CN114106318A - High molecular weight aliphatic polyketone and synthesis method thereof - Google Patents
High molecular weight aliphatic polyketone and synthesis method thereof Download PDFInfo
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Abstract
The invention provides high molecular weight aliphatic polyketone and a synthesis method thereof; the number average molecular weight of the high molecular weight aliphatic polyketone is more than 32 ten thousand, the molecular weight distribution is less than 1.8, and the bulk density is more than 0.3 g/ml; the synthesis method comprises the following steps: a) putting carbon monoxide and olefin compounds in a methanol mixed solvent containing a main catalyst and a cocatalyst; b) under a certain temperature, the high molecular weight aliphatic polyketone is obtained by controlling the mixed gas to be injected and fed into a diffuser at the bottom of the reaction kettle for reaction and circulating the gas at the upper part of the reaction kettle into the diffuser at the bottom of the reaction kettle through a compressor. The reaction medium of the synthesis method is selected from a mixed solvent of methanol and a solvent which can be mutually dissolved with the methanol and does not influence the formation of the active center of the catalyst, reactants are carbon monoxide and olefin compounds, the formation of the active center of the catalyst is promoted by adopting a mode of injecting air at the bottom of a reaction kettle and realizing the circulation of gas outside the kettle in the kettle through a compressor, and meanwhile, the mass transfer and heat transfer efficiency of the gas is improved.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to high molecular weight aliphatic polyketone and a synthesis method thereof.
Background
Polyketones (POK) are novel green polymeric materials synthesized from carbon monoxide, olefins (ethylene, propylene, styrene), have photodegradable and biodegradable properties, and can be further chemically modified, with excellent and broad performance properties, making it a "natural" thermoplastic engineering plastic. The ketone group on the main chain of the polyketone endows the polyketone with excellent photodegradable performance and chemical modification performance, the main raw materials are wide in source, CO in the polyketone can be obtained from coal gas and can also be obtained from CO-containing industrial waste gas through purification, and the polyketone synthesis and application are worthy of being green synthetic polymer materials in the new century.
Aliphatic polyketones having a high molecular weight and a narrow molecular weight distribution are known to have high mechanical properties and thermal properties, and are useful as engineering plastic materials having excellent economical efficiency. Meanwhile, the low stacking density of the polyketone in the polymerization process is always a main factor influencing the productivity, the cost, the storage, transportation and the post-processing.
There have been many patents in the literature reporting methods for synthesizing aliphatic polyketones of high molecular weight, such as lowering the polymerization temperature, replacing the polymerization solvent with t-butanol, and the like, but most of them have been established on the basis of sacrificing the catalytic activity and increasing the production cost.
Disclosure of Invention
In view of the above, the present invention aims to provide a high molecular weight aliphatic polyketone having a number average molecular weight of more than 32 ten thousand, a narrow molecular weight distribution, a good bulk density, and a high catalytic activity, and a method for synthesizing the same.
The invention provides high molecular weight aliphatic polyketone, the number average molecular weight of the high molecular weight aliphatic polyketone is more than 32 ten thousand, the molecular weight distribution is less than 1.8, and the bulk density is more than 0.3 g/ml.
The invention also provides a synthesis method of the high molecular weight aliphatic polyketone, which comprises the following steps:
a) in a methanol mixed solvent containing a main catalyst and a cocatalyst, carbon monoxide and olefin compounds are reacted by controlling the injection and feeding of mixed gas in a diffuser at the bottom of a reaction kettle, and the gas at the upper part of the reaction kettle is circulated into the diffuser at the bottom of the reaction kettle by a compressor, so that the high molecular weight aliphatic polyketone is obtained.
Preferably, the procatalyst in step a) is an organometallic complex of a divalent palladium salt with a bidentate phosphine ligand;
the divalent palladium salt is one or more of palladium nitrate, palladium sulfate, palladium sulfonate and palladium acetate;
the bidentate phosphine ligand has a structure shown in formula (I):
in the formula (I), R1、R2、R3And R4Independently selected from phenyl or substituted phenyl, R5Is an alkylene group having at least 3 carbon atoms.
Preferably, the co-catalyst in step a) is selected from one or more of nitric acid, p-toluenesulfonic acid, sulfamic acid, trifluoromethanesulfonic acid, trichloroacetic acid and trifluoroacetic acid.
