EVA color master batch and preparation method thereof
By introducing modified EVA and modified EVOH into EVA masterbatch, and combining them with poly4-methylpentene-1, the problem of thermal degradation of EVA masterbatch at high temperature was solved, the heat resistance and processability were improved, and the stability and dispersibility of the masterbatch were achieved.
Patent Information
- Application Number
- CN202511203389.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-27
- Publication Date
- 2025-11-14
AI Technical Summary
EVA masterbatch is prone to thermal degradation at high temperatures, which affects the performance of plastic products.
A ternary blend system was constructed using modified EVA and modified EVOH. Benzene rings and anhydride groups were introduced into EVA by grafting 2,3-diphenylmaleic anhydride onto it, and mercapto groups were introduced into modified EVOH to eliminate free radicals. Poly(4-methylpentene-1) was combined to improve heat resistance and compatibility.
It significantly improves the heat resistance and processability of masterbatch, enhances the dispersibility of pigments and inorganic fillers, forms a stable blend, and inhibits thermal degradation reactions.
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer materials technology, specifically relating to an EVA masterbatch and its preparation method. Background Technology
[0002] Plastic masterbatch is a type of plastic granule made by uniformly loading an extraordinary amount of pigment into a resin. This concentrated color formulation allows for direct use of the corresponding masterbatch in the manufacture of plastic products, eliminating the need for additional plastic additives. Therefore, masterbatch is one of the main material forms used in plastic additive applications. Normally, the carrier resin of the masterbatch and the matrix resin of the product should be selected as the same type of polymer to ensure good chemical compatibility between the two. Universal masterbatch, on the other hand, is suitable for a variety of matrix resins.
[0003] EVA is a random copolymer of ethylene and vinyl acetate. The presence of vinyl acetate restricts the crystallization of PE, making it a thermoplastic elastomer. EVA contains both non-polar polyethylene segments and polar vinyl acetate segments, making it suitable for use with general-purpose plastics such as PE, PP, PVC, and PS. In the field of masterbatches, EVA is a commonly used carrier material, favored for its good processability and excellent physical properties.
[0004] However, when EVA masterbatch is used in engineering plastics (such as PA, PBT, PC, PPE, POM, etc.), the processing temperature of engineering plastics is usually high, and EVA will undergo thermal degradation at high temperatures, thus affecting the performance of plastic products. Summary of the Invention
[0005] This invention provides an EVA masterbatch and its preparation method, which can solve the problem of poor high-temperature resistance of EVA masterbatch in the prior art.
[0006] The objective of this invention can be achieved through the following technical solutions: An EVA masterbatch, by weight, comprises the following raw materials: Modified EVA 35-45 parts, modified EVOH 5-15 parts, poly4-methylpentene-1 10-20 parts, pigment 20-30 parts, inorganic filler 6-12 parts, stearic acid 2-8 parts, polyethylene wax 1-3 parts, silane coupling agent 1-2 parts, antioxidant 2-5 parts; The modified EVA is EVA grafted with 2,3-diphenylmaleic anhydride; The modified EVOH is an esterification product of EVOH and mercaptoacetic acid.
[0007] Thermal degradation of EVA triggers the generation of free radicals, which induce continuous thermal degradation reactions. Grafting 2,3-diphenylmaleic anhydride onto EVA introduces rigid benzene rings, increasing steric hindrance of the molecular chains, restricting chain movement, and raising the heat distortion temperature. The anhydride promotes further cross-linking of EVA, forming a three-dimensional cross-linked network and inhibiting the thermal degradation reaction. Introducing highly polar carboxylic anhydride groups onto the EVA chains allows these highly reactive anhydride groups to react with hydroxyl and amino groups, thereby improving compatibility with inorganic fillers and pigments, making the different components in the masterbatch more homogeneous, and imparting better temperature resistance.
[0008] EVOH, a hydrolysis product of EVA, possesses gas barrier properties and contains hydroxyl groups. Using these hydroxyl groups as modification sites, thiol groups are introduced through esterification. Some hydroxyl groups are replaced by mercaptoacetate groups. These thiol groups can scavenge free radicals, effectively inhibiting thermal degradation caused by free radicals. During processing, the modified EVA anhydride and the thiol groups of the modified EVOH form thioester bonds, creating a stable blend that inhibits thermal degradation at high temperatures. Poly(4-methylpentene-1) exhibits high heat resistance and, as an olefin, shows compatibility with other polymers, significantly improving the heat resistance of masterbatches. Simultaneously, poly(4-methylpentene-1) has a low melt viscosity, which helps improve the melt flowability of masterbatches, making them easier to process and disperse.
