A method for preparing aliphatic polyketone by continuous solution polymerization and aliphatic polyketone

Abstract

The present invention provides a method for preparing an aliphatic polyketone by continuous solution polymerization, and the aliphatic polyketone. The method comprises the following steps: a) continuously feeding carbon monoxide, an olefin compound, and a solvent system containing a catalyst into a continuous flow reactor for solution polymerization to obtain an aliphatic polyketone; the aliphatic polyketone has a particle size of 10 μm to 50 μm, a particle size distribution width (Span) of 0.5 to 0.9, and a bulk density of >0.35 g / ml. Compared with the prior art, the method provided by the present invention uses a solvent system containing a catalyst and a continuous solution polymerization reaction to achieve continuous feeding and continuous discharging, thereby effectively solving the problems of traditional batch and slurry processes such as difficulty in controlling polymer particle morphology, easy adhesion of materials to the wall, low single-reactor yield, and poor product reproducibility. The aliphatic polyketone can be obtained by polymerization with a weight-average molecular weight of >200,000, a molecular weight distribution of <2.0, a bulk density of >0.35 g / ml, a particle size of 10 μm to 50 μm, and a particle size distribution width (Span) of 0.5 to 0.9.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical industry, and more particularly to a method for preparing aliphatic polyketone by continuous solution polymerization and the aliphatic polyketone. Background Art

[0002] Carbon monoxide is a major byproduct of many oil, coal, and other energy and petrochemical industries. Converting carbon monoxide into high-value-added products is a crucial step in the chemical industry. With oil resources dwindling and the resource crisis becoming increasingly severe, and in the context of "carbon neutrality," the development of carbon monoxide chemicals has crucial practical significance and broad prospects. Polyketone (POK) is a new type of green polymer material obtained by copolymerizing carbon monoxide and olefins, with carbon monoxide accounting for approximately 50% of the total mass. It exhibits excellent environmental friendliness in terms of raw material composition and energy consumption. Combined with its excellent impact strength, chemical resistance, wear resistance, gas barrier properties, and flame retardancy, it can replace materials such as PA, PBT, POM, and EVOH in applications such as automotive, electronics, and packaging, giving it a wide range of applications.

[0003] Research and development of polyketones began in the 1940s. Currently, only South Korea's Hyosung Group has achieved industrialization globally. Its production process is a slurry polymerization process. Research on polyketones by domestic and international institutions is limited to existing slurry polymerization processes, and no literature has reported on polyketone solution polymerization processes. Traditional batch and slurry polymerization processes suffer from difficulties in controlling polymer particle morphology, easy adhesion of materials to the wall, low single-reactor yields, and poor product reproducibility. Furthermore, the increase in insoluble products during batch slurry polymerization can hinder mass and heat transfer during the reaction, posing technical challenges and safety risks to the industrial production of polyketones. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a new method for preparing aliphatic polyketone using continuous solution polymerization and the prepared aliphatic polyketone. The new method provided by the present invention can solve the problems of difficult control of polymer particle morphology, easy adhesion of materials to the wall, low single-pot output, poor product repeatability, and poor mass transfer and heat transfer in the slurry process, ensure the smoothness of the polyketone production process, and greatly improve product quality, production capacity and equipment investment.

[0005] The present invention provides an aliphatic polyketone prepared by a continuous solution polymerization method. The aliphatic polyketone is obtained by a continuous solution polymerization reaction of carbon monoxide and an olefin compound in a solvent system containing a catalyst. The aliphatic polyketone has a particle size of 10 μm to 50 μm, a particle size distribution width Span of 0.5 to 0.9, and a bulk density greater than 0.35 g / ml.

[0006] Preferably, the weight average molecular weight of the aliphatic polyketone is greater than 200,000 and the molecular weight distribution is less than 2.0.

[0007] Preferably, the solvent system containing the catalyst is a mixed solvent containing a catalyst, a co-catalyst and a co-solvent.

