Preparation method of temperature-resistant and oil-resistant paper barrier coating
By introducing epoxy acrylate crosslinking agent and siloxane modified crosslinking agent into the paper barrier coating, a high-density crosslinking network and nanonetwork are formed, and the addition of furan-maleimide dynamic bonds are solved, and the traditional coating's shortcomings in temperature and oil resistance are achieved, and high temperature stability and self-healing ability are improved.
Patent Information
- Application Number
- CN202510692561.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-27
- Publication Date
- 2025-08-12
AI Technical Summary
Traditional paper barrier coatings have obvious shortcomings in temperature and oil resistance, which are difficult to meet the high-temperature environment and grease corrosion requirements of modern food and electronic packaging, affecting food safety and the stability of electronic components.
Epoxy acrylic ester crosslinking agent and silicone modified epoxy acrylic ester crosslinking agent are used to form a high-density crosslinking network and nanonetwork, combining furan-maleimide dynamic bonds to enhance the temperature and oil resistance of the coating and impart self-healing ability.
It significantly improves the temperature and oil resistance of paper barrier coating, enhances high temperature stability and grease barrier capabilities, and also has self-healing functions to extend the coating life and maintain long-term barrier performance.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of coatings, and in particular to a method for preparing a heat-resistant and oil-resistant paper barrier coating. Background Art
[0002] In the field of packaging and industrial protection, paper barrier coatings are widely used. As key properties, temperature resistance and oil resistance play a decisive role in the actual performance and scope of application of the coating.
[0003] Temperature resistance is crucial for paper barrier coatings. In the food packaging industry, with the continuous advancement of modern food processing techniques, high-temperature sterilization and hot filling are becoming increasingly common. If a paper barrier coating lacks heat resistance, the molecular structure within the coating will change in high-temperature environments, significantly reducing its barrier properties. This allows oxygen, water vapor, and other substances to easily penetrate the coating, accelerating oxidation, deterioration, and mold growth in food, severely damaging its quality and shortening its shelf life. For example, if a paper barrier coating with poor heat resistance is used for packaging food that is commonly retorted, the food could become contaminated during the retorting process due to coating failure, compromising food safety. In the electronics packaging industry, electronic products often experience varying degrees of temperature fluctuations during manufacturing, transportation, and use, particularly during production processes like welding and baking, which generate high temperatures. A paper barrier coating with excellent heat resistance can protect electronic components from heat damage, preventing deformation of the packaging material and coating shedding due to excessive temperatures, thereby ensuring stable performance and product reliability.
[0004] Oil resistance is also essential for paper barrier coatings. Many food packaging, such as fried foods and meat products, contains oil. If the paper barrier coating lacks oil resistance, the oil will gradually penetrate the coating, contaminating the packaging's appearance and degrading the food's flavor and quality, shortening its shelf life. In the industrial sector, some products, such as machinery parts packaging, come into contact with various oily substances during storage and transportation. If the coating's oil resistance is insufficient, the oily substances will erode the coating, destroying the barrier structure, reducing its protective effect on the paper, and ultimately affecting product quality.
[0005] However, traditional styrene-butadiene emulsion-based paper barrier coatings have significant shortcomings in heat and oil resistance, making them difficult to meet the growing demands of today's market. Therefore, developing a paper barrier coating with excellent heat and oil resistance is of great significance. This will not only help improve product quality, ensure food safety, and promote the development of the electronics industry, but also better meet the diverse needs of industrial packaging, which has important practical significance for the development of related industries. Summary of the Invention
[0006] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a method for preparing a heat-resistant and oil-resistant paper barrier coating.
[0007] A method for preparing a heat-resistant and oil-resistant paper barrier coating comprises the following steps: S1. Mix epichlorohydrin, hydroxyethyl acrylate, and triethylamine, seal the mixture, stir in a constant temperature water bath, and cool the mixture to obtain an epoxy acrylate crosslinking agent; S2, mixing an epoxy acrylate crosslinker, γ-methacryloxypropyltrimethoxysilane, and deionized water, adjusting the pH of the system, stirring, and allowing to stand to obtain a siloxane-modified epoxy acrylate crosslinker; S3, mixing butadiene, styrene, acrylic acid, itaconic acid, a silicone-modified epoxy acrylate crosslinker, furan methyl acrylate, and maleimide acrylate, adding sodium lauryl sulfate and deionized water, stirring, heating, adding ammonium persulfate, standing, heating and maintaining the temperature, and cooling to obtain styrene-butadiene latex; S4. Adjust the pH of the styrene-butadiene latex system, add an antioxidant, a leveling agent, and a defoaming agent, stir, sieve, apply to the paper surface under a nitrogen atmosphere, and dry to obtain a heat-resistant paper barrier coating.
