Degradable aliphatic polyketone resin and preparation process thereof

Abstract

The invention relates to the technical field of resin, in particular to degradable aliphatic polyketone resin and a preparation process thereof, and the degradable aliphatic polyketone resin comprises the following components: 20-50 parts by weight of hydroxylated cyclohexene, 0.1-5 parts by weight of ferric acetylacetonate, 0.05-2 parts by weight of 1, 3-dimethylimidazole-2-subunit, and 30-50 parts by weight of toluene. By adding acetoxyphenyl iodide, cyclohexene can be efficiently oxidized into hydroxylated cyclohexene, and hydroxyl can be accurately introduced to a specific position of cyclohexene, so that a high-purity product is obtained; meanwhile, acetoxyl phenyl iodide adjusts the molecular structure of the polyketone resin in the reaction, and the flexibility, crystallinity and other properties of the resin are optimized by influencing the length and branching degree of a molecular chain, so that the polyketone resin is easier to form in the processing process. In addition, tert-butyl hydroperoxide participates in a cross-linking reaction of a molecular chain, and moderate cross-linking can significantly improve the mechanical properties of the resin and enhance the strength and hardness of the resin, so that the durability of the resin is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of resins, and specifically, to a degradable aliphatic polyketone resin and its preparation process. Background Art

[0002] With the increasing global awareness of environmental protection and the growing problem of plastic pollution, the development of degradable materials has become one of the important directions in scientific research; most traditional plastics are made from non-renewable resources and are difficult to degrade in the natural environment, resulting in a large accumulation of waste and posing a long-term threat to the ecosystem; aliphatic polyketone resins, as a new type of environmentally friendly material, have received extensive attention due to their unique molecular structure and excellent physical and chemical properties.

[0003] However, traditional degradable aliphatic polyketone resins often face problems of high brittleness and low toughness, which limits their use in applications that require high impact resistance and good ductility, such as packaging materials and disposable products; specifically, due to the relatively rigid molecular chain structure of traditional aliphatic polyketone resins, the materials are prone to fracture rather than deformation when subjected to external forces, showing poor impact resistance and ductility. In view of this, we propose a degradable aliphatic polyketone resin and its preparation process. Summary of the Invention

[0004] The purpose of the present invention is to provide a degradable aliphatic polyketone resin and its preparation process to solve the problem that traditional aliphatic polyketone resins are prone to fracture rather than deformation when subjected to external forces due to their relatively rigid molecular chain structure, showing poor impact resistance and ductility as mentioned in the above background art.

[0005] To achieve the above purpose, the present invention provides a degradable aliphatic polyketone resin, comprising the following components: 20 - 50 parts by weight of hydroxylated cyclohexene, 0.1 - 5 parts by weight of iron acetylacetonate, 0.05 - 2 parts by weight of 1,3-dimethylimidazol-2-ylidene, and 30 - 50 parts by weight of toluene; The hydroxylated cyclohexene is prepared by oxidizing cyclohexene with acetoxyphenyl iodide and adding tert-butyl hydroperoxide as a co-oxidant.

[0006] Preferably, the preparation process of the hydroxylated cyclohexene is as follows: S1.1. Weigh the following components in parts by weight respectively: 10 - 15 parts by weight of cyclohexene, 12 - 18 parts by weight of acetoxyphenyl iodide, 12 - 20 parts by weight of tert-butyl hydroperoxide, 30 - 40 parts by weight of toluene, 10 - 15 parts by weight of saturated sodium sulfite solution, and 10 - 20 parts by weight of dichloromethane; S1.2, dissolving cyclohexene in toluene, stirring at 300-500 rpm for 10-20 min at room temperature to fully dissolve the cyclohexene; then slowly adding acetoxyphenyl iodine solution dropwise, stirring at 300-500 rpm for 15-30 min to obtain a mixture; The hydroxylated cyclohexene molecules generated by the oxidation of cyclohexene with acetoxyphenyl iodine contain hydroxyl (-OH) functional groups. In the formation process of degradable aliphatic polyketone resin, these hydroxyl groups can form hydrogen bonds with polar groups such as carbonyl (C=O) on the polyketone resin molecular chain. Hydrogen bonds are a strong intermolecular force, and their existence significantly enhances the interaction force between resin molecular chains. When the resin is subjected to external force, relative sliding between the molecular chains is less likely to occur, thereby improving the toughness of the resin and enabling it to withstand greater external forces without breaking.

[0007] The cyclohexene structure in hydroxylated cyclohexene has a certain flexibility. These flexible chain segments are introduced into the polyketone resin molecular chain as an intercalant, making the originally relatively rigid polyketone molecular chain more flexible. When the resin is subjected to external force, these flexible chain segments adapt to the external force through their own twisting, rotation and other movements, thereby effectively dissipating energy and further improving the toughness of the resin. In addition, the participation of acetoxyphenyl iodine enables the hydroxylated cyclohexene to be connected to the polyketone resin molecular chain in a certain way, destroying the regularity of the molecular chain. The reduction in the regularity of the molecular chain means that it is difficult for the molecular chains to form a tight bond. The orderly stacking structure increases the freedom of movement of the molecular chain. This property enables the resin molecular chain to adjust its conformation more easily when subjected to stress, showing better toughness. In the biodegradable aliphatic polyketone resin, hydroxylated cyclohexene is randomly distributed in the molecular chain. When cracks appear inside the resin, the molecular structure of hydroxylated cyclohexene can serve as a physical barrier to prevent the rapid expansion of the cracks. The steric hindrance effect of the cyclohexene structure requires the cracks to bypass these groups during the expansion process, thereby consuming more energy, slowing down the crack expansion rate, and reducing the brittleness of the resin.