[0008] Preferably, the catalyst is an organic metal complex of a divalent palladium salt and a bidentate phosphine ligand;

[0009] The divalent palladium salt is one or more of palladium nitrate, palladium sulfate, palladium sulfonate and palladium acetate;

[0010] The bidentate phosphine ligand has a structure shown in formula (I):

[0011]

[0012] In formula (I), R1, R2, R3 and R4 are independently selected from phenyl or substituted phenyl, and R5 is an alkylene group containing at least 3 carbon atoms.

[0013] Preferably, the co-catalyst is selected from one or more of sulfuric acid, benzenesulfonic acid, perchloric acid, trichloroacetic acid and trifluoroacetic acid.

[0014] Preferably, the cosolvent is a carboxylic acid functionalized imidazole salt having the structure shown in formula (II):

[0015]

[0016] In formula (II), -NM3 is an imidazole substituent, and X is trifluoroacetate, trifluorosulfonate or hexafluorophosphate.

[0017] Preferably, the mixed solvent is a mixed solvent of o-chlorophenol and methanol, a mixed solvent of m-cresol and methanol, a mixed solvent of hexafluoroisopropanol and methanol, or a mixed solvent of DMF and methanol.

[0018] The present invention also provides a method for preparing the aliphatic polyketone described in the above technical solution by continuous solution polymerization, comprising the following steps:

[0019] a) continuously feeding carbon monoxide, an olefin compound and a solvent system containing a catalyst into a continuous flow reactor to carry out a solution polymerization reaction to obtain an aliphatic polyketone.

[0020] Preferably, the temperature of the solution polymerization reaction in step a) is 100° C. to 110° C., and the pressure is 6.5 MPa to 7 MPa;

[0021] The residence time of the solution polymerization reaction is controlled by controlling the monomer and solvent feed rates;

[0022] The solution polymerization reaction adopts a microchannel reactor, monomers are continuously fed, unreacted monomers are separated and reused, and products are continuously discharged.

[0023] Preferably, the step a) further comprises:

[0024] The reaction liquid obtained by the polymerization reaction is subjected to gas-liquid separation, the gas is recycled, and the solvent is removed from the liquid to obtain polyketone powder;

[0025] The solvent removal method is flash evaporation; the recovered solvent can be recycled as a mixed solvent.

[0026] The present invention provides a method for preparing an aliphatic polyketone by continuous solution polymerization and the aliphatic polyketone; the method comprises the following steps: a) continuously feeding carbon monoxide, an olefin compound and a solvent system containing a catalyst into a continuous flow reactor for solution polymerization reaction to obtain an aliphatic polyketone; the aliphatic polyketone has a particle size of 10 μm to 50 μm, a particle size distribution width Span of 0.5 to 0.9, and a bulk density greater than 0.35 g / ml. Compared with the prior art, the method provided by the present invention selects carboxylic acid functionalized imidazole salt as a cosolvent, and mixed solvents such as o-chlorophenol and methanol, m-cresol and methanol, hexafluoroisopropanol and methanol, and DMF and methanol as continuous solution polymerization solvents. The reaction adopts a continuous flow reactor for continuous feeding and continuous discharging, thereby effectively solving the problems of difficult polymer particle morphology control, easy material adhesion to the wall, low single-reactor output, and poor product reproducibility in traditional intermittent and slurry processes. The polymerization can obtain aliphatic polyketones with a weight-average molecular weight greater than 200,000, a molecular weight distribution less than 2.0, a bulk density greater than 0.35 g / ml, a particle size of 10 μm to 50 μm, and a particle size distribution width Span of 0.5 to 0.9.

[0027] Description of the accompanying tables and figures

[0028] Figure 1 This is a scanning electron microscope image of the polyketone powder prepared in Example 1 of the present invention;

[0029] Figure 2 This is a scanning electron microscope image of the polyketone powder prepared in Comparative Example 1;

[0030] Table 1 shows the particle size distribution data of the polyketone powder prepared in Example 1 of the present invention;

[0031] Table 2 shows the particle size distribution data of the polyketone powder prepared in Comparative Example 1;

[0032] Table 3 shows the particle size distribution data of the polyketone powder prepared in Comparative Example 2;

[0033] Table 4 shows the particle size distribution data of the polyketone powder prepared in Example 2 of the present invention;

[0034] Table 5 shows the particle size distribution data of the polyketone powder prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0035] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] The present invention provides an aliphatic polyketone prepared by a continuous solution polymerization method. The aliphatic polyketone is obtained by a continuous solution polymerization reaction of carbon monoxide and an olefin compound in a solvent system containing a catalyst. The aliphatic polyketone has a particle size of 10 μm to 50 μm, a particle size distribution width Span of 0.5 to 0.9, and a bulk density greater than 0.35 g / ml.

