High-strength high-deformation bio-based polyester elastomer and preparation method thereof

Abstract

The invention discloses a high-strength and high-deformation bio-based polyester elastomer and a preparation method thereof, and belongs to the technical field of composite material preparation, the high-strength and high-deformation bio-based polyester elastomer comprises the following raw materials by weight: 100 parts of a total polymer matrix, 15-40 parts of a filler, 0-0.5 part of an activator and 0.5-1.5 parts of a vulcanizing agent; wherein the total polymer matrix consists of bio-based polyester and another bio-based material epoxidized natural rubber, and the mass ratio of the bio-based polyester to the epoxidized natural rubber is (1: 0)-(3: 1). The bio-based polyester elastomer is prepared from the raw materials in a mechanical blending manner, and compared with pure polyester, the tensile strength and the elongation at break of the polyester elastomer are remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite material preparation, and particularly relates to a high-strength and high-deformation bio-based polyester elastomer and a preparation method thereof. Background Art

[0002] Bio-based polyester compounds synthesized relying on biomass resources contain a large number of ester groups in their molecular structures and have good biodegradable properties. In the application of materials, they can effectively solve problems such as the difficult degradation and pollution of traditional polymer materials. At the same time, due to biomass reasons, polyester compounds are free from the dependence on petroleum of traditional polymer materials, meeting the new material development concept of green, low-carbon, environmental protection and sustainability.

[0003] As a representative of bio-based materials, the development of bio-based polyester elastomers provides a new way for the application of traditional rubber elastomers. However, the low relative molecular mass and low cross-linking strength of polyester elastomers limit their application. Traditionally, the physical and mechanical properties of rubber composites can be significantly improved by the reinforcement of fillers. Some studies have shown that adding inorganic nano-scale silica during the in-situ synthesis of polyester elastomers can enhance the mechanical strength of polyester elastomers. The tensile strength of the material can reach 5.3 MPa, which is 5 times that of pure polyester elastomers, but the elongation at break is only about 93% (Wu Yan, Liu Quanyong, Shi Rui, etc. Preparation and properties of nano-silica reinforced biodegradable polyester elastomers [J]. Polymer Materials Science and Engineering, 2010, 26(5): 147 - 150.); and for industrial production, this process also has problems such as the removal of solvents in the subsequent polymer and product drying, posing higher requirements for the existing mature industrial production of polyester elastomers. In addition, introducing kaolin (sheet silicate) and halloysite (tubular silicate) in the traditional mechanical blending method does not show obvious reinforcing effects. This is mainly limited by the low relative molecular mass of polyester elastomers, which cannot produce good shear dispersion with inorganic particles during the mixing process. More importantly, the hydrogen bond interaction between this type of silicate particles and polyester is weak. These two effects result in the filler additives being unable to achieve the due reinforcing effect, and the material cannot meet the use requirements of high strength and high deformation.

[0004] Therefore, there is an urgent need to provide a high-strength and high-deformation bio-based polyester elastomer and a preparation method thereof. Summary of the Invention

[0005] In view of the above technical problems, the present invention provides a high-strength and high-deformation bio-based polyester elastomer and a preparation method thereof.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention:

[0008] A high-strength and high-deformation bio-based polyester elastomer, calculated by weight parts, comprises the following raw materials:

[0009] 100 parts of total polymer matrix, 15 - 40 parts of filler, 0 - 0.5 part of activator, and 0.5 - 1.5 parts of vulcanizing agent;

[0010] Wherein, the total polymer matrix is composed of bio-based polyester and epoxidized natural rubber, and the mass ratio of the bio-based polyester to the epoxidized natural rubber is 1∶0 to 3∶1;

[0011] The filler is at least one of precipitated silica, fumed silica, or carbon black-silica composite hybrid particles.

