CN104558327A - Polypentadiene and preparation method thereof - Google Patents
Polypentadiene and preparation method thereof Download PDFInfo
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Abstract
The invention provides polypentadiene and a preparation method thereof. The preparation method of the polypentadiene comprises steps as follows: (1) contacting a coarse raw material containing pentadiene and cyclopentadiene and/or C5 alkyne with a melt alkoxide to obtain a pentadiene raw material, wherein the total content of the cyclopentadiene and the C5 alkyne is not higher than 20 ppm with the total weight of the pentadiene raw material as the reference under the contact condition; (2) in the presence of an initiator and a polarity modifier, enabling the pentadiene raw material to have a polymerization reaction in a solvent to obtain the polypentadiene with the number-average molecular weight higher than 30,000 and the molecular weight distribution lower than 1.8. With the adoption of the method, the cyclopentadiene and the C5 alkyne in the coarse raw material containing the pentadiene can be basically removed on the premise that the pentadiene is not reduced, and the pentadiene raw material after treatment with the metal alkoxide can have the follow-up polymerization reaction very smoothly.
Description
Technical field
The present invention relates to a kind of poly-m-pentadiene, a kind of preparation method of poly-m-pentadiene and the poly-m-pentadiene that prepared by the method.
Background technology
M-pentadiene is the C that petroleum cracking ethene is formed
5important composition in cut, accounts for C
5the 15-20 % by weight of cut.Containing the coarse raw materials (C of m-pentadiene
5cut) with C
5stable hydrocarbon and/or unsaturated hydrocarbons are main, mainly containing m-pentadiene, cyclopentadiene, C
5alkynes, cyclopentenes and pentamethylene.Relatively, rectificating method is traditionally difficult to them to be separated to the boiling point of above-mentioned various component.At present, after refining by rectifying tower containing the coarse raw materials of m-pentadiene, can obtain the coarse raw materials of the total content about 70 % by weight containing cis-form m-pentadiene and trans-m-pentadiene, it is mainly used in petroleum resin synthesis, but added value of product and energy utilization rate are all lower.CN1445206A discloses a kind of method of purifying and refining piperyene, and specifically disclose the method and comprise the following steps: (1) is carried out rectifying separation containing the coarse raw materials of m-pentadiene and is removed heavy constituent, the working pressure of rectifying tower is 0.03-0.5MPa, bottom temperature is 35-100 DEG C, reflux ratio is 1-8, obtains m-pentadiene material from tower top; (2) the tower top material obtained in step (1) is carried out extracting rectifying to remove light constituent under the existence of stopper, the tower internal pressure of extractive distillation column is 0.03-0.5MPa, bottom temperature is 100-180 DEG C, reflux ratio is 1-10, compare for 1:2-1:10 containing the coarse raw materials of m-pentadiene and the weight rate of extractant feed, tower reactor obtains the material containing m-pentadiene and extraction agent.Wherein, the extraction agent taked is the one in the aqueous solution of dimethyl formamide, N-Methyl pyrrolidone, acetonitrile and acetonitrile; (3) kettle material that step (2) obtains removes extraction agent through rectifying and obtains highly purified m-pentadiene product, and extraction agent recovery returns extracting rectifying process and recycles.Research shows, adopt the method can obtain the m-pentadiene that purity is more than 95%, but purge process is complicated, and cannot removes catalyst posions completely.US4486614 discloses a kind of method adopting the metals such as sodium, potassium, lithium and hydride process thereof to contain the coarse raw materials of m-pentadiene.Research shows, these treatment condition are comparatively harsh, and treatment temp need be carried out more than each melting point metal, and the m-pentadiene purity obtained is lower, thus makes the number-average molecular weight of the poly-m-pentadiene obtained lower.
Summary of the invention
The object of the invention is in order to the poly-m-pentadiene providing the preparation method of a kind of poly-m-pentadiene, a kind of poly-m-pentadiene and prepared by the method.
The invention provides a kind of poly-m-pentadiene, wherein, the number-average molecular weight of described poly-m-pentadiene is more than 30,000, and molecular weight distribution is less than 1.8.
