CN112175122A - Application of tridentate salicylaldiminato titanium complex, poly-conjugated diene, and preparation method and application of poly-conjugated diene - Google Patents
Application of tridentate salicylaldiminato titanium complex, poly-conjugated diene, and preparation method and application of poly-conjugated diene Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Abstract
The invention provides application of a tridentate salicylaldiminato titanium complex, a poly-conjugated diene, a preparation method and application thereof, and relates to the technical field of conjugated diene catalytic polymerization. The invention provides an application of a tridentate salicylaldiminato titanium complex, wherein the tridentate salicylaldiminato titanium complex is used as a catalyst for preparing poly-conjugated diene; the tridentate salicylaldiminato titanium complex has a structure shown in a formula I, wherein R in the formula I1Is tert-butyl or hydrogen, R2Is tert-butyl or hydrogen, R3Is methyl or phenyl. The poly-conjugated diene prepared by using the tridentate salicylaldiminato titanium complex with the structure shown in the formula I as the catalyst has high yield and narrow molecular weight distribution.
Description
Technical Field
The invention relates to the technical field of conjugated diene catalytic polymerization, in particular to application of a tridentate salicylaldiminato titanium complex, a poly-conjugated diene, and a preparation method and application thereof.
Background
The isoprene rubber is a polyisoprene rubber for short, has good elasticity and wear resistance, excellent heat resistance and better chemical stability, can replace natural rubber to manufacture heavy-duty tires and off-road tires, and can also be used for producing various rubber products. The Ziegler-Natta titanium catalyst (TiCl) is mostly adopted for the industrial production of isoprene rubber4-AlR3) The type titanium initiator is prepared by a solution polymerization method. However, the Ziegler-Natta catalyst is a heterogeneous catalyst, has multiple active centers, is not beneficial to regulating the microstructure of a polymer, and one effective way to solve the problem is to adopt a titanium complex catalyst with a definite molecular structure.
Titanium salicylaldiminato complexes are widely used in the polymerization of ethylene and other mono-olefins, and reports on the use of titanium salicylaldiminato complexes in the catalysis of the polymerization of conjugated dienes are rare. So far, only the bidentate salicylaldimine type titanium complex (shown in formula III) synthesized by Claudio Pellecchia et al [ Macromolecules2003,36,9260-9263] achieved isoprene polymerization, but few methods for catalyzing isoprene polymerization by tridentate salicylaldimine titanium complex have been reported. And the yield of the polyisoprene synthesized by the bidentate salicylaldimine catalysis is low and the molecular weight distribution is wide.
Disclosure of Invention
In view of the above, the present invention aims to provide an application of a tridentate salicylaldiminato titanium complex, a poly-conjugated diene, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an application of a tridentate salicylaldiminato titanium complex, wherein the tridentate salicylaldiminato titanium complex is used as a catalyst for preparing poly-conjugated diene; the tridentate salicylaldiminato titanium complex has a structure shown in formula I:
in the formula I, R1Is tert-butyl or hydrogen, R2Is tert-butyl or hydrogen, R3Is methyl or phenyl.
Preferably, the tridentate salicylaldiminato titanium complex has any one of the structures shown in formulas I-1 to I-3:
the invention provides a preparation method of a poly-conjugated diene, which comprises the following steps:
under the anhydrous and oxygen-free conditions, mixing a conjugated diene monomer, a tridentate salicylaldiminato titanium complex with a structure shown in formula I, a cocatalyst and an organic solvent, and carrying out polymerization reaction to obtain poly-conjugated diene;
the conjugated diene monomer includes isoprene and/or butadiene.
Preferably, the cocatalyst comprises methylaluminoxane, modified methylaluminoxane, or a mixture of aluminum alkyl and boron salts.
Preferably, the alkyl aluminum comprises one or more of trimethyl aluminum, triethyl aluminum and triisobutyl aluminum;
the boron salt comprises B (C)6F5)3、[Ph3C][B(C6F5)4]And [ PhNMe2H][B(C6F5)4]One or more of them.
