Non-alternating polyketone with quasi-multi-block structure as well as preparation method and application of non-alternating polyketone

Abstract

The invention belongs to the field of polymer synthesis, chemical engineering and polymer processing, and provides non-alternating polyketone with a quasi-multi-block structure, a preparation method and application, the carbonyl content of the non-alternating polyketone is 0.5-48%, the number-average molecular weight is 1-500 kg / mol, the molecular weight distribution is 1.01-4.00, and the melting point is 80-240 DEG C. The invention further provides a preparation method and application of the non-alternating polyketone with the quasi-multi-block structure. A non-alternating polyketone chain is of a quasi-multi-block structure with a disordered long range and an ordered short range, a polar and non-polar chain structure is shown in a molecular chain, and the carbonyl content is uniformly distributed in the whole macromolecular chain. The non-alternating polyketone is prepared by adopting gas supply operation, and the uniform distribution of carbonyl in a main chain is ensured by maintaining and supplementing the gas with the carbon monoxide content consistent with the carbonyl content of the generated polymer. The non-alternating polyketone prepared by the invention is applied to efficient compatibilization of nylon and polyethylene.

Description

Technical Field

[0001] The present invention belongs to the fields of polymer synthesis, chemical engineering and polymer processing, and relates to a quasi-multiblock non-alternating polyketone, a preparation method thereof and its application in the efficient compatibilization of nylon and polyethylene. Background Art

[0002] Polyketone (PK), a crystalline polymer material obtained by the alternating copolymerization of olefins and carbon monoxide, is a new type of engineering plastic with excellent mechanical properties and chemical stability. The material was first industrially produced in the 1990s and is currently mainly applied to high-end fields such as automotive fuel components, interior materials and oil extraction pipelines.

[0003] The polyketone material has excellent chemical stability and can withstand most organic solvents and chemical media, and its corrosion resistance is significantly better than that of nylon 66 (PA66). At the same time, the unique all-carbon chain rigid chain structure endows it with an extremely low friction coefficient (0.2-0.3) and excellent anti-creep performance, and its wear resistance is 14 times that of polyoxymethylene (POM). Based on these characteristics, polyketone shows significant advantages in replacing traditional engineering plastics (such as POM, PA66, etc.), which can not only extend the service life of products, but also reduce the operating noise of moving parts.

[0004] With the increasing environmental protection requirements, polyketone, as a recyclable high-performance material, has a broader application prospect in fields such as the automotive industry, oil extraction, and precision machinery. Among them, the melting point of polyketone is the most important property determining its processability. Due to the β-scission of the carbonyl group (—C=O—) in the main chain of polyketone at high temperatures, the initial decomposition temperature of polyketone is only about 300 °C. However, the melting point of binary alternating polyketone is also around 260 °C. Therefore, the processing window is extremely narrow. Ethylene / CO binary alternating polyketone has been regarded as a non-thermally processable polymer for a long time, and the processing difficulties have always hindered the development of binary polyketone. However, some researchers have been constantly trying. For example, in 2021, Professor Li Jia and others from the University of Akron prepared a small amount of binary alternating polyketone splines by injection molding (J. Organomet. Chem., 2021, 952, 122045). However, due to the possible partial decomposition of the polymer during processing, the properties of the samples obtained by this direct processing method of alternating polyketone are unstable and not suitable for industrial continuous production. In 2024, Professor Sanjay Rastogi and others from King Abdullah University of Science and Technology processed the relatively low-melting-point α-type single-crystal binary alternating polyketone synthesized in a special way by calendering. However, this processing method has high requirements for the crystal morphology of polymer powders and cannot be synthesized in large quantities (Macromolecules 2024, 57, 7862 - 7877). In 2024, Professor Liu Ye and others from Dalian University of Technology processed this high-melting-point binary alternating polyketone by hexafluoroisopropanol casting molding. Although the solvent casting method avoids the decomposition problem existing in thermal processing to a certain extent, the solvent used for casting is expensive and environmentally unfriendly. Therefore, this method is not suitable for large-scale processing (J. Am. Chem. Soc. 2024, 146, 34560–34567). So far, thermal processing molding is still the mainstream processing method for general plastics. Therefore, to achieve processing, reducing the melting point of the polymer to expand the processing window of this polymer is undoubtedly the most feasible way to realize the processing of binary polyketone.

