Easily degradable corrugated paper auxiliary and preparation method thereof

Abstract

The application relates to a degradable corrugated paper auxiliary and a preparation method thereof, and belongs to the technical field of packaging materials. The auxiliary comprises, in terms of weight parts, 50 parts of oxidized starch, 6-8 parts of a modified reinforcing agent, 0.5-0.7 parts of a thickening agent, 0.15-0.2 parts of a dispersing agent, 0.1-0.13 parts of an antifoaming agent, 0.02-0.03 parts of a mildew-proof agent and 90-100 parts of water; in the process of sizing and curing, the ethoxysilane of the side chain of the modified reinforcing agent is coupled and condensed with the hydroxyl of the paper fiber, the main chain of the ethoxysilane is clamped in the macromolecular chain of the starch, rivet action is generated, the binding strength between the paper fibers is increased, the paper fibers are not prone to cracking in the bending process, in addition, in the process of coupling and condensation, a fluorine-containing organic silicon water-resistant layer is uniformly introduced to the surface of the paperboard substrate, and the water-resistant stability of the paperboard is effectively improved.

Description

Technical Field

[0001] This invention belongs to the field of packaging materials technology, specifically relating to an easily degradable corrugated paper additive and its preparation method. Background Technology

[0002] With the rapid development of the packaging industry, the demand for corrugated cardboard, as an important packaging material, has been increasing year by year. The main function of corrugated cardboard is to provide packaging strength and protect the contents, especially during transportation and storage. However, traditional corrugated cardboard has certain limitations in terms of waterproofing, moisture resistance, and compression resistance, which restricts its application in certain special environments.

[0003] Currently, one of the main methods to improve the performance of corrugated paperboard is sizing treatment, which involves applying sizing agents to the surface or interior of the corrugated paperboard. Existing sizing agents mainly include synthetic resin sizing agents and paraffin sizing agents. While these sizing agents effectively improve the performance of corrugated paperboard, they are difficult to degrade naturally, failing to meet the requirements of environmentally friendly production. Starch sizing agents are a new type of biodegradable and environmentally friendly corrugated paper additive. They are made from natural starch through physical, chemical, or enzymatic treatment to transform it into modified starch with the desired properties, which can improve the performance of corrugated paper to a certain extent. However, their strengthening effect is limited, and their water resistance is insufficient, greatly restricting the application of starch sizing agents. Summary of the Invention

[0004] In order to solve the technical problems mentioned in the background art, the purpose of this invention is to provide an easily degradable corrugated paper additive and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A biodegradable corrugated paper additive, comprising, by weight:

[0007] The ingredients are: 50 parts oxidized starch, 6-8 parts modified reinforcing agent, 0.5-0.7 parts thickener, 0.15-0.2 parts dispersant, 0.1-0.13 parts defoamer, 0.02-0.03 parts mildew inhibitor, and 90-100 parts water.

[0008] The modified reinforcing agent is prepared by the following method:

[0009] Step A1: Mix epoxy silicone oil, triethylamine and acetone, purge with nitrogen for protection, heat to 45-55℃, stir at 120-180 rpm, slowly add 2,2-difluoroethylamine and react for 2.5-3.5 h. After the reaction is complete, rotary evaporate, wash with water and vacuum dry to obtain the intermediate.

[0010] Furthermore, the epoxy silicone oil is selected from branched epoxy silicone oils;

[0011] Furthermore, the epoxy silicone oil is a low molecular weight silicone oil with a room temperature viscosity not exceeding 30 mmHg. 2 / s;

[0012] Furthermore, the epoxy group content of the epoxy silicone oil and the ratio of 2,2-difluoroethylamine, triethylamine and acetone are 0.1 mol: 0.102-0.105 mol: 15-20 mL: 55-70 mL. The active amino group of 2,2-difluoroethylamine opens the ring with the epoxy silicone oil, introducing a fluorine structure into the silicone oil chain.

[0013] Step A2: Mix the intermediate, 3-chloropropyltriethoxysilane and anhydrous dioxane, purge with dry nitrogen, add sodium hydroxide and mix, heat to 80-100℃, stir at 90-120 rpm for 5-7 hours, filter and rotary evaporate after the reaction to obtain the modified reinforcing agent.