[0012] Beneficial effects: Compared with the prior art, in the present invention, epoxidized natural rubber is introduced into the bio-based polyester, and the ring-opening reaction helps the formation of the cross-linked structure in the process of forming the elastomer. The polar interaction between the polyester and the filler (spherical structure rich in hydroxyl groups, where the hydroxyl content ranges from 0.5 wt.% to 5 wt.% of silica) effectively weakens the aggregation of the filler itself, greatly improving the dispersion of the filler in the system, thereby improving the comprehensive mechanical properties of the composite material.

[0013] Optionally, the mass ratio of the bio-based polyester to the epoxidized natural rubber (ENR) is 3∶1.

[0014] Optionally, the high-strength and high-deformation bio-based polyester elastomer, calculated by weight parts, comprises the following raw materials:

[0015] 100 parts of total polymer matrix, 30 - 40 parts of filler, 0.5 part of activator, and 1 part of vulcanizing agent.

[0016] Optionally, the bio-based polyester is prepared from alcohol substances (at least one of binary alcohol monomers synthesized from biomass raw materials such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, or butenediol) and acid substances (at least one of binary acid monomers synthesized from biomass raw materials such as succinic acid, sebacic acid, itaconic acid).

[0017] Beneficial effects: According to the structural composition characteristics of the bio-based polyester material defined by the present invention, it is more conducive to forming hydrogen bond interactions with silica, improving the mechanical properties of the finally prepared bio-based polyester elastomer. In addition, alcohols (1,2-propanediol, 1,3-propanediol, 1,4-butanediol or butenediol) and acid substances (succinic acid, sebacic acid, itaconic acid) are all extracted and synthesized from biomass raw materials (such as corn starch, natural vegetable oil, Corynebacterium glutamicum, glucose, etc.), getting rid of the dependence on petroleum of traditional polymer materials, meeting the new material development concept of green, low-carbon, environmental protection and sustainability, and having biodegradability.

[0018] Optionally, the epoxy degree of the epoxidized natural rubber is 20-50, and this material is also prepared from the natural biomass material natural rubber. The epoxy degree is the percentage of double bonds in natural rubber that are epoxidized.

[0019] Optionally, the filler is at least one of precipitated silica, fumed silica or carbon black-silica composite hybrid particles;

[0020] Among them, the mass ratio of carbon black to silica in the carbon black-silica composite hybrid particles is 1:2-0:1.

[0021] Optionally, the activator is at least one of tetrabutylammonium bromide, sodium hydroxide, potassium hydroxide or triethylamine.

[0022] Optionally, the vulcanizing agent is an organic peroxide vulcanizing agent, including at least one of dicumyl peroxide (DCP), benzoyl peroxide (BPO), di-tert-butyl peroxide (DTBP) or 1,1-bis(di-tert-butylperoxy)-3,3,5-trimethylcyclohexane.

[0023] The second technical solution of the present invention:

[0024] A preparation method of a high-strength and high-deformation bio-based polyester elastomer, comprising the following steps:

[0025] Using the mechanical blending method, the bio-based polyester, epoxidized natural rubber, filler, activator and vulcanizing agent are kneaded evenly, and then hot-pressed into shape to prepare the high-strength and high-deformation bio-based polyester elastomer.

[0026] Beneficial effects: By means of traditional mechanical blending (such as open mill mixing, internal mixer mixing, and extrusion), another bio-based material, epoxidized natural rubber (ENR), is introduced into the polyester matrix. The macromolecular characteristics of ENR strengthen the mixing and shearing effect of the matrix to improve the dispersion of inorganic fillers such as silica or carbon black-silica hybrid particles in the polyester matrix, strengthen the hydrogen bond interaction between polyester and filler particles, and at the same time, the ring-opening reaction and hydrogen bond interaction between ENR and filler particles further enhance the interfacial interaction between the matrix polymer and filler particles. The two work together synergistically. Compared with pure polyester, the tensile strength of the composite material (bio-based polyester elastomer) is increased by 5-15 times, and the elongation at break is increased by 1.5-3.0 times.

