Silicon-based phosphate, composition and catalyst for synthesizing polyketone

Abstract

The invention discloses a silicon-based phosphate and polyketone composition and a catalyst for synthesizing polyketone, and belongs to the technical field of chemical engineering. In the silicon-based phosphate as shown in the formula 1, R1 is selected from C1-C10 straight chain or branched chain alkyl; r < 3 >, R < 4 > and R < 5 > are independently selected from one or more of C1-C10 linear chain or branched chain alkyl groups, C1-C6 alkoxy groups and C1-C10 silyl groups; and Y1 is selected from alkylidene of C1 to C5. The composition composed of the silicon-based phosphate can be used as a catalyst for synthesizing polyketone, the scaling rate of polyketone preparation equipment is remarkably reduced, the catalytic reaction activity of the composition is about 27 kg / (g-Pdh), and the requirements of large-scale industrial production are better met. # imgabs0 # is represented by formula 1.

Description

Technical Field

[0001] The invention relates to the technical field of chemical industry, and in particular to a silicon-based phosphate and polyketone composition and a catalyst for synthesizing polyketone. Background Art

[0002] Polyketone (POK) refers to a new type of green polymer material copolymerized by carbon monoxide and olefins (ethylene, propylene, styrene). The carbon chain structure of polyketone is soft, with high tensile strength and high impact strength. The special molecular structure makes it have excellent chemical resistance, wear resistance, hydrolysis resistance, high and low temperature resistance, high barrier properties, etc. The carbonyl group in the polyketone skeleton gives it photodegradability and modification potential. It is a "natural" thermoplastic engineering plastic that complies with the green sustainable development strategy. Therefore, it has been widely used in the fields of automobiles, machinery, electronic appliances, medical devices, packaging, etc.

[0003] At present, the catalyst used to prepare polyketone is usually composed of a Pd (II) / bisphosphine ligand / acid system. The bisphosphine ligands with higher activity include but are not limited to 1,3-bis [bis (2-methoxyphenyl) phosphino] propane, ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) and the like.

[0004] The catalytic system used in the industry to produce the ternary copolymer of ethylene, propylene and CO is 1,3-bis[bis(2-methoxyphenyl)phosphino]propane-palladium acetate-trifluoromethanesulfonic acid-methanol, and the catalytic activity can reach 33 kg / (g-Pd•h) at a total pressure of 9 MPa. The catalytic activity of these catalysts generally decreases as the reaction proceeds during the polymerization process, and the molecular weight distribution of the prepared copolymer is relatively wide, which has a certain impact on the product performance. In addition, there will be serious reactor fouling, which is not conducive to the large-scale industrial production of polyketones.

[0005] Therefore, it is of great significance to study and develop a new catalyst for the synthesis of polyketones. Summary of the invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a silicon-based phosphate and a composition and a catalyst for synthesizing polyketone. The composition composed of the silicon-based phosphate can be used to catalyze the synthesis of polyketone, effectively reducing the scaling rate of equipment during the synthesis of polyketone.

[0007] In order to achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0008] The present invention provides a silicon-based phosphate ester represented by Formula 1:

[0009]

[0010] Formula 1;

[0011] Among them, R 1 Selected from C 1 -C 10 A straight chain or branched alkyl group;

[0012] R 3 , R 4 , R 5 Independently selected from C 1 -C 10 Straight or branched alkyl, C 1 -C 6 Alkoxy, C 1 -C 10 One or more of the silane groups;

[0013] Y 1 Selected from C 1 -C 5 of alkylene.

[0014] The C 1 -C 10 The straight chain or branched chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, tert-butyl, n-pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.

[0015] The C 1 -C 6 The alkoxy group includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isopropoxy, tert-butoxy, n-pentoxy, isopentoxy, hexoxy and the like.

[0016] The C 1 -C 10 The silane groups include but are not limited to -(CH 2 ) 3 Si(CH 3 ) 3 、-(CH 2 ) 2 Si(CH 3 ) 3 、-(CH 2 ) 2 Si(CH 3 ) 2 CH 2 CH 3 wait.

