Long-carbon-chain nylon elastomer polymer, preparation method thereof, product and recovery method

Abstract

The invention relates to the field of high polymer materials, in particular to a long-carbon-chain nylon elastomer polymer, a preparation method thereof, a product and a recovery method. According to the invention, polylipoic acid is introduced into long-carbon-chain nylon, so that the mechanical property of the prepared polymer is effectively adjusted, and the prepared material can be recycled, has high antibacterial property and good inflammation removal capacity. Tests show that the long-carbon-chain nylon elastomer polymer provided by the invention has recyclability, and the monomer recovery rate is 85% under the condition of inorganic alkali liquor catalysis; recycled monomers can be circularly processed, and the mechanical property is kept above 80% of that of an original sample. The long-carbon-chain nylon elastomer polymer provided by the invention also has a broad-spectrum bactericidal effect, the bactericidal rate of staphylococcus aureus and escherichia coli exceeds 95%, and the long-carbon-chain nylon elastomer polymer has good inflammation clearing ability, particularly has the effect of clearing TNF-alpha, IL-6 and IL-8 inflammatory factors.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, in particular to a long carbon chain nylon elastomeric polymer, a preparation method and a product thereof, and a recycling method. Background Art

[0002] Resources and the environment are major issues facing mankind in achieving sustainable development in the 21st century. Take synthetic nylon and its elastomeric materials as an example. As one of the largest and most important varieties of engineering plastics, according to statistics, its annual output exceeded 8.5 million tons in 2019 alone. However, only less than 20% of nylon can be recycled, and the serious pollution caused by this has caused serious damage to the ecological environment. PA6 and PA66 account for more than 80% of the total nylon production. Their production mainly relies on the conversion of fossil energy and has a significant carbon footprint. With the increasing depletion of oil resources, people are forced to begin to look for and develop sustainable elastomeric materials with degradable and recyclable properties to reduce environmental pollution and resource waste.

[0003] There are inexhaustible biomass resources such as cellulose and castor oil in nature, which can be used as a source to obtain almost the same polymer monomers with structures such as diacids and diamines as fossil resources. Nylon materials prepared with these bio-based monomers, especially long-chain nylons with more than 10 carbon atoms, such as PA11, PA1212, etc., have better mechanical properties, low absorption rate and low temperature resistance than short-chain nylons such as PA6, and are widely used in medical packaging, liquid medicine and blood storage and infusion, various catheters, medical equipment accessories, etc. For example, Wang Zhongkai et al. used C11 monomers derived from castor oil to synthesize a series of crystalline and mechanically adjustable long-chain elastomeric materials (Chem. Mater. 2020, 32, 8325-8332, Industrial Crops & Products, 2022, 181, 114852, CZ201710825333.1). However, nylon and its products have a long life cycle and take decades to degrade by landfill. Existing technologies include high-temperature pyrolysis recycling, physical recycling and chemical recycling, but they consume a lot of energy, produce secondary pollution and are costly. At the same time, various stabilizers and antioxidants are artificially added to improve the performance of nylon products, which greatly increases the difficulty of recycling nylon and its products.

[0004] A dynamic covalent bond is a covalent chemical bond that can undergo a reversible reaction under certain conditions. Common ones include imine bonds, acylhydrazone bonds, disulfide bonds, ester bonds, etc. As a biological antioxidant molecule, lipoic acid can spontaneously form dynamic polymers under conditions such as heat and light. It can not only give the material biological properties such as anti-inflammatory and antibacterial properties, but also has the advantages of self-repair and recyclability (Angew. Chem. Int. Ed. 2020, 59, 5278-5283, Matter, 2021, 4, 1352-1364).

[0005] Currently, there is no technology that can combine polylipoic acid with long-chain nylon to prepare long-chain nylon elastomer materials with multiple functions. The main reason is that bacteria can easily adhere to, grow, and form biofilms on the surface of conventional nylon and its elastomers or medical devices, thereby causing bacterial infection. There is no clear guidance on how to combine polylipoic acid with nylon materials to overcome the problem of bacterial adhesion and thereby give the material anti-inflammatory and antibacterial biological properties. Summary of the invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a long carbon chain nylon elastomeric polymer, its preparation method and product and recycling method. The long carbon chain nylon elastomeric polymer provided by the present invention not only has the characteristics of being recyclable and reprocessable, but also has antibacterial properties and good inflammation clearing ability.