[0027] Optionally, the temperature during the mixing process is 60°C to 80°C.

[0028] Optionally, the conditions during the hot pressing and forming process are as follows:

[0029] The temperature is 170°C to 180°C, the pressure is 11 MPa to 15 MPa, and the forming time is 3 to 7 minutes.

[0030] Compared with the prior art, the present invention has the following advantages and technical effects:

[0031] 1. The present invention relies on a simple bio-based polymer as the matrix of the composite material, and the prepared polyester elastomer has obvious biodegradable characteristics compared with traditional materials;

[0032] 2. By designing a cross-linked structure with synergistic hydrogen bond-covalent bond interaction (mainly hydrogen bonds), the prepared composite material (bio-based polyester elastomer) exhibits practical characteristics of high strength and high deformation, laying a good foundation for the subsequent development and application of bio-based polyesters;

[0033] 3. The raw materials in the formulation system of the composite material of the present invention are relatively simple, which improves the pollution and environmental protection problems caused by the large variety and large dosage of auxiliaries in the traditional vulcanization system to a certain extent. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0035] Figure 1 is the infrared spectrum diagram of the bio-based polyester elastomer prepared in Example 1 of the present invention;

[0036] Figure 2 is a schematic view of the SEM morphology of the brittle fracture surface of the bio-based polyester elastomer prepared in Example 1 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0037] A detailed description of various exemplary embodiments of the present invention will now be given. This detailed description should not be considered as a limitation on the present invention, but rather as a more detailed description of certain aspects, features, and implementation schemes of the present invention.

[0038] It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0039] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the said documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0040] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the present invention specification are obvious to those skilled in the art. The present invention specification and examples are merely exemplary.

[0041] Regarding the use of "comprising", "including", "having", "containing", etc. in this article, they are all open-ended terms, meaning including but not limited to.

[0042] An embodiment of the present invention provides a method for preparing a high-strength and high-deformation bio-based polyester elastomer, comprising the following steps:

[0043] Mechanically blend a bio-based polyester with epoxidized natural rubber (ENR), add fillers after kneading for 2 min, maintain a certain kneading temperature, continue kneading for 10 min, then add an activator and a vulcanizing agent, and continue kneading for 3 min to obtain a polyester elastomer kneaded rubber. Heat press the aforementioned kneaded rubber at a specific temperature and pressure to finally obtain a high-strength and high-deformation bio-based polyester elastomer.

[0044] In some alternative embodiments, the bio-based polyester is prepared from at least one of diol monomers such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol or butenediol synthesized from biomass raw materials and at least one of dicarboxylic acid monomers such as succinic acid (butanedioic acid), sebacic acid, itaconic acid synthesized from biomass raw materials.

[0045] In some alternative embodiments, the epoxidation degree of epoxidized natural rubber (ENR) is 20-50.

[0046] In some alternative embodiments, the mass ratio of the bio-based polyester to ENR is 1:0 to 3:1;

[0047] In some alternative embodiments, the mechanical blending includes at least one of open milling on a two-roll mill, mixing in an internal mixer, and mixing by screw extrusion;

[0048] In some alternative embodiments, the mixing temperature is 60°C to 80°C;

[0049] In some alternative embodiments, the filler is at least one of precipitated silica, fumed silica or carbon black-silica composite hybrid particles, wherein the filler dosage accounts for 15-40 wt% of the total polymer matrix. The total polymer matrix is a blend obtained by homogenizing the bio-based polyester compound and epoxidized natural rubber.