[0014] Furthermore, the ratio of the intermediate, 3-chloropropyltriethoxysilane, sodium hydroxide, and anhydrous dioxane is 50 g: 0.06-0.08 mol: 5-8 g: 120-160 mL. Under the strong alkalinity of sodium hydroxide, 3-chloropropyltriethoxysilane substitutes for the intermediate, introducing an ethoxysilane structure at the ring-opening site.

[0015] Preferably, the thickener is sodium carboxymethyl cellulose.

[0016] Preferably, the dispersant is a polyether-type dispersant.

[0017] Preferably, the defoamer is a polyether-type defoamer.

[0018] Preferably, the mildew inhibitor is a water-based mildew inhibitor.

[0019] A method for preparing an easily degradable corrugated paper additive includes the following steps: premixing a modifier, a dispersant, a defoamer, a mildew inhibitor, and half the amount of water, then adding oxidized starch and mixing, heating to 65±2℃ and stirring for 25-30 minutes, then adding a thickener and the remaining water after premixing and mixing to obtain the easily degradable corrugated paper additive.

[0020] The beneficial effects of this invention are:

[0021] The corrugated paper additive disclosed in this invention is mainly used for sizing corrugated paper. It uses oxidized starch as a base material and has good biodegradability. Compared with traditional synthetic resin sizing and paraffin sizing, it has higher environmental protection.

[0022] This invention significantly improves the folding endurance and wet tensile strength of corrugated paper by adding a self-developed modified reinforcing agent to an oxidized starch sizing agent. The modified reinforcing agent uses low molecular weight branched epoxy silicone oil as raw material. The active amino group of 2,2-difluoroethylamine ring-opens with the epoxy silicone oil, introducing a fluorine structure into the silicone oil chain. Then, 3-chloropropyltriethoxysilane and an intermediate are substituted to introduce an ethoxysilane structure at the ring-opening site. During the sizing and curing process, the ethoxysilane on the side chain of the modified reinforcing agent molecule couples and condenses with the hydroxyl groups of the paper fiber. Its main chain is locked in the macromolecular chain of starch, creating a riveting effect, increasing the bonding strength between paper fibers, and making it less prone to cracking during bending. In addition, during the coupling and condensation process, a fluorinated organosilicon water-resistant layer is uniformly introduced onto the surface of the paperboard substrate, effectively improving the water resistance stability of the paperboard. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0024] Example 1: This example describes the preparation of a biodegradable corrugated paper additive. The specific implementation process is as follows:

[0025] (1) Preparation of the modified reinforcing agent

[0026] Step A1: Mix epoxy silicone oil, triethylamine, and acetone thoroughly, purge with nitrogen for protection, heat to 55°C, stir at 180 rpm, and slowly add 2,2-difluoroethylamine over 1 hour. After complete addition, continue stirring at a constant temperature, controlling the total reaction time to 2.5 hours. The epoxy silicone oil used is X-22-343 type low molecular weight branched epoxy silicone oil with a room temperature viscosity of approximately 25 mmHg. 2 / s, the epoxy content of epoxy silicone oil, and the ratio of 2,2-difluoroethylamine, triethylamine and acetone are 0.1mol:0.105mol:20mL:70mL. After the reaction is completed, acetone is removed by rotary evaporation. Water is added to the rotary evaporated substrate for washing, the aqueous phase is removed and the substrate is dried under vacuum to obtain the intermediate.

[0027] Step A2: Mix the intermediate, 3-chloropropyltriethoxysilane, and anhydrous dioxane, purge with dry nitrogen for protection, add sodium hydroxide and mix, heat to 100℃, stir at 120 rpm, and react for 5 hours. The ratio of the intermediate, 3-chloropropyltriethoxysilane, sodium hydroxide, and anhydrous dioxane is 50 g: 0.08 mol: 8 g: 160 mL. After the reaction is complete, filter to remove insoluble matter, and remove dioxane by rotary evaporation to obtain the modified reinforcing agent.

[0028] (2) Formulation of biodegradable corrugated paper additives

[0029] Ingredients: Raw materials are prepared according to the following proportions by weight: 50 parts oxidized starch (using sizing oxidized starch from Taian Jinshan Modified Starch Co., Ltd.); 6 parts modified reinforcing agent (self-made in this embodiment); 0.7 parts thickener (using FVH6-A type raw material from Weifang Lite Composite Materials Co., Ltd.); 0.15 parts dispersant (using polyether type dispersant AEO-9 from Guangzhou Gongxin Chemical Co., Ltd.); 0.1 parts defoamer (using polyether type defoamer CL-368 from Guangdong Nanhui New Materials Co., Ltd.); 0.02 parts mildew inhibitor (using water-based mildew inhibitor KEPUYIN-M002 from Guangdong Kepuyin Biotechnology Co., Ltd.); and 90 parts water.

