阅读说明：本技术 天然芳香环保型eva复合发泡材料及其制备方法和应用 (Natural aromatic environment-friendly EVA (ethylene-vinyl acetate) composite foaming material as well as preparation method and application thereof ) 是由 丁永煌 伍柃眉 王斌 于 2020-04-25 设计创作，主要内容包括：本发明涉及EVA复合材料技术领域,具体公开一种天然芳香环保型EVA复合发泡材料,由如下重量份数的组分制成：80～100份的橡塑基料,4～8份的发泡剂、0.5～1份的交联剂、0.5～0.8份的矿物油、0.5～1份的硬脂酸以及20～40份的改性薰衣草颗粒,所述橡塑基料含有40％～100％的EVA。本发明采用改性薰衣草颗粒,可有效控制薰衣草香气成分的挥发,达到香气效力持久,同时可增强发泡材料和制品的抗菌性能和除臭,具有除味、透气、提神醒脑、熏香兼驱虫等优点,可提高薰衣草利用率,减少废弃物的浪费和环境污染,绿色环保,适用于鞋底、鞋垫、瑜伽垫、爬行垫等生活用品和运动器材。(The invention relates to the technical field of EVA composite materials, and particularly discloses a natural aromatic environment-friendly EVA composite foaming material which is prepared from the following components in parts by weight: 80-100 parts of a rubber and plastic base material, 4-8 parts of a foaming agent, 0.5-1 part of a cross-linking agent, 0.5-0.8 part of mineral oil, 0.5-1 part of stearic acid and 20-40 parts of modified lavender particles, wherein the rubber and plastic base material contains 40-100% of EVA. The modified lavender particles are adopted, so that volatilization of lavender fragrance components can be effectively controlled, lasting fragrance effect is achieved, meanwhile, the antibacterial performance and deodorization of the foaming material and the product can be enhanced, the foam lavender deodorant has the advantages of deodorization, ventilation, refreshing, fragrance smoking, insect expelling and the like, the utilization rate of lavender can be improved, waste of wastes and environmental pollution are reduced, and the foam lavender deodorant is green and environment-friendly and is suitable for living goods and sports equipment such as soles, insoles, yoga mats and crawling mats.)

1. The natural aromatic environment-friendly EVA composite foaming material is characterized in that: the composite foaming material is prepared from the following components in parts by weight: 80-100 parts of a rubber and plastic base material, 4-8 parts of a foaming agent, 0.5-1 part of a cross-linking agent, 0.5-0.8 part of mineral oil, 0.5-1 part of stearic acid and 20-40 parts of modified lavender particles, wherein the rubber and plastic base material contains 40-100% of EVA.

2. The natural aromatic environment-friendly EVA composite foam material of claim 1, which is characterized in that: the rubber-plastic base material further comprises 0-20% of EPDM (ethylene-propylene-diene monomer), 0-20% of POE (polyolefin elastomer), 0-20% of SEBS (styrene-ethylene-butadiene-styrene), and 0-20% of OBC (OBC).

3. The natural aromatic environment-friendly EVA composite foam material of claim 2, wherein: the rubber-plastic base material consists of 55-70% of EVA, 5-10% of EPDM, 10-15% of POE, 10-15% of SEBS and 5-10% of OBC.

4. The natural aromatic environment-friendly EVA composite foam material of claim 1, which is characterized in that: the foaming agent is one or a mixture of azodicarbonamide, sodium bicarbonate, ammonium bicarbonate and expandable microspheres.

5. The natural aromatic environment-friendly EVA composite foam material of claim 1, which is characterized in that: the cross-linking agent is one or a mixture of two of bis-tert-butylperoxyisopropyl benzene and dicumyl peroxide.

6. The natural aromatic environment-friendly EVA composite foam material according to any one of claims 1 to 5, wherein: the modified lavender particles are prepared from the following components in parts by weight: 20-30 parts of lavender powder, 5-8 parts of waterborne polyurethane resin, 1-1.5 parts of sodium bicarbonate, 2.5-3 parts of ascorbic acid, 1-2 parts of nano zinc oxide and 2.5-3.0 parts of poly N-vinyl acetamide.

