Biological mineral crystal material and preparation method therefor, and sleep-aiding tech pillow

Abstract

The present invention belongs to the technical field of materials, and provides a biological mineral crystal material and a preparation method therefor, and a sleep-aiding tech pillow. The preparation method comprises: modifying the surface of a natural mineral crystal, then mixing same with doped TiO2 / Fe3O4-intercalated montmorillonite to prepare a crystal powder modified by the doped TiO2 / Fe3O4-intercalated montmorillonite, modifying the surface thereof by using polydopamine, allowing same to adsorb an aromatic essential oil, and encapsulating same in sodium alginate, so as to prepare a spherical biological mineral crystal material. The tech pillow prepared by adding the biological mineral crystal material prepared in the present invention can slowly release essential oil molecules, thereby improving the durability thereof; moreover, spherical particles facilitate the stimulation of acupuncture points, which is conducive to improving sleep quality; in addition, by releasing infrared waves, forming a magnetic field and releasing anions into the surrounding environment, the pillow purifies organic pollutants, formaldehyde, etc., in the air, improves the quality of indoor air, alleviates symptoms such as headaches and insomnia, and thus has wide application prospects.

Description

A biomaterial crystal material, a preparation method thereof and a sleep-aiding technology pillow TECHNICAL FIELD

[0001] The present application relates to the technical field of materials, in particular to a biomaterial crystal material, a preparation method thereof and a sleep-aiding technology pillow. BACKGROUND

[0002] With the continuous improvement of living standards, people pay more and more attention to health, safety and healthy products. Due to the acceleration of people's life pace and the heavy life pressure, the population of people with poor sleep quality or even whole-night insomnia is gradually increasing. The mental weakness caused by poor sleep quality and insomnia is also common, and the sleep-aiding pillow emerges as the times require.

[0003] Natural quartz is a quartz crystal mineral, and its main chemical component is silicon dioxide, with a chemical formula of SiO2. It is also known as water crystal, water jade and water pearl. Well-developed single crystals are hexagonal pyramids, so they are usually in the form of massive or granular aggregates. Natural quartz can affect physical health by generating electromagnetic fields and regulating human energy fields, which is called "mineral therapy". In addition, natural quartz can collect negative ions from the outside and release them into the surrounding environment, thereby improving indoor air quality and relieving symptoms such as headache and insomnia.

[0004] However, directly adding natural quartz into a pillow cannot achieve good sleep-aiding effect, so it needs to be modified.

[0005] Chinese patent document CN110101268A discloses a filling of a sleep-aiding pillow and a sleep-aiding pillow. By mixing mugwort, dragon vine, rhubarb flower, lavender and chrysanthemum, the advantages of each component are fully utilized, which can effectively improve insomnia, aid sleep, help people with conditions such as frequent dreams, difficulty falling asleep, and uncomfortable sleep to relax nerves and relieve fatigue, and achieve ideal deep sleep state. However, the traditional Chinese medicine components are directly placed in the pillow, the effective components are released quickly, the effective use time is shortened, and the person feels uncomfortable due to the high concentration of odor in a short time. SUMMARY

[0006] The present application aims to provide a biomaterial crystal material, a preparation method thereof and a sleep-aiding technology pillow, which can slowly release essential oil molecules and improve the durability of use. At the same time, the spherical particles are also convenient for stimulating acupoints, which helps to improve sleep quality. At the same time, by releasing infrared waves and forming a magnetic field, and releasing negative ions into the surrounding environment, the organic pollutants, formaldehyde and the like in the air are purified, the indoor air quality is improved, and the symptoms such as headache and insomnia are relieved, which has a broad application prospect.

[0007] The technical solution of the present application is as follows:

[0008] The application provides a preparation method of a biomaterial crystal material, which comprises the following steps: modifying the surface of a natural mineral crystal, mixing the modified natural mineral crystal with doped TiO2 / Fe3O4 intercalated montmorillonite, preparing doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder, modifying the surface of the doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder by polydopamine, adsorbing aromatic essential oil, and embedding the doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder in sodium alginate to prepare the biomaterial crystal material.

[0009] As a further improvement of the application, the following steps are included:

[0010] S1. Surface modification of a natural mineral crystal: the natural mineral crystal is ball milled, added into ethanol, added with a silane coupling agent, heated and stirred for reaction, filtered, washed, and dried to prepare surface modified natural mineral crystal powder;

[0011] S2. Preparation of doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder: butyl titanate is added into ethanol to form solution A, melamine, iron chloride and ferrous chloride are dissolved in water to obtain solution B, solution B is added dropwise into solution A, stirred uniformly to obtain a columnar agent, the columnar agent is added dropwise into a montmorillonite suspension, ammonia water is added dropwise, the surface modified natural mineral crystal powder prepared in step S1 is added, heated and stirred for reaction, aged, microwave heated and dried, washed, ball milled, and calcined to prepare the doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder;

[0012] S3. Preparation of modified crystal powder: the doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder prepared in step S2 is added into water, added with dopamine hydrochloride and a catalyst, heated and stirred for reaction, filtered, washed, and dried to prepare the modified crystal powder;

[0013] S4. Adsorption of essential oil: the modified crystal powder prepared in step S3 is added into petroleum ether, added with a composite aromatic essential oil, and the solvent is volatilized to prepare the modified crystal powder adsorbing the essential oil;

[0014] S5. Preparation of a biomaterial crystal material: the modified crystal powder adsorbing the essential oil prepared in step S4 is added into water, added with sodium alginate and an emulsifier to obtain an aqueous phase, the aqueous phase is added dropwise into fish oil, emulsified, added dropwise with a calcium chloride solution, solidified at room temperature, filtered, washed, and dried to prepare the biomaterial crystal material.

