Bagasse xylan modified biodegradable material and preparation method

Abstract

The present invention belongs to the technical field of biodegradable polymer materials, and more particularly relates to a bagasse-xylan-modified biodegradable material and its preparation method. The biodegradable material of the present invention, based on a traditional biodegradable material system, partially replaces the raw materials by adding bagasse-xylan phosphate as a modifying material. The bagasse-xylan phosphate effectively ensures the biodegradable material's daily mechanical performance requirements and significantly improves its weather resistance, effectively ensuring the biodegradable material's application stability.

Description

Technical Field

[0001] The invention belongs to the technical field of biodegradable polymer materials, and in particular relates to a bagasse xylan modified biodegradable material and a preparation method thereof. Background Art

[0002] With the widespread use of plastic products, plastic waste is increasingly polluting the environment. Traditional plastic materials are difficult to degrade in the natural environment, placing a huge burden on soil, water sources, and ecosystems. In particular, with the continuous depletion of non-renewable petrochemical resources and the continued pollution of the ecological environment by non-degradable plastic products, the use of renewable resources to produce biodegradable plastics is gaining increasing attention.

[0003] Currently, the market still widely uses traditional petroleum-based materials such as PET and PP. Petroleum-based plastics cannot be naturally degraded, and there are only two ways to dispose of used waste: landfill or incineration. Both of these disposal methods cause great harm to the ecological environment, not only affecting agricultural development, threatening animal survival, polluting air and water bodies, but also becoming a nesting ground for pests, posing certain fire hazards, and wasting resources and energy. Therefore, the field is looking for effective measures to reduce the generation and harm of waste plastics and prohibit and restrict non-degradable single-use plastic products.

[0004] For example, Chinese invention patent application CN116589836A discloses a green and safe biodegradable material whose raw materials include biodegradable polyester, inorganic filler, natural UV stabilizer, natural antioxidant, compatibilizer, plasticizer, lubricant, and masterbatch. However, the biodegradable material uses natural raw materials, requiring the natural UV stabilizer and natural antioxidant to be coated on the capsule wall or to be loaded with a carrier, which to some extent affects its processing ease.

[0005] In view of this, the field is looking forward to developing a biodegradable material that can not only meet daily needs but also reduce environmental pollution, replace traditional petroleum-based plastic products, and reduce the generation and harm of waste plastics, which has important practical significance. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention provides a bagasse xylan modified biodegradable material and a preparation method thereof.

[0007] The present invention provides a bagasse xylan-modified biodegradable material, which comprises the following components by weight based on the total amount of raw materials used for its preparation:

[0008] Biodegradable base material 60-80wt%;

[0009] Bagasse xylan phosphate 8-20wt%;

[0010] Functional materials 10-20wt%;

[0011] Lubricant 0.1-0.5wt%;

[0012] Compatibilizer 0.1-1wt%;

[0013] Antioxidant 0.1-0.5wt%.

[0014] Specifically, in the bagasse xylan modified biodegradable material, the biodegradable base material includes at least one of polybutylene succinate, polybutylene adipate / terephthalate, polyglycolide or polybutylene terephthalate-succinate.

[0015] Specifically, in the bagasse xylan modified biodegradable material, the functional material includes at least one of calcium carbonate whiskers, calcium nitride whiskers, calcium sulfate whiskers, potassium titanate whiskers, talc powder or titanium dioxide.

[0016] Specifically, in the bagasse xylan modified biodegradable material, the lubricant includes at least one of zinc stearate, calcium stearate, ethylene bisstearamide, polypentaerythritol stearate or polyethylene wax.

[0017] Specifically, in the bagasse xylan modified biodegradable material, the compatibilizer includes at least one of silane coupling agent 550, silane coupling agent 560, silane coupling agent 570, silane coupling agent 580 or silane coupling agent A-151.

[0018] Specifically, in the bagasse xylan modified biodegradable material, the antioxidant includes at least one of antioxidant 1010, antioxidant 168, antioxidant 1076 or antioxidant 1098.

