CN113583357B - Sanitary, safe and environment-friendly food packaging box and production method thereof - Google Patents
Sanitary, safe and environment-friendly food packaging box and production method thereof Download PDFInfo
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- CN113583357B CN113583357B CN202111060368.3A CN202111060368A CN113583357B CN 113583357 B CN113583357 B CN 113583357B CN 202111060368 A CN202111060368 A CN 202111060368A CN 113583357 B CN113583357 B CN 113583357B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a sanitary, safe and environment-friendly food packaging box and a production method thereof, wherein the sanitary, safe and environment-friendly food packaging box comprises an inner box and an outer box; the inner box is made of modified polystyrene. The modified polystyrene is prepared from raw materials including polystyrene, a reinforcing agent, a wetting agent, 3-maleimidobenzoic acid succinimidyl ester and a stabilizing agent by melt extrusion through an extruder, and cooling and granulating. The food packaging box prepared by the process method has the advantages of low cost, safety, environmental friendliness, no toxicity, high strength, aging resistance and the like.
Description
Technical Field
The invention relates to the technical field of food packaging boxes, in particular to a sanitary, safe and environment-friendly food packaging box and a production method thereof.
Background
During the circulation of the food before reaching the consumer, the food packaging box plays a non-trivial role in preventing various external pollution such as physics, biology, chemistry and the like; the food packaging box can also effectively maintain the characteristics of the quality, the flavor and the like of the food. The food packaging box is convenient for consumers to use food, can well present the style of the food, and is attractive to the consumers, so that the consumers are helped to get favour, and the brand value of the food product above the material cost is greatly improved. However, the food packages on the market today are poor in pressure resistance, impact resistance and bending resistance and cannot effectively give the food the protection it should be. With the continuous increase of the consumption level and consciousness of people, consumers increasingly need a food packaging material with stronger protection capability. Therefore, the food packaging process becomes a huge component which cannot be ignored in the food and the manufacturing system engineering thereof. The versatility of the food packaging process, however, allows for a relatively independent self-system.
Polystyrene is a nonpolar plastic with high crystallinity, and has the advantages of good heat resistance, cold resistance, temperature impact resistance, good cyclic utilization rate, good chemical stability, oil resistance, acid resistance, high mechanical strength, low cost, wide source and the like. However, polystyrene has poor ageing resistance, and the ageing conditions such as thermal oxidation seriously weaken the performance, so that the polystyrene is greatly limited in the application fields such as food packaging and the like.
Patent CN112142894B provides an application of organosilane in preparing polyethylene, polyethylene and a preparation method and application thereof, and extrusion foaming is performed by taking carbon dioxide or nitrogen as a foaming agent to prepare a high-foaming polyethylene material, and instead of low-density polyethylene, the foaming polyethylene material is prepared by taking butane or pentane and other alkanes as the foaming agent, but the performance of the obtained polyethylene cannot meet the increasingly severe market demands, and the problems of photo aging, mechanical embrittlement and the like possibly occurring after long-term use of the product are not solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a sanitary, safe and environment-friendly food packaging box and a production method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a sanitary, safe and environment-friendly food packaging box comprises an inner box and an outer box. The bottom of interior box can paste and set up from the heat patch, from the heat patch is located the bottom of interior box and the gap between the outer box, is used for prolonging the heat preservation time of food, prevents that the cooling is too fast.
The reaction principle of the self-heating patch is that the primary battery is utilized to accelerate the oxidation reaction speed, and the chemical energy is converted into heat energy. In order to enable longer lasting temperatures, the product uses mineral vermiculite to keep warm. The bag material is very special because the product cannot react before use, and consists of a raw material layer, a gelatin layer and a non-woven bag. The non-woven bag is made of microporous breathable film. It also has a conventional airtight outer bag-gelatin layer. When in use, the outer bag is removed, the inner bag (non-woven bag) is exposed to the air,oxygen in the air enters the inside through the permeable membrane. The time and temperature of the exotherm is controlled by the rate of oxygen permeation through the breathable film. If the oxygen permeation speed is too high, heat can be quickly lost, and the risk of scalding the skin is also caused; if the oxygen permeation speed is too slow, the heat input is too small, and the purpose of heating up and heating cannot be achieved. The black brown solid contains carbon powder, naCl solid, and Fe 2 O 3 Solid and magnesium-aluminum-containing salts.
The material of the outer box is antibacterial PP.
The inner box is made of modified polystyrene.
