Preparation method and application of long-acting natural multifunctional additive

Abstract

A preparation method for a long-acting natural multifunctional additive. A natural filler is coated with a modified polymer; the modified polymer is obtained by modifying any one or more than two of a biodegradable polymer, a water-soluble polymer, polyvinyl chloride, polyamide, polyphenylene sulfide, melamine resin, polyolefin, polyhydroxyalkanoate, a styrene block copolymer, chlorinated polyvinyl chloride, urea-formaldehyde resin, polyurethane, and chitosan; and the natural filler is shell powder or eggshell calcined at high temperature, any one or more than two of calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, and purified Hermetia illucens pupa shell powder, or a compound of nanoparticles and calcined shell powder or eggshell powder. By adoption of the preparation method disclosed by the present invention, the cost is low, and part of raw materials are recycled wastes; the antibacterial property of the natural filler is long-acting, and the natural filler is easy to store; and the preparation method can be applied to various processing techniques, or the addition or adjustment of health care products.

Description

Preparation method and application of long-acting natural multifunctional additive BACKGROUND The invention belongs to the technical field of materials, relates to the sterilization additive technology, and particularly relates to preparation method and application of long-acting natural multifunctional additive. It is estimated that the market value of the global additive market will reach 62.5 billion US dollars in year 2022. Because additives can be used in various industries, the global market share of plastic additives is highly concentrated in comprehensive enterprises, including raw material production to plastics, building manufacturing and even food. There are large industry participants operating globally, including DuPont, PolyOne, Dow Chemical Company, Evonik and BASF. Because antibacterial additives can give products antibacterial and bacteriostatic function, they are believed to have a good market prospect. Harmful bacteria are common in nature, and interfering with human life. The proliferation of harmful bacteria threatens human health, and inhibiting their growth can reduce the occurrence of diseases. Among metal ion antibacterial agents, silver ion antibacterial agents are the most studied at present. because silver has the strongest bactericidal ability. Metal oxide antibacterial agent belongs to photocatalyst, which is a kind of substance that does not change itself under the irradiation of light, but can promote chemical reaction, and convert light energy existing in nature into energy needed for chemical reaction. Common photocatalytic materials include TiO2 and Zn0, among which Ti02 is the most representative, Organic antibacterial agents are mostly obtained by chemical synthesis, including organic acids, esters, quaternary ammonium salts, biguanides, yeasts, nitriles, pyridines, phenols, aldehydes, ethers, peroxides, halogens, imidazoles, thiazoles, etc. Organic antibacterial agents usually have high antibacterial performance, but they also have some disadvantages such as poor heat resistance, poor antibacterial durability or biological toxicity. Natural antibacterial agents are extracted and refined from animals and plants, and most of them are polysaccharides, polypeptides and glycopeptide polymers, including chitosan, protamine, cinnamon oil and Lohan tar, etc., which have the advantages of excellent weather resistance, low toxicity and being safe for using. Chitosan is the deacetylated product of chitin refined from the skins of crabs, shrimp shells, shellfish and insects. The main disadvantages of natural antibacterial agents are poor heat resistance and short duration of efficacy, which is the main development direction of antibacterial additives in the future. To sum up, most of the existing antibacterial agents are expensive, and some of them are harmful to the environment or have biological toxicity, which does not conform to the modem concept of environmental protection and heaith. In addition, most antibacterial agents will reduce their original antibacterial activity with the change of time or the influence of the environment. On the other hand, most antibacterial agents will affect the physical properties of products, which is due to the poor mechanical properties of antibacterial agents and the difficulty in dispersing antibacterial agents. SUMMARY In order to solve the defects exist in the prior art, this invention discloses preparation method of long-acting natural multifunctional additive. This invention provides preparation method of long-acting natural multifunctional additive, which uses