[0008] Preferably, in step S1, the weight ratio of epichlorohydrin, hydroxyethyl acrylate and triethylamine is 85-100:110-120:1-2.
[0009] Preferably, in step S1, the temperature of the constant temperature water bath is 55-65° C., the stirring time of the constant temperature water bath is 4-5 h, and the stirring speed is 400-500 rpm.
[0010] Preferably, in step S2, the weight ratio of epoxy acrylate crosslinking agent, γ-methacryloxypropyltrimethoxysilane, and deionized water is 160-200:25-35:130-170.
[0011] Preferably, in step S2, a 10% by mass HCl solution is used to adjust the pH of the system to 4-5.
[0012] Preferably, in step S2, stirring is performed with a stirring time of 1-2 hours and a stirring speed of 700-800 rpm.
[0013] Preferably, in step S2, the mixture is allowed to stand for 24-28 hours.
[0014] Preferably, in step S3, the weight ratio of butadiene, styrene, acrylic acid, itaconic acid, silicone-modified epoxy acrylate crosslinker, furan methyl acrylate, maleimide acrylate, sodium lauryl sulfate, and deionized water is 150-200:250-300:10-30:5-10:25-35:10-20:3-7:2-6:300-400.
[0015] Preferably, in step S3, stirring is performed with a stirring time of 1-2 hours and a stirring speed of 700-800 rpm.
[0016] Preferably, in step S3, after adding sodium lauryl sulfate and deionized water and stirring, the temperature is raised to 82-86° C., and 5-15 parts of ammonium persulfate are added. Based on the total weight of ammonium persulfate, the addition rate of ammonium persulfate is 20-30% per minute.
[0017] Preferably, in step S3, after standing, the temperature is raised and kept warm, and the temperature is raised to 97-100° C. and kept warm for 1-2 hours.
[0018] Preferably, in step S3, the standing time is 4-5 hours. Preferably, in step S4, the weight ratio of styrene-butadiene latex, antioxidant, leveling agent and defoaming agent is 900-950:2-4:0.05-0.15:0.01-0.1.
[0019] Preferably, in step S4, the antioxidant is 1010, the leveling agent is BYK-333, and the defoaming agent is BYK-024.
[0020] Preferably, in step S4, a 10% by mass NaOH solution is added to the styrene-butadiene latex to adjust the pH of the system to 6.5-7.5.
[0021] Preferably, in step S4, stirring is performed with a stirring time of 0.5-1 h and a stirring speed of 400-500 rpm.
[0022] Preferably, in step S4, the product is sieved through a 200-mesh sieve. Beneficial effects
[0023] The present invention significantly improves the heat resistance of paper barrier coatings through the synergistic effect of molecular structure design and functional groups, while taking into account oil resistance and self-healing functions. Compared with traditional styrene-butadiene latex coatings that rely on a single crosslinker and a simple copolymerization system, the present invention introduces a bifunctional crosslinker, a siloxane hybrid network and a dynamic reversible bond to reconstruct the coating structure at the molecular level to form a multiple heat-resistant and oil-resistant barrier. Specifically, by synthesizing epoxy acrylate crosslinkers, the system forms a high-density crosslinked network, enhancing the flexibility of the molecular chain, which not only effectively blocks the diffusion of oily substances, but also improves the coating's resistance to high-temperature deformation, inhibits the thermal motion of the molecular chain, and enables the coating to maintain structural stability at high temperatures. Secondly, the crosslinker is modified with siloxane to form a nanonetwork in the coating, further improving the heat resistance. At the same time, the nanonetwork effectively blocks the penetration of oxygen and grease. Finally, the introduction of furan-maleimide dynamic bonds gives the coating self-healing ability, thereby extending the coating life and maintaining the long-term stability of the barrier properties.
