Rubber and plastic EVA material surface treating agent and preparation method thereof

Abstract

The invention relates to the technical field of surface treating agents, in particular to a rubber and plastic EVA material surface treating agent and a preparation method thereof. The rubber and plastic EVA material surface treating agent comprises the following raw materials: EVA resin, styrene butadiene rubber, chlorinated polypropylene, a mixed solvent, isobornyl acrylate, an initiator, tackifying resin, a wetting agent and a small molecule auxiliary agent. The invention further provides a preparation method of the rubber and plastic EVA material surface treating agent, and the rubber and plastic EVA material surface treating agent is obtained without using harmful organic solvents containing benzene, methylbenzene, xylene and the like. Under the condition of meeting the requirements of safety and environmental protection at home and abroad, the initial viscosity, peel strength and yellowing resistance of the surface treating agent are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of surface treatment agents, in particular to a surface treatment agent for rubber and plastic EVA materials and a preparation method thereof. Background Art

[0002] EVA surface treatment agents are chemical treatments specifically designed to improve the surface properties of EVA (ethylene-vinyl acetate copolymer) materials. They are widely used in footwear, packaging, sports equipment, automotive interiors, and other fields. Their primary functions include enhancing the surface adhesion of EVA materials, improving printing and coating effects, and enhancing the material's weather resistance and wear resistance. Their primary advantage is their excellent adhesion-enhancing effect. However, existing EVA surface treatment agents also have some drawbacks. After treatment, the chemical substances on the surface of the EVA material are less stable and durable. Summary of the Invention

[0003] In order to meet the purpose of ensuring that the surface treatment agent for rubber and plastic EVA materials has good stability and durability during use, the first purpose of the present invention is to provide a surface treatment agent for rubber and plastic EVA materials, comprising the following raw material components: by weight, comprising the following raw materials: EVA resin: 20-25 parts; styrene-butadiene rubber: 10-15 parts; chlorinated polypropylene: 5-8 parts; mixed solvent: 40-50 parts; isobornyl acrylate: 10-20 parts; initiator: 0.1-0.3 parts; tackifying resin: 3-5 parts; wetting agent: 0.5-1 part; small molecule additive: 0.1-0.5 parts.

[0004] EVA resin refers to ethylene-vinyl acetate copolymer, whose vinyl acetate groups can form hydrogen bonds with polar substrates; styrene-butadiene rubber refers to styrene-butadiene copolymer, whose elastomeric properties can improve the impact resistance of the treatment agent; chlorinated polypropylene refers to chlorine-modified polypropylene resin, whose chlorine element can enhance affinity with polar materials; mixed solvents can balance the solubility and volatilization rate of the resin; isobornyl acrylate refers to an acrylate monomer containing a bicyclic structure, whose steric hindrance effect can slow down the polymerization reaction rate; initiator refers to a free radical initiating substance, which decomposes at a specific temperature to produce active groups that initiate polymerization reactions; tackifying resin refers to a substance that improves interfacial adhesion, whose phenolic hydroxyl groups can form chemical bonds with the surface of the treated material; wetting agent refers to a substance that reduces surface tension, whose molecular structure can be oriented at the solid-liquid interface; small molecule additives are chain transfer agents, which can reduce the average molecular weight by terminating polymer chain growth and initiating new chains, thereby helping to improve the fluidity of the surface treatment agent for rubber and plastic EVA materials.

[0005] Preferably, the weight ratio of the EVA resin to the styrene-butadiene rubber is 2:1.

[0006] Preferably, the initiator is BPO.

[0007] Preferably, the tackifying resin is RX-80.

[0008] Preferably, the small molecule auxiliary agent is 0.2 parts to 0.25 parts.

[0009] Preferably, the small molecule auxiliary agent is phosphoric acid and oxalic acid, and the weight ratio of the phosphoric acid to the oxalic acid is 1:1.

[0010] Preferably, the mixed solvent is ethyl acetate and butanone.

[0011] Preferably, the ethyl acetate is 25 parts to 30 parts, and the butanone is 15 parts to 20 parts.

[0012] Compared with the prior art, the present invention has the following beneficial effects:

[0013] (1) EVA resin forms a three-dimensional skeleton as a continuous phase. Its vinyl acetate group is physically entangled with the benzene ring of styrene-butadiene rubber through van der Waals force. Under the action of the initiator, combined with the effects of isobornyl acrylate and chlorinated polypropylene, the initiator triggers the graft polymerization reaction of isobornyl acrylate, thereby enhancing the crosslinking density of the surface treatment agent. The chlorine element of chlorinated polypropylene can enhance the affinity between the surface treatment agent and the polar material, thereby improving the bonding strength of the surface treatment agent of the rubber and plastic EVA material.