modified polymer for coating the natural filler, the modified polymer is any one or more than two polymers of biodegradable polymer, water-soluble polymer, polyolefin, polyhydroxy fatty acid ester, styrene block copolymer, propylene-butadiene- styrene copolymer, polybutylene terephthalate, polyacryiate, polyvinyl chloride, polyamide, polyphenylene sulfide, melamine resin, chlorinated polyvinyl chloride, urea- formaldehyde resin, polyurethane and chitosan. The natural filler is any one or more of shell powder or eggshell powder calcined at a high temperature of 700-1400°C, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide and purified Hermetia illucens pupariums shell powder, or composite of nanoparticles and calcined shell powder, or a composite of nanoparticles and calcined eggshell powder. The mass ratio of the modified polymer in the mixiure is 5-60%, and the natural filler is 40-05%. Preferably, the mass ratio of nanoparticles to shell powder or eggshell powder in the composite is 100:1 to 1:100. Preferably, nano particles are one or two of nano silver and nano zinc oxide. Preferably, the antioxidant with the content less than 0.6% of the total mass of the mixture is also added. Preferably, the specific coating method is dry mixing, in which natural fillers and modified polymers are mixed and granulated in mixer to form coating. Preferably, the specific coating method is wet mixing, in which, after the modified polymer is disscived in a solvent, natural fillers are added into the dissolved modified polymer solution and stirred evenly; after the solution is dried, the obtained solid mixture is crushed to form particles or powder coating. Preferably, the modification of polymer is graft functional group of polymer or modification by adding compatilizer, and the functional group or compatilizer is any one or more selected from epoxy type, oxazoline type, amino type, anhydride type, carboxylic acid type, hydroxyl type, epoxy type reaction type, titanate type, silane type, dopamine type, aldehyde type, peptidyl imide type and isocyanate type. This invention discloses application of long-acting natural multifunctional additive for using in various plastic processing techniques, or addition or adjustment of skin care products. The method of preparing the long-acting natural multifunctional additive provided by this invention has the following positive effects: 1. The cost is low, and some of the raw materials belong to waste recycling. 2. Make the antibacterial property of natural fillers more lasting and easy to preserve. 3. The natural filler is easier to disperse and less likely 10 agglomerate in the product process. 4. It can improve the mechanical strength of products. 5. It can improve the heat resistance of products. 8. The product has no biological toxicity. 7. ltis safe to store and can be directly touched by human body. After being coated and granulated, the particle size of the natural filler becomes larger, which is not easy to float and scatter randomly along with the airflow, and it is more convenient to apply to the production process. BRIEF DESCRIPTION OF THE FIGURES Fig. 1is a schematic flow diagram of a specific embodiment of wet mixing according to the present invention; Fig. 2 is a schematic flow diagram of an embodiment of dry mixing according to the present invention: Fig. 3 is a schematic diagram of the morphology of the product obtained by wet mixing according to the present invention. The product morphology in real products is generally irregular. Fig. 4 is a schematic diagram of product morphology obtained by dry mixing according to the present invention; The small round particles shown in Fig. 3 and Fig. 4 represent any one of shell powder, eggshell powder, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide and purified Hermetia iflucens pupariums powder, which is coated or attached to the interior or surface of the modified polymer. DESCRIPTION The following is a further detailed description of the specific embodiments of the present invention. In order to make the object, technical scheme and advantages of the present invention clearer, the present invention will be further described in detail with specific embodiments below, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples. Without deviate from that above technical ideas of the invention, various substitution and changes can be made according to the common technical knowledge and conventional means in the field, which should be include in the scope of the invention. This invention provides preparation method of long-acting natural multifunctional additive, which uses modified polymer for coating the natural filler, the modified polymer is any one or more than two polymers of biodegradable polymer, water-soluble polymer, polyolefin, polyhydroxy fatty acid