CN111303325B - Efficient controllable preparation method of polyisoprene - Google Patents

Efficient controllable preparation method of polyisoprene Download PDF

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CN111303325B
CN111303325B CN202010228343.9A CN202010228343A CN111303325B CN 111303325 B CN111303325 B CN 111303325B CN 202010228343 A CN202010228343 A CN 202010228343A CN 111303325 B CN111303325 B CN 111303325B
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王庆刚
王亮
朱广乾
张献辉
荆楚杨
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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Abstract

A method for preparing polyisoprene efficiently and controllably. The invention belongs to the field of conjugated diene catalytic polymerization. The invention aims to solve the problems of the prior artThe iron catalyst has low activity, uncontrollable selectivity and easy deactivation. The method of the invention comprises the following steps: adding an isoprene monomer, a rigid skeleton iron complex, a cocatalyst and a solvent into a reactor in an inert gas atmosphere, stirring and reacting at-40-100 ℃ for 12 s-120 min, adding a hydrochloric acid methanol solution to quench after the reaction is finished, and sequentially filtering, washing and drying in vacuum to obtain polyisoprene; wherein the reactivity can reach up to 108g/mol (Fe)/h, wherein the selectivity of cis-1,4/trans-1,4 is (99: 1) - (1: 99). The method of the invention can be suitable for the preparation of rubber materials with different properties; the method and the application are established for the development of high-performance and special-performance high polymer materials. The catalyst system provided by the invention has strong heat resistance, and can still keep high activity even at a high temperature of 100 ℃, so that the catalyst has better industrial application prospect.

Description

Efficient controllable preparation method of polyisoprene
Technical Field
The invention belongs to the field of conjugated diene catalytic polymerization, and particularly relates to a high-efficiency controllable preparation method of polyisoprene.
Background
Polyisoprene, which is formed by polymerizing isoprene monomers in the presence of a catalyst, is an important synthetic rubber. According to different unit structures, the polyisoprene can be divided into cis-1,4 polyisoprene, trans-1,4 polyisoprene, 1, 2-and 3, 4-polyisoprene, and the specific structure is as follows:
Figure BDA0002428414940000011
the application of polymers with different selectivity is different, and titanium catalysis and rare earth catalysis systems are studied most deeply in isoprene polymerization. But the titanium catalyst has wide molecular weight distribution and complex active species; rare earth metals are expensive and the catalyst cost is high. This set of factors limits their further applications. The Fe catalyst has great potential in the aspects of regulating and controlling polymerization molecular weight, molecular weight distribution and selectivity as a novel cheap green catalyst, but the problems of the prior iron-based catalyst are low activity, uncontrollable selectivity, sensitivity of a main catalyst, short service life and easy inactivation.
Disclosure of Invention
The invention provides a method for preparing polyisoprene in a high-efficiency and controllable manner, aiming at solving the technical problems of low activity, uncontrollable selectivity and easy inactivation of catalyst sensitivity of the existing iron-based catalyst.
The method for preparing polyisoprene efficiently and controllably comprises the following steps:
adding an isoprene monomer, a rigid skeleton iron complex, a cocatalyst and a solvent into a reactor in an inert gas atmosphere, stirring and reacting at-40-100 ℃ for 12 s-120 min, adding a hydrochloric acid methanol solution to quench after the reaction is finished, and sequentially filtering, washing and drying in vacuum to obtain polyisoprene; wherein the reactivity can reach up to 108g/mol (Fe)/h, wherein the selectivity of cis-1,4/trans-1,4 is (99: 1) - (1: 99).
Further defined, the rigid skeletal iron complex has the structural formula:
Figure BDA0002428414940000012
Figure BDA0002428414940000021
further limited, the cocatalyst is MAO and Cl2AlEt、ClAlEt2、EASC、Al(i-Bu)3Or AlEt3。
Further, the inert gas is nitrogen or argon.
Further limiting, the solvent is toluene, petroleum ether, n-hexane, cyclohexane, dichloromethane, tetrahydrofuran or hydrogenated gasoline.
Further, the molar ratio of the isoprene monomer to the rigid skeleton iron complex is (2500-20000): 1.
Further limit, the molar ratio of the cocatalyst to the rigid framework iron complex is (5-1000): 1.
Further defined, the molar ratio of the cocatalyst to the rigid framework iron complex is 500: 1.
Further defined, the ratio of the molar amount of the isoprene monomer to the volume of the solvent is (0.05-2) mol: 1L of the compound.
