A phenyl-bridged phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials, preparation method and application

Abstract

The present invention belongs to the field of polymer synthesis and discloses a phenyl phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials, a preparation method and an application thereof. The synthesis process of the phenyl phosphine-phosphine oxide type nickel catalyst is simple, the raw materials are cheap, the substituents can be modularly controlled, and the catalyst can be used in the range of 30 to 150 o C can efficiently catalyze ethylene / CO and its α -Olefin copolymerization, with an activity of up to 45 kg PK (g of Ni) ‑1 h ‑1 , achieving the comprehensive synthesis of high-performance polyketone products from resins, fibers, and hot-melt adhesives, meeting the technical requirements for polyketone production in the market. Furthermore, the resulting polyketones generally have a number-average molecular weight between 100,000 and 1.6 million, with a molecular weight distribution within the range of 1.5 to 2.5, meeting the molecular weight requirements for polyketone engineering plastics.

Description

Technical Field

[0001] The present invention belongs to the field of polymer synthesis and relates to a phenylphosphine-phosphine oxide nickel catalyst for preparing polyketone materials, as well as its preparation method and application. The phenylphosphine-phosphine oxide nickel catalyst exhibits excellent catalytic activity and stability in the copolymerization of ethylene / CO and its copolymerization with α-olefins, enabling the synthesis of high-performance polyketone products. Background Art

[0002] Aliphatic polyketone (POK) is a polymer formed by the polymerization of olefins (ethylene, propylene) and carbon monoxide (CO). Due to its special molecular structure, it has excellent impact resistance (2.5 times that of PA66), outstanding chemical resistance, wear resistance (14 times that of POM), hydrolysis resistance, high temperature resistance and barrier properties, and at the same time meets low VOC requirements. It is a green and environmentally friendly material with diversified performance. Depending on the monomer type and material application, it is divided into polyketone fiber products formed by binary copolymerization of ethylene and CO and polyketone resin products formed by ternary copolymerization of ethylene, propylene and CO. Among them, the molecular weight of binary polyketone is generally higher (M n >500,000), melting point is ~260 o C, usually processed into polyketone fiber products by solution spinning, mainly used in high-strength tire cord, bulletproof vests and other scenes; while the molecular weight of ternary polyketone is generally low (M n <200,000), melting point is 200~240 o C range, usually made by injection molding. The current POK products on the market include M330, M630, M930, M730, M710 and other series of grades, which are mainly used in aerospace, automobile, electronics, toys and packaging fields (Yang, Y.; Li, S.-Y., et al. Progress in Polyketone Materials: Blends and Composites; Polym Int 2018,67, 1478–1487).

[0003] Commercial polyketone production dates back to 1996, when industrial production was achieved through a slurry polymerization process using a multi-component catalyst system consisting of 1,3-bis(diphenylphosphino)propane derivatives, palladium acetate, a strong acid, and a quinone, using methanol as the solvent. By 2015, a number of polyketone products had been developed (David, V. Finding Openings for Polyketone Compounds. PlasticsNewsEurope, 2015). However, the main drawback of this production technology lies in the use of a precious metal palladium catalyst. The encapsulated nature of slurry polymerization makes palladium catalyst recovery difficult, resulting in a high price for commercial polyketones and limiting their global market penetration. Nickel, a Group VIII element like palladium, offers great industrial potential as a cheaper alternative. However, the highly electrophilic nature of the nickel metal center in the complex makes it particularly prone to forming a 5-coordinated, 18-electron dormant species, which is difficult to undergo olefin insertion reactions. This results in low activity (<10 3 g PK(g of Ni) -1 h -1 ), poor stability, and a narrow temperature control range (Zhu, L.; Li, J., et al. Aliphatic Polyketones from Alternating Copolymerization of CO and Olefins: Phosphinoamidate Nickel Catalyst, Polymerization Study, Mechanical Propertiesand Degradations. ACS Appl. Polym. Mater. 2024, 6, 9829−9836). In particular, the poor tolerance of nickel catalysts to propylene greatly increases the difficulty of synthesizing polyketone products with high propylene content, thereby limiting the application of such polyketone materials.

[0004] In fact, polyketones, due to their polarity and high-temperature resistance conferred by a high density of carbonyl groups in their backbones, as well as their structural tunability, may enhance their bonding strength to polar materials (such as metals, ceramics, and polar plastics), making them promising materials for high-performance hot-melt adhesives. Therefore, designing a class of inexpensive nickel catalysts with high activity and high propylene tolerance, and through structural adjustment and process optimization, developing a new hot-melt adhesive material while synthesizing polyketone resins and fibers, would undoubtedly broaden the application range of polyketones. Summary of the Invention

[0005] The first object of the present invention is to provide a method for synthesizing a phenyl-bridged phosphine-phosphine oxide type nickel catalyst.

[0006] The second object of the present invention is to provide a polyketone resin, fiber and hot melt adhesive material and a preparation method thereof.

