CN110256618A - A kind of poly- pentadiene and its preparation method and application of cis- -1,4 structure - Google Patents
A kind of poly- pentadiene and its preparation method and application of cis- -1,4 structure Download PDFInfo
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Abstract
A kind of poly- pentadiene of cis--Isosorbide-5-Nitrae structure, it is characterised in that: cis- in the poly- pentadiene-Isosorbide-5-Nitrae structural content is not less than 70%, and the number-average molecular weight Mn of the poly- pentadiene is 100,000~1,000,000, and molecular weight distribution Pd is 1.4~4.0.The invention also discloses the preparation method and application of above-mentioned poly- pentadiene.Compared with prior art, formula of the invention is simple, convenient to carry out；Poly- pentadiene molecular weight obtained is high, molecular configuration is regular and cis-content is high.
Description
Technical field
The invention belongs to high polymer synthesis technical fields, and in particular to a kind of poly- pentadiene of cis--Isosorbide-5-Nitrae structure and its
Preparation method and application.
Background technique
By-product and petroleum refinery catalytic cracking of light dydrocarbon (C5) fraction mainly from petroleum through Pintsch process process of producing ethylene
Device.The alkene in C 5 fraction that refinery catalytic cracking device comes is mainly monoolefine, and higher group is worth in chemical utilization
It is divided into iso-amylene.The by-product C 5 fraction of cracking ethylene preparation process, generally can be using rough segmentation as two major classes: one kind be active component, main
It to include isoprene (ISP), cyclopentadiene (CPD) (usually with the form presence of dimer cyclopentadiene (DCPD)), penta
Diene (PIP) and iso-amylene, 1- amylene；Another kind of is inactive ingredients, mainly there is pentane, isopentane and pentamethylene.Wherein
For diolefin due to special molecular structure, chemical property is active, is the important industrial chemicals of most utility value.
Pentadiene can also separate ring penta by hot dimerization method by obtaining when extraction fractional distillation separating isoprene
It is obtained again through conventional distillation after diene.When using extraction fractional distillation, mainly by pre- weight-removing column and weight-removing column rectifying after, tower bottom weight
Group dispensing to pentadiene treating column obtains the coarse piperyene that purity (W) is 70%~80%, carries out again to coarse piperyene
Rectifying can be obtained the pentadiene product that purity (W) is 90%~99%.It is remaining after using hot dimerization method separating cyclopentadiene
Under C 5 fraction carry out again rectifying can get purity be 50% or more pentadiene product.Patent No.
(Authorization Notice No. is a kind of Chinese invention patent " trans- penta 2 dilute production methods of high-purity " of ZL201310078807.2
CN103145523B a kind of method that high-purity pentadiene monomer can be made) is provided, the orientation to realize pentadiene is poly-
Merge and obtains the possibility for the raw material sources that heavy polymer provides acquisition qualification.
The main application of country's pentadiene has at present: (1) manufacturing higher aliphatic Petropols, this kind of resin usually has
There is of light color, density low and the characteristics such as saturation degree is high, is widely used in adhesive, hot melt road marking paint, coating, ink, rubber and helps
The industries such as agent；(2) extraordinary fine chemical product is produced, such as epoxy curing agent, alkyd resin, printing ink, fragrance, insatiable hunger
With alcohol and ester etc..
The correlative study of related pentadiene polymerization is confined to obtain the pentadiene petroleum of various low molecular weights more at present
Resin has on a small quantity about the research for preparing poly- pentadiene rubber, the research of m-pentadiene petro-resin such as application No. is
CN201410512124.8 Chinese invention patent application " it is a kind of light color between penta Petropols manufacturing method " (application publication number
A kind of method for obtaining Petropols using current domestic industry pentadiene product is provided for CN104292390A).It should
Invention is only capable of polymerizeing to obtain the lower sticky m-pentadiene petro-resin of molecular weight by non-directional, cannot polymerize to obtain macromolecule
Amount, the poly- pentadiene product of high cis-1,4-structural content.
