High-strength and high-toughness PET / PEF plastic alloy and preparation method thereof

Abstract

The invention discloses a high-strength and high-toughness PET / PEF plastic alloy and a preparation method thereof.The preparation method comprises the following processes that S1, PEF is prepared, specifically, a polymerization reaction kettle is used, 2, 5-furandicarboxylic acid, ethylene glycol, a catalyst, an antioxidant and a stabilizer are added according to a certain proportion, esterification is conducted for 2-2.5 hours at the temperature of 210-230 DEG C, then slow vacuumizing is conducted till the vacuum degree is smaller than 80 pa, and then the PEF is obtained; carrying out polycondensation at 240-260 DEG C for 2-3 hours, and then pressurizing and discharging to obtain PEF; s2, drying the prepared PEF in a blast drying oven, drying PET at the same time, and then adding PET, PEF, a chain extender and a plasticizer into a high-speed mixer according to certain parts by weight for stirring; and S3, adding the mixed raw materials into a double-screw extruder, setting the temperature of each region and the rotating speed of a screw rod, extruding, and granulating to obtain the PET / PEF plastic alloy. According to the invention, the furan polyester PEF is adopted as a modifier to modify PET, the strength and toughness of the PET are enhanced, the compatibility is good, no complex compatilizer is added, and the high-strength and high-toughness PET / PEF plastic alloy is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemical industry, and in particular relates to a high-strength and high-toughness PET / PEF plastic alloy and a preparation method thereof. Background Art

[0002] PET polyester is a widely used plastic, and is usually reinforced and modified by olefin materials or some inorganic reinforcing materials on the market. However, the two types of materials have disadvantages such as poor compatibility and need to be used with complex compatibilizers. In addition, the use of polyolefin toughening agents and inorganic reinforcing additives and modifiers will reduce its toughness while increasing its strength or reduce its strength while increasing its toughness. In view of the above defects in the prior art, it is necessary to improve the existing process and propose a new method for modifying PET polyester to enhance its strength and toughness. Summary of the invention

[0003] In view of the above problems, the present invention provides a high-strength and high-toughness PET / PEF plastic alloy and a preparation method thereof. PET is modified by using furan polyester PEF as a modifier, thereby enhancing its strength and toughness, and having good compatibility without adding complex compatibilizers, thereby obtaining a high-strength, high-toughness, and fast-crystallization PET / PEF plastic alloy.

[0004] In order to achieve the above object, the technical solution adopted by the present invention is: On the one hand, the present invention provides a method for preparing a high-strength and high-toughness PET / PEF plastic alloy, comprising the following process steps: S1: Preparation of PEF: using a polymerization reactor, adding a certain proportion of 2,5-furandicarboxylic acid, ethylene glycol, catalyst, antioxidant and stabilizer, esterification at 210-230°C for 2-2.5 hours, then slowly evacuating to a vacuum degree of less than 80 Pa, polycondensing at 240-260°C for 2-3 hours, and then pressurizing to obtain PEF; S2: drying the PEF obtained in step S1 in a blast oven, and drying the PET at the same time, and then adding a certain proportion of PET, PEF, chain extender and plasticizer into a high-speed mixer for stirring; 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.

[0005] Furthermore, the added portions of the components in step S1 are: 100 portions of 2,5-furandicarboxylic acid, 50 portions of ethylene glycol, 0.05-0.1 portions of catalyst, 0.05-0.1 portions of antioxidant, and 0.05-0.1 portions of stabilizer.

[0006] Furthermore, in step S1, the catalyst is one of tetrabutyl titanate, germanium oxide, and antimony ethylene glycol; the antioxidant is one of antioxidant 1010, antioxidant 168, and antioxidant 215; and the stabilizer is one of orthophosphoric acid and triphenyl phosphate.

[0007] Furthermore, the added portions of the components in step S2 are: 100 portions of PET, 1-9 portions of PEF, 0.1-0.2 portions of chain extender, and 0.1-0.2 portions of plasticizer.

[0008] Furthermore, 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.

[0009] Furthermore, in step S3, the temperature of each zone is set to 270-290° C. and the screw speed is set to 40-80 r / min.

[0010] On the other hand, the present invention also provides a high-strength and high-toughness PET / PEF plastic alloy prepared by the above preparation method.

[0011] Furthermore, the PET / PEF plastic alloy is obtained by mixing and extruding granulation of 100 parts of PET, 1-9 parts of PEF, 0.1-0.2 parts of chain extender and 0.1-0.2 parts of plasticizer using a twin-screw extruder.