Present invention also offers a kind of preparation method of poly-m-pentadiene, wherein, the method comprises the following steps:
(1) will containing m-pentadiene and cyclopentadiene and/or C
5the coarse raw materials containing m-pentadiene of alkynes contacts with metal alkoxide, and obtain m-pentadiene raw material, the condition of described contact makes with the gross weight of described m-pentadiene raw material for benchmark, described cyclopentadiene and C
5the total content of alkynes is not higher than 20ppm;
(2) under the existence of initiator and polar modifier, described m-pentadiene raw material is carried out polyreaction in a solvent, obtain number-average molecular weight be more than 30,000 and molecular weight distribution be less than 1.8 poly-m-pentadiene.
In addition, present invention also offers the poly-m-pentadiene prepared by aforesaid method.
The present inventor finds after deep research, cyclopentadiene and C
5the polymerization of alkynes to m-pentadiene has inhibition, therefore, in order to develop the m-pentadiene product with high added value, and must by described containing the cyclopentadiene in the coarse raw materials of m-pentadiene and C
5alkynes is removed.And the present invention adopts metal alkoxide as treatment agent, can not only by the cyclopentadiene in the described coarse raw materials containing m-pentadiene and C on the basis of not reducing m-pentadiene
5alkynes is removed substantially completely, and can not produce adverse influence to m-pentadiene.M-pentadiene raw material after metal alkoxide process can be very well carry out follow-up polyreaction, thus obtain poly-m-pentadiene.In addition, adopt method provided by the invention to process the coarse raw materials containing m-pentadiene, easy and simple to handle, mild condition, has prospects for commercial application.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The number-average molecular weight of poly-m-pentadiene provided by the invention is more than 30,000, is preferably more than 80,000, is more preferably 80,000-50 ten thousand; Molecular weight distribution is less than 1.8, is preferably 1-1.8, is more preferably 1.1-1.6.
According to the present invention, may 1,2-paradigmatic structure unit be contained in described poly-m-pentadiene, also may contain Isosorbide-5-Nitrae-paradigmatic structure unit.Wherein, with the gross weight of described poly-m-pentadiene for benchmark, the content of Isosorbide-5-Nitrae-paradigmatic structure unit is preferably 20-90 % by weight, is more preferably 30-70 % by weight; The content of 1,2-paradigmatic structure unit is preferably 10-80 % by weight, is more preferably 30-70 % by weight.
The preparation method of poly-m-pentadiene provided by the invention comprises the following steps:
(1) will containing m-pentadiene and cyclopentadiene and/or C
5the coarse raw materials containing m-pentadiene of alkynes contacts with metal alkoxide, and obtain m-pentadiene raw material, the condition of described contact makes with the gross weight of described m-pentadiene raw material for benchmark, described cyclopentadiene and C
5the total content of alkynes not higher than 20ppm, preferably not higher than 15ppm;
(2) under the existence of initiator and polar modifier, described m-pentadiene raw material is carried out polyreaction in a solvent, obtain number-average molecular weight be more than 30,000 and molecular weight distribution be less than 1.8 poly-m-pentadiene.
It should be noted that, contain in the coarse raw materials of m-pentadiene simultaneously containing cyclopentadiene and C when described
5during alkynes, described cyclopentadiene and C
5the total content of alkynes refers to content and the C of cyclopentadiene
5the content sum of alkynes; Contain in the coarse raw materials of m-pentadiene only containing cyclopentadiene or C when described
5during alkynes, described cyclopentadiene and C
5the total content of alkynes refers to content or the C of cyclopentadiene
5the content of alkynes.
The present invention is to m-pentadiene, cyclopentadiene and the C in the described coarse raw materials containing m-pentadiene
5the content of alkynes is not particularly limited, and such as, with the gross weight of the described coarse raw materials containing m-pentadiene for benchmark, the described content containing the m-pentadiene in m-pentadiene raw material can be 65-99.8 % by weight, cyclopentadiene and C
5the total content of alkynes can be 0.2-35 % by weight.
