CN110804130A - Synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree - Google Patents
Synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree Download PDFInfo
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Abstract
The invention provides a method for synthesizing hyperbranched polyolefin with controllable branched chain length and controllable branched degree; the method comprises the following steps: polymerizing a monomer with three terminal olefins under the condition of a metal organic catalyst, wherein the monomer with three terminal olefins is shown as a formula I:
wherein n is an integer. The invention changes the structure of the monomer, the type of the catalyst, the addition of other copolymers such as cis-cyclooctene, and the concentration of the monomerThe degree, reaction time and the like can realize the control of the branched structure, the branching degree, the molecular weight and the distribution of the polyolefin product. Compared with the prior art, the invention adopts a monomer with a brand new structure and a polymerization process, and can synthesize hyperbranched polyolefin with the accurately controllable branched chain length. The polyolefin material prepared according to the invention has low viscosity, good fluidity and controllable branching degree and molecular weight, and can be widely applied to the fields of coatings, lubricants, polymer processing flow improvers, adhesives, curing agents and the like.
Description
Technical Field
The invention relates to the technical field of polyolefin, in particular to a synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree.
Background
In order to solve the problem, researchers have proposed 'Chain-Walking Polymerization' (CWP) in 1995, the synthesis of hyperbranched polyolefin is realized by catalyzing the Polymerization of polyethylene through a palladium catalyst [ Journal of the American Chemical Society 1995117, 6414-6415], at present, the Polymerization of ethylene and α -olefin can be carried out through catalysts such as palladium, nickel and the like, the control of the polymer structure is realized through the adjustment of reaction conditions, and a method for modifying the ACS terminal of polyolefin [ Catalysis of Polymerization, 5, 20155 ] which has the possibility of expanding the application of hyperbranched polyolefin as branched biological materials, 201555, 2016 and the like ] is provided, so that the application of hyperbranched polyolefin as branched biological materials is developed in the fields of hyperbranched polyolefin synthesis, 2016 and 2016-55.
Although the chain-walking polymerization has many advantages mentioned above, the polymerization mechanism of chain-walking itself means that the structure of its branched chain is random and the length of the branched chain is limited. The length of the branched chains of hyperbranched polyolefins obtained by chain-walking polymerization is generally between 1 and 6 carbon atoms, so that their structure has certain uncertainties and limitations. In view of the uncertainty and limitation of the branched structure in the chain-walking polymerization, it is necessary to research and design a new polymerization mechanism and a new monomer structure to supplement and perfect the synthesis method of the hyperbranched polyolefin.
In addition to chain-walking polymerization, olefin metathesis chemistry is another powerful tool for synthesizing polyolefin materials. Ring-opening metathesis polymerization based on ring-opening metathesis of cyclooctene is widely used for the synthesis of linear polyolefins, while acyclic diene metathesis polymerization based on cross metathesis is a more common approach for the synthesis of polyolefins with regular side chains [ Macromolecules2000,33(24),8963-8970 ]. Compared with chain walking polymerization, the olefin metathesis method has no random chain walking mechanism, so that the branched structure is more definite, and the regional chain structure of the hyperbranched polymer can be better controlled. However, although there are reports in the literature of the synthesis of hyperbranched structures by olefin metathesis (j.am. chem. soc.,2007,129,12672-12673), these methods can only be used for the synthesis of hyperbranched polymers containing heteroatoms such as oxygen, nitrogen, and phosphorus in the polymer chains such as hyperbranched polyesters and polyethers, and cannot be used for the synthesis of hyperbranched polyolefins containing only two elements, namely carbon and hydrogen. The difficulties in the synthesis of hyperbranched polyolefins by olefin metathesis are mainly: monomers containing multiple identical terminal olefins tend to form cross-linked structures during polymerization and are therefore difficult to react without introducing heteroatom groups into the precursor.
