High performance non-polar adhesive material and method of making same

Abstract

This invention discloses a high-performance non-polar adhesive material and its preparation method. The adhesive material is prepared by first preparing an interfacial bridger containing lauryl methacrylate, butyl acrylate, methyl methacrylate, methacrylic acid, and hydroxyethyl methacrylate, and then reacting it with a nano-calcium carbonate modified polyacrylate emulsion, C9 petroleum resin emulsion, emulsified silicone oil, potassium zirconium carbonate, nano-active zinc oxide, LK water-resistant agent, Kathon, and water through a specific process. The interfacial bridger possesses both a non-polar long-chain alkyl structure and polar active groups, which can improve the wetting and interfacial adsorption capacity of non-polar substrates such as polyethylene and polypropylene, and enhance the synergistic effect with the main emulsion and cross-linking system. The adhesive material has advantages such as fast initial tack, high bond strength, good cold water resistance, and excellent system stability, and is suitable for bonding polyethylene or polypropylene to paper, glass, and coated paper.

Description

Technical Field

[0001] This invention relates to the field of polymer adhesives, and in particular to a high-performance non-polar adhesive material and its preparation method. Background Technology

[0002] Adhesives, as important industrial auxiliary materials, are widely used in electronics, packaging, construction, automotive, medical, and many other fields. It is well known that there are many types of adhesives, each with its own application. Bonding polar materials is usually easy, with many adhesives available. However, bonding non-polar materials such as polyethylene, polypropylene, polystyrene, and polyester is extremely difficult. Some adhesives considered to have a wide range of applications, such as polyisobutylene adhesive, F-2 adhesive, EVA hot melt adhesive, polyurethane adhesive, α-cyanoacrylate adhesive, acrylic polyester adhesive, and silicone adhesive, have failed to achieve satisfactory results when bonding these non-polar materials, especially highly crystalline non-polar materials, where they show almost no adhesion. This is mainly because non-polar materials have low surface energy, poor wettability, and a lack of reactive functional groups, making it difficult for traditional adhesives to form effective chemical bonds or physical anchors. The interfacial bonding strength is extremely low, making peeling or detachment very easy. Recently, acrylic adhesives developed abroad have shown good bonding effects on the aforementioned non-polar materials. However, their components are unknown, and they are very expensive, making large-scale promotion difficult.

[0003] To address the challenge of bonding non-polar materials, researchers both domestically and internationally have explored various modification methods in recent years, such as plasma treatment, corona treatment, flame treatment, chemical etching, and surface grafting. However, these methods suffer from drawbacks including uneven processing, unstable results, high equipment investment, and unsuitability for continuous production. In the field of water-based adhesives, existing technologies often employ polyacrylate emulsions combined with tackifying resins. However, these methods generally suffer from insufficient initial tack, poor wetting properties on non-polar substrates, and inadequate water resistance, failing to meet the requirements of modern high-speed labeling machines and other industrial production processes for rapid adhesion and water and moisture resistance. Therefore, the market urgently needs a high-performance, fast-adhesive non-polar material adhesive that offers good initial tack, low cost, environmental friendliness, non-toxicity, wide applicability, and excellent water and moisture resistance. Summary of the Invention

[0004] To address the aforementioned problems, this invention proposes a high-performance non-polar adhesive material and its preparation method. The adhesive material works synergistically with a crosslinking system of nano-calcium carbonate modified polyacrylate emulsion, C9 petroleum resin emulsion, potassium zirconium carbonate, and nano-active zinc oxide to achieve rapid bonding between non-polar and polar materials and significantly improve water resistance.

