CN104558327B - A kind of poly- pentadiene and preparation method thereof - Google Patents
A kind of poly- pentadiene and preparation method thereof Download PDFInfo
- Publication number
- CN104558327B CN104558327B CN201310487790.6A CN201310487790A CN104558327B CN 104558327 B CN104558327 B CN 104558327B CN 201310487790 A CN201310487790 A CN 201310487790A CN 104558327 B CN104558327 B CN 104558327B
- Authority
- CN
- China
- Prior art keywords
- pentadiene
- preparation
- raw materials
- weight
- alkynes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a kind of poly- pentadiene and preparation method thereof.The preparation method of the poly- pentadiene comprises the following steps：（1）Pentadiene and cyclopentadiene and/or C will be contained5The coarse raw materials containing pentadiene of alkynes are contacted with metal alkoxide, obtain pentadiene raw material, and the condition of the contact causes on the basis of the gross weight of the pentadiene raw material, the cyclopentadiene and C5The total content of alkynes is not higher than 20ppm；（2）In the presence of initiator and polar modifier, the pentadiene raw material is subjected to polymerisation in a solvent, the poly- pentadiene that number-average molecular weight is more than 30,000 and molecular weight distribution is less than 1.8 is obtained.Using the method that provides of the present invention can on the basis of not reducing pentadiene by the cyclopentadiene and C in the coarse raw materials containing pentadiene5Alkynes is substantially completely removed, and the pentadiene raw material after being handled by metal alkoxide can carry out follow-up polymerisation very wellly.
Description
Technical field
Prepared the present invention relates to a kind of poly- pentadiene, a kind of preparation method of poly- pentadiene and by this method
Poly- pentadiene.
Background technology
Pentadiene is the C of petroleum cracking ethene formation5Important composition in cut, accounts for C5The 15-20 weights of cut
Measure %.Coarse raw materials containing pentadiene（C5Cut）With C5Based on saturated hydrocarbons and/or unsaturated hydrocarbons, pentadiene, ring are mainly contained
Pentadiene, C5Alkynes, cyclopentene and pentamethylene.The boiling point of above-mentioned various components relatively, according to traditional rectificating method very
Hardly possible separates them.At present, the coarse raw materials containing pentadiene by rectifying column it is refined after, can obtain containing cis-form m-pentadiene and
The weight % of the total content of trans-m-pentadiene about 70 coarse raw materials, its be mainly used in Petropols synthesis, but added value of product and
Energy utilization rate is relatively low.CN1445206A discloses a kind of method of purifying and refining piperyene, and specifically discloses the party
Method comprises the following steps：（1）Coarse raw materials containing pentadiene carry out rectifying separation removal heavy constituent, and the operating pressure of rectifying column is
0.03-0.5MPa, bottom temperature is 35-100 DEG C, and reflux ratio is 1-8, and pentadiene material is obtained from tower top；（2）By step
（1）In obtained tower top material extracting rectifying is carried out in the presence of polymerization inhibitor to remove in light component, the tower of extractive distillation column
Pressure is 0.03-0.5MPa, and bottom temperature is 100-180 DEG C, and reflux ratio is 1-10, coarse raw materials and extractant containing pentadiene
The weight flow ratio of charging is 1:2-1:10, tower reactor obtains the material containing pentadiene and extractant.Wherein, the extraction taken
Agent is one kind in the aqueous solution of dimethylformamide, 1-METHYLPYRROLIDONE, acetonitrile and acetonitrile；（3）Step（2）Obtained tower
Kettle material removes the pentadiene product that extractant obtains high-purity through rectifying, and extractant, which reclaims to return to extracting rectifying process and circulate, to be made
With.Research shows, uses this method to obtain purity for more than 95% pentadiene, but purge process is complicated, and can not be complete
It is complete to remove catalyst posions.US4486614 discloses the metals such as a kind of use sodium, potassium, lithium and its hydride is handled penta 2 between containing
The method of the coarse raw materials of alkene.Research shows that the treatment conditions are more harsh, and treatment temperature need to be carried out more than each melting point metal,
And obtained pentadiene purity is relatively low, so as to make the obtained number-average molecular weight of poly- pentadiene relatively low.
The content of the invention
The invention aims to provide a kind of poly- pentadiene, a kind of preparation method of poly- pentadiene and by this
The poly- pentadiene that method is prepared.
The invention provides a kind of poly- pentadiene, wherein, the number-average molecular weight of the poly- pentadiene is more than 30,000,
Molecular weight distribution is less than 1.8.