The production method of the sanitary, safe and environment-friendly food packaging box comprises the steps of preparing an outer box from antibacterial PP according to a conventional food packaging box production process, preparing an inner box from modified polystyrene according to a conventional food packaging box production process, and placing the inner box in the outer box to obtain the sanitary, safe and environment-friendly food packaging box.
Preferably, the upper surface of the outer box has a size of (10-22) cm, the bottom has a size of (5-15) cm, and the height is 5-12cm.
Preferably, the upper surface of the inner box has a size of (10-22) cm, the bottom has a size of (5-15) cm, and the height is 4-11cm.
Preferably, the inner box is smaller in size than the outer box.
The preparation method of the modified polystyrene comprises the following steps:
f1, mixing polystyrene, cashew seed oil and/or modified cashew seed oil, a wetting agent, 3-maleimide phenylformic acid succinimidyl ester and a stabilizer, and then stirring to obtain a mixture;
and F2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene.
The special relative alignment of two nitrogen-containing five-membered heterocyclic rings and aldehyde groups in the 3-maleimide succinimidyl benzoate can enhance the toughness of the modified polystyrene when the modified polystyrene is used in the modification process of the polystyrene, thereby enhancing the macroscopic mechanical strength of the modified polystyrene; and, 3-maleimidobenzoic acid succinimidyl ester can synergistically enhance the photo-aging resistance of the modified polystyrene with undaria pinnatifida extract and C12-14 secondary alkanol polyether-8, which is presumably related to their electron cloud energy distribution, and can effectively eliminate free radicals generated by illumination.
In a preferred scheme, the preparation method of the modified polystyrene comprises the following steps:
f1, mixing 72-78 parts by weight of polystyrene, 5-7 parts by weight of cashew seed oil and/or modified cashew seed oil, 3-4 parts by weight of wetting agent, 2-5 parts by weight of 3-maleimidobenzoic acid succinimide ester and 4-5 parts by weight of stabilizer, and stirring at 38-43 ℃ for 12-17min at a rotating speed of 500-700rpm to obtain a mixture;
f2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene; the temperature of a machine head in the double-screw extruder is 210-215 ℃, and the rotating speed of a screw is 350-400rpm; the size specification of the pellets was (0.5-2) mm× (0.5-2) mm.
Cashew nut seed oil is widely applied to the fields of motor vehicles, machine tools, ships, wood furniture, home decoration, rubber, PVC, metal and plastic products, chemical equipment, various anti-corrosion paints, coatings and the like; the cashew nut seed oil modified resin material has the advantages of high impact strength, stable friction coefficient, good recovery, low cost and the like. However, if the cashew seed oil is directly applied to polystyrene, the final product is softened, cracked and other adverse phenomena occur under the long-time service state, so in the technical scheme of the invention, the raw materials such as the inositol phosphate, the polyethylene glycol and the like, namely the multi-cashew seed oil, are used for preparing the modified polystyrene after being modified, and then are used for preparing the sanitary, safe and environment-friendly food packaging box.
In a more preferred embodiment, the preparation method of the modified polystyrene comprises the following steps:
f1, mixing 72-78 parts by weight of polystyrene, 5-7 parts by weight of modified cashew seed oil, 3-4 parts by weight of wetting agent, 2-5 parts by weight of 3-maleimide-based succinimide benzoate and 4-5 parts by weight of stabilizer, and stirring at 38-43 ℃ for 12-17min at a rotating speed of 500-700rpm to obtain a mixture;
f2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene; the temperature of a machine head in the double-screw extruder is 210-215 ℃, and the rotating speed of a screw is 350-400rpm; the size specification of the pellets was (0.5-2) mm× (0.5-2) mm.
The wetting agent is at least one of ethyl caproate, spermacetene and palmitoyl myristate. Preferably, the wetting agent is a mixture of ethyl caproate, cetyl alcohol and palmitoyl myristate in a mass ratio of (6-9): (4-5): (0.5-2).
The spermacetene in the wetting agent system adopted by the invention contains one carbon-carbon double bond, so that the distribution uniformity degree of the modified cashew seed oil in the polystyrene can be effectively enhanced, and the destructive phenomena such as cracking and the like of the modified polystyrene possibly occurring under long-time service are avoided; and pi bonds in spermaceti may enhance the capture of free radicals by the 3-maleimidobenzoate.
