Benzene phosphine-phosphine oxide type nickel catalyst for preparing polyketone material, preparation method and application

Abstract

The invention belongs to the field of polymer synthesis, and discloses a bridged phenylphosphine-phosphine oxide type nickel catalyst for preparing a polyketone material, a preparation method and application. The benzene phosphine-phosphine oxide type nickel catalyst is simple in synthesis process, cheap in raw materials and capable of modularly regulating substituent groups, ethylene / CO and copolymerization reaction of ethylene / CO and alpha-olefin can be efficiently catalyzed in a wide temperature range of 30-150 DEG C, the highest activity can reach 45 kg PK (g of Ni) <-1 > h <-1 >, comprehensive synthesis of high-performance polyketone products from resin and fibers to hot melt adhesive materials is achieved, and the catalyst is suitable for industrial production. And the technical requirements of polyketone production in the market are met. In addition, the number-average molecular weight of the obtained polyketone is generally between 100,000 and 16,000,000, the molecular weight is distributed in a range of 1.5 to 2.5, and the requirement of the polyketone engineering plastic on the molecular weight is met.

Description

Technical Field

[0001] The present invention belongs to the field of polymer synthesis and relates to a benzene-bridged phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials, a preparation method and applications thereof. Among them, the benzene-bridged phosphine-phosphine oxide type nickel catalyst exhibits excellent catalytic activity and stability in the copolymerization of ethylene / CO and its copolymerization with α-olefins, realizing 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 the low VOC requirements, making it a green and environmentally friendly material with diversified properties. According to the different monomer types and material uses, it is divided into polyketone fiber products copolymerized from ethylene and CO and polyketone resin products copolymerized from ethylene, propylene and CO. Among them, the molecular weight of binary polyketone is generally relatively high (M n >500,000), and the melting point is ~260 o °C. It is usually processed into polyketone fiber products by solution spinning and is mainly used in scenarios such as high-strength tire cords and bulletproof vests; while the molecular weight of ternary polyketone is generally relatively low (M n <200,000), and the melting point is in the range of 200-240 o °C. It is usually processed by injection molding. Existing POK products on the market include series grades such as M330, M630, M930, M730, M710, etc., and are mainly used in fields such as aerospace, automotive, electronic and electrical, toys and packaging (Yang, Y.; Li, S.-Y., etal. Progress in Polyketone Materials: Blends and Composites; Polym Int 2018,67, 1478–1487).

[0003] The production of commercial polyketones can be traced back to 1996, when industrial production was achieved by slurry polymerization using 1,3-bis(diphenylphosphino)propane derivatives, palladium acetate, strong acid, and quinone multi-component catalyst systems with methanol as the solvent. In 2015, a variety of polyketone products were developed (David, V. Finding Openings for Polyketone Compounds. Plastics News Europe, 2015). However, the main disadvantage of this production technology is the use of precious metal palladium catalysts, and the palladium catalyst is difficult to recover due to the embedding characteristics of slurry polymerization, which makes the price of commercial polyketones high, limiting the promotion of polyketone products in the global market. Nickel and palladium belong to the same group VIII elements. As a cheaper alternative metal, it has great industrial prospects. However, due to the high electrophilicity of the nickel metal center in the complex, it is particularly easy to form a 5-coordinated, 18-electron dormant species, which is difficult to continue the olefin insertion reaction, making most nickel catalytic systems generally have low activity (<10 3 g PK (g of Ni) -1 h -1 ), poor stability, narrow temperature control range and other problems (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 may improve their bonding strength to polar materials (such as metals, ceramics, polar plastics, etc.) due to the polarity and high temperature resistance given by the high density of carbonyl groups in the main chain, as well as their structural adjustability, and have the potential to be used as high-performance hot melt adhesive materials. Therefore, designing a class of highly active, highly propylene-tolerant, inexpensive nickel catalysts, and developing a new type of hot melt adhesive material while synthesizing polyketone resins and fibers through structural adjustment and process optimization will 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, a fiber and a hot melt adhesive material and a preparation method thereof.

