A high temperature resistant and degradable TPE material for elastic toys and preparation method thereof

Abstract

The invention discloses a TPE material for a high temperature resistant and degradable elastic toy and a preparation method thereof, and relates to the technical field of children's toy materials. The TPE material for a high temperature resistant and degradable elastic toy prepared by the invention comprises a modified TPE and a cotton fiber filler, wherein the modified TPE is prepared by introducing a furan ring and isoprene into a bio-based thermoplastic polyester elastomer, wherein the bio-based thermoplastic polyester elastomer is prepared by transesterification and melt polycondensation of 2,5-furandicarboxylic acid dimethyl ester, terminal hydroxyl polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole, and the elasticity and mechanical properties of the modified TPE are enhanced, and the cotton fiber filler is prepared by coating a modified polycaprolactone on the surface of the cotton fiber, wherein the modified polycaprolactone is prepared by reacting a polycaprolactone copolymer with ethanolamine, and the polycaprolactone copolymer is prepared by ring-opening polymerization of caprolactone and then with lactide, and the compatibility of the TPE material is enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of children's toy materials, and in particular to a high-temperature resistant and degradable TPE material for elastic toys and a preparation method thereof. Background Art

[0002] In recent years, various funny and interesting "decompression toys" have become more and more popular among young people. However, many of these toys have quality and safety issues. Take the elastic decompression ball, which is common in venting decompression toys, for example. There is a risk of excessive release of volatile organic compounds. Common volatile organic compounds such as benzene, toluene, ethylbenzene, xylene, styrene, etc. can cause immune disorders in the body, affect the function of the central nervous system, and may also affect the digestive system. In severe cases, it can damage the liver and hematopoietic system. On the other hand, some venting decompression toys are filled with liquid. During the squeezing process, if the venting decompression toys break, they may come into contact with the filling liquid. If the filling liquid contains pathogens or microorganisms that are harmful to the human body, it may affect the health of consumers.

[0003] TPE (thermoplastic elastomer) is a polymer material that combines the properties of plastic and rubber. TPE has high elasticity similar to rubber, can withstand repeated stretching and compression without deformation, and exhibits good wear resistance. It is soft in texture, can adapt to various complex shapes and stress conditions, and is suitable for making products that require touch. TPE has good high temperature resistance and aging resistance, is not easy to degrade after long-term use, and maintains good physical properties. It also has chemical resistance and low shrinkage, and can resist corrosion from a variety of chemical substances. Therefore, it is suitable for use as a raw material for "decompression toys", but there are still problems of insufficient mechanical properties and dimensional stability in the process of preparing decompression toys. Therefore, the present invention studies and prepares a high temperature resistant and degradable elastic toy TPE material to solve the above problems. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a high temperature resistant and degradable TPE material for elastic toys and a preparation method thereof.

[0005] The present invention proposes a technical solution to solve the above technical problems: a high temperature resistant and degradable TPE material for elastic toys, comprising modified TPE, cotton fiber filler, polycarbonate, PBS and additives; the modified TPE is prepared by introducing furan ring and isoprene into a bio-based thermoplastic polyester elastomer; the cotton fiber filler is prepared by coating modified polycaprolactone on the surface of cotton fiber.

[0006] Preferably, the bio-based thermoplastic polyester elastomer is prepared by transesterification and melt polycondensation of dimethyl 2,5-furandicarboxylate, terminal hydroxyl polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole.

[0007] Preferably, the modified polycaprolactone is obtained by reacting a polycaprolactone copolymer with ethanolamine; the polycaprolactone copolymer is obtained by ring-opening polymerization of caprolactone and then ring-opening polymerization of lactide.

[0008] Preferably, the auxiliary agent includes an antioxidant, a stabilizer, an antibacterial agent and a flame retardant; the antioxidant is the antioxidant BHT; the stabilizer is epoxidized soybean oil; the antibacterial agent is polyhexamethylene (bis) arc laurate; and the flame retardant is aluminum hypophosphite.