[0014] (2) Tackifying resin RX-80 can fill the gaps in the EVA / styrene-butadiene rubber network, enhance the interfacial contact through van der Waals force, and improve the initial viscosity of the material; small molecule additives use phosphoric acid and oxalic acid, which serve as weak acids to lower the pH of the system, inhibit the premature decomposition of the initiator BPO, and ensure that the free radical reaction is controllable. At the same time, oxalic acid can complex the trace metal impurities in the reactor to prevent them from catalyzing side reactions; the wetting agent can effectively reduce the surface tension of the treatment agent, increase the wetting angle, and can effectively spread on the surface of the rubber and plastic EVA material, thereby increasing the contact treatment area between the rubber and plastic EVA materials.

[0015] (3) Use mixed solvents, use low-cost ethyl acetate and butanone, and do not use harmful organic solvents such as benzene, toluene, and xylene, so as to reduce pollution, improve the controllability of production, and at the same time reduce the overall cost of the product, in compliance with domestic and international safety and environmental protection requirements.

[0016] The second object of the present invention is to provide a technical solution: a method for preparing a surface treatment agent for rubber and plastic EVA materials, comprising the following steps:

[0017] Step (1): EVA resin, styrene-butadiene rubber, and chlorinated polypropylene are placed in a reaction kettle, a mixed solvent is added, and the mixture is stirred, heated, and melted at 60° C. at a stirring speed of 100 rpm / min for 2 h-2.5 h, and then nitrogen is flushed and the temperature is raised to 80° C. to obtain a mixture A;

[0018] Step (2): adding a small molecule auxiliary agent and isobornyl acrylate to the mixture A in sequence, stirring evenly, adding an initiator to react, and obtaining an EVA prepolymer after the reaction is terminated;

[0019] Step (3): When the temperature of the EVA prepolymer drops below 50° C., add a tackifying resin and a wetting agent in sequence, and stir at a stirring speed of 100 rpm / min for 1 hour to obtain an environmentally friendly rubber and plastic EVA surface treatment agent.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) In step (1), under the action of a mixed solvent, EVA resin, styrene-butadiene rubber, and chlorinated polypropylene are stirred, heated, and melted at 60° C. This is because the EVA resin and styrene-butadiene rubber need to slowly swell at a temperature below their melting points to avoid molecular chain entanglement or degradation due to high temperature. At the same time, the chlorine atoms of the chlorinated polypropylene form hydrogen bonds with the polar groups of the EVA / SBR, thereby enhancing compatibility and enabling the EVA resin, styrene-butadiene rubber, and chlorinated polypropylene to more fully participate in the reaction in subsequent steps.

[0022] (2) In step (1), nitrogen protection is performed and the temperature is raised to 80° C. The nitrogen isolates oxygen and prevents the double bonds in the styrene-butadiene rubber from oxidative cross-linking. 80° C. can improve the mobility of the EVA resin molecular chain and promote complete dissolution and homogenization.

[0023] (3) In step (2), a small molecule auxiliary agent, isobornyl acrylate and an initiator are added. The isobornyl acrylate undergoes a graft polymerization reaction under the action of the initiator. The small molecule auxiliary agent inhibits the premature decomposition of the initiator, ensuring that the free radical reaction is controllable, so that the isobornyl acrylate can undergo a sufficient cross-linking reaction.

[0024] (3) In step (3), when the temperature drops below 50°C, a tackifying resin and a wetting agent are added. Adding the tackifying resin below 50°C can prevent the resin from softening at high temperatures, which causes a sudden increase in viscosity, and facilitates uniform dispersion. Adding the wetting agent below 50°C can prevent the silicone from decomposing and failing due to high temperatures; the tackifying resin RX-80 can fill the gaps in the EVA / styrene-butadiene rubber network and improve the initial viscosity of the material; the wetting agent can effectively reduce the surface tension of the treatment agent and increase the contact treatment area between the rubber and plastic EVA materials.

[0025] (5) This preparation method only involves constant temperature stirring, dissolution and other processes, and the process flow is simple. DETAILED DESCRIPTION

[0026] The following describes the embodiments of the present invention through specific examples. Those skilled in the art will readily understand the other advantages and benefits of the present invention from the disclosure herein. The present invention may also be implemented or applied through various other specific embodiments, and the details in this specification may be modified or altered based on different viewpoints and applications without departing from the spirit of the present invention.

[0027] Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are for describing specific embodiments rather than for limiting the scope of protection of the present invention.

[0028] When numerical ranges are given in the examples, it should be understood that, unless otherwise specified herein, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs.