[0005] However, ethylene / carbon monoxide non-alternating copolymerization is a unique binary copolymerization method that utilizes the additional insertion of ethylene to reduce the regularity of the polyketone molecular chain, thereby improving the polymer fluidity and lowering the melting point. This copolymerization method can improve the processing performance of polyketone, greatly increasing the possibility of its industrial processing. Ethylene / carbon monoxide non-alternating copolymerization can be achieved by coordination polymerization. For example, in 2002, Professor Drent of Shell Laboratory developed a palladium phosphosulfonate catalyst for ethylene / carbon monoxide non-alternating copolymerization (Chem. Commun. 2002, 9, 964 - 965). However, in all studies to date, due to unreasonable monomer feeding, during the preparation of the polymer, the resulting polymer exhibits a block / high-gradient phenomenon due to the imbalance of monomer ratios (Organometallics 2007, 26, 3636 - 3638). The resulting polymer either has a low yield, leading to severe residual palladium metal, or undergoes polar / non-polar phase separation inside. This polyketone with macroscopic phase separation has uneven products, poor tensile and impact properties, and almost no application prospects. Moreover, in almost all studies, the developed non-alternating polyketone coordination polymerization catalysts have problems of large copolymer gradient and low activity during the preparation of non-alternating polyketone. This problem has been hindering the yield / product quality stability / homogeneity of non-alternating polyketone, the continuous production process of the polymer, and the performance research of the polymer. Therefore, since the first synthesis of non-alternating polyketone in 2002, no relevant patents have detailedly described this polymer material, nor have there been further effective regulation and practical performance exploration of such polymers.

[0006] In this invention, a series of non-alternating polyketones with uniform structures were synthesized. After detailed characterization of the polymer microstructure, we found that the structure of the synthesized non-alternating polyketone has a long-range disorder and short-range order structure, with obvious high-carbonyl (polar) regions and low-carbonyl (non-polar) regions. Due to its unique structure of combining polar segments with non-polar segments, macroscopically, the polymer can be regarded as a quasi-block structure, and this structure has great application potential in highly compatibilizing incompatible polymers as a compatibilizer.

[0007] Aliphatic polyamide (PA), also known as Nylon (Ny), is a common type of polymer material. It can be applied not only in textile fabrics, fibers, etc., but also as components such as plates, pipes, gears, and joints that bear mechanical properties, with a very broad application scenario. Due to the nitrogen atoms in the main chain, the molecular polarity is relatively strong, and the N-H bonds in the main chain are prone to form intra- and intermolecular hydrogen bonds, resulting in good crystallization properties. Polyethylene (PE) is the most widely used general-purpose plastic at present. As plastic products, it is widely used in products such as packaging bags, plastic bottles, and mulch films. Due to the very regular molecular chain, high crystallinity, and very small molecular polarity, there are few polymers compatible with it. Polyamide and polyethylene are two types of typical incompatible polymers. They not only have huge differences in solubility parameters and interfacial tensions, but also have large differences in melting points and melt viscosities, so it is very difficult to achieve uniform mixing kinetically. At the same time, due to the weak interfacial adhesion force, if they are directly blended, serious phase separation will occur and it is very easy to be damaged under stress, usually without practical value. However, due to the attractive combination of the good processability / toughness of polyethylene and the good mechanical / thermal properties of polyamide, the HDPE / PA blend has great benefits in industrial applications. Therefore, commercialized clay and reactive compatibilizer maleic anhydride grafted PE have been developed on the market as compatibilizers for the two (Appl.Clay Sci.2019, 184 - 189; Mater.Lett.2004, 58, 3457 - 3460). The former is developed as an inorganic filler, while the latter, as a reactive compatibilizer, can be applied to the broad-spectrum compatibilization of polyethylene. The original intention of developing the two is not specifically for the compatibilization of polyethylene and polyamide, and there are certain defects in this compatibilization system. Among them, the compatibilization ability and application range of inorganic fillers as compatibilizers are also relatively limited and the compatibilization mechanism is not clear. At the same time, for reactive compatibilization, processing polyethylene at the processing temperature of general nylon itself is likely to cause oxidative scission of polyethylene and reduce the polymer performance. Therefore, reactive compatibilization is not applicable to this blend system.