[0007] The present invention provides a long carbon chain nylon elastomeric polymer having a unit of the structure shown in Formula 1;

[0008]

[0009] Wherein, the R is selected from aliphatic diamine or furan diamine;

[0010] The m and n represent the molar percentage of the structural unit in which they are located in the long carbon chain nylon elastomeric polymer.

[0011] The long carbon chain nylon elastomeric polymer of the present invention comprises a copolymer containing a dynamic reversible bond formed by polyamide and polythioic acid. In certain embodiments of the present invention, the long carbon chain nylon elastomeric polymer of the present invention is a bio-based long carbon chain nylon elastomeric polymer, which is a fully bio-based copolymer formed by a ring-opening click reaction of a polyamide diene monomer of biological origin and thioctic acid, comprising a copolymer containing a dynamic reversible bond formed by a bio-based polyamide and polythioic acid. The long carbon chain nylon elastomeric polymer of the present invention has both recyclable and antibacterial and anti-inflammatory properties. The weight average molecular weight of the long carbon chain nylon elastomeric polymer of the present invention is 2000g / mol to 30000g / mol, preferably 4000g / mol to 12000g / mol.

[0012] The m and n in the long carbon chain nylon elastomeric polymer of the present invention represent the repetition number of the structural unit in which they are located. The structural unit in which the m is located can be called a long carbon chain polyamide diene unit, and the unit in which the n is located can be called a polylipoic acid unit. The m is an integer of 1 to 4, preferably an integer of 1 to 2; the n is an integer of 6 to 40, preferably an integer of 18 to 30.

[0013] In the long carbon chain nylon elastomeric polymer of the present invention, R is selected from aliphatic diamine groups or furan diamine groups. In certain embodiments of the present invention, the long carbon chain nylon elastomeric polymer of the present invention is a bio-based long carbon chain nylon elastomeric polymer, wherein R is selected from aliphatic diamine groups or furan diamine groups of biological origin. Specifically, R is selected from C2 to C 15 Alkanediamine or C6~C 18 Furan diamine. Preferably, the R is selected from 1,3-propylene diamine, 1,4-butylene diamine, 1,5-pentane diamine, 1,6-hexane diamine, 1,8-octanediamine, 1,10-decane diamine or 1,12-dodecane diamine; or, the R is selected from any one of the groups of structures shown in formula a to formula g;

[0014]

[0015]

[0016] The present invention also provides a method for preparing a long carbon chain nylon elastomeric polymer, comprising the following steps:

[0017] reacting lipoic acid and at least one polyamide diene under a protective gas atmosphere to obtain a long carbon chain nylon elastomeric polymer;

[0018] The polyamide diene has a structure of formula 2;

[0019]

[0020] Wherein, the R is selected from aliphatic diamine or furan diamine.

[0021] In the present invention, the reaction between lipoic acid and at least one polyamide diene is specifically a ring-opening click reaction. The long carbon chain nylon elastomeric polymer obtained in the present invention is the same as the above, and will not be described in detail.

[0022] The present invention can polymerize lipoic acid and at least one polyamide diene to obtain a long carbon chain nylon elastomeric polymer. Specifically, a lipoic acid melt and at least one polyamide diene are polymerized, and the polymerization reaction can be carried out without a catalyst and a solvent. The temperature of the polymerization reaction of the present invention is 90°C to 150°C, preferably 135°C, and the time of the polymerization reaction is 4h to 24h; below the reaction temperature of 90°C, the polymerization of lipoic acid is not complete, and the result is a mixture; and above 150°C, the product is partially degraded, and there are free small molecules of lipoic acid in the structure, which affects the mechanical properties of the material. After the polymerization reaction of the present invention, the product obtained by the polymerization reaction is aged in a tetrafluoroethylene mold to obtain a long carbon chain nylon elastomeric polymer with a certain thickness. The aging temperature of the present invention is 100°C to 140°C, preferably 120°C, and the aging time is 1h to 6h, preferably 2h.