[0009] Preferably, the method for preparing the high temperature resistant and degradable TPE material for elastic toys comprises the following specific steps:

[0010] S1. Under a nitrogen atmosphere, dimethyl 2,5-furandicarboxylate, terminal hydroxy polyisoprene, polyhydroxy fatty acid ester and p-hydroxyanisole were mixed, heated to 170-180° C., stirred and melted, reacted for 1-2 hours, heated to 182-184° C., continued to react for 1-2 hours, added with tetrabutyl titanate catalyst in an amount of 0.02-0.04 times the mass of dimethyl 2,5-furandicarboxylate, heated to 215-225° C., and polycondensed under reduced pressure for 4-6 hours to obtain a modified TPE;

[0011] S2. The polycaprolactone copolymer, 1,4-epoxyhexacyclic ring and deionized water are mixed in a mass ratio of 1 to 2:50:10, stirred evenly, and a mass fraction of 3 to 5% ethanolamine solution of 1 to 3 times the mass of the polycaprolactone copolymer is added, reacted for 30 to 50 minutes, vacuumed, gelled at 60 to 80°C for 10 to 12 hours, and then placed in a refrigerator at 4°C for extraction for 5 to 7 days, the water is replaced every 6 to 8 hours, and finally freeze-dried at -20 to -40°C to obtain modified polycaprolactone;

[0012] S3. epichlorohydrin, cotton fiber and modified polycaprolactone were mixed in a mass ratio of 20:1:0.1-0.4, stirred evenly, heated to 70-80°C, reacted for 3-5h, filtered and washed with deionized water for 3-5 times, and dried at 55-65°C to obtain a cotton fiber filler;

[0013] S4. The modified TPE, cotton fiber filler, polycarbonate, PBS and additives are mixed, stirred evenly, and extruded and granulated at 130-150° C. to obtain a high-temperature resistant and biodegradable TPE material for elastic toys.

[0014] Preferably, in the above step S1., the preparation method of the terminal hydroxyl polyisoprene is as follows: under a nitrogen atmosphere, isoprene, cyclohexane and initiator sec-butyl lithium are heated to 48-52° C. in a mass ratio of 4-5:20:1, reacted for 5-6 hours, and then 0.18-0.22 times the mass of isoprene ethylene oxide is added, reacted for 2-3 hours, precipitated with ethanol and transferred to tetrahydrofuran with a mass of 2-4 times the mass of isoprene, 0.2-0.4 times the mass of isoprene 1 mol / L hydrochloric acid is added, reacted at room temperature for 3-5 hours, and precipitated with ethanol to obtain the terminal hydroxyl polyisoprene.

[0015] Preferably, in the above step S1., the mass ratio of dimethyl 2,5-furandicarboxylate, hydroxy-terminated polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole is 18-20:11:8:0.06-0.08.

[0016] Preferably, in the above step S2., the preparation method of the polycaprolactone copolymer is: 2,2-dihydroxymethylpropionic acid, caprolactone and stannous octoate are mixed in a mass ratio of 200:6:0.1-0.2, the temperature is raised to 45-55°C, the reaction is carried out for 2-4 hours, 0.2-0.5 times the mass of caprolactone in tetrabutyl titanate and 0.2-0.3 times the mass of caprolactone in lactide are added, the reaction is continued for 2-4 hours, the mixture is filtered, washed with deionized water for 3-5 times and dried to obtain the polycaprolactone copolymer.

[0017] Preferably, in the above step S4., the mass ratio of modified TPE, cotton fiber filler, polycarbonate, PBS and auxiliary agent is 50-80:1-10:5-6:10-20:4-5; the auxiliary agent is an anti-aging agent, a stabilizer, an antibacterial agent and a flame retardant in a mass ratio of 1-2:0.8:0.2-0.4:1.

[0018] Preferably, in the above step S4., the extrusion temperature of the extruder is 140-200°C, the temperatures of zones 1 to 8 of the twin-screw extruder are respectively 140-150°C, 160-170°C, 190-200°C, 200-210°C, 190-200°C, 180-190°C, 160-170°C, 160-170°C, and the head temperature is 160-170°C.

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0020] The high temperature resistant and degradable TPE material for elastic toys prepared by the present invention comprises modified TPE, cotton fiber filler, polycarbonate, PBS polybutylene succinate and additives;

[0021] The modified TPE is prepared by introducing furan ring and isoprene into a bio-based thermoplastic polyester elastomer. The bio-based thermoplastic polyester elastomer is prepared by transesterification and melt polycondensation of 2,5-dimethyl furandicarboxylate, terminal hydroxyl polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole. The furan ring and isoprene are introduced into the thermoplastic polyester elastomer, and the hard segment is poly(2,5-butylene furandicarboxylate) and the soft segment is polyhydroxyalkanoate, so as to enhance the elasticity and mechanical properties of the modified TPE.