7. The natural aromatic environment-friendly EVA composite foam material of claim 6, wherein: the preparation method of the modified lavender particles comprises the following steps:

a) placing 20-30 parts of 100-mesh lavender powder which is crushed into 200 meshes into hydrogen peroxide at the temperature of 90-95 ℃ for treatment for 30-45min to activate hydroxyl in lavender cellulose, filtering and cleaning to obtain hydroxyl activated lavender powder;

b) dissolving the water-based polyurethane resin in ethanol to form an organic solution, respectively adding the hydroxyl-activated lavender powder obtained in the step a), 1-1.5 parts of sodium bicarbonate, 2.5-3 parts of ascorbic acid and 1.5-2.0 parts of poly-N-vinylacetamide, performing ultrasonic dispersion at low temperature, and performing spray drying to obtain reaction particles wrapping the water-based polyurethane resin, the sodium bicarbonate and the ascorbic acid on the surface of the hydroxyl-activated lavender powder;

c) heating and foaming the reaction particles obtained in the step b) at 125-140 ℃ to form microporous foamed lavender particles with an open-cell spherical cell structure;

d) adding the microporous foamed lavender particles obtained in the step c) and 1-2 parts of nano zinc oxide into an ethanol solution, and then performing ultrasonic dispersion for 12-15 hours to obtain a suspension;

e) and d), taking out the upper half part of the suspension liquid obtained in the step d), centrifugally separating, drying in a vacuum drying oven at 70-80 ℃, crushing, and grinding to obtain the modified lavender particles with the surface loaded with the nano zinc oxide.

8. The preparation method of the natural aromatic environment-friendly EVA composite foaming material of claim 1, which is characterized by comprising the following steps: the method comprises the following specific steps:

s1, preparing modified lavender particles;

s2, mixing the modified lavender particles obtained in the step S1 with a rubber-plastic base material, stearic acid and mineral oil for mixing for 15-20 min, adding a foaming agent and a cross-linking agent for continuous banburying when the temperature reaches 100 ℃, discharging to obtain a mixture when the temperature rises to 110-115 ℃, adding the mixture into an open mill for open milling at 80-85 ℃, carrying out thin milling for 2 times, wherein the thickness of a discharged piece is 1mm when the thin milling is carried out, transferring the milled material into a granulator for granulation, cooling and standing to obtain composite granules;

s3, spraying a release agent on a mould of a foaming machine, adding the composite granules for mould pressing and foaming, wherein the foaming temperature is 155-165 ℃, the foaming pressure can be 10-15 Mpa, and the foaming time is 10-12 min, so that the EVA composite foaming material is obtained.

9. The use of the natural aromatic environmentally friendly EVA composite foamed material of claim 1 in shoe soles, shoe insoles, yoga mats, and crawl mats.

Technical Field

The invention belongs to the technical field of EVA composite materials, and particularly relates to a natural aromatic environment-friendly EVA composite foam material, and a preparation method and application thereof.

Background

In the field of articles for daily use and sports equipment, EVA (ethylene-vinyl acetate copolymer) rubber and plastic products are novel environment-friendly plastic foaming materials, have the advantages of good buffering, shock resistance, heat insulation, moisture resistance, chemical corrosion resistance, no toxicity, no water absorption and the like, and are frequently used for slippers, insoles, buffer pads, cushions, basketballs, football and the like.

The lavender, called as the king of all grass, has fresh and elegant fragrance and mild property, is recognized as a plant with the functions of calming, soothing and hypnotizing, can relieve nervous mood, calm mind, relieve pressure and the like, and can be made into a sachet to replace camphor pills to be put in a cabinet for fumigating and expelling insects.

Chinese published patent literature (CN 109401356A) discloses a lavender polymer composite material and a preparation method thereof, wherein the lavender polymer composite material comprises the following components in percentage by mass: 23% -27% of lavender master batch; 55% -65% of rubber plastic material; 8 to 12 percent of resin; 4% -6% of a cross-linking agent, and the lavender master batch is prepared by storing lavender powder and a rubber plastic material at 115-125 ℃ for 18-20 minutes for vulcanization treatment, then entering a mixing roll, fully mixing the vulcanized raw materials by the mixing roll, then conveying the mixture to a granulator, and preparing the lavender master batch by the granulator. According to the technology, the lavender is used as a base material of the lavender high-molecular composite material, the characteristics of the lavender such as fresh fragrance, sedation and hypnosis, spasmolysis, antibiosis, neuroprotection, lipid reduction, neurosis treatment and the like are fully utilized, and when the lavender gel is used, the lavender gel can refresh and refresh the brain, enhance the memory, relieve the nerves, improve the emotion and promote the blood circulation, can treat acne, nourish and beautify hair, inhibit hypertension and nose-sensitive asthma, regulate the physiological function, enhance the immunity and maintain the respiratory tract function, has a good curative effect on nasolaryngeal mucositis, and is particularly suitable for being used for living goods and sports equipment.