[0007] The technical solution of the present invention:

[0008] A phenyl-bridged phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials has the following structure:

[0009] ;

[0010] Among them, Ar 1 and Ar 2 is phenyl, 4-methylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-N,N-dimethylaminophenyl, 4-N,N-dimethylaminophenyl, 2,6-di-N,N-dimethylaminophenyl, 2-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2,6-dimethoxy-4-N,N-dimethylaminophenyl, 2,6-dimethoxy-1,1'-biphenyl, 2,4,6-trimethoxy-1,1'-biphenyl, tert-butyl, isopropyl or cyclohexyl, Ar 1 and Ar 2 Same or different;

[0011] R 1 is hydrogen, methyl, tert-butyl, methoxy, N,N-dimethylamino, N,N-diethylamino, trimethylsilyl, fluoro, trifluoromethyl or perfluorophenyl;

[0012] R 2 and R 3 is methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, N,N-dimethylamino, N,N-diethylamino, N,N-diisopropylamino, phenyl, 4-methylphenyl, pyrrolyl, morpholinyl, piperidinyl or tetrahydropyrrolyl, R 2 and R 3 Same or different;

[0013] X is BArF, AsF6, SbF6, PF6, p-TsO or BF4.

[0014] A method for preparing a phenyl-bridged phosphine-phosphine oxide type nickel catalyst for preparing a polyketone material, comprising the following steps:

[0015] 1) Phenylphosphine oxide A, phosphine chloride B, alkyl lithium, and alkyl lithium activator react in an organic solvent at room temperature for 2-24 hours to form a phenylphosphine-phosphine oxide ligand C;

[0016]

[0017] The alkyl lithium is n-butyl lithium, methyl lithium, sec-butyl lithium or tert-butyl lithium, preferably n-butyl lithium and sec-butyl lithium;

[0018] The alkyl lithium activator is one or a mixture of two or more of potassium tert-butoxide, tetramethylethylenediamine, hexamethylphosphoramide, and 1,4-diazabicyclo[2.2.2]octane, preferably tetramethylethylenediamine and 1,4-diazabicyclo[2.2.2]octane;

[0019] The organic solvent is one or a mixture of two or more of toluene, 1,2-dimethylbenzene, diethyl ether, methyl tert-butyl ether, n-hexane, n-heptane, N,N-dimethylformamide, tetrahydrofuran, and 1,4-dioxane, preferably methyl tert-butyl ether and tetrahydrofuran;

[0020] The molar ratio of the phenylphosphine oxide A, phosphine chloride B, alkyl lithium, and alkyl lithium activator is 1-1.2:1-1.3:1-1.5:1-1.5, preferably 1:1.1:1.2:1.2; the concentration of phenylphosphine oxide A in the reaction system is 0.05-0.5 mol / L, preferably 0.1-0.3 mol / L;

[0021] 2) Reacting a phenylphosphine-phosphine oxide ligand C, an allyl nickel(II) chloride dimer, and a sodium salt in an organic solvent at room temperature for 1-6 h to obtain a phenylphosphine-phosphine oxide nickel catalyst D;

[0022]

[0023] The sodium salt is sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, sodium hexafluoroarsenate, sodium hexafluoroantimonate, sodium hexafluorophosphate, sodium p-toluenesulfonate or sodium tetrafluoroborate;

[0024] The organic solvent is one or a mixture of two or more of toluene, chlorobenzene, benzene, methanol, ethanol, ether, n-hexane, dichloromethane, 1,2-dichloroethane, and chloroform, preferably dichloromethane or toluene;

[0025] The structure of the allyl nickel (II) chloride dimer is ([Ni(allyl)Cl]2);

[0026] The molar ratio of the phenylphosphine-phosphine oxide ligand C, allyl nickel (II) chloride dimer, and sodium salt is 1-1.2:1-1.3:1-1.2, preferably 1:1.1:1; the concentration of the phenylphosphine-phosphine oxide ligand C in the reaction system is 0.01-0.2 mol / L, preferably 0.05-0.1 mol / L.

[0027] A method for preparing a polyketone material using the above-mentioned phenyl-bridged phosphine-phosphine oxide type nickel catalyst, the polyketone structure is as follows:

[0028] ;

[0029] Where n and m are the degree of polymerization; 10 3 < n < 10 5 , 0 ≤ m < 10 4 , 0 ≤ m / (n+m) < 80%;

[0030] R is an olefin within the range of C3 to C10, including propylene, 1-butene, 1-hexene, 1-octene, and 1-decene;

[0031] The specific synthetic route of polyketone is as follows:

[0032]

[0033] The steps are as follows: First, connect the reactor to the polymerization pipeline and use vacuum and nitrogen to replace the reactor and polymerization pipeline; then, set the desired reaction temperature and, under an inert atmosphere, mix the phenylphosphine-phosphine oxide nickel catalyst, co-catalyst, and solvent in the reactor; finally, charge carbon monoxide and olefin compounds into the autoclave and start stirring; after the reaction reaches the specified time, add a quencher to stop the polymerization, and wash with methanol to obtain a white solid, which is the polyketone. The molecular weight M of the polyketone was tested by gel permeation chromatography. n It is generally between 100,000 and 1.6 million, and the molecular weight distribution is within the range of 1.5 to 2.5.