[0012] Furthermore, the PET is commercially available polyethylene terephthalate, and its intrinsic viscosity is 0.65-0.75.

[0013] Furthermore, the PEF is a self-made polyethylene furandicarboxylate 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, a catalyst, an antioxidant, and a stabilizer.

[0014] The technical solution of the present invention adopts furan polyester PEF as a modifier to modify PET, thereby enhancing its strength and toughness, and having good compatibility, and no need to add complex compatibilizers, thereby obtaining a PET / PEF plastic alloy with high strength, high toughness and rapid crystallization. The PET / PEF plastic alloy proposed by the present invention has high strength and high toughness, and its crystallization rate can be adjusted by adjusting the PEF component according to different requirements. Through DSC scanning, it can be seen that it is a single melting point peak, indicating that it has good compatibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 Schematic diagram of crystallization temperature of PET / PEF blended plastic alloy in different embodiments of the present invention; In the figure: F-0, F-1, F-3, F-5, F-7, and F-10 respectively represent the proportion of PEF in the PET / PEF blended plastic alloy being 0 part (Comparative Example 1), 1 part (Example 6), 3 parts (Example 8), 5 parts (Example 9), 7 parts (Example 10), and 10 parts (Example 11); Tc is the crystallization temperature. DETAILED DESCRIPTION

[0016] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention. Example 1

[0017] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after condensation at 250°C for 3 hours to obtain PEF.

[0018] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET and 1 part of PEF into a high-speed mixer and stir for 20 minutes.

[0019] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 40r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Example 2

[0020] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after condensation at 250°C for 3 hours to obtain PEF.

[0021] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 1 part of PEF, and 0.1 part of BASF chain extender 4368CS into a high-speed mixer and stir for 20 minutes.

[0022] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 40r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Example 3

[0023] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after polycondensation at 250°C for 3 hours to obtain PEF.

[0024] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 1 part of PEF, and 0.1 part of BASF chain extender 4688 into a high-speed mixer and stir for 20 minutes.

[0025] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 40r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Example 4

[0026] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 parts of triphenyl phosphate, esterify at 210°C-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after condensation at 250°C for 3 hours to obtain PEF.

[0027] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 1 part of PEF, and 0.1 part of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0028] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 40r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Example 5

[0029] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after condensation at 250°C for 3 hours to obtain PEF.

[0030] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 1 part of PEF, 0.1 parts of BASF chain extender 4368CS, and 0.1 parts of pyromellitic dianhydride into a high-speed mixer and stir for 20 minutes.

[0031] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 40r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Example 6

[0032] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after polycondensation at 250°C for 3 hours to obtain PEF.

[0033] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 1 part of PEF, 0.1 parts of BASF chain extender 4688, and 0.1 parts of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0034] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 40r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Example 7

[0035] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after polycondensation at 250°C for 3 hours to obtain PEF.

[0036] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 1 part of PEF, 0.1 parts of BASF chain extender 4688, 0.1 parts of BASF chain extender 4388CS, and 0.1 parts of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0037] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 40r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Example 8

[0038] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after polycondensation at 250°C for 3 hours to obtain PEF.

[0039] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 3 parts of PEF, 0.1 parts of BASF chain extender 4468, and 0.1 parts of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0040] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF alloy. Example 9

[0041] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after condensation at 250°C for 3 hours to obtain PEF.

[0042] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 5 parts of PEF, 44680.1 parts of BASF chain extender, and 0.1 parts of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0043] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF alloy. Example 10

[0044] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after polycondensation at 250°C for 3 hours to obtain PEF.

[0045] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 7 parts of PEF, 0.1 parts of BASF chain extender 4468, and 0.1 parts of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0046] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF alloy. Embodiment 11

[0047] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after polycondensation at 250°C for 3 hours to obtain PEF.

[0048] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 10 parts of PEF, 0.1 parts of BASF chain extender 4468, and 0.1 parts of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0049] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, and the screw speed to 40r / min. After extrusion, granulate to obtain PET / PEF alloy. Example 12

[0050] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after polycondensation at 250°C for 3 hours to obtain PEF.

[0051] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PET, 1 part of PEF, 0.1 parts of BASF chain extender 4468, and 0.1 parts of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0052] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 60r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Example 13

[0053] 1. Use a polymerization reactor, add 100 parts of 2,5-furandicarboxylic acid, 50 parts of ethylene glycol, 0.05 parts of tetrabutyl titanate, 0.05 antioxidant 1010, and 0.05 triphenyl phosphate, esterify at 210-230°C for 2-2.5 hours, then slowly evacuate to a vacuum degree of less than 80 Pa, and pressurize and discharge the material after polycondensation at 250°C for 3 hours to obtain PEF.