[0037] In the present invention, the weight average molecular weight of the aliphatic polyketone is preferably greater than 200,000, and the molecular weight distribution is preferably less than 2.0.

[0038] In the present invention, the solvent system containing the catalyst is preferably a mixed solvent containing a catalyst, a co-catalyst, and a co-solvent. In the present invention, the catalyst is preferably an organometallic complex of a divalent palladium salt and 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 even more preferably palladium acetate. The present invention has no particular limitation on the source of the divalent palladium salt; commercially available products familiar to those skilled in the art may be used.

[0039] In the present invention, the bidentate phosphine ligand preferably has a structure represented by formula (I):

[0040]

[0041] In formula (I), R1, R2, R3 and R4 are independently selected from phenyl or substituted phenyl groups, and R5 is an alkylene group containing at least 3 carbon atoms; preferably, 1,3-bis[bis(2-methoxyphenyl)phosphino]propane.

[0042] In the present invention, the content of the catalyst in the mixed solvent is preferably 0.01 to 0.05 mmol / L, specifically 0.01 mmol / L, 0.02 mmol / L, 0.03 mmol / L, 0.04 mmol / L, or 0.05 mmol / L.

[0043] In the present invention, the co-catalyst is preferably selected from one or more of sulfuric acid, benzenesulfonic acid, perchloric acid, trichloroacetic acid and trifluoroacetic acid, more preferably sulfuric acid, benzenesulfonic acid, perchloric acid, trichloroacetic acid or trifluoroacetic acid, and even more preferably trifluoroacetic acid. The present invention has no particular restrictions on the source of the co-catalyst, and any commercially available organic or inorganic strong acid known to those skilled in the art can be used. In the present invention, the molar ratio of the co-catalyst to the catalyst is preferably (10-2):1, specifically 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, or 2:1.

[0044] In the present invention, the cosolvent is preferably a carboxylic acid functionalized imidazole salt having the structure shown in formula (II):

[0045]

[0046] In formula (II), -NM3 is an imidazole substituent, and X is trifluoroacetate, trifluorosulfonate, or hexafluorophosphate. In the present invention, the cosolvent can increase the solubility of the monomer and product in the solvent and enhance mass transfer. In the present invention, the molar ratio of the cosolvent to the catalyst is preferably (5-15):1, more preferably 10:1.

[0047] In the present invention, the content of the co-solvent in the mixed solvent is preferably 0.1 to 0.5 mmol / L.

[0048] In the present invention, the mixed solvent is preferably a mixed solvent of o-chlorophenol and methanol, a mixed solvent of m-cresol and methanol, a mixed solvent of hexafluoroisopropanol and methanol, or a mixed solvent of DMF and methanol, more preferably a mixed solvent of hexafluoroisopropanol and methanol. In a preferred embodiment of the present invention, the mixed solvent is a mixed solvent of hexafluoroisopropanol and methanol; wherein the volume ratio of methanol to hexafluoroisopropanol is preferably 1:(3-6), specifically 1:3, 1:4, 1:5, or 1:6.

[0049] The present invention also provides a method for preparing the aliphatic polyketone described in the above technical solution by continuous solution polymerization, comprising the following steps:

[0050] a) continuously feeding carbon monoxide, an olefin compound and a solvent system containing a catalyst into a continuous flow reactor to carry out a solution polymerization reaction to obtain an aliphatic polyketone.

[0051] In the present invention, the solvent system containing the catalyst is preferably a mixed solvent containing a catalyst, a co-catalyst and a co-solvent. In the present invention, the catalyst, the co-catalyst and the co-solvent are first dissolved in a mixed solvent to obtain a solvent system containing the catalyst.