ester, styrene block copolymer, propylene-butadiene- styrene copolymer, polybutylene terephthalate, polyacrylate, polyvinyl chloride, polyamide, polyphenylene sulfide, melamine resin, chlorinated polyvinyl chloride, urea- formaldehyde resin, polyurethane and chitosan, the natural filler is any one or more of shell powder or eggshell powder calcined at a high temperature of 700-1400°C, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide and purified Hermetia illucens pupariums powder, or composite of nanoparticles and calcined shell powder, or a composite of nanoparticles and calcined eggshell powder, the mass ratio of the modified polymer in the mixture is 5-80%, and the natural filler is 40-95%. The modification of polymer is graft functional group of pelymer or modification by adding compatilizer, and the functional group or compatilizer is any one or more selected from epoxy type, oxazoline type, amino type, anhydride type, carboxylic acid type, hydroxyl type, epoxy type reaction type, titanate type, silane type, dopamine type, aldehyde type, peptidyl imide type and isocyanate type. With more functional groups, the modified polymer can form bonding reaction with natural additives such as shell powder or eggshell, calcium oxide and purified Hermetia ifflucens pupariums powder, which improves the compatibility and dispersibility of polymer materials. In the invention, the long-acting natural multifunctional additive can be applied to improve the tensile property and thermal property of plastics and endow them with excellent antibacterial property, and can be stored for a long time without being influenced by the environment. Several specific embodiments of the present invention are given below Embodiment 1 Preparation method of long-acting natural multifunctional additive and its application to polypropylene The 1000 mesh shell powder calcined at high temperature, blending with modified polypropylene (acrylic acid grafted polypropylene) in mixing machine at 180-200°C, and then granulated with granulation diameter of 2-4mm to obtain the natural multifunctional additive of the invention, wherein the mass ratio of shell powder to modified polypropylene is 1:1, and 0.3% of total antioxidant is added additionally. wherein the antioxidant can be 0 15% of 1010 antioxidant and 0.15% of 1010 antioxidant. The natural fillers prepared in embodiment 1 were added to polypropylene in different mass proportions, and the traditional shell powder was added fo polypropylene in corresponding mass proportions as control embodiment. The properties of the added mixed materials are shown in Table 1. The percentages in parentheses of each embodiment in Table 1 indicate the mass ratio of shell powder in polypropylene in the natural multifunctional additive of the present invention, and the percentages in parentheses cf each control embodiment indicate the mass ratio of shell powder in polypropylene, which are similar in the following other tables Table 1 Tensile Sterilizing Sample strength rate MPa (%,; 286 0 359 9574 256 95.26 37.7 99.51 235 09.48 2304 99 97 21.8 99.91 36.3 99.99 173 99.95 Polypropylene Embodiment 1(0.5%) Control embodiment 1 (0.5%) Embodiment 1(1% Control embodiment 1 (1%) Embodiment 1(3%) Control embodiment 1 (3%) Embodiment 1(5% Control embodiment 1 (5%; The results in Table 1 show that the tensile strength of polypropylene decreases with the increase of the content of natural filler shell powder. Because natural filler is incompatible with plastics, it is easy to cause aggregation of filler or phase separation of materials. However, the natural filler of this embodiment will not reduce the performance of plastic, but can effectively improve its tensile strength. In addition, Table 1 shows that the antibacterial activity of the two additives is similar, and the natural filler is better, because the natural filler is easier to disperse in polypropylene plastics. Embodiment 2 Preparation method of long-acting natural multifunctional additive and its application in polyethylene terephthalate. The 1200-mesh shell powder calcined at high temperature is blended with modified polyethylene (maleic anhydride grafted polyethylene) in a mixing machine at 180-185°C, and then granulated with a granulation diameter of 2-4mm to obtain the natural multifunctional additive of the invention. The mass ratio of shell powder to modified polyethylene is 1.2:1, and 0.3% of antioxidant in addition to the total amount is added, and the antioxidant can be a mixture of 0.15% of 1010 antioxidant and 0.15% of 168 antioxidant. In embodiment 2, the percentage in brackets indicates the mass ratio of shell powder in the natural multifuncticnal additive of the present invention to polyethylene terephthalate, and the traditional shell powder is added to polyethylene terephthalate in corresponding