[0015] As a further improvement of the application, the ball milling in step S1 is performed for 0.5-1.5 h, the mass ratio of the natural mineral crystal to the silane coupling agent is 50:4-7, the silane coupling agent is at least one selected from KH550, KH560, KH580, KH590, KH602 and KH792, the heating and stirring for reaction is performed at a temperature of 40-50℃ for 1-3 h.

[0016] Preferably, the silane coupling agent is a mixture of KH550 and KH580 with a mass ratio of 7-10:3-5.

[0017] As a further improvement of the application, the mass ratio of the butyl titanate, melamine, ferric chloride, ferrous chloride, montmorillonite, and surface-modified natural mineral crystal powder in step S2 is 5-7:0.5-1:3.4-3.5:1.2-1.3:30-50:100, the temperature of the heating and stirring reaction is 65-75℃, the time is 2-4h, the time of the ball milling is 1-2h, and the temperature of the calcination is 450-550℃, and the time is 1-3h.

[0018] As a further improvement of the application, the mass ratio of the doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder, dopamine hydrochloride, and catalyst in step S3 is 20-30:14-18:1-2, the temperature of the heating and stirring reaction is 40-50℃, the time is 2-3h, and the catalyst is a Tris-HCl solution with a pH of 8.5-9.

[0019] As a further improvement of the application, the mass ratio of the modified crystal powder and the composite aromatic essential oil in step S4 is 100:15-22, the composite aromatic essential oil is selected from at least two of lemon essential oil, bergamot essential oil, rose essential oil, clove essential oil, lavender essential oil, and wormwood essential oil, and the preparation method of the essential oil is to obtain the essential oil by supercritical fluid extraction of raw materials.

[0020] Preferably, the composite aromatic essential oil is a mixture of rose essential oil and wormwood essential oil with a mass ratio of 5-7:3-4.

[0021] As a further improvement of the application, the mass ratio of the modified crystal powder, sodium alginate, and emulsifier for adsorbing the essential oil in step S5 is 10-13:17-20:1-2, the emulsifier is selected from at least one of Tween-20, Tween-40, Tween-60, Tween-80, and Tween-85, and the time of the normal-temperature curing is 20-30min.

[0022] The application further protects a biomimetic crystal material prepared by the above preparation method.

[0023] The application further protects an application of the above biomimetic crystal material in the preparation of a sleep-aiding product.

[0024] The application further protects a science and technology sleep-aiding pillow, which is filled with the above biomimetic crystal material in a pillow core, and the filling amount is 0.01-100wt%.

[0025] The application has the following beneficial effects:

[0026] The application adopts natural mineral crystals to affect the health of the human body by generating electromagnetic fields, adjusting the human body's qi field, etc., i.e., so-called "mineral therapy". Secondly, the natural mineral crystals can also collect negative ions from the outside and release them into the surrounding environment, thereby improving indoor air quality and relieving symptoms such as headache and insomnia. Meanwhile, the natural mineral crystals are modified by a silane coupling agent, and are modified by KH550 and KH580 to make the surface of the crystal powder have mercapto groups and amino groups, which can form hydrogen bonds and Van der Waals forces with the hydroxyl groups on the surface of the montmorillonite, so that the montmorillonite is fixed on the surface of the crystal powder.

[0027] In the preparation of the doped TiO2 / Fe3O4 intercalated montmorillonite, the anatase TiO2 not only has good adsorption performance, but also has good photocatalytic performance. Under the doping action of melamine, the TiO2 is doped with N and C atoms, and the mercapto groups of the silane coupling agent are also doped with S elements, thereby changing the electronic transition energy level of TiO2, so that it can perform photocatalysis in the wavelength range of visible light, and has good effects of degrading organic pollutants, purifying formaldehyde, and resisting bacteria and mites. In addition, the magnetic Fe3O4 can also form a magnetic field and emit infrared waves, so that people can perform magnetic therapy and infrared wave relaxation during sleep. At the same time, the interlayer spacing of the montmorillonite intercalated with the doped TiO2 / Fe3O4 is increased, which not only maintains the layered structure before intercalation, but also has a structure with layer peeling, thereby improving the specific surface area of the montmorillonite, which is helpful to improve its adsorption performance, purify the environmental air, and improve the adsorption rate of the aromatic essential oil and the slow-release effect of the adsorbed aromatic essential oil.

[0028] The application further modifies the surface of the prepared doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder by polydopamine, so that the surface has rich active groups such as hydroxyl groups, amino groups, and carboxyl groups, which can interact with the molecules of the aromatic essential oil, thereby improving the adsorption of the essential oil molecules and improving the slow-release effect, and improving the durability of the essential oil in sleep aid and its use.