[0009] Furthermore, the modified EVA is prepared as follows: 2,3-Diphenylmaleic anhydride and initiator are dissolved in acetone, EVA is added and stirred evenly, the temperature is raised to 90-100℃ to evaporate and remove acetone, and the mixture is fed into a screw extruder and melt-granulated at 180-200℃ to obtain modified EVA.
[0010] Under the action of an initiator, the maleic anhydride ring of 2,3-diphenylmaleic anhydride is opened and grafted onto the EVA molecular chain through a free radical reaction, introducing a highly polar carboxylic anhydride group onto the EVA backbone.
[0011] Furthermore, the initiator is one of benzoyl peroxide and dicumyl peroxide; The initiator is 10-20 wt% EVA.
[0012] Furthermore, the mass ratio of the 2,3-diphenylmaleic anhydride to the initiator is 15-25:1.
[0013] Furthermore, the modified EVOH is prepared as follows: EVOH was dissolved in N,N-dimethylacetamide to obtain an EVOH solution. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere and heated to 105-115℃ for esterification reaction for 2-3 hours. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0014] Under heating conditions, the hydroxyl groups of EVOH undergo esterification with the carboxyl groups of mercaptoacetic acid to form side chains containing terminal -SH groups.
[0015] Furthermore, the ratio of EVOH to mercaptoacetic acid is n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.5-0.8.
[0016] Furthermore, the pigment is at least one of organic pigments and inorganic pigments.
[0017] Furthermore, the inorganic filler is at least one of nano zinc oxide, nano silicon dioxide, and magnesium hydroxide.
[0018] Furthermore, the silane coupling agent is one of KH570 and KH550.
[0019] Furthermore, the antioxidant is at least one of phosphite antioxidants and hindered phenolic antioxidants.
[0020] This invention also provides a method for preparing EVA masterbatch, comprising the following steps: S1. Prepare the raw materials according to the proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation to obtain EVA masterbatch.
[0021] Furthermore, the melting temperature of the melt granulation is 200-220℃.
[0022] The beneficial effects of this invention are: (1) In this invention, a ternary blend system is constructed using modified EVA, modified EVOH and poly-4-methylpentene-1. Modified EVA is used as the main carrier. By modifying it, benzene rings and anhydride groups are introduced. While improving the thermal stability of the molecular chain itself, the strong anhydride groups can enhance the compatibility with other components in the masterbatch. Thiol groups are introduced into modified EVOH to eliminate free radicals generated by thermal degradation and terminate the chain reaction. The anhydride of modified EVA and the thiol group of modified EVOH form thioester bonds during processing to form a stable blend, which further inhibits the thermal degradation reaction.
[0023] (2) Poly(4-methylpentene-1) as a heat-resistant polyolefin material can be interwoven and compatible with the olefin segments of modified EVA and modified EVOH through entanglement, which can greatly improve the heat resistance of color masterbatch.
[0024] (3) This invention differs from traditional EVA masterbatches by adding modified EVOH and poly4-methylpentene-1, which endow the masterbatches with good gas barrier properties and mechanical properties. The lower melt viscosity of poly4-methylpentene-1 helps to improve the melt flowability of the masterbatch, promotes the mixing and dispersion of pigments, inorganic fillers and other components with polymer materials in the masterbatch, and improves processability. Detailed Implementation
[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0026] Example 1
[0027] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0028] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0029] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts modified EVA, 10 parts modified EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0030] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0031] Example 2
[0032] The only difference from Example 1 is that, in preparing the modified EVA, the mass ratio of 2,3-diphenylmaleic anhydride to benzoyl peroxide is 15:1, and the benzoyl peroxide is 10% of the mass of EVA.
[0033] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 15:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 10% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0034] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0035] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts modified EVA, 10 parts modified EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0036] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0037] Example 3
[0038] The only difference from Example 1 is that, in preparing the modified EVA, the mass ratio of 2,3-diphenylmaleic anhydride to benzoyl peroxide is 25:1, and the benzoyl peroxide is 20% of the mass of EVA.
[0039] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 25:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 20% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0040] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0041] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts modified EVA, 10 parts modified EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0042] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0043] Example 4
[0044] The only difference from Example 1 is that, when preparing modified EVOH, the ratio of EVOH to mercaptoacetic acid is n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.5.
[0045] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0046] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.5. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0047] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts modified EVA, 10 parts modified EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0048] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0049] Example 5
[0050] The only difference from Example 1 is that, when preparing modified EVOH, the ratio of EVOH to mercaptoacetic acid is n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.8.
[0051] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0052] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.8. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0053] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts modified EVA, 10 parts modified EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0054] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0055] Example 6
[0056] The only difference from Example 1 is that the weight of poly4-methylpentene in the EVA masterbatch is adjusted to 20 parts.