Present invention also offers a kind of preparation method of poly- pentadiene, wherein, this method comprises the following steps：
（1）Pentadiene and cyclopentadiene and/or C will be contained5The coarse raw materials and metal alkoxide containing pentadiene of alkynes
Contact, obtains pentadiene raw material, the condition of the contact causes on the basis of the gross weight of the pentadiene raw material, described
Cyclopentadiene and C5The total content of alkynes is not higher than 20ppm；
（2）In the presence of initiator and polar modifier, the pentadiene raw material is carried out in a solvent to polymerize instead
Should, obtain the poly- pentadiene that number-average molecular weight is more than 30,000 and molecular weight distribution is less than 1.8.
In addition, present invention also offers the poly- pentadiene prepared by the above method.
The present inventor has found after in-depth study, cyclopentadiene and C5Polymerization of the alkynes to pentadiene has
There is inhibition, therefore, in order to develop the pentadiene product with high added value, it is necessary to by described containing the thick of pentadiene
Cyclopentadiene and C in raw material5Alkynes is removed.And the present invention uses metal alkoxide as inorganic agent, it can not only not reduce
By the cyclopentadiene and C in the coarse raw materials containing pentadiene on the basis of pentadiene5Alkynes is substantially completely removed, and
Pentadiene will not be had adverse effect on.Pentadiene raw material after being handled by metal alkoxide can very wellly
Follow-up polymerisation is carried out, so as to obtain poly- pentadiene.In addition, the method provided using the present invention is to containing pentadiene
Coarse raw materials are handled, easy to operate, mild condition, great prospects for commercial application.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.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 number-average molecular weight for the poly- pentadiene that the present invention is provided is more than 30,000, preferably more than 80,000, more preferably 8
Ten thousand -50 ten thousand；Molecular weight distribution is less than 1.8, preferably 1-1.8, more preferably 1.1-1.6.
According to the present invention, 1,2- paradigmatic structure units may be contained in the poly- pentadiene, it is also possible to containing Isosorbide-5-Nitrae-gather
Close construction unit.Wherein, on the basis of the gross weight of the poly- pentadiene, the content of Isosorbide-5-Nitrae-paradigmatic structure unit is preferably
20-90 weight %, more preferably 30-70 weight %；The content of 1,2- paradigmatic structure unit is preferably 10-80 weight %, more preferably
30-70 weight %.
The preparation method for the poly- pentadiene that the present invention is provided comprises the following steps：
（1）Pentadiene and cyclopentadiene and/or C will be contained5The coarse raw materials and metal alkoxide containing pentadiene of alkynes
Contact, obtains pentadiene raw material, the condition of the contact causes on the basis of the gross weight of the pentadiene raw material, described
Cyclopentadiene and C5The total content of alkynes is not higher than 20ppm, preferably no greater than 15ppm；
（2）In the presence of initiator and polar modifier, the pentadiene raw material is carried out in a solvent to polymerize instead
Should, obtain the poly- pentadiene that number-average molecular weight is more than 30,000 and molecular weight distribution is less than 1.8.
It should be noted that containing cyclopentadiene and C in the coarse raw materials containing pentadiene described in simultaneously5During alkynes, institute
State cyclopentadiene and C5The total content of alkynes refers to the content and C of cyclopentadiene5The content sum of alkynes；When penta 2 between described contain
Cyclopentadiene or C are comprised only in the coarse raw materials of alkene5During alkynes, the cyclopentadiene and C5The total content of alkynes refers to cyclopentadiene
Content or C5The content of alkynes.
The present invention is to the pentadiene in the coarse raw materials containing pentadiene, cyclopentadiene and C5The content of alkynes does not have
Especially limit, for example, on the basis of the gross weight of the coarse raw materials containing pentadiene, in the raw material containing pentadiene
The content of pentadiene can be 65-99.8 weight %, cyclopentadiene and C5The total content of alkynes can be 0.2-35 weight %.
In addition, the present invention is not particularly limited to the sources of the coarse raw materials containing pentadiene, particularly preferably stone
The C that oil-breaking ethene is obtained5Cut, so can substantially more utilize limited resource, and the economy for improving product is added
Value and energy utilization rate.As a rule, the C5Cut is except containing pentadiene and cyclopentadiene and/or C5Outside alkynes,
Cyclopentene and pentamethylene are also usually contained, also, as a rule, the gross weight using the coarse raw materials containing pentadiene is base
The content of pentadiene in standard, the coarse raw materials containing pentadiene can be 65-80 weight %, and the content of cyclopentadiene can
Think 0.1-0.5 weight %, C5The content of alkynes can be 0.1-0.5 weight %, and the content of cyclopentene can be 10-20 weight %,
The content of pentamethylene can be 5-15 weight %.