The stabilizer is dioctadecyl pentaerythritol diphosphite and/or 4,4' -butylene-bis- (3-methyl-6-tertiary butylbenzene) -tetra (tridecyl) diphosphite. In a preferred embodiment, the stabilizer is a mixture of dioctadecyl pentaerythritol diphosphite, 4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite in a mass ratio of (1-5): 2-7.
The preparation method of the modified cashew seed oil comprises the following steps:
p1, mixing and stirring a inositol phosphate, polyethylene glycol and sodium lactate aqueous solution to obtain emulsion A;
p2, mixing the emulsion A with a synergistic agent, and homogenizing to obtain modified emulsion;
and P3, mixing and stirring the modified emulsion, the cashew seed oil and the tourmaline, and filtering to obtain the modified cashew seed oil.
The phosphorus element in the inositol phosphate has a charge attraction effect on alginic acid, polysaccharide such as algal polysaccharide and fucoidan in the undaria pinnatifida extract, can enhance the compatibility between the modified cashew seed oil and the polystyrene matrix, and avoids the occurrence of brittle failure and damage of the polystyrene possibly occurring after long-time service; and the polyethylene glycol treated by sodium lactate has a more complex chain structure, and can cooperate with the inositol phosphate to enhance the toughness improvement effect of the modified cashew seed oil on polystyrene.
According to the invention, the negative ions released by tourmaline are utilized to promote the grafting and crosslinking reaction between the modified milk and the cashew seed oil to a sufficient degree, so that the modified cashew seed oil with better quality is obtained.
In a preferred scheme, the preparation method of the modified cashew seed oil comprises the following steps:
p1, mixing cyclohexane hexaol phosphate, polyethylene glycol and 8-12wt.% sodium lactate aqueous solution in a mass ratio of (11-14): 8-10): 19-23, and stirring at 75-82 ℃ for 70-90min at 600-700rpm to obtain emulsion A;
p2, mixing the emulsion A and the synergist according to the mass ratio of 6 (0.7-1.3), and homogenizing at the temperature of 50-55 ℃ at the rotating speed of 12000-14000rpm for 4-6min to obtain modified emulsion;
and P3, mixing the modified emulsion, cashew seed oil and tourmaline according to the mass ratio of (0.8-1.2) (7-9) (0.1-0.3), stirring at the temperature of 63-67 ℃ at the rotating speed of 400-500rpm for 420-530min, and filtering to obtain the modified cashew seed oil.
The synergistic agent is Undaria pinnatifida extract and/or C12-14 secondary alkanol polyether-8. More preferably, the synergist is a mixture of undaria pinnatifida extract and C12-14 secondary alkanol polyether-8 in the mass ratio of (1-3). In a more preferred embodiment, the synergistic agent is a mixture of undaria pinnatifida extract and C12-14 secondary alkanol polyether-8 in a mass ratio of 2:1.
The undaria pinnatifida is rich in polysaccharide such as alginic acid, algin and the like and fucoidan, is environment-friendly, safe and nontoxic, can improve the mechanical strength and toughness of materials when being applied to the food packaging industry, and has the advantages of wide sources, low cost, high safety and strong reliability; the extraction capacity of the carbon dioxide supercritical extraction technology for the effective substances is obviously superior to that of the traditional extraction means including ethanol extraction. Therefore, the extract obtained by supercritical carbon dioxide extraction of undaria pinnatifida is added into the modification process of cashew nut seed oil, so that the modified cashew nut seed oil which is higher in service reliability and capable of remarkably improving the mechanical strength of the polystyrene is obtained.
The compatibility of the nonpolar group in the C12-14 secondary alkanol polyether-8 to the polystyrene matrix ensures that the mechanical strength of the modified polystyrene can be further enhanced when the undaria pinnatifida extract prepared by the specific method is compounded and used; and also improves the resistance of the polystyrene to photoaging, unexpected technical effects are obtained, presumably related to the polyether structure in C12-14 secondary alkanol polyether-8 and the ratio of molecular polar surface areas of L-fucoidan-4-sulfate and the like in Undaria pinnatifida extract.
The preparation method of the undaria pinnatifida extract comprises the following steps:
r1 soaking undaria pinnatifida in a sodium citrate aqueous solution, and adopting ultrasonic auxiliary treatment;
r2 freezing the undaria pinnatifida subjected to R1 treatment, then crushing and sieving to obtain undaria pinnatifida powder;
r3, carrying out carbon dioxide critical extraction treatment on the undaria pinnatifida powder to obtain the undaria pinnatifida extract.