[0023] The present invention can also heat-press lipoic acid and at least one polyamide diene to directly obtain a corresponding transparent long carbon chain nylon elastomeric polymer with a certain thickness. The method is simple to operate and does not require a high temperature and high pressure process. The temperature of the heat-press reaction of the present invention is 100°C to 140°C, preferably 120°C; the time of the heat-press reaction is 15min to 30min, preferably 15min.

[0024] The mass ratio of the polyamide diene and thioctic acid of the present invention is (1-4): (3-20), preferably (1-2): (9-15). If the thioctic acid feed ratio is too much> 70%, the obtained copolymer is in a gel state and has no mechanical strength.

[0025] The protective gas of the present invention is selected from any one of argon or nitrogen. The present invention has no particular restrictions on the configuration of the lipoic acid, and D-type, L-type and D / L-type are all acceptable. The present invention also has no particular restrictions on the sources of the protective gas and the lipoic acid, and can be a general commercial product, or can be obtained according to a preparation method well known to those skilled in the art. In some embodiments of the present invention, the lipoic acid is lipoic acid of biological origin.

[0026] In some embodiments of the present invention, the polyamide diene of the present invention is obtained by reacting ω-undecenoic acid ethyl ester and diamine, specifically, by reacting biologically derived ω-undecenoic acid ethyl ester and biologically derived diamine. The polyamide diene of the present invention is prepared by the following steps: ω-undecenoic acid ethyl ester and diamine are subjected to alkaline heating catalytic reaction under the action of a catalyst in a protective gas atmosphere, and the polyamide diene is obtained after recrystallization from ethanol; the catalyst is selected from at least one of sodium methoxide, sodium ethoxide, sodium hydroxide, sodium carbonate, etc.; the amount of the catalyst accounts for 1wt% to 2wt% of the total mass of the ω-undecenoic acid ethyl ester and diamine, preferably 1wt%; the molar ratio of the ω-undecenoic acid ethyl ester to the diamine is (2 to 2.5): 1; the temperature of the alkaline heating catalytic reaction is 55°C to 65°C, preferably 60°C, and the time is 24h to 48h.

[0027] The diamine of the present invention comprises at least one of an aliphatic diamine and an aromatic furan diamine derivative. More specifically, the diamine is selected from at least one of an aliphatic diamine such as 1,3-propylene diamine, 1,4-butylene diamine, 1,5-pentane diamine, 1,6-hexane diamine, 1,8-octanediamine, 1,10-decane diamine or 1,12-dodecane diamine, or the diamine is selected from

[0028] In some other embodiments of the present invention, the polyamide diene of the present invention is obtained by reacting ω-undecenoic acid ethyl ester derived from castor oil and a bio-based diamine; the diamine includes a bio-based aliphatic diamine and a bio-based aromatic furan diamine derivative. The present invention has no special restrictions on the sources of the raw materials such as ω-undecenoic acid ethyl ester, aliphatic diamine and aromatic furan diamine derivative, which are generally commercially available products.

[0029] The present invention also provides a product, at least a part of which is obtained from a polymer material and an optional additional material; the polymer material is obtained from any of the above-mentioned polymers or a polymer obtained by any of the above-mentioned preparation methods. The product of the present invention is a film, a sheet, a coating, a formed or molded product, which can be used as a public health material and applied in the fields of medical devices, textiles, packaging materials and various panels. The product of the present invention can be manufactured in a conventional manner, such as by injection molding, blow molding, extrusion, calendering, etc. The specific operations and conditions are well known to those skilled in the art and can be selected according to actual needs, which will not be repeated here. The additional materials of the present invention can be selectively added or not added, and the additional materials can be selected from additives, such as antioxidants.

