried out under the action of liquid catalyst, obtains alpha-olefin polymers, wherein used acidic ionic liquid catalysts
Stability is high, environmentally friendly, alpha olefin monomers can be promoted to carry out polymerization reaction, and reaction rate is fast, and obtained reaction produces
The high income of alpha-olefin polymers in object is conducive to follow in addition, the acidic ionic liquid catalysts are easier to separate with reaction product
Ring recycles；
The preparation method process flow of the alpha-olefin polymers is simple, stablizes, easily operated, is suitable for industrial volume production.
(2) the present invention provides the applications of alpha-olefin polymers made from a kind of preparation method of alpha-olefin polymers.In view of
Advantage possessed by the preparation method of above-mentioned alpha-olefin polymers, so that the alpha-olefin polymers being prepared using it are in lubricating oil
Base oil field has good application.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
It should be understood that in the present invention, if without particularly illustrating, all embodiments mentioned in this article and
Preferred implementation method can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating
Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating
The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a~b " indicates the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as numberical range " 6~22 " indicate herein all listed " 6~22 " it
Between whole real numbers, " 6~22 " be these combinations of values breviary indicate.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, it is each reaction or operating procedure can sequentially carry out, can also in sequence into
Row.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
According to an aspect of the invention, there is provided the preparation method of alpha-olefin polymers, comprising the following steps:
Alpha olefin monomers are subjected to polymerization reaction under the action of acidic ionic liquid catalysts, obtain alpha-olefin polymers；
Wherein, alpha olefin monomers include in C8-C14 alkene any one or at least two combination；
The raw material of acidic ionic liquid catalysts includes alchlor, organohalogen compounds and solvent, and organohalogen compounds include
Any one in pyridine halogen class, imidazoles halogen class or quaternary ammonium halogen class.
Alpha olefin monomers typically refer to double bond in the monoolefine of strand end, and molecular formula is R-CH=CH2, wherein R is alkane
Base.In the present invention, carbon atom is limited to C8-C14 in alpha olefin monomers, this is because carbon atom number influences whether alpha-olefin polymerization
The cryogenic property and viscosity index (VI) of object, specifically, the obtained alpha-olefin polymers viscosity index (VI) of C8 alpha olefin monomers below compared with
Difference, and the alpha olefin monomers reactivity of C14 or more is lower, is not suitable for being applied to synthesis alpha-olefin polymers.Therefore when carbon atom is
C8-C14 is more excellent selection.
It is specific in view of the structure of alpha olefin monomers itself, therefore polymerization reaction can occurs in it under the effect of the catalyst, generate α
Olefin polymer.
In the present invention, it is ionic liquid that alpha olefin monomers, which carry out catalyst used by polymerization reaction, is furthermore
Acidic ion liquid.Ionic liquid refers to that the liquid being composed entirely of ions, acidic ion liquid had both had the excellent of ionic liquid
Point, and have the advantages that solid acid or liquid acid, such as: non-volatility, acid adjustable denaturation, acid strength be evenly distributed, environment
Friendly and recyclable recycling etc..
Acidic ionic liquid catalysts employed in the present invention are aluminium chloride class ionic liquid, specifically with organic halogenation
Object is cation, the ionic liquid that aluminium chloride is anion composition.The acidic ionic liquid catalysts can promote alpha olefin monomers
Polymerization reaction is carried out, and reaction rate is fast, the high income of obtained reaction product, in addition, the acidic ionic liquid catalysts
Stability is high and friendly to environment green, and is easier to separate with reaction product, is conducive to recycling；
The preparation method process flow of the alpha-olefin polymers is simple, stablizes, easily operated, is suitable for industrial volume production.
As a kind of optional embodiment of the invention, organohalogen compounds include trimethylamine hydrochloride, triethylamine hydrochloride,
1- ethyl pyridinium chloride, 1- ethyl pyridinium bromide, 1- butyl pyridinium chloride, 1- butyl pyridinium bromide, dodecylpyridinium bromide,
Dodecyl pyridinium chloride, cetyl pyridinium bromide, hexadecylpyridinium chloride, 1- ethyl-3-methylimidazole bromide, 1- second
Base -3- methylimidazole villaumite, 1- vinyl -3- butyl imidazole bromide, 1- vinyl -3- butyl imidazole villaumite, 1- butyl -3- first
Any one in base imidazoles bromide or 1- butyl -3- methylimidazole villaumite, preferably includes trimethylamine hydrochloride or triethylamine salt
Hydrochlorate.