[0030] Preparation of additives: The modifier, dispersant, defoamer, mildew inhibitor and half of the water are premixed, and then oxidized starch is added and mixed. The mixture is heated to 65±2℃ and stirred for 25 minutes. Then the thickener and the remaining water are premixed and added and mixed evenly to obtain the easily degradable corrugated paper additive.

[0031] Example 2: This example describes the preparation of a biodegradable corrugated paper additive. The specific implementation process is as follows:

[0032] (1) Preparation of the modified reinforcing agent

[0033] Step A1: Mix epoxy silicone oil, triethylamine, and acetone thoroughly, purge with nitrogen for protection, heat to 45°C, stir at 120 rpm, and slowly add 2,2-difluoroethylamine over 1.5 hours. After complete addition, continue stirring at a constant temperature, controlling the total reaction time to 3.5 hours. The epoxy silicone oil used is X-22-343 type low molecular weight branched epoxy silicone oil with a room temperature viscosity of approximately 25 mmHg. 2 / s, the epoxy content of the epoxy silicone oil, and the ratio of 2,2-difluoroethylamine, triethylamine and acetone were 0.1mol:0.102mol:15mL:55mL. After the reaction was completed, the acetone was removed by rotary evaporation. Water was added to the rotary evaporated substrate for washing to remove the aqueous phase and vacuum drying to obtain the intermediate.

[0034] Step A2: Mix the intermediate, 3-chloropropyltriethoxysilane, and anhydrous dioxane, purge with dry nitrogen for protection, then add sodium hydroxide and mix. Heat to 80°C and stir at 90 rpm for 7 hours. The ratio of intermediate, 3-chloropropyltriethoxysilane, sodium hydroxide, and anhydrous dioxane is 50 g: 0.06 mol: 5 g: 120 mL. After the reaction is complete, filter to remove insoluble matter, and remove dioxane by rotary evaporation to obtain the modified reinforcing agent.

[0035] (2) Formulation of biodegradable corrugated paper additives

[0036] Ingredients: Raw materials are prepared according to the following parts by weight: 50 parts of oxidized starch (using sizing oxidized starch from Taian Jinshan Modified Starch Co., Ltd.); 8 parts of modified reinforcing agent (self-made in this embodiment); 0.5 parts of thickener (using FVH6-A type raw material from Weifang Lite Composite Materials Co., Ltd.); 0.2 parts of dispersant (using polyether type dispersant AEO-9 from Guangzhou Gongxin Chemical Co., Ltd.); 0.13 parts of defoamer (using polyether type defoamer CL-368 from Guangdong Nanhui New Materials Co., Ltd.); 0.03 parts of mildew inhibitor (using water-based mildew inhibitor KEPUYIN-M002 from Guangdong Kepuyin Biotechnology Co., Ltd.); and 100 parts of water.

[0037] Preparation of additives: The modifier, dispersant, defoamer, mildew inhibitor and half of the water are premixed, and then oxidized starch is added and mixed. The mixture is heated to 65±2℃ and stirred for 30 minutes. Then the thickener and the remaining water are premixed and added and mixed evenly to obtain the easily degradable corrugated paper additive.

[0038] Example 3: This example describes the preparation of an easily degradable corrugated paper additive. The specific implementation process is as follows:

[0039] (1) Preparation of the modified reinforcing agent

[0040] Step A1: Mix epoxy silicone oil, triethylamine, and acetone thoroughly, purge with nitrogen for protection, heat to 50°C, stir at 120 rpm, and slowly add 2,2-difluoroethylamine over 1.2 hours. After complete addition, continue stirring at a constant temperature, controlling the total reaction time to 3 hours. The epoxy silicone oil used is X-22-343 type low molecular weight branched epoxy silicone oil with a room temperature viscosity of approximately 25 mmHg. 2 / s, the epoxy content of epoxy silicone oil, and the ratio of 2,2-difluoroethylamine, triethylamine and acetone are 0.1mol:0.103mol:18mL:65mL. After the reaction is completed, acetone is removed by rotary evaporation. Water is added to the rotary evaporated substrate to wash and remove the aqueous phase. The substrate is then dried under vacuum to obtain the intermediate.