Preferably, in the methanol mixed solvent in step a), the solvent miscible with methanol is selected from one or more of ethanol, dimethyl carbonate and diethyl carbonate.
Preferably, the methanol mixed solvent in step a) further comprises:
quinone and/or acid anion having pKa < 6.
Preferably, the quinone comprises benzoquinone and/or naphthoquinone;
the anion of the acid having a pKa < 6 includes one or more of nitrate, p-toluenesulfonate, sulfamate, trifluoromethylsulfonate, trichloroacetate and trifluoroacetate.
Preferably, the reaction temperature in the step a) is 87-95 ℃, and the pressure is 4.0-5.5 MPa.
Preferably, the reaction kettle bottom diffuser in step a) is a spray head type, and the spray angle is 0 °, 10 °, 20 °, 40 ° or 360 °.
Preferably, in the step a), the gas at the upper part of the reaction kettle is circulated into the diffuser at the bottom part of the reaction kettle by the compressor when the solid content in the reaction kettle is higher than 25 percent;
the gas delivery speed of the compressor is more than 5 times of the gas consumption amount of polymerization.
The invention provides high molecular weight aliphatic polyketone and a synthesis method thereof; the number average molecular weight of the high molecular weight aliphatic polyketone is more than 32 ten thousand, the molecular weight distribution is less than 1.8, and the bulk density is more than 0.3 g/ml; the synthesis method comprises the following steps: a) in a methanol mixed solvent containing a main catalyst and a cocatalyst, carbon monoxide and olefin compounds are reacted by controlling the injection and feeding of mixed gas in a diffuser at the bottom of a reaction kettle, and the gas at the upper part of the reaction kettle is circulated into the diffuser at the bottom of the reaction kettle by a compressor, so that the high molecular weight aliphatic polyketone is obtained. Compared with the prior art, the synthesis method provided by the invention takes an organic metal complex of divalent palladium salt and bidentate phosphine ligand as a main catalyst, strong acid as a cocatalyst, a reaction medium is selected from a mixed solvent of methanol and a solvent which can be mutually dissolved with the methanol and does not influence the formation of an active center of the catalyst, reactants are carbon monoxide and olefin compounds (ethylene and propylene gas), the formation of the active center of the catalyst is promoted by adopting the mode of injecting air at the bottom of a reaction kettle and realizing the circulation of gas inside and outside the kettle through a compressor, and the mass transfer and heat transfer efficiency of the gas is improved at the same time, so that the polyketone with the weight average molecular weight of more than 32 ten thousand, the molecular weight distribution of less than 1.8 and the bulk density of more than 0.3g/ml is finally synthesized.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The invention provides high molecular weight aliphatic polyketone, the number average molecular weight of the high molecular weight aliphatic polyketone is more than 32 ten thousand, the molecular weight distribution is less than 1.8, and the bulk density is more than 0.3 g/ml. The invention uses the organic metal complex of divalent palladium salt and bidentate phosphine ligand as a main catalyst, strong acid as a cocatalyst, a reaction medium is selected from a mixed solvent of methanol and a solvent which can be mutually dissolved with the methanol, reactants are carbon monoxide, ethylene and propylene gas, and polyketone with the number average molecular weight of more than 32 ten thousand, the molecular weight distribution of less than 1.8 and the bulk density of more than 0.3g/ml is synthesized by changing the mixed solvent and a gas inlet mode.
The invention also provides a synthesis method of the high molecular weight aliphatic polyketone, which comprises the following steps:
a) in a methanol mixed solvent containing a main catalyst and a cocatalyst, carbon monoxide and olefin compounds are reacted by controlling the injection and feeding of mixed gas in a diffuser at the bottom of a reaction kettle, and the gas at the upper part of the reaction kettle is circulated into the diffuser at the bottom of the reaction kettle by a compressor, so that the high molecular weight aliphatic polyketone is obtained.
The invention relates to a method for synthesizing polyketone with high molecular weight, narrow molecular weight distribution and high bulk density by alternately copolymerizing carbon monoxide and olefin compounds; the method takes an organic metal complex of divalent palladium salt and bidentate phosphine ligand as a main catalyst, strong acid as a cocatalyst, a reaction medium is selected from a mixed solvent of methanol and a solvent which can be mutually dissolved with the methanol and does not influence the formation of an active center of the catalyst, reactants are carbon monoxide, ethylene and propylene gas, the formation of the active center of the catalyst is promoted by adopting the injection gas at the bottom of a reaction kettle and realizing the circulation of the gas outside the kettle in the kettle by a compressor, and simultaneously, the mass transfer and heat transfer efficiency of the gas is improved, and the polyketone with the weight average molecular weight of more than 32 ten thousand, the molecular weight distribution of less than 1.8 and the stacking density of more than 0.3g/ml is synthesized.