[0054] 2. Dry PEF in a forced air oven at 100°C for 4 hours; dry PET at 140°C for 4 hours; then add 100 parts of PEF, 3 parts of PET, 0.1 parts of BASF chain extender 4468, and 0.1 parts of pyromellitic anhydride into a high-speed mixer and stir for 20 minutes.

[0055] 3. Add the mixed raw materials into a twin-screw extruder, set the temperature of each zone to 270-290°C, the screw speed to 80r / min, and granulate after extrusion to obtain PET / PEF plastic alloy. Comparative Example 1

[0056] The PET was dried at 140°C for 4 hours, added into a twin-screw extruder, the temperature of each zone was set at 270-290°C, the screw speed was 40r / min, and PET was obtained by granulation after extrusion.

[0057] 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 following table.

[0058]

[0059] According to 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 when PEF is in the range of 1-5 parts, the strength and toughness are enhanced with the increase of PEF content, and when it exceeds 5 parts, the strength is improved and the toughness is reduced; in addition, chain extenders and plasticizers need to be added to the blending to achieve a better gain effect.

[0060] In addition, the crystallization rate shows that Figure 1 The crystallization rate can be changed after adding PEF. When one part is added, the crystallization rate is accelerated the most, and the promotion effect decreases with the increase of proportion. (1-5 parts promotes crystallization, 5-10 parts reduces crystallization); the crystallization rate mainly refers to the crystallization temperature. The higher the temperature, the faster the crystallization rate.

[0061] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing a high-strength and high-toughness PET / PEF plastic alloy, characterized in that: The process steps include: S1: Preparation of PEF: using a polymerization reactor, adding a certain proportion of 2,5-furandicarboxylic acid, ethylene glycol, catalyst, antioxidant and stabilizer, esterification at 210-230°C for 2-2.5 hours, then slowly evacuating to a vacuum degree of less than 80 Pa, polycondensing at 240-260°C for 2-3 hours, and then pressurizing to obtain PEF; S2: drying the PEF obtained in step S1 in a blast oven, and drying the PET at the same time, and then adding a certain proportion of PET, PEF, chain extender and plasticizer into a high-speed mixer for stirring; 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.

2. The method for preparing a high-strength and high-toughness PET / PEF plastic alloy according to claim 1, characterized in that: The added portions of the components in step S1 are: 100 portions of 2,5-furandicarboxylic acid, 50 portions of ethylene glycol, 0.05-0.1 portions of catalyst, 0.05-0.1 portions of antioxidant, and 0.05-0.1 portions of stabilizer.

3. The method for preparing a high-strength and high-toughness PET / PEF plastic alloy according to claim 1, characterized in that: In step S1, the catalyst is one of tetrabutyl titanate, germanium oxide, and antimony ethylene glycol; the antioxidant is one of antioxidant 1010, antioxidant 168, and antioxidant 215; and the stabilizer is one of orthophosphoric acid and triphenyl phosphate.

4. The method for preparing a high-strength and high-toughness PET / PEF plastic alloy according to claim 1, characterized in that: The added portions of the components in step S2 are: 100 portions of PET, 1-9 portions of PEF, 0.1-0.2 portions of chain extender, and 0.1-0.2 portions of plasticizer.

5. The method for preparing a high-strength and high-toughness PET / PEF plastic alloy according to claim 1, characterized in that: 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.

6. The method for preparing a high-strength and high-toughness PET / PEF plastic alloy according to claim 1, characterized in that: In step S3, the temperature of each zone is set to 270-290° C. and the screw speed is set to 40-80 r / min.

7. A high-strength and high-toughness PET / PEF plastic alloy, characterized in that: The method is prepared according to any one of claims 1 to 6.

8. A high-strength and high-toughness PET / PEF plastic alloy according to claim 7, characterized in that: The composition comprises 100 parts of PET, 1-9 parts of PEF, 0.1-0.2 parts of chain extender and 0.1-0.2 parts of plasticizer, and is mixed and extruded into granules using a twin-screw extruder.

9. A high-strength and high-toughness PET / PEF plastic alloy according to claim 8, characterized in that: The PET is commercially available polyethylene terephthalate, and its intrinsic viscosity is 0.65-0.

75.

10. A high-strength and high-toughness PET / PEF plastic alloy according to claim 9, characterized in that: The PEF is a self-made polyethylene furandicarboxylate 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, a catalyst, an antioxidant, and a stabilizer.

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