Further limiting, the reaction was stirred at 25 ℃ for 10 min.
Further limited, the concentration of the hydrochloric acid methanol solution is 1 mol/L.
Further defined, the feeding sequence is any one of the following three:
(1) sequentially dissolving a cocatalyst, a rigid skeleton iron complex and an isoprene monomer into a solvent;
(2) sequentially dissolving a cocatalyst, an isoprene monomer and a rigid skeleton iron complex into a solvent;
(3) dissolving a rigid skeleton iron complex, an isoprene monomer and a cocatalyst into a solvent in sequence.
Compared with the prior art, the invention has the remarkable effects that:
1) the rigid pyridine imine iron complex catalyst system provided by the invention is insensitive to air, and the catalyst system has extremely high activity (up to 10)8g·(mol ofFe)-1·h-1]And a high molecular weight (number average molecular weight of 30000-500000g/mol,>104) The polymer has wider molecular weight distribution (PDI is 1.8-7.0) and controllable microstructure, the microstructure of the polymer can be regulated and controlled by ortho-position modification of ligand arylamine substituent on a main catalyst, and the selectivity of the system is insensitive to reaction temperature.
2) The preparation method is easy to operate, and the selectivity can be regulated and controlled (the selectivity of cis-1,4 can be well controlled to be 0% -60% or the selectivity of trans-1,4 is 0-82%, the 1, 2-polymerization is controlled to be less than 1%, and the 3, 4-polymerization is controlled to be 18-55%).
3) The method of the invention can be suitable for the preparation of rubber materials with different properties; the method and the application are established for the development of high-performance and special-performance polymer materials.
4) The catalyst system provided by the invention has strong heat resistance, and can still maintain high activity even at a high temperature of 100 ℃, so that the catalyst has better industrial application prospect.
Detailed Description
The first embodiment is as follows: the structural formula of the rigid skeleton iron complex 1a of the present embodiment is:
Figure BDA0002428414940000031
the specific synthesis method comprises the following steps: FeCl was added to a 100mL single neck flask2(146.4mg,1.2mmol,1.0equiv), then dissolved with 2mL of glacial acetic acid, and then added with solutions of 6, 7-dihydro-5H-quinolin-8-one (170.0mg,1.2mmol,1.0equiv) and aniline (107.6mg,1.2mmol,1.0equiv), respectively, in glacial acetic acid (8mL), reacted at 130 ℃ under reflux for 12 hours, cooled to room temperature, added with diethyl ether (50mL), and precipitated a purple solid; filtration and washing with 30mL of diethyl ether 3 times gave a purple solid, rigid skeletal iron complex 1 a.
As a result: the yield was 53.9%.
Infrared analysis: FT-IR (KBr, disk, cm)-1):3060,2948,1623,1585(ν,C＝N),1486,1450,1335,1202,1130,790,698。
Elemental analysis: call for C30H28Cl4Fe2N4:C,51.62％；H,4.04％；N,8.03％.Found:C,51.24％；H,3.65％；N,7.83％。
High resolution mass spectrometry: HRMS (TOF MS ES + [ M-FeCl ]3]+calcd for[C30H28ClFeN4]+m/z 535.1353,foundm/z 535.1367。
The second embodiment is as follows: the structural formula of the rigid skeleton iron complex 2a of the present embodiment is:
Figure BDA0002428414940000032
the specific synthesis method comprises the following steps: FeCl was added to a 100mL single neck flask2(86.1mg,0.7mmol,1.0equiv), then dissolved with 2mL of glacial acetic acid; then respectively adding a glacial acetic acid (8mL) solution of 6, 7-dihydro-5H-quinolin-8-one (100.0mg,0.7mmol,1.0equiv) and p-toluidine (72.8mg,0.7mmol,1.0equiv), refluxing at 130 ℃ for 12 hours, cooling to room temperature, adding an increased amount of diethyl ether (50mL), and precipitating a dark brown solid; filtration and washing with 30mL of diethyl ether 3 times gave a dark brown solid, rigid skeletal iron complex 2 a.
As a result: the yield was 60.6%.