Disclosure of Invention
The invention aims to provide a method for synthesizing hyperbranched polyolefin with controllable branched chain length and controllable branched degree.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a method for synthesizing a polyolefin material with controllable branched chain length and controllable branched degree, which comprises the following steps: carrying out polymerization reaction on a monomer with three terminal olefins under the condition of a metal organic catalyst, wherein the structure of the monomer with three terminal olefins is shown as a formula I:
The monomer with three terminal olefins is obtained by Grignard reaction between trichloromethane or tribromomethane and corresponding olefin magnesium bromide.
The branched structure of the product obtained by the method of the invention depends on the distance between the terminal olefin of the selected monomer and the methine center, so that the branched chain structure of the polymer obtained by the polymerization reaction of the same monomer is clear. The longer the distance between the monomer terminal olefin and its central methine group, the longer the branched chain of the resulting polymer.
Preferably, the monomer having three terminal olefins has a methine center to which three groups are attached as carbon chains having terminal olefins of the same structure.
Preferably, the number of carbon atoms between the terminal olefin and the central methine group is an integer of 1 or more. More preferably, it is an integer of 1 to 8 inclusive. In this case, the cyclic olefin by-product in the product obtained by the polymerization reaction is less, and the branching degree of the obtained polymer is higher.
Preferably, the metal-organic catalyst comprises at least one of ruthenium, molybdenum, tungsten-containing metal-organic catalysts.
Preferably, the catalyst type in the polymerization reaction may be selected from Grubbs first generation catalyst, second generation catalyst, third generation catalyst, Hoveyda-Grubbs second generation catalyst, and the like. The higher the catalytic activity of the catalyst, the fewer by-products of the product obtained by the polymerization reaction under the same condition, and the higher the molecular weight of the product; the lower the activity of the catalyst, the more by-products and the lower the molecular weight of the product obtained by the polymerization under the same conditions.
Preferably, the molar ratio of the monomer with the three terminal olefins to the metal organic catalyst is 50-200: 1. The higher the catalyst content, the faster the polymerization rate and vice versa.
Preferably, the polymerization is a bulk polymerization (without addition of a solvent) or a polymerization in an organic solvent at a concentration of between 0.33M and 1.5M. The monomer concentration is selected to be 0.33M-1.5M, because the reaction rate is slower when the reaction concentration is lower, the polymerization conversion rate of the monomer is lower in the same time, the content of the by-product is higher, and the molecular weight of the obtained product is also lower; when the concentration of the reaction monomer is higher (or bulk polymerization), the reaction rate is higher, the conversion rate of the monomer in the same time is higher, the content of the by-product is lower, and the molecular weight of the obtained product is correspondingly higher.
Preferably, the organic solvent comprises at least one of chloroform, tetrahydrofuran, dichloromethane, and toluene.
Preferably, the temperature of the polymerization reaction is 20-65 ℃, and the reaction time is 8-72 h.
Preferably, the polymerization is carried out under an inert gas flow, or under vacuum, or under an alternating combination of inert gas flow and vacuum.
Preferably, cis-cyclooctene is added into the polymerization reaction as a copolymer to carry out copolymerization reaction with the monomer with the olefin with three terminal groups under the condition of a metal organic catalyst; the molar ratio of the cis-cyclooctene copolymer to the monomer having a three terminal olefin is 10: 1-3: 1. cis-cyclooctene was added to further adjust the length of the branched chain of the resulting polymer. The higher the proportion of cis-cyclooctene in the reaction, the longer the branched chain of the resulting product and the lower the overall degree of branching, and the lower the proportion of cis-cyclooctene in the reaction, the shorter the branched chain of the resulting product and the higher the overall degree of branching. When the molar ratio of cis-cyclooctene to monomer reaches 10: 1, the Mark-Houwink constant of the product reaches 0.855, which shows that the structural characteristic of the product is close to that of a linear structure, the rheological characteristic of a hyperbranched structure is basically not existed, and the branching degree is very low. It is therefore preferred that the molar ratio of the cis-cyclooctene copolymer to the monomer having a three terminal olefin is 10: 1-3: 1.
compared with the prior art, the invention has the following beneficial effects:
1) the present invention synthesizes hyperbranched polyolefin by means of olefin metathesis reaction with three terminal olefin monomers.