[0034] The co-catalyst is one or a mixture of two or more of lithium aluminum hydride, sodium borohydride, lithium borohydride, trimethylaluminum, triethylaluminum, triisobutylaluminum, methylaluminoxane, diethylaluminum monochloride, trimethylsilane, triethylsilane, triphenylsilane, tetraethoxysilane, phenylsilane, 9-borabicyclo[3,3,1]-nonane, lithium triisobutylborohydride, sodium trimethoxyborohydride, pinacol borane, triphenylboron, and tri(perfluorophenyl)borane, preferably triisobutylaluminum, tetraethoxysilane, and tri(perfluorophenyl)borane;

[0035] The solvent is one or a mixture of two or more of toluene, benzene, dichloromethane, acetone, ether, chlorobenzene, n-hexane, cyclohexane, chloroform, acetonitrile, diethyl carbonate, and hexafluoroisopropanol, preferably chlorobenzene, dichloromethane, or diethyl carbonate;

[0036] Taking into account the solubility of the catalyst and co-catalyst and the polymerization efficiency, the molar concentration of the phenylphosphine-phosphine oxide type nickel catalyst in the solvent is 0.01 to 0.5 mmol / L, more preferably 0.05 to 0.2 mmol / L, specifically 0.05 mol / L, 0.1 mmol / L, 0.15 mmol / L, and 0.2 mmol / L; the molar concentration of the co-catalyst in the solvent is 10 to 100 mmol / L, specifically 10 mol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, 50 mmol / L, 60 mol / L, 70 mmol / L, 80 mmol / L, 90 mmol / L, and 100 mmol / L;

[0037] The olefin compound is primarily ethylene. The third olefin component can be propylene, 1-butene, or other C3-C10 olefins. Its primary purpose is to adjust the melting point of the polyketone and facilitate post-processing. Considering production efficiency, propylene is preferred. The gas mass percentage of propylene in the reactor is preferably 5% to 60%, specifically 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, or 60%.

[0038] The ethylene and carbon monoxide gases used in the polymerization reaction are both mixed gases, and the molar ratio of the two is (1-6):1, specifically 1:1, 2:1, 3:1, 4:1, 5:1, 6:1;

[0039] The polymerization reaction pressure is preferably 1-6 MPa, specifically 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa;

[0040] The catalyst has excellent high temperature tolerance, and considering that the temperature of the polymerization reaction greatly affects the structure of the polyketone, the temperature is preferably 30-150°C, more preferably 60-120°C, specifically 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, and 120°C;

[0041] The stirring speed is preferably 100-800 r / min, more preferably 300-600 r / min, specifically 300 r / min, 400 r / min, 500 r / min, and 600 r / min;

[0042] The polymerization reaction time is preferably 0.5-10 h, more preferably 0.5-4 h, specifically 0.5 h, 1 h, 2 h, 3 h, or 4 h.

[0043] A method for preparing a polyketone fiber material, the specific synthesis route is as follows:

[0044] 1) Dissolving polyketone powder in spinning solution;

[0045] 2) Place a coagulation bath on the spinning equipment at room temperature;

[0046] 3) In 100 o C is drawn and processed into polyketone fiber.

[0047] The propylene content of the polyketone is less than 5%, preferably ethylene / CO binary polyketone, with a molecular weight of >500,000;

[0048] The spinning solution is one or a mixture of two or more of hexafluoroisopropanol, m-cresol, benzyl alcohol, zinc chloride aqueous solution, propylene carbonate, and benzyl alcohol;

[0049] The solid content of the polyketone in the spinning solution is 1-20%;

[0050] The coagulation bath is one or a mixture of two or more of acetone, methanol, ethanol and water.

[0051] A method for preparing a polyketone resin material, the specific synthesis route is as follows:

[0052] 1) Set the injection molding machine barrel temperature to 10-15°C higher than the melting point of polyketone and the mold temperature to 80°C;

[0053] 2) Place polyketone powder in a barrel and heat until it melts;

[0054] 3) The polyketone powder is injected into the temperature-controlled mold cavity by high-speed screw propulsion, and the holding time is controlled to 10 s, and finally processed into a polyketone product of the desired shape.

[0055] The propylene content in the polyketone is 5-20%, preferably 5-10%, and the molecular weight is 100,000-200,000.

[0056] A method for preparing a polyketone hot melt adhesive material, the specific synthesis route is as follows:

[0057] 1) Weigh and premix polyketone powder, antioxidant, plasticizer and silane coupling agent according to the raw material composition;

[0058] 2) Heat the mixture to 30~40℃ above the melting point o C is stirred and finally mixed;

[0059] 3) Vacuum to remove bubbles, cool and solidify, and discharge to obtain polyketone hot melt adhesive.

[0060] The propylene content of the polyketone is greater than 20%, preferably 30-50%, and the molecular weight is 50,000-150,000;

[0061] The antioxidant is selected from one or a mixture of two or more of antioxidant 1010, antioxidant 1076, antioxidant 264, and antioxidant 1330;

[0062] The plasticizer includes one or a mixture of two or more of tributyl citrate, N-butylbenzenesulfonamide, dicyclohexyl phthalate, glycerol tribenzoate, and ABS resin;

[0063] The silane coupling agent is selected from one or a mixture of two or more of silane coupling agent KH-550, silane coupling agent A151, silane coupling agent KH-792, and mercaptopropyltrimethoxysilane;

[0064] The raw material composition comprises 90-98 parts of polyketone powder, 0.1-5 parts of antioxidant, 0.5-3 parts of plasticizer and 1-5 parts of silane coupling agent.