[0008] In the present invention, we have conducted detailed research and characterization on the synthesized non-alternating polyketone. It has a quasi-multiblock structure with long-range disorder and short-range order, and there are polar regions and non-polar regions in its molecular chain. Through experimental verification, this non-alternating polyketone can achieve efficient compatibilization of nylon and polyethylene materials. Summary of the Invention

[0009] One of the main objectives of the present invention is to synthesize a class of non-alternating polyketones with different carbonyl contents, molecular weights within the range of easy forming and processing, and uniform distribution of carbonyl groups throughout the molecular chain.

[0010] The second main object of the present invention is to propose a process for synthesizing non-alternating polyketones with different carbonyl contents by an easily controllable coordination solution polymerization method in view of the deficiencies of the prior art. The device is simple and the maintenance cost is low, and the continuous synthesis of non-alternating polyketone resins can be realized.

[0011] The third main object of the present invention is to develop a non-alternating polyketone compatibilizer with a polyethylene-polyketone quasi-multiblock structure as an efficient compatibilizer for compatibilizing nylon and polyethylene.

[0012] The technical solution of the present invention:

[0013] A non-alternating polyketone with a quasi-multiblock structure has the following structure:

[0014]

[0015] Wherein, 0≤k, 1≤l, m, o < 50000, n is a long methylene sequence, 0 < n < 10000, the carbonyl content of the non-alternating polyketone is 0.5-48%, the number average molecular weight is 1 kg / mol-500 kg / mol, the molecular weight distribution is between 1.01 and 4.00, and its melting point is between 80°C and 240°C. The non-alternating polyketone chain presents a quasi-multiblock structure with long-range disorder and short-range order, and the molecular chain shows polar and non-polar chain structures inside, and the carbonyl content is evenly distributed throughout the polymer chain.

[0016] A preparation method of a non-alternating polyketone with a quasi-multiblock structure:

[0017]

[0018] The catalyst, cocatalyst, solvent and auxiliary agent are sequentially added into the reaction kettle. The polymerization reaction kettle is connected to the gas pipeline. First, a mixed gas of ethylene and CO with a molar ratio of (1-1000):1 is charged as the initial gas. After stabilizing for 1-20 minutes, a mixed gas of ethylene and CO is charged as the supplementary gas at the same pressure. The supplementary gas is continuously supplemented into the reaction kettle during the whole reaction process. Under the conditions of controlling the reaction pressure at 2-10 MPa and the heating temperature at 50-120°C, the reaction time is 1-48 h; the reaction is stopped, and the product is recrystallized with methanol and then washed with methanol to obtain the non-alternating polyketone polymer. The number average molecular weight measured by gel permeation chromatography is between 1-500 kg / mol, and the molecular weight distribution is between 1.01-4.00. The melting point measured by differential scanning calorimetry is between 80°C and 240°C.

[0019] The size and model of the polymerization reactor are not limited in the present invention. The reactor needs to have good sealing performance and the characteristics of being able to withstand high pressure and high temperature. The reactor needs to have a feed inlet for adding solid / liquid raw materials. The reactor can be connected to an inlet gas pipeline (including reaction gas and inert protective gas). The reactor has a jacket that can regulate the temperature or can be placed in a temperature control device for heating. The reactor needs to be equipped with a pressure gauge to display the pressure inside the reactor in real time. The reactor needs to have a steam discharge shut-off valve that can exhaust gas. The reactor needs to have a discharge outlet for discharging the polymerization product.

[0020] The gas pipeline connected to the polymerization reactor needs to be connected to two kinds of gases, namely the initial gas and the supplementary gas. The initial gas and the supplementary gas can be connected to the reactor through a three-way valve respectively. The gas pipeline connecting the reactor and the gas contains a shut-off valve for controlling the intake gas and a pressure reducing valve for regulating the intake gas pressure.

[0021] Stirring is required during the reaction process, and the stirring speed is preferably 50 - 1000 r / min;

[0022] The initial gas is to maintain a constant mass ratio of ethylene to carbon monoxide in the polymerization kettle during the entire polymerization reaction cycle. The molar ratio of ethylene to carbon monoxide in the initial gas is preferably (1 - 1000):1

[0023] The carbon monoxide content of the supplementary gas is determined by the carbonyl content of the polymer generated in the initial stage of the polymerization reaction under the condition of the initial gas. The carbon monoxide content of the supplementary gas is preferably close to the carbonyl content of the polymer generated in the initial stage of the polymerization reaction under the condition of the initial gas; the molar ratio of ethylene to carbon monoxide in the supplementary gas is preferably (1 - 100):1.