[0029] The adsorbed rose essential oil and wormwood essential oil not only have good sleep aid effect, but also have the effects of antibacterial, mothproof, antifungal, and acaricidal, thereby improving the use durability of the scientific pillow and having a synergistic effect.

[0030] The application embeds the prepared modified crystal powder adsorbed with essential oil by sodium alginate to prepare spherical embedded particles, which can slowly release the essential oil and improve the use durability, and the spherical particles are also convenient for stimulating acupoints and improving sleep quality.

[0031] The prepared bio-mineral crystal material is added to the prepared scientific pillow, can slowly release essential oil molecules, improve use durability, meanwhile, the spherical particles are convenient for stimulating acupoints, help to improve sleep quality, meanwhile, through releasing infrared waves and forming a magnetic field and releasing negative ions into the surrounding environment, purify organic pollutants, formaldehyde and the like in air, improve indoor air quality, relieve headache, insomnia and the like, and have wide application prospect. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0033] The preparation method of the rose and wormwood essential oil is to obtain essential oil by supercritical fluid extraction of rose and wormwood.

[0034] The natural mineral crystal is a mixed ore containing natural mineral crystal and rare earth concentrate, and the mass ratio is 10:5. The natural mineral crystal is purchased from Lianyungang Haisheng Quartz Technology Co., Ltd., and the rare earth concentrate is purchased from China Northern Rare Earth Group High-tech Co., Ltd.

[0035] Embodiment 1

[0036] The embodiment provides a preparation method of a bio-mineral crystal material, and specifically comprises the following steps:

[0037] S1. Surface modification of natural mineral crystal: 50 parts by weight of natural mineral crystal is ball milled for 0.5 h, added into 200 parts by weight of ethanol, 4 parts by weight of silane coupling agent is added, heated to 40 DEG C, stirred for 1 h, filtered, washed, dried, and a surface modified natural mineral crystal powder is prepared;

[0038] The silane coupling agent is a mixture of KH550 and KH580, and the mass ratio is 7:3;

[0039] S2. Preparation of the modified water crystal powder doped with TiO2 / Fe3O4 intercalated montmorillonite: 5 parts by weight of butyl titanate was added to 100 parts by weight of ethanol to form solution A, 0.5 parts by weight of melamine, 3.4 parts by weight of iron chloride, and 1.2 parts by weight of ferrous chloride were dissolved in 70 parts by weight of water to obtain solution B, solution B was added dropwise to solution A, and stirred for 10 min to obtain a pillaring agent, which was added dropwise to 200 parts by weight of a suspension containing 30 parts by weight of montmorillonite, while 10 parts by weight of 25wt% ammonia water was added dropwise, 100 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 was added under nitrogen protection, heated to 65℃, stirred for 2h, and aged for 1h, dried by microwave heating at 500W, washed, ball milled for 1h, and calcined at 450℃ for 1h to obtain the modified water crystal powder doped with TiO2 / Fe3O4 intercalated montmorillonite;

[0040] S3. Preparation of the modified water crystal powder: 20 parts by weight of the modified water crystal powder doped with TiO2 / Fe3O4 intercalated montmorillonite prepared in step S2 was added to 100 parts by weight of water, 14 parts by weight of dopamine hydrochloride and 1 part by weight of a catalyst were added, heated to 40℃, stirred for 2h, filtered, washed, and dried to obtain the modified water crystal powder;

[0041] The catalyst is Tris-HCl solution with pH = 8.5;

[0042] S4. Adsorbed essential oil modified water crystal powder: 100 parts by weight of the modified water crystal powder prepared in step S3 was added to 100 parts by weight of petroleum ether, 15 parts by weight of a composite aromatic essential oil was added, and the solvent was evaporated to obtain the adsorbed essential oil modified water crystal powder;

[0043] The composite aromatic essential oil is a mixture of rose essential oil and wormwood essential oil with a mass ratio of 5:3;

[0044] S5. Preparation of the biomimetic mineral crystal material: 10 parts by weight of the adsorbed essential oil modified water crystal powder prepared in step S4 was added to 200 parts by weight of water, 17 parts by weight of sodium alginate and 1 part by weight of Tween-20 were added to obtain an aqueous phase, the aqueous phase was added dropwise to 500 parts by weight of fish oil, emulsified at 10000r / min for 15 min, 10 parts by weight of 3wt% calcium chloride solution was added dropwise, and the mixture was cured at room temperature for 20 min, filtered, washed, and dried to obtain the biomimetic mineral crystal material.