In addition, the source of the present invention to the described coarse raw materials containing m-pentadiene is not particularly limited, and is particularly preferably the C that petroleum cracking ethene obtains
5cut, can utilize limited resources so more fully, improves Economic Value Added and the energy utilization rate of product.As a rule, described C
5cut is except containing m-pentadiene and cyclopentadiene and/or C
5outside alkynes, also usually containing cyclopentenes and pentamethylene, and, as a rule, with the gross weight of the described coarse raw materials containing m-pentadiene for benchmark, the described content containing the m-pentadiene in the coarse raw materials of m-pentadiene can be 65-80 % by weight, the content of cyclopentadiene can be 0.1-0.5 % by weight, C
5the content of alkynes can be 0.1-0.5 % by weight, and the content of cyclopentenes can be 10-20 % by weight, and the content of pentamethylene can be 5-15 % by weight.
The condition of the present invention to described contact is not particularly limited, as long as can by described containing the cyclopentadiene in the coarse raw materials of m-pentadiene and C
5alkynes is removed, and as a rule, the condition of described contact comprises Contact Temperature, contact pressure and duration of contact.Wherein, in order to more be conducive to cyclopentadiene and C
5the removal of alkynes, described Contact Temperature is preferably-20 DEG C to 100 DEG C, is more preferably 30-80 DEG C; Described contact pressure is preferably 0-0.3MPa, is more preferably 0-0.1MPa.In the present invention, described pressure all refers to gauge pressure.As well known to those skilled in the art, the boiling point of m-pentadiene is about 42 DEG C, therefore, when Contact Temperature exceedes this boiling point, needs to install reflux additional, or improves contact pressure, in pressure-resistant apparatus, carry out contact reacts.The prolongation of described duration of contact is conducive to improving cyclopentadiene and C
5the clearance of alkynes, but the long raising to above-mentioned clearance amplitude duration of contact not obvious, therefore, consider effect and efficiency, described duration of contact is preferably 0.1-10h, is more preferably 2-5h.
In addition, describedly preferably to carry out under agitation containing the coarse raw materials of m-pentadiene and the contact of metal alkoxide, both contacts can be made so more abundant, and Reaction time shorten.The mode of described stirring can be the routine selection of this area, such as, can adopt magnetic agitation, mechanical stirring, ultrasonic agitation etc.The intensity of described stirring with by mixing of materials evenly for benchmark, can know these those skilled in the art, will repeat no more.
According to the present invention, the kind of described metal alkoxide can be the routine selection of this area, such as, can be one or more in potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium ethylate, sodium tert-butoxide, sodium tert-amyl alcohol and sodium ethylate, be preferably potassium tert.-butoxide and/or tertiary amyl alcohol potassium, more preferably potassium tert.-butoxide.
The consumption of the present invention to described metal alkoxide is not particularly limited, can according to the cyclopentadiene in described m-pentadiene and C
5the content of alkynes is reasonably selected, as a rule, and the mole number of described metal alkoxide and described containing the cyclopentadiene in the coarse raw materials of m-pentadiene and C
5the ratio of the total mole number of alkynes can be 1-10:1, is preferably 1-5:1, so just can ensures described cyclopentadiene and C
5alkynes is removed substantially completely.
According to the present invention, although as long as after the described coarse raw materials containing m-pentadiene is contacted under certain conditions with metal alkoxide, just can by cyclopentadiene wherein and C
5alkynes is removed, but remaining unreacted metal alkoxide also may affect to the follow-up polymerization of m-pentadiene, therefore, in order to improve the purity of m-pentadiene raw material, under preferable case, under the preparation method of poly-m-pentadiene provided by the invention is also included in 0-0.1MPa, distills described containing the coarse raw materials of m-pentadiene and the product of contact of metal alkoxide, and collect the cut of 40-45 DEG C.The method of described distillation is known to the skilled person, and will repeat no more at this.