However, the aroma of the lavender powder is volatilized quickly, and the problem of lasting efficacy exists. In addition, an AC foaming agent is generally added into the EVA foaming material, the AC foaming agent can be decomposed to generate ammonia gas and formamide in the foaming process, the foaming product has pungent odor, and the odor is easy to cause uncomfortable feeling in the daily use process.

Disclosure of Invention

In view of the defects of the prior art, the technical problem to be solved by the invention is to provide a natural aromatic ring-protecting type EVA composite foaming material.

In order to solve the technical problems, the invention adopts the technical scheme that:

the natural aromatic environment-friendly EVA composite foaming material is prepared from the following components in parts by weight: 80-100 parts of a rubber and plastic base material, 4-8 parts of a foaming agent, 0.5-1 part of a cross-linking agent, 0.5-0.8 part of mineral oil, 0.5-1 part of stearic acid and 20-40 parts of modified lavender particles, wherein the rubber and plastic base material contains 40-100% of EVA.

Wherein: the foaming agent is one or a mixture of azodicarbonamide, sodium bicarbonate, ammonium bicarbonate and expandable microspheres; the cross-linking agent is one or a mixture of two of bis-tert-butylperoxyisopropyl benzene and dicumyl peroxide; the modified lavender particles are prepared from the following components in parts by weight: 20-30 parts of lavender powder, 5-8 parts of waterborne polyurethane resin, 1-1.5 parts of sodium bicarbonate, 2.5-3 parts of ascorbic acid, 1-2 parts of nano zinc oxide and 2.5-3.0 parts of poly N-vinyl acetamide.

Meanwhile, the preparation method of the modified lavender particles is disclosed as follows:

a) placing 20-30 parts of 100-mesh lavender powder which is crushed into 200 meshes into hydrogen peroxide at the temperature of 90-95 ℃ for treatment for 30-45min to activate hydroxyl in lavender cellulose, filtering and cleaning to obtain hydroxyl activated lavender powder;

b) dissolving the water-based polyurethane resin in ethanol to form an organic solution, respectively adding the hydroxyl-activated lavender powder obtained in the step a), 1-1.5 parts of sodium bicarbonate, 2.5-3 parts of ascorbic acid and 1.5-2.0 parts of poly-N-vinylacetamide, performing ultrasonic dispersion at low temperature, and performing spray drying to obtain reaction particles wrapping the water-based polyurethane resin, the sodium bicarbonate and the ascorbic acid on the surface of the hydroxyl-activated lavender powder;

c) heating and foaming the reaction particles obtained in the step b) at 125-140 ℃ to form microporous foamed lavender particles with an open-cell spherical cell structure;

d) adding the microporous foamed lavender particles obtained in the step c) and 1-2 parts of nano zinc oxide into an ethanol solution, and then performing ultrasonic dispersion for 12-15 hours to obtain a suspension;

e) and d), taking out the upper half part of the suspension liquid obtained in the step d), centrifugally separating, drying in a vacuum drying oven at 70-80 ℃, crushing, and grinding to obtain the modified lavender particles with the surface loaded with the nano zinc oxide.

The invention further discloses a preparation method of the natural aromatic environment-friendly EVA composite foaming material, which comprises the following specific steps:

s1, preparing modified lavender particles;

s2, mixing the modified lavender particles obtained in the step S1 with a rubber-plastic base material, stearic acid and mineral oil for mixing for 15-20 min, adding a foaming agent and a cross-linking agent for continuous banburying when the temperature reaches 100 ℃, discharging to obtain a mixture when the temperature rises to 110-115 ℃, adding the mixture into an open mill for open milling at 80-85 ℃, carrying out thin milling for 2 times, wherein the thickness of a discharged piece is 1mm when the thin milling is carried out, transferring the milled material into a granulator for granulation, cooling and standing to obtain composite granules;

s3, spraying a release agent on a mould of a foaming machine, adding the composite granules for mould pressing and foaming, wherein the foaming temperature is 155-165 ℃, the foaming pressure can be 10-15 Mpa, and the foaming time is 10-12 min, so that the EVA composite foaming material is obtained.