[0008] S1.3, adding tert-butyl hydroperoxide aqueous solution to the mixture at a rate of 0.1-0.2 mL / min, after the addition is completed, stirring the mixture at a rate of 300-500 rpm at 0-20°C for 3-5 hours; after the reaction is completed, adding a saturated sodium sulfite solution with a concentration of 1-2 mol / L, stirring at a rate of 200-300 rpm for 15-30 minutes to quench the unreacted oxidant; tert-Butyl hydroperoxide can provide additional reactive oxygen species, thereby enhancing the oxidation ability of acetoxyphenyliodine to cyclohexene, making it easier to oxidize cyclohexene to hydroxylated cyclohexene. This synergistic effect not only increases the production rate and yield of the target product but also shortens the reaction time and improves production efficiency. By reducing the residual unreacted cyclohexene, this combination ensures the thoroughness of the oxidation reaction, improves the utilization rate of raw materials, and makes the reaction more inclined to produce hydroxylated cyclohexene rather than other possible by-products.

[0009] During the formation of the degradable aliphatic polyketone resin, tert-butyl hydroperoxide may participate in the cross-linking reaction of the resin molecular chain. Moderate cross-linking can significantly improve the mechanical properties of the resin, such as hardness, strength, and heat resistance, etc., making the resin products have better stability and durability, meeting the requirements of material properties for different application scenarios; the free radicals generated by the decomposition of tert-butyl hydroperoxide may initiate the structural adjustment and modification of the resin molecular chain, such as changing the molecular chain length, degree of branching, etc., thereby optimizing the flexibility, elasticity and other properties of the resin.

[0010] S1.4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane for extraction 2 - 3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter after drying, and obtain hydroxylated cyclohexene through a rotary evaporator.

[0011] Preferably, in S1.2, the acetoxyphenyliodine solution is prepared by dissolving acetoxyphenyliodine in toluene to obtain an acetoxyphenyliodine solution with a concentration of 0.1 - 1 mol / L.

[0012] Preferably, in S1.2, the dropping rate of the acetoxyphenyliodine solution is 0.1 - 0.5 mL / min.

[0013] Preferably, in S1.3, the concentration of the tert-butyl hydroperoxide aqueous solution is 50 - 70%.

[0014] Preferably, in S1.4, the evaporation temperature of the rotary evaporator is 30 - 50 °C, the vacuum degree is -0.08 ~ -0.1 MPa, and the rotation speed is 60 - 120 r / min.

[0015] On the other hand, the present invention provides a preparation process of a degradable aliphatic polyketone resin for the degradable aliphatic polyketone resin described in any one of the above, including the following steps: S2.1. Weigh the following components by weight: 20 - 50 parts by weight of hydroxylated cyclohexene, 0.1 - 5 parts by weight of iron acetylacetonate, 0.05 - 2 parts by weight of 1,3-dimethylimidazol-2-ylidene, and 30 - 50 parts by weight of toluene; S2.2. Add toluene into a high-pressure reactor, and successively add iron acetylacetonate and 1,3-dimethylimidazol-2-ylidene under a stirring speed of 200 - 300 rpm to fully dissolve them; introduce carbon monoxide until the pressure reaches 1 - 10 MPa, then slowly dropwise add hydroxylated cyclohexene. The reaction temperature is 50 - 150 °C, and the reaction time is 12 - 48 h to obtain a reaction mixture. Iron acetylacetonate is an efficient catalyst that can significantly accelerate the polymerization reaction process of aliphatic polyketone resin. Its main mechanism of action is to lower the activation energy of the reaction, making it easier for reactant molecules to reach the required energy state, thereby increasing the reaction rate, shortening the reaction time, and improving production efficiency; in addition, iron acetylacetonate can also improve the thermal stability of polyketone resin to a certain extent. This is because iron acetylacetonate can form a stable structure with the resin molecular chain, hindering the movement and degradation of the molecular chain at high temperatures, thus enhancing the heat resistance of the resin and enabling it to maintain good performance stability in a relatively high-temperature environment.

[0016] As a commonly used ligand, 1,3-dimethylimidazol-2-ylidene can form a stable complex with metal catalysts (such as iron in iron acetylacetonate). This complex not only improves the stability of the catalyst but also prevents the catalyst from decomposing or deactivating during the reaction, thereby ensuring that the catalytic system can function more persistently and efficiently and guaranteeing the smooth progress of the polymerization reaction; through the coordination with the metal center, 1,3-dimethylimidazol-2-ylidene can adjust the electron cloud density and spatial configuration of the metal catalyst, optimizing the activity and selectivity of the catalyst. This optimization makes the catalyst more suitable for specific reaction substrates and reaction conditions, further improving the efficiency of the polymerization reaction and the quality of the product.

[0017] S2.3. After the reaction is completed, slowly release the pressure in the reactor and cool it to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation, and then vacuum dry it at 60 - 80 °C for 6 - 24 h to obtain a degradable aliphatic polyketone resin.

[0018] Preferably, in S2.2, the dropping rate of hydroxylated cyclohexene is 0.1 - 0.5 mL / min.

[0019] Preferably, in S2.3, the pressure relief rate of slowly releasing the pressure in the reactor is 0.05 - 0.2 MPa / min.

[0020] Preferably, in S2.3, the temperature of vacuum distillation is 30 - 40 °C, the temperature of the condenser is 0 - 5 °C, and the time is 1 - 4 h.