The present invention is not particularly limited to the condition of the contact, as long as can be by the coarse raw materials containing pentadiene
In cyclopentadiene and C5Alkynes is removed, as a rule, and the condition of the contact includes Contact Temperature, contact and connect
The time of touching.Wherein, in order to be more beneficial for cyclopentadiene and C5The removal of alkynes, the Contact Temperature is preferably -20 DEG C to 100
DEG C, more preferably 30-80 DEG C；The contact is preferably 0-0.3MPa, more preferably 0-0.1MPa.In the present invention, institute
State pressure and refer both to gauge pressure.As well known to those skilled in the art, the boiling point of pentadiene is about 42 DEG C, therefore, when Contact Temperature exceedes
, it is necessary to install reflux additional during the boiling point, or contact is improved, haptoreaction is carried out in pressure-resistant apparatus.The contact
The extension of time is conducive to improving cyclopentadiene and C5The clearance of alkynes, but time of contact is long to above-mentioned clearance amplitude
Improve unobvious, therefore, consider effect and efficiency, the time of contact is preferably 0.1-10h, more preferably 2-5h.
In addition, the coarse raw materials containing pentadiene contact with metal alkoxide is preferably carried out under agitation, so
It can make it that both contacts are more abundant, and shorten the reaction time.The mode of the stirring can be selected for the conventional of this area
Select, it is for instance possible to use magnetic agitation, mechanical agitation, ultrasonic agitation etc..The intensity of the stirring is so that material to be well mixed
On the basis of, this those skilled in the art can be known, be will not be described in great detail.
According to the present invention, the species of the metal alkoxide can be the conventional selection of this area, for example, can be the tert-butyl alcohol
One or more in potassium, tert-pentyl alcohol potassium, potassium ethoxide, sodium tert-butoxide, sodium tert-amyl alcohol and caustic alcohol, preferably potassium tert-butoxide and/
Or tert-pentyl alcohol potassium, more preferably potassium tert-butoxide.
The present invention is not particularly limited to the consumption of the metal alkoxide, ring penta that can be in the pentadiene
Diene and C5The content of alkynes is reasonably selected, as a rule, the molal quantity of the metal alkoxide and it is described contain between penta 2
Cyclopentadiene and C in the coarse raw materials of alkene5The ratio of the total mole number of alkynes can be 1-10:1, preferably 1-5:1, so just
It ensure that the cyclopentadiene and C5Alkynes is substantially completely removed.
According to the present invention, although as long as the coarse raw materials containing pentadiene are connect under certain conditions with metal alkoxide
, just can be by cyclopentadiene therein and C after touching5Alkynes is removed, but remaining unreacted metal alkoxide may also can
Follow-up polymerization to pentadiene affects, therefore, in order to improve the purity of pentadiene raw material, preferable case
Under, the preparation method for the poly- pentadiene that the present invention is provided is additionally included under 0-0.1MPa, by the thick original containing pentadiene
Expect that the product of contact with metal alkoxide is distilled, and collect 40-45 DEG C of cut.The method of the distillation is art technology
Known in personnel, it will not be described in great detail herein.
According to the present invention, the initiator can be the existing various initiators that pentadiene can be triggered to polymerize, and lead to
Often can be organic single-lithium initiator, it can be represented with R ' Li.Wherein, R ' can be alkyl, cycloalkyl or aryl.Consider
The dissolubility of initiator in a solvent, R ' is preferably C1-C10Straight or branched alkyl.Specifically, organic single-lithium initiator
Example include but is not limited to：Lithium methide, isopropyl lithium, s-butyl lithium, n-BuLi, cyclohexyl lithium, 4- cyclohexylbutyls lithium,
One or more in phenyl lithium, trityl group lithium and 2- naphthyl lithiums.In addition, it is contemplated that the dissolubility of initiator in a solvent
And storage stability, the initiator is particularly preferably n-BuLi and/or s-butyl lithium.The consumption of the initiator can root
The molecular size range of the poly- pentadiene obtained according to the consumption and needs of pentadiene raw material is reasonably selected, for example,
On the basis of the consumption of the pentadiene raw material of 100 parts by weight, the consumption of the initiator can be 0.3-1.0 weight
Part, preferably 0.4-0.6 parts by weight.
As a rule, the main function of the polar modifier is the microstructure for adjusting poly- pentadiene, for example, 1,2-
The content of paradigmatic structure unit and 1,4- paradigmatic structure units.In order that in obtained poly- pentadiene, Isosorbide-5-Nitrae-paradigmatic structure list
The content of member is 20-90 weight %, preferably 30-70 weight %；The content of 1,2- paradigmatic structure unit is 10-80 weight %, preferably
For 30-70 weight %, on the basis of the pentadiene raw material of 100 parts by weight, the consumption of the polar modifier is preferably 1-
100 parts by weight, more preferably 5-70 parts by weight.In addition, the species of the polar modifier can be the conventional selection of this area,
For example, can be ether, butyl oxide, tetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ether, dioxy six
Ring, crown ether, triethylamine, tetramethylethylenediamine, HMPA, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkylbenzene
One or more in potassium sulfonate and sodium alkyl benzene sulfonate.