[0024] The supplementary gas needs to be continuously supplemented into the reactor at a constant pressure during the subsequent reaction process.

[0025] The catalyst is preferably one or a combination of two of the following structures:

[0026]

[0027] The cocatalyst is one of NaBF4, NaPF6, NaSbF6, NaBArF.

[0028] The auxiliary agent is preferably p-benzoquinone and methanol.

[0029] The solvent is preferably one or a mixture of two or more of dichloromethane, n-hexane, tetrahydrofuran, benzene, toluene, chlorobenzene, chloroform, dioxane, tetrachloroethane, acetone.

[0030] The concentration of the catalyst in the reaction system is preferably 0.005 - 50 mmol / L -1。

[0031] The quasi-multiblock non-alternating polyketone obtained by the above preparation is used as a compatibilizer for nylon plastics and polyethylene plastics. According to the relevant principles of resin blending, the compatibilization steps are as follows:

[0032] First, polyethylene plastic, nylon plastic, quasi-multiblock non-alternating polyketone and antioxidant are pre-mixed in proportion to make each component fully pre-mixed and uniform; then the pre-mixed material is sent to a melt blending device for melt blending, controlling the processing temperature within the range of 170 - 270 °C, and the blending process lasts for 1 - 20 minutes; the melt is cooled and formed to obtain the blended plastic.

[0033] The polyethylene plastic is preferably a mixture of one or more of low-density polyethylene, high-density polyethylene, linear low-density polyethylene, and ultra-high molecular weight polyethylene.

[0034] The nylon plastic is preferably a mixture of one or more of nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 56, and nylon 410.

[0035] The mass ratio of the polyethylene plastic to the nylon plastic is preferably 5:5 - 9:1.

[0036] The quasi-multiblock non-alternating polyketone preferably accounts for 1% - 15% of the total mass of the polyethylene plastic and the nylon plastic. The carbonyl content in the quasi-multiblock non-alternating polyketone is preferably 0.5 - 26%, and the molecular weight is preferably 10 - 100 kg / mol.

[0037] The pre-mixing is carried out using a high-speed mixer. The pre-mixing time is preferably 1 - 10 minutes, and the pre-mixing speed is preferably 500 - 2000 rpm.

[0038] The melt blending device is preferably a twin-screw extruder or an internal mixer, and the rotation speed is preferably 20 - 100 rpm.

[0039] The antioxidant includes a main antioxidant and a co-antioxidant, and the addition amount is preferably 0.01% - 2% of the total mass of polyethylene and nylon. The main antioxidant is preferably antioxidant 1010 and / or antioxidant 1098. The co-antioxidant is preferably antioxidant 168 and / or antioxidant 626, and the mass ratio of the main antioxidant to the co-antioxidant is preferably 1:3 - 3:1.

[0040] Advantages of the present invention:

[0041] (1) For the first time, a non-alternating binary polyketone material with a quasi-multiblock structure that is easy to process and has long-range disorder and short-range order was prepared. The carbonyl content of this polyketone material can be precisely regulated within the range of 0.5-48%, and the melting point of the obtained polyketone resin raw material is between 100°C and 240°C, which is suitable for processing with common general plastic processing equipment.

[0042] (2) An air supplement operation was designed. By maintaining a constant gas ratio in the reaction kettle and supplementing a gas with a carbon monoxide content consistent with the carbonyl content of the generated polymer, the regulation of monomer consumption and monomer supplement was successfully achieved, ensuring a uniform distribution of carbonyl groups on the molecular chain and avoiding the formation of a gradient or block structure in the polymer.

[0043] (3) The application field of this non-alternating binary polyketone material with a quasi-multiblock structure was expanded, and an efficient non-alternating polyketone compatibilizer for polyethylene and nylon was prepared. The compatibilizer has a polyethylene-polyketone quasi-multiblock structure. By adding a small amount of the polyketone compatibilizer, the interfacial adhesion force between polyethylene and polyamide materials was significantly improved, and the interfacial compatibility was significantly enhanced. Description of the Drawings

[0044] Figure 1 This is the 1H NMR spectrum of the non-alternating polyketone polymer with a uniform carbonyl structure distribution.

[0045] Figure 2 This is the NMR-time comparison chart of the gas charging method reported in the literature and the gas charging method reported in this article.