[0065] Beneficial effects of the present invention:

[0066] (1) Using only cheap and readily available bulk industrial products, ethylene and carbon monoxide, as raw materials, high value-added and excellent performance polyketone resins, fibers, and hot-melt adhesives can be prepared in one step;

[0067] (2) The polymerization reaction uses cheap metal nickel catalyst instead of precious metal palladium catalyst, saving production costs. The catalyst synthesis route is simple and can be modularly adjusted to three units. At the same time, the required equipment is simple, the product yield is high, and it is safe and easy to industrialize.

[0068] (3) This new type of nickel catalyst has an activity of up to 45 kg PK (g of Ni) for ethylene / CO binary copolymerization. -1 h -1 The highest activity of ethylene / α-olefin / CO ternary copolymerization can reach 15 kg PK (g of Ni) -1 h -1 , meeting the technical requirements of the market for the production of polyketone;

[0069] (4) The polymerization reaction does not generate any by-products, and the temperature can be widely controlled (30~150 o C) The polymer post-processing and separation process is clean and simple, requiring only filtration and washing, meeting industrial requirements;

[0070] (5) By controlling the content of propylene / CO units in polyketone, polyketone can be regulated from fiber, resin to hot melt adhesive material; among them, the number average molecular weight of polyketone materials is generally between 100,000 and 1.6 million, and the molecular weight distribution is in the range of 1.5 to 2.5, which meets the molecular weight requirements of polyketone engineering plastics. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1This is the nuclear magnetic hydrogen spectrum of the nickel catalyst Ni10 according to Example 4 of the present invention.

[0072] Figure 2 This is the nuclear magnetic phosphine spectrum of the nickel catalyst Ni10 according to Example 4 of the present invention.

[0073] Figure 3 This is the nuclear magnetic carbon spectrum of the nickel catalyst Ni10 according to Example 4 of the present invention.

[0074] Figure 4 This is the NMR carbon spectrum of ethylene / CO binary polyketone according to Example 8 of the present invention.

[0075] Figure 5 This is the H NMR spectrum of the ethylene / propylene / CO ternary polyketone according to Example 10 of the present invention.

[0076] Figure 6 This is a graph showing the tensile properties of ethylene / propylene / CO ternary polyketone according to Example 12 of the present invention. DETAILED DESCRIPTION

[0077] The specific implementation of the present invention is described in detail below in conjunction with the technical solutions and drawings.

[0078] Example 1:

[0079] The synthesis of ligand L10 is as follows:

[0080]

[0081] Under nitrogen protection, N,N-diethyl-P,P-diphenylphosphinamide (3.01 g, 10 mmol), tetramethylethylenediamine (1.39 g, 12 mmol), and 100 mL of purified tetrahydrofuran were added to a 250 mL three-necked flask. 4.8 mL of n-butyllithium solution (2.5 mol / L, 12 mmol) was slowly added dropwise at 0°C, and the mixture was allowed to react at room temperature for 1 h. Subsequently, a solution of chlorodiisopropylphosphine (1.67 g, 11 mmol) in THF was slowly added to the three-necked flask via a constant pressure dropping funnel, and the reaction was continued at room temperature for 6 h. After the reaction was complete, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization from dichloromethane / n-hexane to obtain 2.54 g of a white solid in a 61% yield. 1H NMR (400 MHz, CDCl3) δ 7.85-7.82 (m, 1H), 7.69-7.55 (m, 3H), 7.50-7.44 (m, 1H), 7.43-7.36 (m, 2H), 7.33-7.30 (m, 2H), 3.45-3.41 (m, 2H), 2.12-2.19 (m, 1H), 1.99-1.91 (m, 1H), 1.36 (d, 6H), 1.14 (d,6H), 1.07-1.02 (m, 3H), 1.01-0.95 (m, 3H), 0.93-0.85 (m, 3H), 0.71-0.68 (m,3H). 31 P NMR (162 MHz, CDCl3) δ 33.62, -1.70.

[0082] Example 2:

[0083] The synthesis of ligand L12 is as follows:

[0084]

[0085] Under nitrogen protection, phenylbis(N,N-diethylamino)phosphine oxide (2.68 g, 10 mmol), 1,4-diazabicyclo[2.2.2]octane (1.35 g, 12 mmol), and 100 mL of purified tetrahydrofuran were added to a 250 mL three-necked flask. 4.8 mL of n-butyllithium solution (2.5 mol / L, 12 mmol) was slowly added dropwise at 0°C, and the reaction was allowed to proceed at room temperature for 1 h. Subsequently, a solution of chlorobis(2-methoxyphenyl)phosphine (3.08 g, 11 mmol) in THF was slowly added to the three-necked flask via a constant pressure dropping funnel, and the reaction was continued at room temperature for 12 h. After the reaction was complete, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization from tetrahydrofuran / n-hexane to obtain 2.92 g of a white solid in a 57% yield. 1 H NMR (400 MHz, CDCl3) δ 8.27-7.88 (m, 3H), 7.75-7.30 (m, 8H), 6.97-6.91 (m, 4H), 6.86-6.55 (m, 2H), 3.79(s, 6H), 2.90-2.84 (m, 4H), 1.83-1.80 (m, 6H). 31 P NMR (162 MHz, CDCl3) δ32.66, -27.67.