[0041] Step A2: Mix the intermediate, 3-chloropropyltriethoxysilane, and anhydrous dioxane, purge with dry nitrogen, add sodium hydroxide and mix, heat to 90°C, stir at 120 rpm, and react for 5.5 h. The ratio of the intermediate, 3-chloropropyltriethoxysilane, sodium hydroxide, and anhydrous dioxane is 50 g: 0.07 mol: 7 g: 150 mL. After the reaction is complete, filter to remove insoluble matter, and remove dioxane by rotary evaporation to obtain the modified reinforcing agent.

[0042] (2) Formulation of biodegradable corrugated paper additives

[0043] Ingredients: Raw materials are prepared according to the following proportions by weight: 50 parts oxidized starch (using sizing oxidized starch from Taian Jinshan Modified Starch Co., Ltd.); 6.5 parts modified reinforcing agent (self-made in this embodiment); 0.6 parts thickener (using FVH6-A type raw material from Weifang Lite Composite Materials Co., Ltd.); 0.18 parts dispersant (using polyether type dispersant AEO-9 from Guangzhou Gongxin Chemical Co., Ltd.); 0.12 parts defoamer (using polyether type defoamer CL-368 from Guangdong Nanhui New Materials Co., Ltd.); 0.02 parts mildew inhibitor (using water-based mildew inhibitor KEPUYIN-M002 from Guangdong Kepuyin Biotechnology Co., Ltd.); and 95 parts water.

[0044] Preparation of additives: The modifier, dispersant, defoamer, mildew inhibitor and half of the water are premixed, and then oxidized starch is added and mixed. The mixture is heated to 65±2℃ and stirred for 30 minutes. Then the thickener and the remaining water are premixed and added and mixed evenly to obtain the easily degradable corrugated paper additive.

[0045] Example 4: This example describes the preparation of an easily degradable corrugated paper additive. The specific implementation process is as follows:

[0046] (1) Preparation of the modified reinforcing agent

[0047] Step A1: Mix epoxy silicone oil, triethylamine, and acetone thoroughly, purge with nitrogen for protection, heat to 55°C, stir at 180 rpm, and slowly add 2,2-difluoroethylamine over 1.2 hours. After complete addition, continue stirring at a constant temperature, controlling the total reaction time to 2.8 hours. The epoxy silicone oil used is X-22-343 type low molecular weight branched epoxy silicone oil with a room temperature viscosity of approximately 25 mmHg. 2 / s, the epoxy content of epoxy silicone oil, and the ratio of 2,2-difluoroethylamine, triethylamine and acetone are 0.1mol:0.103mol:20mL:65mL. After the reaction is completed, acetone is removed by rotary evaporation. Water is added to the rotary evaporated substrate for washing to remove the aqueous phase and vacuum drying to obtain the intermediate.

[0048] Step A2: Mix the intermediate, 3-chloropropyltriethoxysilane, and anhydrous dioxane, purge with dry nitrogen, add sodium hydroxide and mix, heat to 85°C, stir at 120 rpm, and react for 6.5 h. The ratio of the intermediate, 3-chloropropyltriethoxysilane, sodium hydroxide, and anhydrous dioxane is 50 g: 0.07 mol: 6 g: 140 mL. After the reaction is complete, filter to remove insoluble matter, and remove dioxane by rotary evaporation to obtain the modified reinforcing agent.

[0049] (2) Formulation of biodegradable corrugated paper additives

[0050] Ingredients: Raw materials are prepared according to the following parts by weight: 50 parts of oxidized starch (using sizing oxidized starch from Taian Jinshan Modified Starch Co., Ltd.); 7.2 parts of modified reinforcing agent (self-made in this embodiment); 0.55 parts of thickener (using FVH6-A type raw material from Weifang Lite Composite Materials Co., Ltd.); 0.16 parts of dispersant (using polyether type dispersant AEO-9 from Guangzhou Gongxin Chemical Co., Ltd.); 0.12 parts of defoamer (using polyether type defoamer CL-368 from Guangdong Nanhui New Materials Co., Ltd.); 0.02 parts of mildew inhibitor (using water-based mildew inhibitor KEPUYIN-M002 from Guangdong Kepuyin Biotechnology Co., Ltd.); and 95 parts of water.

