CN104725564A - Polymerization method of isoprene and butadiene - Google Patents
Polymerization method of isoprene and butadiene Download PDFInfo
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Abstract
The invention discloses a polymerization method of isoprene and butadiene. According to the polymerization method, a high-activity rare earth homogeneous catalyst is added during the reaction process and the reaction process is controlled so that the content of cis-1,4 in the product is higher than 98%; at the same time, the product has the good use performances of high molecular weight, narrow distribution, easy processing and the like, so that the production efficiency is improved and the cost is saved.
Description
Technical field
The present invention relates to field of rubber technology, specifically, relate to the polymerization process of a kind of isoprene and divinyl.
Background technology
Along with improving constantly of requiring aspects such as elastomeric material kind and performances, the butadiene-isoprene copolymer glue of being synthesized by divinyl and isoprene copolymer causes the extensive concern of people because having the performances such as excellent resistance to low temperature, wear resistance and low temperature rolling resistance are low.
There is in prior art the copolymerization process of multiple divinyl and isoprene, such as carry out copolymerization with coordination catalyst, the elements such as transition metal used in this type of catalyzer many genus Ti, Co and Ni, the orienting effect of this kind of catalyzer to divinyl and isoprene homopolymerization is different.
Another kind uses the rare earth catalyst be made up of rare-earth compound, and this type of catalyzer can make divinyl, isoprene tactic polymerization become to comprise homopolymer or their multipolymer of cis-Isosorbide-5-Nitrae monomer.European patent EP 76535 discloses a kind of catalyzer, is made up of following three components: a. rare earth compound, as three butoxy neodymium or neodymium naphthenates; B. halohydrocarbon, mainly adopts tertiary butyl chloride, Benzoyl chloride, benzyl chloride, chlorallylene etc.; C.AlR
3or AlR
2h, this catalyzer is heterogeneous catalyst, and using this catalyst system, the highest to obtain cis-Isosorbide-5-Nitrae content be the polyhutadiene of 95%, the multipolymer of polyisoprene and butadiene-isoprene.
How passing through to use a kind of highly active rare earth homogeneous catalyst, improve the content of cis-Isosorbide-5-Nitrae in divinyl, isoprene copolymer, and make the rubber of generation have excellent use properties by controlling copolyreaction process, is the problem needing solution at present badly.
Summary of the invention
The object of the present invention is to provide the polymerization process of a kind of isoprene and divinyl, a kind of high reactivity rare earth homogeneous catalyst is added in reaction process, and by controlling reaction process, to make in resultant cis-1, the content of 4 is more than 98%, and resultant has the excellent use properties such as high molecular, narrow ditribution, easily processing simultaneously.
The polymerization process of isoprene of the present invention and divinyl, by the following technical solutions:
Catalyzer used in the method is rare earth catalyst, and its component and proportioning are:
A. rare earth organic compounds, selects rare earth carboxylate or rare earth acid phosphorus or RE phosphate;
B. the mixture of trialkylaluminium and alkyl aluminium hydride;
C. muriate is: a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter aluminium triethyl, tertiary butyl chloride, benzyl chloride, chlorallylene;
D. conjugated diolefin;
The mol ratio of each component is above: B:A=5-50:1, C:A=1.0-4.0:1, D:A=5-30:1;
The step of the method and reaction conditions are:
Under nitrogen protection; in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl; the total monomer concentration of isoprene and divinyl is 5-30g/100ml; in total monomer, butadiene content is 1%-99%; add B; at 0 DEG C ~ 100 DEG C, reacting 0.5h-2h, then add rare earth catalyst, mole number and the grams ratio adding monomer of the Nd of this catalyzer are 1 ×
~ 3.0 ×
mol/g, reacts 0.5h ~ 24h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Do further optimization to above-mentioned basic technical scheme, the component A of described rare earth catalyst is rare earth carboxylate, preferred neodymium caprate or neodymium iso-octanate.
The component A of described rare earth catalyst can also be rare earth acid phosphorus, preferably (2-ethylhexyl) sour neodymium or (2-ethylhexyl) neodymium phosphate list-2-ethylhexyl.
The B component of described rare earth catalyst is the mixture of triisobutyl aluminium and diisobutyl aluminium hydride.