Preferably, the organic solvent comprises one or more of toluene, hexane, petroleum ether and dichloromethane.
Preferably, the molar ratio of the conjugated diene monomer to the tridentate salicylaldiminato titanium complex is (500-10000): 1;
the molar ratio of the cocatalyst to the tridentate salicylaldiminato titanium complex is (1-1000): 1.
Preferably, the temperature of the polymerization reaction is 25-90 ℃ and the time is 3-12 h.
The invention provides a poly-conjugated diene obtained by the preparation method in the technical scheme, which has a structure shown in a formula II:
in the formula II, R is hydrogen or methyl, and x/(x + y) is 70-90%;
the number average molecular weight of the poly-conjugated diene is 1 to 20 ten thousand, and the molecular weight distribution is 1.5 to 6.1.
The invention also provides the application of the poly-conjugated diene in the technical scheme in a tire product.
The invention provides an application of a tridentate salicylaldiminato titanium complex, wherein the tridentate salicylaldiminato titanium complex is used as a catalyst for preparing poly-conjugated diene; the tridentate salicylaldiminato titanium complex has a structure shown in a formula I, wherein R in the formula I1Is tert-butyl or hydrogen, R2Is tert-butyl or hydrogen, R3Is methyl or phenyl. In the invention, the tridentate salicylaldiminato titanium complex with the structure shown in the formula I is a single-active-site catalyst, and the molecular weight distribution of the poly-conjugated diene prepared by using the tridentate salicylaldiminato titanium complex as the catalyst is narrow.
The invention provides a preparation method of a poly-conjugated diene, which comprises the following steps: under the anhydrous and oxygen-free conditions, mixing a conjugated diene monomer, a tridentate salicylaldiminato titanium complex with a structure shown in formula I, a cocatalyst and an organic solvent, and carrying out polymerization reaction to obtain poly-conjugated diene; the conjugated diene monomer includes isoprene and/or butadiene. According to the preparation method of the poly-conjugated diene provided by the invention, the tridentate salicylaldiminato titanium complex with the structure shown in the formula I is used as a catalyst, and a cocatalyst is used in a matching manner, so that the prepared poly-conjugated diene is high in yield, 1-20 ten thousand in number average molecular weight, 1.5-6.1 in molecular weight distribution and relatively narrow in molecular weight distribution.
Drawings
FIG. 1 is a hydrogen spectrum of a poly-conjugated diene prepared in example 1;
FIG. 2 is a carbon spectrum of the poly-conjugated diene prepared in example 1;
FIG. 3 is a GPC chart of the poly-conjugated diene prepared in example 1.
Detailed Description
The invention provides an application of a tridentate salicylaldiminato titanium complex, wherein the tridentate salicylaldiminato titanium complex is used as a catalyst for preparing poly-conjugated diene; the tridentate salicylaldiminato titanium complex has a structure shown in formula I:
in the formula I, R1Is tert-butyl or hydrogen, R2Is tert-butyl or hydrogen, R3Is methyl or phenyl.
In the present invention, the tridentate salicylaldiminato titanium complex preferably has any one of the structures represented by formulas I-1 to I-3:
the invention provides a preparation method of a poly-conjugated diene, which comprises the following steps:
under the anhydrous and oxygen-free conditions, mixing a conjugated diene monomer, a tridentate salicylaldiminato titanium complex with a structure shown in formula I, a cocatalyst and an organic solvent, and carrying out polymerization reaction to obtain poly-conjugated diene;
the conjugated diene monomer includes isoprene and/or butadiene.
In the present invention, when the conjugated diene monomer includes isoprene and butadiene, the molar ratio of isoprene to butadiene is preferably 1: (0.01 to 100), more preferably 1: (0.1 to 10), and most preferably 1: 1.