[0030] The present invention also provides a method for recovering any of the above-mentioned polymers or polymers obtained by any of the above-mentioned preparation methods or the above-mentioned products, comprising the following steps: soaking any of the above-mentioned polymers or polymers obtained by any of the above-mentioned preparation methods or the above-mentioned products in an alkali solution. The alkali solution of the present invention is an inorganic alkali solution, preferably selected from a sodium hydroxide solution, and most preferably a 0.1wt% sodium hydroxide aqueous solution. The immersion temperature of the present invention is room temperature, specifically 15°C to 35°C, and the immersion time is 24h to 48h, preferably 30h to 42h, and more preferably 36h. In terms of recyclability, the long carbon chain nylon elastomeric polymer of the present invention can achieve monomer recovery under dilute alkali conditions at room temperature, which is also impossible to achieve with traditional nylon recovery (requiring more stringent high temperature and high pressure catalytic conditions); in addition, the present invention also found that although other dynamic bonds such as lipid bonds can be introduced into nylon to achieve recovery, it is impossible to achieve biological functions as the long carbon chain nylon elastomeric polymer of the present invention can achieve multiple properties such as antibacterial and anti-inflammatory functions and mechanical properties.

[0031] The present invention provides a long carbon chain nylon elastomeric polymer, a preparation method and a product thereof, and a recycling method. The present invention effectively adjusts the mechanical properties of the prepared polymer by introducing polylipoic acid into the long carbon chain nylon, and realizes the recyclability, high antibacterial property and good inflammation clearing ability of the prepared material. Experiments show that the long carbon chain nylon elastomeric polymer provided by the present invention has the property of being recyclable, and under the catalytic condition of inorganic alkaline liquid, the recovery rate of the monomer is 85%; the recovered monomer can be recycled, and the mechanical properties remain above 80% of the original. The long carbon chain nylon elastomeric polymer provided by the present invention also has a broad-spectrum bactericidal effect, with a bactericidal rate of more than 95% for Staphylococcus aureus and Escherichia coli, and has good inflammation clearing ability, specifically, it has the effect of clearing TNF-α, IL-6 and IL-8 inflammatory factors. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 A schematic diagram of the synthesis route of the bio-based long carbon chain nylon elastomer material having both recyclability and antibacterial and anti-inflammatory properties described in this application;

[0033] Figure 2 The 1H NMR spectrum of the lipoic acid product obtained in Example 1 of the present invention;

[0034] Figure 3 The infrared spectrum of the lipoic acid product obtained in Example 1 of the present invention is shown in FIG. DETAILED DESCRIPTION

[0035] The present invention discloses a long carbon chain nylon elastomeric polymer, a preparation method and product thereof, and a recycling method. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve it. It is particularly important to point out that all similar substitutions and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention. The method and application of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the method and application of this article without departing from the content, spirit and scope of the present invention to realize and apply the technology of the present invention.

[0036] The present invention melt-polymerizes polyamide diene monomers and lipoic acid to obtain the bio-based long carbon chain nylon elastomer material having both recyclability and antibacterial and anti-inflammatory properties, such as Figure 1 As shown, Figure 1 Schematic diagram of the synthesis route of the bio-based long carbon chain nylon elastomer material with both recyclable and antibacterial and anti-inflammatory properties described in this application.

[0037] The present invention will be further described below in conjunction with embodiments:

[0038] Example 1

[0039] Preparation of polyamide diene monomer: Weigh ω-undecenoic acid ethyl ester and 1,5-pentanediamine in a molar ratio of 2.5:1, mix and dissolve in anhydrous tetrahydrofuran, and react at 60°C for 24 hours (rotation speed is 210 rpm) under nitrogen protection and catalysis of 30% sodium ethanol ethanol solution (the catalyst accounts for 1% of the total mass of ω-undecenoic acid ethyl ester and dibasic fatty amine) under heating and stirring conditions. The crude product obtained after rotary evaporation is recrystallized from ethanol to obtain a white needle-shaped product, which is the polyamide diene monomer.

[0040] Preparation of fat-type elastomer: Take 50 grams of the above-mentioned polyamide diene monomer, add it to the molten reaction liquid of 50 grams of lipoic acid, react for 12 hours under nitrogen protection at 135°C, pour the obtained yellow molten liquid into a polyfluoro mold and age it in a preheated oven at 120°C for 2 hours to obtain a dark yellow transparent long carbon chain nylon elastomer film.