[0019] Specifically, in the bagasse xylan modified biodegradable material, the bagasse xylan phosphate is obtained by phosphate esterification of bagasse xylan.

[0020] The present invention also discloses a method for preparing the bagasse xylan modified biodegradable material, comprising the following steps:

[0021] (1) mixing the biodegradable base material, bagasse xylan phosphate, functional material, lubricant, compatibilizer, and antioxidant in a selected ratio to obtain a mixture;

[0022] (2) The mixed material is extruded through a twin-screw extruder to be granulated, and then water-cooled and granulated to obtain the product.

[0023] Specifically, in the method for preparing the bagasse xylan-modified biodegradable material, the temperature setting procedure of the twin-screw extrusion step in step (2) includes:

[0024] The first stage temperature is 70-80 degrees; the second stage temperature is 110-120 degrees; the third stage temperature is 140-160 degrees; the fourth stage temperature is 160-175 degrees; the fifth stage temperature is 170-180 degrees; the sixth stage temperature is 175-180 degrees; the seventh stage temperature is 175-180 degrees; the eighth stage temperature is 170-180 degrees; the ninth stage temperature is 165-175 degrees; the machine head is 150-160 degrees, and the speed is 150-180 revolutions per minute.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The biodegradable material of the present invention further adds bagasse xylan phosphate as a modified material to replace part of the raw materials on the basis of the traditional biodegradable material system. The bagasse xylan phosphate can effectively ensure the daily mechanical performance requirements of the biodegradable material and realize the replacement of bio-based materials.

[0027] The biodegradable material described in the present invention further incorporates bagasse xylan phosphate as a modifying material to replace some of the raw materials in a conventional biodegradable material system. This bagasse xylan phosphate exhibits anti-aging properties. While its mechanical properties differ slightly from those of conventional biodegradable material systems, its weather resistance is significantly improved, effectively ensuring the biodegradable material's application stability. Furthermore, it is fully biodegradable, replacing traditional non-degradable plastics, reducing environmental pollution and protecting the ecological environment. DETAILED DESCRIPTION

[0028] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are considered to be within the scope of the present invention.

[0029] The following examples of the present invention involve bagasse xylan, a polysaccharide extracted from bagasse and a type of hemicellulose. Bagasse xylan is primarily composed of xylose units and may also contain small amounts of arabinose and glucuronic acid. Bagasse xylan is commonly used as a thickener, stabilizer, and emulsifier in beverages, dairy products, baked goods, and other applications. It can also be used in the processing of environmentally friendly materials such as biodegradable materials and packaging materials.

[0030] In the following examples of the present invention, the bagasse xylan phosphate used for biodegradable material modification is an esterification product prepared by a phosphation reaction based on bagasse xylan in the art. As an exemplary embodiment, the bagasse xylan phosphate used for modification in the following examples of the present invention is prepared according to the method disclosed in Chinese invention patent application CN101962416A, and can also be prepared by improving on this process.

[0031] Preparation Example 1

[0032] The bagasse xylan phosphate described in this preparation example was prepared according to the method disclosed in Example 1 of Chinese invention patent application CN101962416A, specifically comprising the following steps:

[0033] (1) Anhydrous ethanol and water were mixed uniformly in a volume ratio of 1:4 to prepare a solvent;

[0034] (2) Take 10 g of bagasse xylan and 30 mL of solvent and add them into the reactor and stir. Slowly add 1 mol / L hydrochloric acid to adjust the pH of the system to 4 and activate at room temperature for 1 hour.