In the present invention, the cocatalyst preferably comprises Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO), or a mixture of aluminum alkyl and boron salts. In the present invention, the alkyl aluminum preferably includes one or more of trimethyl aluminum, triethyl aluminum and triisobutyl aluminum, and more preferably includes trimethyl aluminum, triethyl aluminum or triisobutyl aluminum. In the present invention, the boron salt preferably includes B (C)6F5)3、[Ph3C][B(C6F5)4]And [ PhNMe2H][B(C6F5)4]More preferably comprises B (C)6F5)3、[Ph3C][B(C6F5)4]Or [ PhNMe2H][B(C6F5)4]. In the present invention, the molar ratio of the alkyl aluminum to the boron salt in the mixture of the alkyl aluminum and the boron salt is preferably (10 to 100):1, and more preferably 10: 1.
In the invention, when the cocatalyst is methylaluminoxane or modified methylaluminoxane, the molar ratio of the conjugated diene monomer to the tridentate salicylaldiminato titanium complex is preferably (500-10000): 1, more preferably (1800-2500), and most preferably 2500: 1; the molar ratio of the cocatalyst to the tridentate salicylaldiminato titanium complex is preferably (1-1000): 1, and more preferably 300: 1. In the invention, when the cocatalyst is a mixture of alkyl aluminum and boron salt, the molar ratio of the conjugated diene monomer to the tridentate salicylaldiminato titanium complex is preferably (500-10000): 1, more preferably (1000-1500): 1, and most preferably 1250: 1; the molar ratio of the cocatalyst to the tridentate salicylaldiminato titanium complex is preferably (1-1000): 1, more preferably (1-100): 1, and even more preferably (1-10): 1, most preferably 1: 1.
In the present invention, the organic solvent preferably includes one or more of toluene, hexane, petroleum ether and dichloromethane. In the present invention, the ratio of the amount of the substance of the conjugated diene monomer to the volume of the organic solvent is preferably 1 mmol: (1-10) mL, more preferably 1 mmol: (2-5) mL.
In the present invention, the conjugated diene monomer, the tridentate salicylaldiminato titanium complex compound described in the above technical scheme, the cocatalyst and the organic solvent are preferably mixed by stirring, and the speed and time of the stirring and mixing are not particularly limited, and the raw materials can be uniformly mixed. In the present invention, the order of mixing the conjugated diene monomer, the tridentate salicylaldiminato titanium complex having a structure represented by formula I, the cocatalyst and the organic solvent preferably includes: mixing a cocatalyst, an organic solvent and a conjugated diene monomer, and then adding the tridentate salicylaldiminato titanium complex, or mixing the cocatalyst, the organic solvent and the tridentate salicylaldiminato titanium complex, and then adding the conjugated diene monomer, or mixing the conjugated diene monomer, the organic solvent and the tridentate salicylaldiminato titanium complex, and then adding the cocatalyst. The invention adopts the 3 mixing sequences, which is beneficial to controlling the molecular weight distribution of the poly-conjugated diene.
In the invention, the polymerization reaction temperature is preferably 25-90 ℃, more preferably 30-80 ℃, and most preferably 40-60 ℃; the time is preferably 3 to 12 hours, more preferably 5 to 10 hours, and most preferably 6 to 8 hours. The vessel for the polymerization reaction of the present invention is not particularly limited, and a reaction vessel known to those skilled in the art, specifically, a Schlenk flask, may be used.
After the polymerization reaction, the method preferably further comprises the steps of adding a quenching agent and an anti-aging agent into the polymerization reaction system, mixing, separating and purifying to obtain the poly-conjugated diene. In the invention, the quenching agent preferably comprises a methanol solution of concentrated hydrochloric acid, methanol, ethanol or acidified ethanol, and the volume ratio of methanol to concentrated hydrochloric acid in the methanol solution of concentrated hydrochloric acid is preferably (40-60): 1, more preferably (45-55): 1, most preferably 50: 1; the mass percentage concentration of the concentrated hydrochloric acid is preferably 36-38%, and more preferably 37%. The amount of the quenching agent is not particularly limited, and the polymerization reaction can be quenched, and specifically, the volume ratio of the quenching agent to the organic solvent for polymerization reaction is preferably (1.5-2.5): 1, and more preferably 2: 1; the function of the quencher is to quench the active center of the polymerization reaction, stopping the polymerization reaction. In the present invention, the anti-aging agent is preferably an alcohol solution of 2, 6-di-tert-butyl-4-methylphenol; the alcohol preferably comprises methanol or ethanol; the mass percentage concentration of the 2, 6-di-tert-butyl-4-methylphenol alcohol solution is preferably 0.8-1.2%, and more preferably 1%; the volume ratio of the anti-aging agent to the organic solvent for polymerization is preferably 1: (4-6), more preferably 1: (4.5-5.5), most preferably 1: 5; the anti-aging agent functions to prevent the poly-conjugated diene from aging during storage and use.