[0024] This invention abandons the reliance on physical blending to enhance heat resistance, instead achieving functional integration at the molecular level. The bifunctional design of the epoxy acrylate crosslinker, the enhanced heat resistance of the siloxane network, and the self-healing capabilities of the dynamic bonds work synergistically to form a closed-loop logic. The crosslinker provides a foundational heat- and oil-resistant framework, the siloxane network enhances stability, and the dynamic bonds compensate for structural damage in harsh environments. This provides a scientific and reliable solution for the development of highly heat-resistant and oil-resistant paper barrier coatings. DETAILED DESCRIPTION
[0025] The present invention will be further explained below with reference to specific embodiments. Example 1
[0026] A method for preparing a heat-resistant and oil-resistant paper barrier coating comprises the following steps: S1. Mix 85 g of epichlorohydrin, 110 g of hydroxyethyl acrylate, and 1 g of triethylamine, seal the mixture, stir in a 55° C. constant temperature water bath at 400 rpm for 4 h, and cool to obtain an epoxy acrylate crosslinking agent; S2, 160g of epoxy acrylate crosslinker, 25g of γ-methacryloxypropyltrimethoxysilane, and 130g of deionized water were mixed, and the pH of the system was adjusted to 4 with a 10% mass fraction of HCl solution. The mixture was stirred for 1h at a stirring speed of 700rpm and allowed to stand for 24h to obtain a siloxane-modified epoxy acrylate crosslinker; S3, 150g butadiene, 250g styrene, 10g acrylic acid, 5g itaconic acid, 25g silicone modified epoxy acrylate crosslinker, 10g furan methacrylate, 3g maleimide acrylate were mixed, 2g sodium lauryl sulfate and 300g deionized water were added, and the mixture was stirred for 1h at a stirring speed of 700rpm. The mixture was transferred to a reactor, vacuumed and replaced with nitrogen, and the temperature was raised to 82°C. 5g ammonium persulfate was added, and the total weight of ammonium persulfate was used as a benchmark, and the rate of addition of ammonium persulfate was 20% per minute. The mixture was allowed to stand for 4h, and the temperature was raised to 97°C and kept warm for 1h. The mixture was cooled to obtain styrene-butadiene latex; S4. Add 5% by mass of NaOH solution to 900 g of styrene-butadiene latex to adjust the pH of the system to 6.5, add 2 g of antioxidant 1010, 0.05 g of leveling agent BYK-333, and 0.01 g of defoaming agent BYK-024, stir for 0.5 h at a stirring speed of 400 rpm, sieve, apply on the surface of paper under a nitrogen atmosphere, and dry to obtain a heat-resistant and oil-resistant paper barrier coating. Example 2
[0027] A method for preparing a heat-resistant and oil-resistant paper barrier coating comprises the following steps: S1. Mix 100 g of epichlorohydrin, 120 g of hydroxyethyl acrylate, and 2 g of triethylamine, seal the mixture, stir in a constant temperature water bath at 65° C. for 5 h at a stirring speed of 500 rpm, and cool to obtain an epoxy acrylate crosslinking agent; S2, 200g of epoxy acrylate crosslinker, 35g of γ-methacryloxypropyltrimethoxysilane, and 170g of deionized water were mixed, and the pH of the system was adjusted to 5 with a 10% mass fraction of HCl solution. The mixture was stirred for 2h at a stirring speed of 800rpm and allowed to stand for 28h to obtain a siloxane-modified epoxy acrylate crosslinker; S3, 200g butadiene, 300g styrene, 30g acrylic acid, 10g itaconic acid, 35g silicone modified epoxy acrylate crosslinker, 20g furan methacrylate, 7g maleimide acrylate were mixed, 6g sodium lauryl sulfate and 400g deionized water were added, and the mixture was stirred for 2h at a stirring speed of 800rpm. The mixture was transferred to a reactor, evacuated and replaced with nitrogen, and the temperature was raised to 86°C. 15g ammonium persulfate was added, and the total weight of ammonium persulfate was used as a benchmark, and the rate of