[0007] The technical solution of the present invention:

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

[0009] ;

[0010] wherein, Ar 1 and Ar 2 are 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 are the 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 are methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, N,N-dimethylamino, N,N-diethylamino, N,N-diisopropylamino, phenyl, 4-methylphenyl, pyrrolyl, morpholinyl, piperidinyl or pyrrolidinyl, R 2 and R 3 are the same or different;

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

[0014] A preparation method of a benzene-bridged phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials comprises the following steps:

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

[0016]

[0017] The alkyllithium is n-butyllithium, methyllithium, sec-butyllithium or tert-butyllithium, preferably n-butyllithium and sec-butyllithium;

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

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

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

[0021] 2) At room temperature, react the benzene-bridged phosphine-oxide ligand C, allyl nickel(II) chloride dimer, and sodium salt in an organic solvent for 1 to 6 h to obtain the benzene-bridged phosphine-oxide type 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 more of toluene, chlorobenzene, benzene, methanol, ethanol, ether, n-hexane, dichloromethane, 1,2-dichloroethane, 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 benzene-bridged phosphine-oxide ligand C, allyl nickel(II) chloride dimer, and sodium salt is 1 to 1.2: 1 to 1.3: 1 to 1.2, preferably 1: 1.1: 1; the concentration of the benzene-bridged phosphine-oxide ligand C in the reaction system is 0.01 to 0.2 mol / L, preferably 0.05 to 0.1 mol / L.

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

[0028] ;

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

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

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

[0032]

[0033] The steps are as follows: First, connect the reaction kettle to the polymerization pipeline, and use vacuum and nitrogen operations to displace the reaction kettle and the polymerization pipeline; then, set the required reaction temperature, and under an inert atmosphere, mix the benzene-bridged phosphine-phosphine oxide type nickel catalyst, co-catalyst and solvent in the reaction kettle; finally, charge carbon monoxide and olefin compounds into the autoclave, start stirring; after reacting for a specified time, add a quenching agent to stop the polymerization, and a white solid can be obtained after washing with methanol, which is the polyketone. Using gel permeation chromatography to test the molecular weight M of the polyketone n is generally between 100,000 and 1.6 million, and the molecular weight distribution is in the range of 1.5 - 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 chloride, trimethylsilane, triethylsilane, triphenylsilane, tetraethoxysilane, phenylsilane, 9-borabicyclo[3,3,1]nonane, lithium triisobutylborohydride, sodium trimethoxyborohydride, pinacolborane, triphenylboron, tris(perfluorophenyl)borane, preferably triisobutylaluminum, tetraethoxysilane and tris(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, hexafluoroisopropanol, preferably chlorobenzene, dichloromethane or diethyl carbonate;

[0036] Considering the dissolution of the catalyst and cocatalyst and the polymerization efficiency, the molar concentration of the benzene-bridged phosphine-phosphine oxide type nickel catalyst in the solvent is 0.01 - 0.5 mmol / L, more preferably 0.05 - 0.2 mmol / L, and specifically can be 0.05 mol / L, 0.1 mmol / L, 0.15 mmol / L, 0.2 mmol / L; the molar concentration of the cocatalyst in the solvent is 10 - 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, 100 mmol / L;

[0037] The olefin compound described is mainly ethylene, and the olefin as the third component can be an olefin within C3 - C10 such as propylene and 1-butene. Its main use is to adjust the melting point of the polyketone, which is beneficial for post-processing. Considering the production efficiency, propylene is preferred. The mass percentage of propylene gas in the reaction kettle is preferably 5% - 60%, and specifically can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%;

[0038] Both the ethylene and carbon monoxide gases used in the polymerization reaction are mixed gases, and their molar ratio is (1 - 6):1, specifically can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1;

[0039] The polymerization reaction pressure is preferably 1 - 6 MPa, specifically can be 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, it is preferably 30 - 150 °C, more preferably 60 - 120 °C, and specifically can be 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C;

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

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

[0043] A preparation method of a polyketone fiber material, and the specific synthesis route is as follows:

[0044] 1) Dissolve the polyketone powder in the spinning dope.