[0017] Preferably, the R 1 Selected from C 1 -C 6 A straight chain or branched alkyl group;

[0018] Preferably, R 3 , R 4 , R 5 Independently selected from C 1 -C 6 Straight or branched alkyl, C 1 -C 4 Alkoxy, C 1 -C 6 One or more of the silane groups;

[0019] Preferably, Y 1 Selected from C 1 -C 3 of alkylene.

[0020] The C 1 -C 6 The straight chain or branched chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, tert-butyl, n-pentyl, isopentyl, and hexyl.

[0021] The C 1 -C 4 The alkoxy group includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isopropoxy, tert-butoxy and the like.

[0022] Preferably, the C 1 -C 6 The silyl group is selected from -(CH 2 ) 3 Si(CH 3 ) 3 、-(CH 2 ) 2 Si(CH 3 ) 3 、-(CH 2 ) 2 Si(CH 3 ) 2 CH 2 CH 3 One or more of .

[0023] It is further preferred that the silicon-based phosphate has any of the following structures:

[0024]

[0025] Formula 1-1;

[0026]

[0027] Formula 1-2;

[0028]

[0029] Formula 1-3.

[0030] The preparation method of the above silicon-based phosphonate comprises the following steps:

[0031] 1) In the absence of water and oxygen, magnesium and halogenated silane are mixed and reacted in a solvent to obtain an organosilicon Grignard reagent;

[0032] 2) Mixing the organosilicon Grignard reagent and dialkoxyphosphoryl chloride to obtain the silicon-based phosphate ester shown in formula 1.

[0033] Preferably, the halogenated silane in step 1) is selected from one or more of chloromethyltrimethylchlorosilane, 3-(trimethylsilyl)propyldimethylchloromethylsilane, and bis[3-(trimethylsilyl)propyl]methylchloromethylsilane.

[0034] Preferably, in step 1), the molar ratio of magnesium to halogenated silane is (1-1.1):1.

[0035] Preferably, in step 2), the molar ratio of the organosilicon Grignard reagent to the dialkoxyphosphoryl chloride is 1:(1-1.1).

[0036] Preferably, the reaction temperature in step 1) is 40°C-70°C.

[0037] Preferably, the reaction temperature in step 2) is 60°C.

[0038] Preferably, the solvent in step 1) is selected from one or more of dry tetrahydrofuran, dry anhydrous ether, and dry methyltetrahydrofuran.

[0039] Preferably, the solvent for the mixed reaction in step 2) is selected from one or more of dry tetrahydrofuran, dry anhydrous ether, and dry methyltetrahydrofuran.

[0040] The present invention also provides a composition comprising the following ingredients:

[0041] The silicon-based phosphonate according to any one of claims 1 to 4;

[0042] Transition metal compounds;

[0043] Phosphine ligands;

[0044] Promoter catalyst;

[0045] The co-catalyst is selected from one or more of an acid, a quinone, and a metal salt with a pKa < 6, and at least includes an acid.

[0046] More preferably, the molar ratio of the silicon-based phosphonate to the transition metal compound is (100-900):1.

[0047] More preferably, the molar ratio of the transition metal compound to the phosphine ligand is (0.8-1.5):1; further preferably (0.9-1.2):1.

[0048] More preferably, the molar ratio of the co-catalyst to the transition metal compound is (5-25):1; further preferably (5-15):1.

[0049] Preferably, the transition metal compound is selected from one or more of palladium compounds, nickel compounds and copper compounds;

[0050] Preferably, the ligand is selected from phosphine ligands.

[0051] More preferably, the palladium compound is selected from one or more of palladium sulfate, palladium sulfonate, palladium nitrate, palladium acetate, and palladium tetraacetonitrile trifluoromethanesulfonate; more preferably palladium acetate or palladium sulfate; and even more preferably palladium acetate.

