High-strength and high-toughness pet / pef plastic alloy and preparation method thereof

Abstract

The application discloses a kind of high-strength high-toughness PET / PEF plastic alloy and preparation method thereof, and the preparation method process is as follows: S1: the preparation of PEF: using polymerization reactor, a certain proportion of 2,5-furandicarboxylic acid, ethylene glycol, catalyst, antioxidant and stabilizer are added, esterification is carried out at 210-230 DEG C for 2-2.5 hours, then slowly vacuum to less than 80pa, after 2-3 hours of polycondensation at 240-260 DEG C, press discharge to obtain PEF;S2: the prepared PEF is dried in blast oven, and PET is dried, then a certain proportion of PET, PEF, chain extender and plasticizer are added to high-speed mixer for stirring;S3: the mixed raw materials are added to double-screw extruder, set temperature and screw speed in each zone, after extrusion, granulation is carried out to obtain PET / PEF plastic alloy.The application uses furan polyester PEF as modifier to modify PET, at the same time, the strength and toughness of PET are enhanced, and the compatibility is good, without adding complex compatilizer, high-strength, high-toughness PET / PEF plastic alloy is obtained.

Description

Technical Field

[0001] This invention belongs to the field of organic chemical technology, specifically relating to a high-strength and high-toughness PET / PEF plastic alloy and its preparation method. Background Technology

[0002] PET polyester is a widely used plastic, and it is typically reinforced and modified using olefin-based materials or inorganic reinforcing materials. However, these two types of materials have drawbacks such as poor compatibility, requiring the use of complex compatibilizers. Furthermore, the use of polyolefin toughening agents and inorganic reinforcing modifiers can increase strength while decreasing toughness, or vice versa. Given these shortcomings in existing technologies, a new method for modifying PET polyester to enhance its strength and toughness is needed to improve current processes. Summary of the Invention

[0003] To address the aforementioned issues, this invention provides a high-strength, high-toughness PET / PEF plastic alloy and its preparation method. By using furan polyester PEF as a modifier to modify PET, its strength and toughness are enhanced, and it exhibits good compatibility without the need for complex compatibilizers, thereby obtaining a high-strength, high-toughness, and rapidly crystallizing PET / PEF plastic alloy.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] On the one hand, this invention proposes a method for preparing a high-strength and high-toughness PET / PEF plastic alloy, comprising the following process steps:

[0006] S1: Preparation of PEF: The polymerization reaction was carried out in a polymerization reactor. A certain proportion of 2,5-furandicarboxylic acid, ethylene glycol, catalyst, antioxidant and stabilizer were added. Esterification was carried out at 210℃-230℃ for 2-2.5 hours. Then, the vacuum was slowly evacuated to a vacuum degree of less than 80pa. After polycondensation at 240-260℃ for 2-3 hours, the material was pressurized and discharged to obtain PEF.

[0007] S2: Dry the PEF obtained in step S1 in a forced-air drying oven, and at the same time dry the PET. Then, add a certain proportion of PET, PEF, chain extender and plasticizer into a high-speed mixer for stirring.

[0008] S3: Add the raw materials mixed in step S2 into a twin-screw extruder, set the temperature of each zone and the screw speed, and granulate after extrusion to obtain the PET / PEF plastic alloy.

[0009] Furthermore, the proportions of each component added in step S1 are as follows: 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05-0.1 parts of catalyst, 0.05-0.1 parts of antioxidant, and 0.05-0.1 parts of stabilizer.

[0010] Furthermore, in step S1, the catalyst is one of tetrabutyl titanate, germanium oxide, and antimony glycolate; the antioxidant is one of antioxidant 1010, antioxidant 168, and antioxidant 215; and the stabilizer is one of orthophosphoric acid and triphenyl phosphate.

[0011] Furthermore, the proportions of each component added in step S2 are as follows: 100 parts PET, 1-9 parts PEF, 0.1-0.2 parts chain extender, and 0.1-0.2 parts plasticizer.

[0012] Furthermore, the chain extender mentioned in step S2 is one or both of BASF chain extender 4468 and BASF chain extender 4368CS; the plasticizer is pyromellitic dianhydride.