[0021] Compared with the prior art, the beneficial effects of the present invention: 1. In this degradable aliphatic polyketone resin and its preparation process, adding acetoxyphenyliodine can efficiently oxidize cyclohexene to hydroxylated cyclohexene. Its oxidation reaction has high selectivity, can accurately introduce hydroxyl groups at specific positions of cyclohexene, significantly reduce side reactions, and thus obtain high-purity products. In addition, acetoxyphenyliodine cleverly adjusts the molecular structure of the polyketone resin during the reaction, such as affecting the length and degree of branching of the molecular chain, and then optimizing the properties such as the flexibility and crystallinity of the resin, making it easier to form during the processing.

[0022] 2. In this degradable aliphatic polyketone resin and its preparation process, adding tert-butyl hydroperoxide as a co-oxidant and acting synergistically with acetoxyphenyliodine significantly increases the reaction rate of oxidizing cyclohexene to hydroxylated cyclohexene, enabling the reaction to reach the expected conversion rate in a shorter time, thereby greatly improving production efficiency. In addition, tert-butyl hydroperoxide participates in the cross-linking reaction of the molecular chain, and appropriate cross-linking can enhance the mechanical properties of the resin, such as increasing its strength and hardness, making it more durable. Detailed implementation mode

[0023] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.

[0024] The present invention provides a degradable aliphatic polyketone resin, which includes the following components: 20-50 parts by weight of hydroxylated cyclohexene, 0.1-5 parts by weight of iron acetylacetonate, 0.05-2 parts by weight of 1,3-dimethylimidazol-2-ylidene, and 30-50 parts by weight of toluene; Hydroxylated cyclohexene is prepared by oxidizing cyclohexene with acetoxyphenyliodine and adding tert-butyl hydroperoxide as a co-oxidant.

[0025] Example 1: A degradable aliphatic polyketone resin and its preparation process include the following steps: S2.1. Weigh the following components by weight: 35 parts by weight of hydroxylated cyclohexene, 0.7 parts by weight of iron acetylacetonate, 1.2 parts by weight of 1,3-dimethylimidazol-2-ylidene, and 40 parts by weight of toluene; S2.2. Add toluene into a high-pressure reaction kettle, and sequentially add iron acetylacetonate and 1,3-dimethylimidazol-2-ylidene at a stirring speed of 300 rpm to make them fully dissolve. Introduce carbon monoxide until the pressure reaches 10 MPa, and then drop hydroxylated cyclohexene at a speed of 0.5 mL / min. The reaction temperature is 120 °C, and the reaction time is 48 h to obtain a reaction mixture; S2.3. After the reaction is completed, release the pressure in the reaction kettle at a pressure relief rate of 0.1 MPa / min and cool it to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation at a temperature of 40 °C, a condenser temperature of 5 °C, and a time of 4 h; then dry it in vacuum at 60 °C for 24 h to obtain the degradable aliphatic polyketone resin.

[0026] The preparation process of hydroxylated cyclohexene is as follows: S1.1. Weigh the following components by weight: 12 parts by weight of cyclohexene, 12 parts by weight of acetoxyphenyliodine, 16 parts by weight of tert-butyl hydroperoxide, 35 parts by weight of toluene, 12 parts by weight of saturated sodium sulfite solution, and 15 parts by weight of dichloromethane. S1.2. Dissolve cyclohexene in toluene and stir it at a speed of 500 rpm for 20 min at room temperature to fully dissolve cyclohexene; dissolve acetoxyphenyliodine in toluene to obtain an acetoxyphenyliodine solution with a concentration of 0.5 mol / L, and then add the acetoxyphenyliodine solution dropwise at a speed of 0.3 mL / min while stirring at a speed of 300 rpm for 30 min to obtain a mixture. S1.3. Drop the 70% aqueous solution of tert-butyl hydroperoxide into the mixture at a speed of 0.2 mL / min. After the dropping is completed, stir and react at a speed of 500 rpm at 20 °C for 5 h; after the reaction is completed, add a saturated sodium sulfite solution with a concentration of 2 mol / L and stir at a speed of 300 rpm for 30 min to quench the unreacted oxidant. S1.4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane for extraction 2 - 3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter it after drying, and use a rotary evaporator with an evaporation temperature of 50 °C, a vacuum degree of -0.1 MPa, and a rotation speed of 120 r / min to obtain hydroxylated cyclohexene.

[0027] Example 2: A degradable aliphatic polyketone resin and its preparation process, including the following steps: S2.1. Weigh the following components by weight: 35 parts by weight of hydroxylated cyclohexene, 0.7 parts by weight of iron acetylacetonate, 1.2 parts by weight of 1,3-dimethylimidazol-2-ylidene, and 40 parts by weight of toluene. S2.2. Add toluene to a high-pressure reaction kettle, and sequentially add iron acetylacetonate and 1,3-dimethylimidazol-2-ylidene while stirring at a speed of 300 rpm to fully dissolve them; introduce carbon monoxide until the pressure reaches 10 MPa, and then add hydroxylated cyclohexene dropwise at a speed of 0.5 mL / min. The reaction temperature is 120 °C and the reaction time is 48 h to obtain a reaction mixture. S2.3. After the reaction is completed, release the pressure in the reaction kettle at a pressure relief rate of 0.1 MPa / min and cool it to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation at a temperature of 40 °C, a condenser temperature of 5 °C, and a time of 4 h; then dry it under vacuum at 60 °C for 24 h to obtain the degradable aliphatic polyketone resin.