2) The invention can realize the control of the branched structure, the branching degree, the molecular weight and the distribution of the polyolefin product by changing the structure of the monomer, the type of the catalyst, the addition of other copolymers such as cis-cyclooctene, the concentration of the monomer, the reaction time and the like.
3) Compared with the prior art, the invention adopts a monomer with a brand new structure and a polymerization process, and can control the hyperbranched polyolefin with the accurately controllable branched chain length.
4) The polyolefin material prepared by the method has low viscosity, good fluidity and controllable branching degree and molecular weight, and can be widely applied to the fields of coatings, lubricants, polymer processing flow improvers, adhesives, curing agents and the like.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic diagram of the synthesis of a hyperbranched polyolefin with controllable branched chain length and controllable branching degree according to the present invention;
FIG. 2 shows the structure and NMR spectrum of monomer M1 synthesized in example 1;
FIG. 3 shows the structure and NMR spectrum of monomer M2 synthesized in examples 2 and 3;
FIG. 4 shows the structure and NMR spectrum of monomer M3 synthesized in examples 4 and 5;
FIG. 5 shows the structure and NMR spectra of the product obtained by polymerizing monomer M1 in example 1 in the presence of Grubbs third generation catalyst;
FIG. 6 shows the structure and NMR spectra of the product obtained by polymerizing monomer M2 in example 2 in the presence of Grubbs third generation catalyst;
FIG. 7 shows the structure and NMR spectra of the product obtained by polymerizing monomer M2 in example 3 in the presence of Grubbs first-generation catalyst;
FIG. 8 shows the structure and NMR spectra of the product obtained by polymerizing the monomer M3 with Grubbs third generation catalyst in example 4;
FIG. 9 shows the structure and NMR spectrum of a product obtained by copolymerizing M3 monomer with cis-cyclooctene in example 5; the structure and the nuclear magnetic resonance hydrogen spectrum of the product obtained in example 6 are very close to the graph, and only a slight integral area difference exists;
FIG. 10 is a schematic diagram showing the topological structures of the products obtained by copolymerizing the monomer M3 with cis-cyclooctene in examples 5 and 6.
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 it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment relates to a synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree, wherein the synthesis route is shown in figure 1, and the synthesis method specifically comprises the following steps:
cuprous iodide (0.1g, 0.53mmol), tribromomethane (5g, 0.020mol), tetrahydrofuran (50mL) were added under argon protection to a 200mL reaction flask equipped with a magnetic stirrer, and allyl magnesium bromide solution (75mL, 0.075mol) was slowly added dropwise while cooling on ice. After 3 hours of reaction, saturated ammonium chloride solution was added to terminate the reaction, and then saturated brine was added and extracted three times with diethyl ether. And drying the obtained solution by adopting anhydrous magnesium sulfate for 30min, and performing rotary evaporation and concentration to obtain a crude product. The crude product was purified by silica gel column (n-hexane as mobile phase) to obtain a pure product (0.79g, yield 27%).
The monomer can be synthesized by replacing bromoform into trichloromethane, and the method comprises the following specific steps: cuprous iodide (0.1g, 0.53mmol), tribromomethane (2.4g, 0.020mol), tetrahydrofuran (50mL) were added to a 200mL reaction flask equipped with a magnetic stir bar under argon, and allyl magnesium bromide solution (75mL, 0.075mol) was slowly added dropwise while cooling on ice. After 3 hours of reaction, saturated ammonium chloride solution was added to terminate the reaction, and then saturated brine was added and extracted three times with diethyl ether. And drying the obtained solution by adopting anhydrous magnesium sulfate for 30min, and performing rotary evaporation and concentration to obtain a crude product. The crude product was purified by silica gel column (n-hexane as mobile phase) to obtain pure product (0.52g, 19% yield).