The Chinese invention patent of the research of poly- pentadiene rubber such as Patent No. ZL201310425930.7 is " between one kind is poly-
Pentadiene and preparation method thereof and vulcanizate " (Authorization Notice No. CN104448085B) provide it is a kind of using rare earth catalyst
Obtain the preparation method of poly- pentadiene of the weight average molecular weight greater than 500,000.Cis--the 1,4 of the poly- pentadiene that this method obtains
Structural content is only 60% or more.
A kind of for another example Chinese invention patent " rare-earth catalysis system and its preparation side of Patent No. ZL201310615623.5
Method and poly- pentadiene preparation method " (Authorization Notice No. CN103709295B) provide it is a kind of using rare earth catalyst prepare
The method of poly- pentadiene.Cis- -1,4 structural content for the poly- pentadiene that this method obtains is no more than 60%.
It is above-mentioned it is poly- between penta 2 dilute rubber research in be all made of rare earth catalyst prepare it is poly- between it is penta 2 dilute, it is considered that,
In coordination catalyst systems (iron series, cobalt system, nickel system, titanium system, Rare Earth etc.), titanium system and Rare Earth can be oriented more effectively
Polymerization, and it is higher to obtain structural regularity, the i.e. higher polymer of cis-content.
Summary of the invention
First technical problem to be solved by this invention is the status for the prior art, provide a kind of molecular weight it is high,
The poly- pentadiene for cis- -1,4 structure that molecular configuration is regular and cis-content is high.
Second technical problem to be solved by this invention is the status for the prior art, provide it is a kind of it is above-mentioned it is cis--
The preparation method of the poly- pentadiene of 1,4 structures.
Third technical problem to be solved by this invention is the status for the prior art, provide it is a kind of it is above-mentioned it is cis--
The application of the poly- pentadiene of 1,4 structures.
The present invention solves technical solution used by above-mentioned first technical problem are as follows: a kind of cis- -1,4 structure it is poly- between
Pentadiene, it is characterised in that: cis- in the poly- pentadiene-Isosorbide-5-Nitrae structural content is not less than 70%, and the number of the poly- pentadiene is equal
Molecular weight Mn is 100,000~1,000,000, and molecular weight distribution Pd is 1.4~4.0.
As an improvement, cis- in the poly- pentadiene-Isosorbide-5-Nitrae structural content is not less than 85%.
The present invention solves technical solution used by above-mentioned second technical problem are as follows: a kind of as described above cis- -1,4
The preparation method of the poly- pentadiene of structure, it is characterised in that step are as follows:
In the presence of complex catalyst and the first organic solvent, by purity be 65%~99.5% (preferably 90%~
99.5%) pentadiene monomer carries out polymerization reaction and obtains poly- pentadiene, and the temperature of polymerization reaction is 0 DEG C~100 DEG C, when
Between be 0.1h~20h；The mass ratio of first organic solvent and pentadiene monomer is 0~20:1 (when organic molten first
When implementing polymerization in agent, the mass ratio of pentadiene monomer and the first organic solvent is preferably 1:9~1:4)；
The complex catalyst includes transistion metal compound, alkyl metal cpd, electron donor；The alkyl gold
The molar ratio for belonging to compound and electron donor is 1:0.1~1:10；The alkyl metal cpd and transistion metal compound
Molar ratio is 1:1~1000:1；
The complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, will first under the conditions of 0 DEG C~20 DEG C
Electron donor is added in advance in the good transistion metal compound of the second organic solvent diluting, is uniformly mixed, is mixed
Close object；Again under the conditions of -20 DEG C~20 DEG C, said mixture is added to alkyl gold good with the second organic solvent diluting in advance
Belong to and being complexed in compound, 30min~300min is then aged under the conditions of 10 DEG C~25 DEG C, obtains complex catalyst；
First organic solvent includes at least one of fat hydrocarbon solvent, aromatic hydrocarbon solvent；Described second has
Solvent includes at least one of fat hydrocarbon solvent, aromatic hydrocarbon solvent.
