CN101157737B - Aza cyclic carbine rear earth catalyst for crystallinity 3,4-polyisoprene - Google Patents
Aza cyclic carbine rear earth catalyst for crystallinity 3,4-polyisoprene Download PDFInfo
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- CN101157737B CN101157737B CN200710056254A CN200710056254A CN101157737B CN 101157737 B CN101157737 B CN 101157737B CN 200710056254 A CN200710056254 A CN 200710056254A CN 200710056254 A CN200710056254 A CN 200710056254A CN 101157737 B CN101157737 B CN 101157737B
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Abstract
The present invention relates to a nitrogen heterocyclic carbene rare earth complex, a catalyst system which consists of the present invention, aluminum alkyl and an organoboron salt can catalyse theisoprene to carry out the solution polymerization, so as to prepare the polyisoprene with the crystallization property, high 3, 4-structure and high glass transition temperature (T<SUB>g</SUB>). The molar ratio of aluminum alkyl and the rare earth complex is within the scope of 1 to 100, the molar ratio of the organoboron salt and the rare earth complex is within the scope of 0.5 to 2.0; the solvent which is used for polymerization can be toluene, bromobenzene, n-hexane, dichloromethane or chlorobenzene; the polymerization temperature range is -20 DEG C to 80 DEG C, the reaction time of polymerization at minus 20 DEG C is 36 hours, the reaction time of polymerization at 80 DEG C is 1 hour, and the monomer conversion rate can be up to 100 percent. The reaction is characterized by active polymerization, the molecular weight of the product can be controlled by the molar ratio of the monomer and the catalyst, the molecular weight of the polyisoprene can achieve 360,000 at most, and the glass transition temperature T<SUB>g</SUB> is equal to 5 DEG C to 50 DEG C. The content of the 3, 4 structure of the polyisoprene is affected by the spatial effect and the electronic effect of the rare earth complex, the solvent type for polymerization reaction and the polymerization reaction temperature and so on, which is changed between 76 percent and 99 percent.
Description
Technical field
The present invention relates to crystallinity 3, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used.
Background technology
Conjugated diolefin obtains the polymkeric substance of various stereoregular structures by polyreaction, wherein many is synthetic rubber of excellent property, thus the rubber synthetic technology is advanced to the brand-new stage, makes the quality of elastomeric structure, product and quantity that great reform and growth all arranged.Synthetic polyisoprene is called for short polyisoprene rubber (IR), mainly is divided into along 1, and 4-IR, anti-1,4-IR and 3 ', 4-IR three major types.Along 1,4-IR is a kind of universal synthetic rubber, because its molecular structure and performance and natural rubber are very similar, therefore can replace natural rubber.Anti-1,4-IR is called synthetic Chinese gutta percha or Ba Lata glue again, exists with the crystalline polymer form under the normal temperature, has developed to be used for medical material, shape-memory material etc.Along 1,4 structure and anti-1,4 structure is naturally occurring structure, yet 3,4-IR also has important effect, thereby people synthesize it at finding method always.
Along with the construction of rapid development of automobile industry, high-grade highway and improving constantly of automobile speed per hour, people have proposed more and more higher requirement to the safety performance of automobile, and hauling ability and wet-sliding resistant performance become the important indicator of weighing the doughnut performance.But the dynamic viscous-elastic behaviour of rubber intrinsic makes when improving the tire hauling ability, often can't avoid the increase of its rolling resistance and Sheng Re and the decline of abrasion resistance.For this reason, with the synthetic rubber of different glass transition temperature (Tg) and natural rubber blend or adopt integrated rubber to prepare tire tread glue.Because 3, the molecular structure characteristics of 4-polyisoprene rubber are that double bond content is low in the main chain, and containing a large amount of bigger side chains on the building block, good wet performance and the low hysteresis loss of high temperature of grabbing is arranged, is the tartan of a kind of low-heat-generation, high wet-sliding resistant.Make the tread rubber with its preparation both have excellent wet-sliding resistant performance, do not have again styrene-butadiene rubber(SBR) (SRR) serious give birth to heat, can improve the safety performance of tire running, also can be used as sealing material, anti-seismic material and polypropylene toughness-increasing modified dose thereby receive much attention.
