A PET material with good ductility and preparation method thereof

Abstract

This invention proposes a PET material with good ductility and its preparation method. The raw materials for preparing the PET material include: 0.2-8 wt% of acrylate polymer, 3-8 wt% of toughening agent, 0.1-1 wt% of antioxidant, 0.1-1 wt% of lubricant, and the balance being PET resin. The acrylate polymer is obtained by polymerizing styrene, glycidyl methacrylate, methyl methacrylate, and butyl methacrylate. The PET material prepared by this invention has an increased molecular weight, improving its viscosity and mechanical properties, enhancing its stability during processing, improving its ductility, and increasing its hydrophobicity and heat resistance.

Description

Technical Field

[0001] This invention relates to the field of C08L47 / 00 technology, specifically to a PET material with good ductility and its preparation method. Background Technology

[0002] PET materials have a long degradation cycle in the natural environment, and their recycling has become increasingly popular to alleviate their environmental impact. However, the low molecular weight and low intrinsic viscosity of PET materials and recycled PET limit their industrial processing applications. To increase the molecular weight of PET and improve its processing performance and mechanical properties, existing technologies often add various additives during PET preparation and processing. Chinese patent CN112279985A discloses a chain extender applicable to PET, which increases the molecular weight and improves the processing performance of PET. The polymer monomers of this chain extender are 2-methylene-1,3-dioxane, styrene, glycidyl methacrylate, acrylonitrile, and 2-methylene-1,3-dioxane, and a trithiocarbonate chain transfer agent is also added. However, the steric hindrance of the groups in the polymer monomers of the chain extender used in this patent limits the reactivity of the reactive groups in the prepared chain extender. Chinese patent CN108440924B discloses a low-flow, easily processed PET, which improves the viscosity of PET and enhances its processing performance by adding carboxyl addition chain extender and isocyanate chain extender.

[0003] Based on this, this application proposes a PET material with good ductility and its preparation method, which improves the ductility, mechanical properties and processing performance of the PET material by adding acrylate polymers, toughening agents and other components. Summary of the Invention

[0004] This invention proposes a PET material with good ductility. The raw materials for preparing the PET material include: 0.1-1 wt% of acrylate polymer and the balance PET resin; the intrinsic viscosity of the PET resin is 0.50-0.68 dL / g.

[0005] In a preferred embodiment, the raw materials for preparing the PET material further include: 0.1-10 wt% toughening agent, 0.1-1 wt% antioxidant, and 0.1-3 wt% lubricant.

[0006] In a preferred embodiment, the raw materials for preparing the PET material include: 0.2-8 wt% of acrylate polymer, 3-8 wt% of toughening agent, 0.1-1 wt% of antioxidant, 0.1-1 wt% of lubricant, and the balance being PET resin.

[0007] In a preferred embodiment, the raw materials for preparing the PET material include: 0.5 wt% acrylate polymer, 6 wt% toughening agent, 1 wt% antioxidant, 0.5 wt% lubricant, and the balance PET resin.

[0008] In a preferred embodiment, the weight-average molecular weight of the acrylate polymer is 3,000-80,000. More preferably, the weight-average molecular weight of the acrylate polymer is 3,000-20,000.

[0009] In a preferred embodiment, the polymerizing monomers in the acrylate polymer include acrylates, and the molecular structure of the acrylates is as follows: Wherein R is selected from at least one of C1-C15 carbon-numbered alkanes, C6-C10 carbon-numbered cycloalkanes, epoxide alkanes, and hydroxyalkyl; and A is selected from at least one of C1-C3 alkyl and hydroxyalkyl.

[0010] In a preferred embodiment, R is selected from epoxide alkanes or C1-C15 carbon alkane.

[0011] In this application, C1-C15 carbon alkane refers to alkanes with 1-15 carbon atoms; C6-C10 carbon cycloalkanes refer to cycloalkanes with 6-10 carbon atoms; epoxide alkanes refer to alkanes with an epoxy group in their molecular structure; and hydroxyalkyl refers to alkyl groups with a hydroxyl group attached to the terminal carbon atom.

[0012] More preferably, the acrylate polymer is selected from at least one of methyl methacrylate, ethyl methacrylate, lauryl methacrylate, 2-butyloctyl methacrylate, ethyl hydroxymethacrylate, cyclohexyl isobutylene acrylate, glycidyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, and 6-hydroxyhexyl methacrylate.