[0046] Among them, Figure 1 This is the 1H NMR spectrum of the non-alternating polyketone with a carbonyl content of 32%. Among them, (1) is the 1H NMR spectrum of the reaction products at different times when a mixed gas of 2 MPa is charged at an initial gas ratio of ethylene / carbon monoxide of 9 / 1 and the reaction kettle valve is closed to seal the system for polymerization; (2) is the 1H NMR spectrum of the reaction products at different times when a mixed gas of 2 MPa is charged at an initial gas ratio of ethylene / carbon monoxide of 9 / 1, stabilized for 10 min, and continuously supplemented with gas at a constant initial gas pressure of 2 MPa throughout the polymerization cycle; (3) is the 1H NMR spectrum of the reaction products at different times when a mixed gas of 2 MPa is charged at an initial gas ratio of ethylene / carbon monoxide of 9 / 1, stabilized for 10 min, and then continuously supplemented with a supplementary gas with an ethylene / carbon monoxide ratio of 3 / 2 throughout the polymerization cycle. Detailed Embodiments

[0047] The following further describes the detailed embodiments of the present invention in combination with the drawings and technical solutions.

[0048] Example 1:

[0049] The mixed gas of the initial gas and the supplementary gas is stored separately in two different gas storage tanks. The ethylene / carbon monoxide mass ratios of the two gas storage tanks (the initial gas tank and the supplementary gas tank) are 50 / 1 and 3 / 1 respectively. A 75 mL polymerization kettle is used and the temperature of the polymerization kettle is heated to 110 °C. 24 mg of catalyst Pd-1, 50 mg of cocatalyst NaBArF, 60 mL of toluene as a solvent, 150 mg of p-benzoquinone and 2.5 mL of methanol as additives are added into the polymerization kettle. Open the cut-off valves of the two gas storage tanks and adjust the pressure reducing valves of the two gas storage tanks to 2 MPa. Open the cut-off valve of the polymerization kettle, open the three-way stopcock valve and keep the polymerization kettle connected to the initial gas. When the readings of the pressure gauge of the polymerization kettle and the pressure gauge of the pressure reducing valve show 2 MPa and do not change significantly within 0.5 - 10 minutes, switch the three-way stopcock valve to connect the polymerization kettle to the supplementary gas. The supplementary gas continuously supplies a constant pressure of 2 MPa into the reaction kettle during the subsequent reaction process. Close the cut-off valve and the pressure reducing valve of the initial gas tank. The polymerization reaction is maintained for 3 h. When the polymerization reaction in the polymerization kettle ends, close all valves, slowly open the vent valve of the polymerization kettle to release the gas. After the gas release ends, open the discharge port of the polymerization kettle to empty the materials in the kettle, and a polymer solution is obtained. The polymer solution is recrystallized with methanol to obtain a white crystalline powder polymer, which is washed three times with methanol to obtain a non-alternating polyketone polymer. The carbonyl content is characterized by 1H NMR to be 26.1%. The product is weighed and the yield is measured to be 6.2 g. The product is characterized by gel permeation chromatography and the molecular weight is measured to be 25.6 kg / mol.

[0050] Example 2: On the basis of Example 1, change the ethylene / carbon monoxide mass ratio of the initial gas to 1000 / 1 and the ethylene / carbon monoxide mass ratio of the supplementary gas to 100 / 1. The carbonyl content is characterized by 1H NMR to be 0.9%. The product is weighed and the yield is measured to be 12.5 g. The product is characterized by gel permeation chromatography and the molecular weight is measured to be 54.1 kg / mol.

[0051] Example 3: On the basis of Example 1, change the ethylene / carbon monoxide mass ratio of the initial gas to 5 / 1 and the ethylene / carbon monoxide mass ratio of the supplementary gas to 10 / 9. The carbonyl content is characterized by 1H NMR to be 47%. The product is weighed and the yield is measured to be 4.1 g. The product is characterized by gel permeation chromatography and the molecular weight is measured to be 145 kg / mol.

[0052] Example 4: On the basis of Example 1, before the polymerization reaction starts, adjust the pressure reducing valves of the two gas storage tanks to 10 MPa and then charge the gas for the polymerization reaction. The carbonyl content of the product is characterized by 1H NMR to be 26.9%. The product is characterized by gel permeation chromatography and the molecular weight is measured to be 28.5 kg / mol. The product is weighed and the yield is measured to be 9.1 g.