[0045] Example 2

[0046] The embodiment provides a preparation method of a biomimetic mineral crystal material, which specifically comprises the following steps:

[0047] S1. Surface modification of natural mineral crystal: 50 parts by weight of natural mineral crystal is ball milled for 1.5 h, added into 200 parts by weight of ethanol, 7 parts by weight of silane coupling agent is added, heated to 50℃, stirred for 3 h, filtered, washed, dried, to obtain surface modified natural mineral crystal powder;

[0048] The silane coupling agent is a mixture of KH550 and KH580 with a mass ratio of 10:5;

[0049] S2. Preparation of TiO2 / Fe3O4 intercalated montmorillonite modified water crystal powder: 7 parts by weight of butyl titanate is added into 100 parts by weight of ethanol to form solution A, 1 part by weight of melamine, 3.5 parts by weight of iron chloride, and 1.3 parts by weight of ferrous chloride are dissolved in 70 parts by weight of water to obtain solution B, solution B is added dropwise into solution A, stirred for 10 min to obtain a pillaring agent, added dropwise into 200 parts by weight of a suspension containing 50 parts by weight of montmorillonite, while adding 20 parts by weight of 28wt% ammonia water dropwise, under nitrogen protection, 100 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 is added, heated to 75℃, stirred for 4 h, aged for 1 h, dried by microwave heating at 500W, washed, ball milled for 2 h, calcined at 550℃ for 3 h, to obtain TiO2 / Fe3O4 intercalated montmorillonite modified water crystal powder;

[0050] S3. Preparation of modified water crystal powder: 30 parts by weight of the TiO2 / Fe3O4 intercalated montmorillonite modified water crystal powder prepared in step S2 is added into 100 parts by weight of water, 18 parts by weight of dopamine hydrochloride and 2 parts by weight of catalyst are added, heated to 50℃, stirred for 3 h, filtered, washed, dried, to obtain modified water crystal powder;

[0051] The catalyst is Tris-HCl solution with pH=9;

[0052] S4. Adsorbed essential oil modified water crystal powder: 100 parts by weight of the modified water crystal powder prepared in step S3 is added into 100 parts by weight of petroleum ether, 22 parts by weight of composite aromatic essential oil is added, the solvent is evaporated, to obtain adsorbed essential oil modified water crystal powder;

[0053] The composite aromatic essential oil is a mixture of rose essential oil and wormwood essential oil with a mass ratio of 74:26;

[0054] S5. Preparation of biomimetic mineral crystal material: 13 parts by weight of the adsorbed essential oil modified water crystal powder prepared in step S4 is added into 200 parts by weight of water, 20 parts by weight of sodium alginate and 2 parts by weight of Tween-40 are added to obtain an aqueous phase, the aqueous phase is added dropwise into 500 parts by weight of fish oil, emulsified at 10000 r / min for 15 min, 10 parts by weight of 3wt% calcium chloride solution is added dropwise, solidified at room temperature for 30 min, filtered, washed, dried, to obtain biomimetic mineral crystal material.

[0055] Example 3

[0056] The embodiment provides a preparation method of a biomaterial crystal material, and specifically comprises the following steps:

[0057] S1. Surface modification of natural mineral crystal: 50 parts by weight of natural mineral crystal is subjected to ball milling for 1 h, 200 parts by weight of ethanol is added, 5 parts by weight of silane coupling agent is added, heated to 45 DEG C, stirred for 2 h, filtered, washed, dried, and natural mineral crystal powder is obtained;

[0058] The silane coupling agent is a mixture of KH550 and KH580, and the mass ratio is 8:4;

[0059] S2. Preparation of TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder: 6 parts by weight of butyl titanate is added to 100 parts by weight of ethanol to form solution A, 0.7 parts by weight of melamine, 3.46 parts by weight of iron chloride and 1.26 parts by weight of ferrous chloride are dissolved in 70 parts by weight of water to obtain solution B, solution B is added dropwise into solution A, stirred for 10 min, a columnar agent is obtained, and the columnar agent is added dropwise into 200 parts by weight of a suspension containing 40 parts by weight of montmorillonite, 15 parts by weight of 26 wt% ammonia water is added dropwise, 100 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 is added under nitrogen protection, heated to 70 DEG C, stirred for 3 h, aged for 1 h, dried by microwave heating at 500 W, washed, ball milled for 1.5 h, calcined at 500 DEG C for 2 h, and TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder is obtained;

[0060] S3. Preparation of modified crystal powder: 25 parts by weight of the TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder prepared in step S2 is added to 100 parts by weight of water, 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst are added, heated to 45 DEG C, stirred for 2.5 h, filtered, washed, dried, and modified crystal powder is obtained;

[0061] The catalyst is Tris-HCl solution with pH = 8.7;

[0062] S4. Adsorbed essential oil modified crystal powder: 100 parts by weight of the modified crystal powder prepared in step S3 is added to 100 parts by weight of petroleum ether, 19 parts by weight of composite aromatic essential oil is added, and the solvent is evaporated to obtain the adsorbed essential oil modified crystal powder;

[0063] The composite aromatic essential oil is a mixture of rose essential oil and wormwood essential oil, and the mass ratio is 6:3.5;

[0064] S5. Preparation of the biomimetic mineral crystal material: 11 parts by weight of the modified water crystal powder adsorbing essential oil prepared in step S4 is added into 200 parts by weight of water, 180 parts by weight of sodium alginate and 1.2 parts by weight of Tween-85 are added to obtain an aqueous phase, the aqueous phase is added dropwise into 500 parts by weight of fish oil, emulsified at 10000 r / min for 15 min, 10 parts by weight of 3 wt% calcium chloride solution is added dropwise, and solidified at room temperature for 25 min, filtered, washed, and dried to obtain the biomimetic mineral crystal material.