mass ratic as a control embodiment. The performance of the added mixed material is shown in Table 2 (the temperature during addition is 260-280°C). Table 2 Sterilizing | Tensile strength | Sample As. pl mpg! rate % _(%) 24.1 0 26.2 94.15 231 03.27 21.4 95.81 21.2 95.24 26.5 99.94 18.4 08.88 24 5 99.99 14.4 98.91 PET(polyethylene terephthalate) Embodiment 2(0.5%) Control embodiment 2 (0.5%, Embodiment 2(1%) Control embodiment 2 (1%) Embodiment 2(3%) Control embodiment 2 (3%) Embodiment 2(6% Control embodiment 2 (6% Embodiment 3 Preparation method of long-acting natural multifunctional additive and its application to polyamide The 800-mesh shell powder calcined at high temperature is blended with modified polyamide 6 (ethylenediamine grafted polyamide) in a mixing machine at 230-240°C, and then granulated with a diameter of 2-4mm, thus obtaining the natural multifunctional additive of the invention. The mass ratio of shell powder to modified polyamide 6 is 1:1, and 0.3% of total antioxidant is added. The antioxidant can be a mixture of 0.15% of 1010 antioxidant and 0.15% of 1688 antioxidant. In embodiment 3, the percentage in brackets indicates the mass ratio of shell powder in polyamide 6 of the natural multifunctional additive of the present invention, and the traditional shell powder is added to polyamide 6 in the corresponding mass ratio as a control example. The properties of the added mixed materials are shown in Table 3 Table 3 Sterilizing | Tensile strength | Rn CT amas C1 rate Sample LT Mpa I rae % _(%) 643 0 67.1 94 85 626 04 45 69.5 96.77 59.1 96.09 122 99.91 57.4 99 89 742 99.99 541 08.69 Polyamide 6 Embodiment 3 (0.5%) Control embodiment 3 (0.5%) Embodiment 3 (1%) Control embodiment 3 (1%; Embodiment 3 (3%) Control embodiment 3 (3%) Embodiment 3 (6%) Control embodiment 3 (6% Embodiment 4 Preparation method of long-acting natural multifunctional additive and its application to biodegradable materials. Blending 800 mesh shell pow calcined at high temperature with modified polylactic acid (maleic acid grafted polylactic acid) in a mixing machine at 180-195C and then granulated to obtain the natural multifunctional additive of that invention . The ratio of shell powder to modified polylactic acid is 0.8:1, and 0.3% of {otal antioxidant is added. The antioxidant can be a mixture of 0.15% 1010 antioxidant and 0.15% 168 antioxidant. In embodiment 4, the percentage in brackets indicates the mass ratio of shell powder in the natural multifunctional additive of the present invention in polylactic acid material, and the traditional shell powder is added to polylactic acid in the corresponding mass ratio as a control embodiment. The properties of the added mixed material are shown in Table 4. Tensile Sterilizing Sample strength rate (MPa) %) 48.3 0 56.5 96.87 44 3 96.5 55.2 98.95 41.0 08.23 57.4 99.94 37.6 99.85 558 99.98 231.2 99.91 Polylactic acid Embodiment 4 (0.5%, Embodiment 4 (1%) Embodiment 4 (3%; Embodiment 4 (6%; Embodiment 5 Preparation method of long-acting natural multifunctional additive and its application to polyethylene 2000 mesh calcium oxide and modified polyethylene (maleic anhydride grafted polyethylene) are blended in a mixing machine at 180-195°C and then granulated to obtain the natural multifunctional additive. The ratio of calcium oxide to modified polyethylene is 1:1, and 0.3% of total antioxidant is added, which can be a mixture of 0.15% 1010 antioxidant and 0.15% 168 antioxidant. Embodiment 5, the percentage in brackets indicates the mass ratio of calcium oxide in the natural multifunctional additive of the present invention in polyethylene material, and traditional calcium oxide is added to polyethylene in corresponding mass ratio as a control embodiment. The properties of the added mixed material are shown in Table 5. Tensile | Sample strength MPa’ Polyethylene 26.7 Embodiment 5 (0.5%) 31.4 25.1 32.5 24.2 32.8 226 304 19.2 Embodiment 6 Preparation method of long-acting natural multifunctional additive and its application to phenyl sulfide The 1000 mesh shell powder calcined at high temperature is blended with modified polyphenylene sulfide (30% mass ratio of polyphenylene sulfide and 70% mass ratio of maleic anhydride grafted polyethylene copolymer) in a mixing machine at 285-300°C, and then granulated to obtain the natural multifunctional additive. The ratio of sheli powder to modified polyphenylene sulfide is 1:1, and 0.3% of total antioxidant is added. The antioxidant can be a mixture of 0.15% 1010 antioxidant and 0.15% 168 antioxidant. In embodiments, the percentage in brackets indicates the mass ratio of shell powder in the natural multifunctional additive of the present invention in polyphenylene sulfide material, and the traditional shell powder is added to polyphenylene sulfide in corresponding mass ratio as a