The present invention is not particularly limited to the species of the solvent, can be the existing various things as reaction medium
Matter, for example, can be the one or more in aromatic hydrocarbons, saturated alkane and cycloalkane.Specifically, the solvent can be benzene, first
Benzene, ethylbenzene, dimethylbenzene（Including ortho-xylene, meta-xylene and paraxylene）, pentane and its isomers（For example：It is pentane, different
Pentane, methyl cyclopentane, 2- methylpentanes and 3- methylpentanes）, hexane and its isomers（For example：N-hexane, hexamethylene）, heptan
Alkane and its isomers（For example：Normal heptane）, octane and its isomers（For example：Normal octane）, hexamethylene and one kind in raffinating oil
Or it is a variety of.As a rule, as long as the consumption of the solvent is so that the concentration of pentadiene raw material is 10-20 weight %.
The present invention is not particularly limited to the condition of the polymerisation, for example, can include polymerization temperature and polymerization
Time.Wherein, the polymerization temperature for example can be 30-100 DEG C, preferably 50-80 DEG C；The polymerization time for example can be
0.5-10 hours, preferably 1-3 hours.In addition, the polymerisation is generally carried out at ambient pressure.
According to the present invention, the polymerisation is substantially anionic polymerisation.Therefore, after polymerization was complete,
Generally also need to inactivate living polymer using various methods well known in the art.For example, polymerization reaction system can be passed through
It is middle to add terminator to make living polymer chains lose activity.The species of the terminator can be the conventional selection of this area,
As long as can inactivate the polymer chain of active end group.Usually, the terminator can be selected from water, C1-C6's
Aliphatic alcohol, C4-C12Aliphatic carboxylic acid, the one or more in aryl polyol.The aryl polyhydroxy chemical combination
Thing refers to that the hydrogen atom at least two on phenyl ring is optionally substituted by a hydroxyl group generated compound.Preferably, the terminator be water,
One or more in methanol, ethanol, isopropanol and 2,6- di-tert-butyl hydroquinones.The consumption of the terminator can also be
The conventional selection of this area, will not be described in great detail herein.
The preparation method for the poly- pentadiene that the present invention is provided is additionally included in after terminating reaction completion, toward polymerisation body
Age resistor is added in system, the poly- pentadiene so enabled to has more excellent ageing-resistant performance.The age resistor
Species can be this area conventional selection, for example, can be BHT（Trade name：Antioxidant 264）、
Four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters（Trade name：Age resistor 1010）, phosphorous acid three (2,
4- di-tert-butyl-phenyls) ester（Trade name：Age resistor 168）, 3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid stearyl
（Trade name：Age resistor 1076）With the mixture of three (nonyl is for phenyl) phosphite esters（Trade name：Age resistor TNPP）In one
Plant or a variety of.In addition, the consumption of the age resistor can be the conventional selection of this area, it will not be described in great detail herein.
Present invention also offers the poly- pentadiene prepared by the above method.
The present invention will be described in detail by way of examples below.
Following preparation example and contrast preparation example in, pending coarse raw materials and processing containing pentadiene obtain between penta 2
The composition of alkene raw material and the content of each component use gas chromatograph（Purchased from Japanese Shimadzu Corporation, model GC1609）Carry out
Analysis.Wherein, instrument parameter is as follows：Quartz capillary column, a length of 60m, internal diameter is 0.32, and thickness of liquid film is 1.0 μm, and liquid film is
PHENYL-METHYL-siloxane polymer, split ratio is 50:1, gasification room temperature is 260 DEG C, and hydrogen flame detector temperature is 260
DEG C, column temperature：35 DEG C continue after 20 minutes to be warming up to 185 DEG C with 10 DEG C/min, and carrier gas is high pure nitrogen.
In following preparation example and contrast preparation example, the pending coarse raw materials containing pentadiene are that petroleum cracking ethene is obtained
The C arrived5Cut, its composition is as follows：On the basis of the gross weight of the coarse raw materials containing pentadiene, trans-m-pentadiene contains
Measure as 42.14 weight %, the content of cis-form m-pentadiene is 25.14 weight %, and the content of isoprene is 0.04 weight %, C5Alkynes
The content of hydrocarbon is 0.21 weight %, and the content of cyclopentadiene is 0.39 weight %, and the content of cyclopentene is 19.19 weight %, pentamethylene
Content be 8.18 weight %, the contents of other cuts is 4.71 weight %.
In following examples and comparative example, number-average molecular weight and molecular weight distributing index are using Viscotek companies of the U.S.