[0005] This invention can be achieved through the following technical solutions: A method for preparing a high-performance non-polar adhesive material includes the following steps: S1. Lauryl methacrylate, butyl acrylate, methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate are mixed, and then pre-emulsified with sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-9 and water. Semi-continuous dropwise polymerization is carried out at 75-82℃ initiated by potassium persulfate. After polymerization, the pH is adjusted to 6.8-7.5 with ammonia water to obtain the interface bridging agent. S2. Add water to the reactor, and under stirring conditions, add nano-calcium carbonate modified polyacrylate emulsion, interfacial bridging agent, C9 petroleum resin emulsion and emulsified silicone oil in sequence, and mix at 42-48℃ for 20-40 min; add ammonia water to adjust the pH of the system to 5.8-6.2, and keep it warm and stir for 10-20 min; add potassium zirconium carbonate, nano-active zinc oxide, LK water-resistant agent and Kathon in sequence at 42-48℃, and continue stirring and reacting for 1.5-2.5 h. After the reaction is completed, add ammonia water to adjust the pH of the system to 6.8-7.2, filter and discharge to obtain high-performance non-polar adhesive material.

[0006] Preferably, the interface bridging agent comprises the following components in parts by weight: 7.0-9.5 parts lauryl methacrylate, 14-18 parts butyl acrylate, 6.5-9.0 parts methyl methacrylate, 2.0-3.5 parts methacrylic acid, 2-3 parts hydroxyethyl methacrylate, 0.8-1.5 parts sodium dodecyl sulfate, 1-2 parts fatty alcohol polyoxyethylene ether AEO-9, 0.3-0.8 parts potassium persulfate, and 55-65 parts water.

[0007] Preferably, the high-performance non-polar adhesive material comprises, by weight: 200 parts water, 150-300 parts nano-calcium carbonate modified polyacrylate emulsion, 150-300 parts C9 petroleum resin emulsion, 8-25 parts interface bridging agent, 2-6 parts emulsified silicone oil, 5-15 parts potassium zirconium carbonate, 2-5 parts nano-active zinc oxide, 2-24 parts LK water-resistant agent, and 1-3 parts Kathon.

[0008] The beneficial effects of this invention are: This invention utilizes a self-made interfacial bridging agent containing lauryl methacrylate, methacrylic acid, and hydroxyethyl methacrylate segments. This agent is then synergistically constructed with a nano-calcium carbonate-modified polyacrylate emulsion, a C9 petroleum resin emulsion, and a potassium zirconium carbonate / nano-active zinc oxide composite crosslinking system. This results in a multiphase network structure that combines non-polar surface affinity, polar film-forming adhesion, and enhanced water resistance. The long-chain alkyl segments significantly improve the wetting, spreading, and interfacial adsorption capabilities of non-polar substrates such as polyethylene and polypropylene, while the carboxyl and hydroxyl groups enhance the association and network-locking effects with the main emulsion and crosslinking components. Consequently, the resulting adhesive material possesses advantages such as fast bonding speed, strong initial tack, high cohesive strength, excellent cold water resistance, good system stability, and a wide range of applicable substrates. It is particularly suitable for efficient bonding of non-polar materials with polar materials such as paper, glass, and coated paper. Detailed Implementation

[0009] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0010] In the following examples, the LK water-resistant agent was provided by Henan Beidou Zhongchuang High-tech Research Institute, and the nano-calcium carbonate modified polyacrylate emulsion was a patented product with the patent number ZL:202310563991.3.