The natural aromatic environment-friendly EVA composite foaming material can be applied to foaming products such as soles, insoles, yoga mats, crawling mats and the like.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the invention, the modified lavender particles are adopted, and the micropores on the surface of the lavender powder are foamed through sodium bicarbonate to form the structure with open spherical cells, so that volatilization of lavender fragrance components can be effectively controlled, the fragrance effect is durable, meanwhile, the nano zinc oxide can be well adsorbed by utilizing the large specific surface area and the poly N-vinylacetamide, the problem that the nano zinc oxide is easy to agglomerate is avoided, the nano zinc oxide has a photocatalytic antibacterial effect, the antibacterial performance of a foaming material and a product can be enhanced, meanwhile, the heat protection effect on the lavender powder is also achieved, and the foaming effect is good. Moreover, sodium carbonate generated by the thermal decomposition of sodium bicarbonate in the modified lavender particles can make the periphery of foam pores alkaline after the foaming material and the product absorb water, and can inhibit the growth of bacteria sensitive to alkaline conditions, such as staphylococcus aureus.

2. According to the invention, hydroxyl in the lavender cellulose is activated through oxidation treatment, the hydroxyl can be subjected to aldol condensation reaction with carbonyl of generated formamide in the foaming process to consume the formamide, and the ascorbic acid on the surface of the foam cell with large specific surface area can also neutralize alkaline ammonia to form ammonium salt, so that the release of ammonia in the foaming material and the product can be greatly reduced, thereby achieving deodorization and ensuring the purity of lavender fragrance.

3. The modified lavender particles comprise poly-N-vinylacetamide which is a spiral nonionic dispersant, so that the compatibility of lavender powder with aqueous polyurethane resin and rubber and plastic base materials can be effectively improved, and the good mechanical properties of the foam material and the product are ensured.

4. The lavender foam material and the product have the advantages of smell removal, ventilation, refreshing, fragrance smoking, insect expelling and the like, are particularly suitable for soles, insoles, yoga mats, crawling mats and other living goods and sports equipment, can be normally foamed without adding calcium carbonate or talcum powder and other fillers in the processing process, can improve the utilization rate of the lavender, reduce waste and environmental pollution of wastes, are green and environment-friendly, and reduce the production cost.

Detailed Description

The invention provides a natural aromatic environment-friendly EVA composite foaming material which is prepared from the following components in parts by weight: 80-100 parts of a rubber and plastic base material, 4-8 parts of a foaming agent, 0.5-1 part of a cross-linking agent, 0.5-0.8 part of mineral oil, 0.5-1 part of stearic acid and 20-40 parts of modified lavender particles, wherein the rubber and plastic base material contains 40-100% of EVA. The natural aromatic environment-friendly EVA composite foaming material can be processed into foaming products such as soles, insoles, yoga mats, crawling mats and the like.

Several specific examples of the natural aromatic environment-friendly EVA composite foam of the present invention are given below, and 3 comparative examples are also given, and the component ratios in each example and comparative example are shown in tables 1 and 2.

The natural aromatic environment-friendly EVA composite foaming material in the embodiments 1-5 of the invention is prepared by the following method:

s1, preparing modified lavender particles;

s2, mixing the modified lavender particles obtained in the step S1 with a rubber-plastic base material, stearic acid and mineral oil for mixing for 15-20 min, adding a foaming agent and a cross-linking agent for continuous banburying when the temperature reaches 100 ℃, discharging to obtain a mixture when the temperature rises to 110-115 ℃, adding the mixture into an open mill for open milling at 80-85 ℃, carrying out thin milling for 2 times, wherein the thickness of a discharged piece is 1mm when the thin milling is carried out, transferring the milled material into a granulator for granulation, cooling and standing to obtain composite granules;

s3, spraying a release agent on a mould of a foaming machine, adding the composite granules for mould pressing and foaming, wherein the foaming temperature is 155-165 ℃, the foaming pressure can be 10-15 Mpa, and the foaming time is 10-12 min, so that the EVA composite foaming material is obtained.

The modified lavender particles in the embodiments 1-5 of the invention are prepared by the following method, specifically:

a) placing 100-mesh lavender powder crushed into 200-mesh lavender powder into hydrogen peroxide at the temperature of 90-95 ℃ for treatment for 30-45min to activate hydroxyl in the lavender cellulose, filtering and cleaning to obtain hydroxyl-activated lavender powder;

b) dissolving the aqueous polyurethane resin in ethanol to form an organic solution, respectively adding the hydroxyl-activated lavender powder obtained in the step a), sodium bicarbonate, ascorbic acid and poly-N-vinylacetamide, performing ultrasonic dispersion at a low temperature uniformly, and performing spray drying to obtain reaction particles wrapping the surface of the hydroxyl-activated lavender powder with the aqueous polyurethane resin, the sodium bicarbonate and the ascorbic acid;

c) heating and foaming the reaction particles obtained in the step b) at 125-140 ℃ to form microporous foamed lavender particles with an open-cell spherical cell structure;

d) adding the microporous foamed lavender particles obtained in the step c) and the nano zinc oxide into an ethanol solution, and then performing ultrasonic dispersion for 12-15 hours to obtain a suspension;

e) and d), taking out the upper half part of the suspension liquid obtained in the step d), centrifugally separating, drying in a vacuum drying oven at 70-80 ℃, crushing, and grinding to obtain the modified lavender particles with the surface loaded with the nano zinc oxide.

