A non-fluorine oil-proof agent for pulp molding and a preparation method thereof

Abstract

The present application relates to pulp molding waterproof and oil-proof technology field, specifically relates to a kind of fluorine-free paper pulp molding oil-proof agent and its preparation method, including the following weight parts of raw materials: short-chain alkane 4-8 parts, long-chain alkane 30-50 parts, antioxidant 0.1-0.5 parts, film-forming agent 4-8 parts, inorganic ash 0.01-0.1 parts, solvent 60-80 parts and other auxiliary agent 0.5-1.0 parts.The oil-proof agent of the present application has good waterproof and oil-proof performance, can effectively prevent oil pollution and penetration, improve the service life and use effect of pulp molding product, while also avoid the harm of fluorine and silicon chemical substances contained in traditional oil-proof agent to human body and environment, more environmentally friendly and healthy, during use, will not have any influence on the appearance and performance of pulp molding product, ensure the overall quality of product.

Description

Technical Field

[0001] This invention relates to the field of waterproof and oil-proof technology for pulp molding, specifically to an oil-proof agent for fluorine-free pulp molding and its preparation method. Background Technology

[0002] Pulp molding packaging boasts advantages such as natural origin, environmental friendliness, safety, hygiene, and easy degradation and recycling, making it increasingly popular among consumers and in the market. However, this packaging product is primarily composed of natural plant fibers, with hydrophilic cellulose and hemicellulose as its main chemical components. The presence of numerous hydroxyl groups in its molecular structure results in a loose and porous structure, exhibiting some liquid absorption but relatively weak barrier properties against air, water, and oils. A common solution is to add waterproof and oil-repellent agents to the pulp during the pulp molding process to prevent oil contamination and penetration, thereby improving the product's lifespan and performance.

[0003] However, existing oil repellents typically contain chemicals such as fluorine and silicon. While these substances offer good oil-repellent properties, they pose certain risks to human health and the environment. Furthermore, existing oil repellents may negatively impact the appearance and performance of molded pulp products during use. Therefore, developing fluorine-free and silicon-free environmentally friendly oil repellents is a crucial problem that needs to be addressed in current technology. Summary of the Invention

[0004] In order to overcome the shortcomings and deficiencies of the existing technology, the purpose of this invention is to provide a fluorine-free oil repellent for pulp molding. This oil repellent has good water and oil repellency, can effectively prevent oil pollution and penetration, improve the service life and performance of pulp molding products, and at the same time avoid the harm to human body and environment caused by fluorine and silicon chemicals contained in traditional oil repellents. It is more environmentally friendly and healthier. During use, it will not affect the appearance and performance of pulp molding products, thus ensuring the overall quality of the products.

[0005] Another objective of this invention is to provide a method for preparing an oil repellent for molding fluorine-free pulp. This method is simple, easy to implement, and conducive to large-scale production and application. It not only solves environmental problems and improves product performance, but also simplifies the preparation process, demonstrating significant advantages.

[0006] The objective of this invention is achieved through the following technical solution: an oil repellent for molding fluorine-free pulp, characterized in that it comprises the following raw materials in parts by weight: 4-8 parts of short-chain alkanes, 30-50 parts of long-chain alkanes, 0.1-0.5 parts of antioxidant, 4-8 parts of film-forming agent, 0.01-0.1 parts of inorganic ash, 60-80 parts of solvent, and 0.5-1.0 parts of other additives.