[0065] Example 4

[0066] Compared with Example 3, the difference is that the silane coupling agent is single KH550.

[0067] Example 5

[0068] Compared with Example 3, the difference is that the silane coupling agent is single KH580.

[0069] Comparative Example 1

[0070] Compared with Example 3, the difference is that step S1 is not performed.

[0071] Specifically as follows:

[0072] S1. Preparation of the TiO2 / Fe3O4 intercalated montmorillonite modified water crystal powder: 6 parts by weight of butyl titanate is added into 100 parts by weight of ethanol to form solution A, 0.7 parts by weight of melamine, 3.46 parts by weight of ferric chloride, and 1.26 parts by weight of ferrous chloride are dissolved in 70 parts by weight of water to obtain solution B, solution B is added dropwise into solution A, stirred for 10 min to obtain a pillaring agent, and then added dropwise into 200 parts by weight of a suspension containing 40 parts by weight of montmorillonite, while 15 parts by weight of 26 wt% ammonia water is added dropwise, 100 parts by weight of natural mineral crystal powder is added under nitrogen protection, heated to 70°C, stirred for 3 h, and aged for 1 h, and then dried by microwave heating at 500 W, washed, ball milled for 1.5 h, and calcined at 500°C for 2 h to obtain the TiO2 / Fe3O4 intercalated montmorillonite modified water crystal powder;

[0073] S2. Preparation of the modified water crystal powder: 25 parts by weight of the TiO2 / Fe3O4 intercalated montmorillonite modified water crystal powder prepared in step S1 is added into 100 parts by weight of water, 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of a catalyst are added, heated to 45°C, stirred for 2.5 h, filtered, washed, and dried to obtain the modified water crystal powder;

[0074] The catalyst is Tris-HCl solution with pH=8.7;

[0075] S3. Adsorbing essential oil: 100 parts by weight of the modified crystal powder prepared in step S2 is added into 100 parts by weight of petroleum ether, 19 parts by weight of the composite aromatic essential oil is added, and the solvent is evaporated to obtain the modified crystal powder adsorbed with the essential oil.

[0076] The composite aromatic essential oil is a mixture of rose essential oil and wormwood essential oil, and the mass ratio is 6:3.5.

[0077] S4. Preparation of the biomaterial crystal material: 11 parts by weight of the modified crystal powder adsorbed with the essential oil prepared in step S3 is added into 200 parts by weight of water, 180 parts by weight of sodium alginate and 1.2 parts by weight of Tween-85 are added to obtain an aqueous phase, the aqueous phase is added dropwise into 500 parts by weight of fish oil, emulsified at 10000 r / min for 15 min, 10 parts by weight of 3wt% calcium chloride solution is added dropwise, and the mixture is solidified at room temperature for 25 min, filtered, washed, and dried to obtain the biomaterial crystal material.

[0078] Comparative Example 2

[0079] Compared with Example 3, the difference is that no melamine is added in step S2.

[0080] Specifically as follows:

[0081] S2. Preparation of the TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder: 6 parts by weight of butyl titanate is added into 100 parts by weight of ethanol to form solution A, 3.46 parts by weight of ferric chloride and 1.26 parts by weight of ferrous chloride are dissolved in 70 parts by weight of water to obtain solution B, solution B is added dropwise into solution A, stirred for 10 min to obtain a pillaring agent, and the pillaring agent is added dropwise into 200 parts by weight of a suspension containing 40 parts by weight of montmorillonite, while 15 parts by weight of 26wt% ammonia water is added dropwise, 100 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 is added under nitrogen protection, heated to 70℃, stirred for 3h, and aged for 1h, and then dried by microwave heating at 500W, washed, ball milled for 1.5h, and calcined at 500℃ for 2h to obtain the TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder.

[0082] Comparative Example 3

[0083] Compared with Example 3, the difference is that no ferric chloride and ferrous chloride are added in step S2.

[0084] Specifically as follows:

[0085] S2. Preparation of the modified water crystal powder doped with TiO2 intercalated montmorillonite: 10.72 parts by weight of butyl titanate was added into 100 parts by weight of ethanol to form solution A, 0.7 parts by weight of melamine was dissolved in 70 parts by weight of water to obtain solution B, solution B was added dropwise into solution A, and stirred for 10 min to obtain a pillaring agent, which was added dropwise into a suspension containing 40 parts by weight of montmorillonite in 200 parts by weight of water, while 15 parts by weight of 26wt% ammonia was added dropwise, 100 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 was added under nitrogen protection, heated to 70℃, and stirred for 3h, and then aged for 1h, and finally dried by microwave heating at 500W, washed, ball milled for 1.5h, and calcined at 500℃ for 2h to obtain the modified water crystal powder doped with TiO2 intercalated montmorillonite.

[0086] Comparative Example 4

[0087] The difference compared with Example 3 is that step S2 is not performed.