According to the present invention, described initiator can be the existing various initiator that can cause m-pentadiene polymerization, and can be organic single-lithium initiator usually, it can represent with R ' Li.Wherein, R ' can be alkyl, cycloalkyl or aryl.Consider initiator solvability in a solvent, R ' is preferably C
1-C
10the alkyl of straight or branched.Particularly, the example of organic single-lithium initiator includes but not limited to: one or more in lithium methide, isopropyl lithium, s-butyl lithium, n-Butyl Lithium, cyclohexyl lithium, 4-cyclohexylbutyl lithium, phenyl lithium, trityl group lithium and 2-naphthyl lithium.In addition, consider initiator solvability in a solvent and stability in storage, described initiator is particularly preferably n-Butyl Lithium and/or s-butyl lithium.The molecular size range of the poly-m-pentadiene that the consumption of described initiator can obtain according to the consumption of m-pentadiene raw material and needs is reasonably selected, such as, with the consumption of the described m-pentadiene raw material of 100 weight parts for benchmark, the consumption of described initiator can be 0.3-1.0 weight part, is preferably 0.4-0.6 weight part.
As a rule, the Main Function of described polar modifier is the microtexture regulating poly-m-pentadiene, such as, and the content of 1,2-paradigmatic structure unit and Isosorbide-5-Nitrae-paradigmatic structure unit.In order to make in the poly-m-pentadiene that obtains, the content of Isosorbide-5-Nitrae-paradigmatic structure unit is 20-90 % by weight, is preferably 30-70 % by weight; The content of 1,2-paradigmatic structure unit is 10-80 % by weight, and be preferably 30-70 % by weight, with the described m-pentadiene raw material of 100 weight parts for benchmark, the consumption of described polar modifier is preferably 1-100 weight part, is more preferably 5-70 weight part.In addition, the kind of described polar modifier can be the routine selection of this area, such as, can be one or more in ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium and sodium alkyl benzene sulfonate.
The kind of the present invention to described solvent is not particularly limited, and can be existingly variously to be used as the material of reaction medium, such as, can be one or more in aromatic hydrocarbons, saturated alkane and naphthenic hydrocarbon.Particularly, described solvent can be benzene, toluene, ethylbenzene, dimethylbenzene (comprising o-Xylol, m-xylene and p-Xylol), pentane and isomer (such as: Skellysolve A, iso-pentane, methylcyclopentane, 2-methylpentane and 3-methylpentane) thereof, hexane and isomer (such as: normal hexane, hexanaphthene), heptane and isomer (such as: normal heptane) thereof, octane and isomer (such as: octane) thereof, hexanaphthene and one or more in raffinating oil.As a rule, as long as the consumption of described solvent makes the concentration of m-pentadiene raw material be 10-20 % by weight.
The condition of the present invention to described polyreaction is not particularly limited, and such as, can comprise polymerization temperature and polymerization time.Wherein, described polymerization temperature can be such as 30-100 DEG C, is preferably 50-80 DEG C; Described polymerization time can be such as 0.5-10 hour, is preferably 1-3 hour.In addition, described polyreaction is carried out usually at ambient pressure.
According to the present invention, described polyreaction essence is anionic polymerisation.Therefore, after polymerization was complete, usually also need to adopt various method well known in the art to make reactive polymer inactivation.Such as, living polymer chains can be lost activity by adding terminator in polymerization reaction system.The kind of described terminator can be the routine selection of this area, as long as can make the polymer chain inactivation with active end group.Usually, described terminator can for being selected from water, C
1-C
6fatty alcohol, C
4-C
12aliphatic carboxylic acid, one or more in aryl polyol.Described aryl polyol refers to that the hydrogen atom on phenyl ring has at least two to be optionally substituted by a hydroxyl group generated compound.Preferably, described terminator is one or more in water, methyl alcohol, ethanol, Virahol and 2,6-di-tert-butyl hydroquinone.The consumption of described terminator also can be the routine selection of this area, will repeat no more at this.
The preparation method of poly-m-pentadiene provided by the invention is also included in after termination reaction completes, and adds anti-aging agent, the poly-m-pentadiene obtained can be made like this to have more excellent ageing-resistant performance in polymerization reaction system.The kind of described anti-aging agent can be the routine selection of this area, such as, can be 2, 6-ditertbutylparacresol (trade(brand)name: antioxidant 264), four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (trade(brand)name: anti-aging agent 1010), tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester (trade(brand)name: anti-aging agent 168), 3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl (trade(brand)name: anti-aging agent 1076) and three (nonyl is for phenyl) phosphorous acid ester mixture (trade(brand)name: anti-aging agent TNPP) in one or more.In addition, the consumption of described anti-aging agent can be the routine selection of this area, will repeat no more at this.