[0011] Example 1: A method for preparing a high-performance non-polar adhesive material, comprising the following steps: S1. Weigh out 7.0 parts of lauryl methacrylate, 14 parts of butyl acrylate, 6.5 parts of methyl methacrylate, 2.0 parts of methacrylic acid, 2 parts of hydroxyethyl methacrylate, 0.8 parts of sodium dodecyl sulfate, 1.0 part of fatty alcohol polyoxyethylene ether AEO-9, 0.3 parts of potassium persulfate, and 65 parts of water. Mix lauryl methacrylate, butyl acrylate, methyl methacrylate, methacrylic acid, and hydroxyethyl methacrylate, then pre-emulsify with sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-9, and water. Perform semi-continuous dropwise polymerization at 75°C using potassium persulfate as an initiator. After polymerization, adjust the pH to 6.8 with ammonia to obtain an interfacial bridging agent. S2. Take 200 parts water, 150 parts nano-calcium carbonate modified polyacrylate emulsion, 150 parts C9 petroleum resin emulsion, 8 parts interface bridging agent, 2 parts emulsified silicone oil, 5 parts potassium zirconium carbonate, 2 parts nano-active zinc oxide, 2 parts LK water-resistant agent, and 1 part Kathon. Add water to a reaction vessel, and under stirring conditions, add the nano-calcium carbonate modified polyacrylate emulsion, interface bridging agent, C9 petroleum resin emulsion, and emulsified silicone oil in sequence, and mix at 42℃ for 20 min. Add ammonia water to adjust the pH of the system to 5.8, and keep it at this temperature and stir for 10 min. At 42℃, add potassium zirconium carbonate, nano-active zinc oxide, LK water-resistant agent, and Kathon in sequence, and continue stirring and reacting for 1.5 h. After the reaction is completed, add ammonia water to adjust the pH of the system to 6.8, filter and discharge to obtain a high-performance non-polar adhesive material.

[0012] Example 2: A method for preparing a high-performance non-polar adhesive material, comprising the following steps: S1. Weigh out 8.25 parts of lauryl methacrylate, 16 parts of butyl acrylate, 7.75 parts of methyl methacrylate, 2.75 parts of methacrylic acid, 2.5 parts of hydroxyethyl methacrylate, 1.15 parts of sodium dodecyl sulfate, 1.5 parts of fatty alcohol polyoxyethylene ether AEO-9, 0.55 parts of potassium persulfate, and 60 parts of water. Mix lauryl methacrylate, butyl acrylate, methyl methacrylate, methacrylic acid, and hydroxyethyl methacrylate, then pre-emulsify with sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-9, and water. Perform semi-continuous dropwise polymerization at 78.5℃ using potassium persulfate as an initiator. After polymerization, adjust the pH to 7.15 with ammonia to obtain an interfacial bridging agent. S2. Take 200 parts water, 225 parts nano-calcium carbonate modified polyacrylate emulsion, 225 parts C9 petroleum resin emulsion, 16.5 parts interface bridging agent, 4 parts emulsified silicone oil, 10 parts potassium zirconium carbonate, 3.5 parts nano-active zinc oxide, 13 parts LK water-resistant agent, and 2 parts Kathon. Add water to a reaction vessel, and under stirring conditions, add the nano-calcium carbonate modified polyacrylate emulsion, interface bridging agent, C9 petroleum resin emulsion, and emulsified silicone oil in sequence, and mix at 45℃ for 30 min. Add ammonia water to adjust the pH of the system to 6.0, and keep it warm and stir for 15 min. At 45℃, add potassium zirconium carbonate, nano-active zinc oxide, LK water-resistant agent, and Kathon in sequence, and continue stirring and reacting for 2.0 h. After the reaction is completed, add ammonia water to adjust the pH of the system to 7.0, filter and discharge to obtain a high-performance non-polar adhesive material.

[0013] Example 3: A method for preparing a high-performance non-polar adhesive material, comprising the following steps: S1. Weigh out 9.5 parts of lauryl methacrylate, 18 parts of butyl acrylate, 9.0 parts of methyl methacrylate, 3.5 parts of methacrylic acid, 3 parts of hydroxyethyl methacrylate, 1.5 parts of sodium dodecyl sulfate, 2.0 parts of fatty alcohol polyoxyethylene ether AEO-9, 0.8 parts of potassium persulfate, and 55 parts of water. Mix lauryl methacrylate, butyl acrylate, methyl methacrylate, methacrylic acid, and hydroxyethyl methacrylate, then pre-emulsify with sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-9, and water. Perform semi-continuous dropwise polymerization at 82°C using potassium persulfate as an initiator. After polymerization, adjust the pH to 7.5 with ammonia to obtain an interfacial bridging agent. S2. Take 200 parts water, 300 parts nano-calcium carbonate modified polyacrylate emulsion, 300 parts C9 petroleum resin emulsion, 25 parts interface bridging agent, 6 parts emulsified silicone oil, 15 parts potassium zirconium carbonate, 5 parts nano-active zinc oxide, 24 parts LK water-resistant agent, and 3 parts Kathon. Add water to a reaction vessel, and under stirring conditions, add the nano-calcium carbonate modified polyacrylate emulsion, interface bridging agent, C9 petroleum resin emulsion, and emulsified silicone oil in sequence, and mix at 48℃ for 40 min. Add ammonia water to adjust the pH of the system to 6.2, and keep it at this temperature and stir for 20 min. At 48℃, add potassium zirconium carbonate, nano-active zinc oxide, LK water-resistant agent, and Kathon in sequence, and continue stirring and reacting for 2.5 h. After the reaction is completed, add ammonia water to adjust the pH of the system to 7.2, filter and discharge to obtain a high-performance non-polar adhesive material.