[0086] Example 3:

[0087] The synthesis of ligand L19 is as follows:

[0088]

[0089] Under N₂ protection, (4-methoxyphenyl)diphenylphosphine oxide (3.08 g, 10 mmol), 1,4-diazabicyclo[2.2.2]octane (1.35 g, 12 mmol), and 100 mL of purified tetrahydrofuran were added to a 250 mL three-necked flask. 4.8 mL of n-butyllithium solution (2.5 mol / L, 12 mmol) was slowly added dropwise at 0°C and the mixture was allowed to react at room temperature for 2 h. Subsequently, a solution of chlorobis(2-methoxyphenyl)phosphine (3.08 g, 11 mmol) in THF was slowly added to the three-necked flask via a constant pressure dropping funnel and allowed to react at room temperature for 8 h. After the reaction, the solvent was removed under reduced pressure, and the crude product was recrystallized from methanol / diethyl ether to obtain 3.95 g of a white solid with a yield of 67% and a purity of 95%. The product was then purified in the next step.

[0090] Example 4:

[0091] The preparation of catalyst Ni10 has the following structure:

[0092]

[0093] Ligand L10 (1.67 g, 4 mmol), [Ni(allyl)Cl]2 (1.19 g, 4.4 mmol), and NaBArF (3.54 g, 4 mmol) were dissolved in 60 mL of purified dichloromethane at room temperature and allowed to react overnight. After the reaction, the filtrate was filtered in a glove box, and the solvent was removed under reduced pressure. The crude product was purified by recrystallization from dichloromethane / n-hexane to obtain 5.30 g of catalyst Ni10 in a 96% yield as a yellow powder. 1H NMR (400 MHz, CD2Cl2) δ 7.93-7.82(m, 1H), 7.63 (d, 11H), 7.57-7.35 (m, 9H), 5.45-5.41 (m, 1H), 4.51-4.28 (m,1H), 3.59-3.55 (m, 1H), 3.34-3.29 (m, 2H), 2.54-2.51 (m, 1H), 2.29-2.25 (m,1H), 2.09-1.77 (m, 1H), 1.54 (d, 1H), 1.26-1.19 (m, 4H), 1.12-0.95 (m, 14H),0.90-0.81 (m, 2H), 0.69-0.63 (m, 3H), 0.43-0.41 (m, 1H). 31 P NMR (162 MHz, CD2Cl2) δ 41.74, 29.01.

[0094] Example 5:

[0095] The preparation of catalyst Ni12 has the following structure:

[0096]

[0097] Ligand L12 (2.05 g, 4 mmol), [Ni(allyl)Cl]2 (1.19 g, 4.4 mmol), and NaBArF (3.54 g, 4 mmol) were dissolved in 60 mL of purified dichloromethane at room temperature and allowed to react overnight. After the reaction, the filtrate was filtered in a glove box, and the solvent was removed under reduced pressure. The crude product was purified by recrystallization from dichloromethane / n-hexane to obtain 5.49 g of catalyst Ni12 in a 93% yield as a yellow powder. 1 H NMR (500 MHz, C CDCl3) δ 7.64-7.61(m, 17H), 7.23 (s, 1H), 7.01 (d, 4H), 6.84 (s, 2H), 5.60-5.53 (m, 1H), 4.03(s, 1H), 3.79 (s, 6H), 3.11 (s, 1H), 2.84-2.79 (m, 7H), 2.01 (s, 1H), 0.95(t, 12H). 31 P NMR (202 MHz, CDCl3) δ 36.49, 0.04.

[0098] Example 6:

[0099] The preparation of catalyst Ni19 has the following structure:

[0100]

[0101] Ligand L19 (2.21 g, 4 mmol), [Ni(allyl)Cl]2 (1.19 g, 4.4 mmol), and NaBArF (3.54 g, 4 mmol) were dissolved in 60 mL of purified dichloromethane at room temperature and allowed to react overnight. After the reaction, the filtrate was filtered in a glove box, and the solvent was removed under reduced pressure. The crude product was purified by recrystallization from dichloromethane / n-hexane to obtain 5.76 g of catalyst Ni19 in a 95% yield as a brown-yellow powder. 1 H NMR (500 MHz, CD2Cl2) δ 7.78-7.68 (m, 8H), 7.57 (m, 7H), 7.53-7.48 (m, 1H), 7.48-7.38 (m, 6H), 7.38-7.27(m, 4H), 7.20-7.17 (m, 1H), 6.92 (t, 2H), 6.83 (t, 2H), 6.75-6.71 (m, 2H), 5.59-5.52 (m, 1H), 3.84 (s, 3H), 3.76 (s, 6H), 3.56-3.51 (m, 1H), 1.27-1.23(m, 2H), 0.94-0.86 (m, 1H). 31 P NMR (202 MHz, CD2Cl2) δ 45.62, -3.57.