[0028] The preparation process of hydroxylated cyclohexene is as follows: S1.1. Weigh the following components by weight: 12 parts by weight of cyclohexene, 13 parts by weight of acetoxyphenyliodine, 16 parts by weight of tert-butyl hydroperoxide, 35 parts by weight of toluene, 12 parts by weight of saturated sodium sulfite solution, and 15 parts by weight of dichloromethane. S1.2. Dissolve cyclohexene in toluene and stir at a speed of 500 rpm for 20 min at room temperature to fully dissolve cyclohexene; dissolve acetoxyphenyliodine in toluene to obtain an acetoxyphenyliodine solution with a concentration of 0.5 mol / L, and then add the acetoxyphenyliodine solution dropwise at a speed of 0.3 mL / min while stirring at a speed of 300 rpm for 30 min to obtain a mixture. S1.3. Drop the 70% aqueous solution of tert-butyl hydroperoxide into the mixture at a speed of 0.2 mL / min. After the dropping is completed, stir and react at a speed of 500 rpm at 20 °C for 5 h; after the reaction is completed, add a 2 mol / L saturated sodium sulfite solution and stir at a speed of 300 rpm for 30 min to quench the unreacted oxidant. S1.4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane for extraction 2 - 3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter it after drying, and obtain hydroxylated cyclohexene through a rotary evaporator at an evaporation temperature of 50 °C, a vacuum degree of -0.1 MPa, and a rotation speed of 120 r / min.

[0029] Example 3: A degradable aliphatic polyketone resin and its preparation process, including the following steps: S2.1. Weigh the following components by weight: 35 parts by weight of hydroxylated cyclohexene, 0.7 parts by weight of iron acetylacetonate, 1.2 parts by weight of 1,3-dimethylimidazol-2-ylidene, and 40 parts by weight of toluene. S2.2. Add toluene to a high-pressure reaction kettle, and successively add iron acetylacetonate and 1,3-dimethylimidazol-2-ylidene while stirring at a speed of 300 rpm to fully dissolve them; introduce carbon monoxide until the pressure reaches 10 MPa, then add hydroxylated cyclohexene dropwise at a speed of 0.5 mL / min, with the reaction temperature at 120 °C and the reaction time of 48 h to obtain a reaction mixture. S2.3. After the reaction is completed, release the pressure in the reaction kettle at a pressure relief rate of 0.1 MPa / min and cool it to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation, the temperature of vacuum distillation is 40 °C, the temperature of the condenser is 5 °C, and the time is 4 h; then dry it in vacuum at 60 °C for 24 h to obtain the degradable aliphatic polyketone resin.

[0030] The preparation process of hydroxylated cyclohexene is as follows: S1.1. Weigh the following components by weight: 12 parts by weight of cyclohexene, 15 parts by weight of acetoxyphenyl iodide, 16 parts by weight of tert-butyl hydroperoxide, 35 parts by weight of toluene, 12 parts by weight of saturated sodium sulfite solution, and 15 parts by weight of dichloromethane; S1.2. Dissolve cyclohexene in toluene and stir at a speed of 500 rpm for 20 min at room temperature to fully dissolve cyclohexene; dissolve acetoxyphenyl iodide in toluene to obtain an acetoxyphenyl iodide solution with a concentration of 0.5 mol / L, and then add the acetoxyphenyl iodide solution dropwise at a speed of 0.3 mL / min while stirring at a speed of 300 rpm for 30 min to obtain a mixture; S1.3. Drop the 70% aqueous solution of tert-butyl hydroperoxide into the mixture at a speed of 0.2 mL / min. After the dropping is completed, stir and react at a speed of 500 rpm at 20 °C for 5 h; after the reaction is completed, add a 2 mol / L saturated sodium sulfite solution and stir at a speed of 300 rpm for 30 min to quench the unreacted oxidant; S1.4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane for extraction 2 - 3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter it after drying, and use a rotary evaporator with an evaporation temperature of 50 °C, a vacuum degree of -0.1 MPa, and a rotation speed of 120 r / min to obtain hydroxylated cyclohexene.

[0031] Example 4: A degradable aliphatic polyketone resin and its preparation process, including the following steps: S2.1. Weigh the following components by weight: 35 parts by weight of hydroxylated cyclohexene, 0.7 parts by weight of iron acetylacetonate, 1.2 parts by weight of 1,3-dimethylimidazol-2-ylidene, and 40 parts by weight of toluene; S2.2. Add toluene to a high-pressure reaction kettle, and sequentially add iron acetylacetonate and 1,3-dimethylimidazol-2-ylidene while stirring at a speed of 300 rpm to make them fully dissolve; introduce carbon monoxide until the pressure reaches 10 MPa, and then add hydroxylated cyclohexene dropwise at a speed of 0.5 mL / min, the reaction temperature is 120 °C, and the reaction time is 48 h to obtain a reaction mixture; S2.3. After the reaction is completed, release the pressure in the reaction kettle at a pressure relief rate of 0.1 MPa / min and cool it to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation at a temperature of 40 °C, a condenser temperature of 5 °C, and a time of 4 h; then dry it under vacuum at 60 °C for 24 h to obtain the degradable aliphatic polyketone resin.

