CN110105400B - Temperature-sensitive ruthenium carbene complex and preparation method and application thereof - Google Patents

Temperature-sensitive ruthenium carbene complex and preparation method and application thereof Download PDF

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CN110105400B
CN110105400B CN201910472333.7A CN201910472333A CN110105400B CN 110105400 B CN110105400 B CN 110105400B CN 201910472333 A CN201910472333 A CN 201910472333A CN 110105400 B CN110105400 B CN 110105400B
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carbene complex
ruthenium carbene
grubbs
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CN110105400A (en
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杨维成
刘建
罗勇
段高坤
付宏伟
乔新峰
乔拟春
李秀君
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Shanghai Research Institute of Chemical Industry SRICI
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Abstract

The invention relates to a temperature-sensitive ruthenium carbene complex and a preparation method and application thereof3Adding the mixture into a solvent for reaction; separating, purifying and drying the reacted materials to obtain the temperature-sensitive ruthenium carbene complex; the temperature-sensitive ruthenium carbene complex is a catalyst with temperature-sensitive property, is applied to catalyzing double decomposition reaction of olefin, and is particularly suitable for catalyzing ring-opening ectopic polymerization reaction of olefin. Compared with the prior art, the catalyst has the advantages of simple preparation process, easily obtained raw materials, small dosage, controllable temperature, capability of realizing temperature-controlled polymerization of olefin, wide industrial application prospect and the like when being used for ring-opening ectopic polymerization of olefin.

Description

Temperature-sensitive ruthenium carbene complex and preparation method and application thereof
Technical Field
The invention relates to a ruthenium carbene complex and a preparation method and application thereof, belongs to the technical field of organic metal catalyst preparation, and particularly relates to a temperature-sensitive ruthenium carbene complex and a preparation method and application thereof.
Background
The research on olefin metathesis reactions and their great value in the fields of medicine, materials, etc. have led to rapid development in recent decades. Ring-opening metathesis polymerization (ROMP) is an important reaction type in olefin metathesis, and research in this field has been mainly focused on the preparation of specific catalysts suitable for respective conditions, and functional materials prepared based on the reaction. Through the development of many years, the catalyst suitable for ring-opening ectopic polymerization generates dispersion of different structure types, wherein the most important catalyst is the carbene-type catalyst which is most widely researched at present. Among these catalysts, the Grubbs catalyst is most widely used, and similarly Schrock catalysts, Grubbs catalyst-derived Hoveyda-Grubbs catalysts, Grela catalysts and Zhan catalysts. The catalysts have the characteristics of high catalytic rate and high catalytic activity.
For a specific forming processing technology, the whole process is from feed liquid preparation, feed liquid injection molding and heating forming, and the process needs certain operation time at each stage. The stability requirement of the system from the preparation of the feed liquid to the injection molding completion stage is high, and the high efficiency of the catalyst greatly restricts the application of the catalyst in the molding processing. There are two main ways to solve this problem. The first way is to add different kinds of additives to suppress the catalytic activity of the catalyst, enabling a controlled regulation of the polymerization process. It is noted that while inhibiting the catalyst activity, the introduction of additives also affects the final properties of the material. The second approach is to use a lower/medium activity catalyst, which has the major disadvantage of requiring a large amount of catalyst to participate, and the cost of the polymeric material is controlled primarily by the amount of catalyst used.
Therefore, how to prepare the catalyst which has higher catalytic activity and can realize the temperature control regulation of the ring-opening ex-situ polymerization of the olefin has great significance for the ring-opening ex-situ polymerization of the olefin. Van der Schaaf et al [ J.organometat.chem., 2000,606:65-74] prepared latent catalysts for initiating ring opening metathesis polymerization of olefins, which were not highly active although the initiation temperature was adjusted by changing the substituent of the pyridine ring. Ung et al [ Organometallics,2004,23: 5399-5401 ] then modulate the catalyst activity by partial isomerization of the structure, but these catalysts cannot be stored for long periods in olefin monomers and complete the polymerization process within 25 min. Verpoort et al [ J.mol.Cat.A: chem.,2006,260:221-226] studied O, N-bidentate Schiff base in combination with a ruthenium carbene catalyst, which can be stored in olefins for months but is relatively poor in activity. At present, the research on the temperature-controlled catalyst is relatively slow, the catalyst can only realize partial functions, and most of the catalysts have low activity, complex structure or certain corrosion.