[0014] Comparative Example 1: The difference between this comparative example and Example 1 is that no interface bridging agent is added.

[0015] A method for preparing a high-performance non-polar adhesive material is as follows: Take 200 parts water, 150 parts nano-calcium carbonate modified polyacrylate emulsion, 150 parts C9 petroleum resin emulsion, 2 parts emulsified silicone oil, 5 parts potassium zirconium carbonate, 2 parts nano-active zinc oxide, 2 parts LK water-resistant agent, and 1 part Kathon; add water to a reaction vessel, and under stirring conditions, add the nano-calcium carbonate modified polyacrylate emulsion, interface bridging agent, C9 petroleum resin emulsion, and emulsified silicone oil sequentially, and mix at 42℃ for 20 min; add ammonia water to adjust the pH of the system to 5.8, and keep it warm and stir for 10 min; add potassium zirconium carbonate, nano-active zinc oxide, LK water-resistant agent, and Kathon sequentially at 42℃, and continue stirring and reacting for 1.5 h; after the reaction is completed, add ammonia water to adjust the pH of the system to 6.8, filter and discharge to obtain the high-performance non-polar adhesive material.

[0016] Comparative Example 2: The difference between this comparative example and Example 1 is that lauryl methacrylate is not added.

[0017] A method for preparing a high-performance non-polar adhesive material includes the following steps: S1. Weigh 14 parts of butyl acrylate, 6.5 parts of methyl methacrylate, 2.0 parts of methacrylic acid, 2 parts of hydroxyethyl methacrylate, 0.8 parts of sodium dodecyl sulfate, 1.0 part of fatty alcohol polyoxyethylene ether AEO-9, 0.3 parts of potassium persulfate, and 65 parts of water. Mix butyl acrylate, methyl methacrylate, methacrylic acid, and hydroxyethyl methacrylate, then pre-emulsify with sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-9, and water. Perform semi-continuous dropwise polymerization at 75°C using potassium persulfate as an initiator. After polymerization, adjust the pH to 6.8 with ammonia to obtain an interfacial bridging agent. S2. Take 200 parts water, 150 parts nano-calcium carbonate modified polyacrylate emulsion, 150 parts C9 petroleum resin emulsion, 8 parts interface bridging agent, 2 parts emulsified silicone oil, 5 parts potassium zirconium carbonate, 2 parts nano-active zinc oxide, 2 parts LK water-resistant agent, and 1 part Kathon. Add water to a reaction vessel, and under stirring conditions, add the nano-calcium carbonate modified polyacrylate emulsion, interface bridging agent, C9 petroleum resin emulsion, and emulsified silicone oil in sequence, and mix at 42℃ for 20 min. Add ammonia water to adjust the pH of the system to 5.8, and keep it at this temperature and stir for 10 min. At 42℃, add potassium zirconium carbonate, nano-active zinc oxide, LK water-resistant agent, and Kathon in sequence, and continue stirring and reacting for 1.5 h. After the reaction is completed, add ammonia water to adjust the pH of the system to 6.8, filter and discharge to obtain a high-performance non-polar adhesive material.