[0045] 2) Inject it into the coagulation bath on the spinning equipment at room temperature.

[0046] 3) Perform stretching at 100 o °C to process into polyketone fibers.

[0047] The propylene content in the polyketone is < 5%, preferably ethylene / CO binary polyketone, and the molecular weight > 500,000.

[0048] The spinning dope 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 dope is 1 - 20%.

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

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

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

[0053] 2) Take the polyketone powder and place it in the barrel to heat to the molten state.

[0054] 3) Inject the polyketone powder into the temperature-controlled mold cavity through high-speed propulsion of the screw, control the holding pressure time for 10 s, and finally process into the required shape of the polyketone product.

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

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

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

[0058] 2) Heat the mixture to 30 - 40 o °C higher than the melting point for stirring and final mixing.

[0059] 3) Perform vacuum degassing to remove bubbles, cool and solidify, and discharge to obtain the polyketone hot melt adhesive.

[0060] The propylene content in the polyketone is > 20%, preferably 30 - 50%, and the molecular weight is 50,000 - 150,000.

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

[0062] The plasticizer includes one or more mixtures of tributyl citrate, N-butylbenzenesulfonamide, dicyclohexyl phthalate, tribenzoyl glycerol, and ABS resin;

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

[0064] The raw material composition is 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] Advantages of the present invention:

[0066] (1) Using only inexpensive 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 adhesive materials can be prepared in one step;

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

[0068] (3) The activity of this new type of nickel catalyst for ethylene / CO binary copolymerization is as high as 45 kg PK (g of Ni) -1 h -1 , and 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 for producing polyketone in the market;

[0069] (4) This polymerization reaction produces no by-products, and the temperature can be widely regulated (30-150 o °C), and the polymer post-treatment separation process is clean and simple, only requiring filtration and washing, meeting the industrialization requirements;

[0070] (5) By controlling the content of propylene / CO units in the polyketone, the regulation of polyketone from fiber, resin to hot-melt adhesive material can be achieved; among them, the number-average molecular weight of the polyketone material is generally between 1 million and 1.6 million, and the molecular weight distribution is in the range of 1.5-2.5, meeting the requirements of polyketone engineering plastics for molecular weight. Brief Description of the Drawings

[0071] Figure 1It is the 1H NMR spectrum of the nickel catalyst Ni10 according to Embodiment 4 of the present invention.

[0072] Figure 2 It is the 31P NMR spectrum of the nickel catalyst Ni10 according to Embodiment 4 of the present invention.

[0073] Figure 3 It is the 13C NMR spectrum of the nickel catalyst Ni10 according to Embodiment 4 of the present invention.

[0074] Figure 4 It is the 13C NMR spectrum of the ethylene / CO binary polyketone according to Embodiment 8 of the present invention.

[0075] Figure 5 It is the 1H NMR spectrum of the ethylene / propylene / CO ternary polyketone according to Embodiment 10 of the present invention.

[0076] Figure 6 It is the tensile property diagram of the ethylene / propylene / CO ternary polyketone according to Embodiment 12 of the present invention. Detailed Embodiments

[0077] The following combines the technical solutions and the drawings to detail the specific embodiments of the present invention.