Disclosure of Invention
The invention aims to prepare a ruthenium carbene complex suitable for ring-opening ectopic polymerization of olefin by optimizing a ligand in the ruthenium carbene complex, and the ruthenium carbene complex has a simple structure and a simple preparation process and has certain potential in the field of olefin temperature control catalysis.
The purpose of the invention can be realized by the following technical scheme:
a temperature-sensitive ruthenium carbene complex has the following chemical general formula:
Figure GDA0003166997280000021
r in the chemical general formula is linear alkyl or aryl.
And R is straight-chain alkyl, and the carbon atom number of the R is 1-16.
And R is aryl, and the aryl has the following general formula:
Figure GDA0003166997280000022
wherein R1, R2, R3, R4 and R5 are all selected from one of hydrogen, amino, alkyl with 1-16 carbon atoms, alkoxy with 1-16 carbon atoms or alkyl phosphorus with 1-16 carbon atoms.
The temperature-sensitive ruthenium carbene complex mainly solves the problem that the catalytic speed of Grubbs second-generation catalyst in the ring-opening ex-situ polymerization of olefin is too high, olefin is not polymerized under the low-temperature condition, and when the system is raised to a certain temperature, the system can be polymerized quickly.
As is known from the mechanism of olefin metathesis, in the catalytic reaction process, the active center of the catalyst is metal carbene (M ═ CHR), and the active center opens the double bond of olefin (C ═ C) to form a metal cyclobutane structure, and then rearranges to realize the catalytic process. Therefore, how to regulate the release of active centers in the present catalytic system is the core point of the present invention. The invention selects the ligand with stronger electron donating property to coordinate with the active center to obtain the target catalyst, and aims to ensure that the catalyst structure is kept stable and the active center is not easy to form based on the strong coordination effect of the ligand when the temperature of the catalyst is lower, and the ligand can be separated from the active center after the temperature is increased, thereby realizing the temperature control catalytic effect of the catalyst. Therefore, the optimization of the ligand with appropriate electron donating property is the key for realizing temperature-controlled catalysis, if the electron donating property is too strong, the catalyst is difficult to release active centers at a very high temperature for realizing catalysis, and if the electron donating property is weaker, the initiation rate of the catalyst can be over-accelerated.
The invention also provides a preparation method of the temperature-sensitive ruthenium carbene complex, which comprises the following steps: taking a Grubbs three-generation catalyst, and reacting the Grubbs three-generation catalyst with NR3Adding the mixture into a solvent for reaction; and separating, purifying and drying the reacted materials to obtain the temperature-sensitive ruthenium carbene complex.
Wherein, the general formula of the Grubbs three-generation catalyst is as follows:
Figure GDA0003166997280000031
in the invention, the Grubbs third-generation catalyst is prepared by taking Grubbs second-generation catalyst and pyridine as reaction raw materials; the general formula of the Grubbs second generation catalyst is as follows:
Figure GDA0003166997280000032
the preparation method of the Grubbs three-generation catalyst comprises the following steps:
mixing the Grubbs second-generation catalyst with pyridine, and reacting under the condition of stirring at room temperature to obtain the Grubbs third-generation catalyst; wherein the reaction time is 12-24 h, preferably 20-24 h.
The NR is3The molar ratio of the Grubbs tertiary catalyst to the Grubbs tertiary catalyst is 1/1-20/1, the reaction temperature is 25-60 ℃,the reaction time is 12-48 h; the solvent is one or more selected from tetrahydrofuran, ethyl acetate, diethyl ether, acetone, acetonitrile, toluene or 1, 4-dioxane.
The synthetic route for preparing the temperature-sensitive ruthenium carbene complex by using the Grubbs second-generation catalyst as the raw material is as follows:
Figure GDA0003166997280000041
the invention starts from Grubbs second-generation catalyst, obtains the target catalyst through two-step reaction, and obtains the target catalyst with the chemical purity of more than 99.0 percent after separation and purification.