The invention firstly dissolves the main catalyst and the cocatalyst in the methanol mixed solvent. In the present invention, the procatalyst is preferably an organometallic complex of a divalent palladium salt with a bidentate phosphine ligand; wherein, the divalent palladium salt is preferably one or more of palladium nitrate, palladium sulfate, palladium sulfonate and palladium acetate, more preferably palladium nitrate, palladium sulfate, palladium sulfonate or palladium acetate, and more preferably palladium acetate; the source of the divalent palladium salt is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, the bidentate phosphine ligand preferably has a structure represented by formula (I):
in the formula (I), R1、R2、R3And R4Independently selected from phenyl or substituted phenyl, R5Is an alkylene group having at least 3 carbon atoms; the preferable concrete is as follows: 1, 3-bis [ bis (2-methoxyphenyl) phosphino]Propane or 3, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl]-1, 5-dioxa-spiro [5,5 ]]Undecane.
In the invention, the content of the main catalyst in the methanol mixed solvent is preferably 0.01-0.05 mmol/L, and specifically may be 0.01mmol/L, 0.02mmol/L, 0.03mmol/L, 0.04mmol/L, 0.05 mmol/L.
In the present invention, the co-catalyst is preferably selected from one or more of nitric acid, p-toluenesulfonic acid, sulfamic acid, trifluoromethanesulfonic acid, trichloroacetic acid and trifluoroacetic acid, more preferably nitric acid, p-toluenesulfonic acid, sulfamic acid, trifluoromethanesulfonic acid, trichloroacetic acid or trifluoroacetic acid, and more preferably trifluoromethanesulfonic acid. The source of the cocatalyst is not particularly limited in the present invention, and commercially available strong organic and inorganic acids known to those skilled in the art can be used. In the invention, the molar ratio of the cocatalyst to the main catalyst is preferably (10-2): 1, and specifically may be 10: 1,9: 1,8: 1,7: 1,6: 1,5: 1,4: 1,3: 1,2: 1.
in the present invention, in the methanol mixed solvent, the solvent miscible with methanol is preferably one or more selected from ethanol, dimethyl carbonate and diethyl carbonate, and more preferably ethanol, dimethyl carbonate or diethyl carbonate. The solvent which is mutually soluble with the methanol does not influence the formation of the active center of the catalyst; meanwhile, the present invention is not particularly limited in its source, and commercially available products known to those skilled in the art may be used.
In a preferred embodiment of the present invention, the methanol mixed solvent is a mixed solvent of methanol and dimethyl carbonate; the volume ratio of methanol to dimethyl carbonate is preferably 1: (3-6), specifically 1: 3. 1: 4. 1: 5. 1: 6, the solvent amount is 30-60% of the volume of the reaction kettle, specifically 30%, 35%, 40%, 45%, 50%, 55%, 60%. The methanol can effectively act with the catalyst to generate a catalyst active center and also act as a chain transfer reagent for reaction, so that the dosage of the methanol directly influences the molecular weight of the polyketone; the dimethyl carbonate is used as a green reagent, can be mutually dissolved with methanol, has no toxic effect on the catalyst, and can improve the molecular weight of the polyketone while ensuring the catalytic activity.
In the present invention, the methanol mixed solvent preferably further comprises:
anions of quinones and/or acids having a pKa < 6;
more preferably:
quinone and anions of acids having a pKa < 6.
In the present invention, the quinone preferably comprises benzoquinone and/or naphthoquinone, more preferably benzoquinone or naphthoquinone; benzoquinones include, but are not limited to, 1, 2-benzoquinone (ortho-benzoquinone), 1, 4-benzoquinone (para-benzoquinone), naphthoquinones include, but are not limited to, 1, 2-naphthoquinone and/or 1, 4-naphthoquinone; the molar ratio of the quinone to the main catalyst is preferably (5-20): 1, specifically 5: 1. 6: 1. 7: 1. 8: 1. 9: 1. 10: 1. 11: 1. 12: 1. 13: 1. 14: 1. 15: 1. 16: 1. 17: 1. 18: 1. 19: 1 or 20: 1. the present invention is not particularly limited in its origin, and commercially available products known to those skilled in the art may be used.