The method for preparing the composite foamed materials of comparative examples 1 to 3 according to the present invention is different from the method for preparing example 1 only in step S1.

Wherein, the modified lavender particles of step S1 of comparative example 1 are prepared by the following method, comprising the specific steps of:

1a) placing 100-mesh lavender powder crushed into 200-mesh lavender powder into hydrogen peroxide at the temperature of 90-95 ℃ for treatment for 30-45min to activate hydroxyl in the lavender cellulose, filtering and cleaning to obtain hydroxyl-activated lavender powder;

1b) adding the hydroxyl activated lavender powder obtained in the step 1 a), ascorbic acid, nano zinc oxide and poly N-vinyl acetamide into an ethanol solution, and performing ultrasonic dispersion for 12-15 hours to obtain a suspension;

1c) taking out the upper half part of the suspension liquid obtained in the step 1 b), centrifugally separating, drying in a vacuum drying oven at 70-80 ℃, crushing and grinding.

Wherein, the modified lavender particles of step S1 of comparative example 2 are prepared by the following method, comprising the specific steps of:

2a) dissolving the waterborne polyurethane resin in ethanol to form an organic solution, respectively adding 100-mesh 200-mesh crushed lavender powder, sodium bicarbonate, citric acid and poly-N-vinylacetamide, performing ultrasonic dispersion at low temperature, and performing spray drying to obtain reaction particles wrapping the waterborne polyurethane resin, the citric acid and the sodium bicarbonate on the surface of the hydroxyl activated lavender powder;

2b) heating and foaming the reaction particles obtained in the step 2 a) at 125-140 ℃ to form microporous foamed lavender particles with an open-cell spherical cell structure;

2c) adding the microporous foamed lavender particles obtained in the step 2b) and the nano zinc oxide into an ethanol solution, and then performing ultrasonic dispersion for 12-15 hours to obtain a suspension;

2d) taking out the upper half part of the suspension liquid in the step 2 c), centrifugally separating, drying in a vacuum drying oven at 70-80 ℃, crushing and grinding.

Wherein, the modified lavender particles of step S1 of comparative example 3 are prepared by the following method, comprising the specific steps of:

3a) placing 20-30 parts of 100-mesh lavender powder which is crushed into 200 meshes into hydrogen peroxide at the temperature of 90-95 ℃ for treatment for 30-45min to activate hydroxyl in lavender cellulose, filtering and cleaning to obtain hydroxyl activated lavender powder;

3b) dissolving the aqueous polyurethane resin in ethanol to form an organic solution, respectively adding the hydroxyl activated lavender powder obtained in the step 3 a), sodium bicarbonate, ascorbic acid and poly-N-vinylacetamide, performing ultrasonic dispersion at a low temperature, and performing spray drying to obtain reaction particles wrapping the surface of the hydroxyl activated lavender powder with the aqueous polyurethane resin, the sodium bicarbonate and the ascorbic acid;

3c) heating and foaming the reaction particles obtained in the step 3 b) at 125-140 ℃ to form an open-cell spherical cell structure, drying the open-cell spherical cell structure in a vacuum drying oven at 70-80 ℃, and crushing and grinding the open-cell spherical cell structure.

The foams prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to tensile strength, rebound value, air permeability, Escherichia coli, Staphylococcus aureus, odor and the like, and the results are shown in Table 3.

Wherein: the air permeability test adopts an air permeability tester to test the air permeability of each product, the test gas is nitrogen, the test time is 24 hours, the test pressure is 0.2MPa, and the larger the air permeability is, the better the air permeability is.

The ammonia odor detection method refers to a sole odor standard (GB 30585-2014), and specifically comprises the following steps: the prepared foam test piece 1 piece is about 126g, after washing for two minutes, water drops on the surface are removed, drying is carried out, then the test piece is placed into a self-sealing bag, the self-sealing bag is placed for 24 hours at room temperature in a sealing mode, when peculiar smell is judged, the self-sealing bag is opened for about 15mm, and the nose is close to the deep suction mode for judging.

While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.