[0078] Embodiment 1:

[0079] Synthesis of ligand L10, the reaction formula is as follows:

[0080]

[0081] Under N2 protection, add N,N-diethyl-P,P-diphenylphosphinic amide (3.01 g, 10 mmol), tetramethylethylenediamine (1.39 g, 12 mmol) and 100 mL of purified tetrahydrofuran into a 250 mL three-necked flask. Slowly drop 4.8 mL of n-butyllithium solution (2.5 mol / L, 12 mmol) at 0 °C, and react at room temperature for 1 h. Subsequently, slowly drop the THF solution of chlorodiisopropylphosphine (1.67 g, 11 mmol) into the three-necked flask through a constant pressure dropping funnel, and react at room temperature for 6 h. After the reaction is completed, remove the solvent under reduced pressure, and purify this crude product by recrystallization with dichloromethane / n-hexane solvent to obtain 2.54 g of white solid, with a yield of 61%. 11H 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 31P NMR (162 MHz, CDCl3) δ 33.62, -1.70.

[0082] Example 2:

[0083] The synthesis of ligand L12 is shown in the following reaction formula:

[0084]

[0085] Under N2 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 mixture was allowed to react at room temperature for 1 h. Subsequently, a solution of chlorobis(2-methoxyphenyl)phosphine (3.08 g, 11 mmol) in THF was slowly added dropwise to the three-necked flask through a constant pressure dropping funnel, and the mixture was allowed to react at room temperature for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization from a tetrahydrofuran / n-hexane solvent to obtain 2.92 g of a white solid with a yield of 57%. 1 1H 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 31P NMR (162 MHz, CDCl3) δ 32.66, -27.67.

[0086] Example 3:

[0087] Synthesis of ligand L19, the reaction formula is as follows:

[0088]

[0089] Under N2 protection, add (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 into a 250 mL three-necked flask. Slowly add 4.8 mL of n-butyllithium solution (2.5 mol / L, 12 mmol) at 0 °C, and react at room temperature for 2 h. Subsequently, slowly add a THF solution of chlorobis(2-methoxyphenyl)phosphine (3.08 g, 11 mmol) dropwise to the three-necked flask through a constant pressure dropping funnel, and react at room temperature for 8 h. After the reaction is completed, remove the solvent under reduced pressure. Recrystallize this crude product with methanol / ether solvent to obtain 3.95 g of white solid, with a yield of 67% and a purity of 95%. Purify it further in the next step.

[0090] Example 4:

[0091] Preparation of catalyst Ni10, specifically with the following structure:

[0092]

[0093] At room temperature, dissolve ligand L10 (1.67 g, 4 mmol), [Ni(allyl)Cl]2 (1.19 g, 4.4 mmol) and NaBArF (3.54 g, 4 mmol) in 60 mL of purified dichloromethane, and react overnight. After the reaction is completed, filter by suction in a glove box, and remove the solvent from the filtrate under reduced pressure. Purify this crude product by recrystallization with dichloromethane / n-hexane solvent to obtain 5.30 g of catalyst Ni10, with a reaction yield of 96%, a yellow powder. 11H 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 31P NMR (162 MHz, CD2Cl2) δ 41.74, 29.01。

[0094] Example 5:

[0095] Preparation of catalyst Ni12, specifically with the following structure:

[0096]

[0097] At room temperature, 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 refined dichloromethane and reacted overnight. After the reaction was completed, filtration was carried out in a glove box, and the solvent was removed under reduced pressure from the filtrate. This crude product was purified by recrystallization with dichloromethane / n - hexane solvent to obtain 5.49 g of catalyst Ni12 with a reaction yield of 93%, a yellow powder. 1 1H 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 31P NMR (202 MHz, CDCl3) δ 36.49, 0.04.