Do further optimization to above-mentioned basic technical scheme, described organic solvent is the hexane of stable hydrocarbon, hexanaphthene, heptane, hydrogenated gasoline or sherwood oil.
Further optimization is done to above-mentioned basic technical scheme; described rare earth catalyst adopts following preparation method: under nitrogen protection; to in the hydrogen-catalyst reactor of drying; the 1.5M hexane solution of B component is added successively according to proportioning; the 0.1M hexane solution of component A; the 1.0M hexane solution of D component; react 10 minutes to 60 minutes at 0 DEG C ~ 60 DEG C; obtain coloured two-phase liquid; then the hexane solution of 0.3M component C is added; react after 24 hours to 96 hours at-10 DEG C ~ 10 DEG C, obtain the rare earth homogeneous catalyst for isoprene, butadiene copolymer.
The catalyzer prepared by above method has very high catalytic activity, catalytic activity is greater than 90%, the butadiene isoprene copolymer of obtained cis-Isosorbide-5-Nitrae content >98%, weight-average molecular weight >170 ten thousand, narrow molecular weight distribution, High Linear.
The microtexture of polymkeric substance adopts coating method, and Bruker company's T ensor 27 type infrared spectrometer records, by calibration curve method (with the curve under blended under BR9000 and IR70 different ratios for typical curve), by absorption band 840,888cm
-1the absorption intensity A at place
840, A
888calculate the cis-content in polyisoprene and butadiene segment content and each segment.
The molecular weight of polymkeric substance adopts Waters gel permeation chromatograph (GPC) to measure, two HM2, HMW6E chromatographic columns, and moving phase is toluene, probe temperature is 35 DEG C, flow velocity is 1.0mL/min, and the concentration of solution is 1 ~ 2mg/ml, utilizes sample introduction after the metre filter of 0.45 μm.
The mooney viscosity of polymkeric substance, by GB/T-1232.1_2000 regulation, adopts the MDR-2000 type mooney viscosity tester produced with alpha scientific & technical corporation to measure.
For the aspect of performance of polymerisate penta fourth rubber, contriver determines the mooney viscosity numerical value of several polymkeric substance rubber, find that penta fourth rubber of high-cis, narrow molecular weight distributions is similar with the character of polyhutadiene blended rubber to polyisoprene, but dynamic property is obviously good.
In sum, adopt the polymerization process of isoprene of the present invention and divinyl, the polymerization penta fourth rubber generated has the following advantages:
1, by using this kind of rare earth catalyst and being polymerized under the specified conditions, reaction yield reaches more than 95%.Reaction yield is high, and reaction monomers without remaining, can save MONOMER RECOVERY unit substantially, greatly reduces raw materials recovery and refining cost.
2, by using this kind of rare earth catalyst and low temperature polymerization under the specified conditions, the cis-Isosorbide-5-Nitrae content of penta fourth rubber of synthesis can reach more than 98%.
3, by using this kind of rare earth catalyst and being polymerized under the specified conditions, specifically by the control of killing assorted amount in advance in catalyst proportion and preparation condition and polymerization process, make the penta fourth rubber distribution prepared lower than 2.5.
4, by using this kind of rare earth catalyst and being polymerized under the specified conditions, specifically by the control of killing assorted amount in advance in catalyst proportion and preparation condition and polymerization process, the Effective Regulation to molecular weight is achieved.Molecular weight ranges can from 50 ten thousand to 200 ten thousand, its middle-molecular-weihydroxyethyl higher than 1,500,000 time reaction yield still can control higher than 90%, distribute lower than 2.5.
5, the polyrubber generated is easy to processing in mixing process, be embodied in molecular weight lower than 1,000,000 time substantially without roll banding now, directly can process use in mill, greatly reduce cost; And the elasticity being greater than the high molecular penta fourth rubber of 1,200,000 is better, can use by mixed refining process in mill.
6, prove by experiment, its good mechanical performance of the polyrubber generated, especially compression heat generation performance is obviously better than polyisoprene rubber, cis-1,4-polybutadiene rubber and Blend rubber thereof.