Present invention also offers the poly-m-pentadiene prepared by aforesaid method.
Below will be described the present invention by embodiment.
Following preparation example is with in contrast preparation example, and the composition of m-pentadiene raw material that the pending coarse raw materials containing m-pentadiene and process obtain and the content of each component all adopt gas chromatograph (purchased from Japanese Shimadzu Corporation, model is GC1609) to analyze.Wherein, instrument parameter is as follows: quartz capillary column, long is 60m, and internal diameter is 0.32, and thickness of liquid film is 1.0 μm, liquid film is PHENYL-METHYL-siloxane polymer, splitting ratio is 50:1, and vaporizer temperature is 260 DEG C, and hydrogen flame detector temperature is 260 DEG C, column temperature: 35 DEG C continue to be warmed up to 185 DEG C with 10 DEG C/min after 20 minutes, and carrier gas is high pure nitrogen.
Following preparation example is with in contrast preparation example, and the pending coarse raw materials containing m-pentadiene is the C that petroleum cracking ethene obtains
5cut, it is composed as follows: with the gross weight of the described coarse raw materials containing m-pentadiene for benchmark, the content of trans-m-pentadiene is 42.14 % by weight, and the content of cis-form m-pentadiene is 25.14 % by weight, and the content of isoprene is 0.04 % by weight, C
5the content of alkynes is 0.21 % by weight, and the content of cyclopentadiene is 0.39 % by weight, and the content of cyclopentenes is 19.19 % by weight, and the content of pentamethylene is 8.18 % by weight, and the content of other cuts is 4.71 % by weight.
In following examples and comparative example, number-average molecular weight and molecular weight distributing index adopt the TDA302 type gel permeation chromatograph (GPC) of Viscotek company of the U.S. to measure, THF is moving phase, flow velocity is 1.0mL/min, test sample concentration is 2-3mg/mL, take Narrow distribution polystyrene as standard specimen, probe temperature is 25 DEG C.Micmstructure of polymer adopts US Varian INOVA400NMR nuclear magnetic resonance spectrometer to measure.
Preparation example 1
This preparation example is for illustration of the preparation method of m-pentadiene raw material provided by the invention.
By coarse raw materials (cyclopentadiene and the C of 100g containing m-pentadiene
5the total mole number of alkynes is 8.99mmol) and 1.2g(10.69mmol) potassium tert.-butoxide mix, and temperature be 30 DEG C, gauge pressure reacts 2h under being 0MPa, obtain reaction product, then carry out air distillation, and collect the cut of 40-45 DEG C, obtain m-pentadiene raw material Y1.Carry out gas chromatographic analysis to m-pentadiene raw material Y1, result is as shown in table 1.
Preparation example 2
This preparation example is for illustration of the preparation method of m-pentadiene raw material provided by the invention.
By coarse raw materials (cyclopentadiene and the C of 100g containing m-pentadiene
5the total mole number of alkynes is 8.99mmol) and 2.1g(18.71mmol) potassium tert.-butoxide mix, and temperature be 50 DEG C, gauge pressure reacts 3h under being 0.1MPa, obtain reaction product, then carry out air distillation, and collect the cut of 40-45 DEG C, obtain m-pentadiene raw material Y2.Carry out gas chromatographic analysis to m-pentadiene raw material Y2, result is as shown in table 1.
Preparation example 3
This preparation example is for illustration of the preparation method of m-pentadiene raw material provided by the invention.
By coarse raw materials (cyclopentadiene and the C of 100g containing m-pentadiene
5the total mole number of alkynes is 8.99mmol) and 3.0g(26.74mmol) potassium tert.-butoxide mix, and temperature be 30 DEG C, gauge pressure reacts 2h under being 0.05MPa, obtain reaction product, then carry out air distillation, and collect the cut of 40-45 DEG C, obtain m-pentadiene raw material Y3.Carry out gas chromatographic analysis to m-pentadiene raw material Y3, result is as shown in table 1.