addition of ammonium persulfate was 30% per minute. The mixture was allowed to stand for 5h, and the temperature was raised to 100°C and kept warm for 2h. The mixture was cooled to obtain styrene-butadiene latex; S4. Add 15% mass fraction of NaOH solution to 950g of styrene-butadiene latex to adjust the pH of the system to 7.5, add 4g of antioxidant 1010, 0.15g of leveling agent BYK-333, and 0.1g of defoaming agent BYK-024, stir for 1h at a stirring speed of 500rpm, sieve, apply on the surface of paper under nitrogen atmosphere, and dry to obtain a heat-resistant and oil-resistant paper barrier coating. Example 3
[0028] A method for preparing a heat-resistant and oil-resistant paper barrier coating comprises the following steps: S1. Mix 92 g of epichlorohydrin, 115 g of hydroxyethyl acrylate, and 1.5 g of triethylamine, seal the mixture, stir in a 60°C constant temperature water bath for 4.5 h at a stirring speed of 450 rpm, and cool to obtain an epoxy acrylate crosslinking agent; S2, 180g of epoxy acrylate crosslinker, 30g of γ-methacryloxypropyltrimethoxysilane, and 150g of deionized water were mixed, and the pH of the system was adjusted to 4.5 with a 10% mass fraction of HCl solution. The mixture was stirred for 1.5h at a stirring speed of 750rpm and allowed to stand for 26h to obtain a siloxane-modified epoxy acrylate crosslinker; S3, 175g butadiene, 275g styrene, 20g acrylic acid, 7.5g itaconic acid, 30g silicone modified epoxy acrylate crosslinker, 15g furan methacrylate, 5g maleimide acrylate were mixed, 4g sodium lauryl sulfate and 350g deionized water were added, stirred for 1.5h, the stirring speed was 750rpm, transferred to a reactor, evacuated and nitrogen purged, heated to 84°C, 10g ammonium persulfate was added, based on the total weight of ammonium persulfate, the addition rate of ammonium persulfate was 25% per minute, let stand for 4.5h, heated to 98°C and kept warm for 1.5h, cooled to obtain styrene-butadiene latex; S4. Add 10% by mass of NaOH solution to 925 g of styrene-butadiene latex to adjust the pH of the system to 7, add 3 g of antioxidant 1010, 0.1 g of leveling agent BYK-333, and 0.05 g of defoaming agent BYK-024, stir for 0.75 h at a stirring speed of 450 rpm, sieve, apply on the surface of paper under a nitrogen atmosphere, and dry to obtain a heat-resistant and oil-resistant paper barrier coating. Comparative Example 1
[0029] The difference between Comparative Example 1 and Example 3 is that the epoxy acrylate crosslinking agent and the siloxane-modified epoxy acrylate crosslinking agent in steps S1 and S2 are replaced by glycidyl methacrylate and diacetone acrylamide.
[0030] A method for preparing a paper barrier coating comprises the following steps: S1, 175g butadiene, 275g styrene, 20g acrylic acid, 7.5g itaconic acid, 1.5g glycidyl methacrylate, 1g diacetone acrylamide, 15g furan methacrylate, 5g maleimide acrylate were mixed, 4g sodium lauryl sulfate and 350g deionized water were added, and the mixture was stirred for 1.5h at a stirring speed of 750rpm. The mixture was transferred to a reactor, vacuumed and replaced with nitrogen, and the temperature was raised to 84°C. 10g ammonium persulfate was added, and the addition rate of ammonium persulfate was 25% per minute based on the total weight of ammonium persulfate. The mixture was allowed to stand for 4.5h, heated to 98°C and kept warm for 1.5h, and cooled to obtain styrene-butadiene latex; S2. To 925 g of styrene-butadiene latex, add 10% NaOH solution by mass to adjust the pH of the system to 7, add 3 g of antioxidant 1010, 0.1 g of leveling agent BYK-333, and 0.05 g of defoaming agent BYK-024, stir for 0.75 h at a stirring speed of 450 rpm, sieve, apply on the surface of paper under a nitrogen atmosphere, and dry to obtain a paper barrier coating. Comparative Example 2
[0031] The difference between Comparative Example 2 and Example 3 is that γ-methacryloxypropyltrimethoxysilane is not used to modify the epoxy acrylate crosslinking agent.