[0088] The details are as follows:

[0089] S1. Surface modification of natural mineral crystal: 50 parts by weight of natural mineral crystal was ball milled for 1h, added into 200 parts by weight of ethanol, and 5 parts by weight of silane coupling agent was added, heated to 45℃, and stirred for 2h to obtain the surface modified natural mineral crystal powder;

[0090] The silane coupling agent is a mixture of KH550 and KH580 with a mass ratio of 8:4;

[0091] S2. Preparation of the modified water crystal powder: 25 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 was added into 100 parts by weight of water, 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst were added, heated to 45℃, and stirred for 2.5h to obtain the modified water crystal powder;

[0092] The catalyst is Tris-HCl solution with pH = 8.7;

[0093] S3. Adsorption of essential oil: 100 parts by weight of the modified water crystal powder prepared in step S2 was added into 100 parts by weight of petroleum ether, and 19 parts by weight of composite aromatic essential oil was added, and then the solvent was evaporated to obtain the modified water crystal powder adsorbed with essential oil;

[0094] The composite aromatic essential oil is a mixture of rose essential oil and wormwood essential oil with a mass ratio of 6:3.5;

[0095] S4. Preparation of the biomimetic crystal material: 11 parts by weight of the modified crystal powder adsorbed with essential oil prepared in step S3 was added to 200 parts by weight of water, 180 parts by weight of sodium alginate and 1.2 parts by weight of Tween-85 were added to obtain an aqueous phase, the aqueous phase was added dropwise into 500 parts by weight of fish oil, emulsified at 10000 r / min for 15 min, 10 parts by weight of 3 wt% calcium chloride solution was added dropwise, and the mixture was solidified at room temperature for 25 min, filtered, washed, and dried to obtain the biomimetic crystal material.

[0096] Comparative Example 5

[0097] Compared with Example 3, the difference is that step S3 is not performed.

[0098] The details are as follows:

[0099] S1. Surface modification of natural mineral crystal: 50 parts by weight of natural mineral crystal was ball milled for 1 h, added to 200 parts by weight of ethanol, 5 parts by weight of silane coupling agent was added, heated to 45℃, stirred for 2 h, filtered, washed, and dried to obtain the surface modified natural mineral crystal powder;

[0100] The silane coupling agent is a mixture of KH550 and KH580 with a mass ratio of 8:4;

[0101] S2. Preparation of TiO2 / Fe3O4 doped intercalated montmorillonite modified crystal powder: 6 parts by weight of butyl titanate was added to 100 parts by weight of ethanol to form solution A, 0.7 parts by weight of melamine, 3.46 parts by weight of ferric chloride, and 1.26 parts by weight of ferrous chloride were dissolved in 70 parts by weight of water to obtain solution B, solution B was added dropwise into solution A, stirred for 10 min to obtain a pillaring agent, which was added dropwise into 200 parts by weight of a suspension containing 40 parts by weight of montmorillonite, while 15 parts by weight of 26 wt% ammonia was added dropwise, 100 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 was added under nitrogen protection, heated to 70℃, stirred for 3 h, aged for 1 h, dried by microwave heating at 500 W, washed, ball milled for 1.5 h, and calcined at 500℃ for 2 h to obtain the TiO2 / Fe3O4 doped intercalated montmorillonite modified crystal powder;

[0102] S3. Adsorption of essential oil: 100 parts by weight of the TiO2 / Fe3O4 doped intercalated montmorillonite modified crystal powder prepared in step S2 was added to 100 parts by weight of petroleum ether, 19 parts by weight of composite aromatic essential oil was added, and the solvent was evaporated to obtain the modified crystal powder adsorbed with essential oil;

[0103] The composite aromatic essential oil is a mixture of rose essential oil and wormwood essential oil with a mass ratio of 6:3.5;

[0104] S4. Preparation of the biomimetic mineral crystal material: 11 parts by weight of the modified water crystal powder adsorbed with essential oil prepared in step S3 is added to 200 parts by weight of water, 180 parts by weight of sodium alginate and 1.2 parts by weight of Tween-85 are added to obtain an aqueous phase, the aqueous phase is added dropwise into 500 parts by weight of fish oil, emulsified at 10000 r / min for 15 min, 10 parts by weight of 3 wt% calcium chloride solution is added dropwise, and solidified at room temperature for 25 min, filtered, washed, and dried to obtain the biomimetic mineral crystal material.

[0105] Comparative Example 6

[0106] The difference compared with Example 3 is that step S4 is not performed.

[0107] The details are as follows:

[0108] S1. Surface modification of natural mineral crystal: 50 parts by weight of natural mineral crystal is ball milled for 1 h, added to 200 parts by weight of ethanol, 5 parts by weight of silane coupling agent is added, heated to 45℃, stirred for 2 h, filtered, washed, and dried to obtain the surface modified natural mineral crystal powder;

[0109] The silane coupling agent is a mixture of KH550 and KH580 with a mass ratio of 8:4;

[0110] S2. Preparation of TiO2 / Fe3O4 doped intercalated montmorillonite modified water crystal powder: 6 parts by weight of butyl titanate is added to 100 parts by weight of ethanol to form solution A, 0.7 parts by weight of melamine, 3.46 parts by weight of ferric chloride, and 1.26 parts by weight of ferrous chloride are dissolved in 70 parts by weight of water to obtain solution B, solution B is added dropwise into solution A, stirred for 10 min to obtain a pillaring agent, added dropwise into 200 parts by weight of a suspension containing 40 parts by weight of montmorillonite, while adding 15 parts by weight of 26 wt% ammonia water dropwise, under nitrogen protection, 100 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 is added, heated to 70℃, stirred for 3 h, aged for 1 h, dried by microwave heating at 500 W, washed, ball milled for 1.5 h, and calcined at 500℃ for 2 h to obtain the TiO2 / Fe3O4 doped intercalated montmorillonite modified water crystal powder;