For this synthesis process, the most important factor affecting the synthesis result is the ratio of the reaction solvent and the reactants. In the synthesis process, a solvent with medium or weak polarity is selected, and a solvent with weak coordination capacity is selected under the condition of ensuring the dissolution of a reaction substrate, so that the target ligand can be effectively coordinated with an active center, and the stability of the catalyst structure is ensured. In addition, the dosage of the ligand determines whether the ligand can coordinate with the metal, the dosage of the ligand with weaker coordination capacity is larger so as to ensure that the target catalyst is obtained, and if the ligand with stronger coordination capacity is slightly stronger, the target catalyst can be obtained by using less ligand. It should be noted that if the amount of the ligand is too large, the structure of the catalyst may be destroyed, which is not favorable for the formation of the target catalyst.
The invention also provides an application of the temperature-sensitive ruthenium carbene complex, wherein the temperature-sensitive ruthenium carbene complex is used as a catalyst with temperature-sensitive property and applied to catalyzing double decomposition reaction of olefin; the olefin is selected from one or more of norbornene, cyclohexene, dicyclopentadiene, cyclooctene, cyclopentadiene, 1-octene, 1-hexene, styrene or derivatives of any of the foregoing olefins.
Preferably, the temperature-sensitive ruthenium carbene complex is used for catalyzing cyclic olefin to carry out ring-opening ectopic polymerization reaction; the temperature-sensitive ruthenium carbene complex and cyclic olefin are mixed according to the molar ratio of 1/30000-1/200000, the cyclic olefin cannot carry out ring-opening ectopic polymerization reaction at the temperature of 25-35 ℃, and the cyclic olefin carries out ring-opening ectopic polymerization reaction at the temperature of 80-200 ℃; the polymerization time of the ring-opening ectopic polymerization reaction is 5-20 min.
From the catalytic mechanism, the formation of metal carbene (M ═ CHR) as the active center in the reaction process is the basis for ensuring that the catalyst has better catalytic activity. For the invention, the temperature-sensitive ruthenium carbene complex keeps stable structure at low temperature, and when the temperature is raised to a certain degree, the ligand is separated from the active center to form a high-activity metal carbene active center, thereby realizing the rapid polymerization of olefin.
Compared with the prior art, the invention has the following advantages:
(1) the temperature-sensitive ruthenium carbene complex prepared by the invention has temperature-sensitive characteristic, and the metal complex can realize temperature-controlled polymerization of olefin, i.e. olefin polymerization is not caused at room temperature, and when a system added with a catalyst is raised to a certain temperature, rapid polymerization of the system can be realized; therefore, in the production process, the stability of a material system is favorably ensured when the material liquid is prepared to the injection molding completion stage, and the polymerization reaction can be efficiently catalyzed after the temperature is raised in the reaction stage; the high-efficiency, safe and stable operation of the whole process is ensured; has wide industrial application prospect.
(2) The preparation method of the temperature-sensitive ruthenium carbene complex has the advantages of simple preparation process, convenient operation and the like; in the preparation process, the reaction condition is mild, the raw materials are easy to obtain, the synthesis route is short, the preparation yield is high, and industrial amplification and production implementation are easy.
(3) The temperature-sensitive ruthenium carbene complex can effectively catalyze olefin temperature-controlled polymerization reaction, and has the advantages of high catalytic activity, small catalyst consumption, short reaction time, controllable temperature and polymer yield up to 95-99%.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment is a preparation method of temperature-sensitive ruthenium carbene complex, and the synthetic route is as follows:
Figure GDA0003166997280000051
the preparation process comprises the following steps:
(1) 20.0g of Grubbs's second generation catalyst is taken into a 250mL flask, 100mL of pyridine (used as a solvent and a reactant) is added, stirring is carried out for 24 hours at room temperature, and then separation and purification are carried out to obtain 16.0g of Grubbs' third generation catalyst with the yield of 93%; the preparation process comprises the following steps: the preparation of Grubbs' third generation catalysts is described in Organometallics,2001,20, 5314-5318.
Performing nuclear magnetic resonance characterization on the prepared Grubbs three-generation catalyst, wherein the detection data are as follows:
1H NMR(CDCl3)19.67(s,1H,CH＝Ph),8.84(s,2H,pyridine),8.39(s,2H,pyridine),8.07(d,2H,ortho CH),7.15(t,1H,para CH),6.83-6.04(m,9H,pyridine,Mes-CH),3.37(d,4H,CH2CH2),2.79(s,6H,Mes-CH3),2.45(s,6H,Mes-CH3),2.04(s,6H,Mes-CH3).