[0053] Example 5: On the basis of Example 1, the catalyst Pd-1 was changed to 27.6 mg of Pd-2, and the other conditions remained unchanged. After the polymerization reaction was completed, the carbonyl content of the product was characterized by nuclear magnetic resonance hydrogen spectrum as 25.9%. The molecular weight of the product was measured by gel permeation chromatography as 14.8 kg / mol. The product was weighed and the yield was measured as 4.3 g.

[0054] Comparative Example 1: On the basis of Example 1, after the initial gas was introduced, the readings of the polymerization kettle pressure gauge and the pressure gauge of the pressure reducing valve showed 2 MPa, and there was no obvious change within 0.5 - 10 minutes. Then the shut-off valve of the polymerization kettle was closed to keep the polymerization kettle in a sealed state until the polymerization reaction ended after 3 h. At the end of the polymerization reaction, the pressure shown on the pressure gauge of the polymerization kettle was almost 0 MPa. The carbonyl content of the product was characterized by nuclear magnetic resonance hydrogen spectrum as 3.1%. Since the polymer underwent phase separation and could not be completely dissolved in the mobile phase solvent, gel permeation chromatography test could not be carried out. The product was weighed and the yield was measured as 2.6 g.

[0055] Comparative Example 2: On the basis of Example 1, after the initial gas was introduced, the readings of the polymerization kettle pressure gauge and the pressure gauge of the pressure reducing valve showed 2 MPa. The polymerization kettle was kept in communication with the initial state throughout the polymerization reaction process, and the pressure of the pressure reducing valve was maintained at 2 MPa until the polymerization reaction ended after 3 h. The carbonyl content of the product was characterized by nuclear magnetic resonance hydrogen spectrum as 2.4%. Since the polymer underwent phase separation and could not be completely dissolved in the mobile phase solvent, gel permeation chromatography test could not be carried out. The product was weighed and the yield was measured as 14.6 g.

[0056] Example 6: 7.0 g of high-density polyethylene, 3.0 g of nylon 12, 0.5 g of a non-alternating polyketone compatibilizer with a carbonyl content of 13%, 50 mg of antioxidant 1010, and 50 mg of antioxidant 168 were placed in a high-speed mixer and mixed at a speed of 1500 revolutions per minute for 5 minutes. The melt blending was completed by a co-rotating twin-screw extruder. The process parameters were: screw speed 60 revolutions per minute, blending time 2 minutes, a conical screw was selected, and the barrel temperature was 220 °C. The mixed resin was injection molded to prepare tensile specimens and impact specimens for mechanical property testing. The results are shown in Table 1, serial numbers 1 - 4.

[0057] Comparative Example 3: On the basis of Example 8, the blending was carried out in the same steps without adding non-alternating polyketone as a compatibilizer. The mixed resin was injection molded to prepare tensile specimens and impact specimens for mechanical property testing. The results are shown in Table 1, serial numbers 5 - 8.

[0058] Table 1. Mechanical property parameters of high-density polyethylene / nylon 12 / 13% non-alternating polyketone in a blend (1 - 4) with a mass ratio of 70 / 30 / 5, and high-density polyethylene / nylon 12 in a blend (5 - 8) with a mass ratio of 70 / 30

[0059]

[0060] Note 1: Tensile tests were measured at an ambient temperature with a fixture displacement rate of 10.0 mm / min. Note 2: Measurements were carried out at 220 °C and a shear rate of 50 s-1.

[0061] The measurement results in Example VI and Comparative Example III show that the elongation at break of the blended plastic sample with 5% non-alternating polyketone added as a compatibilizer is 366.0% ± 65.5%, the elastic modulus is 593.5 MPa ± 36.9 MPa, the yield strength is 24.6 MPa ± 0.1 MPa, the impact strength is 109.3 MPa ± 6.2 MPa, and the shear viscosity is 155.5 ± 11.6 Pa·s. For the blended plastic sample of pure nylon and high-density polyethylene without adding 5% non-alternating polyketone as a compatibilizer, the elongation at break is 42.9% ± 14.4%, the elastic modulus is 510.8 MPa ± 43.0 MPa, the yield strength is 26.1 MPa ± 0.3 MPa, the impact strength is 36.5 MPa ± 12.0 MPa, and the shear viscosity is 119.7 ± 13.2 Pa·s. It can be seen that by adding only a small amount (∼5%) of non-alternating polyketone as a compatibilizer, the tensile and impact strengths of the polymer can be significantly improved.