[0022] Cotton fiber filler is prepared by coating modified polycaprolactone on the surface of cotton fiber. Modified polycaprolactone is prepared by the reaction of polycaprolactone copolymer and ethanolamine. Polycaprolactone copolymer is prepared by ring-opening polymerization of caprolactone and then ring-opening polymerization of lactide. Ethanolamine reacts with polycaprolactone copolymer to form amide bonds. Hydrophilic amino groups and hydroxyl groups are grafted on the surface of polycaprolactone and coated on the surface of cotton fiber. Cotton fiber filler is introduced into TPE material to enhance the size compatibility of TPE material. DETAILED DESCRIPTION

[0023] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention. Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art.

[0024] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the high temperature resistant and degradable elastic toy TPE materials prepared in the examples and comparative examples as follows:

[0025] Tensile properties: The high temperature resistant and degradable elastic TPE materials for toys prepared in the examples and comparative examples were tested with reference to ASTM D-412.

[0026] Biodegradation rate: The high temperature resistant and degradable elastic TPE materials for toys prepared in the examples and comparative examples were tested for biodegradation rate according to GB / T19275.

[0027] Compatibility: The high temperature resistant and biodegradable elastic toy TPE materials prepared in the examples and comparative examples were visually observed to see whether their appearance was uniform or whether there were delaminations or cracks.

[0028] Example 1

[0029] The preparation method of the high temperature resistant and degradable TPE material for elastic toys in this embodiment is as follows:

[0030] S1. In a nitrogen atmosphere, isoprene, cyclohexane and initiator sec-butyl lithium are heated to 48°C in a mass ratio of 4:20:1, reacted for 5 hours, and then 0.18 times the mass of isoprene ethylene oxide is added, reacted for 2 hours, precipitated with ethanol and transferred to tetrahydrofuran with a mass of 2 times the mass of isoprene, and 0.2 times the mass of isoprene 1 mol / L hydrochloric acid is added, reacted at room temperature for 3 hours, and precipitated with ethanol to obtain terminal hydroxyl polyisoprene; Under nitrogen atmosphere, dimethyl 2,5-furandicarboxylate, terminal hydroxyl polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole were mixed in a mass ratio of 18:11:8:0.06, heated to 170°C, stirred and melted, reacted for 1 hour, heated to 182°C, continued to react for 1 hour, added with tetrabutyl titanate as a catalyst with a mass of 0.02 times that of dimethyl 2,5-furandicarboxylate, heated to 215°C, and polycondensed under reduced pressure for 4 hours to obtain modified TPE;

[0031] S2. 2,2-dihydroxymethylpropionic acid, caprolactone and stannous octoate were mixed in a mass ratio of 200:6:0.1, heated to 45°C, reacted for 2h, tetrabutyl titanate with a mass of 0.2 times that of caprolactone and lactide with a mass of 0.2 times that of caprolactone were added, the reaction was continued for 2h, filtered, washed with deionized water for 3 to 5 times and dried to obtain a polycaprolactone copolymer; polycaprolactone copolymer, 1,4-epoxyhexacyclic ring and deionized water were mixed in a mass ratio of 1:50:10, stirred evenly, 3% ethanolamine solution with a mass fraction of 1 times that of the polycaprolactone copolymer was added, reacted for 40min, vacuumized, gelled at 60°C for 10h, then placed in a refrigerator at 4°C for extraction for 5d, water was replaced every 6h, and finally freeze-dried at -20°C to obtain a modified polycaprolactone;

[0032] S3. Epichlorohydrin, cotton fiber and modified polycaprolactone were mixed in a mass ratio of 20:1:0.1, stirred evenly, heated to 70°C, reacted for 3h, filtered and washed with deionized water 3 times, and dried at 55°C to obtain a cotton fiber filler;

[0033] S4. The modified TPE, cotton fiber filler, polycarbonate, PBS and additives are mixed, stirred evenly, and then extruded and granulated at 130°C. The mass ratio of the modified TPE, cotton fiber filler, polycarbonate, PBS and additives is 50:1:5:10:4, and the mass ratio of the additives is 1:0.8:0.2:1, including anti-aging agent, antioxidant BHT, stabilizer, epoxy soybean oil, antibacterial agent, polyhexamethylene (bis) arc laurate and flame retardant aluminum hypophosphite. The extrusion temperature of the extruder is 140°C, and the temperatures of zones 1 to 8 of the twin-screw extruder are 140°C, 160°C, 190°C, 200°C, 190°C, 180°C, 160°C, 160°C, and the head temperature is 160°C, thereby obtaining a high-temperature resistant and degradable TPE material for elastic toys.