In the present invention, the anion of the acid having a pKa < 6 preferably comprises one or more of nitrate, p-toluenesulfonate, sulfamate, trifluoromethylsulfonate, trichloroacetate and trifluoroacetate, more preferably nitrate, p-toluenesulfonate, sulfamate, trifluoromethylsulfonate, trichloroacetate or trifluoroacetate; the metal salt includes but is not limited to one or more of sodium salt, potassium salt, magnesium salt and iron salt, and specifically can be magnesium trifluoromethanesulfonate, zinc trifluoromethanesulfonate and/or iron trifluoromethanesulfonate. In the present invention, the molar ratio of the metal salt to the main catalyst is preferably (2 to 10): 1, specifically 2: 1. 3: 1. 4: 1. 5: 1. 6: 1. 7: 1. 8: 1. 9: 1 or 10: 1.
the invention controls the mixed gas to be sprayed and fed in a diffuser at the bottom of the reaction kettle, and the mixed gas reacts at a certain temperature and a certain pressure; the reaction temperature is preferably 87 to 95 ℃, more preferably 87 to 93 ℃, and the pressure is preferably 4.0 to 5.5MPa, more preferably 4.0 to 5.3 MPa.
In the invention, the feeding of the mixed gas into the bottom diffuser of the reaction kettle is controlled during the reaction process, and the gas at the upper part of the reaction kettle is circulated into the bottom diffuser of the reaction kettle by a compressor at a proper time. It is further noted that the catalytic system material, the methanol mixed solvent and part of the reaction gas are added into the reaction kettle before the reaction is started. The gas proportion of the propylene in the reaction kettle is preferably 20-60%, and specifically can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%. Part of the reaction gas also comprises carbon monoxide and ethylene, and the mass ratio of the carbon monoxide to the ethylene is preferably 1: (1-2), specifically 1: 1.1, 1: 1.2, 1: 1.3, 1: 1.4, 1: 1.5, 1: 1.6, 1: 1.7, 1: 1.8, 1: 1.9, 1: 2. the proportion at the beginning of the reaction is preferably 40-80%, specifically 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, and the total reaction time is 6-8 h.
In the invention, the mixed gas is controlled to be fed into the diffuser at the bottom of the reaction kettle in the reaction process; the bottom diffuser of the reaction kettle is preferably a spray head type, and the spray angle is preferably 30-360 degrees, and more preferably 60-270 degrees.
In the invention, the time for circulating the gas at the upper part of the reaction kettle into the diffuser at the bottom part of the reaction kettle by the compressor is preferably used when the solid content in the reaction kettle is higher than 25%, and is preferably 25-32%.
In the invention, the gas conveying speed of the compressor is more than 5 times of the polymerization gas consumption, preferably 6-10 times; it is to be noted that the gas delivery of the compressor is only a cyclic stage. The aim is to realize effective dispersion of gas and solid through a nozzle type disperser when reaction materials are in a high-viscosity state, the design at the position not only reduces energy consumption, but also can realize high molecular weight and narrow molecular weight distribution, and plays an auxiliary role in selecting a stirring form, and reduces the problems of energy consumption and equipment type selection caused by high-speed stirring in other literature patents; meanwhile, the gas conveying speed of the compressor and the effective gas conveying speed are controlled when the solid content is 27 percent, so that the catalytic activity is kept unchanged in the whole reaction process, the molecular weight distribution of the polyketone is narrowed to be less than 1.8, and the polyketone product with high quality and the bulk density of more than 0.3g/ml is produced.
The invention provides a method for synthesizing high molecular weight aliphatic polyketone, and in the implementation process, the polyketone product obtained by polymerization through the method is narrow in molecular weight distribution, and the change of an air inlet mode can directly influence the mass transfer problem in a reaction kettle, influence the concentration of a catalyst active center monomer, further influence the catalytic activity, improve the catalytic activity and improve the stacking density.