TDA302 types gel permeation chromatograph (GPC) is determined, and THF is mobile phase, and flow velocity is 1.0mL/min, and test sample concentration is 2-
3mg/mL, using Narrow distribution polystyrene as standard specimen, test temperature is 25 DEG C.Micmstructure of polymer uses US Varian
INOVA400NMR nuclear magnetic resonance chemical analysers are measured.
Preparation example 1
The preparation example is used for the preparation method for illustrating the pentadiene raw material that the present invention is provided.
By coarse raw materials of the 100g containing pentadiene（Cyclopentadiene and C5The total mole number of alkynes is 8.99mmol）And 1.2g
（10.69mmol）Potassium tert-butoxide is well mixed, and temperature be 30 DEG C, gauge pressure be to react 2h under 0MPa, obtain reaction product, so
After carry out air-distillation, and collect 40-45 DEG C of cut, obtain pentadiene raw material Y1.Promoting the circulation of qi is entered to pentadiene raw material Y1
Analysis of hplc, as a result as shown in table 1.
Preparation example 2
The preparation example is used for the preparation method for illustrating the pentadiene raw material that the present invention is provided.
By coarse raw materials of the 100g containing pentadiene（Cyclopentadiene and C5The total mole number of alkynes is 8.99mmol）And 2.1g
（18.71mmol）Potassium tert-butoxide is well mixed, and temperature be 50 DEG C, gauge pressure be to react 3h under 0.1MPa, obtain reaction product,
Then air-distillation is carried out, and collects 40-45 DEG C of cut, pentadiene raw material Y2 is obtained.Pentadiene raw material Y2 is carried out
Gas chromatographic analysis, as a result as shown in table 1.
Preparation example 3
The preparation example is used for the preparation method for illustrating the pentadiene raw material that the present invention is provided.
By coarse raw materials of the 100g containing pentadiene（Cyclopentadiene and C5The total mole number of alkynes is 8.99mmol）And 3.0g
（26.74mmol）Potassium tert-butoxide is well mixed, and temperature be 30 DEG C, gauge pressure be to react 2h under 0.05MPa, obtain reaction production
Thing, then carries out air-distillation, and collects 40-45 DEG C of cut, obtains pentadiene raw material Y3.Pentadiene raw material Y3 is entered
Promoting the circulation of qi analysis of hplc, as a result as shown in table 1.
Preparation example 4
The preparation example is used for the preparation method for illustrating the pentadiene raw material that the present invention is provided.
By coarse raw materials of the 100g containing pentadiene（Cyclopentadiene and C5The total mole number of alkynes is 8.99mmol）And 2.1g
（18.71mmol）Potassium tert-butoxide is well mixed, and temperature be 30 DEG C, gauge pressure be to react 5h under 0MPa, obtain reaction product, so
After carry out air-distillation, and collect 40-45 DEG C of cut, obtain pentadiene raw material Y4.Promoting the circulation of qi is entered to pentadiene raw material Y4
Analysis of hplc, as a result as shown in table 1.
Preparation example 5
The preparation example is used for the preparation method for illustrating the pentadiene raw material that the present invention is provided.
By coarse raw materials of the 100g containing pentadiene（Cyclopentadiene and C5The total mole number of alkynes is 8.99mmol）And 1.2g
Potassium tert-butoxide（10.69mmol）It is well mixed, and temperature be 80 DEG C, gauge pressure be to react 2h under 0.05MPa, obtain reaction production
Thing, then carries out air-distillation, and collects 40-45 DEG C of cut, obtains pentadiene raw material Y5.Pentadiene raw material Y5 is entered
Promoting the circulation of qi analysis of hplc, as a result as shown in table 1.
Preparation example 6
The preparation example is used for the preparation method for illustrating the pentadiene raw material that the present invention is provided.
By coarse raw materials of the 100g containing pentadiene（Cyclopentadiene and C5The total mole number of alkynes is 8.99mmol）And 1.2g
Potassium tert-butoxide（10.69mmol）It is well mixed, and temperature be 80 DEG C, gauge pressure be to react 5h under 0.1MPa, obtain reaction product,
Then air-distillation is carried out, and collects 40-45 DEG C of cut, pentadiene raw material Y6 is obtained.Pentadiene raw material Y6 is carried out
Gas chromatographic analysis, as a result as shown in table 1.
Table 1
Embodiment 1
The embodiment is used to illustrate poly- pentadiene of the invention provided and preparation method thereof.
In 5L stainless steel polymeric kettles, 2500g hexamethylenes/hexane mixed solvent is added（Weight ratio is 1:1, similarly hereinafter）、540g
Pentadiene raw material Y1,152mg tetrahydrofurfuryl alcohol ether after purification（ETE, similarly hereinafter）, stirring is opened, it is 180 to control mixing speed
Rev/min, when polymerization temperature in the kettle reaches 80 DEG C, 4mmol n-BuLis are added into polymeric kettle for water bath with thermostatic control heating.At 80 DEG C
After lower reaction 1.5h, 0.3g isopropanol terminating reactions are added, 1.1g age resistor 1010 are then added, then obtained glue is used
Wet agglomeration processing, finally with the number-average molecular weight and molecular weight distributing index of High Performance Gel Permeation chromatogram test polymer.Knot
Fruit is as shown in table 2.