In a preferred embodiment, the preparation method of the undaria pinnatifida extract comprises the following steps:
r1 is prepared by soaking undaria pinnatifida in sodium citrate water solution with the temperature of 30-40 ℃ and the concentration of 22-25wt.% for 20-40min, and adopting ultrasonic auxiliary treatment with the power of 330-350W and the frequency of 35-37.5 kHz; the bath ratio of the undaria pinnatifida to the sodium citrate aqueous solution is 1kg (4-4.6) L;
r2 freezing the undaria pinnatifida subjected to R1 at (-45) - (-40) deg.C for 5-7h, pulverizing, and sieving with 100-120 mesh sieve to obtain undaria pinnatifida powder;
r3, carrying out carbon dioxide critical extraction treatment on the undaria pinnatifida powder to obtain an undaria pinnatifida extract; the technological parameters of the critical extraction of carbon dioxide are that the extraction pressure is 25-27MPa, the extraction temperature is 49-51 ℃, the analysis pressure is 3.5-4MPa, the analysis temperature is 8-12 ℃, the flow of carbon dioxide is 4-5L/h, and the extraction time is 3-4.5h.
The invention has the beneficial effects that:
1. the sanitary, safe and environment-friendly food packaging box comprises an inner box and an outer box; the sanitary, safe and environment-friendly food packaging box has the advantages of high strength, good toughness and light aging resistance.
2. The invention provides a modified polystyrene and a preparation method thereof, which take polystyrene, a wetting agent, 3-maleimide succinimide benzoate, a stabilizing agent and modified cashew seed oil and the like prepared by the specific method of the invention as raw materials to obtain the modified polystyrene with higher strength, better toughness and aging resistance, and the modified polystyrene can be used for the sanitary, safe and environment-friendly food packaging box and the production method thereof, thereby obtaining the sanitary, safe and environment-friendly food packaging box with better quality.
3. The invention provides modified cashew seed oil and a preparation method thereof, which are characterized in that the cashew seed oil is modified by taking substances such as inositol phosphate, polyethylene glycol and undaria pinnatifida extract prepared by the specific method of the invention as raw materials, so as to obtain the modified cashew seed oil capable of effectively improving the mechanical property and the ageing resistance of modified polystyrene.
4. The undaria pinnatifida extract is obtained by means of supercritical carbon dioxide extraction, and is used for preparing the modified cashew nut seed oil, so that the sanitary, safe and environment-friendly food packaging box with stronger mechanical properties and aging resistance is finally obtained.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some of the raw materials in this application:
polystyrene, CAS:9003-53-6, molecular weight purchased from Shanghai Mierer chemical technologies Co., ltd: 26 ten thousand.
3-Maleimidobenzoic acid succinimidyl ester, CAS:58626-38-3, purchased from Anhui Zealand technologies, inc., numbered: s0398, brand: TCL.
Ethyl caproate, CAS:110-38-3, purchased from western asia chemical technology (shandong) limited, cat No.: a18929-500ml.
Spermacetene, CAS:629-73-2, purchased from Anhui zel technologies, inc., numbered: l02637, brand: alfa Aesar.
Myristic acid palmitol ester, CAS:2599-01-1, purchased from Tianjin Sima technology Co.
Cashew seed oil, CAS:8007-24-7, purchased from Nanjing Huaxi chemical Co., ltd.
Dioctadecyl pentaerythritol bisphosphite, CAS:3806-34-6, purchased from the wuhan Hua Xiangke biotechnology company, content: 99.7%.
4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite, CAS:13003-12-8, purchased from Hubei Xinkang pharmaceutical chemical Co., ltd.
Inositol phosphate, CAS:83-86-3, purchased from Anhui Zerewrites Co., ltd., product number: A0114121000.
polyethylene glycol, CAS:25322-68-3, molecular weight, purchased from Shanghai Michelson chemical Co., ltd.): 8000, cargo number: M12024-250G.
Tourmaline, CAS:12197-81-8, obtained from Shijia Xinsheng mineral products Co., ltd., particle size: 40mm, meets the regulation of JC/T2012-2010 tourmaline powder.
C12-14 Secondary Alkanol polyether-8, CAS:84133-50-6, obtained from Wuhan-Han-Kung Bai pharmaceutical chemical Co., ltd., density (20 ℃ C.): 1.04g/mL, purity: 99%.