[0007] The oil-repellent agent of this invention possesses excellent water and oil repellency, effectively preventing oil pollution and penetration, and improving the service life and performance of pulp molded products. Furthermore, the raw materials are free of fluorine and silicon, avoiding the harm to human health and the environment caused by fluorine and silicon chemicals found in traditional oil-repellent agents, making it more environmentally friendly and healthier. During use, it will not affect the appearance or performance of pulp molded products, ensuring the overall quality of the product. The oil-repellent agent of this invention uses organic compounds such as short-chain and long-chain alkanes as raw materials. These raw materials have good biodegradability and low toxicity, conforming to the development trend of environmentally friendly materials, and therefore have broad application prospects in the field of environmentally friendly materials technology. The addition of antioxidants and film-forming agents to the oil-repellent agent improves its stability and oil-repellent effect. Antioxidants prevent oxidation during use, extending its service life, while film-forming agents allow the oil-repellent agent to form a protective film on the surface of the pulp molded product, effectively preventing oil penetration.

[0008] Preferably, the short-chain alkane is at least one selected from starch, short-chain vinyl alkyl ether, and short-chain vinyl carboxylate. Preferably, the starch is cationic starch.

[0009] Preferably, the long-chain alkane is selected from waxes with a carbon chain greater than 40. The long-chain alkane is preferably at least one of microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and polypropylene wax with a carbon chain greater than 40. Therefore, the final oil repellent has a heat resistance to oil exceeding 65°C.

[0010] In this invention, the cationic starch used in the short-chain alkanes is mainly characterized by the introduction of tertiary or quaternary amino groups into the starch, giving it cationic properties. This allows it to effectively bond tightly with the negatively charged paper fiber surface, forming a dense oil-resistant film, thus more effectively preventing the penetration of grease. At the same time, the cationic starch plays a certain emulsifying role in this technology. During the preparation of the oil-resistant agent, it can effectively mix the microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and polypropylene wax used in the long-chain alkanes with water in the solvent (the above-mentioned waxes are slightly soluble in water, and the wax floats on the water surface during the dissolution process and cannot form a homogeneous dispersion), thereby increasing its lubricity and stability, and finally forming a stable wax dispersion. It can also avoid the problem of reducing the waterproof and oil-resistant effect of the oil-resistant agent due to the direct addition of conventional emulsifiers to form a hydrophilic and oleophilic system.

[0011] Preferably, the antioxidant is at least one selected from 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, antioxidant 1010, antioxidant 1076, and antioxidant 168.

[0012] The antioxidants used in this invention can prevent the oil inhibitor from oxidizing during use and extend its service life.

[0013] Preferably, the film-forming agent is at least one of polyvinylpyrrolidone, polyvinyl alcohol, and nanocellulose.

[0014] The specific raw materials used in the film-forming agent of this invention enable the oil repellent to form a protective film on the surface of the pulp molded product, effectively preventing oil penetration. Furthermore, the nanocellulose can be compounded with starch used in the short-chain alkanes in a special manner. On one hand, the combination of nanocellulose and starch achieves high oil repellency, achieving excellent oil-repellent effects with a low coating amount; on the other hand, the starch embedded in and gelatinized in the nanocellulose promotes film formation, reducing the use of polyvinylpyrrolidone and polyvinyl alcohol.

[0015] Preferably, the solvent is water or ethylene glycol.

[0016] Preferably, the inorganic ash is composed of at least one of fumed silica, magnesium oxide powder, and volcanic ash.

[0017] Preferably, the other additives are at least one of polyethylene glycol, sodium carboxymethyl cellulose, and talc.

[0018] The talc used in other additives of this invention can fill the gaps between paper fibers, and starch can also make the wax and talc mix evenly and form a three-dimensional network structure together with sodium carboxymethyl cellulose, which further makes the talc better fixed on the fibers and exerts a synergistic effect.

[0019] This invention also provides a method for preparing an oil-resistant agent for molding fluorine-free pulp, comprising the following steps:

[0020] S1. According to the weight parts, put the short-chain alkanes, long-chain alkanes and solvent into the reaction vessel, heat to 75-80℃, and stir and mix for 1.5-2.5h under the pressure of 0.8-1.2MPa to make the various raw materials fully mixed and uniform, and obtain mixture A for later use.