[0035] (3) Dissolve 2 g of stearic acid polyoxyethylene ether in deionized water to prepare a solution with a concentration of 0.2 g / mL;

[0036] (4) Dissolve 5 g of sodium dihydrogen phosphate / disodium hydrogen phosphate in deionized water to prepare a solution with a concentration of 0.2 g / mL; the mass ratio of the esterifying agents sodium dihydrogen phosphate and disodium hydrogen phosphate is 2:1;

[0037] (5) Raise the temperature of the system to 50°C;

[0038] (6) The catalyst obtained in step (3) and the esterification agent obtained in step (4) were slowly added dropwise to the system using a constant pressure dropping funnel, while maintaining the pH of the system at 5, and reacting for 8 hours;

[0039] (7) The pH of the reaction system was adjusted to 7 with 0.5 mol / L sodium hydroxide, and the crude product was filtered while hot to obtain the crude product; the crude product was repeatedly washed twice with an 80% by volume ethanol aqueous solution until the phosphate concentration in the filter cake was less than 10 mg / kg by the phosphomolybdenum blue method, and then washed and dehydrated with acetone, placed in a vacuum drying oven, and dried at 60°C for 12 hours to obtain the product.

[0040] Preparation Example 2

[0041] The bagasse xylan phosphate described in this preparation example was prepared by improving the method disclosed in Example 1 of Chinese invention patent application CN101962416A, specifically comprising the following steps:

[0042] (1) 1-ethyl-3-methylimidazolium acetate ionic liquid, anhydrous ethanol and water were uniformly mixed in a volume ratio of 2:1:2 to prepare a solvent;

[0043] (2) Take 10 g of bagasse xylan and 30 mL of solvent and add them into the reactor and stir. Slowly add 1 mol / L hydrochloric acid to adjust the pH of the system to 4 and activate at room temperature for 1 hour.

[0044] (3) Dissolve 2 g of stearic acid polyoxyethylene ether in deionized water to prepare a solution with a concentration of 0.2 g / mL;

[0045] (4) Dissolve 5 g of sodium dihydrogen phosphate / disodium hydrogen phosphate in deionized water to prepare a solution with a concentration of 0.2 g / mL; the mass ratio of the esterifying agents sodium dihydrogen phosphate and disodium hydrogen phosphate is 2:1;

[0046] (5) Raise the temperature of the system to 50°C;

[0047] (6) The catalyst obtained in step (3) and the esterification agent obtained in step (4) were slowly added dropwise to the system using a constant pressure dropping funnel, while maintaining the pH of the system at 5, and reacting for 8 hours;

[0048] (7) The pH of the reaction system was adjusted to 7 with 0.5 mol / L sodium hydroxide, and the crude product was filtered while hot to obtain the crude product; the crude product was repeatedly washed twice with an 80% by volume ethanol aqueous solution until the phosphate concentration in the filter cake was less than 10 mg / kg by the phosphomolybdenum blue method, and then washed and dehydrated with acetone, placed in a vacuum drying oven, and dried at 60°C for 12 hours to obtain the product.

[0049] Example 1

[0050] A bagasse xylan modified biodegradable material comprises the following raw material components in the following proportions (wt%): 40% polybutylene succinate, 27.8% polybutylene adipate / terephthalate, 10% calcium sulfate whiskers, 10% bagasse xylan phosphate (Preparation Example 2), 10% talc, 1% calcium carbonate, 0.5% titanium dioxide, 0.1% polypentaerythritol stearate, 0.1% ethylene bisstearamide, 0.3% silane coupling agent KH560, 0.1% antioxidant 1010, and 0.1% antioxidant 168.

[0051] First, place polybutylene succinate and polybutylene adipate / terephthalate into a mixer, then add the silane coupling agent KH560. Stir continuously at 100 rpm for 10 minutes, then add the remaining components. Set the mixer to 100°C and continue stirring at 500 rpm until the temperature reaches 100°C. Continue stirring for another 5 minutes, then stop mixing and set aside.

[0052] Use a twin-screw extruder granulator for granulation, and set the process temperature as follows: 80 degrees for the first section, 120 degrees for the second section, 160 degrees for the third section, 170 degrees for the fourth section, 170 degrees for the fifth section, 175 degrees for the sixth section, 180 degrees for the seventh section, 180 degrees for the eighth section, 175 degrees for the ninth section, the die head is 160 degrees, the speed is 180 revolutions per minute, water-cooled granulation, drying and packaging.