[0102] Example 7:

[0103] The preparation of catalyst Ni27 has the following structure:

[0104]

[0105] Ligand L12 (2.21 g, 4 mmol), [Ni(allyl)Cl]2 (1.19 g, 4.4 mmol), and sodium p-toluenesulfonate (0.776 g, 4 mmol) were dissolved in 60 mL of purified dichloromethane at room temperature and allowed to react overnight. After the reaction, the filtrate was filtered in a glove box, and the solvent was removed under reduced pressure. The crude product was purified by recrystallization from dichloromethane / n-hexane to obtain 2.88 g of catalyst Ni27 in a 92% yield as a brown-yellow powder. 1H NMR (400 MHz, CDCl3) δ7.58 (m, 6H), 7.25-6.58 (m, 10H), 5.55 (m, 1H), 3.78 (s, 6H), 2.80-2.75 (m,7H), 2.18-2.16 (m, 1H), 1.20 (s, 5H), 0.86 (t, 15H). 31 P NMR (162 MHz, CDCl3)δ 34.62, -1.88.

[0106] Example 8:

[0107] In a 150 mL stainless steel autoclave, the following order was added at ambient temperature: a certain amount of phenylphosphine-phosphine oxide nickel catalyst, the amount used was between 1 and 20 μmol; a certain amount of solvent, the volume was between 10 and 50 mL; a mixture of ethylene and carbon monoxide at a specified pressure was introduced and the temperature was quickly raised to the set temperature. The reaction temperature was 30 o C~150 o C, start stirring, and set the speed to 300~600 r / min. The reaction time is between 0.5 and 4 hours. After reaching the set time, stop stirring, slowly release the remaining mixed gas, add methanol to quench, and then add a large amount of methanol to precipitate. Filter the polymer and dry it under vacuum to constant weight. The polymerization results are shown in Table 1 below. The molecular weight and distribution of the polymer were determined by gel permeation chromatography; the Varian INOVA-400MHz was used to determine its 1 The structure of the polyketone was determined by H NMR and its melting point was determined by differential scanning calorimetry.

[0108] Table 1. Ethylene / carbon monoxide binary copolymerization catalyzed by metal nickel complexes

[0109]

[0110] Note 1: Polymerization conditions: Phenylphosphine-phosphine oxide type nickel catalyst structure: , catalyst dosage = 5 μmol, ethylene / CO mixed gas ratio (volume ratio) = 1 / 1, total pressure = 4.0 MPa, reaction temperature = 80 o C, dichloromethane = 20 mL, reaction time = 60 min, rotation speed = 400 r / min, closed mode;

[0111] Note 2: Activity: kg PK (g of Ni) -1 ;

[0112] Note 3: Molecular weight: kg mol -1, molecular weight and molecular weight distribution were determined by gel permeation chromatography at 40 °C with hexafluoroisopropanol as eluent;

[0113] Note 4: The melting temperature of all polyketones is T m At ~260 o C.

[0114] Example 9:

[0115] In a 150 or 500 mL stainless steel autoclave, add in the following order at ambient temperature: a certain amount of phenylphosphine-phosphine oxide nickel catalyst, the amount used is between 1 and 20 μmol; a certain amount of solvent, the volume is between 10 and 50 mL; a mixture of ethylene and carbon monoxide at a specified pressure is introduced and quickly raised to the set temperature, the reaction temperature is 30-150 o C, start stirring, and set the speed to 300~600 r / min. The reaction time is between 0.5 and 4 hours. After reaching the set time, stop stirring, slowly release the remaining mixed gas, add methanol to quench, and then add a large amount of methanol to precipitate. Filter the polymer and dry it under vacuum to constant weight. The polymerization results are shown in Table 2 below. The molecular weight and distribution of the polymer were determined by gel permeation chromatography; the Varian INOVA-400MHz was used to determine its 1 The structure of the polyketone was determined by H NMR and its melting point was determined by differential scanning calorimetry.

[0116] Table 2. Binary copolymerization of ethylene and carbon monoxide catalyzed by nickel complexes

[0117]

[0118] Note 1: Polymerization conditions: Phenylphosphine-phosphine oxide type nickel catalyst structure: , catalyst amount = 5 μmol, dichloromethane = 20 mL, rotation speed = 400 r / min, 150 mL autoclave, closed mode;

[0119] Note 2: Conversion number: g PK (g of Ni) -1 ;

[0120] Note 3: Molecular weight: kg mol -1 , number average molecular weight M n The molecular weight distribution (PDI) was determined by gel permeation chromatography at 40 o C, hexafluoroisopropanol as the eluent;

[0121] Note 4: For sequence 20, the solvent is acetone; for sequence 21, the solvent is n-hexane; for sequence 22, the solvent is toluene; for sequence 23, the solvent is chlorobenzene. Other conditions are the same as in Note 1.