But in the catalysis isoprene polymerization research of existing numerous reports, most catalyzed polymerization products are 1,4-cis and 1, the polyisoprene of 4-transconfiguration.Up to now, had only the minority bibliographical information 3, the polyisoprene catalyzer of 4-structure.As AlEt
3-Ti (OR)
4(R is an alkyl), (dmpe)
2CrCl
2-MAO (dmpe 1,2-two (dimethyl-phosphorus) ethane), and some contain nitrogen-atoms coordinate Fe-series catalyst etc.In these catalyst polymerization gained polyisoprene 3, the content of 4-structure is lower than 80%.Hou Zhaomin etc. have reported a kind of double-core yttrium alkyl complexes that contains cyclopentadienyl, can the catalysis isoprene polymerization obtain complete with 3,4-polyisoprene (reference: L.Zhang, Y.Luo, Z.Hou, J.Am.Chem.Soc.2005,127,14562), this is that present rare earth metal complex causes isoprene 3, the unique one piece of report of 4-polymeric.Between Lido Porri etc. has reported with 3,4-polyisoprene (reference: C.Bazzini, L.Porri, Polymer.2004,45,2871), but 3,4 content are 80%.Therefore, the polyisoprene of high 3,4 content of acquisition isostructure seems more and more important.
Summary of the invention
The purpose of this invention is to provide crystallinity 3, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used, form by rare earth compounding, aluminum alkyls and organic boron salt, it is characterized in that, the rare earth metal of rare earth compounding is with the part chelating that contains N-heterocyclic carbine (NHC) group and be connected initiating group, and its structural formula is as follows:
Formula 1
Wherein, R
1Be the modification group of N-heterocyclic carbine, this group and rare earth ion chelating, normally fluorenyl, indenyl, cyclopentadienyl, amino (=NCH (CH
3)
2Or=NC (CH
3)
3), alkoxyl group (OCH
2-,-OCH (
nBu)-,-OCH (CH
2CH
3)-or-OC (CH
3)
2-);
R
2Being the substituting group on the N-heterocyclic carbine, is methyl, ethyl, n-propyl, sec.-propyl, butyl, the tertiary butyl, (2,4,6) trimethylphenyl, (2,6) diisopropyl phenyl, phenyl, pyridyl, cyclohexyl or adamantyl;
Rare earth metal (Ln) is scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu);
R
3Being the initiating group that links to each other with rare earth metal, is alkyl (CH
2SiMe
3, CH (SiMe
3)
2), benzyl, amino (N (SiMe
3)
2), methoxyl group (OCH
3), oxyethyl group (OC
2H
5), isopropoxy (O
iPr), positive propoxy (OPr), n-butoxy (OBu), tert.-butoxy (O
tBu) or halogen atom (F, Cl, Br or I);
R
4Also being the initiating group that links to each other with rare earth metal, is alkyl (CH
2SiMe
3, CH (SiMe
3)
2), benzyl, amino (N (SiMe
3)
2), methoxyl group (OCH
3), oxyethyl group (OC
2H
5), isopropoxy (O
iPr), positive propoxy (OPr), n-butoxy (OBu), tert.-butoxy (O
tBu) or halogen atom (F, Cl, Br or I); R
3And R
4Can be identical, also can be inequality; N=1,2,3 or 4.
Preferred catalysis isoprene 3,4-polymeric aza cyclic carbine rear earth title complex has suc as formula the molecular structural formula of the title complex 1-5 shown in 2 or the molecular structural formula of the title complex 6-10 shown in the formula 3:
Ln=Y, title complex 1
Ln=Ho, title complex 2
Ln=Lu, title complex 3
Ln=Sc, title complex 4
Ln=Gd, title complex 5
Formula 2
Ln=Y, title complex 6
Ln=Ho, title complex 7
Ln=Lu, title complex 8
Ln=Sc, title complex 9
Ln=Gd, title complex 10
Formula 3
Described aluminum alkyls is (CH
3)
3Al, (CH
3)
2AlCl, (CH
3) AlCl
2, (CH
3)
3Al
2Cl
3, (C
2H
5)
3Al, (C
2H
5)
2AlCl, (C
2H
5) AlCl
2, (C
2H
5)
3Al
2Cl
3, (C
2H
5)
2AlOC
2H
5, (
iPr)
3Al, (Pr)
3Al, (
iPr)
2AlH, (
iBu)
3Al, (
iBu)
2AlCl, (
iBu) AlCl
2, (
iBu)
2AlH, (Bu)
3Al or MAO, wherein preferred (
iBu)
3Al and (C
2H
5)
3Al.The molar ratio of aluminum alkyls and rare earth compounding is in 1～100 scope, and preferred molar ratio is 10.
Described organic boron salt is [Ph
3C] [B (C
6F
5)
4], [PhMe
2NH] [B (C
6F
5)
4] or B (C
6F
5)
3, preferred [Ph
3C] [B (CF
5)
4]; The molar ratio of organic boron salt and rare earth compounding is in 0.5～2.0 scope, and preferred molar ratio is 1.0.
The preparation method of catalysis isoprene 3, the 4 selective polymerisation aza cyclic carbine rear earth title complexs among the present invention is described below, and process is as follows:
Under the anhydrous and oxygen-free condition, part that the following formula of equimolar amount is given (Ligand) and lithium alkylide (LiCH
2SiMe
3) be mixed in 20ml～60ml toluene, react after 1～6 hour, their toluene solution is joined trivalent rare earth compound L nR
3R
4(CH
2SiMe
3)
3(THF)
nToluene solution in, reacted 1～24 hour, be concentrated into 2ml～6ml, add the normal hexane of 1ml～10ml, be put in recrystallization in-30 ℃ of refrigerators, spend the night, solid that obtains or crystal are exactly the synthetic title complex of wanting (Complex), wash with normal hexane, vacuum-drying 2 hours, getting its productive rate is 50-60%.
The aza cyclic carbine rear earth catalyst system that crystallinity 3 of the present invention, 4-polyisoprene are used, its step and condition that is used for catalytic method is as follows:
(1), earlier isoprene with dry 2 days of hydrolith, the pure system of underpressure distillation is frozen with liquid nitrogen then, takes out repeatedly with pump, to remove oxygen, cryopreservation is standby under the anhydrous and oxygen-free condition afterwards.
(2), the solution polymerization process of isoprene:
Polymer solvent is selected toluene, normal hexane and chlorobenzene for use, and polymeric reaction temperature is-20 ℃～80 ℃.When polymerization temperature is 25 ℃, carry out polyreaction in glove box, the polyreaction under other temperature shifts out glove box and carries out outward.The mol ratio of monomer and catalyzer is 500～5000, and the reaction times is 1～72 hour, after reaction finishes, is the ethanolic soln termination reaction of 10% hydrochloric acid with volume ratio, solution is put in a large amount of ethanolic solns precipitated again, obtains polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h claims its quality, calculates monomer conversion.
3 of gained polyisoprene, 4-structural content are 76%～99%.The molecular weight of polyisoprene is measured with gel permeation chromatograph (Waters 410), 3 of polyisoprene, and the 4-structural content is calculated by proton nmr spectra.
Beneficial effect: aza cyclic carbine rear earth alkyl complexes of the present invention and Al (
iBu)
3[Ph
3C] [B (C
5F
5)
4] catalyst system catalysis isoprene 3, the 4 selective polymerisations reaction formed has the feature of living polymerization.At normal temperatures, in the hexane solvent, polymerization rate is very fast, and the reaction times is 12 hours, and monomer can reach 100% and transform.Gained polyisoprene molecular weight is higher, and molecular weight distribution is narrower.And, utilization contains the side group (as fluorenyl or indenyl) of different spaces obstacle, regulate the steric effect and the electronic effect of catalyst active center, change the spatial obstacle and the temperature of reaction of promotor simultaneously, the final realization optionally controlled polymer areas, obtains 3, and the 4-structural content is up to 99%, it wherein, is 60% crystallinity polyisoprene product with content.
Embodiment
Preparation embodiment 1 title complex 1 ((Flu-NHC) Y (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.168g part (Flu-H-NHC-H) Br is joined wherein, behind the room temperature reaction 3h, reaction soln is joined 20ml, 0.1.81g Y (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 5h, concentrate toluene solution to 2ml, add the 2ml normal hexane, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 1.With the normal hexane washing, vacuum-drying 2 hours gets 0.145g.Productive rate is 61.7%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum and elemental analysis the structure of title complex 1.
1H?NMR(400MHz，C
6D
6，25℃)：
1.90，-1.59(AB，
2J
H-H＝10.8Hz，4H，Y-CH
2SiMe
3)，0.22(s，18H，Y-CH
2SiMe
3)，1.85(s，6H，C
6H
2Me
3)，2.17(s，3H，C
6H
2Me
3)，3.05(t，
3J
H-H＝4.8Hz，2H，CH
2CH
2)，3.90(t，
3J
H-H＝4.8Hz，2H，CH
2CH
2)，5.89(s，1H，NCH)，6.12(s，1H，NCH)，6.70(s，2H，C
6H
2Me
3)，7.26(t，
3J＝7.4Hz，2H，fluorene)，7.30(d，
3J＝8.4Hz，2H，fluorene)，7.40(d，
3J＝7.4Hz，2H，fluorene)，8.39(d，
3J
H-H＝8.4Hz，1H，fluorene)。With elemental analysis the structure of title complex 1, its molecular formula is C
35H
47YN
2Si
2Wherein carbon content is 64.33; Hydrogen richness is 7.13; Nitrogen content is 4.19.
Preparation embodiment 2 title complexs 2 ((Flu-NHC) Ho (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.168g part (Flu-H-NHC-H) Br is joined wherein, behind the room temperature reaction 3h, reaction soln is joined 30ml, 0.209g Ho (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 6h, concentrate toluene solution to 2ml, add the 2ml normal hexane,, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 2.With the normal hexane washing, vacuum-drying 2 hours gets 0.164g.Productive rate is 62.4%.With elemental analysis the structure of title complex 2, its molecular formula is C
35H
47HoN
2Si
2Wherein carbon content is 57.53; Hydrogen richness is 6.81; Nitrogen content is 3.16.
Preparation embodiment 3 title complexs 3 ((Flu-NHC) Lu (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.168g part (Flu-H-NHC-H) Br is joined wherein, behind the room temperature reaction 6h, reaction soln is joined 30ml, 0.213g Lu (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 6h, concentrate toluene solution to 2ml, add the 2ml normal hexane, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 3.With the normal hexane washing, drying gets 0.180g.Productive rate is 67.7%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum and elemental analysis the structure of title complex 3.
1H NMR (400MHz, C
6D
6, 25 ℃): δ-2.18 ,-1.90 (AB,
2J
H-H=10.8Hz, 4H, Lu-CH
2SiMe
3), 0.22 (s, 18H, Lu-CH
2SiMe
3), 1.85 (s, 6H, C
6H
2Me
3), 2.18 (s, 3H, C
6H
2Me
3), 3.05 (t,
3J
H-H=4.8Hz, 2H, CH
2CH
2), 3.91 (t,
3J
H-H=4.8Hz, 2H, CH
2CH
2), 5.90 (d,
3J
H-H=1.2Hz, 1H, NCH), 6.12 (d,
3J
H-H=1.2Hz, 1H, NCH), 6.70 (s, 2H, C
6H
2Me
3), 7.27 (t,
3J=6.8Hz, 2H, fluorene), 7.32 (d,
3J=8.4Hz, 2H, fluorene), 7.40 (d,
3J=6.8Hz, 2H, fluorene), 8.39 (d,
3J
H-H=8.4Hz, 1H, fluorene); With elemental analysis the structure of title complex 3, its molecular formula is C
35H
47LuN
2Si
2Wherein carbon content is 57.03; Hydrogen richness is 6.67; Nitrogen content is 3.73.
Preparation embodiment 4 title complexs 6 ((Ind-NHC) Y (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.150g part (Ind-H-NHC-H) Br is joined wherein, behind the room temperature reaction 5h, reaction soln is joined 10ml, 0.181g Y (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 6h, concentrate toluene solution to 2ml, add the 3ml normal hexane, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 6.With the normal hexane washing, drying gets 0.135g, and productive rate is 62.5%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum and elemental analysis the structure of title complex 6.
1H NMR (400MHz, C
6D
6, 25 ℃): δ-2.09 ,-1.81 (ABX, dd,
2J
H-H=12.0Hz,
2J
Y-H=4.0Hz, 2H, Y-CH
2SiMe
3) ,-0.86 ,-0.57 (ABX, dd,
2J
H-H=12.0Hz,
2J
Y-H=4.0Hz, 2H, Y-CH
2SiMe
3), 0.28 (s, 9H, Y-CH
2SiMe
3), 0.44 (s, 9H, Y-CH
2SiMe
3), 1.79 (s, 3H, C
6H
2Me
3), 1.92 (s, 3H, C
6H
2Me
3), 2.21 (s, 3H, C
6H
2Me
3), 2.72-2.77 (multi, 1H, CH
2CH
2), 2.81-2.87 (multi, 1H, CH
2CH
2), 3.57-3.62 (multi, 1H, CH
2CH
2), 3.81-3.87 (multi, 1H, CH
2CH
2), 5.88 (d,
3J
H-H=1.2Hz, 1H, NCH), 6.07 (d,
3J
H-H=1.2Hz, 1H, NCH), 6.70 (s, 1H, C
6H
2Me
3), 6.80 (s, 1H, C
6H
2Me
3), 6.77,6.81 (AB,
3J
HH=3.2Hz, 2H, indene), 7.08-7.19 (multi, 3H, indene), 7.93-7.95 (d,
3J
H-H=8.4Hz, 1H, indene); With elemental analysis the structure of title complex 6, its molecular formula is C
31H
45YN
2Si
2Wherein carbon content is 62.91; Hydrogen richness is 7.56; Nitrogen content is 4.69.
Preparation embodiment 5 title complexs 7 ((Ind-NHC) Ho (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.150g part (Ind-H-NHC-H) Br is joined wherein, behind the room temperature reaction 4h, reaction soln is joined 30ml, 0.209gHo (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 1h, concentrate toluene solution to 3ml, add the 4ml normal hexane,, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 7.With the normal hexane washing, drying gets 0.154g, and productive rate is 63.1%.With elemental analysis the structure of title complex 7, its molecular formula is C
31H
45HoN
2Si
2, wherein carbon content is 64.92; Hydrogen richness is 6.87; Nitrogen content is 4.08.Preparation embodiment 6 title complexs 8 ((Ind-NHC) Lu (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.150g part (Ind-H-NHC-H) Br is joined wherein, behind the room temperature reaction 1h, reaction soln is joined 30ml, 0.213g Lu (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 6h, concentrate toluene solution to 2ml, add the 3ml normal hexane, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 8.With the normal hexane washing, drying gets 0.171g, and productive rate is 68.9%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum and elemental analysis the structure of title complex 8.
1H NMR (400MHz, C
6D
6, 25 ℃): δ-2.44 ,-2.09 (AB,
2J
H-H=2.0Hz, 2H, Lu-CH
2SiMe
3) ,-1.08 ,-0.78 (AB,
2J
H-H=12.0Hz, 2H, Lu-CH
2SiMe
3), 0.30 (s, 9H, Lu-CH
2SiMe
3), 0.45 (s, 9H, Lu-CH
2SiMe
3), 1.77 (s, 3H, C
6H
2Me
3), 1.92 (s, 3H, C
6H
2Me
3), 2.21 (s, 3H, C
6H
2Me
3), 2.70-2.76 (multi, 1H, CH
2CH
2), 2.79-2.86 (multi, 1H, CH
2CH
2), 3.54-3.59 (multi, 1H, CH
2CH
2), 3.83-3.90 (multi, 1H, CH
2CH
2), 5.87 (d,
3J
H-H=1.6Hz, 1H, NCH), 6.06 (d,
3J
H-H=1.6Hz, 1H, NCH), 6.69 (s, 1H, C
6H
2Me
3), 6.75,6.76 (AB,
3J=2.4Hz, 2H, indene), 6.79 (s, 1H, C
6H
2Me
3), 7.10 (s, 1H, Indene), 7.11 (s, 1H, indene), 7.16-7.21 (multi, 1H, indene), 7.93-7.95 (d,
3J
H-H=8.0Hz, 1H, indene); With elemental analysis the structure of title complex 8, its molecular formula is C
31H
45LuN
2Si
2Wherein carbon content is 54.49; Hydrogen richness is 6.11; Nitrogen content is 3.97.
Application Example 1
In glove box, take by weighing 0.0064g (10 μ mol) title complex 1, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and title complex 1 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.7 ten thousand, M
w/ M
n=1.09.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 98% in the chain microstructure.Glass transition temperature Tg=42 ℃.
Application Example 2
In glove box, take by weighing 0.0072g (10 μ mol) title complex 2, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 2 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=3.9 ten thousand, M
w/ M
n=1.08.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 98% in the chain microstructure.Glass transition temperature Tg=43 ℃.
Application Example 3
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.0 ten thousand, M
w/ M
n=1.12.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 99% in the chain microstructure.Glass transition temperature Tg=45 ℃.
Application Example 4
In glove box, take by weighing 0.0059g (10 μ mol) title complex 6, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 6 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.17g, transformation efficiency 50%.Use gpc analysis, the molecular weight M of polyisoprene
n=2.1 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 89% in the chain microstructure.Glass transition temperature Tg=23 ℃.
Application Example 5
In glove box, take by weighing 0.0067g (10 μ mol) title complex 7, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 7 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.1 ten thousand, M
w/ M
n=1.4.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 76% in the chain microstructure.Glass transition temperature Tg=5 ℃.
Application Example 6
In glove box, take by weighing 0.0068g (10 μ mol) title complex 8, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 8 is 500.React on 25 ℃ and carry out 36h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=3.7 ten thousand, M
w/ M
n=1.16.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 91% in the chain microstructure.Glass transition temperature Tg=20 ℃.
Application Example 7
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 40 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 40 ℃ carry out 3h after, after the ethanolic soln that adds 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=3.3 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 97% in the chain microstructure.Glass transition temperature Tg=49 ℃.
Application Example 8
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 50 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 50 ℃ and carry out 3h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.0 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 97% in the chain microstructure.Glass transition temperature Tg=47 ℃.
Application Example 9
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 60 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 60 ℃ and carry out 2h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=3.5 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 95% in the chain microstructure.Glass transition temperature Tg=47 ℃.
Application Example 10
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mo1) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 70 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 70 ℃ and carry out 2h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight of polyisoprene is bimodal distribution, M
n=4.6 ten thousand, 1.2 ten thousand, M
w/ M
n=1.2,1.1.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 95% in the chain microstructure.Glass transition temperature Tg=45 ℃.
Application Example 11
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 80 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 80 ℃ and carry out 2h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight of polyisoprene is bimodal distribution, M
n=4.6 ten thousand, 1.2 ten thousand, M
w/ M
n=1.2,1.1.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 94% in the chain microstructure.Glass transition temperature Tg=46 ℃.
Application Example 12
In glove box, take by weighing 0.0068g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Hexane solution, again to the hexane that wherein adds 2.6ml; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4, and with [Ph
3C] [B (C
6F
5)
4] powder is in the round-bottomed flask of containing catalyzer.After 30 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 25 ℃ and carry out 12h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.05g, transformation efficiency 15%.Use gpc analysis, the molecular weight of the molecular weight isoprene of polyisoprene is bimodal distribution, M
n=5.1 ten thousand, 3.3 ten thousand, M
w/ M
n=1.2,1.6.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 98% in the chain microstructure.Glass transition temperature Tg=42 ℃.
Application Example 13
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Hexane solution, add the hexane of 2.6ml again; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], and with [Ph
3C] [B (C
6F
5)
4] powder is added in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 40 ℃ of oil baths, after 10 minutes, in reaction vessel, add 0.5ml (5mmol) isoprene, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 40 ℃ and carry out 12h, after the ethanolic soln of adding 1ml10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight of polyisoprene is bimodal distribution, M
n=3.5 ten thousand, 2.2 ten thousand, M
w/ M
n=1.2,1.7.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 97% in the chain microstructure.Glass transition temperature Tg=41 ℃.
Application Example 14
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Hexane solution, add the hexane of 2.6ml again; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], and with [Ph
3C] [B (C
6F
5)
4] powder is added in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 50 ℃ of oil baths, after 10 minutes, in reaction vessel, add 0.5ml (5mmol) isoprene, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 50 ℃ and carry out 12h, after the ethanolic soln of adding 1ml10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight of polyisoprene is bimodal distribution, M
n=2.8 ten thousand, 1.6 ten thousand, M
w/ M
n=1.2,1.8.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 97% in the chain microstructure.Glass transition temperature Tg=40 ℃.
Application Example 15
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Chlorobenzene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml chlorobenzene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 25 ℃ and carry out 3h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.2 ten thousand, M
w/ M
n=1.07.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 98% in the chain microstructure.Glass transition temperature Tg=45 ℃.
Application Example 16
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 5.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 1.0ml (10mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 1000.React on 25 ℃ and carry out 24h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.68g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=8.6 ten thousand, M
w/ M
n=1.2.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 96% in the chain microstructure.Glass transition temperature Tg=49 ℃.
Application Example 17
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 8.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 2.0ml (10mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 2000.React on 25 ℃ and carry out 36h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 1.36g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=23.8 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 96% in the chain microstructure.Glass transition temperature Tg=48 ℃.
Application Example 18
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 10.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 3.0ml (30mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 3000.React on 25 ℃ and carry out 48h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 2.04g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=30.9 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 96% in the chain microstructure.Glass transition temperature Tg=49 ℃.
Application Example 19
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 10.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 4.0ml (40mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 4000.React on 25 ℃ and carry out 56h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 2.64g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=32.5 ten thousand, M
w/ M
n=1.4.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 94% in the chain microstructure.Glass transition temperature Tg=46 ℃.
Application Example 20
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 12.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add emerging 5.0ml (50mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 5000.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 3.40g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=35.9 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 93% in the chain microstructure.Glass transition temperature Tg=47 ℃.