[0032] The preparation process of hydroxylated cyclohexene is as follows: S1.1. Weigh the following components by weight: 12 parts by weight of cyclohexene, 18 parts by weight of acetoxyphenyl iodide, 16 parts by weight of tert-butyl hydroperoxide, 35 parts by weight of toluene, 12 parts by weight of saturated sodium sulfite solution, and 15 parts by weight of dichloromethane. S1.2. Dissolve cyclohexene in toluene and stir it at a speed of 500 rpm for 20 min at room temperature to fully dissolve cyclohexene; dissolve acetoxyphenyl iodide in toluene to obtain an acetoxyphenyl iodide solution with a concentration of 0.5 mol / L, and then add the acetoxyphenyl iodide solution dropwise at a speed of 0.3 mL / min while stirring at a speed of 300 rpm for 30 min to obtain a mixture. S1.3. Drop the 70% aqueous solution of tert-butyl hydroperoxide into the mixture at a speed of 0.2 mL / min. After the dropping is completed, stir and react at a speed of 500 rpm at 20 °C for 5 h; after the reaction is completed, add a 2 mol / L saturated sodium sulfite solution and stir it at a speed of 300 rpm for 30 min to quench the unreacted oxidant. S1.4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane for extraction 2 - 3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter it after drying, and use a rotary evaporator with an evaporation temperature of 50 °C, a vacuum degree of -0.1 MPa, and a rotation speed of 120 r / min to obtain hydroxylated cyclohexene.

[0033] Example 5: A degradable aliphatic polyketone resin and its preparation process, including the following steps: S2.1. Weigh the following components by weight: 20 parts by weight of hydroxylated cyclohexene, 1 part by weight of iron acetylacetonate, 0.05 part by weight of 1,3-dimethylimidazol-2-ylidene, and 30 parts by weight of toluene. S2.2. Add toluene to a high-pressure reaction kettle, and sequentially add iron acetylacetonate and 1,3-dimethylimidazol-2-ylidene while stirring at a speed of 300 rpm to fully dissolve them; introduce carbon monoxide until the pressure reaches 10 MPa, and then add hydroxylated cyclohexene dropwise at a speed of 0.5 mL / min. The reaction temperature is 120 °C and the reaction time is 48 h to obtain a reaction mixture. S2.3. After the reaction is completed, release the pressure in the reaction kettle at a pressure relief rate of 0.1 MPa / min and cool it to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation at a temperature of 40 °C, a condenser temperature of 5 °C, and a time of 4 h; then dry it under vacuum at 60 °C for 24 h to obtain the degradable aliphatic polyketone resin.

[0034] The preparation process of hydroxylated cyclohexene is as follows: S1.1. Weigh the following components by weight: 12 parts by weight of cyclohexene, 13 parts by weight of acetoxyphenyliodine, 12 parts by weight of tert-butyl hydroperoxide, 30 parts by weight of toluene, 10 parts by weight of saturated sodium sulfite solution, and 10 parts by weight of dichloromethane. S1.2. Dissolve cyclohexene in toluene and stir it at a speed of 500 rpm for 20 min at room temperature to fully dissolve cyclohexene; dissolve acetoxyphenyliodine in toluene to obtain an acetoxyphenyliodine solution with a concentration of 0.5 mol / L, and then add the acetoxyphenyliodine solution dropwise at a speed of 0.3 mL / min while stirring at a speed of 300 rpm for 30 min to obtain a mixture. S1.3. Drop the 70% aqueous solution of tert-butyl hydroperoxide into the mixture at a speed of 0.2 mL / min. After the dropping is completed, stir and react at a speed of 500 rpm at 20 °C for 5 h; after the reaction is completed, add a 2 mol / L saturated sodium sulfite solution and stir at a speed of 300 rpm for 30 min to quench the unreacted oxidant. S1.4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane for extraction 2 - 3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter it after drying, and use a rotary evaporator with an evaporation temperature of 50 °C, a vacuum degree of -0.1 MPa, and a rotation speed of 120 r / min to obtain hydroxylated cyclohexene.

[0035] Example 6: A degradable aliphatic polyketone resin and its preparation process, including the following steps: S2.1. Weigh the following components by weight: 30 parts by weight of hydroxylated cyclohexene, 1 part by weight of iron acetylacetonate, 0.05 part by weight of 1,3-dimethylimidazol-2-ylidene, and 30 parts by weight of toluene. S2.2. Add toluene to a high-pressure reaction kettle, and sequentially add iron acetylacetonate and 1,3-dimethylimidazol-2-ylidene while stirring at a speed of 300 rpm to fully dissolve them; introduce carbon monoxide until the pressure reaches 10 MPa, and then add hydroxylated cyclohexene dropwise at a speed of 0.5 mL / min. The reaction temperature is 120 °C, and the reaction time is 48 h to obtain a reaction mixture. S2.3. After the reaction is completed, release the pressure in the reaction kettle at a pressure relief rate of 0.1 MPa / min and cool it to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation, with the temperature of vacuum distillation being 40 °C, the condenser temperature being 5 °C, and the time being 4 h; then dry it under vacuum at 60 °C for 24 h to obtain the degradable aliphatic polyketone resin.

[0036] The preparation process of hydroxylated cyclohexene is as follows: S1.1. Weigh the following components by weight: 12 parts by weight of cyclohexene, 13 parts by weight of acetoxyphenyl iodide, 12 parts by weight of tert-butyl hydroperoxide, 30 parts by weight of toluene, 10 parts by weight of saturated sodium sulfite solution, and 10 parts by weight of dichloromethane; S1.2. Dissolve cyclohexene in toluene and stir at a speed of 500 rpm for 20 min at room temperature to fully dissolve cyclohexene; dissolve acetoxyphenyl iodide in toluene to obtain an acetoxyphenyl iodide solution with a concentration of 0.5 mol / L, and then add the acetoxyphenyl iodide solution dropwise at a speed of 0.3 mL / min while stirring at a speed of 300 rpm for 30 min to obtain a mixture; S1.3. Drop the 70% aqueous solution of tert-butyl hydroperoxide into the mixture at a speed of 0.2 mL / min. After the dropping is completed, stir and react at a speed of 500 rpm at 20 °C for 5 h; after the reaction is completed, add a 2 mol / L saturated sodium sulfite solution and stir at a speed of 300 rpm for 30 min to quench the unreacted oxidant; S1.4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane for extraction 2 - 3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter it after drying, and use a rotary evaporator with an evaporation temperature of 50 °C, a vacuum degree of -0.1 MPa, and a rotation speed of 120 r / min to obtain hydroxylated cyclohexene.