In the invention, the separation and purification comprises the steps of settling, washing with water, washing with alcohol and drying in sequence. In the present invention, the solvent for sedimentation is preferably ethanol. In the present invention, the water washing is preferably distilled water washing. In the present invention, the alcohol washing is preferably an ethanol washing or a methanol washing. In the invention, the drying temperature is preferably 30-50 ℃, more preferably 40 ℃, the drying time is not particularly limited, and the drying is carried out until the weight is constant.
The invention provides a poly-conjugated diene obtained by the preparation method in the technical scheme, which has a structure shown in a formula II:
in the formula II, R is hydrogen or methyl, and x/(x + y) is 70-90%;
the number average molecular weight of the poly-conjugated diene is 1 to 20 ten thousand, and the molecular weight distribution is 1.5 to 6.1.
In the present invention, the poly-conjugated diene has a cis-1,4 structure
And 1, 2-or 3, 4-structures
In the present invention, the ratio of x/(x + y) is 70 to 90%, preferably 75 to 85%, and more preferably 80%, that is, the molar ratio of the cis-1,4 structure in the poly-conjugated diene. In the present invention, the molar ratio of the 1, 2-or 3, 4-structure in the poly-conjugated diene is 10 to 30%, preferably 15 to 25%, and more preferably 20%.
In the present invention, the number average molecular weight of the poly-conjugated diene is 1 to 20 ten thousand, preferably 2 to 15 ten thousand, and more preferably 5 to 10 ten thousand. In the present invention, the molecular weight distribution of the poly-conjugated diene is 1.5 to 6.1, preferably 2.0 to 6.0, and most preferably 3.0 to 5.0. The molecular weight distribution of the poly-conjugated diene provided by the invention is narrow.
The invention also provides the application of the poly-conjugated diene in the technical scheme in a tire product.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 0.8mmol of methylaluminoxane MAO, 5mL of toluene, 8 mu mol of tridentate salicylaldiminato titanium complex I-1 and 1mL of toluene in a 25mL Schlenk bottle in sequence, stirring for 2min at 25 ℃, adding 20mmol of isoprene, uniformly mixing, carrying out polymerization reaction for 6h at 50 ℃, adding 2mL of a methanol solution of hydrochloric acid with the concentration of 1mol/L to quench the reaction, adding 50mL of ethanol to carry out sedimentation, washing obtained solid products by using distilled water and ethanol, and drying in a vacuum drying oven at 40 ℃ to constant weight to obtain white poly-conjugated diene.
The hydrogen spectrum and the carbon spectrum of the poly-conjugated diene prepared in this example are shown in FIG. 1 and FIG. 2, respectively. As can be seen from FIGS. 1 to 2, the present invention provides a poly-conjugated diene having a structure represented by formula I.
GPC results of the poly-conjugated diene prepared in this example are shown in FIG. 3 and Table 1, in which the interval of the base line region 1 is 4.28 to 4.46min, the interval of the base line region 2 is 7.95 to 8.11min, and the interval of the peak 1 is 4.48 to 7.95 min; the trace of peak 1 is RI, the maximum retention time of peak 1 is 5.81min, the peak area of peak 1 is 1750385.154mv · s, and the peak height of peak 1 is 22394.000 mv.