Preferably, the transistion metal compound is chloride, bromide, iodide, the oxygen of transition metals cobalt or nickel
Chloride, acetylacetonate, diacetyl acetone solvate, cyclopentadienyl group chloride, bicyclic pentadiene chloride, carboxylic acid
One of salt, phosphate, phosphite, nitrate, nitrite, sulfate, alkoxide.Even more preferably, the transition gold
Belong to the diacetyl acetone solvate that compound is transition metals cobalt or nickel.
Preferably, the alkyl metal cpd include triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium,
Diethylaluminum hydride, dibutyl aluminum hydride, diisobutyl aluminium hydride, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, Dichloroethyl
At least one of aluminium, a chlorine isobutylaluminiumhydride.Even more preferably, the alkyl metal cpd is ethyl aluminum dichloride.
Preferably, the electron donor is Lewis alkali, including pyridine, isoquinolin, thiophene, furans, tetrahydrofuran, two
At least one of ethylether, diethyl sulfide, trialkylamine.Even more preferably, the electron donor is anhydrous pyridine.
In the above scheme, the pentadiene monomer is the mixed of cis-form m-pentadiene monomer and trans-m-pentadiene monomer
Object is closed, the content of the trans-m-pentadiene monomer is 60%~100%.
As an improvement, the fat hydrocarbon solvent includes pentane, pentamethylene, methyl cyclopentane, n-hexane, hexamethylene, heptan
At least one of alkane, octane, isooctane, nonane, decane, hendecane, 12 carbon alkane and its isomer；The aromatic hydrocarbons
Class solvent is at least one of benzene,toluene,xylene, trimethylbenzene and its isomer.
The temperature of the polymerization reaction is preferably 0 DEG C~60 DEG C, and the time is preferably 0.5h~5h.
The present invention solves technical solution used by above-mentioned third technical problem are as follows: a kind of as described above cis- -1,4
The poly- pentadiene of structure is in the application for preparing rubber type of material.
Compared with the prior art, the advantages of the present invention are as follows: the complex catalyst that the present invention uses includes transition metal
Compound, alkyl metal cpd, electron donor, the catalyst system and reported catalyst system are different, formula letter
It is single, it is convenient to carry out；
According to the present invention, not special to the dosage of the catalyst when implementing polymerization reaction to pentadiene monomer
Limitation；
Under complex catalyst effect used in specially inventing at this, pentadiene monomer can be oriented polymerization, obtain suitable
Formula-Isosorbide-5-Nitrae content is not less than 70%, and the poly- pentadiene that number-average molecular weight is higher, molecular configuration is regular, and the polymer is through using
Natural rubber or the commonly used formula of isoprene rubber vulcanization can be used as rubber type of material with after technique vulcanization.It is with excellent
The mechanical properties such as different elastic, lesser permanent deformation and good tensile strength, elongation at break are and previous sticky, low
The m-pentadiene petro-resin of molecular weight have apparent performance difference, can be widely used for tread rubber, rubber product, adhesive,
The fields such as footwear material, medical supplies；
And polymerization reaction of the invention can carry out under the first organic solvent, can also implement without using the first organic solvent
Polymerization reaction.Reason is complex catalyst with the initial contact phase of pentadiene monomer, since system viscosity is low, is catalyzed
Agent can sufficiently be uniformly dispersed in pentadiene monomer.Due to the present invention without using the first organic solvent also can be implemented it is poly-
It closes, so that energy consumption needed for removing solvent and solvent circulation purification can be reduced in industrialization, and to the molecule of optimization polymer
Amount and cis-structure have no significant effect.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
Embodiment 1:
To with the following substance measured is added in the 100ml reaction kettle that nitrogen is replaced and is full of:
First organic solvent (selects dry toluene, certainly also 50ml in the present embodiment