[0111] S3. Preparation of the modified water crystal powder: 25 parts by weight of the TiO2 / Fe3O4 doped intercalated montmorillonite modified water crystal powder prepared in step S2 is added to 100 parts by weight of water, 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst are added, heated to 45℃, stirred for 2.5 h, filtered, washed, and dried to obtain the modified water crystal powder;

[0112] The catalyst is Tris-HCl solution with pH = 8.7;

[0113] S4. Preparation of the biomimetic mineral crystal material: 11 parts by weight of the modified water crystal powder prepared in step S3 was added to 200 parts by weight of water, 180 parts by weight of sodium alginate and 1.2 parts by weight of Tween-85 were added to obtain an aqueous phase, the aqueous phase was added dropwise into 500 parts by weight of fish oil, emulsified at 10000 r / min for 15 min, 10 parts by weight of 3 wt% calcium chloride solution was added dropwise, and the mixture was solidified at room temperature for 25 min, filtered, washed, and dried to obtain the biomimetic mineral crystal material.

[0114] Comparative Example 7

[0115] Compared with Example 3, the difference is that step S5 is not performed.

[0116] The details are as follows:

[0117] S1. Surface modification of natural mineral crystal: 50 parts by weight of natural mineral crystal was ball milled for 1 h, added to 200 parts by weight of ethanol, 5 parts by weight of silane coupling agent was added, heated to 45℃, stirred for 2 h, filtered, washed, and dried to obtain the surface modified natural mineral crystal powder;

[0118] The silane coupling agent is a mixture of KH550 and KH580 with a mass ratio of 8:4;

[0119] S2. Preparation of TiO2 / Fe3O4 intercalated montmorillonite doped modified water crystal powder: 6 parts by weight of butyl titanate was added to 100 parts by weight of ethanol to form solution A, 0.7 parts by weight of melamine, 3.46 parts by weight of ferric chloride, and 1.26 parts by weight of ferrous chloride were dissolved in 70 parts by weight of water to obtain solution B, solution B was added dropwise into solution A, stirred for 10 min to obtain a pillaring agent, added dropwise into 200 parts by weight of a suspension containing 40 parts by weight of montmorillonite, while adding 15 parts by weight of 26 wt% ammonia water dropwise, under nitrogen protection, 100 parts by weight of the surface modified natural mineral crystal powder prepared in step S1 was added, heated to 70℃, stirred for 3 h, aged for 1 h, dried by microwave heating at 500 W, washed, ball milled for 1.5 h, and calcined at 500℃ for 2 h to obtain the TiO2 / Fe3O4 intercalated montmorillonite doped modified water crystal powder;

[0120] S3. Preparation of modified water crystal powder: 25 parts by weight of the TiO2 / Fe3O4 intercalated montmorillonite doped modified water crystal powder prepared in step S2 was added to 100 parts by weight of water, 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst were added, heated to 45℃, stirred for 2.5 h, filtered, washed, and dried to obtain the modified water crystal powder;

[0121] The catalyst is Tris-HCl solution with pH = 8.7;

[0122] S4. Adsorbing essential oil: 100 parts by weight of the modified crystal powder prepared in step S3 is added into 100 parts by weight of petroleum ether, and 19 parts by weight of the composite aromatic essential oil is added, and the solvent is evaporated to obtain the modified crystal powder adsorbed with the essential oil, which is the biomimetic crystal material;

[0123] The composite aromatic essential oil is a mixture of rose essential oil and wormwood essential oil, and the mass ratio is 6:3.5.

[0124] Test Example 1

[0125] The biomimetic crystal materials prepared in Examples 1-5 and Comparative Examples 1-7 are measured by using an IR-2 type dual-band emissivity measuring instrument to measure the dual-band infrared emissivity of the powder materials in the temperature environment of 3 μm-5 μm and 8 μm-14 μm, and the results are shown in Table 1.

[0126] Table 1

[0127] As shown in the above table, the biomimetic crystal materials prepared in Examples 1-3 have higher dual-band infrared emissivity in the temperature environment of 3 μm-5 μm and 8 μm-14 μm.

[0128] Test Example 2

[0129] The products prepared in step S2 in Examples 1-5 and Comparative Examples 1-3 are measured by using the product prepared in step S1 in Comparative Example 4 to determine the specific surface area and pore distribution of the samples by using a TriStar II 3020 type specific surface area and porosity analyzer. The results are shown in Table 2.

[0130] Table 2

[0131] As shown in the above table, the products prepared in step S2 in Examples 1-3 have larger specific surface area and pore volume.