(2) further preparing a temperature-sensitive ruthenium carbene complex by adopting the Grubbs third-generation catalyst prepared in the step (1); the preparation method comprises the following steps: 1.0g of Grubbs's tertiary catalyst was reacted with 0.081g N (CH)3)3(1.0 equiv.) 5mL tetrahydrofuran was added and magnetically stirred at 25 ℃ for 12 h; after the reaction is finished, 0.76g of temperature-sensitive ruthenium carbene complex is obtained through separation, purification and drying, and is marked as a catalyst Cat-1, and the yield of the catalyst is 88%.
Performing nuclear magnetic resonance characterization on the prepared catalyst Cat-1, wherein the detection data are as follows:
1H NMR(CDCl3)δ(ppm)＝2.12(s,12H,Mes-CH3),2.26(s,6H,Mes-CH3),2.27(s,9H,N-CH3),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.23(t,2H,Ar-H),7.54(t,1H,ArH),7.75(d,2H,Ar-H),19.03(d,Ru＝CH-Ph).
wherein the structure of the Cat-1 catalyst is as follows:
Figure GDA0003166997280000061
(3) catalyzing the polymerization reaction of 5-ethylidene-2-norbornene by using the Cat-1 catalyst prepared in the step (2): in a reaction flask, 100.0g of 5-ethylidene-2-norbornene and 17.4mg of cat. -1 (olefin/cat. ═ 30000/1, molar ratio) were added, followed by stirring at 25 ℃ for 1 h. Then, the mixture was heated to 80 ℃ and polymerized for 10min, and the yield of the polymer was 98%.
The obtained polymer was subjected to a performance test, and the detection data are as follows: tensile strength of 56MPa, yield elongation of 8.35%, tensile modulus of 1425MPa, bending strength of 71MPa, bending modulus of 1130MPa, and impact strength of 11.5KJ/m2。
Example 2
In the implementation, the Grubbs third-generation catalyst obtained in the step (1) in the example 1 is adopted to further prepare a temperature-sensitive ruthenium carbene complex, namely a catalyst Cat-2; and the prepared catalyst is used for catalyzing the polymerization reaction of the 2, 5-dimethyl-2, 4-hexadiene.
(1) 1.0g of Grubbs's tertiary catalyst was mixed with 4.86gN (C)8H17)3(10.0 equiv.) was added to 5mL ethyl acetate solvent and magnetically stirred at 40 ℃ for 12 h; after the reaction is finished, 1.04g of catalyst Cat-2 is obtained by separation, purification and drying, and the catalyst yield is 82%.
Performing nuclear magnetic resonance characterization on the prepared catalyst Cat-2, wherein the detection data are as follows:
1H NMR(CDCl3)δ(ppm)＝0.88(t,9H,CH2-CH3),1.26(t,36H,-CH2-),2.12(s,12H,Mes-CH3),2.26(s,6H,Mes-CH3),2.34(t,6H,N-CH2),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.23(t,2H,Ar-H),7.54(t,1H,ArH),7.75(d,2H,Ar-H),19.03(d,Ru＝CH-Ph).
wherein the structure of the Cat-2 catalyst is as follows:
Figure GDA0003166997280000071
(2) in a reaction flask, 100.0g of 2, 5-dimethyl-2, 4-hexadiene and 16.8mg of cat. -2 (olefin/cat. ═ 50000/1, molar ratio) were added, followed by stirring at 30 ℃ for 1 h. Then, the mixture was heated to 100 ℃ and polymerized for 15min, and the yield of the polymer was 99%.
The obtained polymer was subjected to a performance test, and the detection data are as follows: tensile strength 49MPa, yield elongation 6.9%, tensile modulus 1380MPa, bending strength 78MPa, bending modulus 1070MPa, impact strength 9.7KJ/m2。
Example 3
In the implementation, the Grubbs third-generation catalyst obtained in the step (1) in the example 1 is adopted to further prepare a temperature-sensitive ruthenium carbene complex, namely a catalyst Cat-3; and the prepared catalyst is used for catalyzing the polymerization reaction of dicyclopentadiene.