[0032] A method for preparing a paper barrier coating comprises the following steps: S1. Mix 92 g of epichlorohydrin, 115 g of hydroxyethyl acrylate, and 1.5 g of triethylamine, seal the mixture, stir in a 60°C constant temperature water bath for 4.5 h at a stirring speed of 450 rpm, and cool to obtain an epoxy acrylate crosslinking agent; S2, 175g butadiene, 275g styrene, 20g acrylic acid, 7.5g itaconic acid, 30g epoxy acrylate crosslinker, 15g furan methacrylate, 5g maleimide acrylate were mixed, 4g sodium lauryl sulfate and 350g deionized water were added, stirred for 1.5h, the stirring speed was 750rpm, transferred to a reactor, evacuated and nitrogen purged, the temperature was raised to 84°C, 10g ammonium persulfate was added, based on the total weight of ammonium persulfate, the addition rate of ammonium persulfate was 25% per minute, the mixture was allowed to stand for 4.5h, the temperature was raised to 98°C and kept warm for 1.5h, cooled, and styrene-butadiene latex was obtained; S3. Add 10% by mass of NaOH solution to 925 g of styrene-butadiene latex to adjust the pH of the system to 7, add 3 g of antioxidant 1010, 0.1 g of leveling agent BYK-333, and 0.05 g of defoaming agent BYK-024, stir for 0.75 h at a stirring speed of 450 rpm, sieve, apply on the surface of paper under a nitrogen atmosphere, and dry to obtain a paper barrier coating. Comparative Example 3
[0033] The difference between Comparative Example 3 and Example 3 is that furan methacrylate and maleimide acrylate are not added in step S3.
[0034] A method for preparing a paper barrier coating comprises the following steps: S1. Mix 92 g of epichlorohydrin, 115 g of hydroxyethyl acrylate, and 1.5 g of triethylamine, seal the mixture, stir in a 60°C constant temperature water bath for 4.5 h at a stirring speed of 450 rpm, and cool to obtain an epoxy acrylate crosslinking agent; S2, 180g of epoxy acrylate crosslinker, 30g of γ-methacryloxypropyltrimethoxysilane, and 150g of deionized water were mixed, and the pH of the system was adjusted to 4.5 with a 10% mass fraction of HCl solution. The mixture was stirred for 1.5h at a stirring speed of 750rpm and allowed to stand for 26h to obtain a siloxane-modified epoxy acrylate crosslinker; S3, 175g butadiene, 275g styrene, 20g acrylic acid, 7.5g itaconic acid, 30g silicone modified epoxy acrylate crosslinking agent were mixed, 4g sodium lauryl sulfate and 350g deionized water were added, stirred for 1.5h, the stirring speed was 750rpm, transferred to a reactor, evacuated and nitrogen purged, the temperature was raised to 84°C, 10g ammonium persulfate was added, based on the total weight of ammonium persulfate, the addition rate of ammonium persulfate was 25% per minute, the mixture was allowed to stand for 4.5h, the temperature was raised to 98°C and kept warm for 1.5h, cooled, and styrene-butadiene latex was obtained; S4. Add 10% by mass of NaOH solution to 925 g of styrene-butadiene latex to adjust the pH of the system to 7, add 3 g of antioxidant 1010, 0.1 g of leveling agent BYK-333, and 0.05 g of defoaming agent BYK-024, stir for 0.75 h at a stirring speed of 450 rpm, sieve, apply on the surface of paper under a nitrogen atmosphere, and dry to obtain a paper barrier coating. Comparative Example 4
[0035] The difference between Comparative Example 4 and Example 3 is that in step S1, the molar ratio of epichlorohydrin to hydroxyethyl acrylate is increased, that is, the mass of hydroxyethyl acrylate is 92 g.
[0036] A method for preparing a paper barrier coating comprises the following steps: S1. Mix 92 g of epichlorohydrin, 92 g of hydroxyethyl acrylate, and 1.5 g of triethylamine, seal the mixture, stir in a constant temperature water bath at 60° C. for 4.5 h at a stirring speed of 450 rpm, and cool to obtain an epoxy acrylate crosslinking agent; S2, 180g of epoxy acrylate crosslinker, 30g of γ-methacryloxypropyltrimethoxysilane, and 150g of deionized water were mixed, and the pH of the system was adjusted to 4.5 with a 10% mass fraction of HCl solution. The mixture was stirred for 1.5h at a stirring speed of 750rpm and allowed to stand for 26h to obtain a siloxane-modified epoxy acrylate crosslinker; S3, 175g butadiene, 275g styrene, 20g acrylic acid, 7.5g itaconic acid, 30g silicone modified epoxy acrylate crosslinker, 15g furan methacrylate, 5g maleimide acrylate were mixed, 4g sodium lauryl sulfate and 350g deionized water were added, stirred for 1.5h, the stirring speed was 750rpm, transferred to a reactor, evacuated and nitrogen purged, heated to 84°C, 10g ammonium persulfate was added, based on the total weight of ammonium persulfate, the addition rate of ammonium persulfate was 25% per minute, let stand for 4.5h, heated to 98°C and kept warm for 1.5h, cooled to obtain styrene-butadiene latex; S4. Add 10% by mass of NaOH solution to 925 g of styrene-butadiene latex to adjust the pH of the system to 7, add 3 g of antioxidant 1010, 0.1 g of leveling agent BYK-333, and 0.05 g of defoaming agent BYK-024, stir for 0.75 h at a stirring speed of 450 rpm, sieve, apply on the surface of paper under a nitrogen atmosphere, and dry to obtain a paper barrier coating. Performance Testing
[0037] Temperature Resistance: According to ASTM E1131, the coatings prepared in Examples 1-3 and Comparative Examples 1-4 were tested in a nitrogen atmosphere using a thermogravimetric analyzer (PerkinElmer TGA 4000). The temperature was measured at a heating rate of 10°C / min from room temperature to 800°C, and the temperature at which the sample lost 5% weight was recorded. According to ASTM D3418, the coatings prepared in Examples 1-3 and Comparative Examples 1-4 were tested using differential scanning calorimetry (DSC) at a heating rate of 10°C / min from room temperature to 150°C, and the temperature corresponding to the inflection point of the DSC curve was recorded. The results are shown in Table 1.