[0018] Comparative Example 3: The difference between this comparative example and Example 1 is that potassium zirconium carbonate and nano-active zinc oxide are not added.

[0019] A method for preparing a high-performance non-polar adhesive material includes the following steps: S1. Weigh out 7.0 parts of lauryl methacrylate, 14 parts of butyl acrylate, 6.5 parts of methyl methacrylate, 2.0 parts of methacrylic acid, 2 parts of hydroxyethyl methacrylate, 0.8 parts of sodium dodecyl sulfate, 1.0 part of fatty alcohol polyoxyethylene ether AEO-9, 0.3 parts of potassium persulfate, and 65 parts of water. Mix lauryl methacrylate, butyl acrylate, methyl methacrylate, methacrylic acid, and hydroxyethyl methacrylate, then pre-emulsify with sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-9, and water. Perform semi-continuous dropwise polymerization at 75°C using potassium persulfate as an initiator. After polymerization, adjust the pH to 6.8 with ammonia to obtain an interfacial bridging agent. S2. Take 200 parts water, 150 parts nano-calcium carbonate modified polyacrylate emulsion, 150 parts C9 petroleum resin emulsion, 8 parts interface bridging agent, 2 parts emulsified silicone oil, 2 parts LK water-resistant agent, and 1 part Kathon. Add water to a reaction vessel, and under stirring conditions, add nano-calcium carbonate modified polyacrylate emulsion, interface bridging agent, C9 petroleum resin emulsion, and emulsified silicone oil in sequence, and mix at 42℃ for 20 min. Add ammonia water to adjust the pH of the system to 5.8, and keep it at the temperature and stir for 10 min. Add LK water-resistant agent and Kathon in sequence at 42℃, and continue stirring and reacting for 1.5 h. After the reaction is completed, add ammonia water to adjust the pH of the system to 6.8, filter and discharge to obtain a high-performance non-polar adhesive material.

[0020] Performance testing 1 Viscosity The viscosity of adhesive materials shall be determined in accordance with GB / T 2794-2022.

[0021] 2. Solid content The solid content of adhesive materials shall be determined in accordance with GB / T 2793-1995.

[0022] 3. Bonding speed The adhesive material to be tested was uniformly coated on a polyethylene (PE) film with a coating amount of 10 g / m2. The coated paper was immediately bonded to the coated surface and a pressure of 0.2 MPa was applied for 1 second. The time required from bonding to the point where the paper fibers began to break when the paper surface was gently rubbed with a finger was recorded. Each sample was tested 5 times and the average value was taken.

[0023] 4 Cold water resistance test Prepare bonding samples according to the bonding speed test method (after pressing, let them stand at room temperature for 24 hours to fully cure). Immerse the samples completely in 4℃ cold water, with the water depth completely covering the samples. Observe every 4 hours and record the time when the samples delaminate and blister. Test 3 samples for each sample and take the shortest time as the water resistance time.

[0024] 5. pH Measurement The pH of the adhesive material was determined according to GB / T 14518-1993.

[0025] Table 1 Performance test results of adhesive materials

[0026] As shown in Table 1, the viscosity of the adhesive materials prepared in Examples 1-3 gradually increased from 40,000 mPa·s to 68,000 mPa·s, the solid content increased from 25% to 34%, while the bonding speed decreased from 6 s to 2 s, and the cold water resistance test time increased from 180 h to 300 h. This indicates that by introducing a self-made interfacial bridging agent containing lauryl methacrylate segments, the excellent physical adsorption and molecular chain entanglement between its long-chain alkyl groups and the surfaces of non-polar materials such as polyethylene and polypropylene significantly improved the initial wettability and adhesion of the adhesive to non-polar substrates. Simultaneously, the active functional groups contained in the methacrylic acid and hydroxyethyl methacrylate segments of the interfacial bridging agent can form a synergistic crosslinking network with nano-calcium carbonate modified polyacrylate emulsion, potassium zirconium carbonate, and nano-active zinc oxide. With the increase of the amount of each component, the crosslinking density continuously increases, thereby maintaining rapid positioning and bonding capabilities while progressively enhancing cohesive strength and water and moisture resistance.