[0021] S2. According to the weight parts, the antioxidant, film-forming agent, inorganic ash and other additives are mixed and ultrasonically treated until uniformly mixed to obtain mixture B. Then, mixture B is added to mixture A, heated to 80-85℃, and stirred and mixed for 0.6-1.0h under a pressure of 1.0-1.2MPa. After cooling, the oil-resistant agent is obtained.

[0022] The oil-repellent agent of this invention is prepared by the above method. The oil-repellent agent prepared by this method has excellent water and oil repellency, effectively preventing oil pollution and penetration, and improving the service life and performance of pulp molded products. Its preparation method is simple and easy to implement, which is conducive to large-scale production and application. It not only solves environmental problems and improves product performance, but also simplifies the preparation process, showing significant advantages. During the preparation process, the viscosity, density, and pH value of the oil-repellent agent are adjusted to be within a suitable range to ensure the effectiveness and safety of the oil-repellent agent. Specifically, the density is controlled between 0.95 and 1.0, and the pH value is controlled between 4 and 7. 4. Optimize the oil repellency level: Through experiments and tests, the oil repellency level of the oil-repellent agent is controlled between 8 and 10 to meet the needs of different application scenarios. This effectively solves the problems existing in the prior art, preparing a fluorine-free and silicone-free environmentally friendly oil-repellent agent while ensuring the oil repellency effect and not affecting the appearance and performance of pulp molded products.

[0023] The beneficial effects of this invention are as follows: the oil repellent of this invention has good waterproof and oil-repellent properties, which can effectively prevent oil pollution and penetration, improve the service life and performance of pulp molded products, and at the same time avoid the harm to human body and environment caused by fluorine and silicon chemicals contained in traditional oil repellents, making it more environmentally friendly and healthy. During use, it will not have any impact on the appearance and performance of pulp molded products, thus ensuring the overall quality of the products.

[0024] The present invention provides a simple and easy-to-implement method for preparing an oil-resistant agent for molding fluorine-free pulp, which is conducive to large-scale production and application. It not only solves the environmental protection problem and improves product performance, but also simplifies the preparation process, and has significant advantages. Detailed Implementation

[0025] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to embodiments. The content mentioned in the embodiments is not intended to limit the present invention.

[0026] Example 1

[0027] An oil repellent for molding fluorine-free pulp is characterized by comprising the following raw materials in parts by weight: 4 parts short-chain alkanes, 30 parts long-chain alkanes, 0.1 parts antioxidant, 4 parts film-forming agent, 0.01 parts inorganic ash, 60 parts solvent, and 0.5 parts other additives.

[0028] The short-chain alkane is starch, and the starch is cationic starch.

[0029] The long-chain alkane is microcrystalline wax; the antioxidant is 2,6-di-tert-butyl-p-cresol.

[0030] The film-forming agent is polyvinylpyrrolidone; the solvent is water.

[0031] The inorganic ash is composed of fumed silica.

[0032] The other additives are composed of polyethylene glycol, sodium carboxymethyl cellulose and talc in a weight ratio of 0.8:0.6:0.4.

[0033] A method for preparing an oil-resistant agent for molding fluorine-free pulp includes the following steps:

[0034] S1. According to the weight parts, put the short-chain alkanes, long-chain alkanes and solvent into the reaction vessel, heat to 75°C, and stir and mix for 1.5 hours under a pressure of 0.8 MPa to ensure that the various raw materials are fully mixed and homogeneous, so as to obtain mixture A for later use.

[0035] S2. According to the weight parts, the antioxidant, film-forming agent, inorganic ash and other additives are mixed and ultrasonically treated until uniformly mixed to obtain mixture B. Then, mixture B is added to mixture A, heated to 80°C, and stirred and mixed for 0.6 hours under a pressure of 1.0 MPa. After cooling, the oil-resistant agent is obtained.