[0037] Example 7: A degradable aliphatic polyketone resin and its preparation process, including the following steps: S2.1. Weigh the following components by weight: 50 parts by weight of hydroxylated cyclohexene, 1 part by weight of iron acetylacetonate, 0.05 part by weight of 1,3-dimethylimidazol-2-ylidene, and 30 parts by weight of toluene; S2.2. Add toluene to a high-pressure reaction kettle, and sequentially add iron acetylacetonate and 1,3-dimethylimidazol-2-ylidene while stirring at a speed of 300 rpm to fully dissolve them; introduce carbon monoxide until the pressure reaches 10 MPa, and then add hydroxylated cyclohexene dropwise at a speed of 0.5 mL / min. The reaction temperature is 120 °C and the reaction time is 48 h to obtain a reaction mixture; S2.3. After the reaction is completed, release the pressure in the reaction kettle at a pressure relief rate of 0.1 MPa / min and cool it to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation at a temperature of 40 °C, a condenser temperature of 5 °C, and a time of 4 h; then dry it under vacuum at 60 °C for 24 h to obtain the degradable aliphatic polyketone resin.

[0038] The preparation process of hydroxylated cyclohexene is as follows: S1.1. Weigh the following components by weight: 12 parts by weight of cyclohexene, 13 parts by weight of acetoxyphenyl iodide, 12 parts by weight of tert-butyl hydroperoxide, 30 parts by weight of toluene, 10 parts by weight of saturated sodium sulfite solution, and 10 parts by weight of dichloromethane; S1.2. Dissolve cyclohexene in toluene and stir at a speed of 500 rpm for 20 min at room temperature to fully dissolve cyclohexene; dissolve acetoxyphenyl iodide in toluene to obtain an acetoxyphenyl iodide solution with a concentration of 0.5 mol / L, and then add the acetoxyphenyl iodide solution dropwise at a speed of 0.3 mL / min while stirring at a speed of 300 rpm for 30 min to obtain a mixture; S1.3. Drop the 70% aqueous solution of tert-butyl hydroperoxide into the mixture at a speed of 0.2 mL / min. After the dropping is completed, stir and react at a speed of 500 rpm at 20 °C for 5 h; after the reaction is completed, add a 2 mol / L saturated sodium sulfite solution and stir at a speed of 300 rpm for 30 min to quench the unreacted oxidant; S1.4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane for extraction 2 - 3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter it after drying, and obtain hydroxylated cyclohexene through a rotary evaporator at an evaporation temperature of 50 °C, a vacuum degree of -0.1 MPa, and a rotation speed of 120 r / min.

[0039] Comparative Example 1

[0040] Adopt the method of Example 3, without using hydroxylated cyclohexene, and directly use cyclohexene to prepare the degradable aliphatic polyketone resin.

[0041] Comparative Example 2

[0042] Adopt the method of Example 3. In the preparation process of hydroxylated cyclohexene, tert-butyl hydroperoxide is not added.

[0043] Comparative Example 3

[0044] Adopt the method of Example 3. In the preparation process of the degradable aliphatic polyketone resin, 1,3-dimethylimidazol-2-ylidene is not added.

[0045] The degradable aliphatic polyketone resin prepared by the hydroxylation of cyclohexene in the present invention, wherein the performance index test items and test standards of the degradable aliphatic polyketone resin are as follows: According to the national standard GB / T 1040, install the specimen in the fixture of the testing machine, ensure that the center line of the specimen is completely aligned with the tensile axis, set the tensile speed to 50 mm / min, start the testing machine, and record in real time the elongation of the specimen when it reaches the maximum tensile force during the tensile process; calculate the elongation at break through the formula. This index reflects the ductility and toughness of the material. A high value means that the material can withstand a large deformation under force without being easily broken.

[0046] According to the national standard GB / T 1043.1, place the specimen in the fixture of the impact testing machine, adjust the pendulum energy to the range of 1 - 50 J, start the impact test, and record in real time the failure mode and the absorbed energy value of the specimen after being impacted; calculate the impact strength through the formula. This index reflects the anti-destruction ability of the material when subjected to impact loads. A high value indicates that the material has strong toughness, can effectively resist sudden impact forces, and reduce the risk of damage or rupture.

[0047] Through the above standards, the degradable aliphatic polyketone resins prepared in Examples 1 - 7 and Comparative Examples 1 - 3 are tested, and the obtained data are shown in Table 1: Table 1 Performance data of degradable aliphatic polyketone resins in Examples 1 - 7 and Comparative Examples 1 - 3