By to the specific kind of restriction of organohalogen compounds, so that it is formed by acid ion after being complexed with alchlor
Liquid catalyst has good catalytic performance, stability and recyclable property.
As a kind of optional embodiment of the invention, the molar ratio of organohalogen compounds and alchlor is (0.2-0.8):
1, preferably (0.3-0.7): 1.
Organohalogen compounds and the typical but non-limiting molar ratio of alchlor be 0.2:1,0.3:1,0.4:1,0.5:1,
0.6:1,0.67:1,0.7:1 or 0.8:1.
By the restriction to organohalogen compounds and the specific molar ratio of alchlor, so that alchlor is in the acidic ionic liquid
Content in body catalyst is in suitable range, to guarantee there is certain catalytic activity in polymerization process.
As a kind of optional embodiment of the invention, acidic ionic liquid catalysts account for alpha olefin monomers and acid ion
The 5-20% of liquid catalyst gross mass, preferably 10-18%.
Acidic ionic liquid catalysts account for alpha olefin monomers and acidic ionic liquid catalysts total amount mass fraction include but
It is not limited to 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.It should be noted that sour
The dosage of property ionic-liquid catalyst should not be excessive, is excessively then easy to cause by-product in reaction product to increase, target product (α
Olefin polymer) yield reduction；The dosage of acidic ionic liquid catalysts is unsuitable very few, excessively few then to will lead to polymerization reaction reaction
Rate is slow, and the by-product that having can be more generates, and is unfavorable for the acquisition of target product.
It further include solvent other than alchlor and organohalogen compounds in the raw material of acidic ionic liquid catalysts.
As a kind of optional embodiment of the invention, solvent is saturated alkane, preferably includes normal heptane, n-hexane or ring
In hexane any one or at least two combination.
By to the specific kind of restriction of solvent, so that alchlor and organohalogen compounds can be easier to form ionic liquid.
As a kind of optional embodiment of the invention, polymeric reaction temperature is 25-75 DEG C, preferably 30-70 DEG C, typical
But unrestricted polymeric reaction temperature be 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C or
75℃；
And/or polymerization reaction time 1-6h, preferably 1.5-5h, typical but non-limiting polymerization reaction time are
1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h.
By the restriction to polymeric reaction temperature and time, so that acidic ionic liquid catalysts are in suitable work
Property, to be conducive to going on smoothly for polymerization reaction.
As a kind of optional embodiment of the invention, the preparation methods of alpha-olefin polymers the following steps are included:
By alpha olefin monomers under the catalytic action of acidic ionic liquid catalysts, in 25-75 DEG C of progress polymerization reaction 1-
6h refines the reaction product that polymerization obtains, and separates, obtains alpha-olefin polymers.
After carrying out polymerization reaction, impurity content is higher in the reaction product that polymerize, therefore needs to obtain alpha-olefin polymerization
Object needs a series of the step of carrying out purifications and separation to the reaction product that polymerization obtains.
As a kind of optional embodiment of the invention, above-mentioned purification includes the steps that alkali cleaning and washing.Alkali cleaning and washing
Mainly remove the acid in reaction product.
It is separated again after purification, unreacted alpha olefin monomers and solvent can be removed.Specific separation may include filtering
The step of with distillation.Technological means commonly used in the art can be used in filtering and distillation.
As a kind of optional embodiment of the invention, the preparation method of acidic ionic liquid catalysts includes following step
It is rapid:
By organohalogen compounds, alchlor and solvent formed mixed liquor once stirred, then heating and while into
Row secondary agitation, obtains acidic ionic liquid catalysts.
Preparation method simple process, the stabilization of the acidic ionic liquid catalysts, obtained presence of acidic ionic liquid catalyst
Agent stability is good.
As a kind of optional embodiment of the invention, the time once stirred is 20-40min；It is typical but non-limiting
The time once stirred be, for example, 20min, 25min, 30min, 35min or 40min；
As a kind of optional embodiment of the invention, the time of secondary agitation is 3-8h, typical but non-limiting two
The time of secondary stirring is, for example, 3h, 4h, 5h, 6h, 7h or 8h；
As a kind of optional embodiment of the invention, the temperature of heating is 40-90 DEG C, typical but non-limiting heating
Temperature be 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C；
By to a mixing time in acidic ionic liquid catalysts preparation process, secondary agitation time and temperature
It limits, so that the acidic ionic liquid catalysts being prepared have good physics and chemical property.