[0013] In a preferred embodiment, the acrylate is glycidyl methacrylate, methyl methacrylate, or butyl methacrylate, in a content ratio of (50-70):(3-10):1.

[0014] In a preferred embodiment, the acrylate polymer contains 68-85 wt% acrylates. More preferably, the content is 75 wt%.

[0015] In a preferred embodiment, the polymer monomers of the acrylate polymer further include at least one of olefin monomers, cycloalkenone monomers, polyol monomers, and epoxy monomers.

[0016] In a preferred embodiment, the monomers of the acrylate polymer further include olefinic monomers. More preferably, the monomers of the acrylate polymer further include styrene.

[0017] During the experiment, the applicant discovered that the acrylate polymers prepared using styrene, glycidyl methacrylate, methyl methacrylate, and butyl methacrylate as monomers increased the reactivity of acrylate polymers by improving the polymerization reactivity between styrene and methacrylates. Therefore, when added to PET resin, it can increase the reaction sites with PET material, improve the mixing uniformity of PET with PET, increase the viscosity of PET material, improve the crystallinity of PET material, improve the stability of PET material during processing, and improve its mechanical properties.

[0018] In a preferred embodiment, the mass ratio of the toughening agent to the acrylate polymer is (5-10):1.5. More preferably, the mass ratio of the toughening agent to the acrylate polymer is 6:1.

[0019] In a preferred embodiment, the toughening agent is selected from at least one of styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, acrylonitrile-styrene-butadiene copolymer, and methyl methacrylate-olefin copolymer.

[0020] In a preferred embodiment, the toughening agent is an ethylene-acrylic acid copolymer.

[0021] In this application, the acrylic acid content in the ethylene-acrylic acid copolymer is selected to be 10-25 wt%, and more preferably, the acrylic acid content in the ethylene-acrylic acid copolymer is selected to be 20 wt%.

[0022] During the experiment, the applicant discovered that when ethylene-acrylic acid copolymer with an acrylic acid content of 20 wt% is added, it can participate in the chain extension process of PET material through the reactivity of the active groups. This not only further increases the molecular weight and viscosity of PET material, but also improves the ductility of PET material due to the introduction of long carbon chains. Furthermore, it improves the hydrophobicity and heat resistance of PET material, and further improves the stability of PET material in processing and subsequent use.

[0023] In a preferred embodiment, the antioxidant is selected from at least one of alcohol ester antioxidants, phenolic ester antioxidants, and phosphite antioxidants.

[0024] Preferably, the alcohol ester antioxidant is selected from at least one of distearate thiodipropionate, dilaurate thiodipropionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0025] In a preferred embodiment, the antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0026] In a preferred embodiment, the lubricant is selected from at least one of amide compounds, stearic acid metal soaps, fatty acid esters, and hydrocarbons.

[0027] In a preferred embodiment, the lubricant is a fatty acid ester, more preferably, the fatty acid ester is pentaerythritol stearate.

[0028] The present invention also proposes a method for preparing a PET material with good extensibility, comprising the following steps: mixing PET resin, acrylate polymer, toughening agent, antioxidant and lubricant evenly, and extruding and granulating using a twin-screw extruder.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. The PET material prepared by this invention incorporates an acrylate polymer prepared using styrene, glycidyl methacrylate, methyl methacrylate, and butyl methacrylate as monomers. By increasing the polymerization reactivity of the monomers in the acrylate polymer, the reactivity of the acrylate polymer is improved, thereby increasing the reaction sites between the acrylate polymer and the PET material, improving the mixing uniformity of the acrylate polymer and PET, increasing the viscosity of the PET material, improving the crystallinity of the PET material, improving the stability of the PET material during processing, and improving its mechanical properties.

[0031] 2. The PET material prepared by this invention also incorporates an ethylene-acrylic acid copolymer with an acrylate polymer mass ratio of 6:1, further limiting the acrylic acid content in the ethylene-acrylic acid copolymer to 20wt%. This allows the ethylene-acrylic acid copolymer to participate in the chain extension process of the PET material, increasing the molecular weight and viscosity of the PET material. Furthermore, the introduction of long carbon chains improves the ductility of the PET material, as well as its hydrophobicity and heat resistance.