[0048] It can be seen from Examples 1 - 4 that when the mass ratio of acetoxyphenyliodine to cyclohexene in hydroxylated cyclohexene gradually increases, the elongation at break and impact strength of the degradable aliphatic polyketone resin gradually increase. However, when the mass ratio of acetoxyphenyliodine to cyclohexene reaches a certain value, the elongation at break and impact strength of the degradable aliphatic polyketone resin gradually decrease. Thus, it can be known that with the increase of the mass ratio of acetoxyphenyliodine, both the elongation at break and impact strength of the degradable aliphatic polyketone resin are improved, but excessive increase may reduce the elongation at break and impact strength of the degradable aliphatic polyketone resin; Acetoxyphenyl iodide is an oxidant that can oxidize cyclohexene to hydroxylated cyclohexene. As the mass ratio of acetoxyphenyl iodide to cyclohexene increases, the amount of hydroxylated cyclohexene produced increases. These hydroxylated products carry hydroxyl functional groups, which can participate in the polymerization reaction and introduce more polar groups during the synthesis of biodegradable aliphatic polyketone resins. Intermolecular forces such as hydrogen bonds can form between polar groups, thus enhancing the interaction between molecular chains, but not making the molecular chains overly rigid. This property enables the molecular chains to be neither easily slipped when stressed nor lack the ability to move and deform to a certain extent, thereby improving the flexibility and toughness of the resin. After an appropriate amount of hydroxylated cyclohexene is incorporated into the polyketone resin molecular chain as a structural unit, its cyclic structure and introduced functional groups can play an internal plasticization role in the molecular chain, increasing the distance between molecular chains, making the internal rotation of molecular chains easier, and increasing the overall flexibility. When the resin is subjected to external tensile or impact forces, the molecular chains can more freely adjust their conformations and absorb and disperse energy through their own deformation, thereby increasing the elongation at break and impact resistance.

[0049] The increase in the proportion of acetoxyphenyl iodide helps to form a more suitable crosslinked network structure. During the resin polymerization process, it may promote the formation of moderate crosslinking points between molecular chains. Moderate crosslinking not only ensures that the resin has a certain integrity and strength but also does not overly restrict the movement of molecular chains. When subjected to external forces, the crosslinked network can effectively disperse stress and avoid stress concentration in a local area leading to material rupture. Therefore, the resin can withstand greater deformation during stretching and better absorb energy during impact, thereby increasing the elongation at break and impact strength.

[0050] Furthermore, by comparing Examples 5-7, it can be seen that when other components remain unchanged, only when the proportion of hydroxylated cyclohexene gradually increases, the elongation at break and the impact strength of the degradable aliphatic polyketone resin gradually increase. It can be seen that the cyclohexene ring in the molecular structure of hydroxylated cyclohexene has a certain flexibility. When its proportion in the polyketone resin increases, the flexible chain segments are introduced into the molecular chain of the resin. These flexible chain segments can absorb and disperse energy through their own twisting, rotation and other movements when subjected to external forces, so that the molecular chain can be elongated without breaking, thereby improving the elongation at break of the resin; when subjected to impact, it can also effectively buffer the impact. In addition, the hydroxyl group (-OH) on hydroxylated cyclohexene is a polar group, which can form hydrogen bonds with polar groups such as carbonyl group (C=O) on the polyketone resin molecular chain. As the proportion of hydroxylated cyclohexene increases, the number of hydrogen bonds formed between the molecular chains increases, and the interaction between the molecular chains increases. This enhanced intermolecular force enables the molecular chains to move better in coordination. When the resin is subjected to external force, the molecular chains will not easily slide relative to each other, but will jointly resist the external force, thereby improving the toughness and impact resistance of the resin, which is reflected in the numerical increase in elongation at break and impact strength.

[0051] The introduction of hydroxylated cyclohexene will destroy the regularity of the molecular chain of the polyketone resin, making it difficult for the molecular chain to form a perfect crystalline structure, thereby reducing the crystallinity of the resin. Lower crystallinity means an increase in the amorphous region inside the resin. The molecular chains in the amorphous region are arranged more disorderly, with a larger free volume and better flexibility. When subjected to force, the amorphous region can deform more flexibly, absorb and disperse energy, avoiding the decline in the overall performance of the resin due to the brittle fracture of the crystalline region, thereby improving the elongation at break and impact strength.

[0052] Comparing Example 3 with Comparative Example 1, it can be seen that when hydroxylated cyclohexene is not used and cyclohexene is directly used to prepare the degradable aliphatic polyketone resin, the elongation at break and the impact strength of the degradable aliphatic polyketone resin are significantly reduced.

[0053] Taking Example 3 as the best example and combining it with Comparative Example 2, it can be seen that in the preparation process of hydroxylated cyclohexene, when tert-butyl hydroperoxide is removed, the elongation at break and impact strength of the degradable aliphatic polyketone resin are significantly reduced; During the preparation of hydroxylated cyclohexene, tert-butyl hydroperoxide acts as a co-oxidant in synergy with acetoxyphenyl iodide, significantly accelerating the oxidation reaction rate of cyclohexene and improving the reaction efficiency. If tert-butyl hydroperoxide is removed, the oxidation reaction rate will slow down significantly, and the amount of hydroxylated cyclohexene produced will also decrease significantly. Hydroxylated cyclohexene is a key intermediate for improving the properties of degradable aliphatic polyketone resins. Insufficient content thereof will lead to insufficient effective components for optimizing the molecular structure and properties in the resin. An appropriate amount of hydroxylated cyclohexene can introduce flexible chain segments and polar functional groups into the resin molecular chain, thereby improving the flexibility and intermolecular interaction of the resin. When the production amount of hydroxylated cyclohexene decreases, these beneficial structure-regulating effects cannot be fully exerted, resulting in an increase in the rigidity of the resin molecular chain and a deterioration in flexibility, making it difficult to effectively deform to absorb and disperse energy when subjected to external forces, and thus reducing the elongation at break and impact strength.