Embodiment 2
The embodiment is used to illustrate poly- pentadiene of the invention provided and preparation method thereof.
In 5L stainless steel polymeric kettles, the pentadiene of 2500g hexamethylenes/hexane mixed solvent, 540g after purification is added former
Expect Y2,152mg tetrahydrofurfuryl alcohol ether, open stirring, it is 180 revs/min to control mixing speed, and water bath with thermostatic control is heated, in polymeric kettle
When temperature reaches 60 DEG C, 4mmol n-BuLis are added into polymeric kettle.Reacted at 60 DEG C after 0.5h, add 0.3g isopropanols
Terminating reaction, adds 1.1g age resistor 1010, then obtained glue is handled using Wet agglomeration, finally uses High Performance Gel Permeation
The number-average molecular weight and molecular weight distributing index of chromatogram test polymer.As a result it is as shown in table 2.
Embodiment 3
The embodiment is used to illustrate poly- pentadiene of the invention provided and preparation method thereof.
In 5L stainless steel polymeric kettles, the pentadiene of 2500g hexamethylenes/hexane mixed solvent, 540g after purification is added former
Expect Y3,1510mg tetrahydrofurfuryl alcohol ether, open stirring, it is 180 revs/min to control mixing speed, and water bath with thermostatic control is heated, in polymeric kettle
When temperature reaches 50 DEG C, 4mmol n-BuLis are added into polymeric kettle.Reacted at 50 DEG C after 3h, add 0.3g isopropanols whole
Only react, then add 1.1g age resistor 1010, then obtained glue is handled using Wet agglomeration, finally oozed with efficient gel
The number-average molecular weight and molecular weight distributing index of saturating chromatogram test polymer.As a result it is as shown in table 2.
Embodiment 4
The embodiment is used to illustrate poly- pentadiene of the invention provided and preparation method thereof.
In 5L stainless steel polymeric kettles, the pentadiene of 2500g hexamethylenes/hexane mixed solvent, 540g after purification is added former
Expect Y4,831mg tetrahydrofurfuryl alcohol ether, open stirring, it is 180 revs/min to control mixing speed, and water bath with thermostatic control is heated, in polymeric kettle
When temperature reaches 80 DEG C, 4mmol n-BuLis are added into polymeric kettle.Reacted at 80 DEG C after 1.0h, add 0.3g isopropanols
Terminating reaction, then adds 1.1g age resistor 1010, then obtained glue is handled using Wet agglomeration, finally uses efficient gel
The number-average molecular weight and molecular weight distributing index of permeation chromatography test polymer.As a result it is as shown in table 2.
Embodiment 5
The embodiment is used to illustrate poly- pentadiene of the invention provided and preparation method thereof.
In 5L stainless steel polymeric kettles, the pentadiene of 2500g hexamethylenes/hexane mixed solvent, 540g after purification is added former
Expect Y5,1510mg tetrahydrofurfuryl alcohol ether, open stirring, it is 180 revs/min to control mixing speed, and water bath with thermostatic control is heated, in polymeric kettle
When temperature reaches 80 DEG C, 4mmol n-BuLis are added into polymeric kettle.Reacted at 80 DEG C after 0.5h, add 0.3g isopropanols
Terminating reaction, then adds 1.1g age resistor 1010, then obtained glue is handled using Wet agglomeration, finally uses efficient gel
The number-average molecular weight and molecular weight distributing index of permeation chromatography test polymer.As a result it is as shown in table 2.
Embodiment 6
The embodiment is used to illustrate poly- pentadiene of the invention provided and preparation method thereof.
In 5L stainless steel polymeric kettles, the pentadiene of 2500g hexamethylenes/hexane mixed solvent, 540g after purification is added former
Expect Y6,152mg tetrahydrofurfuryl alcohol ether, open stirring, it is 180 revs/min to control mixing speed, and water bath with thermostatic control is heated, in polymeric kettle
When temperature reaches 50 DEG C, 4mmol n-BuLis are added into polymeric kettle.Reacted at 50 DEG C after 0.5h, add 0.3g isopropanols
Terminating reaction, then adds 1.1g age resistor 1010, then obtained glue is handled using Wet agglomeration, finally uses efficient gel
The number-average molecular weight and molecular weight distributing index of permeation chromatography test polymer.As a result it is as shown in table 2.