[0038] Self-repair performance: According to the T / CSCP 0003-2023 standard, the coatings prepared in Examples 1-3 and Comparative Examples 1-5 were tested for self-repair performance. The crack repair rate of the coatings was calculated according to the following formula and the data was recorded. The results are shown in Table 1.
[0039] Calculation formula: Crack repair rate ; Loriginal is the original crack length; L remaining is the length of the crack after 24 hours.
[0040] Oxygen Transmission Rate: The coatings prepared in Examples 1-3 and Comparative Examples 1-5 were tested for oxygen barrier properties using an oxygen transmission rate tester (Labthink TOY-C1) at 23°C, 50% RH, and an oxygen flow rate of 100 mL / min. The results are shown in Table 1.
[0041] Oil resistance: Contact angle measurements were performed on the coatings prepared in Examples 1-3 and Comparative Examples 1-5 at 23°C and 50% RH using a contact angle meter. The angle formed when the liquid droplet made contact with the coating surface was recorded. The results are shown in Table 1.
[0042] Table 1 Performance test results
[0043] Data Analysis: As can be seen from the data of Examples 1-3 in Table 1, the heat-resistant paper barrier coating prepared by the present invention has obvious advantages in heat resistance, self-healing performance, and oil resistance. The average thermal decomposition temperature (Td) is about 334°C, and the maximum can reach 335.8°C; the average glass transition temperature (Tg) is about 102°C, and the maximum can reach 103.5°C; the average crack repair rate is 87.0%, and the maximum can reach 87.3%; the average oxygen transmission rate is 5.0cc / m²·day, and the minimum can reach 4.8cc / m²·day; and the average contact angle is 115.4°, and the maximum can reach 115.8°.
[0044] As can be seen from the data of Example 3 and Comparative Example 1 in Table 1, Example 3 is significantly superior to Comparative Example 1 in terms of the coating's heat resistance, oil resistance, and self-healing ability. This is primarily due to the bifunctional design of Example 3, which forms a high-density cross-linked network, enhancing the flexibility of the molecular chain and improving the coating's resistance to high-temperature deformation and oil resistance. Siloxane modification further forms a nanonetwork within the coating, effectively blocking the penetration of oxygen and grease, significantly improving heat resistance. Furthermore, the furan-maleimide introduced in Example 3 imparts self-healing capabilities to the coating, enabling it to autonomously repair microcracks generated during high-temperature and grease erosion, thereby extending the coating's lifespan and maintaining the long-term stability of its barrier properties.
[0045] As shown in Table 1, Example 3 and Comparative Example 2 demonstrate significant superiority in terms of heat resistance, oil resistance, and self-healing ability. This is primarily due to the siloxane modification of the epoxy acrylate crosslinker in Example 3, which significantly enhances the coating's heat resistance and enables it to maintain structural stability even at high temperatures. Furthermore, the siloxane network effectively blocks the penetration of oxygen and grease, reducing oxygen transmission rate. Furthermore, the introduced furan-maleimide dynamic bonds impart self-healing capabilities to the coating, enabling it to autonomously repair microcracks generated during exposure to high temperatures and grease, thereby extending the coating's lifespan and maintaining the long-term stability of its barrier properties.