It is other that benzene, dimethylbenzene, trimethylbenzene and its isomer etc. can be selected
Aromatic hydrocarbon solvent)；
Complex catalyst； 1.2ml
(trans-m-pentadiene monomer contains 15ml to the pentadiene monomer that purity is 95%
Amount 97%~98%)；
Wherein, the composition of complex catalyst is as follows:
Alkyl metal cpd (selects ethyl aluminum dichloride, works as 0.9ml in the present embodiment
Triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three different so also can be selected
Butyl aluminium, diethylaluminum hydride, dibutyl aluminum hydride, diisobutyl
Aluminum hydride, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, a chlorine are different
Butyl aluminum hydride etc.)；
Electron donor (selects thiophene, different 0.3ml also can be selected certainly in the present embodiment
Quinoline, tetrahydrofuran, Anaesthetie Ether, diethyl sulfide, trialkylamine
Etc. other Lewis alkali)；
Transistion metal compound (selects diacetyl acetonation cobalt, 0.0026g in the present embodiment
Certainly also can be selected the chloride of cobalt or nickel, bromide, iodide,
It is oxychlorination things, acetylacetonate, cyclopentadienyl group chloride, double
Cyclopentadienyl group chloride, carboxylate, phosphate, phosphite,
Nitrate, nitrite, sulfate, alkoxide etc.)；
Complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first under the conditions of 18 DEG C, by electron donor
It is added in the transistion metal compound diluted in advance with the second organic solvent (selecting n-hexane), is uniformly mixed, obtains
To mixture；Again under the conditions of -12 DEG C, said mixture is added to metal alkyl good with the second organic solvent diluting in advance
It is complexed in compound, is then aged 100min under the conditions of 18 DEG C, obtains complex catalyst；
Cis- -1,4 structure it is poly- between penta 2 it is dilute the preparation method comprises the following steps:
Under agitation, material in kettle is kept to be reacted at 0 DEG C, when reaction a length of 10h.Then it is added into kettle
A little methanol terminates polymerization reaction.Discharging, and excessive methanol, which is added, is precipitated poly- pentadiene from solvent, then uses
Water cleaning cleaning polyalcohol, is finally dried in vacuo and is down to room temperature.
Weighing, obtains the poly- pentadiene product of 7.8g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content is 87%.
It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 580,000, and molecular weight distribution Pd is 2.8.
Embodiment 2:
To with the following substance measured is added in the 100ml reaction kettle that nitrogen is replaced and is full of:
First organic solvent (selects dry toluene)； 70ml
Complex catalyst； 1.55ml
(trans-m-pentadiene monomer contains 15ml to the pentadiene monomer that purity is 95%
Amount 97%~98%)；
Wherein, the composition of complex catalyst is as follows:
Alkyl metal cpd (selects ethyl aluminum dichloride)； 1.05ml
Electron donor (selects anhydrous pyridine)； 0.50ml
Transistion metal compound (selects diacetyl acetonation cobalt)； 0.0028g
Complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first under the conditions of 16 DEG C, by electron donor
It is added in the transistion metal compound diluted in advance with the second organic solvent (selecting n-hexane), is uniformly mixed, obtains
To mixture；Again under the conditions of -12 DEG C, said mixture is added to metal alkyl good with the second organic solvent diluting in advance
It is complexed in compound, is then aged 200min under the conditions of 18 DEG C, obtains complex catalyst；
Cis- -1,4 structure it is poly- between penta 2 it is dilute the preparation method comprises the following steps:
Under agitation, material in kettle is kept to be reacted at 0 DEG C, when reaction a length of 12h.Then it is added into kettle
A little methanol terminates polymerization reaction.Discharging, and excessive methanol, which is added, is precipitated poly- pentadiene from solvent, then uses
Water cleaning cleaning polyalcohol, is finally dried in vacuo and is down to room temperature.
Weighing, obtains the poly- pentadiene product of 8.5g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content is 90%.
It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 620,000, and molecular weight distribution Pd is 2.0.