Infrared analysis: FT-IR (KBr, disk, cm)-1):2943,1578(ν,C＝N),1505,14551357,1337,1219,1110,837,791,770。
Elemental analysis: anal.Calcd for [ C32H32Cl4Fe2N4][CH3COOH][H2O]:C,50.78％；H,4.76％；N,6.97％.Found:C,50.03％；H,3.85％；N,6.96％。
High-resolution mass spectrometry: HRMS (TOF MS ES + [ M-FeCl ]3]+calcd for[C32H32ClFeN4]+m/z 563.1666,foundm/z 563.1669。
The third concrete implementation mode: the structural formula of the rigid skeleton iron complex 3a of the present embodiment is:
Figure BDA0002428414940000041
the specific synthesis method comprises the following steps: FeCl was added to a 100mL single neck flask2(99.0mg,0.8mmol,1.0equiv), then dissolved with 2mL of glacial acetic acid; then adding a glacial acetic acid (8mL) solution of 6, 7-dihydro-5H-quinolin-8-one (115.0mg,0.8mmol,1.0equiv) and 1-naphthylamine (111.9mg,0.8mmol,1.0equiv), respectively, refluxing at 130 ℃ for 12 hours, cooling to room temperature, adding a large amount of diethyl ether (50mL), and precipitating a gray brown solid; filtration and washing 3 times with 30mL of diethyl ether gave a grayish brown solid, rigid skeletal iron complex 3 a.
As a result: the yield was 51.6%.
Infrared analysis: FT-IR (KBr, disk, cm)-1):3054,2942,1626,1583(ν,C＝N),1452,1390,1333,1285,1216,1130,781。
Elemental analysis: anal.Calcd for [ C38H32Cl4Fe2N4][3H2O]:C,53.56％；H,4.49％；N,6.57％.Found:C,52.87％；H,3.80％；N,6.56％。
High resolution mass spectrometry: HRMS (TOF MS ES + [ M-FeCl ]3]+calcd for[C38H32ClFeN4]+m/z 635.1666,foundm/z 635.1671。
The fourth concrete implementation mode: the structural formula of the rigid skeleton iron complex 4a of the present embodiment is:
Figure BDA0002428414940000042
the specific synthesis method comprises the following steps: FeCl was added to a 100mL single neck flask2(86.1mg,0.7mmol,1.0equiv), then dissolved with 2mL of glacial acetic acid; then respectively adding 6, 7-dihydro-5H-quinolin-8-one (100.0mg,0.7mmol,1.0equiv) and a glacial acetic acid (8mL) solution of 2, 6-diisopropylaniline (87.8mg,0.7mmol,1.0equiv), refluxing at 130 ℃ for 12 hours, cooling to room temperature, adding more diethyl ether (50mL), and separating out an orange solid; filtration and washing with 30mL of diethyl ether 3 times gave an orange-red solid, rigid skeletal iron complex 4 a.
As a result: the yield was 57.9%.
Infrared analysis: FT-IR (KBr, disk, cm)-1):2961,2868,1618,1582(ν,C＝N),1460,1215,1129,1044,926,778,770,661。
Elemental analysis: anal.Calcd for [ C42H52ClFeN4·FeCl4]:C,55.94％；H,5.81％；N,6.21％.Found:C,55.50％；H,5.56％；N,6.38％。
High resolution mass spectrometry: HRMS (TOF MS ES + (M-FeCl)4)+calcd for[C42H52Cl5Fe2N4]+m/z 703.3231,foundm/z 703.3227。
The fifth concrete implementation mode: the structural formula of the rigid skeleton iron complex 5a of the present embodiment is:
Figure BDA0002428414940000051
the specific synthesis method comprises the following steps: FeCl was added to a 100mL single neck flask2(56.0mg,0.4mmol,1.0equiv), then dissolved with 2mL of glacial acetic acid; then respectively adding 6, 7-dihydro-5H-quinolin-8-one (65.0mg,0.4mmol,1.0equiv) and a glacial acetic acid (8mL) solution of 2,4, 6-triphenylaniline (142.0mg,0.4mmol,1.0equiv), refluxing at 130 ℃ for 12 hours, cooling to room temperature, adding more diethyl ether (50mL), and separating out a tan solid; filtration and washing with 30mL of diethyl ether 3 times gave a tan solid, rigid skeletal iron complex 5 a.
As a result: the yield was 70.2%.