(1) 1.0g of Grubbs' tertiary catalyst was reacted with 18.95g N (C)16H33)3(20.0 equiv.) is added into 20mL of ether solvent, and magnetic stirring is carried out for 48h at the temperature of 60 ℃; after the reaction is finished, 1.19g of catalyst Cat-3 is obtained by separation, purification and drying, and the yield is 69%.
Performing nuclear magnetic resonance characterization on the prepared catalyst Cat-3, wherein the detection data are as follows:
1H NMR(CDCl3)δ(ppm)＝0.88(t,9H,CH2-CH3),1.27(t,84H,-CH2-),2.12(s,12H,Mes-CH3),2.26(s,6H,Mes-CH3),2.34(t,6H,N-CH2),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.23(t,2H,Ar-H),7.54(t,1H,ArH),7.75(d,2H,Ar-H),19.03(d,Ru＝CH-Ph).
wherein the structure of the Cat-3 catalyst is as follows:
Figure GDA0003166997280000081
(2) in a reaction flask, 100.0g of dicyclopentadiene and 9.5mg of cat "-3 (olefin/cat. ═ 100000/1, molar ratio) were added, followed by stirring at 35 ℃ for 1 h. Then, the mixture was heated to 150 ℃ and polymerized for 20min, resulting in a polymer yield of 95%.
The obtained polymer was subjected to a performance test, and the detection data are as follows: tensile strength of 46MPa, yield elongation of 10.2%, tensile modulus of 1580MPa, bending strength of 73MPa, bending modulus of 1250MPa, and impact strength of 8.5KJ/m2。
Example 4
In the implementation, the Grubbs third-generation catalyst obtained in the step (1) in the example 1 is adopted to further prepare a temperature-sensitive ruthenium carbene complex, namely a catalyst Cat-4; and the prepared catalyst is used for catalyzing polymerization reaction of bicyclohexene.
(1) 1.0g Grubbs of the third generation catalyst was mixed with 0.67gN (C)6H5)3(2.0 equiv.) 5mL acetone was added and magnetically stirred at 30 ℃ for 15 h; after the reaction is finished, 0.95g of catalyst Cat-4 is obtained through separation, purification and drying, and the yield of the catalyst is 85%.
Performing nuclear magnetic resonance characterization on the prepared catalyst Cat-4, wherein the detection data are as follows:
1H NMR(CDCl3)δ(ppm)＝2.12(s,12H,Mes-CH3),2.26(s,6H,Mes-CH3),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.02(t,3H,Ar-H),7.18(d,6H,Ar-H),7.29(t,6H,Ar-H),7.23(t,2H,Ar-H),7.54(t,1H,ArH),7.75(d,2H,Ar-H),19.03(d,Ru＝CH-Ph).
wherein the structure of the Cat-4 catalyst is as follows:
Figure GDA0003166997280000091
(2) in a reaction flask, 100.0g of cyclohexene and 4.9mg of cat. -4 (olefin/cat. ═ 200000/1, molar ratio) were added, followed by stirring at 30 ℃ for 1 h. Then, the mixture was heated to 180 ℃ and polymerized for 10min, and the polymer yield was 96%.
The obtained polymer was subjected to a performance test, and the detection data are as follows: tensile strength 38MPa, elongation at yield 5.6%, tensile modulus 980MPa, bending strength 57MPa, bending modulus 990MPa, and impact strength 6.5KJ/m2。
Example 5
In the implementation, the Grubbs third-generation catalyst obtained in the step (1) in the example 1 is adopted to further prepare a temperature-sensitive ruthenium carbene complex, namely a catalyst Cat-5; and the prepared catalyst is used for catalyzing polymerization reaction of cyclooctene.
(1) 1.0g of Grubbs' tertiary catalyst was reacted with 1.98g N (C)7H7)3(5.0 equiv.) 5mL acetonitrile was added and magnetically stirred at 50 ℃ for 24 h; after the reaction is finished, 0.93g of catalyst Cat-5 is obtained by separation, purification and drying, and the catalyst yield is 79%.