Embodiment 3:
To with the following substance measured is added in the 100ml reaction kettle that nitrogen is replaced and is full of:
First organic solvent (selects dry toluene)； 60ml
Complex catalyst； 1.33ml
(trans-m-pentadiene monomer contains 16ml to the pentadiene monomer that purity is 95%
Amount 97%~98%)；
Wherein, the composition of complex catalyst is as follows:
Alkyl metal cpd (selects ethyl aluminum dichloride)； 1.00ml
Electron donor (selects thiophene)； 0.33ml
Transistion metal compound (selects cobaltous octadecanate)； 0.026g
Complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first under the conditions of 15 DEG C, by electron donor
It is added in the transistion metal compound diluted in advance with the second organic solvent (selecting n-hexane), is uniformly mixed, obtains
To mixture；Again under the conditions of -10 DEG C, said mixture is added to metal alkyl good with the second organic solvent diluting in advance
It is complexed in compound, is then aged 260min at 20 °C, obtain complex catalyst；
Cis- -1,4 structure it is poly- between penta 2 it is dilute the preparation method comprises the following steps:
Under agitation, material in kettle is kept to be reacted at 18 DEG C, when reaction a length of 5h.Then it is added into kettle
A little methanol terminates polymerization reaction.Discharging, and excessive methanol, which is added, is precipitated poly- pentadiene from solvent, then uses
Water cleaning cleaning polyalcohol, is finally dried in vacuo and is down to room temperature.
Weighing, obtains the poly- pentadiene product of 8.7g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content is 79%.
It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 600,000, and molecular weight distribution Pd is 3.4.
Embodiment 4:
To with the following substance measured is added in the 50ml reaction kettle that nitrogen is replaced and is full of:
First organic solvent (selects dry toluene)； 25ml
Complex catalyst； 1.40ml
(trans-m-pentadiene monomer contains 8ml to the pentadiene monomer that purity is 90%
Amount 97%~98%)；
Wherein, the composition of complex catalyst is as follows:
Alkyl metal cpd (selects ethyl aluminum dichloride)； 0.60ml
Electron donor (selects thiophene)； 0.80ml
Transistion metal compound (selects diacetyl acetonation cobalt)； 0.0020g
Complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first under the conditions of 16 DEG C, by electron donor
It is added in the transistion metal compound diluted in advance with the second organic solvent (selecting hexamethylene), is uniformly mixed, obtains
To mixture；Again under the conditions of -12 DEG C, said mixture is added to metal alkyl good with the second organic solvent diluting in advance
It is complexed in compound, is then aged 30min under the conditions of 22 DEG C, obtains complex catalyst；
Cis- -1,4 structure it is poly- between penta 2 it is dilute the preparation method comprises the following steps:
Under agitation, material in kettle is kept to be reacted at 25 DEG C, when reaction a length of 5h.Then it is added into kettle
A little methanol terminates polymerization reaction.Discharging, and excessive methanol, which is added, is precipitated poly- pentadiene from solvent, then uses
Water cleaning cleaning polyalcohol, is finally dried in vacuo and is down to room temperature.
Weighing, obtains the poly- pentadiene product of 4.5g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content is 84%.
It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 630,000, and molecular weight distribution Pd is 2.8.