[0052] In the present invention, the catalyst is preferably an organic metal complex of a divalent palladium salt and 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 even more preferably palladium acetate; the present invention has no special restrictions on the source of the divalent palladium salt, and commercially available products familiar to those skilled in the art can be used.

[0053] In the present invention, the bidentate phosphine ligand preferably has a structure represented by formula (I):

[0054]

[0055] In formula (I), R1, R2, R3 and R4 are independently selected from phenyl or substituted phenyl groups, and R5 is an alkylene group containing at least 3 carbon atoms; preferably, 1,3-bis[bis(2-methoxyphenyl)phosphino]propane.

[0056] In the present invention, the content of the catalyst in the mixed solvent is preferably 0.01 to 0.05 mmol / L, specifically 0.01 mmol / L, 0.02 mmol / L, 0.03 mmol / L, 0.04 mmol / L, or 0.05 mmol / L.

[0057] In the present invention, the co-catalyst is preferably selected from one or more of sulfuric acid, benzenesulfonic acid, perchloric acid, trichloroacetic acid and trifluoroacetic acid, more preferably sulfuric acid, benzenesulfonic acid, perchloric acid, trichloroacetic acid or trifluoroacetic acid, and even more preferably trifluoroacetic acid. The present invention has no particular restrictions on the source of the co-catalyst, and any commercially available organic or inorganic strong acid known to those skilled in the art can be used. In the present invention, the molar ratio of the co-catalyst to the catalyst is preferably (10-2):1, specifically 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, or 2:1.

[0058] In the present invention, the cosolvent is preferably a carboxylic acid functionalized imidazole salt having the structure shown in formula (II):

[0059]

[0060] In formula (II), -NM3 is an imidazole substituent, and X is trifluoroacetate, trifluorosulfonate, or hexafluorophosphate. In the present invention, the cosolvent can increase the solubility of the monomer and product in the solvent and enhance mass transfer. In the present invention, the molar ratio of the cosolvent to the catalyst is preferably (5-15):1, more preferably 10:1.

[0061] In the present invention, the content of the co-solvent in the mixed solvent is preferably 0.1 to 0.5 mmol / L.

[0062] In the present invention, the mixed solvent is preferably a mixed solvent of o-chlorophenol and methanol, a mixed solvent of m-cresol and methanol, a mixed solvent of hexafluoroisopropanol and methanol, or a mixed solvent of DMF and methanol, more preferably a mixed solvent of hexafluoroisopropanol and methanol. In a preferred embodiment of the present invention, the mixed solvent is a mixed solvent of hexafluoroisopropanol and methanol; wherein the volume ratio of methanol to hexafluoroisopropanol is preferably 1:(3-6), specifically 1:3, 1:4, 1:5, or 1:6.

[0063] Subsequently, the present invention continuously feeds carbon monoxide, an olefin compound, and the mixed solvent containing the catalyst, co-catalyst, and co-solvent into a continuous flow reactor, and controls the reaction temperature, reaction pressure, and residence time to carry out a solution polymerization reaction. In the present invention, the temperature of the solution polymerization reaction is preferably 100° C. to 110° C., and the pressure is preferably 6.5 MPa to 7 MPa.

[0064] In the present invention, the residence time of the solution polymerization reaction is preferably controlled by controlling the monomer and solvent feed rates; the monomer described here is a mixture of carbon monoxide and one or more olefinic unsaturated compounds, and the molar ratio of olefin to carbon monoxide is preferably (0.5-5):1; the solvent is the mixed solvent described in the above technical solution, and in the present invention, the solvent can be recycled.

[0065] In the present invention, the solution polymerization reaction preferably utilizes a microchannel reactor, a continuous plug flow reactor capable of efficient heat and mass transfer. This allows the reaction to be completed rapidly within a controlled time and space, at higher temperatures, higher concentrations, and with faster mixing, thereby achieving the combined effects of increased conversion, enhanced safety, and improved efficiency. Furthermore, the present invention enables continuous monomer feeding, separation and reuse of unreacted monomer, and continuous product discharge.