[0052] More preferably, the phosphine ligand is selected from the bisphosphine ligand shown in Formula 2:

[0053]

[0054] Formula 2;

[0055] Among them, R 6 is selected from cyclohexylene or alkylene containing at least 1 carbon atom;

[0056] R 7 , R 8 , R 9 , R 10 independently selected from hydrogen, C 1 -C 6 Straight or branched alkyl, C 1 -C 4 One or more of the alkoxy groups.

[0057] In the present invention, the bisphosphine ligand is further preferably selected from (2,2-dimethoxy-1,3-bis[bis(2-methoxyphenyl)phosphino]propane) and / or 1,3-bis-[bis(2-methoxyphenyl)phosphino]propane.

[0058] It is further preferred that the acid is selected from one or more of phosphoric acid, nitric acid, p-toluenesulfonic acid, aminosulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, and trifluoroacetic acid;

[0059] It is further preferred in the present invention that the quinone is selected from benzoquinone and / or naphthoquinone;

[0060] The benzoquinone includes but is not limited to 1,2-benzoquinone, 1,4-benzoquinone and the like.

[0061] The naphthoquinone includes but is not limited to 1,2-naphthoquinone and / or 1,4-naphthoquinone and the like.

[0062] It is further preferred that the metal salt with a pKa < 6 is selected from one or more of phosphate, nitrate, p-toluenesulfonate, aminosulfonate, trifluoromethanesulfonate, trichloroacetate and trifluoroacetate.

[0063] The metal salt with pKa < 6 includes, but is not limited to, one or more of potassium salt, magnesium salt, zinc salt and iron salt.

[0064] In the present invention, the metal salt with pKa < 6 is further preferably one or more of magnesium phosphate, zinc phosphate, iron phosphate, magnesium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, and iron trifluoromethanesulfonate.

[0065] The present invention further preferably comprises the following components:

[0066] The silicon-based phosphate shown in formula 1-1;

[0067] Palladium acetate;

[0068] (2,2-dimethoxy-1,3-bis[bis(2-methoxyphenyl)phosphino]propane);

[0069] Promoter catalyst;

[0070] The co-catalyst is selected from p-benzoquinone, magnesium phosphate and phosphoric acid;

[0071] Wherein, the molar ratio of the silicon-based phosphate ester represented by Formula 1-1 to palladium acetate is 200:1;

[0072] The molar ratio of palladium acetate to (2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane) is 1.0:1;

[0073] The molar ratio of p-benzoquinone, magnesium phosphate and phosphoric acid is 6:3:1;

[0074] The molar ratio of the p-benzoquinone to the palladium acetate is 13:1.

[0075] The present invention further preferably comprises the following components:

[0076] The silicon-based phosphate shown in formula 1-1;

[0077] Palladium acetate;

[0078] (2,2-dimethoxy-1,3-bis[bis(2-methoxyphenyl)phosphino]propane);

[0079] Promoter catalyst;

[0080] The co-catalyst is selected from p-benzoquinone, magnesium phosphate and phosphoric acid;

[0081] Wherein, the molar ratio of the silyl phosphate ester represented by Formula 1-1 to palladium acetate is 900:1;

[0082] The molar ratio of palladium acetate to (2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane) is 1.0:1;

[0083] The molar ratio of p-benzoquinone, magnesium phosphate and phosphoric acid is 6:3:1;

[0084] The molar ratio of the p-benzoquinone to the palladium acetate is 13:1.

[0085] The present invention further preferably comprises the following components:

[0086] The silicon-based phosphate shown in formula 1-2;

[0087] Palladium acetate;

[0088] (2,2-dimethoxy-1,3-bis[bis(2-methoxyphenyl)phosphino]propane);

[0089] Promoter catalyst;

[0090] The co-catalyst is selected from p-benzoquinone, magnesium phosphate and phosphoric acid;

[0091] Wherein, the molar ratio of the silicon-based phosphate ester represented by Formula 1-2 to palladium acetate is 200:1;

[0092] The molar ratio of palladium acetate to (2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane) is 1.0:1;

[0093] The molar ratio of p-benzoquinone, magnesium phosphate and phosphoric acid is 6:3:1;

[0094] The molar ratio of the p-benzoquinone to the palladium acetate is 13:1.