[0098] Example 6:

[0099] Preparation of catalyst Ni19, specifically with the following structure:

[0100]

[0101] At room temperature, 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, and the reaction was carried out overnight. After the reaction was completed, filtration was performed in a glove box, and the solvent was removed from the filtrate under reduced pressure. This crude product was purified by recrystallization from dichloromethane / n-hexane solvent to obtain 5.76 g of catalyst Ni19, with a reaction yield of 95%, as a pale 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] Preparation of catalyst Ni27, specifically with the following structure:

[0104]

[0105] At room temperature, 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, and the reaction was carried out overnight. After the reaction was completed, filtration was performed in a glove box, and the solvent was removed from the filtrate under reduced pressure. This crude product was purified by recrystallization from dichloromethane / n-hexane solvent to obtain 2.88 g of catalyst Ni27, with a reaction yield of 92%, as a pale yellow powder. 11H NMR (400 MHz, CDCl3) δ 7.58 (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 31P NMR (162 MHz, CDCl3) δ 34.62, -1.88.

[0106] Example 8:

[0107] In a 150 mL stainless steel autoclave, the following were added in sequence at ambient temperature: a certain amount of benzene-bridged phosphine-phosphine oxide type nickel catalyst, with the usage amount between 1 and 20 μmol; a certain amount of solvent, with the volume between 10 and 50 mL; ethylene and carbon monoxide mixed gas at a specified pressure was introduced and quickly raised to the set temperature, and the reaction temperature was 30 o °C to 150 o °C, the stirring was started, and the set rotation speed was 300 - 600 r / min. The reaction time was between 0.5 and 4 h. After reaching the set time, the stirring was stopped, the remaining mixed gas was slowly released, methanol was added to quench, and then a large amount of methanol was added for precipitation. The polymer was filtered and dried to a constant weight under vacuum. The polymerization results are shown in Table 1 below. Gel permeation chromatography was used to measure the molecular weight and its distribution of the polymer; Varian INOVA-400MHz was used to measure its 1 1H NMR to obtain the structure of the polyketone. Differential scanning calorimetry was used to test its melting point.

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

[0109]

[0110] Note 1: Polymerization conditions: Structure of benzene-bridged phosphine-phosphine oxide type nickel catalyst: , 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, the molecular weight and molecular weight distribution were determined by gel permeation chromatography at 40 °C, with hexafluoroisopropanol as the eluent;

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

[0114] Example 9:

[0115] In a 150 or 500 mL stainless steel autoclave, at ambient temperature, add in the following order: a certain amount of benzene-bridged phosphine-phosphine oxide type nickel catalyst, with the usage amount between 1 and 20 μmol; a certain amount of solvent, with the volume between 10 and 50 mL; introduce a mixed gas of ethylene and carbon monoxide at a specified pressure and quickly raise the temperature to the set temperature, the reaction temperature is 30 - 150 o °C, start stirring, and set the rotation speed to 300 - 600 r / min. The reaction time is between 0.5 and 4 h. After reaching the set time, stop stirring, slowly release the remaining mixed gas, add methanol to quench, then add a large amount of methanol for precipitation, filter the polymer, and dry it to a constant weight under vacuum. The polymerization results are shown in Table 2 below. Use gel permeation chromatography to determine the molecular weight and its distribution of the polymer; use Varian INOVA-400MHz to determine its 1 1H NMR to obtain the structure of the polyketone. Use differential scanning calorimetry to test its melting point.

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

[0117]

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

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

[0120] Note 3: Molecular weight: kg mol -1 , number average molecular weight Mn n and molecular weight distribution PDI were determined by gel permeation chromatography at 40 o °C, with hexafluoroisopropanol as the eluent;

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

[0122] Note 5: For Sequences 24 - 26, the dosage of the phenyl-bridged phosphine-phosphine oxide nickel catalyst = 10 μmol. Continuously introduce the ethylene / CO mixed gas. Dichloromethane = 100 mL, 500 mL mechanical autoclave;

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

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

[0125] Example 10:

[0126] In a 150 mL stainless steel autoclave, at ambient temperature, add in the following order: a certain amount of phenyl-bridged phosphine-phosphine oxide nickel catalyst, with the dosage between 1 - 20 μmol; a certain amount of cocatalyst, with the dosage between 1 - 10 mmol; a certain amount of solvent, with the volume between 10 - 50 mL; a certain amount of C3 - C10 olefin, with the mass between 1 - 50 g; introduce the ethylene and carbon monoxide mixed gas at the specified pressure and quickly raise the temperature to the set temperature. The reaction temperature is 30 - 150 o °C, and start stirring. The reaction time is between 0.5 - 4 h. After reaching the set time, stop stirring, slowly release the remaining mixed gas, add methanol for quenching, then add a large amount of methanol for precipitation, filter the polymer, and dry it to a constant weight under vacuum. The polymerization results are shown in Table 3 below. Use gel permeation chromatography to determine the molecular weight and its distribution of the polymer; use Varian INOVA - 400MHz to determine its 1 1H NMR to obtain the structure of the polyketone. Use differential scanning calorimetry to test its melting point.

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

[0128]

[0129] Note 1: Polymerization conditions: Structure of the phenyl-bridged phosphine-phosphine oxide nickel catalyst: , 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: Turnover number: g PK (g of Ni) -1 ;

[0131] Note 3: Insertion ratio of C3 - C10 in mol% ( 1 determined by 1H NMR spectroscopy);

[0132] Note 4: Molecular weight: kg / mol -1 , number - average molecular weight Mn n and polydispersity index PDI were determined by gel permeation chromatography at 40 o °C, with hexafluoroisopropanol as the eluent;

[0133] Note 5: Melting temperature Tm m was determined by differential scanning calorimetry (DSC), second heating, and a broad melting endotherm peak.

[0134] Example 11:

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

[0136] Example 12:

[0137] Set the barrel temperature of the injection molding machine to 245 °C and the mold temperature to 80 °C. Take 10 g of the ternary polyketone powder prepared in Example 10 (propylene insertion 5.8%, molecular weight 195 kg / mol -1 , melting point 231 °C) and place it in the barrel to heat to the molten state. Then, it was injected into the temperature - controlled mold cavity by high - speed propulsion of the screw, and the holding pressure time was controlled for 10 s, finally processing into dumbbell - shaped polyketone specimens. The tensile properties were tested using a universal testing machine according to the GB / T 41758.2 - 2022 standard. The results were: breaking strength 58 MPa, elongation at break 193%, yield strength 51 MPa, and Young's modulus 1260 MPa.

[0138] Example 13:

[0139] Set the barrel temperature of the injection molding machine to 210 °C and the mold temperature to 80 °C. Take 10 g of the ternary polyketone powder prepared in Example 10 (propylene insertion 12.6%, molecular weight 145 kg / mol -1, with a melting point of 195 °C) was placed in the barrel and heated to a molten state. Subsequently, it was injected into the temperature-controlled mold cavity by high-speed propulsion of the screw, and the holding pressure time was controlled for 10 s. Finally, dumbbell-shaped polyketone strips were processed. The tensile properties were tested using a universal testing machine according to the standard of GB / T 41758.2-2022. The results were: the breaking strength was 75 MPa, the elongation at break was 423%, the yield strength was 43 MPa, and the Young's modulus was 739 MPa.

[0140] Example 14:

[0141] The temperature of the injection molding machine barrel was set to 200 °C, and the mold temperature was 80 °C. 10 g of the terpolyketone powder prepared in Example 10 (inserted propylene 19.6%, molecular weight 138 kg mol -1 , with a melting point of 186 °C) was placed in the barrel and heated to a molten state. Subsequently, it was injected into the temperature-controlled mold cavity by high-speed propulsion of the screw, and the holding pressure time was controlled for 10 s. Finally, dumbbell-shaped polyketone strips were processed. The tensile properties were tested using a universal testing machine according to the standard of GB / T 41758.2-2022. The results were: the breaking strength was 84 MPa, the elongation at break was 710%, the yield strength was 29 MPa, and the Young's modulus was 653 MPa.