[0041] Recovery of lipoic acid monomer: Take 20 grams of the long carbon chain nylon elastomer film prepared above, cut it into pieces with scissors, add it to 0.1wt% sodium hydroxide aqueous solution and stir for 24 hours, filter and wash with water, the white product after filtration is the propane polyamide diene monomer, and the filtrate is the sodium salt solution of lipoic acid. Add 10wt% dilute hydrochloric acid to the filtrate, adjust the pH value of the filtrate to 7, filter and collect the precipitated lipoic acid product, weigh it after drying, and determine the monomer recovery rate and purity by hydrogen nuclear magnetic resonance and infrared spectroscopy. The monomer recovery rate is 87% and the purity is 90%. Figure 2 and Figure 3 As shown, Figure 2The 1H NMR spectrum of the lipoic acid product obtained in Example 1 of the present invention; Figure 3 The infrared spectrum of the lipoic acid product obtained in Example 1 of the present invention is shown in FIG.

[0042] Recycling: The diene monomers hydrolyzed by the alkaline solution are mixed evenly with lipoic acid, and hot-pressed at 120° C. for 15 minutes to obtain a corresponding recycled membrane material with a certain thickness.

[0043] Example 2

[0044] Preparation of polyamide diene monomer: Weigh ω-undecenoic acid ethyl ester and 1,10-decanediamine in a molar ratio of 2.5:1, mix and dissolve in anhydrous tetrahydrofuran, and react at 60°C for 24 hours (rotation speed is 210 rpm) under nitrogen protection and catalysis of 30% sodium ethanol ethanol solution (the catalyst accounts for 1% of the total mass of ω-undecenoic acid ethyl ester and dibasic fatty amine) to obtain a crude product after rotary evaporation and recrystallization with ethanol to obtain a white needle-shaped product, which is the polyamide diene monomer.

[0045] Preparation of fat-type elastomer: Take 35 grams of the above-mentioned polyamide diene monomer, add it to the molten reaction liquid of 65 grams of lipoic acid, react at 135°C under nitrogen protection for 12 hours, pour the obtained yellow molten liquid into a polyfluoro mold and age it in a preheated oven at 120°C for 2 hours to obtain a dark yellow transparent long carbon chain nylon elastomer film.

[0046] Recovery of lipoic acid monomer: Take 20 grams of the long carbon chain nylon elastomer film prepared above and cut it into pieces with scissors, add it into 0.1wt% sodium hydroxide aqueous solution and stir for 36h, filter and wash with water, the filtered white product is the polyamide diene monomer of 1,10-decanediamine, and the filtrate is the sodium salt solution of lipoic acid. Add 10wt% dilute hydrochloric acid to the filtrate, adjust the pH value of the filtrate to 7, filter and collect the precipitated lipoic acid product, weigh it after drying, and determine the recovery rate and purity of the monomer by hydrogen nuclear magnetic resonance. The monomer recovery rate is 90% and the purity is 92%.

[0047] Recycling: The diene monomers hydrolyzed by the alkaline solution are mixed evenly with lipoic acid, and hot-pressed at 120° C. for 15 minutes to obtain a corresponding recycled membrane material with a certain thickness.

[0048] Example 3

[0049] Preparation of polyamide diene monomer: Weigh ω-undecenoic acid ethyl ester and furan dimethylamine in a molar ratio of 2.5:1, mix and dissolve in anhydrous tetrahydrofuran, and react at 60°C for 36 hours (rotation speed is 210 rpm) under nitrogen protection and catalysis of 30% sodium ethanol ethanol solution (the catalyst accounts for 1% of the total mass of ω-undecenoic acid ethyl ester and dibasic fatty amine) to obtain a crude product after rotary evaporation and recrystallization with ethanol to obtain a white needle-shaped product, which is the polyamide diene monomer.

[0050] Preparation of aromatic elastomer: Take 45 grams of the above-mentioned polyamide diene monomer, add it to the molten reaction liquid of 55 grams of lipoic acid, react for 18 hours under nitrogen protection at 135°C, pour the obtained yellow molten liquid into a polyfluoro mold and age it in a preheated oven at 120°C for 2 hours to obtain a yellow transparent long carbon chain nylon elastomer film.