[0036] Example 2

[0037] An oil repellent for molding fluorine-free pulp, characterized in that it comprises the following raw materials in parts by weight: 5 parts short-chain alkanes, 33 parts long-chain alkanes, 0.2 parts antioxidant, 5 parts film-forming agent, 0.03 parts inorganic ash, 65 parts solvent, and 0.6 parts other additives.

[0038] The short-chain alkane is a short-chain vinyl alkyl ether. The long-chain alkane is a Fischer-Tropsch wax.

[0039] The antioxidant is butylated hydroxyanisole. The film-forming agent is polyvinylpyrrolidone.

[0040] The solvent is water. The inorganic ash is magnesium oxide powder.

[0041] The other additives are composed of polyethylene glycol, sodium carboxymethyl cellulose and talc in a weight ratio of 0.9:0.7:0.5.

[0042] A method for preparing an oil-resistant agent for molding fluorine-free pulp includes the following steps:

[0043] S1. According to the weight parts, put the short-chain alkanes, long-chain alkanes and solvent into the reaction vessel, heat to 76°C, and stir and mix for 1.8 hours under a pressure of 0.9 MPa to ensure that the various raw materials are fully mixed and homogeneous, so as to obtain mixture A for later use.

[0044] S2. According to the weight parts, the antioxidant, film-forming agent, inorganic ash and other additives are mixed and ultrasonically treated until they are uniformly mixed to obtain mixture B. Then, mixture B is added to mixture A, heated to 82°C, and stirred and mixed for 0.7 hours under a pressure of 1.2 MPa. After cooling, the oil-resistant agent is obtained.

[0045] Example 3

[0046] An oil repellent for molding fluorine-free pulp, characterized in that it comprises the following raw materials in parts by weight: 6 parts short-chain alkanes, 40 parts long-chain alkanes, 0.3 parts antioxidant, 6 parts film-forming agent, 0.05 parts inorganic ash, 70 parts solvent, and 0.8 parts other additives.

[0047] The short-chain alkane is composed of starch, short-chain vinyl alkyl ether, and short-chain vinyl carboxylate in a weight ratio of 0.8:0.7:0.5. The starch is cationic starch.

[0048] The long-chain alkane is composed of microcrystalline wax, Fischer-Tropsch wax, polyethylene wax and polypropylene wax in a weight ratio of 1.2:0.6:0.8:0.7.

[0049] The antioxidant is composed of 2,6-di-tert-butyl-p-cresol and antioxidant 1010 in a weight ratio of 0.6:0.7.

[0050] The film-forming agent is nanocellulose.

[0051] The solvent is water.

[0052] The inorganic ash is composed of fumed silica, magnesium oxide powder and volcanic ash in a weight ratio of 0.6:0.7:0.8.

[0053] The other additives are composed of polyethylene glycol, sodium carboxymethyl cellulose and talc in a weight ratio of 1.0:0.8:0.6.

[0054] A method for preparing an oil-resistant agent for molding fluorine-free pulp includes the following steps:

[0055] S1. According to the weight parts, put the short-chain alkanes, long-chain alkanes and solvent into the reaction vessel, heat to 78°C, and stir and mix for 1.8 hours under a pressure of 1.0 MPa to make the various raw materials fully mixed and uniform, and obtain mixture A for later use.

[0056] S2. According to the weight parts, the antioxidant, film-forming agent, inorganic ash and other additives are mixed and ultrasonically treated until they are uniformly mixed to obtain mixture B. Then, mixture B is added to mixture A, heated to 83°C, and stirred and mixed for 0.8 hours under a pressure of 1.1 MPa. After cooling, the oil-resistant agent is obtained.

[0057] Example 4

[0058] An oil repellent for molding fluorine-free pulp, characterized in that it comprises the following raw materials in parts by weight: 7 parts short-chain alkanes, 45 parts long-chain alkanes, 0.4 parts antioxidant, 7 parts film-forming agent, 0.08 parts inorganic ash, 75 parts solvent, and 0.9 parts other additives.

[0059] The short-chain alkane is a short-chain ethylene carboxylate.