control example. The properties of the added mixed material are shown in Table 6. Table 6 Tensile Sterilizing Sample strength rate (MPa) (%) 69.5 93.18 67.3 93.21 71.2 95.34 68.1 95.16 75.4 90 84 70.8 99.77 ————————— a re er —— ——— ——— » The [Embodiment 6 (5%) 78.4 99.99 | resulis in Table 6 | Control embodiment 6 (5%) 73.8 99.99 | show that the EE 5 a Se —— — Ne 80.4 99.99 : het Lv A os. Te tensile "5 iol embodiment 6 (10%) 74.1 soos | strength of 78.2 99.99 68.3 BN 99 99 Polyphenylene sulfide 66.6 0 Embodiment 6 (0.5%) 69.5 93.18 Control embodiment 6 (0.5%) 67.3 93.21 Embodiment 6 (1%) 71.2 95.34 Control embodiment 6 (1%) 68.1 95.16 Embodiment 6 (2%) 75.4 99.84 Control embodiment 6 (2%) 70.8 99.77 e Embodiment 6 (5%) 78.4 99.99 | & | Control embodiment 6 (5%) 73.8 99.99 | Embodiment 6 (10%) 80.4 99.99 Control embodiment 6 (10% 74.1 99.99 | Embodiment 6 (12.5%) 78.2 99.99 68.3 99.99 polyphenylene sulfide is improved with the increase of the content of the two additives, and the additive obtained by the present invention is more improved than the commen additive. In addition, the table alsc shows that the efficacy of the two additives in antibacterial activity is similar. Embodiment 7 Preparation method of long-acting natural multifunctional additive and its application to HDPE. The modified ultra-high molecular weight polyethylene (blend of maleic anhydride grafted polyethylene 50% and ultra-high molecular weight polyethylene 50%) is dissolved by using decalin as solvent, then 1200 mesh shell powder caicined at high temperature is added into the modified polyethylene solution, and the sclution is stirred and dispersed at 500rpm by a fast stirrer, and then the solution is dried, and the remaining solid matter is crushed and screened by a 50 mesh sieve, thus obtaining the additive of the invention. The mass ratio of shell powder to modified polyethylene is 9:1, and no additional antioxidant is needed In embodiment 7, the percentage in brackets indicates the mass ratio of shell powder in the natural multifunctional additive of the present invention to high density polyethylene, and the traditional shell powder is added to the high density polyethylene in corresponding mass ratio as a control embodiment. The performance of the added mixed material is shown in Table 7, and the improvement effect of tensile strength of the present invention is significantly better than that of shell powder. Sterilizing Tensile strength | Sample TALIS ArT gE pl mPa) | rate % (Nn) 26.4 0 322 93.83 240 90.78 30.7 95.14 229 94.26 304 99.11 21.2 97.55 288 99.97 19.0 97.78 Embodiment 7 (0.5%) Control embodiment 7 (0.5%) Embodiment 7(1%) Control embodiment 7 (1%) Embodiment 7 (3%, Control embodiment 7 (3%) Embodiment 7(6%) Control embodiment 7 (6%) Embodiment 8 Comparison of antibacterial properties after adding additives and simulating long- term storage 1,000-mesh shell powder calcined at high temperature is blended with modified polypropylene (maleic anhydride grafted polypropylene) in a mixing machine at 180- 195°C, and then granulated with a granulation diameter of 2-4mm to obtain the additive of the invention. The mass ratio of shell powder to modified polypropylene is 1:1, and 0.3% of total antioxidant is added. The antioxidant can be a mixture of 0.15% of 1010 antioxidant and 0 15% of 188 antioxidant The above-mentioned additive and single shell powder are placed in a constant temperature and humidity box with a relative humidity of 80% and a temperature of 30°C for 1 week, and then placed in ultraviolet light for 7 days, and then added to polypropylene with a mass content of 3%. The properties of the prepared materials are shown in Table 8. The natural multifunctional additive of the present invention is blended with polypropylene as embodiment 8 and blended with polypropylene as control embodiment 8. Table 8 Sterilizing Sample rate % _ (%) | NG Goeratin Embodiment 8 99.99 Pp 9g Control embodiment 8 09.98 S| EEE ARIE EE Mn we | and humidity and UV Emoodiment 8 ee. tol TE Control embodiment 8 9998 | canbe n Constant temperature ; that | and humidity and UV Embodiment 8 99.97 light for 7 days each peepee See Ig! y: Control embodiment 8 Q1 51 | ~ Control embodiment 8 91.51 sterilization rate of the present invention is lower than that of shell powder after a certain preservation time, and the shell powder in the present invention can be preserved and used for a longer period of time without being affected by the environment, and is easy to disperse in plastics, so it will have a better effect in plastics, and has better compatibility with plastics, which can improve the mechanical strength of materials. Due to the protection of modified polypropylene coated on the outer layer, after constant temperature and humidity UV, it is hardly deliquescent, not easy to photoaging, and