[0095] The present invention further preferably comprises the following components:

[0096] The silicon-based phosphate shown in formula 1-3;

[0097] Palladium acetate;

[0098] (2,2-dimethoxy-1,3-bis[bis(2-methoxyphenyl)phosphino]propane);

[0099] Promoter catalyst;

[0100] The co-catalyst is selected from p-benzoquinone, magnesium phosphate and phosphoric acid;

[0101] Wherein, the molar ratio of the silicon-based phosphate ester represented by Formula 1-3 to palladium acetate is 200:1;

[0102] The molar ratio of palladium acetate to (2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane) is 1.0:1;

[0103] The molar ratio of p-benzoquinone, magnesium phosphate and phosphoric acid is 6:3:1;

[0104] The molar ratio of the p-benzoquinone to the palladium acetate is 13:1.

[0105] The present invention also provides a catalyst for synthesizing polyketone, comprising the above composition.

[0106] The silicon-based phosphonate in the composition is insoluble in the alcohol solvent, and then exists in the alcohol solvent in the form of tiny droplets. The silicon-based phosphonate in the form of tiny droplets has a strong intermolecular force with the transition metal compound, especially the palladium compound. The intermolecular force makes the active sites of the catalyst for synthesizing polyketone more dispersed, so that the prepared polyketone powder has a high bulk density, thereby reducing the scaling rate of the equipment for synthesizing polyketone.

[0107] The equipment for synthesizing polyketone includes but is not limited to a reaction agitator, a reaction kettle, etc.

[0108] The present invention also provides a method for preparing polyketone, comprising the following steps:

[0109] The above catalyst, carbon monoxide, olefin and solvent are mixed in a closed environment to carry out polymerization reaction to prepare polyketone.

[0110] The molar ratio of carbon monoxide to olefin is preferably 1:(0.5-5).

[0111] The molar ratio of carbon monoxide to olefin may specifically be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:2, 1:2.3, 1:2.5, 1:2.7, 1:3, 1:3.2, 1:3.5, 1:3.7, 1:4, 1:4.2, 1:4.5, 1:4.7 or 1:5.

[0112] The polymerization reaction temperature is preferably 40°C to 150°C.

[0113] The temperature of the polymerization reaction can specifically be 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C.

[0114] The pressure of the polymerization reaction is provided by the gas filled into the closed environment.

[0115] The polymerization reaction pressure is preferably 2-10 MPa.

[0116] The pressure of the polymerization reaction can specifically be 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, 8.5MPa, 9MPa, 9.5MPa or 10MPa.

[0117] The polymerization reaction time is preferably 1 to 12 h.

[0118] The polymerization reaction time may specifically be 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, 10 h, 10.5 h, 11 h, 11.5 h or 12 h.

[0119] The type of polymerization reaction is preferably a batch reaction.

[0120] The stirring rate of the polymerization reaction is preferably 100 r / min to 500 r / min.

[0121] The stirring rate may specifically be 100 r / min, 150 r / min, 200 r / min, 250 r / min, 300 r / min, 350 r / min, 400 r / min, 450 r / min or 500 r / min.

[0122] The olefins include, but are not limited to, one or more of ethylene, propylene, and butene.

[0123] In some specific embodiments of the present invention, the olefins are preferably propylene and ethylene.

[0124] The solvent is selected from lower aliphatic alcohols, specifically including but not limited to one or more of methanol, ethanol, isopropanol, ethylene glycol, and glycerol.

[0125] The closed environment can be achieved by equipment such as a reactor.

[0126] The effective solvent ratio of the solvent to the reactor is preferably (0.2-0.7):1, more preferably (0.3-0.5):1; further preferably 0.3:1 or 0.4:1 or 0.5:1.

[0127] After the polymerization reaction is completed, the process further includes filtering, washing and drying.

[0128] The washing solvent is preferably methanol.