According to the second aspect of the invention, α alkene made from a kind of preparation method using alpha-olefin polymers is additionally provided
Application of the hydrocarbon polymer in lube base oil.
Advantage possessed by preparation method in view of above-mentioned alpha-olefin polymers, so that poly- using the alhpa olefin that it is prepared
Closing object has good application in lube base oil field.
Combined with specific embodiments below and comparative example, the invention will be further described.
Embodiment 1
Present embodiments provide a kind of preparation method of alpha-olefin polymers, comprising the following steps:
30mL alpha olefin monomers are added to acidic ionic liquid catalysts, are made in the catalysis of acidic ionic liquid catalysts
Under, in 40 DEG C of progress polymerization reaction 5h, after the reaction product (upper layer oligomer) that polymerization is obtained carries out alkali cleaning and washing, mistake
It is distilled after filter, obtains alpha-olefin polymers.
Wherein, alpha olefin monomers are 1- decene, and acidic ionic liquid catalysts account for alpha olefin monomers and acidic ion liquid is urged
The 13.21% of agent gross mass, acidic ionic liquid catalysts are triethylamine hydrochloride alchlor ionic liquid,
The preparation method of triethylamine hydrochloride alchlor ionic liquid, comprising the following steps:
It takes 1.38g triethylamine hydrochloride, 2g alchlor to be placed in 20mL normal heptane, is once stirred at room temperature, one
Secondary mixing time is 30min, then heats to 80 DEG C of progress secondary agitations, and the secondary agitation time is 5h, obtains triethylamine hydrochloric acid
Salt alchlor ionic liquid.
The molar ratio of triethylamine hydrochloride and alchlor is 0.67 in triethylamine hydrochloride alchlor ionic liquid:
1。
Embodiment 2
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to triethylamine hydrochloride alchlor from
Except the preparation method and 1 difference of embodiment of sub- liquid, remaining is same as Example 1.
Wherein, in the present embodiment triethylamine hydrochloride alchlor ionic liquid preparation method, comprising the following steps:
It takes 1.03g triethylamine hydrochloride, 2g alchlor to be placed in 20mL normal heptane, is once stirred at room temperature, one
Secondary mixing time is 30min, then heats to 80 DEG C of progress secondary agitations, and the secondary agitation time is 5h, obtains triethylamine hydrochloric acid
Salt alchlor ionic liquid.
The molar ratio of triethylamine hydrochloride and alchlor is 0.50 in triethylamine hydrochloride alchlor ionic liquid:
1。
Embodiment 3
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to triethylamine hydrochloride alchlor from
Except the preparation method and 1 difference of embodiment of sub- liquid, remaining is same as Example 1.
Wherein, in the present embodiment triethylamine hydrochloride alchlor ionic liquid preparation method, comprising the following steps:
It takes 0.31g triethylamine hydrochloride, 2g alchlor to be placed in 20mL normal heptane, is once stirred at room temperature, one
Secondary mixing time is 30min, then heats to 80 DEG C of progress secondary agitations, and the secondary agitation time is 5h, obtains triethylamine hydrochloric acid
Salt alchlor ionic liquid.
The molar ratio of triethylamine hydrochloride and alchlor is 0.15 in triethylamine hydrochloride alchlor ionic liquid:
1。
Embodiment 4
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to triethylamine hydrochloride alchlor from
Except the preparation method and 1 difference of embodiment of sub- liquid, remaining is same as Example 1.
Wherein, in the present embodiment triethylamine hydrochloride alchlor ionic liquid preparation method, comprising the following steps:
It takes 1.65g triethylamine hydrochloride, 2g alchlor to be placed in 20mL normal heptane, is once stirred at room temperature, one
Secondary mixing time is 30min, then heats to 80 DEG C of progress secondary agitations, secondary agitation 5h obtains triethylamine hydrochloride
Alchlor ionic liquid.
The molar ratio of triethylamine hydrochloride and alchlor is 0.8 in triethylamine hydrochloride alchlor ionic liquid:
1。
Embodiment 5
Present embodiments provide a kind of preparation method of alpha-olefin polymers, comprising the following steps:
30mL alpha olefin monomers are added to acidic ionic liquid catalysts, are made in the catalysis of acidic ionic liquid catalysts
Under, in 50 DEG C of progress polymerization reaction 5h, after the reaction product (upper layer oligomer) that polymerization is obtained carries out alkali cleaning and washing, mistake
It is distilled after filter, obtains alpha-olefin polymers.