[0029] The present invention does not limit the sources of raw materials. Unless otherwise specified, the raw materials used are common commercial products.

[0030] Example 1:

[0031] The surface treatment agent for rubber and plastic EVA materials includes the following raw materials by weight: EVA resin: 24 parts; styrene-butadiene rubber: 12 parts; chlorinated polypropylene: 7 parts; ethyl acetate: 28 parts; butanone: 18 parts; isobornyl acrylate: 15 parts; BPO: 0.2 parts; RX-80: 3 parts to 5 parts; wetting agent 1250: 0.5 parts to 1 part; and small molecule additive: 0.25 parts.

[0032] The preparation method of the surface treatment agent for rubber and plastic EVA materials includes the following specific steps:

[0033] Step (1): EVA resin, styrene-butadiene rubber, and chlorinated polypropylene were placed in a reaction kettle, and a mixed solvent was added. The mixture was stirred, heated, and melted at 60° C. at a stirring speed of 100 rpm / min for 2.3 h, and then nitrogen was flushed and the temperature was raised to 80° C. to obtain a mixture A;

[0034] Step (2): adding a small molecule auxiliary agent and isobornyl acrylate to the mixture A in sequence, stirring evenly, adding BPO to react, and obtaining an EVA prepolymer after the reaction is terminated;

[0035] Step (3): When the temperature of the EVA prepolymer drops below 50°C, add tackifying resin RX-80 and wetting agent 1250 in sequence, and stir at a stirring speed of 100 rpm / min for 1 hour to obtain an environmentally friendly rubber and plastic EVA surface treatment agent.

[0036] Example 2:

[0037] The surface treatment agent for rubber and plastic EVA materials includes the following raw materials by weight: EVA resin: 20 parts; styrene-butadiene rubber: 10 parts; chlorinated polypropylene: 5 parts; ethyl acetate: 25 parts; butanone: 15 parts; isobornyl acrylate: 10 parts; BPO: 0.1 parts; RX-80: 3 parts; wetting agent 1250: 0.5 parts; and small molecule additive: 0.1 parts.

[0038] The preparation method of the surface treatment agent for rubber and plastic EVA materials includes the following specific steps:

[0039] Step (1): EVA resin, styrene-butadiene rubber, and chlorinated polypropylene were placed in a reaction kettle, and a mixed solvent was added. The mixture was stirred, heated, and melted at 60° C. at a stirring speed of 100 rpm / min for 2 h, and then nitrogen was flushed and the temperature was raised to 80° C. to obtain a mixture A;

[0040] Step (2): adding a small molecule auxiliary agent and isobornyl acrylate to the mixture A in sequence, stirring evenly, adding BPO to react, and obtaining an EVA prepolymer after the reaction is terminated;

[0041] Step (3): When the temperature of the EVA prepolymer drops below 50°C, add tackifying resin RX-80 and wetting agent 1250 in sequence, and stir at a stirring speed of 100 rpm / min for 1 hour to obtain an environmentally friendly rubber and plastic EVA surface treatment agent.

[0042] Example 3:

[0043] The surface treatment agent for rubber and plastic EVA materials includes the following raw materials by weight: EVA resin: 25 parts; styrene-butadiene rubber: 15 parts; chlorinated polypropylene: 8 parts; ethyl acetate: 30 parts; butanone: 20 parts; isobornyl acrylate: 20 parts; BPO: 0.3 parts; RX-80: 5 parts; wetting agent 1250: 1 part; and small molecule additive: 0.5 parts.

[0044] The preparation method of the surface treatment agent for rubber and plastic EVA materials includes the following specific steps:

[0045] Step (1): EVA resin, styrene-butadiene rubber, and chlorinated polypropylene were placed in a reaction kettle, and a mixed solvent was added. The mixture was stirred, heated, and melted at 60° C. at a stirring speed of 100 rpm / min for 2.5 h, and then nitrogen was flushed and the temperature was raised to 80° C. to obtain a mixture A;

[0046] Step (2): adding a small molecule auxiliary agent and isobornyl acrylate to the mixture A in sequence, stirring evenly, adding BPO to react, and obtaining an EVA prepolymer after the reaction is terminated;

[0047] Step (3): When the temperature of the EVA prepolymer drops below 50°C, add tackifying resin RX-80 and wetting agent 1250 in sequence, and stir at a stirring speed of 100 rpm / min for 1 hour to obtain an environmentally friendly rubber and plastic EVA surface treatment agent.