[0051] Recovery of lipoic acid monomer: Take the above-prepared 20 grams of long carbon chain nylon elastomer film and cut it into pieces with scissors, add it into 0.1wt% sodium hydroxide aqueous solution and stir for 36h, filter water for washing, the filtered white product is the polyamide diene monomer of furan dimethylamine, and the filtrate is the sodium salt solution of lipoic acid. Add 10wt% dilute hydrochloric acid to the filtrate, adjust the pH value of the filtrate to 7, filter and collect the precipitated lipoic acid product, weigh it after drying and determine the recovery rate and purity of the monomer by hydrogen nuclear magnetic, the monomer recovery rate is 88%, and the purity is 80%.

[0052] Recycling: The diene monomers hydrolyzed by the alkaline solution are mixed evenly with lipoic acid, and hot-pressed at 120° C. for 15 minutes to obtain a corresponding recycled membrane material with a certain thickness.

[0053] Example 4

[0054] Preparation of polyamide diene monomer: Weigh ω-undecenoic acid ethyl ester and furan dimethylamine in a molar ratio of 2.5:1, mix and dissolve in anhydrous tetrahydrofuran, and react at 60°C for 36 hours (rotation speed is 210 rpm) under nitrogen protection and catalysis of 30% sodium ethanol ethanol solution (the catalyst accounts for 1% of the total mass of ω-undecenoic acid ethyl ester and dibasic fatty amine). The crude product obtained after rotary evaporation is recrystallized from ethanol to obtain a white needle-shaped product, which is furan dimethylamine-based polyamide diene monomer.

[0055] Weigh ω-undecenoic acid ethyl ester and hexamethylenediamine in a molar ratio of 2.5:1, mix and dissolve in anhydrous tetrahydrofuran, and react at 60°C with stirring for 48 hours (rotation speed is 210 rpm) under nitrogen protection and catalysis of 30% sodium ethoxide ethanol solution (the catalyst accounts for 1% of the total mass of ω-undecenoic acid ethyl ester and dibasic fatty amine). The crude product obtained after rotary evaporation is recrystallized from ethanol to obtain a white needle-shaped product, which is the hexamethylenediamine-based polyamide diene monomer.

[0056] Preparation of fat / aromatic blended elastomer: Take 25 grams of the above-mentioned furandimethylamino polyamide diene monomer and 25 grams of the above-mentioned hexamethylenediamine polyamide diene monomer, add them to the molten reaction liquid of 50 grams of lipoic acid, react at 135°C under nitrogen protection for 24 hours, and pour the obtained yellow molten liquid into a polyfluoro mold and age it in a preheated oven at 120°C for 2 hours to obtain a yellow transparent long carbon chain nylon elastomer film.

[0057] Recovery of lipoic acid monomer: Take the above-prepared 20 grams of long carbon chain nylon elastomer film and cut it into pieces with scissors, add it into 0.1wt% sodium hydroxide aqueous solution and stir for 36h, filter water for washing, the filtered white product is a polyamide diene monomer mixture of furan dimethylamine and hexamethylenediamine, and the filtrate is a sodium salt solution of lipoic acid. Add 10wt% dilute hydrochloric acid to the filtrate, adjust the pH value of the filtrate to 7, filter and collect the precipitated lipoic acid product, weigh it after drying and determine the recovery rate and purity of the monomer by hydrogen nuclear magnetic resonance, the monomer recovery rate is 85%, and the purity is 87%.

[0058] Recycling: The mixed diene monomers hydrolyzed by the alkaline solution and lipoic acid are mixed evenly, and after hot pressing at 120° C. for 15 minutes, a corresponding recycled membrane material with a certain thickness is obtained.

[0059] Example 5

[0060] Preparation of polyamide diene monomer: Weigh ω-undecenoic acid ethyl ester and 1,10-decanediamine in a molar ratio of 2.5:1, mix and dissolve in anhydrous tetrahydrofuran, and react at 60°C for 24 hours (speed of 210 rpm) under nitrogen protection and catalysis of 30% sodium ethanol ethanol solution (the catalyst accounts for 1% of the total mass of ω-undecenoic acid ethyl ester and dibasic fatty amine). The crude product obtained after rotary evaporation is recrystallized from ethanol to obtain a white needle-shaped product, which is 1,10-decanediamine polyamide diene monomer.