[0129] The drying temperature is preferably 70°C to 90°C, more preferably 70°C, 75°C, 80°C, 85°C or 90°C.

[0130] The drying time is preferably 1 h to 5 h, more preferably 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h or 5 h.

[0131] After the above polymerization reaction and post-treatment, polyketone powder is obtained.

[0132] Compared with the prior art, the present invention provides a silicon-based phosphate represented by Formula 1, wherein R 1 Selected from C 1 -C 10 A straight chain or branched alkyl group; R 3 , R 4 , R 5 Independently selected from C 1 -C 10 Straight or branched alkyl, C 1 -C 6 Alkoxy, C 1 -C 10 One or more of the silane groups; Y 1 Selected from C 1 -C 5 The composition composed of silicon-based phosphate can be used as a catalyst for synthesizing polyketone, which significantly reduces the fouling rate of polyketone preparation equipment, and the catalytic reaction activity of the composition is about 27 kg / (g-Pd•h), which better meets the needs of large-scale industrial production. DETAILED DESCRIPTION

[0133] To further illustrate the present invention, the silicon-based phosphate ester and composition and the catalyst for synthesizing polyketone provided by the present invention are described in detail below with reference to the examples.

[0134] The raw materials and solvents used below are all common commercially available products.

[0135] The calculation formula of the following powder bulk density is: powder bulk density = mass of polyketone obtained by polymerization / volume of polyketone obtained by polymerization. The following Examples 1-3 are methods for synthesizing silicon-carbon-substituted phosphate esters, and three silicon-carbon-substituted phosphate esters are obtained respectively. Examples 4-7 are methods for preparing CO / ethylene / propylene terpolymers using the silicon-carbon-substituted phosphate esters prepared in Examples 1-3 as components of the catalyst composition.

[0136] Example 1

[0137] Under anhydrous and oxygen-free conditions, 1.58 g of magnesium flakes were added to 300 mL of dry tetrahydrofuran, and the temperature was raised to 60°C, and 7.63 g of chloromethyltrimethylsilyl chloride was added dropwise. After the addition was completed, the reaction was stirred at 60°C until the magnesium flakes completely disappeared. After cooling to room temperature, 10.75 g of diethoxyphosphoryl chloride was added dropwise. After the addition was completed, the temperature was raised to 60°C and the reaction was continued with stirring. The reaction was tracked and detected to be complete, and the reaction was cooled, filtered to remove magnesium chloride, washed with water three times, dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure to obtain 12.96 g of silicon-based phosphonate 1-1 (structure as shown in Formula 1-1), with a yield of 92.58%. 1H NMR (400 MHz, C6D6) 4.15 (m,4H, CH2CH3), 1.26 (t, 6H,CH2CH3),1.10(d, 2H, CH2P), 0.03 (m, 9H, SiCH3).

[0138]

[0139] Formula 1-1

[0140] Example 2

[0141] Under anhydrous and oxygen-free conditions, 0.79 g of magnesium flakes were added to 300 mL of dry tetrahydrofuran, and the temperature was raised to 60°C before 6.94 g of 3-(trimethylsilyl)propyldimethylchloromethylsilane was added dropwise. After the addition was completed, the mixture was stirred at 80°C until the magnesium flakes completely disappeared. After cooling to room temperature, 5.38 g of diethoxyphosphoryl chloride was added dropwise. After the addition was completed, the mixture was heated to 60°C and the stirring reaction was continued. The reaction was followed and detected to be complete. The mixture was cooled, filtered to remove magnesium chloride, washed with water three times, dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure to obtain 9.23 g of silylphosphonate 1-2 (structure as shown in Formula 1-2), with a yield of 91.13%. 1H NMR (400 MHz, C6D6)4.15 (m, 4H, CH2CH3), 1.26 (t, 6H,CH2CH3),1.10(d, 2H, CH2P), 0.21 (m, 6H,SiCH3), 0.60 (m, 4H, SiCH2), 1.21 (m, 2H, SiCH2CH2), 0.07 (m, 9H, SiCH3).