Wherein, alpha olefin monomers are 1- decene, and acidic ionic liquid catalysts account for alpha olefin monomers and acidic ion liquid is urged
The 12.01% of agent gross mass, acidic ionic liquid catalysts are triethylamine hydrochloride alchlor ionic liquid.
The preparation method of triethylamine hydrochloride alchlor ionic liquid, comprising the following steps:
It takes 1.03g triethylamine hydrochloride, 2g alchlor to be placed in 20mL normal heptane, is once stirred at room temperature, one
Secondary mixing time is 30min, then heats to 80 DEG C of progress secondary agitations, and the secondary agitation time is 5h, obtains triethylamine hydrochloric acid
Salt alchlor ionic liquid.
The molar ratio of triethylamine hydrochloride and alchlor is 0.5 in triethylamine hydrochloride alchlor ionic liquid:
1。
Embodiment 6
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to used alpha olefin monomers are 30mL1-
The mixture of decene and 1-tetradecylene, wherein the volume ratio of 1- decene and 1-tetradecylene is 1:0.3, remaining and 2 phase of embodiment
Together.
Embodiment 7
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to polymeric reaction temperature is 30 DEG C, remaining step
It is rapid same as Example 2.
Embodiment 8
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to polymeric reaction temperature is 60 DEG C, remaining step
It is rapid same as Example 2.
Embodiment 9
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to polymeric reaction temperature is 70 DEG C, remaining step
It is rapid same as Example 2.
Embodiment 10
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to polymerization reaction time is 3h, remaining step
It is same as Example 2.
Embodiment 11
The preparation method for present embodiments providing a kind of alpha-olefin polymers, in addition to polymerization reaction time is 6h, remaining step
It is same as Example 2.
Embodiment 12
Present embodiments provide a kind of preparation method of alpha-olefin polymers, comprising the following steps:
30mL alpha olefin monomers are added to acidic ionic liquid catalysts, are made in the catalysis of acidic ionic liquid catalysts
Under, in 40 DEG C of progress polymerization reaction 5h, after the reaction product (upper layer oligomer) that polymerization is obtained carries out alkali cleaning and washing, mistake
It is distilled after filter, obtains alpha-olefin polymers.
Wherein, alpha olefin monomers are 1- decene, and acidic ionic liquid catalysts account for alpha olefin monomers and acidic ion liquid is urged
The 13.38% of agent gross mass, acidic ionic liquid catalysts are 1- ethyl-3-methylimidazole bromide alchlor ionic liquid
Body.
The preparation method of 1- ethyl-3-methylimidazole bromide alchlor ionic liquid, comprising the following steps:
It takes 1.43g 1- ethyl-3-methylimidazole bromide, 2g alchlor to be placed in 20mL normal hexane, carries out one at room temperature
Secondary stirring, a mixing time are 40min, then heat to 50 DEG C of progress secondary agitations, and the secondary agitation time is 8h, obtain 1-
Ethyl-3-methylimidazole bromide alchlor ionic liquid.
1- ethyl-3-methylimidazole bromide and trichlorine in 1- ethyl-3-methylimidazole bromide alchlor ionic liquid
The molar ratio for changing aluminium is 0.5:1.
Embodiment 13
Present embodiments provide a kind of preparation method of alpha-olefin polymers, comprising the following steps:
30mL alpha olefin monomers are added to acidic ionic liquid catalysts, are made in the catalysis of acidic ionic liquid catalysts
Under, in 75 DEG C of progress polymerization reaction 2h, after the reaction product (upper layer oligomer) that polymerization is obtained carries out alkali cleaning and washing, mistake
It is distilled after filter, obtains alpha-olefin polymers.
Wherein, alpha olefin monomers are 1- laurylene, and acidic ionic liquid catalysts account for alpha olefin monomers and acidic ion liquid
The 18.02% of catalyst gross mass, acidic ionic liquid catalysts are cetyl pyridinium bromide alchlor ionic liquid.
The preparation method of cetyl pyridinium bromide alchlor ionic liquid, comprising the following steps:
It takes 2.88g cetyl pyridinium bromide, 2g alchlor to be placed in 20mL normal hexane, is once stirred at room temperature
It mixes, a mixing time is 40min, then heats to 50 DEG C of progress secondary agitations, and the secondary agitation time is 8h, obtains hexadecane
Base pyridinium bromide alchlor ionic liquid.