[0050] In some alternative embodiments, the mass ratio of carbon black to silica in the carbon black-silica composite hybrid particles is 1:2 to 0:1; wherein the carbon black is at least one of high abrasion furnace black, reinforcing carbon black or semi-reinforcing carbon black;

[0051] In some alternative embodiments, the activator is mainly used to promote the ring-opening reaction of the epoxy group. The activator is at least one of tetrabutylammonium bromide, sodium hydroxide, potassium hydroxide or triethylamine, and the dosage of the activator accounts for 0% to 0.5% of the total polymer matrix;

[0052] In some alternative embodiments, the vulcanizing agent is an organic peroxide vulcanizing agent, including at least one of dicumyl peroxide (DCP), benzoyl peroxide (BPO), di-tert-butyl peroxide (DTBP) or 1,1-bis(di-tert-butylperoxy)-3,3,5-trimethylcyclohexane, and the dosage is 0.5% to 1.5% of the total polymer matrix;

[0053] In some alternative embodiments, the temperature during the hot pressing and molding process of the mixed rubber is 170°C to 180°C, the pressure is 11 MPa to 15 MPa, and the molding time is 3 to 7 minutes.

[0054] In some alternative embodiments, the tensile strength of the bio-based polyester elastomer prepared by the above preparation method is increased by 5 to 15 times compared to pure polyester, and the elongation at break is increased by 1.5 to 3.0 times.

[0055] An embodiment of the present invention also provides a bio-based polyester elastomer prepared by the above preparation method.

[0056] In the present invention, "phr", unless otherwise specified, all refer to parts by mass.

[0057] All raw materials used in the present invention are obtained by purchasing on the market. The precipitated silica (hydroxyl content is ~3%, the shape of the silica is spherical particles, and the particle size is 0.1 to 5 μm) used in the following examples is purchased from Shenzhen Huana Xinyang Technology Co., Ltd.; epoxidized natural rubber (ENR-40, ENR-50) is purchased from Shandong Kepler Biotechnology Co., Ltd.; the bio-based polyester compound used in the following Examples 1-4 is prepared from a diol (1,3-propanediol, 1,4-butanediol, and butenediol, with a molar ratio of 1:1:1) and a diacid (succinic acid, sebacic acid, with a molar ratio of 1:1) according to a molar ratio of 3:2. The preparation process refers to the invention patent CN202011291623.0 (a bio-based polyester elastomer softening modified polyester plastic composite material and preparation method). The finally prepared bio-based polyester has Mn = 17202, Mw = 44003, Mz = 88366, and a degree of polymerization of 36.

[0058] The technical solution of the present invention will be further described below through examples.

[0059] Example 1: (Polyester: ENR = 3:1, 30 phr SiO 2 )

[0060] 1) Plasticize the bio-based polyester compound (polyester, the same below) and epoxidized natural rubber (ENR-40, epoxy degree 40) according to a mass ratio of 3:1 on a two-roll mill for 2 min. The total is 100 phr to obtain a homogenized blend (total polymer matrix, the same below);

[0061] 2) Under the open-milling state, weigh 30 phr of precipitated silica and add it to the blend obtained in step 1), and continue open-milling for 10 min. During this period, turn the material multiple times to promote the dispersion of silica in the blend. The temperature of the mixing roll is maintained at 60 °C;

[0062] 3) Then add 0.5 phr of tetrabutylammonium bromide and 1.0 phr of dicumyl peroxide (DCP) in sequence, and continue mixing for 3 min before ending;

[0063] 4) The obtained blend is subjected to hot pressing at a forming temperature of 175 °C, a pressure of 13 MPa, and a time of 4 min to obtain a bio-based polyester elastomer.

[0064] Figure 1 This is the infrared spectrum of the bio-based polyester elastomer prepared in this example. Based on this spectrum, the hydrogen bond interaction in the matrix of the bio-based polyester elastomer is analyzed. From Figure 1 it can be seen that the hydroxyl stretching vibration absorption peak of silica in the bio-based polyester elastomer moves from the original 3384 cm -1 to 3358 cm -1 , and the stretching vibration absorption peaks of C=O and C-O in the polyester component of the bio-based polyester elastomer move from the original 1728 cm -1 and 1153 cm -1 to 1722 cm -1 and 1148 cm -1 , respectively, showing a typical trend of moving to lower frequency and lower wavenumber, which proves the existence of hydrogen bond interaction in the bio-based polyester elastomer; at the same time, the symmetric stretching vibration absorption peak of the epoxy group at 1243 cm -1 , the asymmetric stretching vibration absorption peaks at 871 cm -1 and 841 cm -1 all disappear after the formation of the bio-based polyester elastomer, indicating that the epoxy group undergoes a ring-opening reaction during the preparation of the bio-based polyester elastomer, facilitating the formation of a co-crosslinked structure in the system. In summary, this infrared spectrum proves the mechanism of the synergistic action of hydrogen bonds and epoxy ring-opening in the bio-based polyester elastomer.