Comparative example 1
The comparative example is used to illustrate poly- pentadiene of reference and preparation method thereof.
Method according to embodiment 3 prepares poly- pentadiene, unlike, pentadiene raw material Y3 after purification is with identical
The undressed coarse raw materials containing pentadiene of parts by weight are substituted.As a result it is as shown in table 2.
Table 2
As can be seen from the above results, the method provided using the present invention is handled the coarse raw materials containing pentadiene,
Can be by cyclopentadiene therein and C5Alkynes is removed well, and pentadiene does not almost lose.By metal alcohol
Pentadiene raw material after salt treatment can carry out follow-up polymerisation very wellly, so as to obtain poly- pentadiene.
In addition, the method provided using the present invention is handled the coarse raw materials containing pentadiene, easy to operate, mild condition is great
Prospects for commercial application.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
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.
Claims (14)
1. a kind of preparation method of poly- pentadiene, wherein, this method comprises the following steps：
(1) pentadiene and cyclopentadiene and/or C will be contained5The coarse raw materials containing pentadiene of alkynes are contacted with metal alkoxide,
Pentadiene raw material is obtained, the condition of the contact causes on the basis of the gross weight of the pentadiene raw material, the ring penta
Diene and C5The total content of alkynes is not higher than 20ppm；
(2) in the presence of initiator and polar modifier, the pentadiene raw material is subjected to polymerisation in a solvent, obtained
The poly- pentadiene that to number-average molecular weight be more than 30,000 and molecular weight distribution is less than 1.8.
2. preparation method according to claim 1, wherein, the gross weight using the coarse raw materials containing pentadiene is base
The content of pentadiene in standard, the coarse raw materials containing pentadiene is 65-99.8 weight %, cyclopentadiene and C5Alkynes
Total content is 0.2-35 weight %.
3. preparation method according to claim 1, wherein, in the coarse raw materials containing pentadiene also containing cyclopentene and
Pentamethylene；And on the basis of the gross weight of the coarse raw materials containing pentadiene, in the coarse raw materials containing pentadiene between
The content of pentadiene is 65-80 weight %, and the content of cyclopentadiene is 0.1-0.5 weight %, C5The content of alkynes is 0.1-0.5
Weight %, the content of cyclopentene is 10-20 weight %, and the content of pentamethylene is 5-15 weight %.
4. preparation method according to claim 3, wherein, the coarse raw materials containing pentadiene are petroleum cracking ethene
Obtained C5Cut.
5. the preparation method according to any one in claim 1-4, wherein, the condition of the contact includes：Contact temperature
Spend for -20 DEG C to 100 DEG C；Contact is 0-0.3MPa；The time of contact is 0.1-10h.
6. preparation method according to claim 5, wherein, Contact Temperature is 30-80 DEG C；Contact is 0-0.1MPa；
The time of contact is 2-5h.
7. the preparation method according to any one in claim 1-4, wherein, the molal quantity of the metal alkoxide with it is described
Cyclopentadiene and C in coarse raw materials containing pentadiene5The ratio of the total mole number of alkynes is 1-10:1.
8. preparation method according to claim 7, wherein, the molal quantity of the metal alkoxide is with described containing pentadiene
Cyclopentadiene and C in coarse raw materials5The ratio of the total mole number of alkynes is 1-5:1.
9. the preparation method according to any one in claim 1-4, wherein, the metal alkoxide is potassium tert-butoxide, uncle
One or more in amylalcohol potassium, potassium ethoxide, sodium tert-butoxide, sodium tert-amyl alcohol and caustic alcohol.
10. preparation method according to claim 9, wherein, the metal alkoxide is potassium tert-butoxide and/or tert-pentyl alcohol potassium.
11. preparation method according to claim 10, wherein, the metal alkoxide is potassium tert-butoxide.
12. the preparation method according to any one in claim 1-4, wherein, this method is additionally included under 0-0.1MPa,
The product of contact of the coarse raw materials containing pentadiene and metal alkoxide is distilled, and collects 40-45 DEG C of cut.
13. the preparation method according to any one in claim 1-4, wherein, the condition of the polymerisation includes：It is poly-
It is 30-100 DEG C to close temperature, and polymerization time is 0.5-10 hours.