[0142]

[0143] Formula 1-2

[0144] Example 3

[0145] Under anhydrous and oxygen-free conditions, 0.39 g of magnesium flakes was added to dry tetrahydrofuran, and the temperature was raised to 70°C before 5.03 g of bis[3-(trimethylsilyl)propyl]methylchloromethylsilane was added dropwise. After the addition was completed, the mixture was stirred and reacted at 80°C until the magnesium flakes completely disappeared. After cooling to room temperature, 2.69 g of diethoxyphosphoryl chloride was added dropwise. After the addition was completed, the mixture was heated to 60°C and the reaction was continued with stirring. The reaction was followed and detected to be complete. The mixture was cooled, filtered to remove magnesium chloride, washed with water three times, dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure to obtain silylphosphonate 1-3 (structure shown below), which was a viscous liquid of 5.96 g with a yield of 89.96%. 1H NMR (400MHz, C6D6) 4.15 (m, 4H, CH2CH3), 1.26 (t, 6H,CH2CH3), 1.10 (d, 2H, CH2P), 0.21 (m, 3H, SiCH3), 0.62 (m, 8H, SiCH2), 1.22 (m, 4H, SiCH2CH2), 0.07 (m, 18H,SiCH3).

[0146]

[0147] Formula 1-3

[0148] Example 4

[0149] 250 mL of methanol, 9.70 mg of p-benzoquinone, 11.82 mg of magnesium phosphate, 311.33 mg of silicon-substituted phosphoric acid (Formula 1-1, prepared in Example 1), and 2.0 mL of phosphoric acid (7.5 mmol / L) were added to a 500 mL autoclave. After adding the above substances, nitrogen was charged into the autoclave to maintain pressure and replace. Then, 4.11 mg of 2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane and 1.56 mg of palladium acetate were dissolved in 3.0 mL of acetone under anhydrous and oxygen-free conditions to prepare a main catalyst solution, which was added to the autoclave. Then, 15 g of propylene was charged, and the temperature was started to rise. The temperature was set to 95°C, and CO:C was continuously charged. 2 H 4 =46:54 mixed gas, and maintained the reaction pressure at 5MPa, stirring speed at 400r / min, and reaction time at 4h.

[0150] After the reaction, the product stirring paddle and the kettle wall were slightly scaled, with a scaling rate of 10%. The obtained polyketone product was filtered, washed with methanol, and then dried in a vacuum drying oven at 80°C for 3 h. The amount of product obtained was 87.93 g, the catalytic activity was 27.65 kg / (g-Pd•h), and the powder bulk density was 0.29 g / mL.

[0151] Example 5

[0152] In a 500 mL autoclave were added 250 mL methanol, 9.70 mg p-benzoquinone, 11.82 mg magnesium phosphate, 1400.98 mg silicon-substituted phosphoric acid (Formula 1-1, prepared in Example 1), and 2.0 mL phosphoric acid (7.5 mmol / L). After adding the above substances, nitrogen was filled into the autoclave to maintain pressure and replace, and then 4.11 mg 2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane and 1.56 mg palladium acetate were dissolved in 3.0 mL acetone under anhydrous and oxygen-free conditions to prepare a main catalyst solution, which was added to the autoclave; the rest of the polymerization method and experimental conditions were the same as those in Example 4 above.

[0153] After the reaction, the product stirring paddle and the kettle wall were slightly scaled, with a scaling rate of 10%. The obtained polyketone product was filtered, washed with methanol, and then dried in a vacuum drying oven at 80°C for 3 h. The amount of product obtained was 84.83 g, the catalytic activity was 26.68 kg / (g-Pd•h), and the powder bulk density was 0.29 g / mL.