[0053] Example 2

[0054] A bagasse xylan modified biodegradable material comprises the following raw material components in the following proportions (wt%): 40% polybutylene succinate, 27.8% polybutylene adipate / terephthalate, 15% bagasse xylan phosphate (Preparation Example 2), 5% calcium sulfate whiskers, 10% talc, 1% calcium carbonate, 0.5% titanium dioxide, 0.1% polypentaerythritol stearate, 0.1% ethylene bisstearamide, 0.3% silane coupling agent KH560, 0.1% antioxidant 1010, and 0.1% antioxidant 168.

[0055] First, place the above-mentioned polybutylene succinate and polybutylene adipate / terephthalate into a high-speed mixer, then add the silane coupling agent KH560 and stir continuously at 100 rpm for 10 minutes. Add all the remaining components, set the temperature to 100 degrees, and stir continuously at 500 rpm. After the temperature rises to 100 degrees, continue stirring for another 5 minutes. Discharge the mixed materials for later use.

[0056] Use a twin-screw extruder for granulation, and set the process temperature as follows: 80 degrees for the first section, 120 degrees for the second section, 160 degrees for the third section, 175 degrees for the fourth section, 180 degrees for the fifth section, 180 degrees for the sixth section, 175 degrees for the seventh section, 175 degrees for the eighth section, 170 degrees for the ninth section, 160 degrees for the head, 180 revolutions per minute, cold water granulation, drying and packaging.

[0057] Example 3

[0058] A bagasse xylan modified biodegradable material comprises the following raw material components in the following proportions (wt%): 40% polybutylene succinate, 27.3% polybutylene adipate / terephthalate, 20% bagasse xylan phosphate (Preparation Example 2), 5% calcium sulfate whiskers, 4% talc, 2% calcium sulfate, 1% titanium dioxide, 0.1% pentaerythritol stearate, 0.1% ethylene bisstearamide, 0.3% silane coupling agent KH560, and 0.2% antioxidant 1010.

[0059] First, place the above-mentioned polybutylene succinate and polybutylene adipate / terephthalate into a high-speed mixer, then add the silane coupling agent KH560 and stir continuously at 100 rpm for 10 minutes. Add all the remaining components, set the temperature to 100 degrees, and stir continuously at 500 rpm. After the temperature rises to 100 degrees, continue stirring for another 5 minutes. Discharge the mixed materials for later use.

[0060] Use a twin-screw extruder for granulation, and set the process temperature as follows: one section 80 degrees, two sections 120 degrees, three sections 160 degrees, four sections 170 degrees, five sections 175 degrees, six sections 180 degrees, seven sections 180 degrees, eight sections 170 degrees, nine sections 165 degrees, the head is 160 degrees, the speed is 180 revolutions per minute, cold water granulation, drying and packaging.

[0061] Example 4

[0062] A bagasse xylan-modified biodegradable material comprises the following raw material components in the following proportions (wt%): 40% polybutylene succinate, 20% polybutylene adipate / terephthalate, 15% bagasse xylan-modified phosphate (Preparation Example 1), 7% calcium sulfate whiskers, 4% talc, 3% calcium carbonate, 0.3% pentaerythritol stearate, 0.2% ethylene bisstearamide, 0.3% silane coupling agent KH560, 0.1% antioxidant 1010, and 0.1% antioxidant 168.

[0063] Place the polybutylene succinate and polybutylene adipate / terephthalate into a high-speed mixer, followed by the silane coupling agent KH560. Stir continuously at 100 rpm for 10 minutes. Add all remaining components, set the mixer to 100°C, and stir at 500 rpm until the temperature reaches 100°C. Stir for an additional 5 minutes, and then set aside.

[0064] Use a twin-screw extruder for granulation, and set the process temperature as follows: 80 degrees for the first section, 120 degrees for the second section, 160 degrees for the third section, 170 degrees for the fourth section, 180 degrees for the fifth section, 180 degrees for the sixth section, 175 degrees for the seventh section, 170 degrees for the eighth section, 165 degrees for the ninth section, 150 degrees for the head, 150 revolutions per minute, cold water granulation, drying and packaging.