[0034] Example 2

[0035] The preparation method of the high temperature resistant and degradable TPE material for elastic toys in this embodiment is as follows:

[0036] S1. Under nitrogen atmosphere, isoprene, cyclohexane and initiator sec-butyl lithium were heated to 50°C in a mass ratio of 4.5:20:1, reacted for 5.5 hours, and then 0.2 times the mass of isoprene ethylene oxide was added, reacted for 2.5 hours, precipitated with ethanol and transferred to tetrahydrofuran 3 times the mass of isoprene, and 0.3 times the mass of isoprene 1 mol / L hydrochloric acid was added, reacted at room temperature for 4 hours, and precipitated with ethanol to obtain terminal hydroxyl polyisoprene; Under nitrogen atmosphere, dimethyl 2,5-furandicarboxylate, terminal hydroxyl polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole were mixed in a mass ratio of 19:11:8:0.07, heated to 175°C, stirred to melt, reacted for 1.5 hours, heated to 183°C, continued to react for 1.5 hours, added with tetrabutyl titanate as a catalyst with a mass of 0.03 times that of dimethyl 2,5-furandicarboxylate, heated to 220°C, and polycondensed under reduced pressure for 5 hours to obtain modified TPE;

[0037] S2. 2,2-dihydroxymethylpropionic acid, caprolactone and stannous octoate were mixed in a mass ratio of 200:6:0.15, heated to 50°C, reacted for 3h, tetrabutyl titanate with a mass of 0.4 times that of caprolactone and lactide with a mass of 0.25 times that of caprolactone were added, the reaction was continued for 3h, filtered, washed 4 times with deionized water and dried to obtain a polycaprolactone copolymer; polycaprolactone copolymer, 1,4-epoxyhexacyclic ring and deionized water were mixed in a mass ratio of 1.5:50:10, stirred evenly, 4% ethanolamine solution with a mass fraction of 2 times that of the polycaprolactone copolymer was added, reacted for 40min, vacuumized, gelled at 70°C for 11h, then placed in a refrigerator at 4°C for extraction for 6d, water was replaced every 7h, and finally freeze-dried at -30°C to obtain a modified polycaprolactone;

[0038] S3. Epichlorohydrin, cotton fiber and modified polycaprolactone were mixed in a mass ratio of 20:1:0.2, stirred evenly, heated to 75°C, reacted for 4 hours, filtered and washed with deionized water 4 times, and dried at 60°C to obtain a cotton fiber filler;

[0039] S4. The modified TPE, cotton fiber filler, polycarbonate, PBS and additives are mixed, stirred evenly, and then extruded and granulated at 140°C. The mass ratio of the modified TPE, cotton fiber filler, polycarbonate, PBS and additives is 65:6:5.5:15:4.5, and the mass ratio of the additives is 1.5:0.8:0.3:1, including the antioxidant BHT, the stabilizer epoxy soybean oil, the antibacterial agent polyhexamethylene (bis) arc laurate and the flame retardant aluminum hypophosphite. The extrusion temperature of the extruder is 1700°C, and the temperatures of zones 1 to 8 of the twin-screw extruder are 145°C, 165°C, 195°C, 205°C, 195°C, 185°C, 165°C, and 165°C, respectively. The head temperature is 160-170°C, and a high-temperature resistant and degradable TPE material for elastic toys is obtained.