the sterilization rate decays very litfle. Embodiment S Comparison of antibacterial properties after simulated long-term storage 1,000 mesh shell powder / nano zinc oxide particles calcined at high temperature are blended with modified polypropylene (maleic anhydride grafted polypropylene) in a mixing machine at 180-195°C, and then granulated with a granulation diameter of 2-4dmm to obtain the additive of the invention. The mass ratio of shell powder / nano zinc oxide particles to modified polypropylene is 1:1, and 0.3% of total antioxidant is added. Wherein the mass ratio of shell powder to nano zinc oxide particles is 1:1. The additive and the composite of shell powder / nano zinc oxide particles obtained above are placed in a constant temperature and humidity box with a relative humidity of 80% and a temperature of 30°C for 1 week, and then placed in ultraviolet light for 7 days, and then added to polypropylene with a mass content of 5%, and the properties of the prepared materials are shown in Table 8. The natural multifunctional additive of the present invention is blended with polypropylene as embodiment 9 and polypropylene as control embodiment 9. Table © Sterilizing Sample rate % _ (%) Embodiment 9 (0.5%) . 97.68 | No ooetalin Embodiment 9 (0.5%) 99.99 psrating Control embodiment 9 (0.5%) 99.97 Constant temperature Embodiment 9 (0.5%) 97.68 and humidity and UV ” an oh | Control embodiment 9 (0.5%) | 88.85 and humidity ana UV i light for 7 days esch | Control embodiment 9 (0.5%) | 88.85 Tables 8 and @ show that the sterilization rate degradation caused by cracking, thermal cross-linking or deliquescence caused by common additives in constant temperature and humidity box and UV light irradiation for 7 days respectively. In the invention, the modified polymer is adopted to coat the natural filler, so that the thermal oxygen aging of the additive caused by the change of time or the influence of environment can be delayed, and the antibacterial activity of the additive is prolonged. Embodiment 10 Preparation method of long-acting natural multifunctional additive and its application to polycaprolactone biodegradable material Bleding 800 mesh eggshell powder caicine at high temperature with modified polycaprolactone (i. e., acrylic acid grafted polycaprolactone) in a mixing machine at 75- 85°C, and granulating to obtain that natural multifunctional additive; The ratio of shell powder to modified polycaprolactone is 1:1, and 0.3% of total antioxidant is added. The antioxidant can be a mixture of 0.15% 1010 antioxidant and 0.15% 188 antioxidant. In embodiment 10, the percentage in brackets indicates that the eggshell powder in the natural multifunctional additive of the present invention is in the polycaprolactone material, and the traditional eggshell powder is added to the polycaprolactone in a corresponding mass ratio as a control example. The performance of the added mixed material is shown in Table 4. Table 10 Sterilizing Sample Tensile strength rate (MPa) (%) 17.6 0 2135 97.37 15.0 06.4 21.8 08.54 embodiment 14.3 97.01 221 09.49 embodiment 13.9 98.12 20.8 99.91 embodiment 10.4 08.56 polycaprolactone Embodiment 10 (0.5%) Control embodiment 10 (0.5%) Embodiment 10 (1%) Control embodiment 10 (1%) Embodiment 10 (3%) Control embodiment 10 (3%) Embodiment 10(6%) Control embodiment 10 (6%) Embodiment 11 Preparation method of long-acting natural multifunctional additive and its application in polyvinyt chioride Blending 800 mesh shell powder calcine at high temperature with modified chlorinated polyethylene at 85-90°C, and granulating to obtain that natural multifunctional additive. The ratio of shell powder to modified chlorinated polyethylene is 1:1. and 0.3% antioxidant is added. In embodiment 11, the percentage in brackets indicates the mass ratio of shell powder in the natural multifunctional additive of the present invention in PVC material, and the traditional shell powder is added to PVC in corresponding mass ratio as a control embodiment. The properties of the added mixed material are shown in Table 11. Table 11 3 Sterilizing Tensile strength | Sample (MPa) iy polyvinyl chloride 51.3 0 Embodiment 11 (0.5%) | 54.5 96.37 Control embodiment 11 (0.5%) 49.2 92.88 Embodiment 11 (1%) 56.8 98.11 Control embodiment 11 (1%) 47.7 94.33 Embodiment 11 (3%, 55.1 99.69 Control embodiment 11 (3%) 43.3 97.45 Embodiment 11(6%) 54.5 99.99 Control embodiment 11 (6%) 416 98.81 Preparation method of long-acting natural multifunctional additive and its application to polyvinyl alcohol. Blend 800 mesh calcium oxide with modified polyvinyl alcohol (with glutaraldehyde as compatilizer) in a mixing machine at 200-225°C and then granulated to obtain the natural multifunctional additive. The ratio of shell powder calcined at 300°C (screened by 2000 mesh) to modified polyvinyl