[0060] The long-chain alkane is polyethylene wax. The antioxidant is antioxidant 1076.

[0061] The film-forming agent is polyvinyl alcohol. The solvent is water. The inorganic ash is volcanic ash.

[0062] The other additives are composed of polyethylene glycol, sodium carboxymethyl cellulose and talc in a weight ratio of 1.2:1.0:0.8.

[0063] A method for preparing an oil-resistant agent for molding fluorine-free pulp includes the following steps:

[0064] S1. According to the weight parts, put the short-chain alkanes, long-chain alkanes and solvent into the reaction vessel, heat to 79°C, and stir and mix for 2.3 hours under a pressure of 1.1 MPa to ensure that the various raw materials are fully mixed and homogeneous, so as to obtain mixture A for later use.

[0065] S2. According to the weight parts, the antioxidant, film-forming agent, inorganic ash and other additives are mixed and ultrasonically treated until they are uniformly mixed to obtain mixture B. Then, mixture B is added to mixture A, heated to 84°C, and stirred and mixed for 1.0 h under a pressure of 1.0 MPa. After cooling, the oil-resistant agent is obtained.

[0066] Example 5

[0067] An oil repellent for molding fluorine-free pulp, characterized in that it comprises the following raw materials in parts by weight: 8 parts short-chain alkanes, 50 parts long-chain alkanes, 0.5 parts antioxidant, 8 parts film-forming agent, 0.1 parts inorganic ash, 80 parts solvent, and 1.0 part other additives.

[0068] The short-chain alkane is starch. The starch is cationic starch. The long-chain alkane is microcrystalline wax.

[0069] The antioxidant is 2,6-di-tert-butyl-p-cresol. The film-forming agent is polyvinylpyrrolidone. The solvent is water. The inorganic ash is fumed silica.

[0070] The other additives are composed of polyethylene glycol, sodium carboxymethyl cellulose and talc in a weight ratio of 1.2:1.0:0.8.

[0071] A method for preparing an oil-resistant agent for molding fluorine-free pulp includes the following steps:

[0072] S1. According to the weight parts, put the short-chain alkanes, long-chain alkanes and solvent into the reaction vessel, heat to 80°C, and stir and mix for 2.5 hours under a pressure of 1.2 MPa to ensure that the various raw materials are fully mixed and homogeneous, so as to obtain mixture A for later use.

[0073] S2. According to the weight parts, the antioxidant, film-forming agent, inorganic ash and other additives are mixed and ultrasonically treated until uniformly mixed to obtain mixture B. Then, mixture B is added to mixture A, heated to 85°C, and stirred and mixed for 1.0 h under a pressure of 1.2 MPa. After cooling, the oil-resistant agent is obtained.

[0074] Comparative Example 1

[0075] The difference between this comparative example and Example 3 above is that in this comparative example, only short-chain vinyl alkyl ethers are used for the preparation of the oil repellent, and the remaining raw materials are mixed in the proportions of Example 3. The rest of the contents of this comparative example are the same as those of Example 3, and will not be repeated here.

[0076] Comparative Example 2

[0077] The difference between this comparative example and Example 3 above is that no film-forming agent or other additives were added when preparing the anti-oil agent in this comparative example. The rest of the contents of this comparative example are the same as those of Example 3, and will not be repeated here.

[0078] Performance testing

[0079] The oil repellents prepared in Specific Example 3 and Comparative Examples 1-2 were used to prepare molded products of the same size and their performance was tested:

[0080] 1. Waterproof performance: The surface water absorption of the molded material was measured using a Cobb value tester in a constant temperature and humidity chamber (temperature 23℃, humidity 50%) using the 60s (45s+15s) method. The lower the Cobb value, the stronger the water resistance of the molded material and the better its waterproof performance.

[0081] The Cobb value of the product obtained in Example 3 was 14.2 g / m³. 2 The Cobb value of the product obtained in Comparative Example 1 was 19.2 g / m³. 2 The Cobb value of the product obtained in Comparative Example 2 was 18.5 g / m³. 2 .