[0065] Figure 2 This is the schematic SEM morphology of the brittle fracture surface of the bio-based polyester elastomer prepared in this example; from Figure 2 it can be seen that silica is well dispersed in the polyester matrix, and no obvious aggregates are observed, indicating that the polar interaction between polyester and silica effectively weakens the self-aggregation of silica itself, resulting in a significant improvement in the comprehensive mechanical properties of the bio-based polyester elastomer composite.

[0066] Example 2: (Polyester: ENR = 3:1, 40 phr SiO 2 )

[0067] 1) The bio-based polyester compound and epoxidized natural rubber (ENR-40, epoxy degree 40) are kneaded on a two-roll mill for 2 min at a mass ratio of 3:1, with a total of 100 phr for both, to obtain a homogenized blend;

[0068] 2) In the open mill state, weigh 40 phr of precipitated silica and add it to the blend obtained in step 1), and continue open milling for 10 min. During this period, promote the dispersion of silica in the blend by turning the material over multiple times, and keep the temperature of the mixing rolls at 60 °C;

[0069] 3) Add 0.5 phr of tetrabutylammonium bromide and 1.0 phr of dicumyl peroxide (DCP) in sequence, and continue mixing for 3 min before ending;

[0070] 4) Hot press the blend or mixed rubber obtained by mixing, with a forming temperature of 175 °C, a pressure of 13 MPa, and a time of 5 min to obtain a bio-based polyester elastomer.

[0071] Example 3: (Polyester: ENR = 4:1, 25 phr CB-SiO 2 = 1:4)

[0072] 1) Plasticize the bio-based polyester compound and epoxidized natural rubber (ENR-50, epoxy degree 50) in a mass ratio of 4:1 on a two-roll open mill for 2 min. The total of the two is 100 phr to obtain a homogenized blend;

[0073] 2) In the open mill state, weigh 25 phr of carbon black N234-precipitated silica composite particles and add them to the blend in step 1). The mass ratio of carbon black N234 to precipitated silica is 1:4, and continue open milling for 10 min. During this period, promote the dispersion of silica in the blend by turning the material over multiple times, and keep the temperature of the mixing rolls at 70 °C;

[0074] 3) Add 0.3 phr of tetrabutylammonium bromide and 1.5 phr of dicumyl peroxide (DCP) in sequence, and continue mixing for 3 min before ending;

[0075] 4) Hot press the blend or mixed rubber obtained by mixing, with a forming temperature of 175 °C, a pressure of 14 MPa, and a time of 5 min to obtain a bio-based polyester elastomer.

[0076] Example 4: (Polyester∶ENR = 1∶0, 30 phr SiO 2 )

[0077] 1) Plasticize the bio-based polyester compound on a two-roll open mill for 2 min, and its dosage is 100 phr;

[0078] 2) In the open mill state, weigh 30 phr of precipitated silica and add it to the blend in step 1), and continue open milling for 10 min. During this period, promote the dispersion of silica in the blend by turning the material over multiple times, and keep the temperature of the mixing rolls at 65 °C;

[0079] 3) Add 1.0 phr of dicumyl peroxide (DCP), and continue mixing for 3 min before ending;

[0080] 4) Thermally press and mold the blend or the mixed rubber obtained from mixing. The molding temperature is 175 °C, the pressure is 13 MPa, and the time is 5 min to obtain the bio - based polyester elastomer.