[0013] Furthermore, in step S3, the temperature of each zone is set to 270-290℃, and the screw speed is set to 40-80 r / min.

[0014] On the other hand, the present invention also proposes a high-strength and high-toughness PET / PEF plastic alloy prepared by the above preparation method.

[0015] Furthermore, the PET / PEF plastic alloy is obtained by blending and extruding granulation using a twin-screw extruder with a composition of 100 parts PET, 1-9 parts PEF, 0.1-0.2 parts chain extender, and 0.1-0.2 parts plasticizer.

[0016] Furthermore, the PET is commercially available polyethylene terephthalate with an intrinsic viscosity of 0.65-0.75.

[0017] Furthermore, the PEF is a self-made polyethylene furanate dicarboxylate with an intrinsic viscosity of 0.7-0.75; it is prepared by esterification and polycondensation of a certain proportion of 2,5-furandicarboxylic acid, ethylene glycol, catalyst, antioxidant, and stabilizer.

[0018] This invention utilizes furan polyester PEF as a modifier to modify PET, enhancing its strength and toughness while maintaining good compatibility. This eliminates the need for complex compatibilizers, resulting in a high-strength, high-toughness, and rapidly crystallizing PET / PEF plastic alloy. The proposed PET / PEF plastic alloy exhibits high strength and toughness, and its crystallization rate can be adjusted by modifying the PEF composition to meet different requirements. DSC scanning reveals a single melting point peak, indicating good compatibility. Attached Figure Description

[0019] Figure 1 This is a schematic diagram showing the crystallization temperature of the PET / PEF blended plastic alloy in different embodiments of the present invention;

[0020] In the figure: F-0, F-1, F-3, F-5, F-7, and F-10 represent the number of PEF parts in the PET / PEF blended plastic alloy as 0 parts (Comparative Example 1), 1 part (Example 6), 3 parts (Example 8), 5 parts (Example 9), 7 parts (Example 10), and 10 parts (Example 11), respectively; Tc is the crystallization temperature. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention. Example 1

[0022] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0023] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET and 1 part PEF together to a high-speed mixer and stir for 20 minutes.

[0024] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Example 2

[0025] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0026] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 1 part PEF, and 0.1 parts BASF chain extender 4368CS to a high-speed mixer and stir for 20 minutes.

[0027] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Example 3

[0028] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0029] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 1 part PEF, and 0.1 parts BASF chain extender 4688 to a high-speed mixer and stir for 20 minutes.

[0030] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Example 4

[0031] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210℃-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0032] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 1 part PEF, and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0033] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Example 5

[0034] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0035] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 1 part PEF, 0.1 parts BASF chain extender 4368CS and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0036] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Example 6

[0037] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0038] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 1 part PEF, 0.1 parts BASF chain extender 4688, and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0039] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Example 7

[0040] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0041] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 1 part PEF, 0.1 parts BASF chain extender 4688, 0.1 parts BASF chain extender 4388CS, and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0042] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Example 8

[0043] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0044] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 3 parts PEF, 0.1 parts BASF chain extender 4468 and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0045] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF alloy. Example 9

[0046] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0047] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 5 parts PEF, 0.1 parts BASF chain extender 4468 and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0048] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF alloy. Example 10

[0049] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0050] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 7 parts PEF, 0.1 parts BASF chain extender 4468 and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0051] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF alloy. Example 11

[0052] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0053] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 10 parts PEF, 0.1 parts BASF chain extender 4468, and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0054] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF alloy. Example 12

[0055] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0056] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PET, 1 part PEF, 0.1 parts BASF chain extender 4468 and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0057] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 60r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Example 13

[0058] 1. Using a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 parts of antioxidant 1010, and 0.05 parts of triphenyl phosphate. Esterify at 210-230℃ for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa. Polycondense at 250℃ for 3 hours, then pressurize and discharge to obtain PEF.

[0059] 2. Dry PEF in a 100℃ forced-air oven for 4 hours; dry PET in a 140℃ oven for 4 hours; then add 100 parts PEF, 3 parts PET, 0.1 parts BASF chain extender 4468 and 0.1 parts pyromellitic dianhydride to a high-speed mixer and stir for 20 minutes.