Infrared analysis: FT-IR (KBr, disk, cm)-1):2923,1659,1588(ν,C＝N),1456,1429,1356,1207,1112,826,759,702。
Elemental analysis: call for C33H26Cl2FeN2:C,68.65；H,4.54；N,4.85％.Found:C,68.93；H,4.28；N,4.59％。
High resolution mass spectrometry: HRMS (TOF MS ES + [ M-Cl ]]+calcd for[C33H26ClFeN2]+m/z 541.1135,found 541.1149。
The sixth specific implementation mode is as follows: the structural formula of the rigid skeleton iron complex 6a of the present embodiment is:
Figure BDA0002428414940000061
the specific synthesis method comprises the following steps: FeCl was added to a 100mL single neck flask2(86.1mg,0.7mmol,1.0equiv), then dissolved with 2mL of glacial acetic acid; then respectively adding 6, 7-dihydro-5H-quinoline-8-ketone (100.0mg,0.7mmol,1.0equiv) and glacial acetic acid (8mL) solution of 2, 6-xylyl-4-methylaniline (289.2mg,0.7mmol,1.0equiv), refluxing and reacting at 130 ℃ for 12 hours, cooling to room temperature, adding more diethyl ether (50mL), and separating out dark brown solid; filtered and washed 3 times with 30mL of diethyl etherTo obtain a dark brown solid, namely the rigid skeleton iron complex 6 a.
As a result: the yield was 71.0%.
Infrared analysis: FT-IR (KBr, disk, cm)-1):3028,2926,2030,1589(ν,C＝N),1571,1445,1206,1022,834,726。
Elemental analysis: anal.Calcd for C42H36Cl2FeN2:C,72.53；H,5.22；N,4.03％.Found:C,72.61；H,5.37；N,4.16％。
High resolution mass spectrometry: HRMS (TOF MS ES + [ M-Cl ]]+calcd for[C42H36ClFeN2]+m/z 659.1911,found 659.1909。
The seventh embodiment: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (4mmol,500equiv.), toluene 5mL, isoprene monomer (20mmol,2500equiv.), rigid framework iron complex 1a (8. mu. mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring and reacting at 25 ℃ for 10min, adding 1M hydrochloric acid methanol solution to quench after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then drying in a vacuum drying oven at 40 ℃ to constant weight to obtain polyisoprene.
As a result: yield of>99.0 percent. The reaction selectivity was 52% cis-1,4, 3% trans-1,4 and 45% 3, 4-polyisoprene, Mn12.7 kg/mol and PDI of 2.6.
The specific implementation mode eight: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
adding MAO (0.4mmol,50equiv.), toluene 5mL, isoprene monomer (20mmol,2500equiv.), rigid skeleton iron complex 1a (8. mu. mol,1equiv.) in sequence into a 25mL Schlenk tube under argon atmosphere, stirring and reacting at 25 ℃ for 10min, adding 1M hydrochloric acid methanol solution to quench after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, and obtaining a solidThe substance was washed with ethanol three times, and then dried in a vacuum oven at 40 ℃ to constant weight to obtain polyisoprene. As a result: yield of>99.0 percent. The reaction selectivity was 53% cis-1,4 and 47% 3, 4-polyisoprene, Mn3.2 ten thousand g/mol, PDI 2.3.
The specific implementation method nine: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (0.04mmol,5equiv.), toluene 5mL, isoprene monomer (20mmol,2500equiv.), rigid framework iron complex 1a (8. mu. mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring and reacting at 25 ℃ for 10min, adding 1M hydrochloric acid methanol solution after the reaction is finished, quenching, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then placing in a vacuum drying oven to dry at 40 ℃ to constant weight to obtain polyisoprene.
As a result: yield of>99.0 percent. The reaction selectivity was 52% cis-1,4 and 48% 3, 4-polyisoprene, Mn9.3 kg/mol and PDI of 1.9.
The specific implementation mode is ten: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (100 mu mol,50equiv.), toluene 5mL, isoprene monomer (20mmol,10000equiv.), rigid skeleton iron complex 1a (2 mu mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring and reacting at 25 ℃ for 10min, adding 1M hydrochloric acid methanol solution to quench after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then placing in a vacuum drying oven to dry at 40 ℃ until constant weight to obtain polyisoprene.
As a result: yield of>99.0 percent. The reaction selectivity was 52% cis-1,4 and 48% 3, 4-polyisoprene, Mn13.0 ten thousand g/mol, PDI 2.1.
The concrete implementation mode eleven: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (100. mu. mol,100equiv.), toluene 5mL, isoprene monomer (20mmol,20000equiv.), rigid skeleton iron complex 1a (1. mu. mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring and reacting at 25 ℃ for 60min, adding 1M hydrochloric acid methanol solution to quench after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then placing in a vacuum drying oven to dry to constant weight at 40 ℃ to obtain polyisoprene.
As a result: yield of>99.0 percent. The reaction selectivity was 52% cis-1,4, 2% trans-1,4 and 46% 3, 4-polyisoprene, Mn30.5 kg/mol and PDI of 2.2.