[0081] Comparative Example 1 (using bio - based pure polyester (100 phr) as the raw material to prepare the elastomer)

[0082] The difference from the preparation process used in Example 1 is that it does not add ENR, precipitated silica, and tetrabutylammonium bromide. Other preparation processes, condition parameters, and raw material dosages are the same as those in Example 1.

[0083] Comparative Example 2

[0084] The difference from Comparative Example 1 is that 30 phr of halloysite filler is added, and other preparation processes and condition parameters are the same as those in Comparative Example 1.

[0085] Comparative Example 3

[0086] The difference from Comparative Example 1 is that 30 phr of kaolin filler is added, and other preparation processes and condition parameters are the same as those in Comparative Example 1.

[0087] Comparative Example 4

[0088] The difference from the preparation process used in Example 1 is that 30 phr of precipitated silica in step 2) is replaced with an equal weight of halloysite, and other preparation processes and condition parameters are the same as those in Example 1.

[0089] Comparative Example 5

[0090] Carbon black - reinforced pure polyester elastomer (literature source: Fang Bowen, Kang Hailan, Wang Zhen, etc. Oil resistance of bio - based polyester elastomer / carbon black composites [J]. Synthetic Rubber Industry, 2014, 37(4): 315 - 318. DOI: 10.3969 / j.issn.1000 - 1255.2014.04.019):

[0091] 100 parts of BEE (bio - based pure polyester), 40 parts of carbon black, kneaded in a Banbury mixer for 40 min. The tensile strength of the vulcanized and molded elastomer reaches 12.1 MPa, but the elongation at break is only 263%. It can also be highly reinforced, but it cannot meet the requirements for large deformations.

[0092] Comparative Example 6

[0093] Addition of nano-silica in in-situ synthesis of polyester (Literature source: Wu Yan, Liu Quanyong, Shi Rui, etc. Preparation and properties of nano-silica reinforced biodegradable polyester elastomers [J]. Polymer Materials Science & Engineering, 2010, 26(5): 147-150. DOI: CN KI:SUN:GFZC.0.2010-05-043.)

[0094] 20 parts of nano-silica, 100 parts of pure polyester, the tensile strength of the composite elastomer is 5.3 MPa, and the elongation at break is only 93%.

[0095] Effect verification

[0096] The mechanical property parameters of the bio-based polyester elastomers prepared in Examples 1-4 and the elastomers prepared in Comparative Examples 1-4 were detected using the test standard of GBT 528-2009, and the comparison results are as follows:

[0097] Table 1

[0098]

[0099] Conclusion: As can be seen from Table 1, compared with pure polyester elastomer: the modulus at a specified elongation, tensile strength and elongation at break of the bio-based polyester elastomer in Example 1 are all significantly improved. Among them, the tensile strength reaches 11.30 MPa, an increase of 11 times; the elongation at break reaches 658%, an increase of 2.54 times, showing the characteristics of an excellent high-strength and high-deformation polyester elastomer; the modulus at a specified elongation, tensile strength and elongation at break of the bio-based polyester elastomer in Example 2 are all significantly improved. Among them, the tensile strength reaches 10.81 MPa, an increase of 10.5 times; the elongation at break reaches 670%, an increase of 2.60 times, showing the characteristics of an excellent high-strength and high-deformation polyester elastomer; the modulus at a specified elongation, tensile strength and elongation at break of the bio-based polyester elastomer in Example 3 are all significantly improved. Among them, the tensile strength reaches 13.50 MPa, an increase of 13.1 times; the elongation at break reaches 460%, an increase of 1.8 times, showing the characteristics of an excellent high-strength and high-deformation polyester elastomer; the modulus at a specified elongation, tensile strength and elongation at break of the bio-based polyester elastomer in Example 4 are all significantly improved compared with pure polyester. Among them, the tensile strength reaches 8.50 MPa, an increase of 8.2 times; the elongation at break reaches 415%, an increase of 1.6 times, showing the characteristics of an excellent high-strength and high-deformation polyester elastomer. In addition, it can also be seen from Table 1 that compared with Comparative Example 1, halloysite is added to the elastomer in Comparative Example 2, and its strength is equivalent to that of the pure bio-based polyester in Comparative Example 1, without obvious reinforcing effect; in Comparative Example 3, kaolin is added to the pure bio-based polyester, and its tensile strength and elongation at break are not significantly improved compared with the pure bio-based polyester; Comparative Example 4 is based on Example 1, replacing precipitated silica with halloysite, and the tensile strength and elongation at break of the obtained elastomer are also much lower than those of Examples 1-4 of the present invention. That is, the above comparative examples prove from the side that adding specific fillers (silica or carbon black-silica hybrid particles with higher hydroxyl groups and spherical structures) to bio-based polyesters (pure polyesters or mixtures of polyesters and epoxidized natural rubber) defined by the present invention can significantly improve the mechanical properties of bio-based elastomers.