[0066] In the present invention, before the reaction of the microchannel reactor begins, nitrogen is first filled in for displacement. After the displacement is completed, the heating module of the reactor is heated to the reaction temperature, and then the material is continuously fed into the reactor.

[0067] The present invention also includes:

[0068] The reaction liquid obtained by the polymerization reaction is subjected to gas-liquid separation, the gas is recycled, and the solvent is removed from the liquid to obtain polyketone powder;

[0069] The solvent removal method is flash evaporation; the recovered solvent can be recycled as a mixed solvent.

[0070] In the present invention, when the system pressure is higher than the reaction pressure, the reaction liquid begins to be continuously and stably extracted and enters the gas-liquid separation equipment for gas-liquid separation; the separated gas is recycled, and the liquid is freed of solvent to obtain polyketone powder.

[0071] In the present invention, the solvent removal method is preferably flash evaporation, which can be done by using a flash tank well known to those skilled in the art; the recovered solvent can be recycled as a mixed solvent.

[0072] The invention removes the solvent by flash evaporation to obtain dense and uniform polyketone powder, and the solvent is recovered and reused.

[0073] The present invention develops a continuous, solution polymerization process, preferably using a microchannel reactor, which continuously feeds and discharges materials while ensuring the normal progress of the reaction, thereby solving the problems of wall adhesion, poor mass transfer, and heat transfer caused by product aggregation in traditional intermittent processes. After the reaction is completed, the reaction liquid is separated and the unreacted monomers are recovered, and the solvent is preferably removed by flash evaporation to obtain a product with uniform and stable particle morphology.

[0074] The invention uses an organic metal complex of a divalent palladium salt and a bidentate phosphine ligand as a main catalyst, a strong acid as a co-catalyst, a carboxylic acid functionalized imidazole salt as a co-solvent, selects a group of mixed solvents such as o-chlorophenol and methanol, m-cresol and methanol, hexafluoroisopropanol and methanol, DMF and methanol as reaction reagents, and reactants are carbon monoxide, ethylene and propylene gas. Monomers are continuously fed, the reaction temperature, pressure and residence time are controlled, the reaction liquid is continuously withdrawn, unreacted monomers can be recovered and reused, and the solvent can be removed and reused by flash evaporation to obtain a polyketone powder with a weight average molecular weight greater than 200,000, a molecular weight distribution less than 2.0, a powder particle size of 10 to 50 μm, a particle size distribution width Span of 0.5 to 0.9, and a bulk density greater than 0.35 g / ml. The slurry polymerization process mentioned in the present invention has poor mass transfer and heat transfer effects, and the resulting polyketone product particles are large and fluffy, with severe wall adhesion. The powder bulk density is 0.1-0.2 g / mL, the powder particle size is 20-480 μm, and the particle size distribution width Span is 3.3-4.0. The polyketone product particles obtained by the solution polymerization process are finer and denser, with a bulk density greater than 0.35 g / ml, a powder particle size of 10 μm-50 μm, and a particle size distribution width Span of 0.5-0.9.

[0075] The present invention provides a method for preparing an aliphatic polyketone by continuous solution polymerization and the aliphatic polyketone; the method comprises the following steps: a) continuously feeding carbon monoxide, an olefin compound and a solvent system containing a catalyst into a continuous flow reactor for solution polymerization reaction to obtain an aliphatic polyketone; the aliphatic polyketone has a particle size of 10 μm to 50 μm, a particle size distribution width Span of 0.5 to 0.9, and a bulk density greater than 0.35 g / ml. Compared with the prior art, the method provided by the present invention selects carboxylic acid functionalized imidazole salt as a cosolvent, and mixed solvents such as o-chlorophenol and methanol, m-cresol and methanol, hexafluoroisopropanol and methanol, and DMF and methanol as continuous solution polymerization solvents. The reaction adopts a continuous flow reactor for continuous feeding and continuous discharging, thereby effectively solving the problems of difficult polymer particle morphology control, easy material adhesion to the wall, low single-reactor output, and poor product reproducibility in traditional intermittent and slurry processes. The polymerization can obtain aliphatic polyketones with a weight-average molecular weight greater than 200,000, a molecular weight distribution less than 2.0, a bulk density greater than 0.35 g / ml, a particle size of 10 μm to 50 μm, and a particle size distribution width Span of 0.5 to 0.9.