The specific implementation mode twelve: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (50 mu mol,50equiv.), toluene 5mL, isoprene monomer (20mmol,20000equiv.), rigid skeleton iron complex 1a (1 mu mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring and reacting at 25 ℃ for 60min, adding 1M hydrochloric acid methanol solution to quench after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then placing in a vacuum drying oven to dry to constant weight at 40 ℃ to obtain polyisoprene.
As a result: the yield was 90%. The reaction selectivity was 52% cis-1,4 and 48% 3, 4-polyisoprene, Mn9.4 kg/mol and PDI of 2.0.
The specific implementation mode is thirteen: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
to a 25mL Schlenk tube, MAO (4mmol,500equiv.), toluene 5mL, isoprene monomer (20mmol,2500equiv.), rigid skeletal iron complex 1a (8 μmol,1equiv.) were sequentially added under an argon atmosphere, stirred at 25 ℃ for reaction for 1min, 1M hydrochloric acid methanol solution was added after the reaction was completed to quench, the viscous polymer solution was poured into 50mL ethanol to allow the polymer to settle out, the filtrate was filtered off, the resulting solid matter was washed three times with ethanol, and then placed in a vacuum drying oven at 40 ℃ to be dried to constant weight, obtaining polyisoprene.
As a result: yield of the product>99.0 percent. The reaction selectivity was 53% cis-1,4, 2% trans-1,4 and 45% 3, 4-polyisoprene, Mn9.3 kg/mol and PDI 2.5.
The specific implementation mode is fourteen: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (4mmol,1000equiv.), toluene 5mL, isoprene monomer (20mmol,5000equiv.), rigid skeleton iron complex 1a (4. mu. mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring at 25 ℃ for 12s, adding 1M hydrochloric acid methanol solution after the reaction is finished, quenching, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then drying in a vacuum drying oven at 40 ℃ to constant weight to obtain polyisoprene.
As a result: yield of>99.0% and a polymerization activity of 1.02X 108g/(mol of ofFe)/h. The reaction selectivity was 54% cis-1,4 and 46% 3, 4-polyisoprene, Mn12.2 ten thousand g/mol, PDI 2.7.
The concrete implementation mode is fifteen: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (4mmol,500equiv.), toluene 5mL, isoprene monomer (20mmol,2500equiv.), rigid framework iron complex 1a (8. mu. mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring at 50 ℃ for reaction for 10min, adding 1M hydrochloric acid methanol solution for quenching after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then placing the solid matter in a vacuum drying oven at 40 ℃ to be dried to constant weight to obtain polyisoprene.
As a result: yield of>99.0％。The reaction selectivity was 43% cis-1,4, 14% trans-1,4 and 43% 3, 4-polyisoprene, Mn9.7 kg/mol and PDI 2.5.
The specific implementation mode is sixteen: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (4mmol,500equiv.), toluene 5mL, isoprene monomer (20mmol,2500equiv.), rigid framework iron complex 1a (8. mu. mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring and reacting at 75 ℃ for 10min, adding 1M hydrochloric acid methanol solution to quench after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then drying in a vacuum drying oven at 40 ℃ to constant weight to obtain polyisoprene.
As a result: yield of>99.0 percent. The reaction selectivity was 42% cis-1,4, 19% trans-1,4 and 39% 3, 4-polyisoprene, Mn6.9 kg/mol and PDI 2.3.
Seventeenth embodiment: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (4mmol,500equiv.), toluene 5mL, isoprene monomer (20mmol,2500equiv.), rigid framework iron complex 1a (8. mu. mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring at 100 ℃ for reaction for 10min, adding 1M hydrochloric acid methanol solution for quenching after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then placing the solid matter in a vacuum drying oven at 40 ℃ to be dried to constant weight to obtain polyisoprene.
As a result: yield of>99.0 percent. The reaction selectivity was 40% cis-1,4, 22% trans-1,4 and 38% 3, 4-polyisoprene, Mn6.4 ten thousand g/mol, PDI 2.2.
The specific implementation mode is eighteen: the method for preparing polyisoprene efficiently and controllably comprises the following specific steps:
under argon atmosphere, adding MAO (4mmol,500equiv.), toluene 5mL, isoprene monomer (20mmol,2500equiv.), rigid framework iron complex 1a (8 mu mol,1equiv.) in sequence into a 25mL Schlenk tube, stirring and reacting at 25 ℃ for 2h, adding 1M hydrochloric acid methanol solution to quench after the reaction is finished, pouring the viscous polymer solution into 50mL ethanol, allowing the polymer to settle out, filtering to remove the filtrate, washing the obtained solid matter with ethanol for three times, and then placing in a vacuum drying oven to dry at 40 ℃ until constant weight to obtain polyisoprene.