Mole of cetyl pyridinium bromide and alchlor in cetyl pyridinium bromide alchlor ionic liquid
Than for 0.5:1.
Embodiment 14
Present embodiments provide a kind of preparation method of alpha-olefin polymers, comprising the following steps:
30mL alpha olefin monomers are added to acidic ionic liquid catalysts, are made in the catalysis of acidic ionic liquid catalysts
Under, in 75 DEG C of progress polymerization reaction 2h, after the reaction product (upper layer oligomer) that polymerization is obtained carries out alkali cleaning and washing, mistake
It is distilled after filter, obtains alpha-olefin polymers.
Wherein, alpha olefin monomers are 1- octene, and acidic ionic liquid catalysts account for alpha olefin monomers and acidic ion liquid is urged
The 13.60% of agent gross mass, acidic ionic liquid catalysts are 1- vinyl -3- butyl imidazole villaumite alchlor ion
Liquid.
The preparation method of 1- vinyl -3- butyl imidazole villaumite alchlor ionic liquid, comprising the following steps:
It takes 1.40g 1- vinyl -3- butyl imidazole villaumite, 2g alchlor to be placed in 20mL hexane, carries out at room temperature
Primary stirring, a mixing time are 40min, then heat to 50 DEG C of progress secondary agitations, and the secondary agitation time is 8h, are obtained
1- vinyl -3- butyl imidazole villaumite alchlor ionic liquid.
In 1- vinyl -3- butyl imidazole villaumite alchlor ionic liquid 1- vinyl -3- butyl imidazole villaumite with
The molar ratio of alchlor is 0.5:1.
Comparative example 1
This comparative example provides a kind of preparation method of alpha-olefin polymers, comprising the following steps:
30mL alpha olefin monomers are added in the solution of catalyst and normal heptane, under the catalytic action of catalyst, in 50
DEG C polymerization reaction 5h is carried out, will be distilled after filtering after the obtained reaction product (upper layer oligomer) of polymerization carries out alkali cleaning and washing,
Obtain alpha-olefin polymers.
Wherein, alpha olefin monomers are 1- decene, and catalyst is alchlor, and the quality of alchlor is 2g, the use of normal heptane
Amount is 20mL.
For the effect for verifying embodiment and comparative example, ad hoc following experimental example.
Experimental example 1
The mass parameter of alpha-olefin polymers made from each embodiment and comparative example is measured, concrete outcome is shown in Table 1.
Wherein, the measuring method of viscosity index (VI) is according to GB/T265-1988, and the measuring method of condensation point is according to GB/T510-
1983。
The mass parameter of alpha-olefin polymers made from each embodiment and comparative example of table 1
It can be seen from the data in Table 1 that α alkene made from preparation method using alpha-olefin polymers provided by embodiment
The mass parameter of hydrocarbon polymer is obviously better than the mass parameter of alpha-olefin polymers made from comparative example.
Specifically, it can be seen from the data in Table 1 that composition, alhpa olefin of the performance parameter of alpha-olefin polymers by catalyst
The influence of composition, polymeric reaction temperature, the polymerization reaction time of monomer etc..With organic halogenation in acidic ionic liquid catalysts
The molar ratio of object and alchlor increases (proportion of namely alchlor becomes smaller), and Ionic Liquids Acidity is on the weak side, may cause
Reaction is not thorough, so that yield and viscosity index (VI) are relatively low；As the molar ratio of organohalogen compounds and alchlor reduces (tri-chlorination
The increase of aluminium proportion), yield and viscosity index (VI) increase (such as Examples 1 and 2 2), but excessively high alchlor proportion is easy to make to react
Product cracking and isomery, cause yield to reduce (such as embodiment 3), therefore organohalogen compounds only in acidic ionic liquid catalysts
The performance being most preferably catalyzed with the molar ratio of alchlor in specific numberical range energy competence exertion.