[0040] Example 3

[0041] The preparation method of the high temperature resistant and degradable TPE material for elastic toys in this embodiment is as follows:

[0042] S1. In a nitrogen atmosphere, isoprene, cyclohexane and initiator sec-butyl lithium are heated to 52°C in a mass ratio of 5:20:1, reacted for 6 hours, and then 0.22 times the mass of isoprene ethylene oxide is added, reacted for 3 hours, precipitated with ethanol and transferred to tetrahydrofuran 4 times the mass of isoprene, 0.4 times the mass of isoprene 1 mol / L hydrochloric acid is added, reacted at room temperature for 5 hours, and precipitated with ethanol to obtain terminal hydroxyl polyisoprene; Under nitrogen atmosphere, dimethyl 2,5-furandicarboxylate, terminal hydroxyl polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole were mixed in a mass ratio of 20:11:8:0.08, heated to 180°C, stirred to melt, reacted for 2 hours, heated to 184°C, continued to react for 2 hours, added with tetrabutyl titanate as a catalyst with a mass of 0.04 times that of dimethyl 2,5-furandicarboxylate, heated to 225°C, and polycondensed under reduced pressure for 6 hours to obtain modified TPE;

[0043] S2. 2,2-dihydroxymethylpropionic acid, caprolactone and stannous octoate were mixed in a mass ratio of 200:6:0.2, heated to 55°C, reacted for 4 hours, tetrabutyl titanate with a mass of 0.5 times that of caprolactone and lactide with a mass of 0.3 times that of caprolactone were added, the reaction was continued for 4 hours, filtered, washed with deionized water 5 times and dried to obtain a polycaprolactone copolymer; polycaprolactone copolymer, 1,4-epoxyhexacyclic ring and deionized water were mixed in a mass ratio of 2:50:10, stirred evenly, 3 times the mass of the polycaprolactone copolymer and a mass fraction of 5% ethanolamine solution were added, reacted for 50 minutes, vacuumed, gelled at 80°C for 12 hours, and then placed in a refrigerator at 4°C for extraction for 7 days, the water was replaced every 8 hours, and finally freeze-dried at -40°C to obtain a modified polycaprolactone;

[0044] S3. Epichlorohydrin, cotton fiber and modified polycaprolactone were mixed in a mass ratio of 20:1:0.4, stirred evenly, heated to 80°C, reacted for 5h, filtered and washed with deionized water 5 times, and dried at 65°C to obtain a cotton fiber filler;

[0045] S4. The modified TPE, cotton fiber filler, polycarbonate, PBS and additives are mixed, stirred evenly, and then extruded and granulated at 150°C. The mass ratio of the modified TPE, cotton fiber filler, polycarbonate, PBS and additives is 80:10:6:20:5, and the mass ratio of the additives is 2:0.8:0.4:1, including the antioxidant BHT, the stabilizer epoxy soybean oil, the antibacterial agent polyhexamethylene (bis) arc laurate and the flame retardant aluminum hypophosphite. The extrusion temperature of the extruder is 200°C, and the temperatures of zones 1 to 8 of the twin-screw extruder are 150°C, 170°C, 200°C, 210°C, 200°C, 190°C, 170°C, 170°C, and the head temperature is 170°C, thereby obtaining a high-temperature resistant and degradable TPE material for elastic toys.

[0046] Comparative Example 1

[0047] The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between the high temperature resistant and degradable elastic toy TPE material and Example 2 is that step S1. is different, and step S1. is modified as follows: in a nitrogen atmosphere, 2,5-furandicarboxylic acid dimethyl ester, 1,4-propylene glycol, polyhydroxyalkanoate and p-hydroxyanisole are mixed in a mass ratio of 19:11:8:0.07, heated to 175°C, stirred and melted, reacted for 1.5h, heated to 183°C, continued to react for 1.5h, added with a catalyst of tetrabutyl titanate with a mass of 0.03 times that of 2,5-furandicarboxylic acid dimethyl ester, heated to 220°C, and polycondensed under reduced pressure for 5h to obtain a modified TPE.

[0048] Comparative Example 2

[0049] The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between the high temperature resistant and degradable elastic toy TPE material and Example 2 is that step S1. is different, and step S1. is modified as follows: under a nitrogen atmosphere, isoprene, cyclohexane and initiator sec-butyl lithium are heated to 50°C in a mass ratio of 4.5:20:1, reacted for 5.5 hours, and then 0.2 times the mass of isoprene ethylene oxide is added, reacted for 2.5 hours, precipitated with ethanol and the precipitate is transferred to 3 times the mass of isoprene tetrahydrofuran, and 0.3 times the mass of isoprene 1 mol / L hydrochloric acid, react at room temperature for 4 hours, and precipitate with ethanol to obtain terminal hydroxyl polyisoprene; under a nitrogen atmosphere, isophthalic acid, terminal hydroxyl polyisoprene, polyhydroxyalkanoic acid ester and p-hydroxyanisole are mixed in a mass ratio of 19:11:8:0.07, heated to 175°C, stirred to melt, reacted for 1.5 hours, heated to 183°C, continued to react for 1.5 hours, added with tetrabutyl titanate as a catalyst with a mass of 0.03 times that of isophthalic acid, heated to 220°C, and polycondensed under reduced pressure for 5 hours to obtain modified TPE.