[0048] Example 4:

[0049] The surface treatment agent for rubber and plastic EVA materials includes the following raw materials by weight: EVA resin: 24 parts; styrene-butadiene rubber: 12 parts; chlorinated polypropylene: 7 parts; ethyl acetate: 28 parts; butanone: 18 parts; isobornyl acrylate: 15 parts; BPO: 0.2 parts; RX-80: 3 parts to 5 parts; wetting agent 1250: 0.5 parts to 1 part; and small molecule additive: 0.1 part.

[0050] The preparation method of the surface treatment agent for rubber and plastic EVA materials includes the following specific steps:

[0051] Step (1): EVA resin, styrene-butadiene rubber, and chlorinated polypropylene were placed in a reaction kettle, and a mixed solvent was added. The mixture was stirred, heated, and melted at 60° C. at a stirring speed of 100 rpm / min for 2.3 h, and then nitrogen was flushed and the temperature was raised to 80° C. to obtain a mixture A;

[0052] Step (2): adding a small molecule auxiliary agent and isobornyl acrylate to the mixture A in sequence, stirring evenly, adding BPO to react, and obtaining an EVA prepolymer after the reaction is terminated;

[0053] Step (3): When the temperature of the EVA prepolymer drops below 50°C, add tackifying resin RX-80 and wetting agent 1250 in sequence, and stir at a stirring speed of 100 rpm / min for 1 hour to obtain an environmentally friendly rubber and plastic EVA surface treatment agent.

[0054] Example 5:

[0055] The surface treatment agent for rubber and plastic EVA materials includes the following raw materials by weight: EVA resin: 24 parts; styrene-butadiene rubber: 12 parts; chlorinated polypropylene: 7 parts; ethyl acetate: 28 parts; butanone: 18 parts; isobornyl acrylate: 15 parts; BPO: 0.2 parts; RX-80: 3 parts to 5 parts; wetting agent 1250: 0.5 parts to 1 part; and small molecule additive: 0.15 parts.

[0056] The preparation method of the surface treatment agent for rubber and plastic EVA materials includes the following specific steps:

[0057] Step (1): EVA resin, styrene-butadiene rubber, and chlorinated polypropylene were placed in a reaction kettle, and a mixed solvent was added. The mixture was stirred, heated, and melted at 60° C. at a stirring speed of 100 rpm / min for 2.3 h, and then nitrogen was flushed and the temperature was raised to 80° C. to obtain a mixture A;

[0058] Step (2): adding a small molecule auxiliary agent and isobornyl acrylate to the mixture A in sequence, stirring evenly, adding BPO to react, and obtaining an EVA prepolymer after the reaction is terminated;

[0059] Step (3): When the temperature of the EVA prepolymer drops below 50°C, add tackifying resin RX-80 and wetting agent 1250 in sequence, and stir at a stirring speed of 100 rpm / min for 1 hour to obtain an environmentally friendly rubber and plastic EVA surface treatment agent.

[0060] Example 6:

[0061] The surface treatment agent for rubber and plastic EVA materials includes the following raw materials by weight: EVA resin: 24 parts; styrene-butadiene rubber: 12 parts; chlorinated polypropylene: 7 parts; ethyl acetate: 28 parts; butanone: 18 parts; isobornyl acrylate: 15 parts; BPO: 0.2 parts; RX-80: 3 parts to 5 parts; wetting agent 1250: 0.5 parts to 1 part; and small molecule additive: 0.2 parts.

[0062] The preparation method of the surface treatment agent for rubber and plastic EVA materials includes the following specific steps:

[0063] Step (1): EVA resin, styrene-butadiene rubber, and chlorinated polypropylene were placed in a reaction kettle, and a mixed solvent was added. The mixture was stirred, heated, and melted at 60° C. at a stirring speed of 100 rpm / min for 2.3 h, and then nitrogen was flushed and the temperature was raised to 80° C. to obtain a mixture A;

[0064] Step (2): adding a small molecule auxiliary agent and isobornyl acrylate to the mixture A in sequence, stirring evenly, adding BPO to react, and obtaining an EVA prepolymer after the reaction is terminated;

[0065] Step (3): When the temperature of the EVA prepolymer drops below 50°C, add tackifying resin RX-80 and wetting agent 1250 in sequence, and stir at a stirring speed of 100 rpm / min for 1 hour to obtain an environmentally friendly rubber and plastic EVA surface treatment agent.

[0066] In combination with Examples 1-6, some samples were taken and laminated onto rubber-plastic EVA materials to test their initial bonding strength, peel strength, heat aging resistance and shear strength. The results are shown in Table 1.

[0067] The initial tack is determined in accordance with the method specified in GB / T 19340-2014.

[0068] The peel strength is determined according to the method specified in GB / T 19340-2014.