Embodiment
embodiment 1
Under nitrogen protection; the 0.5M triisobutyl aluminium of 15ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying; wherein the molar fraction of diisobutyl aluminium hydride is 50%; the 0.1M Nd(vers of 15ml) 3 hexane solutions; the hexane solution of the 1.0M isoprene of 15ml; be placed in 50 DEG C of water-baths and leave standstill 10min; add the 0.1M sesquialter aluminium triethyl hexane solution of 15ml, after being placed in the standing 24h of 0 DEG C of water-bath, obtain the homogeneous phase rare earth catalyst for isoprene, butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 20g/100mL, and in total monomer, butadiene content is 20%, add B 2.0 ×
mol/100mL polymer fluid, reacts 0.5h at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 3 ×
mol/g, reacts 24h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 97%, and recording cis-1.4 structural contents through infrared spectra is 97.6%, and recording weight-average molecular weight through GPC is 1297200, and number-average molecular weight is 592700, and molecular weight distribution is 2.19, and mooney viscosity is 65.9.
example 2
Under nitrogen protection; the 2.0M triisobutyl aluminium of 15ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying; wherein the molar fraction of diisobutyl aluminium hydride is 50%; the 0.1M Nd(vers of 15ml) 3 hexane solutions; the hexane solution of the 3.0M isoprene of 15ml; be placed in 0 DEG C of water-bath and leave standstill 60min; add the 0.4M sesquialter aluminium triethyl hexane solution of 15ml, after being placed in the standing 24h of 10 DEG C of water-baths, obtain the homogeneous phase rare earth catalyst for isoprene, butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 20g/100mL, and in total monomer, butadiene content is 15%, add B 8.0 ×
mol/100mL polymer fluid, reacts 2h at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 9 ×
mol/g, reacts 0.5h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 95%, and recording cis-1.4 structural contents through infrared spectra is 98.3%, and recording weight-average molecular weight through GPC is 1450500, and number-average molecular weight is 601800, and molecular weight distribution is 2.41, and mooney viscosity is 73.7.
example 3
Under nitrogen protection; the 5.0M triisobutyl aluminium of 15ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying; wherein the molar fraction of diisobutyl aluminium hydride is 50%; the 0.1M Nd(vers of 15ml) 3 hexane solutions; the hexane solution of the 0.5M isoprene of 15ml; be placed in 30 DEG C of water-baths and leave standstill 20min; add the 0.3M sesquialter aluminium triethyl hexane solution of 15ml, after being placed in the standing 96h of-9 DEG C of refrigerators, obtain the homogeneous phase rare earth catalyst for isoprene, butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 20g/100mL, and in total monomer, butadiene content is 20%, add B 6.1 ×
mol/100mL polymer fluid, reacts 1h at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 1 ×
mol/g, reacts 5h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 96%, and recording cis-1.4 structural contents through infrared spectra is 97.5%, and recording weight-average molecular weight through GPC is 1191600, and number-average molecular weight is 494400, and molecular weight distribution is 2.41, and mooney viscosity is 60.9.
example 4
Under nitrogen protection; the 2.0M triisobutyl aluminium of 20ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying; wherein the molar fraction of diisobutyl aluminium hydride is 50%; the 0.1M Nd(vers of 20ml) 3 hexane solutions; the hexane solution of the 3.0M isoprene of 20ml; be placed in 35 DEG C of water-baths and leave standstill 18min; add the 0.3M sesquialter aluminium triethyl hexane solution of 20ml, after being placed in the standing 24h of 8 DEG C of water-baths, obtain the homogeneous phase rare earth catalyst for isoprene, butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 5g/100mL, and in total monomer, butadiene content is 1%, add B 9.0 ×
mol/100mL polymer fluid, reacts 0.5h at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 2 ×
mol/g, reacts 5h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 96%, and recording cis-1.4 structural contents through infrared spectra is 97.8%, and recording weight-average molecular weight through GPC is 129400, and number-average molecular weight is 458700, and molecular weight distribution is 2.41, and mooney viscosity is 68.3.
example 5
Under nitrogen protection; the 4.0M triisobutyl aluminium of 20ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying; wherein the molar fraction of diisobutyl aluminium hydride is 10%; the 0.1M Nd(vers of 20ml) 3 hexane solutions; the hexane solution of the 1.0M divinyl of 20ml; be placed in 40 DEG C of water-baths and leave standstill 15min; add the 0.2M sesquialter aluminium triethyl hexane solution of 20ml, after being placed in the standing 36h of 6 DEG C of water-baths, obtain the homogeneous phase rare earth catalyst for isoprene, butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 30g/100mL, and in total monomer, butadiene content is 99%, add B 8.7 ×
mol/100mL polymer fluid, reacts 0.5h at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 1 ×
mol/g, reacts 5h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 97%, and recording cis-1.4 structural contents through infrared spectra is 98.8%, and recording weight-average molecular weight through GPC is 573000, and number-average molecular weight is 221600, and molecular weight distribution is 2.58, and mooney viscosity is 39.2.