[0122] Note 5: For sequences 24-26, the amount of phenylphosphine-phosphine oxide nickel catalyst was 10 μmol, ethylene / CO mixed gas was continuously introduced, dichloromethane was 100 mL, and the reaction mixture was in a 500 mL mechanical reactor.

[0123] Note 6: Sequence 27, speed = 300 r / min; Sequence 28, speed = 500 r / min, other conditions are the same as Note 5;

[0124] Note 7: The melting temperature of all polyketones is T m At ~260 o C.

[0125] Example 10:

[0126] In a 150 mL stainless steel autoclave, the following order was added at ambient temperature: a certain amount of phenylphosphine-phosphine oxide nickel catalyst, the amount of which was between 1 and 20 μmol; a certain amount of co-catalyst, the amount of which was between 1 and 10 mmol; a certain amount of solvent, the volume of which was between 10 and 50 mL; a certain amount of C3-C10 olefin, the mass of which was between 1 and 50 g; a mixture of ethylene and carbon monoxide at a specified pressure was introduced and the temperature was rapidly raised to the set value. The reaction temperature was 30-150°C. o C, start stirring. The reaction time is between 0.5 and 4 hours. After reaching the set time, stop stirring, slowly release the remaining mixed gas, add methanol to quench, add a large amount of methanol to precipitate, filter the polymer, and dry it under vacuum to constant weight. The polymerization results are shown in Table 3 below. The molecular weight and distribution of the polymer were determined by gel permeation chromatography; the Varian INOVA-400MHz was used to determine its 1 The structure of the polyketone was determined by H NMR and its melting point was determined by differential scanning calorimetry.

[0127] Table 3. Copolymerization of ethylene, C3-C10 olefins, and carbon monoxide catalyzed by nickel complexes

[0128]

[0129] Note 1: Polymerization conditions: Phenylphosphine-phosphine oxide type nickel catalyst structure: , catalyst dosage = 10 μmol, tetraethoxysilane = 3 mmol, ethylene / CO mixed gas ratio (volume ratio) = 1 / 1, total pressure = 4.0 MPa, reaction temperature = 100 o C, dichloromethane = 30 mL, reaction time = 120 min, rotation speed = 400 r / min, 150 mL autoclave, continuous mode;

[0130] Note 2: Conversion number: g PK (g of Ni) -1 ;

[0131] Note 3: C3~C10 insertion ratio mol% ( 1 H NMR spectroscopy);

[0132] Note 4: Molecular weight: kg mol -1 , number average molecular weight M n The molecular weight distribution (PDI) was determined by gel permeation chromatography at 40 o C, hexafluoroisopropanol as the eluent;

[0133] Note 5: Melting temperature T m Determined by differential scanning calorimetry (DSC), secondary heating, broad melting endotherm.

[0134] Example 11:

[0135] 10 g of the binary polyketone powder (molecular weight 526 kg mol) prepared in Example 8 was added to -1 ) was dissolved in benzyl alcohol with a solid content of ~10%, and poured into an ethanol coagulation bath on a laboratory small spinning device at room temperature and heated to 100 o C was drawn to form polyketone fiber. The tensile properties were tested using a single-filament tensile testing machine according to JIS-L-1013 standard, with the results showing a tensile strength of 17.6 cN / dtex, an elongation at break of 9.2%, and a Young's modulus of 413 cN / dtex.

[0136] Example 12:

[0137] The injection molding machine barrel temperature was set to 245 °C, the mold temperature was set to 80 °C, and 10 g of the ternary polyketone powder prepared in Example 10 (5.8% propylene inserted, molecular weight 195 kg mol -1 , melting point 231°C) was heated in a barrel until molten. It was then injected into a temperature-controlled mold cavity via a high-speed screw, with a holding time of 10 seconds, ultimately forming dumbbell-shaped polyketone bars. Tensile properties were tested using a universal testing machine in accordance with GB / T 41758.2-2022. The results showed a breaking strength of 58 MPa, an elongation at break of 193%, a yield strength of 51 MPa, and a Young's modulus of 1260 MPa.

[0138] Example 13:

[0139] The injection molding machine barrel temperature was set to 210 °C, the mold temperature was set to 80 °C, and 10 g of the ternary polyketone powder prepared in Example 10 (12.6% propylene inserted, molecular weight 145 kg mol) was taken. -1, melting point 195°C) was heated in a barrel until molten. It was then injected into a temperature-controlled mold cavity via a high-speed screw, with a holding time of 10 seconds, to form dumbbell-shaped polyketone bars. Tensile properties were tested using a universal testing machine according to GB / T 41758.2-2022. The results showed a breaking strength of 75 MPa, an elongation at break of 423%, a yield strength of 43 MPa, and a Young's modulus of 739 MPa.

[0140] Example 14:

[0141] The injection molding machine barrel temperature was set to 200 °C, the mold temperature was set to 80 °C, and 10 g of the ternary polyketone powder prepared in Example 10 (19.6% propylene inserted, molecular weight 138 kg mol) was taken. -1 , melting point 186°C) was heated in a barrel until molten. It was then injected into a temperature-controlled mold cavity via a high-speed screw, with a holding time of 10 seconds, to form dumbbell-shaped polyketone strips. Tensile properties were tested using a universal testing machine according to GB / T 41758.2-2022. The results showed a breaking strength of 84 MPa, an elongation at break of 710%, a yield strength of 29 MPa, and a Young's modulus of 653 MPa.