[0154] Example 6

[0155] In a 500 mL autoclave were added 250 mL of methanol, 9.70 mg of p-benzoquinone, 11.82 mg of magnesium phosphate, 449.71 mg of silicon-substituted phosphoric acid (Formula 1-2, prepared in Example 2), and 2.0 mL of phosphoric acid (7.5 mmol / L). After the addition of the above substances, nitrogen was filled into the autoclave to maintain pressure and replace, and then 4.11 mg of 2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane and 1.56 mg of palladium acetate were dissolved in 3.0 mL of acetone under anhydrous and oxygen-free conditions to prepare a main catalyst solution, which was added to the autoclave; the rest of the polymerization method and experimental conditions were the same as those in the above Example 4.

[0156] After the reaction, there was no obvious scaling on the product stirring paddle and the kettle wall, with a scaling rate of 7%. The obtained polyketone product was filtered, washed with methanol, and then dried in a vacuum drying oven at 80°C for 3 h. The amount of product obtained was 88.59 g, the catalytic activity was 27.85 kg / (g-Pd•h), and the powder bulk density was 0.33 g / mL.

[0157] Example 7

[0158] In a 500 mL autoclave were added 250 mL of methanol, 9.70 mg of p-benzoquinone, 11.82 mg of magnesium phosphate, 588.84 mg of silicon-substituted phosphoric acid (Formula 1-3, prepared in Example 3), and 2 mL of phosphoric acid (7.5 mmol / L). After the addition of the above substances, nitrogen was filled into the autoclave to maintain pressure and replace, and then 4.11 mg of 2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane and 1.56 mg of palladium acetate were dissolved in 3.0 mL of acetone under anhydrous and oxygen-free conditions to prepare a main catalyst solution, which was added to the autoclave; the rest of the polymerization method and experimental conditions were the same as those in the above Example 4.

[0159] After the reaction, there was almost no scaling on the product stirring paddle and the kettle wall, with a scaling rate of 5%. The obtained polyketone product was filtered, washed with methanol, and then dried in a vacuum drying oven at 80°C for 3 h. The amount of product obtained was 88.47 g, the catalytic activity was 27.82 kg / (g-Pd•h), and the powder bulk density was 0.35 g / mL.

[0160] Comparative Example 1

[0161] 250 mL of methanol, 9.70 mg of p-benzoquinone, 14.80 mg of magnesium trifluoromethanesulfonate, and 2.0 mL of trifluoromethanesulfonic acid (7.5 mmol / L) were added to a 500 mL autoclave. After the above substances were added, nitrogen was filled into the autoclave to maintain pressure and replace. Then, 3.69 mg of 1,3-bis[bis(2-methoxyphenyl)phosphino]propane and 1.56 mg of palladium acetate were dissolved in 3.0 mL of acetone under anhydrous and oxygen-free conditions to prepare a main catalyst solution, which was added to the autoclave. The remaining polymerization methods and experimental conditions were the same as those in Example 4 above.

[0162] After the reaction, the product stirring paddle and the kettle wall had obvious scaling, with a scaling rate of 20%. The obtained polyketone product was filtered, washed with methanol, and then dried in a vacuum drying oven at 80°C for 3 h. The amount of product obtained was 84.05 g, the catalytic activity was 26.43 kg / (g-Pd•h), and the powder bulk density was 0.22 g / mL.

[0163] Comparative Example 2

[0164] 250 mL of methanol, 9.70 mg of p-benzoquinone, 11.82 mg of magnesium phosphate, and 2.0 mL of phosphoric acid (7.5 mmol / L) were added to a 500 mL high-pressure reactor. After the above substances were added, nitrogen was filled into the autoclave to maintain pressure and replace. Then, 4.11 mg of 2,2-dimethoxy-1,3-bis[di(2-methoxyphenyl)phosphino]propane and 1.56 mg of palladium acetate were dissolved in 3.0 mL of acetone under anhydrous and oxygen-free conditions to prepare a main catalyst solution, which was added to the high-pressure reactor; the rest of the polymerization method and experimental conditions were the same as those in the above Example 4.

[0165] After the reaction, the product stirring paddle and the kettle wall had obvious scaling, with a scaling rate of 18%. The obtained polyketone product was filtered, washed with methanol, and then dried in a vacuum drying oven at 80°C for 3 h. The amount of product obtained was 83.27 g, the catalytic activity was 26.18 kg / (g-Pd•h), and the powder bulk density was 0.22 g / mL.