Preparation example 4
This preparation example is for illustration of the preparation method of m-pentadiene raw material provided by the invention.
By coarse raw materials (cyclopentadiene and the C of 100g containing m-pentadiene
5the total mole number of alkynes is 8.99mmol) and 2.1g(18.71mmol) potassium tert.-butoxide mix, and temperature be 30 DEG C, gauge pressure reacts 5h under being 0MPa, obtain reaction product, then carry out air distillation, and collect the cut of 40-45 DEG C, obtain m-pentadiene raw material Y4.Carry out gas chromatographic analysis to m-pentadiene raw material Y4, result is as shown in table 1.
Preparation example 5
This preparation example is for illustration of the preparation method of m-pentadiene raw material provided by the invention.
By coarse raw materials (cyclopentadiene and the C of 100g containing m-pentadiene
5the total mole number of alkynes is 8.99mmol) and 1.2g potassium tert.-butoxide (10.69mmol) mix, and temperature be 80 DEG C, gauge pressure reacts 2h under being 0.05MPa, obtain reaction product, then carry out air distillation, and collect the cut of 40-45 DEG C, obtain m-pentadiene raw material Y5.Carry out gas chromatographic analysis to m-pentadiene raw material Y5, result is as shown in table 1.
Preparation example 6
This preparation example is for illustration of the preparation method of m-pentadiene raw material provided by the invention.
By coarse raw materials (cyclopentadiene and the C of 100g containing m-pentadiene
5the total mole number of alkynes is 8.99mmol) and 1.2g potassium tert.-butoxide (10.69mmol) mix, and temperature be 80 DEG C, gauge pressure reacts 5h under being 0.1MPa, obtain reaction product, then carry out air distillation, and collect the cut of 40-45 DEG C, obtain m-pentadiene raw material Y6.Carry out gas chromatographic analysis to m-pentadiene raw material Y6, result is as shown in table 1.
Table 1
Embodiment 1
This embodiment is for illustration of poly-m-pentadiene provided by the invention and preparation method thereof.
In 5L stainless steel polymeric kettle, (weight ratio is 1:1 to add 2500g hexanaphthene/hexane mixed solvent, down together), m-pentadiene raw material Y1,152mg tetrahydrofurfuryl alcohol ether (ETE after 540g purifying, lower same), open stirring, controlling stirring velocity is 180 revs/min, and water bath with thermostatic control is heated, when polymerization temperature in the kettle reaches 80 DEG C, in polymeric kettle, add 4mmol n-Butyl Lithium.React 1.5h at 80 DEG C after, add 0.3g Virahol termination reaction, then add 1.1g anti-aging agent 1010, then the glue obtained is adopted Wet agglomeration process, finally use number-average molecular weight and the molecular weight distributing index of High Performance Gel Permeation chromatogram test polymer.Result is as shown in table 2.
Embodiment 2
This embodiment is for illustration of poly-m-pentadiene provided by the invention and preparation method thereof.
In 5L stainless steel polymeric kettle, add m-pentadiene raw material Y2,152mg tetrahydrofurfuryl alcohol ether after 2500g hexanaphthene/hexane mixed solvent, 540g purifying, open stirring, controlling stirring velocity is 180 revs/min, water bath with thermostatic control is heated, when polymerization temperature in the kettle reaches 60 DEG C, in polymeric kettle, add 4mmol n-Butyl Lithium.React 0.5h at 60 DEG C after, add 0.3g Virahol termination reaction, add 1.1g anti-aging agent 1010, then the glue obtained is adopted Wet agglomeration process, finally use number-average molecular weight and the molecular weight distributing index of High Performance Gel Permeation chromatogram test polymer.Result is as shown in table 2.
Embodiment 3
This embodiment is for illustration of poly-m-pentadiene provided by the invention and preparation method thereof.