[0061] Weigh ω-undecenoic acid ethyl ester and hexamethylenediamine in a molar ratio of 2.5:1, mix and dissolve in anhydrous tetrahydrofuran, and react at 60°C with stirring for 24 to 48 hours (rotation speed is 210 rpm) under nitrogen protection and catalysis of 30% sodium ethoxide ethanol solution (the catalyst accounts for 1% of the total mass of ω-undecenoic acid ethyl ester and dibasic fatty amine). The crude product obtained after rotary evaporation is recrystallized from ethanol to obtain a white needle-shaped product, which is the hexamethylenediamine-based polyamide diene monomer.

[0062] Preparation of mixed fat-type elastomer: Take 20 grams of the above-mentioned hexamethylenediamine polyamide diene monomer and 30 grams of the above-mentioned 1,10-decanediamine polyamide diene monomer, add them to the molten reaction liquid of 50 grams of lipoic acid, react at 135°C under nitrogen protection for 18 hours, and pour the obtained yellow molten liquid into a polyfluoro mold and age it in a preheated oven at 120°C for 2 hours to obtain a yellow transparent long carbon chain nylon elastomer film.

[0063] Recovery of lipoic acid monomer: Take 20 grams of the long carbon chain nylon elastomer film prepared above, cut it into pieces with scissors, add it into 0.1wt% sodium hydroxide aqueous solution and stir for 36h, filter and wash with water, the filtered white product is a mixture of polyamide diene monomers of hexamethylenediamine and 1,10-decanediamine, and the filtrate is a sodium salt solution of lipoic acid. Add 10wt% dilute hydrochloric acid to the filtrate, adjust the pH value of the filtrate to 7, filter and collect the precipitated lipoic acid product, weigh it after drying, and determine the recovery rate and purity of the monomer by hydrogen nuclear magnetic resonance. The monomer recovery rate is 87% and the purity is 92%.

[0064] Recycling: The mixed diene monomers hydrolyzed by the alkaline solution and lipoic acid are mixed evenly, and after hot pressing at 120° C. for 15 minutes, a corresponding recycled membrane material with a certain thickness is obtained.

[0065] Comparative Example 1

[0066] VESTAMID Care ML16 nylon 12 resin from Evonik, Germany.

[0067] Comparative Example 2

[0068] Arkema 7033SA01 medical grade elastomer material.

[0069] Mechanical properties test:

[0070] The recyclable and anti-inflammatory and antibacterial long carbon chain nylon elastomer materials of the above-mentioned Examples 1 to 5 and their corresponding recycled samples and Comparative Examples 1 to 2 were injection molded into 40mm×4mm×2mm strips, and mechanical properties were tested. The results are shown in Table 1. Table 1 is a table of mechanical test results of Examples 1 to 5 and their corresponding recycled samples and Comparative Examples 1 to 2.

[0071] Table 1

[0072]

[0073]

[0074] Note: Comparative Examples 1 to 2 are difficult to recycle under the degradation and recycling conditions described in the present invention.

[0075] As shown in the data in Table 1, compared with commercially available nylon 12 (Comparative Example 1) and nylon elastomer (Comparative Example 2), the mechanical properties of the long carbon chain nylon elastomer material described in the present application can be regulated by controlling the type of polyamide diene monomer and the ratio with thioctic acid, and it also has the characteristics of being recyclable and recoverable. The samples recovered by hot pressing still maintain good mechanical properties, and the recovery rate of its mechanical properties is above 80%.

[0076] Antibacterial effect test:

[0077] The antibacterial effect test was carried out according to the method of China's national standard GB / T 31402-2015 "Test Method for Antibacterial Performance of Plastic Surfaces", and the sample size and culture conditions were adjusted according to the actual situation. The specific operation was as follows: The long carbon chain nylon elastomer materials obtained in Examples 1 to 5 were pressed into 1 cm × 1 cm square slices, irradiated under ultraviolet light for 20 minutes for sterilization, and then the prepared bacterial solution was dripped on the slices, covered with PE film and incubated at 37°C for 6 hours. Ultrasonication for 3 minutes, diluted 100 times and placed on a solid culture medium and cultured at 37°C for 24 hours. The conventional long carbon chain nylon 12 and elastomer materials obtained in Comparative Examples 1 to 2 were used as the control group. The bacteria used for detection were Staphylococcus aureus (S. aureus) ATCC6538 and Escherichia coli (E. coli) ATCC25922. The results are shown in Table 2, which is a table showing the antibacterial test results of the elastomeric materials obtained in Examples 1 to 5.