The structure is shown as formula M1.
Polymerization reaction: the monomer (0.58mmol) was placed in a 4ml sample vial and Grubbs' third generation catalyst (2.4mg in 40. mu.L THF) was added and the reaction was quenched under argon for 12h (reaction temperature 20-30 ℃ C.) and then 2ml of vinyl ether/THF solution (v: v ═ 50%) was added and the product structure is shown in FIG. 5: the products are mostly five-membered ring structures formed by rearrangement and dimers thereof, and the molecular weight is between 108Da and 188 Da.
Example 2
The embodiment relates to a synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree, wherein the synthesis route is shown in figure 1, and the synthesis method specifically comprises the following steps:
under the protection of argon, cuprous iodide (0.1g, 0.53mmol), tribromomethane (5g, 0.020mol), and tetrahydrofuran (50mL) were added to a 200mL reaction flask equipped with a magnetic stirrer, and a 1-butene-4-magnesium bromide solution (200mL, 0.075mol) was slowly added dropwise while cooling on ice. After 3 hours of reaction, saturated ammonium chloride solution was added to terminate the reaction, and then saturated brine was added and extracted three times with diethyl ether. And drying the obtained solution by adopting anhydrous magnesium sulfate for 30min, and performing rotary evaporation and concentration to obtain a crude product. The crude product was purified by silica gel column (n-hexane as mobile phase) to obtain pure product (1.81g, 51% yield).
The structure is shown as formula M2.
The NMR spectrum of M2 is shown in FIG. 3.
Polymerization reaction: the monomer (0.58mmol) was placed in a 4ml sample bottle, Grubbs third generation catalyst (2.4mg, dissolved in 40 μ L THF) was added and the reaction was terminated by adding 2ml of vinyl ether/THF solution (v: v ═ 50%) after 12h under argon (reaction temperature 20-30 ℃), the structure of the product is shown in fig. 6, the ratio of the cyclic structures is 22% and the ratio of the hyperbranched structures is 78%: the number average molecular weight of the product was 4.8kDa, and the molecular weight distribution was 1.8.
Example 3
The embodiment relates to a synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree, wherein the synthesis route is shown in figure 1, and the synthesis method specifically comprises the following steps:
under the protection of argon, cuprous iodide (0.1g, 0.53mmol), tribromomethane (5g, 0.020mol), and tetrahydrofuran (50mL) were added to a 200mL reaction flask equipped with a magnetic stirrer, and a 1-butene-4-magnesium bromide solution (200mL, 0.075mol) was slowly added dropwise while cooling on ice. After 3 hours of reaction, saturated ammonium chloride solution was added to terminate the reaction, and then saturated brine was added and extracted three times with diethyl ether. And drying the obtained solution by adopting anhydrous magnesium sulfate for 30min, and performing rotary evaporation and concentration to obtain a crude product. The crude product was purified by silica gel column (n-hexane as mobile phase) to obtain pure product (1.81g, 51% yield).
The structure is shown as formula M2.
Polymerization reaction: the monomer (0.58mmol) was placed in a 4ml sample bottle, Grubbs first generation catalyst (2.2mg, dissolved in 40 μ L THF) was added and the reaction was terminated by adding 2ml of vinyl ether/THF solution (v: v ═ 50%) after 12h under argon (reaction temperature 20-30 ℃), the structure of the product is shown in fig. 7, the ratio of cyclic structures is 29% and the ratio of hyperbranched structures is 71%: the product had a number average molecular weight of 3.1kDa and a molecular weight distribution of 1.7.