In 5L stainless steel polymeric kettle, add m-pentadiene raw material Y3,1510mg tetrahydrofurfuryl alcohol ether after 2500g hexanaphthene/hexane mixed solvent, 540g purifying, open stirring, controlling stirring velocity is 180 revs/min, water bath with thermostatic control is heated, when polymerization temperature in the kettle reaches 50 DEG C, in polymeric kettle, add 4mmol n-Butyl Lithium.React 3h at 50 DEG C after, add 0.3g Virahol termination reaction, then add 1.1g anti-aging agent 1010, then the glue obtained is adopted Wet agglomeration process, finally use number-average molecular weight and the molecular weight distributing index of High Performance Gel Permeation chromatogram test polymer.Result is as shown in table 2.
Embodiment 4
This embodiment is for illustration of poly-m-pentadiene provided by the invention and preparation method thereof.
In 5L stainless steel polymeric kettle, add m-pentadiene raw material Y4,831mg tetrahydrofurfuryl alcohol ether after 2500g hexanaphthene/hexane mixed solvent, 540g purifying, open stirring, controlling stirring velocity is 180 revs/min, water bath with thermostatic control is heated, when polymerization temperature in the kettle reaches 80 DEG C, in polymeric kettle, add 4mmol n-Butyl Lithium.React 1.0h at 80 DEG C after, add 0.3g Virahol termination reaction, then add 1.1g anti-aging agent 1010, then the glue obtained is adopted Wet agglomeration process, finally use number-average molecular weight and the molecular weight distributing index of High Performance Gel Permeation chromatogram test polymer.Result is as shown in table 2.
Embodiment 5
This embodiment is for illustration of poly-m-pentadiene provided by the invention and preparation method thereof.
In 5L stainless steel polymeric kettle, add m-pentadiene raw material Y5,1510mg tetrahydrofurfuryl alcohol ether after 2500g hexanaphthene/hexane mixed solvent, 540g purifying, open stirring, controlling stirring velocity is 180 revs/min, water bath with thermostatic control is heated, when polymerization temperature in the kettle reaches 80 DEG C, in polymeric kettle, add 4mmol n-Butyl Lithium.React 0.5h at 80 DEG C after, add 0.3g Virahol termination reaction, then add 1.1g anti-aging agent 1010, then the glue obtained is adopted Wet agglomeration process, finally use number-average molecular weight and the molecular weight distributing index of High Performance Gel Permeation chromatogram test polymer.Result is as shown in table 2.
Embodiment 6
This embodiment is for illustration of poly-m-pentadiene provided by the invention and preparation method thereof.
In 5L stainless steel polymeric kettle, add m-pentadiene raw material Y6,152mg tetrahydrofurfuryl alcohol ether after 2500g hexanaphthene/hexane mixed solvent, 540g purifying, open stirring, controlling stirring velocity is 180 revs/min, water bath with thermostatic control is heated, when polymerization temperature in the kettle reaches 50 DEG C, in polymeric kettle, add 4mmol n-Butyl Lithium.React 0.5h at 50 DEG C after, add 0.3g Virahol termination reaction, then add 1.1g anti-aging agent 1010, then the glue obtained is adopted Wet agglomeration process, finally use number-average molecular weight and the molecular weight distributing index of High Performance Gel Permeation chromatogram test polymer.Result is as shown in table 2.
Comparative example 1
This comparative example is for illustration of the poly-m-pentadiene and preparation method thereof of reference.
According to the poly-m-pentadiene of method preparation of embodiment 3, unlike, the undressed coarse raw materials containing m-pentadiene of the m-pentadiene raw material Y3 identical weight part after purifying substitutes.Result is as shown in table 2.
Table 2
As can be seen from the above results, method provided by the invention is adopted to process the coarse raw materials containing m-pentadiene, can by cyclopentadiene wherein and C
5alkynes is removed well, and m-pentadiene does not almost lose.M-pentadiene raw material after metal alkoxide process can be very well carry out follow-up polyreaction, thus obtain poly-m-pentadiene.In addition, adopt method provided by the invention to process the coarse raw materials containing m-pentadiene, easy and simple to handle, mild condition, has prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. a poly-m-pentadiene, is characterized in that, the number-average molecular weight of described poly-m-pentadiene is more than 30,000, and molecular weight distribution is less than 1.8.