In addition, the performance of alpha-olefin polymers also changes therewith, such as embodiment when the composition of alpha olefin monomers changes
6, the introducing of Long carbon chain 1-tetradecylene improves the condensation point and viscosity index (VI) of alpha-olefin polymers, but the reduction of reactivity is also made
At the decline of yield.Embodiment 13,14 also embodies this variation, i.e. Long carbon chain alpha olefin monomers can reduce alpha-olefin polymers
Yield, but condensation point and viscosity index (VI) increase.Embodiment 5,7,8 and 9 reflects influence of the temperature to polymerization reaction.Reaction temperature
It is excessively high to induce unwanted reaction and generate complicated polymer, the viscosity of polymer is reduced, so as to cause condensation point and viscosity
The reduction of index.Embodiment 2,10 and 11 reflects influence of the polymerization reaction time to polymerization reaction, i.e., with polymerization reaction when
Between extension, yield increases, but polymerization reaction time it is too long make catalyst and product contact for a long time easily cause it is unnecessary instead
It answers, yield cannot be made to continue growing.
In conclusion through the foregoing embodiment with comparative example comparison it is found that the present invention uses acidic ionic liquid catalysts
Stability is high, environmentally friendly, alpha olefin monomers can be promoted to carry out polymerization reaction, and reaction rate is fast, and obtained reaction produces
The high income of alpha-olefin polymers in object, and its viscosity index (VI) and condensation point are also in optimum range.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of alpha-olefin polymers, which comprises the following steps:
Alpha olefin monomers are subjected to polymerization reaction under the action of acidic ionic liquid catalysts, obtain alpha-olefin polymers；
Wherein, the alpha olefin monomers include in C8-C14 alkene any one or at least two combination；
The raw material of the acidic ionic liquid catalysts includes alchlor, organohalogen compounds and solvent, the organohalogen compounds
Including any one in pyridine halogen class, imidazoles halogen class or quaternary ammonium halogen class.
2. the preparation method of alpha-olefin polymers according to claim 1, which is characterized in that the organohalogen compounds include
Trimethylamine hydrochloride, triethylamine hydrochloride, 1- ethyl pyridinium chloride, 1- ethyl pyridinium bromide, 1- butyl pyridinium chloride, 1- butyl
Pyridinium bromide, dodecylpyridinium bromide, dodecyl pyridinium chloride, cetyl pyridinium bromide, hexadecylpyridinium chloride,
1- ethyl-3-methylimidazole bromide, 1- ethyl-3-methylimidazole villaumite, 1- vinyl -3- butyl imidazole bromide, 1- vinyl -
Any one in 3- butyl imidazole villaumite, 1- butyl -3- methylimidazole bromide or 1- butyl -3- methylimidazole villaumite, preferably
Including trimethylamine hydrochloride or triethylamine hydrochloride.
3. the preparation method of alpha-olefin polymers according to claim 1, which is characterized in that the organohalogen compounds and institute
The molar ratio for stating alchlor is (0.2-0.8): 1, preferably (0.3-0.7): 1.
4. the preparation method of alpha-olefin polymers according to claim 1, which is characterized in that the acidic ion liquid is urged
Agent accounts for the 5-20% of the alpha olefin monomers and acidic ionic liquid catalysts gross mass, preferably 10-18%.
5. the preparation method of alpha-olefin polymers according to any one of claims 1-4, which is characterized in that the solvent
For saturated alkane, preferably include in normal heptane, n-hexane or hexamethylene any one or at least two combination.
6. the preparation method of alpha-olefin polymers according to any one of claims 1-4, which is characterized in that the polymerization
Reaction temperature is 25-75 DEG C, preferably 30-70 DEG C；
And/or the polymerization reaction time is 1-6h, preferably 1.5-5h.
7. the preparation method of alpha-olefin polymers according to any one of claims 1-4, which is characterized in that including following
Step:
It, will in 25-75 DEG C of progress polymerization reaction 1-6h by alpha olefin monomers under the catalytic action of acidic ionic liquid catalysts
It polymerize obtained reaction product to be refined, separates, obtain alpha-olefin polymers.
8. the preparation method of alpha-olefin polymers according to any one of claims 1-4, which is characterized in that the acidity
The preparation method of ionic liquid includes the following steps:
The mixed liquor that organohalogen compounds, alchlor and solvent are formed once is stirred, then heating and simultaneously progress two
Secondary stirring, obtains acidic ionic liquid catalysts.
9. the preparation method of alpha-olefin polymers according to claim 8, which is characterized in that the time once stirred
For 20-40min；
And/or the time of the secondary agitation is 3-8h；
And/or the temperature of the heating is 40-90 DEG C.
10. alpha-olefin polymers made from the preparation method using alpha-olefin polymers described in any one of claim 1-9 exist
Application in lube base oil.
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