[0132] Test Example 3

[0133] 130 SPF Kunming mice are randomly divided into a blank group, Example 1-5 groups and Comparative Example 1-7 groups, 10 mice in each group, and the mice are allowed to freely eat and drink during the feeding period, the temperature is 25±2℃, and the humidity is 50±10%. After adaptive feeding for 1 week, the biomimetic crystal materials prepared in Examples 1-5 and Comparative Examples 1-7 are mixed with cotton according to a mass ratio of 2:8 to fill the non-woven fabric bag to prepare a pillow. The blank group is filled with cotton to obtain a pillow. The prepared sleep-aiding pillow or pillow is placed on the top cover of the mouse cage, and the top cover is kept fastened during the test. On the 15th day of the test, the mice are put into the mouse self-activity instrument in batches, adapted for 5 minutes, and then the number of self-activities of the mice within 5 minutes is recorded. The number of self-activities of the animals in the test group and the control group is compared, and the results are shown in Table 3.

[0134] Table 3 Note: *P<0.05 compared with the blank group.

[0135] From the above table, it can be seen that the pillow filled with the biomineral crystal material prepared in Examples 1-3 can obviously reduce the activity frequency of mice and promote the sleep of mice.

[0136] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method of producing a biomineral crystal material, characterized by, The surface of natural mineral crystal is modified, mixed with doped TiO2 / Fe3O4 intercalated montmorillonite, doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder is prepared, and then the surface is modified by polydopamine, aromatic essential oil is adsorbed, and spherical biomaterial crystal material is prepared by embedding with sodium alginate.

2. The production method according to claim 1, characterized by, The method comprises the following steps: S1. Surface modification of natural mineral crystal: the natural mineral crystal is ball milled, added into ethanol, added with silane coupling agent, heated and stirred to react, filtered, washed, and dried to prepare surface modified natural mineral crystal powder; S2. Preparation of doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder: butyl titanate is added into ethanol to form solution A, melamine, iron chloride and ferrous chloride are dissolved in water to obtain solution B, solution B is added dropwise into solution A, stirred to obtain a columnar agent, and then added dropwise into a montmorillonite suspension, while adding ammonia water, adding the surface modified natural mineral crystal powder prepared in step S1, heating and stirring to react, standing and aging, microwave heating and drying, washing, ball milling, and calcining to prepare doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder; S3. Preparation of modified crystal powder: the doped TiO2 / Fe3O4 intercalated montmorillonite modified crystal powder prepared in step S2 is added into water, added with dopamine hydrochloride and a catalyst, heated and stirred to react, filtered, washed, and dried to prepare modified crystal powder; S4. Adsorption of essential oil: the modified crystal powder prepared in step S3 is added into petroleum ether, added with composite aromatic essential oil, and the solvent is evaporated to prepare essential oil adsorbed modified crystal powder; S5. Preparation of biomaterial crystal material: the essential oil adsorbed modified crystal powder prepared in step S4 is added into water, added with sodium alginate and an emulsifier to obtain an aqueous phase, the aqueous phase is added dropwise into fish oil, emulsified, added dropwise with a calcium chloride solution, and solidified at room temperature, filtered, washed, and dried to prepare biomaterial crystal material.

3. The method of manufacture according to claim 2, characterized in that, In step S1, the ball milling time is 0.5-1.5h, the mass ratio of the natural mineral crystal to the silane coupling agent is 50:4-7, the silane coupling agent is at least one selected from KH550, KH560, KH580, KH590, KH602 and KH792, the heating and stirring reaction temperature is 40-50℃, and the time is 1-3h.

4. The production method according to claim 2, characterized by, In step S2, the mass ratio of butyl titanate, melamine, iron chloride, ferrous chloride, montmorillonite and surface modified natural mineral crystal powder is 5-7:0.5-1:3.4-3.5:1.2-1.3:30-50:100, the heating and stirring reaction temperature is 65-75℃, the time is 2-4h, the ball milling time is 1-2h, the calcination temperature is 450-550℃, and the time is 1-3h.

5. The preparation method according to claim 2, characterized in that, The mass ratio of the modified water crystal powder, dopamine hydrochloride and catalyst in step S3 is 20-30:14-18:1-2, the temperature of the heating and stirring reaction is 40-50℃, the time is 2-3h, and the catalyst is Tris-HCl solution with pH=8.5-9.

6. The method of claim 2, wherein, The mass ratio of the modified water crystal powder and the composite aromatic essential oil in step S4 is 100:15-22, the composite aromatic essential oil is selected from at least two of lemon essential oil, bergamot essential oil, rose essential oil, clove essential oil, lavender essential oil and wormwood essential oil, and the preparation method of the essential oil is to obtain the essential oil by supercritical fluid extraction of raw materials.

7. The preparation method according to claim 2, characterized in that, The mass ratio of the modified water crystal powder, sodium alginate and emulsifier in step S5 is 10-13:17-20:1-2, the emulsifier is selected from at least one of Tween-20, Tween-40, Tween-60, Tween-80 and Tween-85, and the time of the normal temperature curing is 20-30min.

8. A biological mineral crystal material prepared by the preparation method of any one of claims 1-7.

9. Use of the biological mineral crystal material of claim 8 in the preparation of a sleep aid product.

10. A science and technology sleep-aiding pillow, characterized in that, The biological mineral crystal material of claim 8 is filled in a pillow, and the filling amount is 0.01-100wt%.

Images