[0065] Example 5

[0066] A bagasse xylan modified biodegradable material comprises the following raw material components in the following proportions (wt%): 38% polybutylene succinate, 30% polybutylene adipate / terephthalate, 20% bagasse xylan phosphate (Preparation Example 1), 8% calcium sulfate whiskers, 2.5% talc, 0.5% titanium dioxide, 0.3% pentaerythritol stearate, 0.2% ethylene bisstearamide, 0.3% silane coupling agent KH560, 0.1% antioxidant 1010, and 0.1% antioxidant 168.

[0067] Place the polybutylene succinate and polybutylene adipate / terephthalate into a high-speed mixer, followed by the silane coupling agent KH560. Stir continuously at 100 rpm for 10 minutes. Add all remaining components, set the mixer to 100°C, and stir at 500 rpm until the temperature reaches 100°C. Stir for an additional 5 minutes, and then set aside.

[0068] Use a twin-screw extruder granulator for granulation, set the process temperature as follows: one section 70 degrees, two sections 110 degrees, three sections 140 degrees, four sections 160 degrees, five sections 170 degrees, six sections 180 degrees, seven sections 180 degrees, eight sections 170 degrees, nine sections 165 degrees, the head is 160 degrees, the speed is 180 revolutions per minute, cold water granulation, drying and packaging.

[0069] Example 6

[0070] A bagasse xylan modified biodegradable material comprises the following raw material components in the following proportions (wt%): 20% polybutylene succinate, 20% polybutylene adipate / terephthalate, 20% polybutylene terephthalate-succinate, 18.4% bagasse xylan phosphate (Preparation Example 2), 15% calcium sulfate whiskers, 2.5% talc, 2.5% titanium dioxide, 0.1% pentaerythritol stearate, 1% silane coupling agent KH570, 0.2% antioxidant 1010, and 0.3% antioxidant 168.

[0071] The preparation method of the bagasse xylan modified biodegradable material described in this example is the same as that in Example 1.

[0072] Example 7

[0073] A bagasse xylan modified biodegradable material comprises the following raw material components in the following proportions (wt%): 38% polybutylene succinate, 30% polybutylene adipate / terephthalate, 12% polyglycolide, 9.3% bagasse xylan phosphate (Preparation Example 1), 7% calcium sulfate whiskers, 2.5% talc, 0.5% titanium dioxide, 0.3% pentaerythritol stearate, 0.2% ethylene bisstearamide, 0.1% silane coupling agent KH560, and 0.1% antioxidant 168.

[0074] The preparation method of the bagasse xylan modified biodegradable material described in this example is the same as that in Example 1.

[0075] Example 8

[0076] The composition and preparation method of the bagasse xylan modified biodegradable material described in this example are the same as those in Example 1, the only difference being that the bagasse xylan phosphate is prepared using the method in Preparation Example 1.

[0077] Comparative Example 1

[0078] The raw material system of this comparative example is the same as that of Example 1, the only difference being that bagasse xylan is used to replace bagasse xylan phosphate.

[0079] Comparative Example 2

[0080] The raw material system of this comparative example is the same as that of Example 1, except that bagasse xylan phosphate is not added and is replaced by a certain amount of polybutylene succinate.

[0081] Application Example 1

[0082] Taking the bagasse xylan modified biodegradable material prepared in Example 1 as an example, an extrusion calendering machine was used for processing.

[0083] The prepared biodegradable material is added to the extruder through a feeder. In a molten state, it is extruded into a narrow strip through a die at the head of the extruder. It is then cooled, stretched once, heated and stretched twice, and coiled to finally be made into a packing tape with a width of 16 mm and a thickness of 0.8 mm (specification 1608) or a width of 19 mm and a thickness of 1 mm (specification 1910).

[0084] Experimental example

[0085] 1. Mechanical properties test

[0086] The tensile strength, tensile strain at break and Shore hardness of the biodegradable specimens prepared in Example 1, Example 8 and Comparative Example 1 and Comparative Example 2 were measured using a universal testing machine and a Shore hardness tester. The specific data results are shown in Table 1.