The invention provides high molecular weight aliphatic polyketone and a synthesis method thereof; the number average molecular weight of the high molecular weight aliphatic polyketone is more than 32 ten thousand, the molecular weight distribution is less than 1.8, and the bulk density is more than 0.3 g/ml; the synthesis method comprises the following steps: a) in a methanol mixed solvent containing a main catalyst and a cocatalyst, carbon monoxide and olefin compounds are reacted by controlling the injection and feeding of mixed gas in a diffuser at the bottom of a reaction kettle, and the gas at the upper part of the reaction kettle is circulated into the diffuser at the bottom of the reaction kettle by a compressor, so that the high molecular weight aliphatic polyketone is obtained. Compared with the prior art, the synthesis method provided by the invention takes an organic metal complex of divalent palladium salt and bidentate phosphine ligand as a main catalyst, strong acid as a cocatalyst, a reaction medium is selected from a mixed solvent of methanol and a solvent which can be mutually dissolved with the methanol and does not influence the formation of an active center of the catalyst, reactants are carbon monoxide and olefin compounds (ethylene and propylene gas), the formation of the active center of the catalyst is promoted by adopting the mode of injecting air at the bottom of a reaction kettle and realizing the circulation of gas inside and outside the kettle through a compressor, and the mass transfer and heat transfer efficiency of the gas is improved at the same time, so that the polyketone with the weight average molecular weight of more than 32 ten thousand, the molecular weight distribution of less than 1.8 and the bulk density of more than 0.3g/ml is finally synthesized.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available products.
Example 1
3.5L of mixed solution of methanol and dimethyl carbonate (0.7L of methanol and 2.8L of dimethyl carbonate) and a main catalyst (3, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl) are added into a 10L high-pressure reaction kettle]-1, 5-dioxa-spiro [5,5 ]]Organometallic complex of undecane with palladium acetate) 88.93mg, 40ml (7.5mmol/L) of methanol trifluoromethanesulfonate solution, 86.4mg of p-benzoquinone, 197.33mg of magnesium trifluoromethanesulfonate; after the above substances were added, the autoclave was purged with nitrogen for pressure maintaining and displacement, then purged with 350g of propylene, purged with CO and C2H4The mass ratio is 1: 1.1 g of mixed gas, starting to heat, setting the temperature to 90 ℃, stirring at the speed of 200r/min, and continuously spraying CO and C through a diffuser (the spraying angle is 40 ℃) at the bottom of the reaction kettle when the temperature rises to 87 DEG2H4The mass ratio is 1: 1, maintaining the reaction pressure at 5.0MPa, starting a compressor when the solid content in the reaction kettle is 26%, pumping gas out of the top of the reaction kettle, spraying the gas into the bottom of the reaction kettle through a bottom disperser, wherein the gas conveying speed is 7 times of the gas consumption of polymerization, and the reaction time is 6 hours.
After the reaction is finished, the product is layered with methanol and directly discharged from an autoclave, the obtained polyketone product is filtered, washed by methanol and then dried for 4 hours in a vacuum drying oven at 80 ℃, the obtained product has the weight of 1.30kg, the catalytic activity of 20.44 kg/(g-Pd.h), the weight average molecular weight of 34 ten thousand, the molecular weight distribution of 1.6 and the bulk density of 0.33 g/mL.
Example 2
4.0L of methanol and carbonic acid are added into a 10L high-pressure reaction kettleDimethyl ester mixed solution (1.0L methanol and 3.0L dimethyl carbonate), main catalyst (3, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl)]-1, 5-dioxa-spiro [5,5 ]]Organometallic complex of undecane with palladium acetate) 133.4mg, methanol solution of trifluoromethanesulfonate 80ml (7.5mmol/L), p-benzoquinone 162mg, magnesium trifluoromethanesulfonate 493 mg; after the above substances were added, the autoclave was filled with nitrogen for pressure maintaining and displacement, then charged with 450g of propylene, charged with CO and C2H4The mass ratio is 1: 1.1 g of mixed gas, starting to heat up, setting the temperature to 90 ℃, stirring at the speed of 200r/min, and continuously spraying CO and C through a diffuser (the spraying angle is 360 ℃) at the bottom of the reaction kettle when the temperature rises to 92 DEG2H4The mass ratio is 1: 1, maintaining the reaction pressure at 4.8MPa, starting a compressor when the solid content in the reaction kettle is 27%, pumping gas out of the top of the reaction kettle, spraying the gas into the bottom of the reaction kettle through a bottom disperser, wherein the gas conveying speed is 5 times of the gas consumption of polymerization, and the reaction time is 6 hours.
