High-performance bio-based polyester material and preparation method thereof

Abstract

The invention discloses a high-performance bio-based polyester material and a preparation method thereof. The high-performance bio-based polyester material is prepared from the following components in percentage by mass: 95-99.5% of bio-based polyester, 0.4-4% of glycidyl ester and the balance of a catalyst. Epoxy groups of the catalyst and the catalytic glycidyl ester react with terminal groups of the bio-based polyester to achieve a chain extension crosslinking effect, and due to the improvement of the molecular weight and internal crosslinking, the performance of the bio-based polyester is greatly improved, and the bio-based polyester is easier to form during extrusion processing.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a high-performance bio-based polyester material and a preparation method thereof. Background Art

[0002] With the development of society and the decreasing petroleum resources, bio-based materials have received more and more attention. Bio-based polyester, as a relatively mature bio-based material, has received great attention. At present, bio-based polyester materials are only widely used in packaging bags, habits, films and other fields. However, due to the defects of bio-based polyester materials themselves, such as poor performance and poor processing crystallinity, they are greatly limited in practical applications. At present, in order to improve the processing and performance of bio-based polyester, chain extenders are usually added in the processing of bio-based polyester. The representative chain extender is BASF ADR4468, but the cost of chain extenders is high, which is not conducive to the promotion of bio-based polyester. Summary of the invention

[0003] In view of this, the present invention provides a high-performance bio-based polyester material and a preparation method thereof to solve the problems raised in the above background technology. Suitable catalysts and glycidyl esters are selected and mixed evenly with bio-based polyesters, and then the mixture is mixed and reacted internally by a twin-screw extruder. Due to the presence of catalysts and glycidyl esters, the bio-based polyester reacts. Compared with bio-based polyesters using traditional chain extenders, its room temperature performance is equivalent and the cost is lower. This method is applicable to various bio-based polyester materials, has universality, and can be applied to various different uses.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] In a first aspect, the present invention discloses a high-performance bio-based polyester material, which is prepared from the following components in terms of mass percentage:

[0006] Bio-based polyester 95-99.5%,

[0007] Glycidyl ester 0.4-4%,

[0008] Catalyst Remaining Amount.

[0009] As a further solution of the present invention: the bio-based polyester is at least one of polylactic acid and polybutylene terephthalate-adipate.

[0010] As a further embodiment of the present invention: the cross-linking agent is glycidyl ester.

[0011] As a further solution of the present invention: the catalyst is at least one of 4-dimethylaminopyridine and triphenylphosphine.

[0012] In a second aspect, the present invention discloses a method for preparing the high-performance bio-based polyester material as described above, comprising the following steps:

[0013] The bio-based polyester, glycidyl ester and catalyst are mixed evenly and then put into a twin-screw extruder for extrusion to obtain a high-performance bio-based polyester material.

[0014] As a further solution of the present invention: the temperature of the twin-screw extruder is 170-220° C. and the rotation speed is 120-350 r / min.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] 1. The present invention utilizes a catalyst to catalyze the reaction between the epoxy groups of glycidyl ester and the terminal groups of bio-based polyester to obtain the effect of chain extension and cross-linking. Due to the increase in its molecular weight and internal cross-linking, its performance is greatly improved, and it is easier to shape during extrusion processing.

[0017] 2. The method provided by the present invention is applicable to various types of bio-based polyesters and has excellent universality.

[0018] 3. The method of the present invention uses low-cost raw materials and simple processing and operation methods, and is suitable for large-scale industrial use. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Schematic diagram of the microstructure of high-performance polylactic acid (PLA) after chain extension with TGIC and DMAP. DETAILED DESCRIPTION

[0020] For ease of understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0022] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0023] Polylactic acid PLA, model selected from Fengyuan FY801, Fengyuan FY802, Fengyuan FY201;

[0024] Polybutylene terephthalate-adipate PBAT, brand name KHB21AP11;

[0025] Triglycidyl ester, brand name TGIC, produced by Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0026] Diglycidyl ester, produced by Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0027] Chain extender, brand ADR4468;

[0028] The catalyst used was 4-dimethylaminopyridine, DMAP, produced by Shanghai Aladdin Biochemical Technology Co., Ltd.

[0029] All materials are commercially available conventional products.

[0030] It is to be understood that the above raw materials and reagents are only examples of some specific embodiments of the present invention, so that the technical solution of the present invention is clearer, and it does not mean that the present invention can only use the above reagents, and the specific scope in the claims shall prevail. In addition, the "parts" described in the examples and comparative examples, unless otherwise specified, refer to parts by weight.

[0031] Any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0032] Example 1

[0033] 98 parts of FY801 polylactic acid, 1.8 parts of triglycidyl ester TGIC, and 0.2 parts of catalyst DMAP were put into a blender and mixed evenly, and then poured into a twin-screw extruder at 185°C and 350r / min, and reacted by high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0034] Example 2

[0035] 95 parts of FY801 polylactic acid, 4 parts of triglycidyl ester TGIC, and 1 part of catalyst DMAP were put into a blender and mixed evenly, and then poured into a 200°C, 200r / min twin-screw extruder to react through high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0036] Example 3

[0037] 95 parts of FY201 polylactic acid, 4 parts of triglycidyl ester TGIC, and 1 part of catalyst DMAP were put into a blender and mixed evenly, and then poured into a 200°C, 200r / min twin-screw extruder to react through high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0038] Example 4