TABLE 1 molecular weight of the Polyconjugated dienes
| Peak(s) | Mp | Mn | Mw | Mz | Mz+1 | | PDI |
| Peak | |||||||
| 1 | 398734 | 144253 | 635595 | 1506010 | 2421487 | 1377113 | 4.413 |
As is clear from fig. 3 and table 1, the molecular weight distribution of the poly-conjugated diene prepared in this example was 4.413.
Examples 2 to 11
The preparation conditions of examples 2 to 11 are shown in Table 2, and the characterization results of the prepared poly-conjugated diene are shown in Table 3.
Comparative examples 1 to 3
The preparation conditions of the poly-conjugated diene prepared according to the method of example 1 and comparative examples 1 to 3 are shown in Table 2, and the characterization results of the prepared poly-conjugated diene are shown in Table 3, wherein the titanium tridentate salicylaldiminate complex used in comparative examples 2 to 3 is
TABLE 2 preparation conditions of examples 1 to 11 and comparative examples 1 to 3
TABLE 3 characterization results of the Poly-conjugated dienes prepared in examples 1 to 11 and comparative examples 1 to 3
As can be seen from Table 3, the poly-conjugated diene prepared by the present invention has a cis-1,4 content of 77 to 85%, a 1, 2-or 3, 4-structure content of 13 to 23%, a number average molecular weight of 15072 to 192813, and a molecular weight distribution of 2.3 to 6.1, indicating that the poly-conjugated diene prepared by the present invention has a high yield.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Use of a tridentate salicylaldiminato titanium complex as a catalyst for the preparation of a poly-conjugated diene, the tridentate salicylaldiminato titanium complex having a structure according to formula I:
in the formula I, R1Is tert-butyl or hydrogen, R2Is tert-butyl or hydrogen, R3Is methyl or phenyl.
2. The use according to claim 1, wherein the tridentate salicylaldiminato titanium complex has any one of the structures represented by formulae I-1 to I-3:
3. a method for producing a poly-conjugated diene, comprising the steps of:
under the anhydrous and oxygen-free conditions, mixing a conjugated diene monomer, a tridentate salicylaldiminato titanium complex with a structure shown in formula I, a cocatalyst and an organic solvent, and carrying out polymerization reaction to obtain poly-conjugated diene;
the conjugated diene monomer includes isoprene and/or butadiene.
4. The method of claim 3, wherein the cocatalyst comprises methylaluminoxane, modified methylaluminoxane, or a mixture of aluminum alkyls and boron salts.
5. The preparation method according to claim 4, wherein the alkyl aluminum comprises one or more of trimethyl aluminum, triethyl aluminum and triisobutyl aluminum;
the boron salt comprises B (C)6F5)3、[Ph3C][B(C6F5)4]And [ PhNMe2H][B(C6F5)4]One or more of them.
6. The method according to claim 3, wherein the organic solvent comprises one or more of toluene, hexane, petroleum ether and dichloromethane.
7. The method according to any one of claims 3 to 5, wherein the molar ratio of the conjugated diene monomer to the tridentate salicylaldiminato titanium complex is (500 to 10000): 1;
the molar ratio of the cocatalyst to the tridentate salicylaldiminato titanium complex is (1-1000): 1.
8. The method according to any one of claims 3 to 6, wherein the polymerization reaction is carried out at a temperature of 25 to 90 ℃ for 3 to 12 hours.
9. The method of any one of claims 3 to 8, wherein the poly-conjugated diene has a structure represented by formula II:
in the formula II, R is hydrogen or methyl, and x/(x + y) is 70-90%;
the number average molecular weight of the poly-conjugated diene is 1 to 20 ten thousand, and the molecular weight distribution is 1.5 to 6.1.
10. Use of the polyconjugated diene as claimed in claim 9 in a tyre product.
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| WO2005035121A2 (en) * | 2003-10-16 | 2005-04-21 | Universiteit Gent | Schiff base metal complexes for use as catalysts in organic synthesis |
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