Performing nuclear magnetic resonance characterization on the prepared catalyst Cat-5, wherein the detection data are as follows:
1H NMR(CDCl3)δ(ppm)＝2.12(s,12H,Mes-CH3),2.26(s,6H,Mes-CH3),2.32(t,9H,Ar-CH3),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.18(d,6H,Ar-H),7.29(t,6H,Ar-H),7.23(t,2H,Ar-H),7.54(t,1H,ArH),7.75(d,2H,Ar-H),19.03(d,Ru＝CH-Ph).
wherein the structure of the Cat-5 catalyst is as follows:
Figure GDA0003166997280000101
(2) in a reaction flask, 100.0g of cyclooctene and 7.7mg of cat. -5 (olefin/cat. ═ 100000/1, molar ratio) were added, followed by stirring at 30 ℃ for 1 h. Then, the mixture was heated to 200 ℃ and polymerized for 10min, and the polymer yield was 97%.
The obtained polymer was subjected to a performance test, and the detection data are as follows: tensile strength of 42MPa, yield elongation of 6.2%, tensile modulus of 910MPa, bending strength of 61MPa, bending modulus of 960MPa, and impact strength of 6.2KJ/m2。
Example 6
In the implementation, the Grubbs third-generation catalyst obtained in the step (1) in the example 1 is adopted to further prepare a temperature-sensitive ruthenium carbene complex, namely a catalyst Cat-6; and the prepared catalyst is used for catalyzing the polymerization reaction of styrene and dicyclopentadiene.
(1) 1.0g of Grubbs' tertiary catalyst was reacted with 4.0g N (C)6H4N3)3(10.0 equiv.) 10mL of toluene was added and magnetically stirred at 50 ℃ for 24 h; after the reaction is finished, 0.97g of catalyst Cat-6 is obtained by separation, purification and drying, and the yield of the catalyst is 82%.
Performing nuclear magnetic resonance characterization on the prepared catalyst Cat-6, wherein the detection data are as follows:
1H NMR(CDCl3)δ(ppm)＝2.12(s,12H,Mes-CH3),2.26(s,6H,Mes-CH3),4.04(s,4H,N-CH2-CH2-N),4.52(s,6H,NH2),6.63(s,4H,Mes-CH),7.18(d,6H,Ar-H),7.29(t,6H,Ar-H),7.23(t,2H,Ar-H),7.54(t,1H,ArH),7.75(d,2H,Ar-H),19.03(d,Ru＝CH-Ph).
wherein the structure of the Cat-6 catalyst is as follows:
Figure GDA0003166997280000111
(2) in a reaction flask, 50.0g of styrene, 63.5g of dicyclopentadiene and 15.6mg of cat "-6 (olefin/cat. ═ 50000/1, molar ratio) were added, followed by stirring at 25 ℃ for 1 h. Then, the mixture was heated to 150 ℃ and polymerized for 10min, with a yield of 98%.
The obtained polymer was subjected to a performance test, and the detection data are as follows: tensile strength 38MPa, yield elongation 4.8%, tensile modulus 880MPa, bending strength 56MPa, bending modulus 790MPa, and impact strength 4.5KJ/m2。
Example 7
In the implementation, the Grubbs third-generation catalyst obtained in the step (1) in the example 1 is adopted to further prepare a temperature-sensitive ruthenium carbene complex, namely a catalyst Cat-7; and the prepared catalyst is used for catalyzing the polymerization reaction of 1-hexene, cyclopentene and norbornene.
(1) 1.0g of Grubbs's tertiary catalyst was reacted with 9.24g N (C)7H7O3)3(20.0 equiv.) 10mL of 1, 4-dioxane was added and magnetically stirred at 50 ℃ for 24 h; after the reaction is finished, separating, purifying and drying to obtain 0.81g of catalyst Cat-7, wherein the yield of the catalyst is 65%;
performing nuclear magnetic resonance characterization on the prepared catalyst Cat-7, wherein the detection data are as follows:
1H NMR(CDCl3)δ(ppm)＝2.12(s,12H,Mes-CH3),2.26(s,6H,Mes-CH3),3.81(s,9H,CH3-O-),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.18(d,6H,Ar-H),7.29(t,6H,Ar-H),7.23(t,2H,Ar-H),7.54(t,1H,ArH),7.75(d,2H,Ar-H),19.03(d,Ru＝CH-Ph).
wherein the structure of the Cat-7 catalyst is as follows:
Figure GDA0003166997280000121
(2) in a reaction flask, 20.0g of 1-hexene, 31.4g of cyclopentadiene, 44.8g of norbornene and 18.0mg of cat-7 (olefin/cat.: 70000/1, molar ratio) were added, followed by stirring at 25 ℃ for 1 hour. Then, the mixture was heated to 120 ℃ and polymerized for 15min, and the polymer yield was 99%.