2. poly-m-pentadiene according to claim 1, wherein, the number-average molecular weight of described poly-m-pentadiene is more than 80,000, is preferably 80,000-50 ten thousand; Molecular weight distribution is 1-1.8, is preferably 1.1-1.6.
3. poly-m-pentadiene according to claim 1 and 2, wherein, with the gross weight of described poly-m-pentadiene for benchmark, the content of Isosorbide-5-Nitrae-paradigmatic structure unit is 20-90 % by weight, is preferably 30-70 % by weight; The content of 1,2-paradigmatic structure unit is 10-80 % by weight, is preferably 30-70 % by weight.
4. a preparation method for poly-m-pentadiene, wherein, the method comprises the following steps:
(1) will containing m-pentadiene and cyclopentadiene and/or C
5the coarse raw materials containing m-pentadiene of alkynes contacts with metal alkoxide, and obtain m-pentadiene raw material, the condition of described contact makes with the gross weight of described m-pentadiene raw material for benchmark, described cyclopentadiene and C
5the total content of alkynes is not higher than 20ppm;
(2) under the existence of initiator and polar modifier, described m-pentadiene raw material is carried out polyreaction in a solvent, obtain number-average molecular weight be more than 30,000 and molecular weight distribution be less than 1.8 poly-m-pentadiene.
5. preparation method according to claim 4, wherein, with the gross weight of the described coarse raw materials containing m-pentadiene for benchmark, the described content containing the m-pentadiene in the coarse raw materials of m-pentadiene is 65-99.8 % by weight, cyclopentadiene and C
5the total content of alkynes is 0.2-35 % by weight.
6. preparation method according to claim 4, wherein, described containing in the coarse raw materials of m-pentadiene also contains cyclopentenes and pentamethylene; And with the gross weight of the described coarse raw materials containing m-pentadiene for benchmark, the described content containing the m-pentadiene in the coarse raw materials of m-pentadiene is 65-80 % by weight, and the content of cyclopentadiene is 0.1-0.5 % by weight, C
5the content of alkynes is 0.1-0.5 % by weight, and the content of cyclopentenes is 10-20 % by weight, and the content of pentamethylene is 5-15 % by weight.
7. preparation method according to claim 6, wherein, the described coarse raw materials containing m-pentadiene is the C that petroleum cracking ethene obtains
5cut.
8. according to the preparation method in claim 4-7 described in any one, wherein, the condition of described contact comprises: Contact Temperature is-20 DEG C to 100 DEG C, is preferably 30-80 DEG C; Contact pressure is 0-0.3MPa, is preferably 0-0.1MPa; The time of contact is 0.1-10h, is preferably 2-5h.
9. the cyclopentadiene according to the preparation method in claim 4-7 described in any one, wherein, in the mole number of described metal alkoxide and the described coarse raw materials containing m-pentadiene and C
5the ratio of the total mole number of alkynes is 1-10:1, is preferably 1-5:1.
10. according to the preparation method in claim 4-7 described in any one, wherein, described metal alkoxide is one or more in potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium ethylate, sodium tert-butoxide, sodium tert-amyl alcohol and sodium ethylate, is preferably potassium tert.-butoxide and/or tertiary amyl alcohol potassium, is more preferably potassium tert.-butoxide.
11. according to the preparation method in claim 4-7 described in any one, wherein, under the method is also included in 0-0.1MPa, distills, and collect the cut of 40-45 DEG C by described containing the coarse raw materials of m-pentadiene and the product of contact of metal alkoxide.
12. according to the preparation method in claim 4-7 described in any one, and wherein, the condition of described polyreaction comprises: polymerization temperature is 30-100 DEG C, and polymerization time is 0.5-10 hour.
13. according to the preparation method in claim 4-7 described in any one, wherein, described polar modifier is one or more in ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium and sodium alkyl benzene sulfonate.
The 14. poly-m-pentadienes prepared by the method in claim 4-13 described in any one.
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