[0078] Table 2

[0079]

[0080] Inflammatory factor test:

[0081] A 0.5 cm × 0.5 cm square sheet of Example 1 was implanted into the back of mice to establish a trauma infection model. After 8 hours of implantation, the tissue of the implanted site was sliced, and mice not implanted with Example 1 were used as blank groups to test the expression of TNF-α, IL-6 and IL-8 inflammatory factors. The slice results showed that compared with the slices of the infection group, the experimental group implanted with Example 1 could effectively reduce the expression of TNF-α, IL-6 and IL-8 inflammatory factors in the infection site, and the expression levels were comparable to those of the blank group, demonstrating the good ability of the material to clear inflammation.

[0082] As shown in Tables 1 to 2 and the inflammatory factor test data, the recyclable and anti-inflammatory and antibacterial long carbon chain nylon elastomer material described in this application not only has the performance of being recyclable and usable, but also has a broad-spectrum antibacterial effect, and its antibacterial effect is much stronger than that of commercially available nylon 12 and its elastomer (see Comparative Examples 1 to 2). At the same time, the material can also effectively remove TNF-α, IL-6 and IL-8 inflammatory factors, and has obvious advantages in the fields of public health.

[0083] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A long carbon chain nylon elastomeric polymer, characterized in that: It has a unit having a structure shown in Formula 1; Wherein, the R is selected from aliphatic diamine or furan diamine; The m and n represent the number of repetitions of the structural unit in which they are located.

2. The polymer according to claim 1, characterized in that The weight average molecular weight of the long carbon chain nylon elastomeric polymer is 2000 g / mol to 30000 g / mol.

3. The polymer according to claim 1, characterized in that The m is an integer of 1-4, and the n is an integer of 6-40.

4. The polymer material according to claim 1, characterized in that The R is selected from any one of 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, and 1,12-dodecanediamine; Alternatively, the R is selected from any one of the groups represented by the structures of formula a to formula g; 5. A method for preparing the long carbon chain nylon elastomeric polymer according to any one of claims 1 to 4, characterized in that: The following steps are involved: reacting lipoic acid and at least one polyamide diene under a protective gas atmosphere to obtain a long carbon chain nylon elastomeric polymer; The polyamide diene has a structure of formula 2; Wherein, the R is selected from aliphatic diamine or furan diamine.

6. The preparation method according to claim 5, characterized in that: The lipoic acid is biologically derived lipoic acid; The polyamide diene is obtained by reacting bio-derived ω-undecenoic acid ethyl ester and bio-derived diamine.

7. The preparation method according to claim 5, characterized in that: Conducting polymerization reaction between lipoic acid and at least one polyamide diene, wherein the polymerization reaction temperature is 90° C. to 150° C., and the polymerization reaction time is 4 h to 24 h; Alternatively, lipoic acid and at least one polyamide diene are subjected to a hot pressing reaction, wherein the temperature of the hot pressing reaction is 100° C. to 140° C., and the time of the hot pressing reaction is 15 min to 30 min.

8. The preparation method according to claim 5, characterized in that: The lipoic acid and at least one polyamide diene are polymerized and then aged. The aging temperature is 100° C. to 140° C. and the aging time is 1 hour to 6 hours.

9. A product, characterized in that At least a part of the polymer is obtained from the polymer described in any one of claims 1 to 4 or the polymer obtained by the preparation method described in any one of claims 5 to 8 and optional additional materials.

10. A method for recovering the polymer according to any one of claims 1 to 4, the polymer obtained by the preparation method according to any one of claims 5 to 8, or the product according to claim 9, characterized in that: The following steps are involved: The polymer described in any one of claims 1 to 4, or the polymer obtained by the preparation method described in any one of claims 5 to 8, or the product described in claim 9 is soaked in an alkali solution.

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