After the reaction is finished, the product is layered with methanol, the polyketone product is directly poured out from an autoclave, the obtained polyketone product is filtered, washed by the methanol and then dried for 4 hours in a vacuum drying oven at the temperature of 80 ℃, the obtained product has the weight of 2.0kg, the catalytic activity of 20.96 kg/(g-Pd.h), the weight average molecular weight of 33 ten thousand, the molecular weight distribution of 1.75 and the bulk density of 0.35 g/mL.
Example 3
4L of mixed solution of methanol and dimethyl carbonate (1L of methanol and 3L of dimethyl carbonate) and a main catalyst (1, 3-bis [ bis (2-methoxyphenyl) phosphino) are added into a 10L high-pressure reaction kettle]Organometallic complex of propane with palladium acetate) 151.31mg, 133.2ml (7.5mmol/L) of methanolic trifluoromethanesulfonate, 108mg of p-benzoquinone, 644.89mg of magnesium trifluoromethanesulfonate; after the above substances were added, the autoclave was filled with nitrogen for pressure maintaining and displacement, then filled with 400g of propylene, and filled with CO and C2H4The mass ratio is 1: 1.1 g of mixed gas, starting to heat, setting the temperature to 90 ℃, stirring at the speed of 150r/min, and continuously spraying CO and C through a diffuser (the spraying angle is 10 ℃) at the bottom of the reaction kettle when the temperature rises to 90 DEG2H4The mass ratio is 1: 1, when the reaction pressure is maintained to be 5.0MPa and the solid content in the reaction kettle is 27 percent, starting a compressor to perform the reactionThe gas extracted from the top of the reaction kettle is sprayed into the bottom of the reaction kettle through the bottom disperser, the gas conveying speed is 5 times of the gas consumption amount of polymerization, and the reaction time is 8 hours.
After the reaction is finished, the product is layered with methanol, the polyketone product is directly poured out from an autoclave, the obtained polyketone product is filtered, washed by the methanol and then dried for 4 hours in a vacuum drying oven at the temperature of 80 ℃, the obtained product has the weight of 2.2kg, the catalytic activity of 12.97 kg/(g-Pd.h), the weight average molecular weight of 36 ten thousand, the molecular weight distribution of 1.78 and the bulk density of 0.4 g/mL.
Example 4
5L of a mixed solution of methanol and dimethyl carbonate (0.71L of methanol and 4.28L of dimethyl carbonate) and a main catalyst (1, 3-bis [ bis (2-methoxyphenyl) phosphino ] catalyst) are added into a 10L high-pressure reaction kettle]Organometallic complex of propane with palladium acetate) 113.5mg, methanol trifluoromethanesulfonate solution 80ml (7.5mmol/L), 97.2mg of p-benzoquinone, 295.8mg of magnesium trifluoromethanesulfonate; after the above substances were added, the autoclave was filled with nitrogen for pressure maintaining and displacement, then filled with 360g of propylene, and filled with CO and C2H4The mass ratio is 1: 1.2 g of mixed gas, starting to heat, setting the temperature to 90 ℃, stirring at the speed of 100r/min, and continuously spraying CO and C through a diffuser (the spraying angle is 10 ℃) at the bottom of the reaction kettle when the temperature rises to 93 DEG2H4The mass ratio is 1: 1, maintaining the reaction pressure at 5.3MPa, starting a compressor when the solid content in the reaction kettle is 28%, pumping gas from the top of the reaction kettle, spraying the gas into the bottom of the reaction kettle through a bottom disperser, wherein the gas conveying speed is 7 times of the gas consumption of polymerization, and the reaction time is 8 hours.
After the reaction is finished, the product is layered with methanol, the polyketone product is directly poured out from an autoclave, the obtained polyketone product is filtered, washed by the methanol and then dried for 4 hours in a vacuum drying oven at the temperature of 80 ℃, the obtained product has the weight of 1.76kg, the catalytic activity of 13.83 kg/(g-Pd.h), the weight average molecular weight of 40 ten thousand, the molecular weight distribution of 1.72 and the bulk density of 0.38 g/mL.