[0057] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0058] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0059] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts modified EVA, 10 parts modified EVOH, 20 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0060] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0061] Example 7
[0062] The only difference from Example 1 is that the weight of poly4-methylpentene in the EVA masterbatch is adjusted to 10 parts.
[0063] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0064] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0065] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts modified EVA, 10 parts modified EVOH, 10 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0066] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0067] Example 8
[0068] The only difference from Example 1 is that the weight of modified EVA is adjusted to 35 parts and the weight of modified EVOH is adjusted to 15 parts.
[0069] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0070] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0071] An EVA masterbatch, by weight, comprises the following raw materials: 35 parts modified EVA, 15 parts modified EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0072] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0073] Example 9
[0074] The only difference from Example 1 is that the weight of modified EVA is adjusted to 45 parts and the weight of modified EVOH is adjusted to 5 parts.
[0075] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0076] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0077] An EVA masterbatch, by weight, comprises the following raw materials: 45 parts modified EVA, 5 parts modified EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0078] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0079] Comparative Example 1
[0080] The only difference from Example 1 is that, in this comparative example, an equal mass of EVA is used to replace the modified EVA.
[0081] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0082] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts EVA, 10 parts modified EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0083] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0084] Comparative Example 2
[0085] The only difference from Example 1 is that the modified EVOH was replaced with an equal mass of EVOH in this comparative example.
[0086] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0087] An EVA masterbatch, by weight, comprises the following raw materials: Modified EVA 40 parts, EVOH 10 parts, poly-4-methylpentene-1 15 parts, titanium dioxide 25 parts, nano silica 10 parts, stearic acid 5 parts, polyethylene wax 2 parts, silane coupling agent KH550 1.5 parts, antioxidant 1010 4 parts.
[0088] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0089] Comparative Example 3
[0090] The only difference from Example 1 is that, in this comparative example, an equal mass of modified EVA is used to replace the modified EVOH.
[0091] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0092] An EVA masterbatch, by weight, comprises the following raw materials: Modified EVA 50 parts, poly4-methylpentene-1 15 parts, titanium dioxide 25 parts, nano silica 10 parts, stearic acid 5 parts, polyethylene wax 2 parts, silane coupling agent KH550 1.5 parts, antioxidant 1010 4 parts.
[0093] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0094] Comparative Example 4
[0095] The only difference from Example 1 is that in this comparative example, the modified EVA is replaced by an equal mass of EVA, and the modified EVOH is replaced by an equal mass of EVOH.
[0096] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts EVA, 10 parts EVOH, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0097] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0098] Comparative Example 5
[0099] The only difference from Example 1 is that poly-4-methylpentene-1 is not added in this comparative example.
[0100] Preparation of modified EVA: 2,3-Diphenylmaleic anhydride and benzoyl peroxide were dissolved in acetone to form a 10 wt% solution with a mass ratio of 20:1. EVA was added and stirred until homogeneous. The benzoyl peroxide content was 15% of the mass of EVA. The solution was heated to 95°C to evaporate and remove the acetone. The solution was then fed into a screw extruder and melt-granulated at 190°C to obtain modified EVA.
[0101] Preparation of modified EVOH: EVOH was dissolved in N,N-dimethylacetamide in a water bath at 60℃ to obtain an EVOH solution with a concentration of 10 wt%. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution with a concentration of 5 wt%. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere. The ratio of EVOH to mercaptoacetic acid was n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.7. The mixture was heated to 110℃ and stirred for 2.5 h for esterification. The solvent was removed by vacuum distillation to obtain modified EVOH.
[0102] An EVA masterbatch, by weight, comprises the following raw materials: 40 parts modified EVA, 10 parts modified EVOH, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0103] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0104] Comparative Example 6
[0105] The only difference from Example 1 is that in this comparative example, the modified EVA and modified EVOH are replaced with equal masses of EVA.
[0106] An EVA masterbatch, by weight, comprises the following raw materials: 50 parts EVA, 15 parts poly-4-methylpentene-1, 25 parts titanium dioxide, 10 parts nano silica, 5 parts stearic acid, 2 parts polyethylene wax, 1.5 parts silane coupling agent KH550, and 4 parts antioxidant 1010.
[0107] Preparation of EVA masterbatch: S1. Prepare the raw materials according to the above proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation at a melting temperature of 200-220℃ to obtain EVA masterbatch.
[0108] The performance of the EVA masterbatches prepared in Examples 1-9 and Comparative Examples 1-6 was tested, and the results are shown in Table 1.
[0109] Heat resistance test: EVA masterbatch was mixed with PA6 resin at a mass percentage of 3%, and the mixture was injected into a 20×50×1mm plastic sample using an injection molding machine. The injection molding machine was heated to 220℃. The tensile strength of the plastic sample was tested. The sample was placed at 120℃ for 1000h, and the tensile strength was measured again. The tensile strength retention rate was calculated.