Example 4
The embodiment relates to a synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree, wherein the synthesis route is shown in figure 1, and the synthesis method specifically comprises the following steps:
under the protection of argon, cuprous iodide (0.1g, 0.53mmol), tribromomethane (5g, 0.020mol), and tetrahydrofuran (50mL) were added to a 200mL reaction flask equipped with a magnetic stirrer, and a 1-octene-8-magnesium bromide solution (200mL, 0.075mol) was slowly added dropwise while cooling on ice. After 3 hours of reaction, saturated ammonium chloride solution was added to terminate the reaction, and then saturated brine was added and extracted three times with diethyl ether. And drying the obtained solution by adopting anhydrous magnesium sulfate for 30min, and performing rotary evaporation and concentration to obtain a crude product. The crude product was purified by silica gel column (n-hexane as mobile phase) to obtain pure product (2.43g, 35% yield).
The structure is shown as formula M3.
Polymerization reaction: the monomer (0.58mmol) was placed in a 4ml sample vial, an equal volume of tetrahydrofuran solvent was added, Grubbs' third generation catalyst (2.4mg in 40. mu.L THF) was added and the reaction was carried out for 36h under a slow argon flow at 20-30 deg.C (vacuum was applied every 12h and then tetrahydrofuran was added again). Then 2ml of a vinyl ethyl ether/THF solution (v: v ═ 50%) was added to terminate the reaction, and the structure of the product is shown in FIG. 8, and is a hyperbranched structure substantially free from cyclic products, the number average molecular weight of the product was 4.2kDa, the molecular weight distribution was 4.18, and the Mark-Houwink constant was 0.340.
Example 5
The embodiment relates to a synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree, wherein the synthesis route is shown in figure 1, and the synthesis method specifically comprises the following steps:
under the protection of argon, cuprous iodide (0.1g, 0.53mmol), tribromomethane (5g, 0.020mol), and tetrahydrofuran (50mL) were added to a 200mL reaction flask equipped with a magnetic stirrer, and a 1-octene-8-magnesium bromide solution (200mL, 0.075mol) was slowly added dropwise while cooling on ice. After 3 hours of reaction, saturated ammonium chloride solution was added to terminate the reaction, and then saturated brine was added and extracted three times with diethyl ether. And drying the obtained solution by adopting anhydrous magnesium sulfate for 30min, and performing rotary evaporation and concentration to obtain a crude product. The crude product was purified by silica gel column (n-hexane as mobile phase) to obtain pure product (2.43g, 35% yield).
The structure is shown as formula M3.
Polymerization (monomer to cis-cyclooctene molar ratio about 3: 1): the monomer (0.58mmol), cis-cyclooctene (1.73mmol in 3ml tetrahydrofuran) was placed in a 4ml sample vial, Grubbs' third generation catalyst (2.4mg, dissolved in 40. mu.L THF) was added and reacted under a slow argon flow for 12h at 20-30 deg.C. The reaction was then terminated with 10ml of a vinyl ether/THF solution (v: v ═ 50%), the product had a hyperbranched structure substantially free of cyclic products, the number average molecular weight of the product was 4.4kDa, the molecular weight distribution was 1.85, and the Mark-Houwink constant was 0.367, as shown in FIG. 9. The branched structure of the product follows the structure of fig. 10, corresponding to the case where m is 6 and n has an average value of 1.
Example 6
The embodiment relates to a synthesis method of hyperbranched polyolefin with controllable branched chain length and controllable branched degree, wherein the synthesis route is shown in figure 1, and the synthesis method specifically comprises the following steps:
under the protection of argon, cuprous iodide (0.1g, 0.53mmol), tribromomethane (5g, 0.020mol), and tetrahydrofuran (50mL) were added to a 200mL reaction flask equipped with a magnetic stirrer, and a 1-octene-8-magnesium bromide solution (200mL, 0.075mol) was slowly added dropwise while cooling on ice. After 3 hours of reaction, saturated ammonium chloride solution was added to terminate the reaction, and then saturated brine was added and extracted three times with diethyl ether. And drying the obtained solution by adopting anhydrous magnesium sulfate for 30min, and performing rotary evaporation and concentration to obtain a crude product. The crude product was purified by silica gel column (n-hexane as mobile phase) to obtain pure product (2.43g, 35% yield).