14. the preparation method according to any one in claim 1-4, wherein, the polar modifier is ether, two fourths
Ether, tetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, tetramethyl
Base ethylenediamine, HMPA, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate potassium and sodium alkyl benzene sulfonate
In one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310487790.6A CN104558327B (en) | 2013-10-17 | 2013-10-17 | A kind of poly- pentadiene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310487790.6A CN104558327B (en) | 2013-10-17 | 2013-10-17 | A kind of poly- pentadiene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558327A CN104558327A (en) | 2015-04-29 |
| CN104558327B true CN104558327B (en) | 2017-09-29 |
Family
ID=53075472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310487790.6A Active CN104558327B (en) | 2013-10-17 | 2013-10-17 | A kind of poly- pentadiene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558327B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114152691B (en) * | 2021-11-26 | 2024-01-02 | 黄河三角洲京博化工研究院有限公司 | Method for analyzing cyclopentane and extracting agent content by gas chromatography |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482771A (en) * | 1983-01-03 | 1984-11-13 | The Dow Chemical Company | Anionic polymerization of cis- and trans-1,3-pentadiene from a mixture of saturated and unsaturated hydrocarbons |
| US4486614A (en) * | 1983-07-25 | 1984-12-04 | The Dow Chemical Company | Anionic polymerization of cis- and trans-1,3-pentadiene from a mixture of saturated and unsaturated hydrocarbons |
| CN101643379A (en) * | 2009-08-31 | 2010-02-10 | 山东玉皇化工有限公司 | Preparation method of high-purity 1,3-pentadiene |
| CN102351970A (en) * | 2011-07-21 | 2012-02-15 | 中国科学院长春应用化学研究所 | Method for preparing poly-1,3-pentadiene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7902309B2 (en) * | 2009-02-23 | 2011-03-08 | Bridgestone Corporation | Process and catalyst system for polydiene production |
-
2013
- 2013-10-17 CN CN201310487790.6A patent/CN104558327B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482771A (en) * | 1983-01-03 | 1984-11-13 | The Dow Chemical Company | Anionic polymerization of cis- and trans-1,3-pentadiene from a mixture of saturated and unsaturated hydrocarbons |
| US4486614A (en) * | 1983-07-25 | 1984-12-04 | The Dow Chemical Company | Anionic polymerization of cis- and trans-1,3-pentadiene from a mixture of saturated and unsaturated hydrocarbons |
| CN101643379A (en) * | 2009-08-31 | 2010-02-10 | 山东玉皇化工有限公司 | Preparation method of high-purity 1,3-pentadiene |
| CN102351970A (en) * | 2011-07-21 | 2012-02-15 | 中国科学院长春应用化学研究所 | Method for preparing poly-1,3-pentadiene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558327A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2181640A (en) | Process and products relating to production of valuable hydrocarbons | |
| SA109300461B1 (en) | Process for Preparing Isobutene by Cleaving MTBE-Containing Mixtures | |
| TW574196B (en) | Process for preparing methyl tert-butyl and isobutene-free C4-hydrocarbon mixture | |
| CN101332432B (en) | Load-type solid acid catalyst with selective oligomerisation for mixed C4 | |
| CN104710288A (en) | Method for producing high carbon aldehyde through using olefin hydroformylation reaction | |
| JP2013067613A (en) | Method for separating 2-butene from c4 fraction containing 2-butene and 1-butene by selective oligomerization of 1-butene | |
| CN103304717A (en) | Method for preparing high-viscosity-index synthetic lubricating oil through copolymerization of ethylene and alpha-olefin and applications thereof | |
| CN104558327B (en) | A kind of poly- pentadiene and preparation method thereof | |
| CN104725225B (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| US2342074A (en) | Hydrocarbon mixture | |
| CN107879885B (en) | A kind of method and apparatus that mixing carbon four produces raw material for alkylation | |
| CN104718276B (en) | Method for preparing poor benzoline by reclaiming high-purity benzene from the unprocessed cracked naphtha containing organic peroxide | |
| CN100500709C (en) | Gel inhibition method for conjugated diolefin homopolymerization and copolymerization technology | |
| CN104558328B (en) | A kind of polybutadiene rubber and preparation method thereof and oil-extended rubber | |
| CN107879884B (en) | A kind of method and apparatus that mixing carbon four produces iso-butane | |
| CN103586075B (en) | Light petrol etherification catalyst and preparation method thereof | |
| CN104557411B (en) | The processing method of the coarse raw materials containing pentadiene and the pentadiene raw material obtained by the method | |
| CN108658763A (en) | A kind of to generate isooctene using acetic acid mixing C4, repeated hydrogenation produces the manufacturing method of high pure isooctane | |
| US6949671B2 (en) | Process for the production of acetic acid C4-esters | |
| CN104909998A (en) | Method for production of methyl ethyl ketone from refinery C4 fraction | |
| US9115226B2 (en) | Heterogeneous supports for homogeneous catalysts | |
| WO2021000685A1 (en) | Method for catalytic preparation of alkylated oil by using functionalized ionic liquid acid coupling system | |
| JP4446229B2 (en) | Method for increasing added value of hydrocarbon feedstock and reducing vapor pressure of the feedstock | |
| US2468507A (en) | Manufacture of safety fuel | |
| CN105037108A (en) | Method for producing MTBE by using refinery C4 distillate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |