CN104017121A - Method for preparation of isoprene and myrcene regional block copolymers by chain transfer reaction - Google Patents
Method for preparation of isoprene and myrcene regional block copolymers by chain transfer reaction Download PDFInfo
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- CN104017121A CN104017121A CN201410237912.0A CN201410237912A CN104017121A CN 104017121 A CN104017121 A CN 104017121A CN 201410237912 A CN201410237912 A CN 201410237912A CN 104017121 A CN104017121 A CN 104017121A
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Abstract
The invention belongs to the technical field of conjugated olefin polymerization, and in particular relates to a method for preparation of isoprene and myrcene regional block copolymers by chain transfer reaction. The method uses a rare earth / organic boron salt catalytic system for catalyzing isoprene and myrcene for solution polymerization, a 3, 4 and 1, 4-poly conjugated olefin regional block copolymer can be obtained by use of only a monomer and addition of two different alkyl aluminum reagents, or a three or four-block or multi-block copolymer can be obtained by use of two or more than two monomers. The monomer conversion rate can reach 100%. The block length and composition of a product can be highly controllable. In the copolymer, 3, 4-product content is usually controlled between 10% and 90%, the molecular weight of the product is i 60000-125000, and the molecular weight distribution is between 1.4 and 1.8. All regional block copolymers obtained by the method are reported for the first time; by changing of the added monomer type and amount, high molecular materials with different structural composition can be obtained, and the method has broad application prospects.
Description
Technical field
The invention belongs to conjugated alkene polymerization technique field, be specifically related to a kind of method of energy catalysis isoprene or myrcene polymerization generation two or many blocks region multipolymer.
Background technology
Polyolefine, as the important macromolecular material of a class, has improved the mankind's living environment and living condition greatly.Accordingly, polyolefin industry also becomes mainstay of the national economy industry, is the important symbol of a national petrochemical industry development.In various polyolefine materials, poly-conjugated alkene is that one has multiple advantageous property, the polymkeric substance of broad prospect of application.In them, be much rubber or the plastics of excellent property.Wherein, can be manually in a large number synthetic polyisoprene (IR) can be divided into cis Isosorbide-5-Nitrae-IR, trans Isosorbide-5-Nitrae-IR and 3,4-IR.And cis Isosorbide-5-Nitrae-IR is main natural rubber substitute.Trans Isosorbide-5-Nitrae-IR also claims gutta-percha, has many application in the field such as medical material, material with memory.3,4-IR is a kind of rubber that has applications well potentiality.Research shows, along with the increase of 3,4 Structure mass fractions, the rebound resilience of 3,4-polyisoprene rubber reduces, and oil-proofness, water tolerance and electrical property improve, aspect ventilation property and water-permeable close to isoprene-isobutylene rubber.The content that improves 3,4 structures is very significant to the raising of its wet-sliding resistant performance, and the raising of thermogenesis performance is not fairly obvious.Therefore, 3,4 Structure mass fractions high 3,4-polyisoprene rubber has had both excellent wet-sliding resistant performance and relatively low rolling resistance, is a kind of comparatively ideal sizing material of preparing high-performance tire.As Wolpers(reference: Wolpers, J. U.S. Patent 5,104,941,
1992) find, when 3,4-polyisoprene rubber is used as to tire tread glue, not only can improves the wet-sliding resistant performance of tire, and make tire keep good low-rolling-resistance and abrasion resistance.
Above tire manufacturing process, all relates to blending technology.But 2005, Cherian etc. proposed a kind of use single monomer, realize the technology (reference: A. E. Cherian, J. M. Rose, E. B. Lobkovsky, G. W. Coates. of polypropylene region copolymerization by controlling temperature of reaction
j. Am. Chem. Soc. 2005, 127,13770-13771).So-called region multipolymer, refers to that the structural unit of multipolymer or section are to embody different zones selectivity by a kind of monomer when the polymerization and the multipolymer that forms.This concept is very novel, owing to only using a kind of monomer in synthetic, but can obtain having the new multipolymer of different physicochemical property, and this method is saved cost greatly, and theoretical and practical application has huge meaning.At present, mostly be blend therein 3 for the method for modifying of Isosorbide-5-Nitrae-polyisoprene, 4-polyisoprene, this needs first to synthesize respectively Isosorbide-5-Nitrae-PI and 3,4-PI bi-material by different catalysts conventionally, is then mixed in proportion.In process, to use a large amount of solvents, the energy to complete mixing, be dried etc., be unfavorable for environmental protection and energy saving requirement, also improve production cost.Up to now, although Cai Zhengguo etc. have synthesized many blocks region multipolymer (reference: Z. Cai, M. Shinzawa, Y. Nakayama, T. Shiono. of divinyl
macromolecules 2009, 42,7642-7643), but there is not yet the report of the synthetic method of the report, particularly block length of isoprene region multipolymer and controlled two or the many blocks region multipolymer of component.Based on a class amidino groups rare earth dialkyl compound (L. Zhang, M. Nishiura, M. Yuki, Y. Luo, the Z. Hou. of the reports such as Zhang Lixin
angew. Chem. Int. Ed. 2008, 47,2642-2645), the present invention proposes a kind of method of preparing the region segmented copolymer of isoprene, myrcene by chain transfer reaction.
Summary of the invention
The object of this invention is to provide the method for preparing the region segmented copolymer of isoprene, myrcene by chain transfer reaction, use the method can prepare two or many blocks region multipolymer of isoprene, myrcene, and block length, component ratio can regulate arbitrarily.
The method of the region segmented copolymer of preparing isoprene, myrcene provided by the invention, the catalyst body of use is: the two alkyl catalysts (being rare earth compounding) of amidino groups rare earth metal, aurin tricarboxylic acid and organic boron salt;
Wherein, rare earth compounding structure is as follows:
Formula 1
Wherein, R
1group can be: alkyl ((CH
2)
n (n=2 ~ 6)), aryl (as phenyl, substituted-phenyl etc.); R group can be-CH
2c
6h
4nMe
2-
o,-CH
2siMe
3,-CH (SiMe
3)
2,-CH
2c
6h
5in alkyl; Rare earth metal (Ln) can be: scandium (Sc), yttrium (Y) and all lanthanon (as lanthanum (La), neodymium (Nd), samarium (Sm), lutetium (Lu) etc.).
Preferred catalyzer is: rare earth metal Ln=Y, R=-CH
2c
6h
4nMe
2-
o, R
1=-C
4h
9(
1a) or R
1=Ph (
1b).
In this system, aluminum alkyls can be aluminium isobutyl and aluminium trimethide, and the mol ratio of aluminum alkyls and rare earth compounding can be 1-10.
Described organic boron salt is [Ph
3c] [B (C
6f
5)
4] (borate); The mol ratio of organic boron salt and rare earth compounding is 0.8-1.2, and the mol ratio of preferred organic boron salt and rare earth compounding is 1.
Reaction solvent can be toluene, chlorobenzene.
In the present invention, the step of synthetic Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is:
(1) method of use casings in twice, the first step, in toluene or chlorobenzene, use 1 equivalent rare earth catalyst, 1 to 10 equivalent aluminium isobutyl and 1 equivalent organic boron salt to spend to room temperature initiation reaction-20, add first part of monomer, generating 3,4-structural unit is main polymkeric substance;
(2) second step, second step, first adds 3 to 10 equivalent aurin tricarboxylic acid-trimethyl aluminiums, then adds second part of monomer, and it is main polymkeric substance that the new conjugated alkene selective polymerisation adding of this system energy catalysis becomes cis Isosorbide-5-Nitrae-structural unit;
(3) finally use settling process, obtain the diblock region multipolymer of the poly-conjugated alkene of 3,4-and Isosorbide-5-Nitrae-poly-conjugated alkene.
In the present invention, the step of synthetic segmented copolymer is:
(1) use repeatedly reinforced method, the first step, in toluene or chlorobenzene, use 1 equivalent rare earth catalyst, 1 to 10 equivalent aluminium isobutyl and 1 equivalent organic boron salt to spend to room temperature initiation reaction-20, add first part of monomer, generating 3,4-structural unit is main polymkeric substance;
(2) second step, continues to add another kind of conjugated alkene monomer;
(3) the 3rd steps, add 3 to 10 equivalent aurin tricarboxylic acid-trimethyl aluminiums, add afterwards the 3rd part of monomer, and it is main polymkeric substance that the new conjugated alkene selective polymerisation adding of this system energy catalysis becomes cis Isosorbide-5-Nitrae-structural unit;
(4) the 4th steps, add another kind of conjugated alkene monomer;
(5) finally use settling process, obtain 4 block region multipolymers of the poly-conjugated alkene of 3,4-and Isosorbide-5-Nitrae-poly-conjugated alkene.
Above 5 steps, can not do the 2nd or the 4th step, just can obtain triblock copolymer.
The present invention can carry out the composite structure target macromolecular material different with performance from addition by the kind of controlling the monomer adding at every turn.
The representative chemical equation of preparing the region segmented copolymer of isoprene, myrcene by chain transfer reaction is described below:
Synthetic Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock:
Synthetic segmented copolymer:
The method of preparing the region segmented copolymer of isoprene, myrcene by chain transfer reaction provided by the invention, its method specifically for catalysis and step are as follows:
(1) dry monomer and solvent:
Isoprene or myrcene are added CaH is housed under room temperature
2round-bottomed flask in, stir two days, reflux after 1 hour, under low temperature decompression steam, degassed three times, remove oxygen.Then low temperature (35 under anhydrous and oxygen-free condition
oc) preserve.Chlorobenzene or toluene solvant are all with CaH is housed
2distilling flask reflux 8 hours, then underpressure distillation is out, degassed three times, remove oxygen, under anhydrous and oxygen-free condition, preserve.
(2) solution polymerization process of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock:
25 degrees Celsius, under anhydrous and oxygen-free condition (in glove box), get a certain amount of catalyzer, put into eggplant-shape bottle, and add chlorobenzene dissolving, then claim a certain amount of conjugated alkene and Al
ibu
3add wherein.Take promotor boron salt, its solution is added to dropping funnel, the rear eggplant-shape bottle that adds fast to be dissolved.After having reacted, add a certain amount of AlMe
3, to react 2 minutes, then add another part of monomer, reaction for some time is to finishing.In system, inject the ethanol quencher of 2 mL containing a small amount of concentrated hydrochloric acid (volume ratio 5-10%) rapidly.After 10 minutes, slowly add ethanol, until solid is separated out completely.Gained solid is put into 60 degrees Celsius of vacuum drying ovens and is dried to constant weight.
(3) solution polymerization process of segmented copolymer:
The first step: 25 degrees Celsius, under anhydrous and oxygen-free condition (in glove box), get a certain amount of catalyzer, put into eggplant-shape bottle, and add chlorobenzene dissolving, then claim a certain amount of conjugated alkene
aand Al
ibu
3add wherein.Take promotor boron salt, its solution is added to dropping funnel, the rear eggplant-shape bottle that splashes into fast to be dissolved;
Second step: after having reacted, add another part of conjugated alkene
b, reaction for some time;
The 3rd step: add a certain amount of AlMe
3, react 2 minutes, then add
aor
bmonomer, reaction for some time;
The 4th step: add from reinforced different for the third time
bor
amonomer, reaction is to finishing (if second or four step inoperation, be triblock copolymer).In system, inject (volume ratio 5-10%) ethanol quencher reaction of 2 mL containing a small amount of concentrated hydrochloric acid rapidly.After 10 minutes, slowly add ethanol, until solid is separated out completely.Gained solid is put into 60 degrees Celsius of vacuum drying ovens and is dried to constant weight.
In gained 3,4 and Isosorbide-5-Nitrae-poly-conjugated alkene blend 3,4-structural content can be with being intended to 10%-90% adjusting, gel permeation chromatography molecular weight for of polymkeric substance (GPC, Waters 410 1515_2707_2414 systems) mensuration.In multipolymer, the content of 3,4 and Isosorbide-5-Nitrae-poly-conjugated alkene structure is calculated by nuclear magnetic resonance spectrum.
The present invention utilizes rare earth/organic boron salt catalyst system catalysis isoprene, myrcene to carry out solution polymerization, only utilize a kind of monomer, obtain 3 by adding two kinds of different alkyllithium reagents, 4 and 1, the region multipolymer of the poly-conjugated alkene of 4-, or apply two or more monomer, obtain three or four block or segmented copolymers.Two kinds of aluminum alkylss act on simultaneously, and the mol ratio of itself and rare earth compounding is all in 1 10, and the mol ratio of organic boron salt and rare earth compounding is 0.8-1.2.Polymer solvent can be toluene, chlorobenzene.Polymerization temperature is-30 degrees Celsius 80 degrees Celsius, and the transformation efficiency of monomer can reach 100%.The block length of product and component height are controlled.In multipolymer, the content of 3,4-product is controlled between 10%-90% conventionally, and molecular weight of product is conventionally between 60000-125000, and molecular weight distribution is between 1.4-1.8.A kind of method of preparing the region segmented copolymer of isoprene, myrcene by chain transfer reaction shown in the present is first can feasible region copolymerization isoprene and the method for myrcene, the All Ranges multipolymer that the method obtains is reported first, and the region multipolymer that synthesized goes out is the multipolymer of brand-new kind.Meanwhile, add monomeric species and add-on can also obtain structure by change and form different macromolecular material, have broad application prospects.
Brief description of the drawings
Fig. 1 is embodiment 3 and the GPC image with the product described in table 1.
Fig. 2 is the GPC image of the product of embodiment 5-7.
Embodiment
Embodiment 1
Take 0.0155 g (0.01 mmol) title complex
1ain 100 mL eggplant-shape bottles, dissolve with 18 mL chlorobenzenes, then take 0.511 g (7.5 mmol) isoprene and add wherein, the Al that is 1M by 100 μ L concentration with syringe
i bu
3hexane solution injects said mixture.Take 0.0185 g (0.02 mmol) [Ph3C] [B (C6F5) 4] (promotor borate), add 2 mL chlorobenzenes and dissolve, go in dropping funnel.Dropping funnel and eggplant-shape bottle are assembled, open and stir, after 25 degrees Celsius of lower constant temperature, promotor is added in solution fast.After 10 minutes, add the AlMe that 100 μ L concentration are 1M
3n-heptane solution, stir, then add 0.511 g(7.5 mmol 2 minutes) isoprene, react 45 minutes.After having reacted, stir lower slowly dropping ethanol until solid is separated out completely.The liquid that inclines, 3,4 and the Isosorbide-5-Nitrae-polyisoprene copolymers obtaining is white solid.60 degrees Celsius of vacuum drying ovens are dried to constant weight, obtain multipolymer net production 1.020 g, and transformation efficiency is about 100%.With gpc analysis, can obtain one unimodal, its molecular weight is: 5.8 ten thousand, molecular weight distribution is: 1.37.Use hydrogen nuclear magnetic resonance spectrum analysis, wherein 3, the content of 4-structure is 63.5%.
Embodiment 2
Take 0.0156 g (0.01 mmol) title complex
1bin 100 mL eggplant-shape bottles, dissolve with 18 mL chlorobenzenes, then take 0.511 g (7.5 mmol) isoprene and add wherein, the Al that is 1M by 100 μ L concentration with syringe
i bu
3hexane solution injects said mixture.Take 0.0185 g (0.02 mmol) [Ph3C] [B (C6F5) 4] (promotor borate), add 2 mL chlorobenzenes and dissolve, go in dropping funnel.Dropping funnel and eggplant-shape bottle are assembled, open and stir, after 25 degrees Celsius of lower constant temperature, promotor is added in solution fast.After 10 minutes, add the AlMe that 100 μ L concentration are 1M
3n-heptane solution, stir, then add 0.511 g(7.5 mmol 2 minutes) isoprene, react 45 minutes.After having reacted, stir lower slowly dropping ethanol until solid is separated out completely.The liquid that inclines, 3,4 and the Isosorbide-5-Nitrae-polyisoprene copolymers obtaining is white solid.60 degrees Celsius of vacuum drying ovens are dried to constant weight, obtain multipolymer net production 1.021 g, and transformation efficiency is about 100%.With gpc analysis, can obtain one unimodal, its molecular weight is: 6.5 ten thousand, molecular weight distribution is: 1.42.Use hydrogen nuclear magnetic resonance spectrum analysis, wherein 3, the content of 4-structure is 63.0%.
Embodiment 3
Take 0.0156 g (0.01 mmol) title complex
1bin 100 mL eggplant-shape bottles, dissolve with 18 mL chlorobenzenes, then take 0.511 g (7.5 mmol) isoprene and add wherein, the Al that is 1M by 100 μ L concentration with syringe
i bu
3hexane solution injects said mixture.Take 0.0185 g (0.02 mmol) [Ph3C] [B (C6F5) 4] (promotor borate), add 2 mL chlorobenzenes and dissolve, go in dropping funnel.Dropping funnel and eggplant-shape bottle are assembled, open and stir, after 25 degrees Celsius of lower constant temperature, promotor is added in solution fast.After 10 minutes, add the AlMe that 140 μ L concentration are 1M
3n-heptane solution, stir, then add 0.511 g(7.5 mmol 2 minutes) isoprene, react 45 minutes.After having reacted, stir lower slowly dropping ethanol until solid is separated out completely.The liquid that inclines, 3,4 and the Isosorbide-5-Nitrae-polyisoprene copolymers obtaining is white solid.In 60 degrees Celsius of vacuum drying ovens, be dried to constant weight, obtain multipolymer net production 1.019 g, transformation efficiency is about 100%.With gpc analysis, can obtain one unimodal, its molecular weight is: 6.1 ten thousand, molecular weight distribution is: 1.43.Use hydrogen nuclear magnetic resonance spectrum analysis, wherein 3, the content of 4-structure is 51.9%.
In the situation that adding all the other conditions of amount of monomer constant (reaction times is in Table) for twice, change uses
1bgenerate 3,4 and the results are shown in Table shown in 1 of Isosorbide-5-Nitrae-polyisoprene copolymers as one pot of catalyst isoprene:
Table 1
The GPC of the product described in embodiment 3 and table 1 as shown in Figure 1.
Embodiment 4
Take 0.0156 g (0.01 mmol) title complex
1bin 100 mL eggplant-shape bottles, dissolve with 18 mL chlorobenzenes, then take 0.511 g (7.5 mmol) isoprene and add wherein, the Al that is 1M by 100 μ L concentration with syringe
ibu
3hexane solution injects said mixture.Take 0.0185 g (0.02 mmol) [Ph3C] [B (C6F5) 4] (promotor borate), add 2 mL chlorobenzenes and dissolve, go in dropping funnel.Dropping funnel and eggplant-shape bottle are assembled, put into-20 degrees Celsius of cryostat devices, open and stir, after constant temperature, promotor is added in solution fast.After 20 minutes, add the AlMe that 140 μ L concentration are 1M
3n-heptane solution, stir, then add 0.511 g(7.5 mmol 2 minutes) isoprene, react 90 minutes.After having reacted, stir lower slowly dropping ethanol until solid is separated out completely.The liquid that inclines, 3,4 and the Isosorbide-5-Nitrae-polyisoprene copolymers obtaining is white solid.This solid is put into 60 degrees Celsius of vacuum drying ovens and be dried to constant weight, obtain multipolymer net production 1.022 g, transformation efficiency is about 100%.With gpc analysis, can obtain one unimodal, its molecular weight is: 7.8 ten thousand, molecular weight distribution is: 1.50.Use hydrogen nuclear magnetic resonance spectrum analysis, wherein 3, the content of 4-structure is 50.5%.
Embodiment 5
Take 0.0156 g (0.01 mmol) title complex
1bin 100 mL eggplant-shape bottles, dissolve with 18 mL chlorobenzenes, then take 0.511 g (7.5 mmol) isoprene and add wherein, the Al that is 1M by 100 μ L concentration with syringe
i bu
3hexane solution injects said mixture.Take 0.0185 g (0.02 mmol) [Ph3C] [B (C6F5) 4] (promotor borate), add 2 mL chlorobenzenes and dissolve, go in dropping funnel.Dropping funnel and eggplant-shape bottle are assembled, open and stir, after 25 degrees Celsius of constant temperature, promotor is added in solution fast.After 10 minutes, add the AlMe that 140 μ L concentration are 1M
3n-heptane solution, stir, then add 0.511 g(3.75 mmol 2 minutes) myrcene, react 90 minutes.After having reacted, stir lower slowly dropping ethanol until solid is separated out completely.The liquid that inclines, obtain 3,4-polyisoprene and Isosorbide-5-Nitrae-polyoxyethylene lauryl alkene copolymer are white solid.In 60 degrees Celsius of vacuum drying ovens, be dried to constant weight, obtain multipolymer net production 1.017 g, transformation efficiency is about 100%.With gpc analysis, can obtain one unimodal, its molecular weight is: 5.7 ten thousand, molecular weight distribution is: 1.80.
Embodiment 6
Take 0.0156 g (0.01 mmol) title complex
1bin 100 mL eggplant-shape bottles, dissolve with 18 mL chlorobenzenes, then take 0.511 g (7.5 mmol) isoprene and add wherein, the Al that is 1M by 100 μ L concentration with syringe
i bu
3hexane solution injects said mixture.Take 0.0185 g (0.02 mmol) [Ph3C] [B (C6F5) 4] (promotor borate), add 2 mL chlorobenzenes and dissolve, go in dropping funnel.Dropping funnel and eggplant-shape bottle are assembled, open and stir, after 25 degrees Celsius of constant temperature, promotor is added in solution fast.After 10 minutes, add 0.511 g(3.75 mmol) myrcene, reacts 20 minutes, then adds the AlMe that 140 μ L concentration are 1M
3n-heptane solution, stir, then add 0.511 g(7.5 mmol 2 minutes) isoprene, react 45 minutes.After having reacted, stir lower slowly dropping ethanol until solid is separated out completely.The liquid that inclines, obtain 3,4-polyisoprene and 3,4-polyoxyethylene lauryl alkene and Isosorbide-5-Nitrae-polyisoprene triblock copolymer are white solid.In 60 degrees Celsius of vacuum drying ovens, be dried to constant weight, obtain multipolymer net production 1.526 g, transformation efficiency is about 100%.With gpc analysis, can obtain one unimodal, its molecular weight is: 8.8 ten thousand, molecular weight distribution is: 1.53.
Embodiment 7
Take 0.0156 g (0.01 mmol) title complex
1bin 100 mL eggplant-shape bottles, dissolve with 18 mL chlorobenzenes, then take 0.511 g (7.5 mmol) isoprene and add wherein, the Al that is 1M by 100 μ L concentration with syringe
i bu
3hexane solution injects said mixture.Take 0.0185 g (0.02 mmol) [Ph3C] [B (C6F5) 4] (promotor borate), add 2 mL chlorobenzenes and dissolve, go in dropping funnel.Dropping funnel and eggplant-shape bottle are assembled, open and stir, after 25 degrees Celsius of constant temperature, promotor is added in solution fast.After 10 minutes, add 0.511 g(3.75 mmol) myrcene, reacts 20 minutes, then adds the AlMe that 140 μ L concentration are 1M
3n-heptane solution, stir, then add 0.511 g(7.5 mmol 2 minutes) isoprene, react, finally add 0.511 g(3.75 mmol 45 minutes) myrcene, react 90 minutes.After having reacted, stir lower slowly dropping ethanol until solid is separated out completely.The liquid that inclines, obtain 3, the Tetrablock copolymer of 4-polyisoprene and 3,4-polyoxyethylene lauryl alkene and Isosorbide-5-Nitrae-polyisoprene and Isosorbide-5-Nitrae-polyoxyethylene lauryl alkene is white solid.60 degrees Celsius of vacuum drying ovens are dried to constant weight, obtain multipolymer net production 2.040 g, and transformation efficiency is about 100%.With gpc analysis, can obtain one unimodal, its molecular weight is: 11.1 ten thousand, molecular weight distribution is: 1.73.