[0110] Dispersion rating: The obtained plastic sample is pressed into a film, and the number of color spots is observed with an optical microscope. Dispersion test is carried out with reference to "QB 1648-1992 Polyethylene Coloring Masterbatch".
[0111] Coloring strength: Coloring strength was tested in accordance with "QB 1648-1992 Polyethylene Coloring Masterbatch".
[0112] Table 1
[0113] As shown in Table 1, the temperature resistance in Examples 1-3 was controlled by adjusting the amount of 2,3-diphenylmaleic anhydride grafted onto the modified EVA. Compared to Example 1, Example 2 showed a decrease in the amount of benzene rings introduced, resulting in a decrease in temperature resistance. In Example 3, excessive grafting disrupted the molecular weight regularity of the benzene rings, affecting thermal stability, inducing chain breakage and free radical generation, thus reducing the temperature resistance of the plastic sample. Examples 4 and 5 adjusted the content of grafted thiol groups in the modified EVOH based on Example 1. A lower grafting amount reduced the degree of crosslinking with the modified EVA, leading to a decrease in the overall temperature resistance of the material. In Example 5, even with an increased grafting amount, the temperature resistance was not as good as in Example 1. In Example 6, the weight percentage of poly4-methylpentene was increased. Although the temperature resistance was improved compared to Example 1, the limited compatibility with modified EVA and modified EVOH affected the compositional uniformity of the masterbatch and reduced its dispersion performance. Among Examples 1, 8, and 9, the modified EVA to modified EVOH ratio in Example 1 was optimal, achieving the best overall performance of the PA6 plastic product prepared after adding the color masterbatch. Analysis of the results from Comparative Examples 1-6 and Example 1 shows that there is a synergistic effect between modified EVA and modified EVOH, which can improve the temperature resistance of the color masterbatch and mitigate its impact on the performance of the plastic product.
[0114] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0115] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. An EVA masterbatch, characterized in that, By weight, it includes the following ingredients: Modified EVA 35-45 parts, modified EVOH 5-15 parts, poly4-methylpentene-1 10-20 parts, pigment 20-30 parts, inorganic filler 6-12 parts, stearic acid 2-8 parts, polyethylene wax 1-3 parts, silane coupling agent 1-2 parts, antioxidant 2-5 parts; The modified EVA is EVA grafted with 2,3-diphenylmaleic anhydride; The modified EVOH is an esterification product of EVOH and mercaptoacetic acid.
2. The EVA masterbatch according to claim 1, characterized in that, The modified EVA is prepared as follows: 2,3-Diphenylmaleic anhydride and initiator are dissolved in acetone, EVA is added and stirred evenly, the temperature is raised to 90-100℃ to evaporate and remove acetone, and the mixture is fed into a screw extruder and melt-granulated at 180-200℃ to obtain modified EVA.
3. The EVA masterbatch according to claim 2, characterized in that, The initiator is one of benzoyl peroxide and dicumyl peroxide; The initiator is 10-20 wt% EVA.
4. The EVA masterbatch according to claim 2, characterized in that, The mass ratio of 2,3-diphenylmaleic anhydride to initiator is 15-25:
1.
5. The EVA masterbatch according to claim 1, characterized in that, The modified EVOH is prepared as follows: EVOH was dissolved in N,N-dimethylacetamide to obtain an EVOH solution. Mercaptoacetic acid was added to toluene to obtain a mercaptoacetic acid solution. The EVOH solution and the mercaptoacetic acid solution were mixed under a nitrogen atmosphere and heated to 105-115℃ for esterification reaction for 2-3 hours. The solvent was removed by vacuum distillation to obtain modified EVOH.
6. The EVA masterbatch according to claim 5, characterized in that, The ratio of EVOH to mercaptoacetic acid is n(vinyl alcohol in EVOH):n(mercaptoacetic acid in EVOH) = 1:0.5-0.
8.
7. An EVA masterbatch according to claim 2, characterized in that, The inorganic filler is at least one of nano zinc oxide, nano silicon dioxide, and magnesium hydroxide.
8. The EVA masterbatch according to claim 1, characterized in that, The antioxidant is at least one of phosphite antioxidants and hindered phenolic antioxidants.
9. A method for preparing EVA masterbatch as described in any one of claims 1-8, characterized in that, Includes the following steps: S1. Prepare the raw materials according to the proportions, put the raw materials into the mixer and mix them evenly to obtain the mixture; S2. The mixture is fed into a screw extruder for melt granulation to obtain EVA masterbatch.
10. The method for preparing EVA masterbatch according to claim 9, characterized in that, The melting temperature of the melt granulation is 200-220℃.