example 6
Under nitrogen protection; the 4.0M triisobutyl aluminium of 20ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying; wherein the molar fraction of diisobutyl aluminium hydride is 20%; the 0.1M Nd(vers of 20ml) 3 hexane solutions; the hexane solution of the 1.0M isoprene of 20ml; be placed in 20 DEG C of water-baths and leave standstill 35min; add the 0.3M sesquialter aluminium triethyl hexane solution of 20ml, after being placed in the standing 96h of-5 DEG C of refrigerators, obtain the homogeneous phase rare earth catalyst for isoprene, butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 20g/100mL, and in total monomer, butadiene content is 10%, add B 7.0 ×
mol/100mL polymer fluid, reacts 45min at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 2 ×
mol/g, reacts 5h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 95%, and recording cis-1.4 structural contents through infrared spectra is 97.7%, and recording weight-average molecular weight through GPC is 675200, and number-average molecular weight is 288500, and molecular weight distribution is 2.34, and mooney viscosity is 42.2.
example 7
Under nitrogen protection; the 2.0M triisobutyl aluminium of 15ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying; wherein the molar fraction of diisobutyl aluminium hydride is 50%; the 0.1M Nd(vers of 15ml) 3 hexane solutions; the hexane solution of the 1.0M isoprene of 15ml; be placed in 15 DEG C of water-baths and leave standstill 35min; add the 1.0M sesquialter aluminium triethyl hexane solution of 15ml, after being placed in the standing 72h of 0 DEG C of water-bath, obtain the homogeneous phase rare earth catalyst for isoprene, butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 20g/100mL, and in total monomer, butadiene content is 5%, add B 5.0 ×
mol/100mL polymer fluid, reacts 1.5h at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 1 ×
mol/g, reacts 4h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 85%, and recording cis-1.4 structural contents through infrared spectra is 97.8%, and recording weight-average molecular weight through GPC is 1295411, and number-average molecular weight is 608100, and molecular weight distribution is 2.13, and mooney viscosity is 64.7.
example 8
Under nitrogen protection, the 2.0M triisobutyl aluminium of 15ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying, wherein the molar fraction of diisobutyl aluminium hydride is 50%, the 0.1M Nd(vers of 15ml) 3 hexane solutions, the hexane solution of the 1.0M isoprene of 15ml, the hexane solution of the 2.0M divinyl of 15ml, be placed in 10 DEG C of water-baths and leave standstill 45min, add the 0.3M sesquialter aluminium triethyl hexane solution of 15ml, being placed in after 3 DEG C of water-baths leave standstill 48h obtains for isoprene, the homogeneous phase rare earth catalyst of butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 20g/100mL, and in total monomer, butadiene content is 60%, add B 3.0 ×
mol/100mL polymer fluid, reacts 0.5h at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 1 ×
mol/g, reacts 4h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 96%, and recording cis-1.4 structural contents through infrared spectra is 98.4%, and recording weight-average molecular weight through GPC is 629900, and number-average molecular weight is 209900, and molecular weight distribution is 2.5, and mooney viscosity is 44.2.
example 9
Under nitrogen protection, the 6.0M triisobutyl aluminium of 20ml and the mixing hexane solution of diisobutyl aluminium hydride is added rapidly successively in the hydrogen-catalyst reactor of drying, wherein the molar fraction of diisobutyl aluminium hydride is 20%, the 0.1M Nd(vers of 20ml) 3 hexane solutions, the hexane solution of the 1.5M isoprene of 20ml, the hexane solution of the 1.5M divinyl of 20ml, be placed in 25 DEG C of water-baths and leave standstill 30min, add the 0.2M sesquialter aluminium triethyl hexane solution of 20ml, being placed in after 1 DEG C of water-bath leaves standstill 72h obtains for isoprene, the homogeneous phase rare earth catalyst of butadiene copolymer.