Comparative example 1
3.5L of mixed solution of methanol and dimethyl carbonate (0.7L of methanol and 2.8L of dimethyl carbonate) and a main catalyst (3, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl) are added into a 10L high-pressure reaction kettle]-1, 5-dioxa-spiro [5,5 ]]Of undecane with palladium acetateOrganometallic complex) 88.93mg, 40ml (7.5mmol/L) of a methanol solution of trifluoromethanesulfonic acid, 86.4mg of p-benzoquinone, 197.33mg of magnesium trifluoromethanesulfonate; after the above substances were added, the autoclave was purged with nitrogen for pressure maintaining and displacement, then purged with 350g of propylene, purged with CO and C2H4The mass ratio is 1: 1.1 g of mixed gas, starting to heat up, setting the temperature to 90 ℃, stirring at the speed of 200r/min, and continuously introducing CO and C through the top of the reaction kettle when the temperature rises to 87 DEG C2H4The mass ratio is 1: 1, maintaining the reaction pressure at 5.0MPa and the reaction time at 6 h.
After the reaction is finished, opening the kettle to find that all the methanol is absorbed by the polyketone product and can not be discharged from the bottom of the autoclave, transferring the polyketone product out of the autoclave, filtering the polyketone product, washing the polyketone product with methanol, and then drying the polyketone product for 4 hours in a vacuum drying oven at 80 ℃ to obtain the polyketone product with the product weight of 0.95kg, the catalytic activity of 13.99 kg/(g-Pd.h), the weight average molecular weight of 35 ten thousand, the molecular weight distribution of 2.2 and the product bulk density of 0.21 g/mL.
Comparative example 2
3.5L of methanol and a main catalyst (3, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl) are added into a 10L high-pressure reaction kettle]-1, 5-dioxa-spiro [5,5 ]]Organometallic complex of undecane with palladium acetate) 88.93mg, 40ml (7.5mmol/L) of methanol trifluoromethanesulfonate solution, 86.4mg of p-benzoquinone, 197.33mg of magnesium trifluoromethanesulfonate; after the above substances were added, the autoclave was purged with nitrogen for pressure maintaining and displacement, then purged with 350g of propylene, purged with CO and C2H4The mass ratio is 1: 1.1 g of mixed gas, starting to heat, setting the temperature to 90 ℃, stirring at the speed of 200r/min, and continuously spraying CO and C through a diffuser (the spraying angle is 40 ℃) at the bottom of the reaction kettle when the temperature rises to 87 DEG2H4The mass ratio is 1: 1, maintaining the reaction pressure at 5.0MPa, starting a compressor when the solid content in the reaction kettle is 27%, pumping gas out of the top of the reaction kettle, spraying the gas into the bottom of the reaction kettle through a bottom disperser, wherein the gas conveying speed is 7 times of the gas consumption of polymerization, and the reaction time is 6 hours.
After the reaction is finished, opening the kettle to find that all the methanol is absorbed by the polyketone product and can not be discharged from the bottom of the autoclave, transferring the polyketone product out of the autoclave, filtering the polyketone product, washing the polyketone product with methanol, and then drying the polyketone product for 4 hours in a vacuum drying oven at 80 ℃ to obtain the polyketone product with the product weight of 1.50kg, the catalytic activity of 23.58 kg/(g-Pd.h), the weight average molecular weight of 25 ten thousand, the molecular weight distribution of 2.0 and the product bulk density of 0.15 g/mL.
Comparative example 3
4L of mixed solution of methanol and dimethyl carbonate (1L of methanol and 3L of dimethyl carbonate) and a main catalyst (1, 3-bis [ bis (2-methoxyphenyl) phosphino) are added into a 10L high-pressure reaction kettle]Organometallic complex of propane with palladium acetate) 151.31mg, 133.2ml (7.5mmol/L) of methanolic trifluoromethanesulfonate, 108mg of p-benzoquinone, 644.89mg of magnesium trifluoromethanesulfonate; after the above substances were added, the autoclave was filled with nitrogen for pressure maintaining and displacement, then filled with 400g of propylene, and filled with CO and C2H4The mass ratio is 1: 1.1 g of mixed gas, starting to heat up, setting the temperature to 90 ℃, stirring at the speed of 150r/min, and continuously introducing CO and C through the top of the reaction kettle when the temperature rises to 90 DEG C2H4The mass ratio is 1: 1, maintaining the reaction pressure at 5.0MPa and the reaction time at 6 h.
After the reaction is finished, the product is layered with methanol, the polyketone product is directly poured out from an autoclave, the obtained polyketone product is filtered, washed by the methanol and then dried for 4 hours in a vacuum drying oven at the temperature of 80 ℃, the obtained product has the weight of 1.7kg, the catalytic activity of 10.02 kg/(g-Pd.h), the weight average molecular weight of 33 ten thousand, the molecular weight distribution of 2.1 and the bulk density of 0.25 g/mL.