As a result: yield of>99.0 percent. The reaction selectivity was 54% cis-1,4, 2% trans-1,4 and 44% 3, 4-polyisoprene, Mn10.8 kg/mol and PDI of 2.2.
The detailed embodiment is nineteen: the present embodiment is different from the specific embodiment in eighteenth: the other steps and parameters of the rigid skeleton iron complex 2a are the same as those of the embodiment eighteen.
As a result: yield of>99.0 percent. The reaction selectivity was 43% cis-1,4, 2% trans-1,4 and 55% 3, 4-polyisoprene, Mn22.7 ten thousand g/mol and PDI of 1.9.
The specific implementation mode twenty: the present embodiment is different from the specific embodiment in eighteenth: the rigid skeleton iron complex 3a, other steps and parameters are the same as those of embodiment eighteen.
As a result: yield of>99.0 percent. The reaction selectivity was 58% cis-1,4, 2% trans-1,4 and 40% 3, 4-polyisoprene, Mn6.1 kg/mol and PDI of 3.7.
The specific implementation mode is twenty one: the present embodiment is different from the specific embodiment in eighteenth: the rigid skeleton iron complex 4a, other steps and parameters are the same as those of embodiment eighteen.
As a result: the yield was 6.1%. The reaction selectivity was 54% cis-1,4, 11% trans-1,4 and 35% 3, 4-polyisoprene, Mn3.0 ten thousand g/mol, PDI 2.8.
Specific embodiment twenty-two: the present embodiment is different from the specific embodiment in eighteenth: the rigid skeleton iron complex 5a, other steps and parameters are the same as those of the eighteenth embodiment.
As a result: yield of>99.0 percent. The reaction selectivity was 50% cis-1,4, 18% trans-1,4 and 32% 3, 4-polyisoprene, Mn2.8 kg/mol and PDI 6.9.
Specific embodiment twenty-three: the present embodiment is different from the specific embodiment in eighteenth: the rigid skeleton iron complex 6a, other steps and parameters are the same as those of the embodiment eighteen.
As a result: the yield was 59.7%. The reaction selectivity was 82% trans-1,4 and 18% 3, 4-polyisoprene, Mn2.3 kg/mol and PDI 6.9.

Claims (9)

1. A method for controllably preparing polyisoprene, which is characterized by comprising the following steps:
adding an isoprene monomer, a rigid skeleton iron complex, a cocatalyst and a solvent into a reactor in an inert gas atmosphere, stirring and reacting at-40-100 ℃ for 12 s-120 min, adding a hydrochloric acid methanol solution to quench after the reaction is finished, and sequentially filtering, washing and drying in vacuum to obtain polyisoprene; wherein the reactivity is up to 108The selectivity of g/mol (Fe)/h, cis-1,4/trans-1,4 is (99: 1) - (1: 99), and the structural formula of the rigid framework iron complex is as follows:
Figure FDA0003555278990000011
2. the method for preparing polyisoprene as claimed in claim 1, wherein said cocatalyst is MAO or Cl2AlEt、ClAlEt2、EASC、Al(i-Bu)3Or AlEt3。
3. The method for the controlled preparation of polyisoprene according to claim 1, wherein the inert gas is nitrogen or argon.
4. The controllable polyisoprene preparation method as claimed in claim 1, wherein the solvent is toluene, petroleum ether, n-hexane, cyclohexane, dichloromethane, tetrahydrofuran or hydrogenated gasoline.
5. The controllable preparation method of polyisoprene according to claim 1, wherein the molar ratio of isoprene monomer to rigid skeleton iron complex is (2500-20000): 1.
6. The controllable preparation method of polyisoprene according to claim 1, wherein the molar ratio of the cocatalyst to the rigid skeleton iron complex is (5-1000): 1.
7. The controllable preparation method of polyisoprene according to claim 1, wherein the molar ratio of the cocatalyst to the rigid backbone iron complex is 500: 1.
8. The controllable preparation method of polyisoprene according to claim 1, wherein the ratio of the mole amount of isoprene monomer to the volume of solvent is (0.05-2) mol: 1L of the total amount of the active ingredients.
9. The controllable preparation method of polyisoprene according to claim 1, wherein the reaction is carried out at 25 ℃ for 10min with stirring.
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