[0087] Table 1

[0088]

[0089] It can be seen that the present invention uses bagasse xylan modified with bagasse xylan phosphate to process biodegradable materials, which can effectively ensure the mechanical properties of the biodegradable materials, and the bagasse xylan phosphate prepared in the ionic liquid solvent system has a slightly better effect on the mechanical properties of the biodegradable materials.

[0090] 2. Artificial accelerated photoaging experiment

[0091] Take the biodegradable strips prepared in Example 1, Example 8 and Comparative Example 1 and Comparative Example 2, and use a fluorescent ultraviolet lamp with a wavelength of 365 mm and an irradiation intensity of 2 W / m 2 , cycle process: 8 hours of light, irradiation intensity 2W / m 2 After 240 hours of continuous testing, the tensile mechanical properties of the samples were tested. The test results are shown in Table 2 below.

[0092] Table 2

[0093]

[0094] It can be seen that the present invention uses bagasse xylan modified with bagasse xylan phosphate to process biodegradable materials, which can effectively improve the weather resistance of biodegradable materials. In particular, the bagasse xylan phosphate prepared in an ionic liquid solvent system has a more significant advantage in the anti-aging performance of biodegradable materials.

[0095] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention.

Claims

1. A bagasse xylan modified biodegradable material, characterized in that: Calculated based on the total amount of raw materials used in its preparation, it includes the following components by mass: Biodegradable base material 60-80wt%; Bagasse xylan phosphate 8-20wt%; Functional materials 10-20wt%; Lubricant 0.1-0.5wt%; Compatibilizer 0.1-1wt%; Antioxidant 0.1-0.5wt%; The functional material includes at least one of calcium carbonate whiskers, calcium nitride whiskers, calcium sulfate whiskers, potassium titanate whiskers, talc powder or titanium dioxide.

2. The bagasse xylan modified biodegradable material according to claim 1, characterized in that: The biodegradable base material includes at least one of polybutylene succinate, polybutylene adipate / terephthalate, polyglycolide or polybutylene terephthalate-succinate.

3. The bagasse xylan modified biodegradable material according to claim 1, characterized in that: The lubricant includes at least one of zinc stearate, calcium stearate, ethylene bisstearamide or polyethylene wax.

4. The bagasse xylan modified biodegradable material according to claim 1, characterized in that: The compatibilizer includes at least one of silane coupling agent 550, silane coupling agent 560, silane coupling agent 570, silane coupling agent 580, or silane coupling agent A-151.

5. The bagasse xylan modified biodegradable material according to claim 1, characterized in that: The antioxidant includes at least one of antioxidant 1010, antioxidant 168, antioxidant 1076 or antioxidant 1098.

6. The bagasse xylan modified biodegradable material according to any one of claims 1 to 5, characterized in that: The bagasse xylan phosphate is obtained by phosphate esterification of bagasse xylan.

7. A method for preparing a bagasse xylan-modified biodegradable material according to any one of claims 1 to 6, characterized in that: The steps include: (1) mixing the biodegradable base material, bagasse xylan phosphate, functional material, lubricant, compatibilizer, and antioxidant in a selected ratio to obtain a mixture; (2) The mixed material is extruded through a twin-screw extruder to be granulated, and then water-cooled and granulated to obtain the product.

8. The method for preparing a bagasse xylan-modified biodegradable material according to claim 7, characterized in that: In step (2), the temperature setting procedure of the twin-screw extrusion step includes: The first stage temperature is 70-80 degrees; the second stage temperature is 110-120 degrees; the third stage temperature is 140-160 degrees; the fourth stage temperature is 160-175 degrees; the fifth stage temperature is 170-180 degrees; the sixth stage temperature is 175-180 degrees; the seventh stage temperature is 175-180 degrees; the eighth stage temperature is 170-180 degrees; the ninth stage temperature is 165-175 degrees; the machine head is 150-160 degrees, and the speed is 150-180 revolutions per minute.

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