[0032] 3. The PET material prepared by this invention has a stable output when extruded by a screw extruder, and the screw extruder head is not prone to material accumulation or blockage. The surface of the granules is smooth and flat during the extrusion granulation process. Detailed Implementation

[0033] Example 1

[0034] This embodiment proposes a PET material with good ductility. The raw materials for preparation include: 0.5 wt% acrylate polymer, 6 wt% toughening agent, 1 wt% antioxidant, 0.5 wt% lubricant and the balance PET resin.

[0035] The acrylate polymers were purchased from Shanghai Handian Technology Co., Ltd., and contained 75 wt% acrylates and 25 wt% styrene. The preparation method of the acrylate polymers was as follows: 25 g styrene, 4 g methyl methacrylate, 1 g butyl methacrylate, and 70 g glycidyl methacrylate were added to a reaction vessel, followed by 1000 g water, 0.5 g calcium chloride, 1.5 g sodium hydroxide, and 0.5 g styrene-maleic anhydride copolymer. The mixture was stirred at 75°C for 1 hour, then 0.5 g benzoyl peroxide and 2 g dodecyl mercaptan were added, and the reaction was maintained at 75°C for 24 hours. The mixture was then filtered to obtain the acrylate polymers.

[0036] The toughening agent is an ethylene-acrylic acid copolymer, purchased from Shanghai Aojia Industrial Co., Ltd., model EAA5980, with an acrylic acid content of 20%.

[0037] The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0038] The lubricant is pentaerythritol stearate.

[0039] The PET resin was purchased from Yizheng Chemical Fiber, model number FG640.

[0040] This embodiment also proposes a PET material with good extensibility and its polyester derivatives, including the following steps: mixing PET resin, acrylate polymer, toughening agent, antioxidant, and lubricant evenly, and extruding and granulating using a twin-screw extruder.

[0041] Example 2

[0042] This embodiment proposes a PET material with good ductility. The raw materials for preparation include: 0.5 wt% acrylate polymer, 6 wt% toughening agent, 1 wt% antioxidant, 0.5 wt% lubricant and the balance PET resin.

[0043] The acrylate polymers were purchased from Shanghai Handian Technology Co., Ltd., and contained 72 wt% acrylates and 28 wt% styrene. The preparation method of the acrylate polymers was as follows: 28 g styrene, 6 g methyl methacrylate, 1 g butyl methacrylate, and 65 g glycidyl methacrylate were added to a reaction vessel, followed by 1000 g water, 0.5 g calcium chloride, 1.5 g sodium hydroxide, and 0.5 g styrene-maleic anhydride copolymer. The mixture was stirred at 75°C for 1 hour, then 0.5 g benzoyl peroxide and 2 g dodecyl mercaptan were added, and the reaction was maintained at 75°C for 24 hours. The mixture was then filtered to obtain the acrylate polymers.

[0044] The toughening agent is an ethylene-acrylic acid copolymer, purchased from Shanghai Aojia Industrial Co., Ltd., model EAA5980, with an acrylic acid content of 20%.

[0045] The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0046] The lubricant is pentaerythritol stearate.

[0047] The PET resin was purchased from Yizheng Chemical Fiber, model number FG640.

[0048] This embodiment also proposes a PET material with good extensibility and its polyester derivatives, including the following steps: mixing PET resin, acrylate polymer, toughening agent, antioxidant, and lubricant evenly, and extruding and granulating using a twin-screw extruder.

[0049] Example 3

[0050] This embodiment proposes a PET material with good ductility. The raw materials for preparation include: 1.2 wt% acrylate polymer, 6 wt% toughening agent, 1 wt% antioxidant, 0.5 wt% lubricant and the balance PET resin.

[0051] The acrylate polymers were purchased from Shanghai Handian Technology Co., Ltd., and contained 75 wt% acrylates and 25 wt% styrene. The preparation method of the acrylate polymers was as follows: 25 g styrene, 4 g methyl methacrylate, 1 g butyl methacrylate, and 70 g glycidyl methacrylate were added to a reaction vessel, followed by 1000 g water, 0.5 g calcium chloride, 1.5 g sodium hydroxide, and 0.5 g styrene-maleic anhydride copolymer. The mixture was stirred at 75°C for 1 hour, then 0.5 g benzoyl peroxide and 2 g dodecyl mercaptan were added, and the reaction was maintained at 75°C for 24 hours. The mixture was then filtered to obtain the acrylate polymers.