Under nitrogen protection, in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl, the total monomer concentration of isoprene and divinyl is 20g/100mL, and in total monomer, butadiene content is 95%, add B 3.6 ×
mol/100mL polymer fluid, reacts 1h at 0 DEG C ~ 100 DEG C, then adds the rare earth catalyst of preparation catalysis isoprene, butadiene copolymer, and mole number and the grams ratio adding monomer of the Nd of this catalyzer are 1 ×
mol/g, reacts 5h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
Polymer yield is 99%, and recording cis-1.4 structural contents through infrared spectra is 97.8%, and recording weight-average molecular weight through GPC is 853700, and number-average molecular weight is 404500, and molecular weight distribution is 2.11, and mooney viscosity is 51.3.
Claims (6)
1. a polymerization process for isoprene and divinyl, catalyzer used in the method is rare earth catalyst, and its component and proportioning are:
A. rare earth organic compounds, selects rare earth carboxylate or rare earth acid phosphorus or RE phosphate;
B. the mixture of trialkylaluminium and alkyl aluminium hydride;
C. muriate is: a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter aluminium triethyl, tertiary butyl chloride, benzyl chloride, chlorallylene;
D. conjugated diolefin;
The mol ratio of each component is above: B:A=5-50:1, C:A=1.0-4.0:1, D:A=5-30:1;
It is characterized in that, the step of the method and reaction conditions are:
Under nitrogen protection; in the autoclave of dry deoxygenation, add organic solvent, isoprene and be dissolved with the organic solvent of divinyl; the total monomer concentration of isoprene and divinyl is 5-30g/100ml; in total monomer, butadiene content is 1%-99%; add B; at 0 DEG C ~ 100 DEG C, reacting 0.5h-2h, then add rare earth catalyst, mole number and the grams ratio adding monomer of the Nd of this catalyzer are 1 ×
~ 3.0 ×
mol/g, reacts 0.5h ~ 24h at 0 DEG C ~ 100 DEG C, stops, condense polymkeric substance with excessive ethanol with ethanol, then after steaming extruding, vacuum drying, obtains the multipolymer of isoprene and divinyl.
2. the polymerization process of isoprene according to claim 1 and divinyl, is characterized in that, the component A of described rare earth catalyst is rare earth carboxylate, preferred neodymium caprate or neodymium iso-octanate.
3. the polymerization process of isoprene according to claim 1 and divinyl, is characterized in that, the component A of described rare earth catalyst is rare earth acid phosphorus, preferably (2-ethylhexyl) sour neodymium or (2-ethylhexyl) neodymium phosphate list-2-ethylhexyl.
4. the polymerization process of isoprene according to claim 1 and divinyl, is characterized in that, the B component of described rare earth catalyst is the mixture of triisobutyl aluminium and diisobutyl aluminium hydride.
5. the polymerization process of isoprene according to claim 1 and divinyl, is characterized in that, described organic solvent is the hexane of stable hydrocarbon, hexanaphthene, heptane, hydrogenated gasoline or sherwood oil.
6. the polymerization process of isoprene according to any one of claim 1 to 5 and divinyl, is characterized in that, described rare earth catalyst adopts following preparation method:
Under nitrogen protection; to in the hydrogen-catalyst reactor of drying; the 1.5M hexane solution of B component is added successively according to proportioning; the 0.1M hexane solution of component A, the 1.0M hexane solution of D component, reacts 10 minutes to 60 minutes at 0 DEG C ~ 60 DEG C; obtain coloured two-phase liquid; then add the hexane solution of 0.3M component C, react after 24 hours to 96 hours at-10 DEG C ~ 10 DEG C, obtain the rare earth homogeneous catalyst for isoprene, butadiene copolymer.
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| CN110903423A (en) * | 2018-09-18 | 2020-03-24 | 中国石油天然气股份有限公司 | Rare earth catalyst, preparation method and application thereof |
| CN113929802A (en) * | 2020-06-29 | 2022-01-14 | 中国石油天然气股份有限公司 | Rare earth catalyst and preparation method and application thereof |
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| CN113929802A (en) * | 2020-06-29 | 2022-01-14 | 中国石油天然气股份有限公司 | Rare earth catalyst and preparation method and application thereof |
| CN113929802B (en) * | 2020-06-29 | 2024-04-30 | 中国石油天然气股份有限公司 | Rare earth catalyst and preparation method and application thereof |
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