[0039] 48 parts of FY801 polylactic acid, 45 parts of FY201 polylactic acid, 5 parts of PBAT, 1.8 parts of triglycidyl ester TGIC, and 0.2 parts of catalyst DMAP were put into a blender and mixed evenly, and then poured into a 200°C, 200r / min twin-screw extruder to react through high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0040] Example 5

[0041] 99.5 parts of FY201 polylactic acid, 0.4 parts of triglycidyl ester TGIC, and 0.1 parts of catalyst DMAP were put into a blender and mixed evenly, and then poured into a twin-screw extruder at 180°C and 350r / min, and reacted by high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0042] Example 6

[0043] 99.5 parts of FY801 polylactic acid, 0.4 parts of triglycidyl ester TGIC, and 0.1 parts of catalyst DMAP were put into a blender and mixed evenly, and then poured into a twin-screw extruder at 180°C and 150r / min, and reacted by high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0044] Example 7

[0045] 95 parts of FY201 polylactic acid, 4 parts of diglycidyl ester, and 1 part of catalyst DMAP were put into a blender and mixed evenly, and then poured into a 200°C, 200r / min twin-screw extruder to react through high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0046] Example 8

[0047] 99 parts of PBAT, 0.8 parts of triglycidyl ester TGIC, and 0.2 parts of catalyst DMAP were put into a blender and mixed evenly, and then poured into a 200°C, 200r / min twin-screw extruder to react through high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0048] Comparative Example 1

[0049] 100 parts of FY201 polylactic acid were poured into a twin-screw extruder at 180°C and 350 r / min, and reacted by high temperature and screw shearing, and pellets were prepared by extrusion, cooling and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0050] Comparative Example 2

[0051] 99.5 parts of FY201 polylactic acid and 0.5 parts of ADR4468 chain extender were put into a blender and mixed evenly, then poured into a twin-screw extruder at 180°C and 350r / min, reacted by high temperature and screw shearing, and pellets were prepared by extrusion, cooling and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0052] Comparative Example 3

[0053] 99.5 parts of FY201 polylactic acid and 0.5 parts of triglycidyl ester TGIC were put into a blender and mixed evenly, and then poured into a twin-screw extruder at 180°C and 150r / min, and reacted by high temperature and screw shearing action, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0054] Comparative Example 4

[0055] 50 parts of FY801 polylactic acid, 45 parts of FY201 polylactic acid, and 5 parts of PBAT were put into a blender and mixed evenly, and then poured into a 200°C, 200r / min twin-screw extruder to react through high temperature and screw shearing, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0056] Comparative Example 5

[0057] 100 parts of FY801 polylactic acid were poured into a twin-screw extruder at 185°C and 350 r / min, and reacted by high temperature and screw shearing, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0058] Comparative Example 6

[0059] 100 parts of PBAT were poured into a twin-screw extruder at 185°C and 350 r / min, and reacted by high temperature and screw shearing, and pellets were prepared by extrusion, cooling, and pelletizing. The pellets were injection molded in an injection molding machine at 210°C.

[0060] The bio-based polyester materials obtained in the examples and comparative examples were injection molded into samples, and tensile tests and melt index tests were performed. The test results are shown in Table 1.

[0061] Table 1

[0062]

[0063]

[0064] Note: The test standards for tensile strength and melt index in Table 1 are GB / T 1040 and GB / T 3682 respectively.

[0065] By comparing Example 5 with Comparative Examples 1 and 2, it is obvious that the use of TGIC and DMAP blended with bio-based polyester, in the same proportion as ADR4468, can effectively achieve chain extension of bio-based polyester, enhance the performance of bio-based polyester, and improve its melt index to improve its extrusion molding effect. Comparing the data of Example 5 with Comparative Examples 2 and 3, it can be found that if DMAP is not added as a catalyst, the chain extension effect is not good when TGIC is added alone. The two have a synergistic effect, and the performance improvement and extrusion molding improvement effect are quite different from ADR4468.

[0066] Although this specification is described according to implementation modes, not every implementation mode includes only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

[0067] Therefore, the above description is only a preferred embodiment of the present application and is not intended to limit the scope of implementation of the present application; that is, all equivalent changes made according to the scope of the claims of the present application are within the protection scope of the claims of the present application.

Claims

1. A high-performance bio-based polyester material, characterized in that: It is prepared by the following components according to mass percentage: Bio-based polyester 95-99.5%, Glycidyl ester 0.4-4%, Catalyst Remaining Amount.

2. The high-performance bio-based polyester material according to claim 1, characterized in that: The bio-based polyester is at least one of polylactic acid and polybutylene terephthalate-adipate.

3. The high-performance bio-based polyester material according to claim 1, characterized in that: The crosslinking agent is glycidyl ester.

4. The high-performance bio-based polyester material according to claim 1, characterized in that: The catalyst is at least one of 4-dimethylaminopyridine and triphenylphosphine.

5. The method for preparing a high-performance bio-based polyester material according to any one of claims 1 to 4, characterized in that: The following steps are involved: The bio-based polyester, glycidyl ester and catalyst are mixed evenly and then put into a twin-screw extruder for extrusion to obtain a high-performance bio-based polyester material.

6. The high-performance bio-based polyester material according to claim 4, characterized in that: The temperature of the twin-screw extruder is 170-220° C. and the rotation speed is 120-350 r / min.

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