[0076] To further illustrate the present invention, the following examples are provided for detailed description. The raw materials used in the following examples are all commercially available products; a terpolymer of CO, ethylene, and propylene was prepared according to the following method.

[0077] Example 1

[0078] To a quantitative mixture of methanol and hexafluoroisopropanol (Vmethanol:Vhexafluoroisopropanol=1:4), the main catalyst 1,3-bis[bis(2-methoxyphenyl)phosphino]propane and palladium acetate organic metal complex, the co-catalyst trifluoroacetic acid and the co-solvent carboxylic acid functionalized imidazole salt were added, wherein the main catalyst concentration was 0.02mmol / L, the co-catalyst concentration was 0.08mmol / L, and the co-solvent concentration was 0.2mmol / L; before the reaction started, the microchannel reactor was filled with nitrogen for replacement. After the replacement was completed, the reactor heating module was heated to 100°C, and then the mixed solution was continuously introduced into the reactor (reactor flux was 50ml) at a flow rate of 5ml / min, The propylene flow rate is 0.6 g / min, and the feed rate of the mixed gas with a mass ratio of CO and ethylene of 1:1.1 is 30 g / min. The system is pressurized to a reaction pressure of 6.5 MPa to 7.0 MPa, and the residence time is controlled to 10 min. When the system pressure is higher than the reaction pressure, the reaction liquid begins to be extracted and enters the gas-liquid separation equipment, the gas is recycled, and the liquid enters the flash tank. The solvent is flashed to remove dense and uniform polyketone powder, and the solvent is recovered and reused; a polyketone powder with a weight average molecular weight of 220,000, a molecular weight distribution of 1.8, a bulk density of 0.37 g / ml, a particle size of 10 μm to 50 μm, and a particle size distribution width Span of 0.507 is obtained.

[0079] See Table 1 for the powder particle size; see Table 1 for the powder SEM image. Figure 1 shown.

[0080] Table 1 Particle size distribution data of polyketone powder prepared in Example 1 of the present invention

[0081] Sample name Particle refractive index <![CDATA[D 10 ]]> <![CDATA[D 50 ]]> <![CDATA[D 90 ]]> Polyketone powder 1.5 23.2 28.0 37.4

[0082] Comparative Example 1

[0083] To a 10L autoclave, 3.5L of methanol solvent, 48.58mg of the main catalyst (an organic metal complex of 1,3-bis[bis(2-methoxyphenyl)phosphino]propane and palladium acetate), and 3.4mg of the co-catalyst trifluoroacetic acid were added; after adding the above substances, nitrogen was filled into the autoclave to maintain pressure and replace it, and then 400g of propylene and 350g of a mixed gas with a mass ratio of CO and C2H4 of 1:1.1 were charged. The temperature began to rise and was set to 95°C. After the temperature was constant, a mixed gas of CO:C2H4=1:1.1 was continuously charged, and the reaction pressure was maintained at 3.5MPa~4.0MPa, the stirring speed was 400r / min, and the reaction time was 2h.

[0084] After the reaction is completed, the obtained polyketone powder product is filtered, washed with methanol, and then dried in vacuum at 80°C for 3 hours to obtain a polyketone powder; the obtained polyketone powder has a weight average molecular weight of 190,000, a molecular weight distribution of 2.2, a bulk density of 0.18 g / ml, a particle size of 20 μm to 480 μm, and a particle size distribution width Span of 3.954.

[0085] See Table 2 for the powder particle size; see Table 2 for the powder SEM image. Figure 2 shown.