[0082] 2. Heat resistance oil test: The hot oil penetration time of the sample is tested using hot oil at 70℃ at room temperature.

[0083] The hot oil penetration time of the product obtained in Example 3 was greater than 130 min, while the hot oil penetration time of the products obtained in the comparative examples was less than 100 min.

[0084] 3. Oil Resistance Test: The oil resistance rating was determined using the TAPPI T 559cm-12 standard. Specifically, 12 test solutions (numbered 1-12) were prepared using castor oil, toluene, and n-heptane in different volume ratios. The oil and grease resistance of the molded paper made from the products of Example 3 and the comparative examples was then determined using these 12 test solutions with different surface tensions. During the test, the molded paper was flattened, and one drop of test solution was dropped at a height of 25mm (1 inch). After 15 seconds, the remaining test solution was wiped away, and the molded paper was immediately observed for any penetration. The test was repeated until the molded paper surface of the numbered test solution no longer showed any penetration or discoloration. The oil resistance rating of the molded paper is the numerical value of that number. A higher oil resistance rating indicates stronger oil resistance and better practicality of the molded paper. Ultimately, the oil resistance rating of Example 3 was 10, while the oil resistance ratings of the products obtained in the comparative examples were all <5.

[0085] The above embodiments are preferred implementations of the present invention. In addition, the present invention can be implemented in other ways. Any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A non-fluorine oil-proof agent for pulp molding, characterized by comprising: The raw materials include the following weight parts: short-chain alkane 4-8 parts, long-chain alkane 30-50 parts, antioxidant 0.1-0.5 parts, film forming agent 4-8 parts, inorganic ash 0.01-0.1 parts, solvent 60-80 parts and other auxiliary agents 0.5-1.0 parts; The short-chain alkane is composed of starch, short-chain vinyl alkyl ether and short-chain vinyl carboxylate according to a weight ratio of 0.8:0.7:0.5; the film forming agent is nano-cellulose; and the other auxiliary agents are composed of polyethylene glycol, sodium carboxymethyl cellulose and talc powder according to a weight ratio of 1.0:0.8:0.

6.

2. The oil repellent agent for pulp molding according to claim 1, characterized by: The starch is cationic starch.

3. The oil repellent agent for pulp molding according to claim 1, characterized by: The long-chain alkane is at least one of microcrystalline wax, Fischer-Tropsch wax, polyethylene wax and polypropylene wax.

4. The oil repellent agent for pulp molding according to claim 1, wherein: The antioxidant is at least one of 2,6-di-tert-butyl-p-cresol, butylated hydroxyl anisole, antioxidant 1010, antioxidant 1076 and antioxidant 168.

5. The oil repellent agent for pulp molding according to claim 1, wherein: The solvent is water or ethylene glycol.

6. The oil repellent agent for pulp molding according to claim 1, wherein: The inorganic ash is at least one of fumed silica, magnesium powder and volcanic ash.

7. A process for the preparation of a fluorochemical paper pulp moulding oil repellent agent as claimed in any one of claims 1 to 6, characterised in that: The method comprises the following steps: S1, according to weight parts, the short-chain alkane, long-chain alkane and solvent are put into a reaction kettle, heated to 75-80℃, and stirred and mixed under the condition of a pressure of 0.8-1.2 MPa for 1.5-2.5 h, so that various raw materials are fully mixed and uniform, to obtain a mixture A for standby; S2, according to weight parts, the antioxidant, film forming agent, inorganic ash and other auxiliary agents are mixed and then ultrasonically treated until mixed uniformly to obtain a mixture B, and then the mixture B is added to the mixture A, heated to 80-85℃, and stirred and mixed under the condition of a pressure of 1.0-1.2 MPa for 0.6-1.0 h, and then cooled to obtain the oil-proof agent.