[0166] Table 1 Polymerization performance data of Examples 4-7 and Comparative Examples 1-2

[0167] Catalyst activity kg / (g-Pd•h) Powder bulk density g / mL Scaling rate Example 4 27.65 0.29 10 Example 5 26.68 0.29 10 Example 6 27.85 0.33 7 Example 7 27.82 0.35 5 Comparative Example 1 26.43 0.22 20 Comparative Example 2 26.18 0.22 18

[0168] The above data show that compared with the traditional synthesis process in Comparative Example 1, the catalyst composition of the present invention, while ensuring the catalytic activity reaches 27.82 kg / (g-Pd•h) or above, the powder bulk density is increased from 0.22 to 0.35, and the scaling rate is reduced from 20% to 5%, which effectively solves the scaling problem and better meets the needs of industrial production.

[0169] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A silicon-based phosphate ester represented by formula 1: Formula 1; in, R 1 Selected from C1-C 10 A straight chain or branched alkyl group; R 3 , R 4 , R 5 Independently selected from C1-C 10 Straight or branched alkyl, C1-C6 alkoxy, C1-C 10 One or more of the silane groups; Y 1 An alkylene group selected from C1-C5.

2. The silicon-based phosphate according to claim 1, characterized in that The R 1 A straight or branched chain alkyl group selected from C1-C6; R 3 , R 4 , R 5 One or more independently selected from C1-C6 straight or branched alkyl, C1-C4 alkoxy, C1-C6 silane; Y 1 An alkylene group selected from C1-C3.

3. The silicon-based phosphate according to claim 2, characterized in that The C1-C6 silane group is selected from one or more of -(CH2)3Si(CH3)3, -(CH2)2Si(CH3)3, and -(CH2)2Si(CH3)2CH2CH3.

4. The silicon-based phosphate according to any one of claims 1 to 3, characterized in that The silicon-based phosphate has any of the following structures: Formula 1-1; Formula 1-2; Formula 1-3.

5. A composition, characterized in that Includes the following ingredients: The silicon-based phosphonate according to any one of claims 1 to 4; Transition metal compounds; Phosphine ligands; Promoter catalyst; The co-catalyst is selected from one or more of an acid, a quinone, and a metal salt with a pKa < 6, and at least includes an acid.

6. The composition according to claim 5, characterized in that The molar ratio of the silicon-based phosphonate to the transition metal compound is (100-900): 1; The mass ratio of the transition metal compound to the phosphine ligand is (0.8-1.5): 1; The molar ratio of the co-catalyst to the transition metal compound is (5-25):

1.

7. The composition according to claim 5 or 6, characterized in that The transition metal compound is selected from one or more of palladium compounds, nickel compounds and copper compounds; The ligands are selected from phosphine ligands.

8. The composition according to claim 7, characterized in that The palladium compound is selected from one or more of palladium sulfate, palladium sulfonate, palladium nitrate, palladium acetate, and palladium tetraacetonitrile trifluoromethanesulfonate; The phosphine ligand is selected from the diphosphine ligand shown in Formula 2: Formula 2; Among them, R 6 is selected from cyclohexylene or alkylene containing at least 1 carbon atom; R 7 , R 8 , R 9 , R 10 Independently selected from one or more of hydrogen, C1-C6 straight or branched alkyl, and C1-C4 alkoxy.

9. The composition according to claim 5, characterized in that The acid is selected from one or more of phosphoric acid, nitric acid, p-toluenesulfonic acid, aminosulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, and trifluoroacetic acid; The quinone is selected from benzoquinone and / or naphthoquinone; The metal salt with pKa < 6 is selected from one or more of phosphate, nitrate, p-toluenesulfonate, aminosulfonate, trifluoromethanesulfonate, trichloroacetate and trifluoroacetate.

10. A catalyst for synthesizing polyketone, characterized in that The invention comprises a composition according to any one of claims 5 to 9.

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