The structure is shown as formula M3.
Polymerization (monomer to cis-cyclooctene molar ratio about 10: 1): the monomer (0.173mmol), cis-cyclooctene (1.73mmol in 3ml tetrahydrofuran) was placed in a 4ml sample vial, Grubbs' third generation catalyst (2.4mg, dissolved in 40. mu.L THF) was added and reacted under a slow argon flow for 12h at 20-30 deg.C. The reaction was then terminated with 10ml of a vinyl ether/THF solution (v: v ═ 50%), and the nuclear magnetic spectrum of the product was, similarly to example 5, a hyperbranched structure substantially free of cyclic products, the product having a number average molecular weight of 8.2kDa, a molecular weight distribution of 1.45 and a Mark-Houwink constant of 0.855. The branched structure of the product followed the structure of fig. 10, corresponding to the case where m is 6 and n has an average value of 3.3.
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 (9)
1. A method for synthesizing a polyolefin material with controllable branched chain length and controllable branched degree, which is characterized in that the method comprises the following steps: carrying out polymerization reaction on a monomer with three terminal olefins under the condition of a metal organic catalyst, wherein the structure of the monomer with three terminal olefins is shown as a formula I:
2. The method for synthesizing polyolefin material with controllable branched chain length and controllable branched degree according to claim 1, wherein the monomer with three terminal olefins has a methine center, and three groups connected with the methine center are carbon chains with terminal olefins with the same structure.
3. The method for synthesizing polyolefin material with controllable branched chain length and controllable branched degree as claimed in claim 2, wherein the number of carbon atoms between the terminal olefin and the central methine group is an integer of 1 or more.
4. The method for synthesizing polyolefin material with controllable branched chain length and controllable branched degree according to claim 1, wherein the metal organic catalyst comprises at least one of metal organic catalysts containing ruthenium, molybdenum and tungsten.
5. The method for synthesizing the polyolefin material with controllable branched chain length and controllable branched degree according to claim 1, wherein the molar ratio of the monomer with three terminal olefins to the metal organic catalyst is 50-200: 1.
6. The method for synthesizing the polyolefin material with controllable branched chain length and controllable branched degree according to claim 1, wherein the polymerization reaction temperature is 20-65 ℃, and the reaction time is 8-72 h.
7. The method for synthesizing polyolefin material with controllable branched chain length and controllable branched degree according to claim 1, wherein the polymerization is carried out under bulk polymerization conditions or in the presence of organic solvent; the organic solvent comprises at least one of chloroform, tetrahydrofuran, dichloromethane and toluene.
8. The method for synthesizing polyolefin material with controllable branched chain length and controllable branched degree according to claim 1, wherein the polymerization reaction is carried out under inert gas flow, or under vacuum condition, or under the alternating combination of inert gas flow and vacuum condition.
9. The method for synthesizing polyolefin material with controllable branched chain length and controllable branched degree according to claim 1, wherein cis-cyclooctene is added as copolymer to copolymerize with the monomer with three terminal olefins under the condition of metal organic catalyst, and the molar ratio of the cis-cyclooctene copolymer to the monomer with three terminal olefins is 10: 1-3: 1.
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| CN102498133A (en) * | 2009-07-29 | 2012-06-13 | 陶氏环球技术有限责任公司 | Dual- or multi-headed chain shuttling agents and their use for the preparation of block copolymers |
| CN108456228A (en) * | 2017-02-22 | 2018-08-28 | 李达刚 | A kind of small empty barrier organophosphorus ligand and preparation method thereof and the application in ethylene 1- octenes and 1- hexenes |
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