[0086] Table 2 Particle size distribution data of polyketone powder prepared in Comparative Example 1

[0087] Sample name Particle refractive index <![CDATA[D 10 ]]> <![CDATA[D 50 ]]> <![CDATA[D 90 ]]> Polyketone powder 1.5 35.1 111 474

[0088] Comparative Example 2

[0089] To a 10L autoclave, 3.5L of methanol solvent, 48.58mg of the main catalyst (an organic metal complex of 1,3-bis[bis(2-methoxyphenyl)phosphino]propane and palladium acetate), and 3.4mg of the co-catalyst trifluoroacetic acid were added; after adding the above substances, nitrogen was filled into the autoclave to maintain pressure and replace it, and then 400g of propylene was filled into it, and 350g of a mixed gas with a mass ratio of CO and C2H4 of 1:1.1 was filled into it. The temperature began to rise and was set to 100°C. After the temperature was constant, a mixed gas of CO:C2H4=1:1.05 was continuously filled in, and the reaction pressure was maintained at 3.5MPa~4.0MPa, the stirring speed was 400r / min, and the reaction time was 2.5h.

[0090] After the reaction is completed, the obtained polyketone powder product is filtered, washed with methanol, and then dried in vacuum at 80°C for 3 hours to obtain a polyketone powder; the obtained polyketone powder has a weight average molecular weight of 179,000, a molecular weight distribution of 2.25, a bulk density of 0.16 g / ml, a particle size of 20 μm to 480 μm, and a particle size distribution width Span of 3.371.

[0091] The powder particle size is shown in Table 3.

[0092] Table 3 Particle size distribution data of polyketone powder prepared in Comparative Example 2

[0093] Sample name Particle refractive index <![CDATA[D 10 ]]> <![CDATA[D 50 ]]> <![CDATA[D 90 ]]> Polyketone powder 1.5 25.8 103 373

[0094] Example 2

[0095] To a quantitative mixture of methanol and hexafluoroisopropanol (Vmethanol:Vhexafluoroisopropanol=1:4), the main catalyst 1,3-bis[bis(2-methoxyphenyl)phosphino]propane and palladium acetate organic metal complex, the co-catalyst trifluoroacetic acid and the co-solvent carboxylic acid functionalized imidazole salt were added, wherein the main catalyst concentration was 0.02mmol / L, the co-catalyst concentration was 0.08mmol / L, and the co-solvent concentration was 0.2mmol / L; before the reaction started, the microchannel reactor was filled with nitrogen for replacement. After the replacement was completed, the reactor heating module was heated to 110℃, and then the mixed liquid with a flow rate of 5ml / min and propylene were continuously introduced into the reactor (the reactor flux was 50ml). The flow rate is 0.6 g / min, the feed rate of the mixed gas with a mass ratio of CO and ethylene of 1:1.1 is 30 g / min, the system is pressurized to a reaction pressure of 6.5 MPa to 7.0 MPa, and the residence time is controlled to 10 min. When the system pressure is higher than the reaction pressure, the reaction liquid begins to be extracted and enters the gas-liquid separation equipment, the gas is recycled, and the liquid enters the flash tank. The solvent is flashed to remove dense and uniform polyketone powder, and the solvent is recovered and reused; a polyketone powder with a weight average molecular weight of 205,000, a molecular weight distribution of 1.75, a bulk density of 0.38 g / ml, a particle size of 10 μm to 50 μm, and a particle size distribution width Span of approximately 0.776 is obtained.

[0096] The powder particle size is shown in Table 4.

[0097] Table 4 Particle size distribution data of polyketone powder prepared in Example 2 of the present invention

[0098] Sample name Particle refractive index <![CDATA[D 10 ]]> <![CDATA[D 50 ]]> <![CDATA[D 90 ]]> Polyketone powder 1.5 20.5 28.6 42.7