[0100] The above is only the preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A high-strength and high-deformation bio-based polyester elastomer, characterized in that: According to weight parts, it includes the following raw materials: 100 parts total polymer matrix, 15-40 parts filler, 0-0.5 parts activator and 0.5-1.5 parts vulcanizing agent; Wherein, the total polymer matrix is ​​composed of bio-based polyester and epoxidized natural rubber, and the mass ratio of the bio-based polyester to the epoxidized natural rubber is 1:0 to 3:1; The filler is at least one of precipitated silica, fumed silica or carbon black-silicon dioxide composite hybrid particles.

2. The high-strength and high-deformation bio-based polyester elastomer according to claim 1, characterized in that: The mass ratio of the bio-based polyester to the epoxidized natural rubber is 3:

1.

3. The high-strength and high-deformation bio-based polyester elastomer according to claim 1, characterized in that: The high-strength and high-deformation bio-based polyester elastomer comprises the following raw materials in parts by weight: 100 parts total polymer matrix, 30-40 parts filler, 0.5 parts activator and 1 part vulcanizing agent.

4. The high-strength and high-deformation bio-based polyester elastomer according to claim 1, characterized in that: The bio-based polyester is prepared from at least one of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol or butene glycol and at least one of succinic acid, sebacic acid and itaconic acid.

5. The high-strength and high-deformation bio-based polyester elastomer according to claim 1, characterized in that: The epoxidation degree of the epoxidized natural rubber is 20-50.

6. The high-strength and high-deformation bio-based polyester elastomer according to claim 1, characterized in that: The mass ratio of carbon black to silicon dioxide in the carbon black-silicon dioxide composite hybrid particles is 1:2 to 0:

1.

7. The high-strength and high-deformation bio-based polyester elastomer according to claim 1, characterized in that: The activator is at least one of tetrabutylammonium bromide, sodium hydroxide, potassium hydroxide or triethylamine; and / or The vulcanizing agent is at least one of dicumyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide or 1,1-bis(di-tert-butylperoxy)-3,3,5-trimethylcyclohexane.

8. A method for preparing a high-strength and high-deformation bio-based polyester elastomer, characterized in that: The following steps are involved: The bio-based polyester, epoxidized natural rubber, filler, activator and vulcanizer are uniformly mixed by mechanical blending, and then hot-pressed to prepare the high-strength and high-deformation bio-based polyester elastomer according to any one of claims 1 to 7.

9. The method for preparing a high-strength and high-deformation bio-based polyester elastomer according to claim 8, characterized in that: The temperature during the mixing process is always maintained at 60°C to 80°C.

10. The method for preparing a high-strength and high-deformation bio-based polyester elastomer according to claim 8, characterized in that: The conditions in the hot pressing process are: The temperature is 170℃~180℃, the pressure is 11MPa~15MPa, and the molding time is 3~7min.

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