Claims (7)
1. crystallinity 3, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used, form by rare earth compounding, aluminum alkyls and organic boron salt, it is characterized in that, the rare earth metal of described rare earth compounding is with the part chelating that contains N-heterocyclic carbine (NHC) group and be connected initiating group, its structural formula as shown in Equation 1:
Formula 1
Wherein, R
1Be fluorenyl, be the modification group of N-heterocyclic carbine, this group and rare earth ion chelating;
R
2Being the substituting group on the N-heterocyclic carbine, is the tertiary butyl, (2,4,6) trimethylphenyl, (2,6) diisopropyl phenyl, phenyl, cyclohexyl or adamantyl;
Rare earth metal (Ln) is scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu);
R
3Being the initiating group that links to each other with rare earth metal, is CH
2SiMe
3, CH (SiMe
3)
2, benzyl, N (SiMe
3)
2, methoxyl group (OCH
3), oxyethyl group (OC
2H
5), isopropoxy (O
iPr), positive propoxy (OPr), n-butoxy (OBu), tert.-butoxy (O
tBu) or the F of halogen atom, Cl, Br or I;
R
4Also being the initiating group that links to each other with rare earth metal, is CH
2SiMe
3, CH (SiMe
3)
2, benzyl, N (SiMe
3)
2, methoxyl group (OCH
3), oxyethyl group (OC
2H
5), isopropoxy (O
iPr), positive propoxy (OPr), n-butoxy (OBu), tert.-butoxy (O
tBu) or the F of halogen atom, Cl, Br or I; R
3And R
4Identical or inequality; N=1,2,3 or 4;
Wherein said aluminum alkyls is (CH
3)
3Al, (CH
3)
2AlCl, (CH
3) AlCl
2, (CH
3)
3Al
2Cl
3, (C
2H
5)
3Al, (C
2H
5)
2AlCl, (C
2H
5) AlCl
2, (C
2H
5)
3Al
2Cl
3, (C
2H
5)
2AlOC
2H
5, (
iPr)
3Al, (
iPr)
2AlH, (
iBu)
3Al, (
iBu)
2AlCl, (
iBu) AlCl
2, (
iBu)
2AlH or MAO; The molar ratio of aluminum alkyls and rare earth compounding is 10～100.
2. crystallinity 3 as claimed in claim 1, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, the R of described rare earth compounding
1Be fluorenyl, the molecular structural formula of title complex 1-5 is as follows:
Ln=Y, title complex 1
Ln=Ho, title complex 2
Ln=Lu, title complex 3
Ln=Sc, title complex 4
Ln=Gd, title complex 5.
3. crystallinity 3 as claimed in claim 1, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, described aluminum alkyls be (
iBu)
3Al or (C
2H
5)
3Al.
4. crystallinity 3 as claimed in claim 1 or 2, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, the mol ratio of described aluminum alkyls and rare earth compounding is 10.
5. crystallinity 3 as claimed in claim 1, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, described organic boron salt is [Ph
3C] [B (C
6F
5)
4], [PhMe
2NH] [B (C
6F
5)
4] or B (C
6F
5)
3The mol ratio of organic boron salt and rare earth compounding is 0.5～2.0.
6. crystallinity 3 as claimed in claim 5, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, described organic boron salt is [Ph
3C] [B (C
6F
5)
4].
7. as claim 5 or 6 described crystallinity 3, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, the mol ratio of described organic boron salt and rare earth compounding is 1.0.
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| CN102675614A (en) * | 2012-05-08 | 2012-09-19 | 南京工业大学 | Method for preparing polyamino acid block poly-hydroxy acid copolymer |
| CN103739747B (en) * | 2013-12-16 | 2016-06-01 | 中国科学院长春应用化学研究所 | Rare earth catalyst combination and the 3,4-for isoprene compounds thereof are polymerized |
| CN104311585A (en) * | 2014-09-10 | 2015-01-28 | 安徽师范大学 | Rare earth complex, catalyst composition for preparation of isoprene rubber and preparation method thereof, and preparation method of isoprene rubber |
| CN104650270B (en) * | 2014-11-10 | 2018-04-27 | 中国科学院长春应用化学研究所 | A kind of preparation method of the poly- beta-myrcenes of 3,4- |
| CN106397648B (en) * | 2016-08-30 | 2019-03-05 | 中国科学院长春应用化学研究所 | The poly- conjugated diolefin of high 3,4- of the side arm with unsaturated group or functional group and its their preparation method |
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| CN110218274B (en) * | 2019-06-20 | 2020-07-31 | 中国科学院长春应用化学研究所 | Preparation method of ethylene-conjugated diene random copolymer |
| CN114437273B (en) * | 2020-10-30 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of butyl rubber |
| CN113307901B (en) * | 2021-06-09 | 2022-07-15 | 中国科学院长春应用化学研究所 | Preparation method of ethylene-isoprene random copolymer, rubber composition and rubber product |
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| US8664343B2 (en) * | 2008-06-20 | 2014-03-04 | Bridgestone Corporation | Catalysts for preparing cis 1,4-polydienes |
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