alcohol is 0.8:1. In addition, 0.4% of total antioxidant is added, which is a mixture of 0.2% of 1010 antioxidant and 0.2% of 168 antioxidant. In addition, 5% glycerol was added as plasticizer. In embodiment 12, the percentage in brackets indicates the mass ratio of the shell powder in the natural multifunctional additive of the present invention in the polyvinyl alcohol material, and the shell powder is added to polyethylene in the corresponding mass ratio as a control example. The properties of the added mixed material are shown in Table 12. Table 12 Sterilizing Sample Tensile strsl ngth rate (MPa) % CO 38.1 0 41.3 92.46 37.8 90.18 432 04.27 embodiment 357 93.09 48.3 9943 embodiment 246 98.12 489 99.99 olyvinyl alcohol Embodiment 12 (0.5%) Control embodiment 12 (0.5%) Embodiment 12 (1%) Control embodiment 12 (1%) Embodiment 12 (3%) Control embodiment 12 (3%) Embodiment 12(6%) Control embodiment 12 (6%) Control embodiment 12 (6%) 33.1 99.79 Embodiment 13 Preparation method of long-acting natural multifunctional additive and its application to polyethylene. Blend 800 mesh calcium oxide with modified polyethylene (maleic anhydride grafted polyethylene; in a mixing machine at 180-195°C and then granulated to obtain the natural multifunctional additive. The ratio of shell powder (1000 mesh), hydrangea pupa shell extract powder (1000 mesh) and modified polyethylene after high temperature calcination at 100°C is 0.6:0.2:1, and 0.4% of total antioxidant is added, which is a mixture of 0.2% of 1010 antioxidant and 0.2% of 168 antioxidant. In embodiment 13, the percentage in brackets indicates the mass ratio of the shell powder and the extract of the pupa shell of the hydra in polyethylene material, and the shell powder and the extract of the pupa shell of the hydra are added into polyethylene in the corresponding mass ratio as a control embodiment. The properties of the added mixed material are shown in Tabie13. Table 13 Sterilizing Sample Tensile stre ngth rate (MPa) (%) 26.7 0 29.7 Q7.74 24 2 96.02 230.8 99.99 embodiment 201 99.21 295 99.99 embodiment 203 99 99 polyethylene Embodiment 13 (0.5%) Control embodiment 13 (0.5%) Embodiment 13 (1%) Control embodiment 13 (1%) Embodiment 13 (3%) Control embodiment 13 (3%) Embodiment 14 Preparation method of long-acting natural multifunctional additive and its application in polyethylene Blend 1600 mesh calcium hydroxide with modified polyethylene (maleic anhydride grafted polyethylene) in a mixing machine at 180-195°C and granulated to obtain the natural multifunctional additive. The ratio of magnesium oxide to modified polyethylene is 1:1, and 0.3% of total antioxidant is added. The antioxidant can be a mixture of 0.15% 1010 antioxidant and 0.15% 168 antioxidant. In embodiment 14, the percentage in brackets indicates the mass ratio of calcium hydroxide in the natural multifunctional additive of the present invention in polyethylene material, and traditional magnesium oxide is added to polyethylene in corresponding mass ratio as a control embodiment. The properties of the added mixed material are shown in Table 5. Table 14 Sterilizing Sample Tensile iki ngth rate (MPa) (%) 26.7 0 231.9 92.11 olyethylene Embodiment 14 (0.5%) Embodiment 15 Preparation method of long-acting natural multifunctional additive and its application to polypropylene. Blend 1600 mesh magnesium oxide with modified polypropylene (acrylic acid grafted polypropylene) in a mixing machine at 180-200°Cand then granulated, and the diameter of granulation is 2.5-4mm to obtain the natural multifunctional additive, wherein the mass ratio of magnesium oxide to modified polypropylene is 1:1, and 0.3% of antioxidant is added, and the antioxidant can be a mixture of 0.15% of 1010 antioxidant and 0.15% of 168 antioxidant. The natural fillers prepared in embodiment 15 were added to polypropylene in different mass ratios, and the traditional magnesium oxide was added to polypropylene in corresponding mass ratios as control embodiment. The properties of the added mixed materials are shown in Table 1. The percentages in parentheses of each example in Table 15 indicate the mass ratio of magnesium oxide in polypropylene in the natural multifunctional additive of the present invention, and the percentages in parentheses of each comparative example indicate the mass ratio of added magnesium oxide in polypropylene, which are similar in other tables below Table 15 Sterilizing Sample Tensile sa nth rate (MPa) (%) 286 0 33.8 97.45 242 06.32 36.9 99.91 embodiment 200 99.21 37.6 99.99 embodiment 20.8 99.95 32.5 99.989 embodiment 16.8 99.95 Polypropylene Embodiment 15 (0.5%) Control embodiment 15 (0.5%) Embodiment 15 (1%) Control embodiment 15(1%) Embodiment 15 (3%) Control embodiment 15(3%) Embodiment 15 (5%) Control embodiment 15(5%) Embodiment 16 Preparation method of