[0069] The heat aging resistance is determined in accordance with the heat aging resistance method specified in GB / T 19340-2014;

[0070] The shear strength is determined according to the shear strength method specified in GB / T 19340-2014.

[0071] Table 1

[0072]

[0073] Note: "Material Breakage" indicates that the strength of the surface treatment agent exceeds the strength of the substrate itself, meeting high bonding requirements.

[0074] The results in Table 1 demonstrate that the surface treatment agent for rubber and plastic EVA prepared by the present invention exhibits excellent performance. When other conditions remain the same, the treatment effect of the environmentally friendly mesh treatment agent changes with the proportion of the small molecule additive. When the proportion of the small molecule additive is 2.0 and 0.25, the system exhibits optimal initial adhesion, peel strength, hydrolysis aging resistance, and shear strength.

[0075] The method uses EVA resin, styrene-butadiene rubber, chlorinated polypropylene and BPO to obtain EVA prepolymer, and then adds tackifying resin, mixed solvent, wetting agent and small molecule additive to obtain rubber and plastic EVA surface treatment agent. The rubber and plastic EVA surface treatment agent has better performance stability and durability during use, and can improve the bonding strength by improving the polarity and adhesion of the material surface, so that the material has better performance.

[0076] The method does not use harmful organic solvents such as benzene, toluene, and xylene, and meets domestic and international safety and environmental protection requirements. The prepared plastic EVA material surface treatment agent has good initial adhesion and peel strength properties for the EVA material and excellent hydrolysis and aging resistance.

[0077] The above is a further detailed description of the present invention in conjunction with specific preferred embodiments, and the specific implementation of the present invention should not be considered to be limited to these descriptions. For those skilled in the art of the present invention, without departing from the concept of the present invention, several simple deductions or substitutions can be made, which should be considered to fall within the scope of protection of the present invention.

Claims

1. A surface treatment agent for rubber and plastic EVA materials, characterized by: By weight, it includes the following raw materials: EVA resin: 20 parts to 25 parts; Styrene-butadiene rubber: 10-15 parts; Chlorinated polypropylene: 5-8 parts; Mixed solvent: 40-50 parts; Isobornyl acrylate: 10-20 parts; Initiator: 0.1-0.3 parts; Tackifying resin: 3-5 parts; Wetting agent: 0.5-1 part; Small molecule additives: 0.1-0.5 parts.

2. The surface treatment agent for rubber and plastic EVA materials according to claim 1, characterized in that: The weight ratio of the EVA resin to the styrene-butadiene rubber is 2:

1.

3. The surface treatment agent for rubber and plastic EVA material according to claim 1, characterized in that: The initiator is BPO.

4. The surface treatment agent for rubber and plastic EVA material according to claim 1, characterized in that: The tackifying resin is RX-80.

5. The surface treatment agent for rubber and plastic EVA material according to claim 1, characterized in that: The wetting agent is 1250.

6. The surface treatment agent for rubber and plastic EVA material according to claim 1, characterized in that: The small molecule auxiliary agent is 0.2 parts to 0.25 parts.

7. The surface treatment agent for rubber and plastic EVA material according to claim 1, characterized in that: The small molecule auxiliary agents are phosphoric acid and oxalic acid, and the weight ratio of the phosphoric acid to the oxalic acid is 1:

1.

8. The surface treatment agent for rubber and plastic EVA material according to claim 1, characterized in that: The mixed solvent is ethyl acetate and butanone.

9. The surface treatment agent for rubber and plastic EVA material according to claim 8, characterized in that: The ethyl acetate is 25 parts to 30 parts, and the butanone is 15 parts to 20 parts.

10. A method for preparing a surface treatment agent for rubber and plastic EVA materials according to any one of claims 1 to 9, characterized in that: The following steps are involved: Step (1): EVA resin, styrene-butadiene rubber, and chlorinated polypropylene are placed in a reaction kettle, a mixed solvent is added, and the mixture is stirred, heated, and melted at 60° C. at a stirring speed of 100 rpm / min for 2 h-2.5 h, and then nitrogen is flushed and the temperature is raised to 80° C. to obtain a mixture A; Step (2): adding a small molecule auxiliary agent and isobornyl acrylate to the mixture A in sequence, stirring evenly, adding an initiator to react, and obtaining an EVA prepolymer after the reaction is terminated; Step (3): When the temperature of the EVA prepolymer drops below 50° C., add a tackifying resin and a wetting agent in sequence, and stir at a stirring speed of 100 rpm / min for 1 hour to obtain an environmentally friendly rubber and plastic EVA surface treatment agent.

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