[0099] Example 3

[0100] To a quantitative mixture of methanol and hexafluoroisopropanol (Vmethanol:Vhexafluoroisopropanol=1:4), the main catalyst 1,3-bis[bis(2-methoxyphenyl)phosphino]propane and palladium acetate organic metal complex, the co-catalyst trifluoroacetic acid and the co-solvent carboxylic acid functionalized imidazole salt were added, wherein the main catalyst concentration was 0.02mmol / L, the co-catalyst concentration was 0.08mmol / L, and the co-solvent concentration was 0.2mmol / L; before the reaction started, the microchannel reactor was filled with nitrogen for replacement. After the replacement was completed, the reactor heating module was heated to 100℃, and then the mixed solution with a flow rate of 10ml / min and propane was continuously introduced into the reactor (reactor flux was 50ml). The olefin flow rate is 1.2 g / min, the feed rate of the mixed gas with a mass ratio of CO to ethylene of 1:1.1 is 60 g / min, the system pressure is prepared to a reaction pressure of 6.5 MPa to 7.0 MPa, and the residence time is controlled to 5 min. When the system pressure is higher than the reaction pressure, the reaction liquid begins to be withdrawn and enters the gas-liquid separation equipment, the gas is recycled, and the liquid enters the flash tank, and the solvent is flashed to remove dense and uniform polyketone powder, and the solvent is recovered and reused; a polyketone powder with a weight average molecular weight of 201,000, a molecular weight distribution of 1.95, a bulk density of 0.35 g / ml, a particle size of 10 μm to 50 μm, and a particle size distribution width Span of approximately 0.826 is obtained.

[0101] The powder particle size is shown in Table 5.

[0102] Table 5 Particle size distribution data of polyketone powder prepared in Example 3 of the present invention

[0103] Sample name Particle refractive index <![CDATA[D 10 ]]> <![CDATA[D 50 ]]> <![CDATA[D 90 ]]> Polyketone powder 1.5 18.1 30.5 43.3

[0104] The above description of the disclosed embodiments will enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. An aliphatic polyketone prepared by a continuous solution polymerization process, wherein the aliphatic polyketone is obtained by a continuous solution polymerization reaction of carbon monoxide and an olefin compound in a solvent system containing a catalyst; The solvent system containing the catalyst is a mixed solvent containing a catalyst, a co-catalyst and a co-solvent; The cosolvent is a carboxylic acid functionalized imidazole salt having the structure shown in formula (II): In formula (II), -NM3 is an imidazole substituent, and X is trifluoroacetate, trifluorosulfonate or hexafluorophosphate; The mixed solvent is a mixed solvent of o-chlorophenol and methanol, a mixed solvent of m-cresol and methanol, a mixed solvent of hexafluoroisopropanol and methanol, or a mixed solvent of DMF and methanol; The particle size of the aliphatic polyketone is 10 μm to 50 μm, the particle size distribution width Span is 0.5 to 0.9, and the bulk density is greater than 0.35 g / ml.

2. The aliphatic polyketone prepared by the continuous solution polymerization method according to claim 1, characterized in that: The weight average molecular weight of the aliphatic polyketone is greater than 200,000, and the molecular weight distribution is less than 2.

0.

3. The aliphatic polyketone prepared by the continuous solution polymerization method according to claim 1, characterized in that: The catalyst is an organic metal complex of a divalent palladium salt and 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 formula (I), R1, R2, R3 and R4 are independently selected from phenyl or substituted phenyl, and R5 is an alkylene group containing at least 3 carbon atoms.

4. The aliphatic polyketone prepared by the continuous solution polymerization method according to claim 1, characterized in that: The co-catalyst is selected from one or more of sulfuric acid, benzenesulfonic acid, perchloric acid, trichloroacetic acid and trifluoroacetic acid.

5. A method for preparing the aliphatic polyketone according to any one of claims 1 to 4 by continuous solution polymerization, comprising the following steps: a) continuously feeding carbon monoxide, an olefin compound and a solvent system containing a catalyst into a continuous flow reactor to carry out a solution polymerization reaction to obtain an aliphatic polyketone.

6. The method according to claim 5, characterized in that The temperature of the solution polymerization reaction in step a) is 100° C. to 110° C., and the pressure is 6.5 MPa to 7 MPa; The residence time of the solution polymerization reaction is controlled by controlling the monomer and solvent feed rates; The solution polymerization reaction adopts a microchannel reactor, monomers are continuously fed, unreacted monomers are separated and reused, and products are continuously discharged.

7. The method according to any one of claims 5 to 6, characterized in that The step a) further comprises: The reaction liquid obtained by the polymerization reaction is subjected to gas-liquid separation, the gas is recycled, and the solvent is removed from the liquid to obtain polyketone powder; The solvent removal method is flash evaporation; the recovered solvent can be recycled as a mixed solvent.

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