[0052] The toughening agent is an ethylene-acrylic acid copolymer, purchased from Shanghai Aojia Industrial Co., Ltd., model EAA5980, with an acrylic acid content of 20%.

[0053] The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0054] The lubricant is pentaerythritol stearate.

[0055] The PET resin was purchased from Yizheng Chemical Fiber, model number FG640.

[0056] This embodiment also proposes a PET material with good extensibility and its polyester derivatives, including the following steps: mixing PET resin, acrylate polymer, toughening agent, antioxidant, and lubricant evenly, and extruding and granulating using a twin-screw extruder.

[0057] Example 4

[0058] This embodiment proposes a PET material with good ductility. The raw materials for preparation include: 0.5 wt% acrylate polymer, 6 wt% toughening agent, 1 wt% antioxidant, 0.5 wt% lubricant and the balance PET resin.

[0059] The acrylate polymers were purchased from BASF ADR4468.

[0060] The toughening agent is an ethylene-acrylic acid copolymer, purchased from Shanghai Aojia Industrial Co., Ltd., model EAA5980, with an acrylic acid content of 20%.

[0061] The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0062] The lubricant is pentaerythritol stearate.

[0063] The PET resin was purchased from Yizheng Chemical Fiber, model number FG640.

[0064] This embodiment also proposes a PET material with good extensibility and its polyester derivatives, including the following steps: mixing PET resin, acrylate polymer, toughening agent, antioxidant, and lubricant evenly, and extruding and granulating using a twin-screw extruder.

[0065] Performance testing

[0066] The PET particles prepared in the examples were tested for intrinsic viscosity, particle surface smoothness, and impact strength.

[0067] 1. Intrinsic viscosity: After drying the PET particles prepared in the example, the intrinsic viscosity was tested in accordance with the standard ISO1628 / 5.

[0068] 2. Surface smoothness of granules: After drying the PET granules prepared in the example, 100 PET granules were randomly selected, and the number of granules with surface adhesion, roughness, or tailing phenomena was recorded. When the number of granules with surface adhesion, roughness, or tailing phenomena was 1-2, it was recorded as A; when the number of granules with surface adhesion, roughness, or tailing phenomena was 3-8, it was recorded as B; when the number of granules with surface adhesion, roughness, or tailing phenomena was 8-15, it was recorded as C; and when the number of granules exceeded 15, it was recorded as D.

[0069] 3. Impact strength: After drying the PET granules prepared in the example, the impact strength was tested according to the standard ASTM D256.

[0070] The test data above is recorded in Table 1.

[0071] Table 1

[0072] Intrinsic viscosity dL / g Surface smoothness <![CDATA[Impact strength KJ / M 2 > Example 1 0.6623 A 3.86 Example 2 0.6602 B 3.84 Example 3 0.5852 C 3.47 Example 4 0.6137 B 3.55 No chain extender added 0.5297 B 2.12

Claims

1. A PET material with good ductility, characterized in that, The raw materials for preparation include: 0.5 wt% acrylate polymer, 6 wt% toughening agent, 1 wt% antioxidant, 0.5 wt% lubricant and the balance PET resin; The acrylate polymer contains 75 wt% acrylates and 25 wt% styrene. The preparation method of acrylate polymers is as follows: 25g styrene, 4g methyl methacrylate, 1g butyl methacrylate, and 70g glycidyl methacrylate are added to a reaction vessel, followed by 1000g water, 0.5g calcium chloride, 1.5g sodium hydroxide, and 0.5g styrene-maleic anhydride copolymer. The mixture is stirred at 75°C for 1 hour, then 0.5g benzoyl peroxide and 2g dodecyl mercaptan are added. The reaction is maintained at 75°C for 24 hours. After filtration, acrylate polymers are obtained. The toughening agent is an ethylene-acrylic acid copolymer, wherein the acrylic acid content is 20%; The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; The lubricant is pentaerythritol stearate; The method for preparing the PET material includes the following steps: The PET resin, acrylate polymer, toughening agent, antioxidant, and lubricant are mixed evenly and then extruded and granulated using a twin-screw extruder.