[0027] In contrast, Comparative Example 1, lacking an interfacial bridging agent, lacked long-chain alkyl segments with affinity for non-polar surfaces, resulting in a drastically extended bonding speed of 16s and a cold water resistance of only 12h. This demonstrates that the interfacial bridging agent is an irreplaceable core component for achieving rapid bonding of non-polar materials. Comparative Example 2, without lauryl methacrylate, lacked effective intermolecular forces between C12 and higher long-chain alkyl groups and non-polar substrates such as polyethylene and polypropylene. Its bonding speed (12s) and water resistance (36h) were significantly worse than Example 1, indicating that the long-chain structure of lauryl methacrylate has a unique contribution to the affinity for non-polar surfaces. Comparative Example 3, without potassium zirconium carbonate and nano-active zinc oxide, lacked cross-linking reinforcement components. Insufficient cohesive strength led to a significant decrease in water resistance to 48h, far lower than the 180h of Example 1. This confirms that the cross-linking network formed by potassium zirconium carbonate and nano-active zinc oxide plays a crucial role in improving the density, water penetration resistance, and long-term durability of the adhesive layer.

[0028] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a high-performance non-polar adhesive material, characterized in that, Includes the following steps: S1. Lauryl methacrylate, butyl acrylate, methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate are mixed, and then pre-emulsified with sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-9 and water. Semi-continuous dropwise polymerization is carried out at 75-82℃ initiated by potassium persulfate. After polymerization, the pH is adjusted to 6.8-7.5 with ammonia water to obtain the interface bridging agent. S2. Add water to the reactor, and under stirring conditions, add nano-calcium carbonate modified polyacrylate emulsion, interfacial bridging agent, C9 petroleum resin emulsion and emulsified silicone oil in sequence, and mix at 42-48℃ for 20-40 min; add ammonia water to adjust the pH of the system to 5.8-6.2, and keep it warm and stir for 10-20 min; add potassium zirconium carbonate, nano-active zinc oxide, LK water-resistant agent and Kathon in sequence at 42-48℃, and continue stirring and reacting for 1.5-2.5 h. After the reaction is completed, add ammonia water to adjust the pH of the system to 6.8-7.2, filter and discharge to obtain high-performance non-polar adhesive material.

2. The method for preparing the high-performance non-polar adhesive material according to claim 1, characterized in that, The interface bridging agent comprises the following components in parts by weight: 7.0-9.5 parts lauryl methacrylate, 14-18 parts butyl acrylate, 6.5-9.0 parts methyl methacrylate, 2.0-3.5 parts methacrylic acid, 2-3 parts hydroxyethyl methacrylate, 0.8-1.5 parts sodium dodecyl sulfate, 1-2 parts fatty alcohol polyoxyethylene ether AEO-9, 0.3-0.8 parts potassium persulfate, and 55-65 parts water.

3. The method for preparing the high-performance non-polar adhesive material according to claim 1, characterized in that, The high-performance non-polar adhesive material comprises, by weight: 200 parts water, 150-300 parts nano-calcium carbonate modified polyacrylate emulsion, 150-300 parts C9 petroleum resin emulsion, 8-25 parts interface bridging agent, 2-6 parts emulsified silicone oil, 5-15 parts potassium zirconium carbonate, 2-5 parts nano-active zinc oxide, 2-24 parts LK water-resistant agent, and 1-3 parts Kathon.

4. The method for preparing the high-performance non-polar adhesive material according to claim 1, characterized in that, The high-performance non-polar adhesive material has a viscosity of 30,000-70,000 mPa·s at 27°C, a solid content of 25-35 wt%, and a bonding speed of 2-4 s at 30°C.

5. The method for preparing the high-performance non-polar adhesive material according to claim 1, characterized in that, The high-performance non-polar adhesive material is used for bonding polyethylene or polypropylene to paper, glass, or coated paper.

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