Claims

1. A non-alternating polyketone with a quasi-multiblock structure, characterized in that The structure of the non-alternating polyketone is as follows: Wherein, 0 ≤ k, 1 ≤ l, m, o < 50000, n is a long methylene sequence, 0 < n < 10000, the carbonyl content of the non-alternating polyketone is 0.5-48%, the number-average molecular weight is 1 kg / mol - 500 kg / mol, the molecular weight distribution is between 1.01 and 4.00, and its melting point is between 80°C and 240°C; the non-alternating polyketone chain presents a quasi-multi-block structure with long-range disorder and short-range order, the molecular chain shows polar and non-polar chain structures inside, and the carbonyl content is evenly distributed throughout the polymer chain.

2. A method for preparing a quasi-multiblock non-alternating polyketone, characterized in that, The steps are as follows: Add the catalyst, co-catalyst, solvent and additive into the reaction kettle in sequence, connect the reaction kettle to the gas pipeline, first charge a mixture of ethylene and CO with a molar ratio of (1 - 1000):1 as the initial gas, after stabilizing for 1 - 20 minutes, charge a mixture of ethylene and CO with the same pressure as the supplementary gas, and the supplementary gas is continuously supplemented into the reaction kettle during the whole reaction process. Under the conditions of controlling the reaction pressure at 2 - 10 MPa and the heating temperature at 50 - 120°C, the reaction time is 1 - 48 h; stop the reaction, and the product is recrystallized with methanol and then washed with methanol to obtain the non-alternating polyketone.

3. The preparation method according to claim 2, wherein, Stirring is required during the reaction process, and the stirring speed is 50 - 1000 r / min.

4. The preparation method according to claim 2, characterized in that, The carbon monoxide content in the supplementary gas is determined according to the carbonyl content of the polymer generated in the initial stage of the polymerization reaction under the initial gas conditions; the molar ratio of ethylene to carbon monoxide in the supplementary gas is (1 - 100):

1.

5. According to the preparation method described in claim 2, characterized in that, The catalyst is one or a combination of two of the following structures: The co-catalyst is one of NaBF4, NaPF6, NaSbF6, NaBArF; The additive is p-benzoquinone or methanol; The solvent is one or a mixture of two or more of dichloromethane, n-hexane, tetrahydrofuran, benzene, toluene, chlorobenzene, chloroform, dioxane, tetrachloroethane, acetone; The concentration of the catalyst in the reaction system is preferably 0.005 to 50 mmol / L -1 .

6. Use of the non-alternating polyketone obtained by the preparation method according to claim 2 as a compatibilizer for nylon plastics and polyethylene plastics, characterized in that, The steps are as follows: First, premix polyethylene plastic, nylon plastic, non-alternating polyketone and antioxidant in proportion to make each component fully premixed and uniform; then send the premix into a melt blending device for melt blending, control the processing temperature within the range of 170 - 270°C, and the blending process lasts for 1 - 20 minutes; the melt is cooled and formed to obtain the blended plastic.

7. According to the application described in claim 6, characterized in that, The polyethylene plastic is one or a mixture of two or more of low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-high molecular weight polyethylene; The nylon plastic is one or a mixture of two or more of nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 56, nylon 410; The main antioxidant is antioxidant 1010 and / or antioxidant 1098; the auxiliary antioxidant is antioxidant 168 and / or antioxidant 626, and the mass ratio of the auxiliary main antioxidant to the auxiliary antioxidant is 1:3 - 3:

1.

8. According to the application described in claim 7, characterized in that, The mass ratio of the polyethylene plastic to the nylon plastic is 5:5 - 100:1; The non-alternating polyketone accounts for 1% to 15% of the total mass of the polyethylene plastic and the nylon plastic. The carbonyl content in the non-alternating polyketone is preferably 0.5% to 26%, and the molecular weight is preferably 10 to 100 kg / mol; The antioxidants include primary antioxidants and secondary antioxidants, and the addition amount is 0.01% to 2% of the total mass of the polyethylene plastic and the nylon plastic.

9. The application according to claim 7, wherein The premixing is carried out by a high-speed mixer, the premixing time is 1 - 10 minutes, and the premixing rotation speed is 500 - 2000 rpm; The melt blending equipment is a twin-screw extruder or an internal mixer, and the rotation speed is 20 - 100 rpm.

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