The invention takes the above examples and comparative examples as comparison, wherein comparative examples 1-2 and examples 1-2 are one catalyst, and comparative example 3 and examples 3-4 are another catalyst; from this, it is understood that the present invention is effective in increasing the molecular weight and decreasing the molecular weight distribution of both catalysts in terms of catalytic activity. Experimental results show that the high molecular weight aliphatic polyketone provided by the invention has the number average molecular weight of more than 32 ten thousand, the molecular weight distribution of less than 1.8 and the bulk density of more than 0.3 g/ml.
Comparative examples 1 to 3 are not within the scope of the present invention, and are only for comparison in the present invention; the comparative example 1 shows that the polymerization speed is obviously slowed down along with the progress of the polyketone reaction, the weight average molecular weight can meet the requirement under the condition of only using a mixed solvent and not changing an aeration mode, but the polymerization speed, the molecular weight distribution and the bulk density can not meet the production requirement; in comparative example 2, the aeration mode was changed effectively, the reaction rate was significantly increased, the molecular weight distribution was also narrowed, but the weight average molecular weight and the bulk density were still to be improved; in comparative example 3, another catalyst (organometallic complex of 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane and palladium acetate) was used, and the weight average molecular weight was satisfied by using only a mixed solvent without changing the conditions of aeration, but the polymerization rate, the molecular weight distribution and the bulk density were not satisfactory for the production. It should be noted that: because the polyketone with different grades has larger mechanical property, use and price difference and high molecular weight, the product performance given by narrow distribution has the price far higher than that of the common product, and in addition, because different catalysts are used, the difference of catalytic activity is larger, and the catalytic activity is not sacrificed.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (11)
1. A high molecular weight aliphatic polyketone having a number average molecular weight of greater than 32 million, a molecular weight distribution of less than 1.8, and a bulk density of greater than 0.3 g/ml.
2. A process for synthesizing aliphatic polyketone having high molecular weight according to claim 1, wherein said process comprises subjecting carbon monoxide and an olefin compound to a methanol mixed solvent containing a main catalyst and a cocatalyst to obtain aliphatic polyketone having high molecular weight.
3. The synthesis method of claim 2, wherein the high molecular weight aliphatic polyketone is obtained by controlling the mixed gas to be injected and fed into the bottom diffuser of the reaction kettle for reaction at a certain temperature and circulating the gas at the upper part of the reaction kettle into the bottom diffuser of the reaction kettle by a compressor.
4. The synthesis method according to claim 2, wherein the procatalyst is an organometallic complex of a divalent palladium salt with a bidentate phosphine ligand;
the divalent palladium salt is one or more of palladium nitrate, palladium sulfate, palladium sulfonate and palladium acetate;
the bidentate phosphine ligand has a structure shown in formula (I):
in the formula (I), R1、R2、R3And R4Independently selected from phenyl or substituted phenyl, R5Is an alkylene group having at least 3 carbon atoms.
5. The synthesis method according to claim 2, wherein the cocatalyst is selected from one or more of nitric acid, p-toluenesulfonic acid, sulfamic acid, trifluoromethanesulfonic acid, trichloroacetic acid and trifluoroacetic acid.
6. The synthesis method according to claim 2, wherein the methanol mixed solvent is one or more solvents miscible with methanol selected from ethanol, dimethyl carbonate and diethyl carbonate.
7. The synthesis method according to claim 2, wherein the methanol mixed solvent further comprises:
quinone and/or acid anion having pKa < 6.
8. The method of synthesizing as claimed in claim 7 wherein the quinone comprises benzoquinone and/or naphthoquinone;
the anion of the acid having a pKa < 6 includes one or more of nitrate, p-toluenesulfonate, sulfamate, trifluoromethylsulfonate, trichloroacetate and trifluoroacetate.
9. The synthesis method according to claim 3, characterized in that the reaction temperature is 87-95 ℃ and the pressure is 4.0-5.5 MPa.
10. The synthesis method according to claim 3, wherein the bottom diffuser of the reaction kettle is a spray head type, and the spray angle is 30-360 degrees.
11. The synthesis method of claim 3, wherein the gas at the upper part of the reaction kettle is circulated into the diffuser at the bottom part of the reaction kettle by the compressor when the solid content in the reaction kettle is higher than 25%;
the gas delivery speed of the compressor is more than 5 times of the gas consumption amount of polymerization.
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