[0142] Example 15:

[0143] 20 g of the polyketone powder prepared in Example 10 (inserted propylene 32.3%, molecular weight 129 kg mol -1 , with a melting point of 138 °C), 400 mg of antioxidant 1010, 200 mg of N-butylbenzenesulfonamide, and 600 mg of silane coupling agent A151 were mixed evenly, heated to 170 °C, degassed by vacuum pumping, cooled and solidified, and the polyketone hot melt adhesive was obtained after discharging. The bonding strength was tested using a metal steel plate. The hot melt adhesive was evenly coated on a specific area of the steel plate using a hot melt gun, and then the two test plates were bonded and cured at room temperature for 1 - 2 h. The tensile strength was tested using a universal testing machine according to the standard of GB / T 41758.2-2022, and it was 7.2 MPa.

[0144] Example 16:

[0145] 20 g of the polyketone powder prepared in Example 10 (inserted propylene 45.7%, molecular weight 106 kg mol -1, with a melting point of 109 °C), 200 mg of antioxidant 1330, 100 mg of N-butylbenzenesulfonamide, and 800 mg of silane coupling agent KH-560 were mixed evenly, heated to 170 °C, evacuated to remove air bubbles, cooled and cured, and the polyketone hot melt adhesive was obtained by discharging. The bonding strength was tested using a metal steel plate. The hot melt adhesive was evenly coated on a specific area of the steel plate using a hot melt gun, and then the two test plates were bonded and cured at room temperature for 1 - 2 h. The tensile strength was tested using a universal testing machine according to the standard of GB / T 41758.2-2022, and it was 6.1 Mpa.

Claims

1. A benzene-bridged phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials, characterized in that, The structure of the benzene-bridged phosphine-phosphine oxide type nickel catalyst is as follows: ； Among them, Ar 1 and Ar 2 are 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 are the same or different; R 1 is hydrogen, methyl, tert-butyl, methoxy, N,N-dimethylamino, N,N-diethylamino, trimethylsilyl, fluoro, trifluoromethyl or perfluorophenyl; 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 pyrrolidinyl, R 2 and R 3 are the same or different; X is BArF, AsF6, SbF6, PF6, p-TsO or BF4.

2. The preparation method of the benzene-bridged phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials according to claim 1, characterized in that, The steps are as follows: 1) Phenylphosphine oxide A, phosphine chloride B, alkyllithium and alkyllithium activator react in an organic solvent at room temperature for 2 to 24 h to form a benzene-bridged phosphine–phosphine oxide ligand C; , 2) At room temperature, react the benzene-bridged phosphine-oxide ligand C, allyl nickel(II) chloride dimer and sodium salt in an organic solvent for 1 to 6 h to obtain the benzene-bridged phosphine-oxide type nickel catalyst D; 。 3. The preparation method of the benzene-bridged phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials according to claim 2, characterized in that, In step 1), the alkyllithium is n-butyllithium, methyllithium, sec-butyllithium or tert-butyllithium; the alkyllithium activator is one or a mixture of two or more of potassium tert-butoxide, tetramethylethylenediamine, hexamethylphosphoramide, 1,4-diazabicyclo[2.2.2]octane; the organic solvent is one or a mixture of two or more of toluene, 1,2-xylene, diethyl ether, methyl tert-butyl ether, n-hexane, n-heptane, N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane; the molar ratio of phenylphosphine oxide A, phosphine chloride B, alkyllithium, alkyllithium activator is 1~1.2:1~1.3:1~1.5:1~1.5; the concentration of phenylphosphine oxide A in the reaction system is 0.05~0.5 mol / L.