[0142] Example 15:

[0143] 20 g of polyketone powder (32.3% propylene insertion, molecular weight 129 kg mol) prepared in Example 10 was added. -1 , melting point 138°C), 400 mg of antioxidant 1010, 200 mg of N-butylbenzenesulfonamide, and 600 mg of silane coupling agent A151 were mixed uniformly, heated to 170°C, vacuumed to remove bubbles, and cooled to solidify. The resulting polyketone hot melt adhesive was then discharged. The adhesive strength was tested on steel plates by evenly applying the hot melt adhesive to a specific area of ​​the steel plate using a hot melt gun. The two test plates were then bonded together and cured at room temperature for 1-2 hours. The tensile strength was tested using a universal testing machine according to GB / T 41758.2-2022 and was 7.2 MPa.

[0144] Example 16:

[0145] 20 g of polyketone powder (45.7% propylene insertion, molecular weight 106 kg mol) prepared in Example 10 was added. -1, melting point 109°C), 200 mg of antioxidant 1330, 100 mg of N-butylbenzenesulfonamide, and 800 mg of silane coupling agent KH-560 were mixed uniformly, heated to 170°C, vacuumed to remove bubbles, and cooled to solidify. The resulting polyketone hot melt adhesive was then discharged. The adhesive strength was tested on steel plates by evenly applying the hot melt adhesive to a specific area of ​​the steel plate using a hot melt gun. The two test plates were then bonded together and cured at room temperature for 1-2 hours. The tensile strength was tested using a universal testing machine according to GB / T 41758.2-2022 and was 6.1 MPa.

Claims

1. A method for preparing polyketone using a phenylphosphine-phosphine oxide type nickel catalyst, characterized in that: The polyketone structure is as follows: ； Where n and m are the degree of polymerization; 10 3 < n < 10 5 , 0 ≤ m < 10 4 , 0 ≤ m / (n+m) < 80%; R is an olefin within the range of C3 to C10; The specific synthetic route of polyketone is as follows: ； The steps are as follows: first, a reactor is connected to a polymerization pipeline, and the air in the reactor and the polymerization pipeline is replaced by vacuum and nitrogen operation; then, the desired reaction temperature is set, and under an inert atmosphere, a phenylphosphine-phosphine oxide type nickel catalyst, a co-catalyst, and a solvent are mixed in the reactor; finally, carbon monoxide and an olefin compound are charged into the autoclave and stirring is started; after the reaction is carried out for a specified time, a quencher is added to stop the polymerization, and a white solid is obtained after washing with methanol, which is the polyketone; The co-catalyst is one or a mixture of two or more of lithium aluminum hydride, sodium borohydride, lithium borohydride, trimethylaluminum, triethylaluminum, triisobutylaluminum, methylaluminoxane, diethylaluminum monochloride, trimethylsilane, triethylsilane, triphenylsilane, tetraethoxysilane, phenylsilane, 9-borabicyclo[3,3,1]-nonane, lithium triisobutylborohydride, sodium trimethoxyborohydride, pinacol borane, triphenylboron, and tri(perfluorophenyl)borane; The solvent is one or a mixture of two or more of toluene, benzene, dichloromethane, acetone, ether, chlorobenzene, n-hexane, cyclohexane, chloroform, acetonitrile, diethyl carbonate, and hexafluoroisopropanol; The structure of the phenyl bridged phosphine-phosphine oxide type nickel catalyst is shown below: ； Among them, Ar 1 and Ar 2 is 2-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-N,N-dimethylaminophenyl, 4-N,N-dimethylaminophenyl, 2-trifluoromethylphenyl, or isopropyl, Ar 1 and Ar 2 Same or different; R 1 is hydrogen, methyl, tert-butyl, methoxy, N,N-diethylamino or trifluoromethyl; R 2 and R 3 is methyl, isopropyl, tert-butyl, methoxy, N,N-dimethylamino, N,N-diethylamino, N,N-diisopropylamino, pyrrolyl, morpholinyl or tetrahydropyrrolyl, R 2 and R 3 Same or different; X is BArF; The molar concentration of the phenylphosphine-phosphine oxide type nickel catalyst in the solvent is 0.01~0.5 mmol / L; The molar concentration of the co-catalyst in the solvent is 10-100 mmol / L; The olefin compound is ethylene and a third component, the third component is an olefin within the range of C3 to C10, and the gas mass of the third component in the reactor accounts for 5% to 60%; The molar ratio of ethylene to carbon monoxide gas is (1-6):1; The reaction pressure is 1~6 MPa; The reaction temperature is 30~150℃; Stirring speed is 100~800 r / min; The specified time is 0.5~10 h.

2. The method for preparing polyketone using a phenyl-bridged phosphine-phosphine oxide type nickel catalyst according to claim 1, characterized in that: R is selected from propylene, 1-butene, 1-hexene, 1-octene or 1-decene.

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