Embodiment 5:
To with the following substance measured is added in the 50ml reaction kettle that nitrogen is replaced and is full of:
First organic solvent (selects dry toluene)； 50ml
Complex catalyst； 0.55ml
(trans-m-pentadiene monomer contains 15ml to the pentadiene monomer that purity is 95%
Amount 97%~98%)；
Wherein, the composition of complex catalyst is as follows:
Alkyl metal cpd (selects ethyl aluminum dichloride)； 0.40ml
Electron donor (selects anhydrous pyridine)； 0.15ml
Transistion metal compound (selects diacetyl acetonation nickel)； 0.0060g
Complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first under the conditions of 16 DEG C, by electron donor
It is added in the transistion metal compound diluted in advance with the second organic solvent (selecting hexamethylene), is uniformly mixed, obtains
To mixture；Again under the conditions of -12 DEG C, said mixture is added to metal alkyl good with the second organic solvent diluting in advance
It is complexed in compound, is then aged 120min under the conditions of 18 DEG C, obtains complex catalyst；
Cis- -1,4 structure it is poly- between penta 2 it is dilute the preparation method comprises the following steps:
Under agitation, material in kettle is kept to be reacted at 25 DEG C, when reaction a length of 10h.Then add into kettle
Enter a little methanol to terminate polymerization reaction.Discharging, and excessive methanol, which is added, is precipitated poly- pentadiene from solvent, then
Polymer is washed with water, is finally dried in vacuo and is down to room temperature.
Weighing, obtains the poly- pentadiene product of 7.8g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content is 81%.
It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 600,000, and molecular weight distribution Pd is 2.2.
Embodiment 6:
To with the following substance measured is added in the 50ml reaction kettle that nitrogen is replaced and is full of:
First organic solvent (pentane is selected in the present embodiment, it certainly can also 50ml
Select methyl cyclopentane, hexane, hexamethylene, heptane, octane, different
Other fat hydrocarbon solvents such as octane, nonane, decane)；
Complex catalyst； 0.55ml
(trans-m-pentadiene monomer contains 15ml to the pentadiene monomer that purity is 90%
Amount 97%~98%)；
Wherein, the composition of complex catalyst is as follows:
Alkyl metal cpd (selects ethyl aluminum dichloride)； 0.40ml
Electron donor (selects anhydrous pyridine)； 0.15ml
Transistion metal compound (selects nickel stearate)； 0.0060g
Complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first under the conditions of 14 DEG C, by electron donor
It is added in the transistion metal compound diluted in advance with the second organic solvent (selecting n-hexane), is uniformly mixed, obtains
To mixture；Again under the conditions of -10 DEG C, said mixture is added to metal alkyl good with the second organic solvent diluting in advance
It is complexed in compound, is then aged 180min under the conditions of 19 DEG C, obtains complex catalyst；
Cis- -1,4 structure it is poly- between penta 2 it is dilute the preparation method comprises the following steps:
Under agitation, material in kettle is kept to be reacted at 25 DEG C, when reaction a length of 10h.Then add into kettle
Enter a little methanol to terminate polymerization reaction.Discharging, and excessive methanol, which is added, is precipitated poly- pentadiene from solvent, then
Polymer is washed with water, is finally dried in vacuo and is down to room temperature.
Weighing, obtains the poly- pentadiene product of 8.0g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content is 79%.
It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 640,000, and molecular weight distribution Pd is 3.2.
Embodiment 7:
100.0 parts of obtained poly- pentadiene products of (mass parts, similarly hereinafter) embodiment 2 are being opened together with further auxiliary
It is blended in mill:
Said mixture is vulcanized 40 minutes under the conditions of 150 DEG C, the mechanical property of obtained rubbery state sulfur product is surveyed
Test result is as follows:
Embodiment 8:
On the basis of the sulfurizing formula of embodiment 7,40 parts of carbon blacks (N330) are added.Blending on a mill is obtained
Mixture vulcanizes 40 minutes under the conditions of 150 DEG C, and the tensile strength of obtained rubbery state sulfur product is improved to 24.2MPa.
Embodiment 9:
Substantially the same manner as Example 2, the first organic solvent is not being added in difference in this present embodiment.
The poly- pentadiene product that the present embodiment obtains has 8.6g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content
It is 89%.It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 1,000,000, and molecular weight distribution Pd is 3.6.