[0046] The data from Example 3 and Comparative Example 3 in Table 1 demonstrate that Example 3 significantly outperforms Comparative Example 3 in terms of heat resistance, oil resistance, and self-healing ability. This is primarily due to the addition of furan methacrylate and maleimide acrylate in Example 3, which impart self-healing capabilities to the coating, thereby extending its lifespan and maintaining the long-term stability of its barrier properties. Furthermore, the nanonetwork formed by siloxane modification in Example 3 effectively blocks the penetration of oxygen and oil, significantly improving heat resistance.
[0047] From the data of Example 3 and Comparative Example 4 in Table 1, it can be seen that Example 3 is significantly better than Comparative Example 4 in terms of the temperature resistance, oil resistance and self-repairing ability of the coating. This is mainly due to the increase in the molar ratio of epichlorohydrin to hydroxyethyl acrylate, which leads to a decrease in the performance of the epoxy acrylate crosslinker in Comparative Example 4, affecting the temperature resistance and self-repairing ability of the coating. Although siloxane-modified epoxy acrylate crosslinker and furan-maleimide dynamic bond are still used in Comparative Example 4, the overall effect is not as good as that of Example 3 due to the decline in the performance of the crosslinker. In comparison, the crosslinker design in Example 3 is more reasonable, and can form a high-density crosslinked network, enhance the flexibility of the molecular chain, and improve the coating's resistance to high-temperature deformation. At the same time, through the introduction of siloxane modification and dynamic bonds, the temperature resistance, oil resistance and self-repairing ability are further improved.
[0048] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Within the scope of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.
Claims
1. A method for preparing a heat-resistant and oil-resistant paper barrier coating, characterized in that: The steps include: S1. Mix epichlorohydrin, hydroxyethyl acrylate, and triethylamine, seal the mixture, stir in a constant temperature water bath, and cool the mixture to obtain an epoxy acrylate crosslinking agent; S2, mixing an epoxy acrylate crosslinker, γ-methacryloxypropyltrimethoxysilane, and deionized water, adjusting the pH of the system, stirring, and allowing to stand to obtain a siloxane-modified epoxy acrylate crosslinker; S3, mixing butadiene, styrene, acrylic acid, itaconic acid, a silicone-modified epoxy acrylate crosslinker, furan methyl acrylate, and maleimide acrylate, adding sodium lauryl sulfate and deionized water, stirring, heating, adding ammonium persulfate, standing, heating and maintaining the temperature, and cooling to obtain styrene-butadiene latex; S4. Adjust the pH of the styrene-butadiene latex system, add an antioxidant, a leveling agent, and a defoaming agent, stir, sieve, apply to the paper surface under a nitrogen atmosphere, and dry to obtain a heat-resistant and oil-resistant paper barrier coating.
2. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In the step S1, the weight ratio of epichlorohydrin, hydroxyethyl acrylate, and triethylamine is 85-100:110-120:1-2.
3. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In step S1, the temperature of the constant temperature water bath is 55-65° C., the stirring time of the constant temperature water bath is 4-5 hours, and the stirring speed is 400-500 rpm.
4. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In step S2, the weight ratio of epoxy acrylate crosslinking agent, γ-methacryloxypropyltrimethoxysilane, and deionized water is 160-200:25-35:130-170.
5. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In step S2, a 10% by mass HCl solution is used to adjust the pH of the system to 4-5.
6. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In step S3, the weight ratio of butadiene, styrene, acrylic acid, itaconic acid, silicone-modified epoxy acrylate crosslinker, furan methyl acrylate, maleimide acrylate, sodium lauryl sulfate, and deionized water is 150-200:250-300:10-30:5-10:25-35:10-20:3-7:2-6:300-400.
7. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In step S3, sodium lauryl sulfate and deionized water are added and stirred, then the temperature is raised to 82-86° C., and 5-15 parts of ammonium persulfate are added. The addition rate of ammonium persulfate is 20-30% per minute based on the total weight of ammonium persulfate.
8. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In the step S3, after standing, the temperature is raised and kept warm, and the temperature is raised to 97-100° C. and kept warm for 1-2 hours.
9. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In step S4, the weight ratio of styrene-butadiene latex, antioxidant, leveling agent and defoaming agent is 900-950:2-4:0.05-0.15:0.01-0.
1.
10. The method for preparing the heat-resistant and oil-resistant paper barrier coating according to claim 1, characterized in that: In the step S4, a 10% by mass NaOH solution is added to the styrene-butadiene latex to adjust the pH of the system to 6.5-7.5.