4. The preparation method of the benzene-bridged phosphine-phosphine oxide type nickel catalyst for preparing polyketone materials according to claim 2, characterized in that, In step 2), the sodium salt is sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, sodium hexafluoroarsenate, sodium hexafluorostibate, sodium hexafluorophosphate, sodium p-toluenesulfonate or sodium tetrafluoroborate; the organic solvent is one or a mixture of two or more of toluene, chlorobenzene, benzene, methanol, ethanol, diethyl ether, n-hexane, dichloromethane, 1,2-dichloroethane, chloroform; The structure of the allylnickel(II) chloride dimer is ; the molar ratio of the benzene-bridged phosphine–phosphine oxide ligand C, allyl nickel(II) chloride dimer, sodium salt is 1~1.2:1~1.3:1~1.2; the concentration of the benzene-bridged phosphine–phosphine oxide ligand C in the reaction system is 0.01~0.2 mol / L.

5. A method for preparing polyketone using the benzene-bridged phosphine-phosphine oxide type nickel catalyst according to claim 1, characterized in that, The polyketone structure is as follows: ； wherein, n and m are degrees of polymerization; 10 3 10 < n < 10 5 , 0 ≤ m < 10 4 , 0 ≤ m / (n+m) < 80%; R is an olefin within C3~C10, including propylene, 1-butene, 1-hexene, 1-octene, 1-decene; The specific synthesis route of the polyketone is as follows: , the steps are as follows: First, connect the reactor to the polymerization pipeline, and use vacuum and nitrogen operations to displace the air in the reactor and the polymerization pipeline; subsequently, set the required reaction temperature, and under an inert atmosphere, mix the benzene-bridged phosphine-phosphine oxide type nickel catalyst, cocatalyst and solvent in the reactor; finally, charge carbon monoxide and olefin compounds into the autoclave, start stirring; after reacting for a specified time, add a quenching agent to stop the polymerization, and obtain a white solid after washing with methanol, which is polyketone.

6. The method for preparing polyketone using the benzene-bridged phosphine-phosphine oxide type nickel catalyst according to claim 5, characterized in that the cocatalyst is one or a mixture of two or more of lithium aluminum hydride, sodium borohydride, lithium borohydride, trimethylaluminum, triethylaluminum, triisobutylaluminum, methylaluminoxane, diethylaluminum chloride, trimethylsilane, triethylsilane, triphenylsilane, tetraethoxysilane, phenylsilane, 9-borabicyclo[3,3,1]nonane, lithium triisobutylborohydride, sodium trimethoxyborohydride, pinacolborane, triphenylboron, tris(perfluorophenyl)borane; the solvent is one or a mixture of two or more of toluene, benzene, dichloromethane, acetone, diethyl ether, chlorobenzene, n-hexane, cyclohexane, chloroform, acetonitrile, diethyl carbonate, hexafluoroisopropanol; the molar concentration of the benzene-bridged phosphine-phosphine oxide type nickel catalyst in the solvent is 0.01~0.5 mmol / L; the molar concentration of the cocatalyst in the solvent is 10~100 mmol / L; the olefin compound is ethylene and a third component, the third component is an olefin within C3~C10, and the gas mass ratio of the third component in the reaction kettle is 5%~60%; The molar ratio of the ethylene and carbon monoxide gases is (1~6):1; The reaction pressure is 1~6 MPa; The reaction temperature is 30~150 °C; The stirring speed is 100~800 r / min; The specified time is 0.5~10 h.

7. Use of a polyketone obtained by a method for preparing a polyketone using the benzene-bridged phosphine-phosphine oxide type nickel catalyst according to claim 5, characterized in that, It is used for preparing polyketone fiber materials, polyketone resin materials or polyketone hot melt adhesive materials.

8. Use of the polyketone obtained by the method for preparing polyketone using the benzene-bridged phosphine-phosphine oxide type nickel catalyst according to claim 7, characterized in that, When the propylene content in the polyketone product < 5%, it can be used for fiber materials; when the propylene content in the polyketone product is 5~20%, it is used for resin materials; when the propylene content in the polyketone product > 20%, it can be used for hot melt adhesive materials.

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