By poly- pentadiene product made from the present embodiment according to the method vulcanization of embodiment 8 after, obtained rubbery state sulphur
The mechanical experimental results for changing product are as follows:
Embodiment 10:
To with the following substance measured is added in the 100ml reaction kettle that nitrogen is replaced and is full of:
First organic solvent (selects pentamethylene)； 50ml
Complex catalyst； 1.2ml
(trans-m-pentadiene monomer contains 15ml to the pentadiene monomer that purity is 65%
Amount is 60%)；
Wherein, the composition of complex catalyst is as follows:
Alkyl metal cpd (selects dichloro aluminium isobutyl)； 0.3ml
Electron donor (selects furans)； 1.5ml
Transistion metal compound (selects waterless cobaltous chloride)； 0.00028g
Complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first under the conditions of 0 DEG C, by electron donor
It is added in the transistion metal compound diluted in advance with the second organic solvent (selecting pentamethylene), is uniformly mixed, obtains
To mixture；Again under the conditions of -20 DEG C, said mixture is added to metal alkyl good with the second organic solvent diluting in advance
It is complexed in compound, is then aged 30min under the conditions of 25 DEG C, obtains complex catalyst；
Cis- -1,4 structure it is poly- between penta 2 it is dilute the preparation method comprises the following steps:
Under agitation, material in kettle is kept to be reacted at 0 DEG C, when reaction a length of 20h.Then it is added into kettle
A little methanol terminates polymerization reaction.Discharging, and excessive methanol, which is added, is precipitated poly- pentadiene from solvent, then uses
Water cleaning cleaning polyalcohol, is finally dried in vacuo and is down to room temperature.
Weighing, obtains the poly- pentadiene product of 6.8g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content is 70%.
It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 100,000, and molecular weight distribution Pd is 1.4.
Embodiment 11:
To with the following substance measured is added in the 100ml reaction kettle that nitrogen is replaced and is full of:
First organic solvent (selects hendecane, certainly also 50ml in the present embodiment
The molten 1.2ml of other fat hydrocarbons such as 12 carbon alkane and its isomer can be selected
Agent)；
Complex catalyst；
(trans-m-pentadiene monomer contains 15ml to the pentadiene monomer that purity is 99.5%
Amount is 100%)；
Wherein, the composition of complex catalyst is as follows:
Alkyl metal cpd (selects triethyl aluminum)； 0.3ml
Electron donor (selects tetrahydrofuran)； 0.8ml
Transistion metal compound (selects anhydrous nitric acid cobalt)； 0.40g
Complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first at 20 °C, by electron donor
It is added to what prior second organic solvent (selecting pentamethylene, the aromatic hydrocarbon solvents such as benzene, toluene also can be selected certainly) had diluted
It in transistion metal compound, is uniformly mixed, obtains mixture；Again at 20 °C, said mixture is added to thing
It is first complexed in the good alkyl metal cpd of the second organic solvent diluting, is then aged 300min under the conditions of 10 DEG C,
Obtain complex catalyst；
Cis- -1,4 structure it is poly- between penta 2 it is dilute the preparation method comprises the following steps:
Under agitation, material in kettle is kept to be reacted at 100 DEG C, when reaction a length of 0.1h.Then into kettle
A little methanol is added to terminate polymerization reaction.Discharging, and excessive methanol, which is added, is precipitated poly- pentadiene from solvent, so
After wash with water polymer, be finally dried in vacuo and be down to room temperature.
Weighing, obtains the poly- pentadiene product of 7.0g.Through examination of infrared spectrum, cis- Isosorbide-5-Nitrae-structural content is 70%.
It is measured through gel permeation chrommatograph, number-average molecular weight Mn is 280,000, and molecular weight distribution Pd is 4.0.
Claims (10)
1. a kind of poly- pentadiene of cis--Isosorbide-5-Nitrae structure, it is characterised in that: cis- in the poly- pentadiene-Isosorbide-5-Nitrae structural content
Not less than 70%, the number-average molecular weight Mn of the poly- pentadiene is 100,000~1,000,000, and molecular weight distribution Pd is 1.4~4.0.
2. the poly- pentadiene of cis--Isosorbide-5-Nitrae structure according to claim 1, it is characterised in that: in the poly- pentadiene
Cis- -1,4 structural content is not less than 85%.