The obtained polymer was subjected to a performance test, and the detection data are as follows: tensile strength of 31MPa, yield elongation of 3.5%, tensile modulus of 780MPa, bending strength of 55MPa, bending modulus of 760MPa, and impact strength of 4.5KJ/m2。
Embodiments 1 to 7 provide a preparation method of a ruthenium carbene complex and an application of the ruthenium carbene complex in an olefin ring-opening ex-situ polymerization reaction, which mainly solve the problem that a Grubbs second-generation catalyst has too high catalytic speed in the olefin ring-opening ex-situ polymerization, so that olefin does not polymerize under a low temperature condition, and when a system is raised to a certain temperature, the system can rapidly polymerize. The invention starts from Grubbs second-generation catalyst, obtains the target catalyst through two-step reaction, and after separation and purification, the chemical purity reaches more than 99.0%.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (7)

1. A temperature-sensitive ruthenium carbene complex is characterized by having the following chemical general formula:
Figure FDA0003266143180000011
wherein R is a straight-chain alkyl or aryl;
when R is straight-chain alkyl, the number of carbon atoms is 1-16;
when R is an aryl group, the aryl group has the formula:
Figure FDA0003266143180000012
wherein R1, R2, R3, R4 and R5 are all selected from one of hydrogen, amino, alkyl with 1-16 carbon atoms, alkoxy with 1-16 carbon atoms or alkyl phosphorus with 1-16 carbon atoms.
2. The preparation method of the temperature-sensitive ruthenium carbene complex according to claim 1, characterized by comprising the following steps: taking a Grubbs three-generation catalyst, and reacting the Grubbs three-generation catalyst with NR3Adding the mixture into a solvent for reaction; and separating, purifying and drying the reacted materials to obtain the temperature-sensitive ruthenium carbene complex.
3. The temperature-sensitive ruthenium carbene complex according to claim 2A process for the preparation of said compound, characterized in that said NR3The molar ratio of the Grubbs tertiary catalyst to the Grubbs tertiary catalyst is 1/1-20/1, the reaction temperature is 25-60 ℃, and the reaction time is 12-48 h; the solvent is one or more selected from tetrahydrofuran, ethyl acetate, diethyl ether, acetone, acetonitrile, toluene or 1, 4-dioxane.
4. The preparation method of the temperature-sensitive ruthenium carbene complex according to claim 2, wherein the general formula of the Grubbs three-generation catalyst is as follows:
Figure FDA0003266143180000021
5. the preparation method of the temperature-sensitive ruthenium carbene complex according to claim 3, wherein the Grubbs third-generation catalyst is prepared by taking Grubbs second-generation catalyst and pyridine as reaction raw materials;
the general formula of the Grubbs second generation catalyst is as follows:
Figure FDA0003266143180000022
the reaction temperature of the Grubbs secondary catalyst and pyridine is room temperature, and the reaction time is 12-24 h.
6. The application of the temperature-sensitive ruthenium carbene complex as claimed in claim 1, wherein the temperature-sensitive ruthenium carbene complex is a catalyst with temperature-sensitive property and is applied to catalyzing metathesis reaction of olefin; the olefin is selected from norbornene, cyclohexene, dicyclopentadiene, cyclooctene, cyclopentadienes, 1-octene, 1-hexene or styrene.
7. The application of the temperature-sensitive ruthenium carbene complex according to claim 6, wherein the temperature-sensitive ruthenium carbene complex is used for catalyzing cyclic olefins to perform ring-opening ectopic polymerization; the temperature-sensitive ruthenium carbene complex and cyclic olefin are mixed according to the molar ratio of 1/30000-1/200000, the cyclic olefin cannot carry out ring-opening ectopic polymerization reaction at the temperature of 25-35 ℃, and the cyclic olefin carries out ring-opening ectopic polymerization reaction at the temperature of 80-200 ℃; the polymerization time of the ring-opening ectopic polymerization reaction is 5-20 min.
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