[0050] Comparative Example 3

[0051] The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between the high temperature resistant and degradable elastic toy TPE material and Example 2 is that step S1. is different, and step S1. is modified as follows: in a nitrogen atmosphere, isophthalic acid, 1,4-propylene glycol, polyhydroxyalkanoate and p-hydroxyanisole are mixed in a mass ratio of 19:11:8:0.07, heated to 175°C, stirred and melted, reacted for 1.5h, heated to 183°C, continued to react for 1.5h, added with a catalyst of tetrabutyl titanate with a mass of 0.03 times that of isophthalic acid, heated to 220°C, and polycondensed under reduced pressure for 5h to obtain a modified TPE.

[0052] Comparative Example 4

[0053] The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between the high temperature resistant and degradable TPE material for elastic toys and Example 2 is that the high temperature resistant and degradable TPE material for elastic toys includes modified TPE and cotton fiber.

[0054] Effect example

[0055] Table 1 below shows the performance analysis results of the high temperature resistant and degradable elastic toy TPE materials prepared by Examples 1 to 3 of the present invention and Comparative Examples 1 to 4:

[0056] Table 1

[0057]

[0058]

[0059] By comparing the experimental data of the examples and the comparative examples in Table 1, it can be clearly found that the high temperature resistant and degradable TPE materials for elastic toys prepared by using Examples 1, 2 and 3 have excellent elasticity, mechanical properties and compatibility.

[0060] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 1, Comparative Example 2, Comparative Example 3, it can be found that the introduction of furan ring and isoprene into the thermoplastic polyester elastomer, and the hard segment is poly(butylene 2,5-furandicarboxylate) and the soft segment is polyhydroxyalkanoate, enhances the elasticity and mechanical properties of the modified TPE.

[0061] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 4, it can be found that ethanolamine reacts with the polycaprolactone copolymer to form an amide bond, hydrophilic amino groups and hydroxyl groups are grafted on the surface of the polycaprolactone, and the cotton fiber filler is coated on the surface of the cotton fiber, thereby introducing the cotton fiber filler into the TPE material, enhancing the compatibility and improving the dimensional stability of the TPE material.

[0062] Obviously, the above embodiments are merely examples for clearly illustrating the embodiments of the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. However, these obvious changes or modifications derived from the spirit of the present invention are still within the scope of protection of the present invention.

Claims

1. A high temperature resistant and degradable TPE material for elastic toys, characterized in that: The invention comprises modified TPE, cotton fiber filler, polycarbonate, PBS and additives; the modified TPE is prepared by introducing furan ring and isoprene into bio-based thermoplastic polyester elastomer; the cotton fiber filler is prepared by coating modified polycaprolactone on the surface of cotton fiber.

2. The high temperature resistant and degradable TPE material for elastic toys according to claim 1, characterized in that: The bio-based thermoplastic polyester elastomer is prepared by transesterification and melt polycondensation of dimethyl 2,5-furandicarboxylate, terminal hydroxyl polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole.

3. The high temperature resistant and degradable TPE material for elastic toys according to claim 1, characterized in that: The modified polycaprolactone is prepared by reacting a polycaprolactone copolymer with ethanolamine; the polycaprolactone copolymer is prepared by ring-opening polymerization of caprolactone and then ring-opening polymerization of lactide.

4. The high temperature resistant and degradable TPE material for elastic toys according to claim 1, characterized in that: The auxiliary agent comprises an anti-aging agent, a stabilizer, an antibacterial agent and a flame retardant; the anti-aging agent is an antioxidant BHT; the stabilizer is epoxidized soybean oil; the antibacterial agent is polyhexamethylene (bis) arc laurate; and the flame retardant is aluminum hypophosphite.