The GPC image of the product of embodiment 5-7 as shown in Figure 2.
Claims (2)
1. prepare a method for the region segmented copolymer of isoprene, myrcene by chain transfer reaction, it is characterized in that the catalyst body using is: the two alkyl catalysts of amidino groups rare earth metal are rare earth compounding, aurin tricarboxylic acid and organic boron salt; Wherein, rare earth compounding structure is as follows:
Formula 1
Wherein, R
1group is: alkyl ((CH
2)
n (n=2 ~ 6)), aryl; R group is-CH
2c
6h
4nMe
2-
o,-CH
2siMe
3,-CH (SiMe
3)
2,-CH
2c
6h
5in alkyl; Rare earth metal Ln is: scandium, yttrium and all lanthanon, neodymium, samarium, lutetium;
Described aluminum alkyls is aluminium isobutyl and aluminium trimethide, and the mol ratio of aluminum alkyls and rare earth compounding is 1-10;
Described organic boron salt is [Ph
3c] [B (C
6f
5)
4], the mol ratio of organic boron salt and rare earth compounding is 0.8-1.2;
Reaction solvent is toluene or chlorobenzene.
2. method according to claim 1, is characterized in that:
The step of synthetic Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is:
(1) method of use casings in twice, the first step, in toluene or chlorobenzene, use 1 equivalent rare earth catalyst, 1 to 10 equivalent aluminium isobutyl and 1 equivalent organic boron salt to spend to room temperature initiation reaction-20, add first part of monomer, generating 3,4-structural unit is main polymkeric substance;
(2) second step, first adds 3 to 10 equivalent aurin tricarboxylic acid-trimethyl aluminiums, then adds second part of monomer, and it is main polymkeric substance that the new conjugated alkene selective polymerisation adding of this system energy catalysis becomes cis Isosorbide-5-Nitrae-structural unit;
(3) finally use settling process, obtain the diblock region multipolymer of the poly-conjugated alkene of 3,4-and Isosorbide-5-Nitrae-poly-conjugated alkene;
The step of synthetic segmented copolymer is:
(1) use repeatedly reinforced method, in toluene or chlorobenzene, use 1 equivalent rare earth catalyst, 1 to 10 equivalent aluminium isobutyl and 1 equivalent organic boron salt to spend to room temperature initiation reaction-20, add first part of monomer, generating 3,4-structural unit is main polymkeric substance;
(2) second step, continues to add another kind of conjugated alkene monomer;
(3) the 3rd steps, add 3 to 10 equivalent aurin tricarboxylic acid-trimethyl aluminiums, add afterwards the 3rd part of monomer, and it is main polymkeric substance that the new conjugated alkene selective polymerisation adding of this system energy catalysis becomes cis Isosorbide-5-Nitrae-structural unit;
(4) the 4th steps, add another kind of conjugated alkene monomer;
(5) finally use settling process, obtain 4 block region multipolymers of the poly-conjugated alkene of 3,4-and Isosorbide-5-Nitrae-poly-conjugated alkene;
Above 5 steps, do not do the 2nd or the 4th step, obtain triblock copolymer.
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| CN106084108A (en) * | 2016-06-14 | 2016-11-09 | 郭云琴 | A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber |
| CN111087508A (en) * | 2019-12-30 | 2020-05-01 | 复旦大学 | Coordination chain transfer polyisoprene system based on amidino rare earth alkyl compound |
| CN112592421A (en) * | 2020-11-22 | 2021-04-02 | 复旦大学 | Method for preparing isoprene multi-block region copolymer by chain shuttle reaction |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106084108A (en) * | 2016-06-14 | 2016-11-09 | 郭云琴 | A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber |
| CN111087508A (en) * | 2019-12-30 | 2020-05-01 | 复旦大学 | Coordination chain transfer polyisoprene system based on amidino rare earth alkyl compound |
| CN112592421A (en) * | 2020-11-22 | 2021-04-02 | 复旦大学 | Method for preparing isoprene multi-block region copolymer by chain shuttle reaction |
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