[0051] Preparation of additives: The modifier, dispersant, defoamer, mildew inhibitor and half of the water are premixed, and then oxidized starch is added and mixed. The mixture is heated to 65±2℃ and stirred for 30 minutes. Then the thickener and the remaining water are premixed and added and mixed evenly to obtain the easily degradable corrugated paper additive.

[0052] Comparative Example 1

[0053] This comparative example refers to Example 4, except that the modifier is replaced with the same amount of oxidized starch, and the rest of the implementation process is exactly the same.

[0054] Comparative Example 2

[0055] This comparative example refers to the existing technology and uses a compound of fluorinated silane coupling agents to prepare the additives. The implementation process is the same as in Example 4. Based on production experience, 2.2 parts of tridecafluorooctyltrimethoxysilane were used to replace the modifier and reinforcing agent. The rest of the implementation process is exactly the same.

[0056] To facilitate the testing of the strengthening effect of the prepared additives on corrugated paper, dried paperboard was used as the substrate. The additives were coated onto the surface of the substrate, with the coating amount controlled at 3.5 g / m². 2 Then, it is placed in an oven and dried at 60°C for 2 hours to obtain paper sheets;

[0057] Samples were taken from the paper sheets prepared above, and folding endurance was tested according to GB / T457-2008 standard; tensile strength was tested according to GB / T12914-2018 standard, including dry and wet state tests. For the dry state, the paper sheets were directly sampled; for the wet state, the paper sheets were soaked in room temperature water for 10 minutes before sampling. Tear strength was tested according to GB / T455-2002 standard; stiffness was tested according to GB / T2679.3-1996 standard; bursting strength was tested according to GB / T454-2020 standard. The specific test results are shown in the table below.

[0058]

[0059] As can be seen from the test results in the table above, the additives in the examples endow corrugated paper with excellent comprehensive properties, especially with significant improvements in folding endurance and wet tensile strength, which can effectively extend the service life of corrugated paper and improve the packaging stability of corrugated paper.

[0060] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0061] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A readily degradable corrugated paper aid, characterized in that, By weight parts including: oxidized starch 50 parts, modified reinforcing agent 6-8 parts, thickening agent 0.5-0.7 parts, dispersant 0.15-0.2 parts, defoaming agent 0.1-0.13 parts, mildewcide 0.02-0.03 parts and water 90-100 parts; The modified reinforcing agent is prepared by the following method: Step A1: mix epoxy silicone oil, triethylamine and acetone, protect with nitrogen, heat to 45-55℃, slowly add 2,2-difluoroethylamine, stir and react for 2.5-3.5h, after reaction, rotary evaporation, water washing, vacuum drying, to obtain intermediate; Step A2: mix intermediate, 3-chloropropyl triethoxysilane and anhydrous dioxane, protect with dry nitrogen, then add sodium hydroxide, heat to 80-100℃, stir and react for 5-7h, after reaction, filter, rotary evaporation, to obtain modified reinforcing agent.

2. The easily degradable corrugated paper aid according to claim 1, characterized in that, The ratio of the amount of epoxy group content of epoxy silicone oil, 2,2-difluoroethylamine, triethylamine and acetone is 0.1mol:0.102-0.105mol:15-20mL:55-70mL.

3. The easily degradable corrugated paper aid according to claim 2, characterized in that, The epoxy silicone oil is a branched epoxy silicone oil with a room temperature viscosity of not higher than 30 mm 2 / s.

4. The easily degradable corrugated paper aid according to claim 3, characterized in that, The ratio of the amount of intermediate, 3-chloropropyl triethoxysilane, sodium hydroxide and anhydrous dioxane is 50g:0.06-0.08mol:5-8g:120-160mL.

5. The easily degradable corrugated paper aid according to claim 1, characterized in that, The thickening agent is sodium carboxymethyl cellulose.

6. The easily degradable corrugated paper according to claim 1, wherein, The dispersant is polyether type dispersant.

7. The easily degradable corrugated paper according to claim 1, wherein, The defoaming agent is polyether type defoaming agent.

8. The easily degradable corrugated paper according to claim 1, wherein, The mildewcide is water-based mildewcide.

9. A process for the preparation of a readily degradable corrugated paper aid according to any one of claims 1 to 8, characterized in that, The specific operation is: pre-mix the modified reinforcing agent, dispersant, defoaming agent, mildewcide and half amount of water, then add oxidized starch, heat to 65±2℃, stir for 25-30min, then pre-mix the thickening agent and the remaining amount of water, add and mix, to obtain easily degradable corrugated paper additive.

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