natural additives for skin care products. Preparation of chitosan gel with deacetylation degree of 60%: weigh 0.1g of chitosan. In a 100mL clean beaker, add about 50mL of water, and adjust the pH value of the aqueous solution to § with lactic acid. Under the stirring condition, the weighed chitosan is put into a beaker until it is dissolved, and the gel preparation is completed. Weigh 3 grams of 3000 mesh oyster shell powder and slowly add it into chitosan gel, so that it can be evenly dispersed in the gel. The method for preparing natural additives for skin care products is completed by freeze drying to remove water, and then crushing or grinding. In addition to making the skin care products have antibacterial and mildew- proof properties and prolonging the shelf life, the skin care products can be used for moisture absorption adjustment and pH adjustment. As shown in Table 16, control embodiment 16 is an emulsion without the additive of the present invention, and the emulsion is prepared from olive oil and emulsifier. In the embodiment, the additive prepared by the above method is added to the emulsion at a mass ratio of 0.3%, and it can be known that the emulsion containing natural additives has excellent antibacterial performance. Table 16 Sterilizing rate | Sample (%) 99.99 326 Embodiment 16 (0.3%) Control embodiment 16 (0%) The foregoing are all preferred embodiments of the present invention. If the preferred embodiments in each preferred embodiment are not obviously self- contradictory or based on a certain preferred embodiment, each preferred embodiment can be used in any superposition and combination. The embodiments and specific parameters in the embodiments are only for clearly describing the inventor's invention verification process, and are not used to limit the patent protection scope of the present invention. The patent protection scope of the present invention is still subject to its claims. Any equivalent structural changes made by using the contents of the specification of the present invention should be included in the same way.

Claims

CLAIMS 1. Preparation method and application of long-acting natural multifunctional additive is characterized in using modified polymer for coating the natural filler, the modified polymer is any one or more than two polymers of biodegradable polymer, water-soluble polymer, polyolefin, polyhydroxy fatty acid ester, styrene block copolymer, propylene- butadiene-styrene copolymer, polybutylene terephthalate, polyacrylate, polyvinyl chloride, polyamide, polyphenylene sulfide, melamine resin, chlorinated polyvinyl chloride, urea-formaldehyde resin, polyurethane and chitosan, the natural filler is any one or mere of sheil powder or eggshell powder calcined at a high temperature of 700-~ 1400°C, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide and purified Hermetia illucens pupariums shell powder, or composite of nanoparticles and calcined shell powder, or a composite of nanoparticles and calcined eggshell powder, the mass ratio of the modified polymer in the mixture is 5-80%, and the natural filler is 40-95%, 2. The preparation method, according to claim 1, is characterized in that the mass ratio of nanoparticles to shell powder or eggshell powder in the composite is 100:1 to 1-100.

3. The preparation method, according to claim 1, is characterized in that the nano particles are one or two of nano silver and nano zinc oxide.

4. The preparation method, according to claim 1, is characterized in that the antioxidant with the content less than 0.5% of the total mass of the mixture is also added &. The preparation method, according to claim 1, is characterized in that the specific coating method is dry mixing, in which natural fillers and modified polymers are mixed and granulated in mixer to form coating.

6. The preparation method, according to claim 1, is characterized in that the specific coating method is wet mixing, in which, after the modified polymer is dissolved in a solvent, natural fillers are added into the dissolved modified polymer solution and stirred evenly; after the solution is dried, the obtained solid mixture is crushed to form particles or powder coating.

7. The preparation method, according to claim 1, the modification of polymer is graft functional group of polymer or modification by adding compatilizer, and the functional group or compatilizer is any one or more selected from epoxy type, oxazoline type, amino type, anhydride type, carboxylic acid type, hydroxyl type, epoxy type reaction type, titanate type, silane type, dopamine type, aldehyde type, peptidyl imide type and isocyanate type.

8. The application of long-acting natural multifunctional additive is characterized in being applied for various plastic processing techniques, or addition or adjustment of skin care products.