5. A method for preparing a high temperature resistant and degradable TPE material for elastic toys as claimed in claim 1, characterized in that: The specific steps include: S1. Under a nitrogen atmosphere, dimethyl 2,5-furandicarboxylate, terminal hydroxy polyisoprene, polyhydroxy fatty acid ester and p-hydroxyanisole were mixed, heated to 170-180° C., stirred and melted, reacted for 1-2 hours, heated to 182-184° C., continued to react for 1-2 hours, added with tetrabutyl titanate catalyst in an amount of 0.02-0.04 times the mass of dimethyl 2,5-furandicarboxylate, heated to 215-225° C., and polycondensed under reduced pressure for 4-6 hours to obtain a modified TPE; S2. The polycaprolactone copolymer, 1,4-epoxyhexacyclic ring and deionized water are mixed in a mass ratio of 1 to 2:50:10, stirred evenly, and a mass fraction of 3 to 5% ethanolamine solution of 1 to 3 times the mass of the polycaprolactone copolymer is added, reacted for 30 to 50 minutes, vacuumed, gelled at 60 to 80°C for 10 to 12 hours, and then placed in a refrigerator at 4°C for extraction for 5 to 7 days, the water is replaced every 6 to 8 hours, and finally freeze-dried at -20 to -40°C to obtain modified polycaprolactone; S3. epichlorohydrin, cotton fiber and modified polycaprolactone were mixed in a mass ratio of 20:1:0.1-0.4, stirred evenly, heated to 70-80°C, reacted for 3-5h, filtered and washed with deionized water for 3-5 times, and dried at 55-65°C to obtain a cotton fiber filler; S4. The modified TPE, cotton fiber filler, polycarbonate, PBS and additives are mixed, stirred evenly, and then extruded and granulated at 130-150° C. to obtain a high-temperature resistant and biodegradable TPE material for elastic toys.

6. The method for preparing a high temperature resistant and degradable TPE material for elastic toys according to claim 5, characterized in that: In the above step S1., the preparation method of terminal hydroxyl polyisoprene is as follows: under a nitrogen atmosphere, isoprene, cyclohexane and initiator sec-butyl lithium are heated to 48-52° C. in a mass ratio of 4-5:20:1, reacted for 5-6 hours, and then 0.18-0.22 times the mass of isoprene ethylene oxide is added, reacted for 2-3 hours, precipitated with ethanol and transferred to tetrahydrofuran with a mass of 2-4 times the mass of isoprene, 0.2-0.4 times the mass of isoprene 1 mol / L hydrochloric acid is added, reacted at room temperature for 3-5 hours, and precipitated with ethanol to obtain terminal hydroxyl polyisoprene.

7. The method for preparing a high temperature resistant and degradable TPE material for elastic toys according to claim 5, characterized in that: In the above step S1., the mass ratio of dimethyl 2,5-furandicarboxylate, terminal hydroxy polyisoprene, polyhydroxyalkanoate and p-hydroxyanisole is 18-20:11:8:0.06-0.

08.

8. The method for preparing a high temperature resistant and degradable TPE material for elastic toys according to claim 5, characterized in that: In the above step S2., the preparation method of the polycaprolactone copolymer is: 2,2-dihydroxymethylpropionic acid, caprolactone and stannous octoate are mixed in a mass ratio of 200:6:0.1-0.2, the temperature is raised to 45-55°C, the reaction is carried out for 2-4 hours, 0.2-0.5 times the mass of caprolactone tetrabutyl titanate and 0.2-0.3 times the mass of caprolactone lactide are added, the reaction is continued for 2-4 hours, the mixture is filtered, washed with deionized water for 3-5 times and dried to obtain the polycaprolactone copolymer.

9. The method for preparing a high temperature resistant and degradable TPE material for elastic toys according to claim 5, characterized in that: In the above step S4., the mass ratio of modified TPE, cotton fiber filler, polycarbonate, PBS and auxiliary agent is 50-80:1-10:5-6:10-20:4-5; the auxiliary agent is an anti-aging agent, a stabilizer, an antibacterial agent and a flame retardant in a mass ratio of 1-2:0.8:0.2-0.4:

1.

10. The method for preparing a high temperature resistant and degradable TPE material for elastic toys according to claim 9, characterized in that: In the above step S4., the extrusion temperature of the extruder is 140-200°C, the temperatures of zones 1 to 8 of the twin-screw extruder are respectively 140-150°C, 160-170°C, 190-200°C, 200-210°C, 190-200°C, 180-190°C, 160-170°C, 160-170°C, and the head temperature is 160-170°C.

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