[0054] Taking Example 3 as the optimal example and combining with Comparative Example 2, it can be seen that in the preparation process of degradable aliphatic polyketone resin, when 1,3-dimethylimidazol-2-ylidene is removed, the elongation at break and impact strength of the degradable aliphatic polyketone resin are significantly reduced. 1,3-Dimethylimidazol-2-ylidene has a unique electronic structure and can reduce the activation energy of the reaction by interacting with reactants or catalysts, thereby promoting the reaction of monomers such as hydroxylated cyclohexene. The characteristics of its electronic structure make it play a key role in the polymerization reaction. In addition, the electronic properties of 1,3-dimethylimidazol-2-ylidene also enable it to participate in cross-linking reactions, helping to form a moderate cross-linking network and enhancing the intermolecular interaction, thereby improving the strength and toughness of the material. After removing 1,3-dimethylimidazol-2-ylidene, the number of reaction active centers decreases, resulting in a slower reaction rate, incomplete polymerization reaction, and it is difficult for the molecular weight of the resin to reach the ideal state, with shorter molecular chains, which will directly affect the mechanical properties of the resin and reduce the elongation at break and impact strength.

[0055] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. The above embodiments and the descriptions in the specification are only preferred examples of the present invention and are not used to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

1. A degradable aliphatic polyketone resin, characterized in that: The invention comprises the following components: 20-50 parts by weight of hydroxylated cyclohexene, 0.1-5 parts by weight of ferric acetylacetonate, 0.05-2 parts by weight of 1,3-dimethylimidazole-2-ylidene, and 30-50 parts by weight of toluene; Hydroxylated cyclohexene is prepared by oxidation of cyclohexene with acetoxyphenyl iodide and addition of tert-butyl hydroperoxide.

2. The degradable aliphatic polyketone resin according to claim 1, characterized in that: The preparation process of the hydroxylated cyclohexene is as follows: S1.

1. Weigh the following components in parts by weight respectively: 10-15 parts by weight of cyclohexene, 12-18 parts by weight of acetoxyphenyl iodide, 12-20 parts by weight of tert-butyl hydroperoxide, 30-40 parts by weight of toluene, 10-15 parts by weight of saturated sodium sulfite solution, and 10-20 parts by weight of dichloromethane; S1.2, dissolving cyclohexene in toluene, stirring at 300-500 rpm for 10-20 min at room temperature to fully dissolve the cyclohexene; then slowly adding acetoxyphenyl iodine solution dropwise, stirring at 300-500 rpm for 15-30 min to obtain a mixture; S1.3, adding tert-butyl hydroperoxide aqueous solution to the mixture at a rate of 0.1-0.2 mL / min, after the addition is completed, stirring the mixture at a rate of 300-500 rpm at 0-20°C for 3-5 hours; after the reaction is completed, adding a saturated sodium sulfite solution with a concentration of 1-2 mol / L, stirring at a rate of 200-300 rpm for 15-30 minutes to quench the unreacted oxidant; S1.

4. Transfer the reaction mixture in S1.3 to a separatory funnel, add dichloromethane to extract 2-3 times, and separate the organic phase; dry the organic phase with anhydrous sodium sulfate, filter it after drying, and obtain the hydroxylated cyclohexene by a rotary evaporator.

3. The degradable aliphatic polyketone resin according to claim 2, characterized in that: In S1.2, the acetoxyphenyl iodine solution is prepared by dissolving acetoxyphenyl iodine in toluene to obtain an acetoxyphenyl iodine solution having a concentration of 0.1-1 mol / L.

4. The degradable aliphatic polyketone resin according to claim 2, characterized in that: In S1.2, the acetoxyphenyl iodine solution is slowly added dropwise at a speed of 0.1-0.5 mL / min.

5. The degradable aliphatic polyketone resin according to claim 2, characterized in that: In the S1.3, the concentration of the aqueous solution of tert-butyl hydroperoxide is 50-70%.

6. The degradable aliphatic polyketone resin according to claim 2, characterized in that: In S1.4, the evaporation temperature of the rotary evaporator is 30-50° C., the vacuum degree is -0.08 to -0.1 MPa, and the rotation speed is 60-120 r / min.

7. A process for preparing a degradable aliphatic polyketone resin, for preparing the degradable aliphatic polyketone resin as claimed in any one of claims 1 to 6, characterized in that: The preparation process of the degradable aliphatic polyketone resin is as follows: S2.

1. Weigh the following components in parts by weight respectively: 20-50 parts by weight of hydroxylated cyclohexene, 0.1-5 parts by weight of ferric acetylacetonate, 0.05-2 parts by weight of 1,3-dimethylimidazole-2-ylidene, and 30-50 parts by weight of toluene; S2.2, add toluene to the autoclave, add ferric acetylacetonate and 1,3-dimethylimidazole-2-ylidene in sequence at a stirring speed of 200-300rpm to fully dissolve them; introduce carbon monoxide until the pressure reaches 1-10MPa, and then slowly add hydroxylated cyclohexene dropwise, the reaction temperature is 50-150°C, the reaction time is 12-48h, and a reaction mixture is obtained; S2.

3. After the reaction is completed, slowly release the pressure in the reactor and cool to room temperature; transfer the reaction mixture to a separation container, filter it, remove toluene by vacuum distillation, and then vacuum dry it at 60-80°C for 6-24h to obtain a degradable aliphatic polyketone resin.

8. The process for preparing the degradable aliphatic polyketone resin according to claim 7, characterized in that: In the above S2.2, the hydroxylated cyclohexene is slowly added dropwise at a speed of 0.1-0.5 mL / min.

9. The process for preparing the degradable aliphatic polyketone resin according to claim 7, characterized in that: In S2.3, the pressure release rate for slowly releasing the pressure in the reactor is 0.05-0.2 MPa / min.

10. The process for preparing the degradable aliphatic polyketone resin according to claim 7, characterized in that: In S2.3, the temperature of the reduced pressure distillation is 30-40°C, the temperature of the condenser is 0-5°C, and the time is 1-4h.

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