[0060] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290℃, and the screw speed to 80r / min. After extrusion, granulate to obtain PET / PEF plastic alloy. Comparative Example 1

[0061] PET was dried at 140℃ for 4 hours and then fed into a twin-screw extruder. The temperature of each zone was set to 270-290℃ and the screw speed was 40 r / min. After extrusion, PET was granulated to obtain PET.

[0062] The relevant performance parameters of the PET / PEF plastic alloys obtained in each embodiment and the PET obtained in the comparative example are shown in the table below.

[0063]

[0064] As can be seen from the above embodiments, the strength and toughness of the PET / PEF plastic alloy obtained by adding PEF to PET polyester and then melt-blending and extruding are significantly improved. It is shown that in the range of 1-5 parts of PEF, the strength and toughness are enhanced with the increase of PEF content. However, when the content exceeds 5 parts, the strength increases while the toughness decreases. In addition, chain extenders and plasticizers need to be added during blending to achieve a better blending effect.

[0065] In addition, regarding the crystallization rate, reference... Figure 1 Adding PEF can alter the crystallization rate. A single-part addition results in the greatest acceleration of the crystallization rate, with the accelerating effect decreasing as the proportion increases. (1-5 parts promote crystallization, 5-10 parts reduce it). The crystallization rate is primarily determined by the crystallization temperature; higher temperatures result in a faster crystallization rate.

[0066] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for producing a high-strength high-toughness PET / PEF plastic alloy, characterized by, The preparation method comprises the following steps: S1: preparation of PEF: using a polymerization reactor, adding 2,5-furandicarboxylic acid, ethylene glycol, a catalyst, an antioxidant and a stabilizer in a certain proportion, esterifying at 210-230 DEG C for 2-2.5 hours, then slowly vacuuming to less than 80 pa, and then polycondensing at 240-260 DEG C for 2-3 hours to obtain PEF; S2: drying the PEF prepared in step S1 in a blast oven, and drying PET, then adding PET, PEF, a chain extender and a plasticizer in a certain proportion into a high-speed mixer to stir; S3: adding the mixed raw materials in step S2 into a double-screw extruder, setting the temperature and screw speed of each zone, and then granulating to obtain the PET / PEF plastic alloy; In step S1, the components are added in the following proportions: 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05-0.1 parts of a catalyst, 0.05-0.1 parts of an antioxidant and 0.05-0.1 parts of a stabilizer; In step S2, the components are added in the following proportions: 100 parts of PET, 1-9 parts of PEF, 0.1-0.2 parts of a chain extender and 0.1-0.2 parts of a plasticizer; In step S2, the chain extender is one or both of BASF chain extender 4468 and BASF chain extender 4368CS; and the plasticizer is pyromellitic dianhydride.

2. The method according to claim 1, wherein the PET / PEF plastic alloy has high strength and high toughness. In step S1, the catalyst is one of tetrabutyl titanate, germanium oxide and ethylene glycol antimony; the antioxidant is one of antioxidant 1010, antioxidant 168 and antioxidant 215; and the stabilizer is one of orthophosphoric acid and triphenyl phosphate.

3. The method according to claim 1, wherein the PET / PEF plastic alloy has high strength and high toughness. In step S3, the temperature of each zone is set to 270-290 DEG C, and the screw speed is 40-80 r / min.

4. A high-strength, high-toughness PET / PEF plastic alloy, characterized by, The PET / PEF plastic alloy is prepared by the preparation method in any one of claims 1-3.

5. The high-strength, high-toughness PET / PEF plastic alloy of claim 4, wherein, The PET is commercially available polyethylene terephthalate with an intrinsic viscosity of 0.65-0.

75.

6. The high-strength, high-toughness PET / PEF plastic alloy of claim 5, wherein, The PEF is self-prepared polyethylene furandicarboxylate with an intrinsic viscosity of 0.7-0.75, and is prepared by esterification and polycondensation of 2,5-furandicarboxylic acid, ethylene glycol, a catalyst, an antioxidant and a stabilizer in a certain proportion.

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