3. a kind of preparation method of the poly- pentadiene of cis--Isosorbide-5-Nitrae structure as claimed in claim 1 or 2, it is characterised in that step
Suddenly are as follows:
In the presence of complex catalyst and the first organic solvent, the pentadiene monomer that purity is 65%~99.5% is gathered
It closes reaction and obtains poly- pentadiene, the temperature of polymerization reaction is 0 DEG C~100 DEG C, and the time is 0.1h~20h；Described first is organic
The mass ratio of solvent and pentadiene monomer is 0~20:1；
The complex catalyst includes transistion metal compound, alkyl metal cpd, electron donor；The metal alkyl
The molar ratio for closing object and electron donor is 1:0.1~1:10；Mole of the alkyl metal cpd and transistion metal compound
Than for 1:1~1000:1；
The complex catalyst the preparation method comprises the following steps: in inert gas shielding atmosphere, first under the conditions of 0 DEG C~20 DEG C, will power
Daughter is added in advance in the good transistion metal compound of the second organic solvent diluting, is uniformly mixed, is obtained mixture；
Again under the conditions of -20 DEG C~20 DEG C, said mixture is added to metal alkyl good with the second organic solvent diluting in advance
It closes and is complexed in object, 30min~300min is then aged under the conditions of 10 DEG C~25 DEG C, obtains complex catalyst；
First organic solvent includes at least one of fat hydrocarbon solvent, aromatic hydrocarbon solvent；Described second is organic molten
Agent includes at least one of fat hydrocarbon solvent, aromatic hydrocarbon solvent.
4. preparation method according to claim 3, it is characterised in that: the transistion metal compound be transition metals cobalt or
The chloride of nickel, bromide, iodide, oxychlorination things, acetylacetonate, diacetyl acetone solvate, cyclopentadienyl group chlorination
Object, bicyclic pentadiene chloride, carboxylate, phosphate, phosphite, nitrate, nitrite, sulfate, in alkoxide
It is a kind of.
5. preparation method according to claim 3, it is characterised in that: the alkyl metal cpd include triethyl aluminum,
Tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium, diethylaluminum hydride, dibutyl aluminum hydride, diisobutyl aluminium hydride, a chlorine two
At least one of aluminium isobutyl, dichloro aluminium isobutyl, ethyl aluminum dichloride, a chlorine isobutylaluminiumhydride.
6. preparation method according to claim 3, it is characterised in that: the electron donor be Lewis alkali, including pyridine,
At least one of isoquinolin, thiophene, furans, tetrahydrofuran, Anaesthetie Ether, diethyl sulfide, trialkylamine.
7. preparation method according to claim 3, it is characterised in that: the pentadiene monomer is cis-form m-pentadiene list
The mixture of body and trans-m-pentadiene monomer, the content of the trans-m-pentadiene monomer are 60%~100%.
8. preparation method according to claim 3, it is characterised in that: the fat hydrocarbon solvent include pentane, pentamethylene,
Methyl cyclopentane, n-hexane, hexamethylene, heptane, octane, isooctane, nonane, decane, hendecane, 12 carbon alkane and its same point
At least one of isomers；The aromatic hydrocarbon solvent be benzene,toluene,xylene, trimethylbenzene and its isomer in extremely
Few one kind.
9. preparation method according to claim 3, it is characterised in that: the temperature of the polymerization reaction is 0 DEG C~60 DEG C, when
Between be 0.5h~5h.
10. a kind of poly- pentadiene of cis- -1,4 structure as claimed in claim 1 or 2 is preparing answering for rubber type of material
With.
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| CN104837877A (en) * | 2012-12-20 | 2015-08-12 | 维尔萨利斯股份公司 | Process for the preparation of (co)polymers of conjugated dienes in the presence of a catalytic system comprising an oxo-nitrogenated complex of cobalt |
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| SU364626A1 (en) * | 1971-01-12 | 1972-12-28 | •• UNION! | |
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