Castor oil, CAS:8001-79-4, purchased from Anhui zel technologies, inc., numbered: l04224, brand: alfa Aesar.
Example 1
A sanitary, safe and environment-friendly food packaging box comprises an inner box and an outer box; the upper surface of the outer box has the size of 17cm, and the bottom has the size of 10cm; the height was 7cm. The upper surface of the inner box has the size of 15cm x 15cm, and the bottom has the size of 9cm x 9cm; the height is 5cm.
The material of the outer box is antibacterial PP.
The inner box is made of modified polystyrene.
The preparation method of the modified polystyrene comprises the following steps:
f1, mixing 75 parts by weight of polystyrene, 6 parts by weight of modified cashew seed oil, 3 parts by weight of a wetting agent, 4 parts by weight of 3-maleimidobenzoic acid succinimidyl ester and 5 parts by weight of a stabilizer, and stirring at 40 ℃ for 15min at a rotating speed of 600rpm to obtain a mixture;
f2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene; the temperature of a machine head in the double-screw extruder is 215 ℃, and the rotating speed of a screw is 350rpm; the size specification of the pellets was 1mm×1mm.
The wetting agent is a mixture of ethyl caproate, spermacetene and palmitoyl myristate in a mass ratio of 7:5:2.
The stabilizer is a mixture of distearyl pentaerythritol diphosphite and 4,4' -butylidenebis- (3-methyl-6-tertiary butylbenzene group) -tetra (tridecyl) diphosphite with the mass ratio of 1:4.
The preparation method of the modified cashew seed oil comprises the following steps:
p1, mixing cyclohexane phosphate, polyethylene glycol and 11wt.% sodium lactate aqueous solution at a mass ratio of 13:9:20, and stirring at 80 ℃ for 80min at a rotation speed of 700rpm to obtain emulsion A;
p2, mixing the emulsion A and the synergist according to a mass ratio of 6:1.3, and homogenizing at a speed of 14000rpm for 5min at 50 ℃ to obtain modified emulsion;
p3, mixing the modified emulsion, cashew seed oil and tourmaline according to the mass ratio of 1:8:0.3, stirring at 65 ℃ for 480 minutes at the rotating speed of 500rpm, and filtering to obtain the modified cashew seed oil.
The synergistic agent is a mixture of undaria pinnatifida extract and C12-14 secondary alkanol polyether-8 in a mass ratio of 2:1.
The preparation method of the undaria pinnatifida extract comprises the following steps:
r1 is prepared by soaking undaria pinnatifida in sodium citrate aqueous solution with the temperature of 40 ℃ and the concentration of 25wt.% for 20min, and adopting ultrasonic auxiliary treatment with the power of 330W and the frequency of 35 kHz; the bath ratio of the undaria pinnatifida to the sodium citrate aqueous solution is 1kg:4.2L;
r2 freezing the undaria pinnatifida treated by R1 at-45 ℃ for 5 hours, then crushing, and sieving with a 120-mesh sieve to obtain undaria pinnatifida powder;
r3, carrying out carbon dioxide critical extraction treatment on the undaria pinnatifida powder to obtain an undaria pinnatifida extract; the technological parameters of the carbon dioxide critical extraction are that the extraction pressure is 26MPa, the extraction temperature is 51 ℃, the analysis pressure is 4MPa, the analysis temperature is 12 ℃, the flow of carbon dioxide is 4.3L/h, and the extraction time is 3h.
Example 2
Substantially the same as in example 1, the only difference is that: the synergistic agent is undaria pinnatifida extract.
Example 3
Substantially the same as in example 1, the only difference is that: the synergist is C12-14 secondary alkanol polyether-8.
Example 4
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified cashew seed oil comprises the following steps:
p1, mixing cyclohexane phosphate, polyethylene glycol and 11wt.% sodium lactate aqueous solution at a mass ratio of 13:9:20, and stirring at 80 ℃ for 80min at a rotation speed of 700rpm to obtain emulsion A;
p2, homogenizing the emulsion A at 50 ℃ at 14000rpm for 5min to obtain modified emulsion;
p3, mixing the modified emulsion, cashew seed oil and tourmaline according to the mass ratio of 1:8:0.3, stirring at 65 ℃ for 480 minutes at the rotating speed of 500rpm, and filtering to obtain the modified cashew seed oil.
Example 5
Substantially the same as in example 2, the only difference is that:
the preparation method of the undaria pinnatifida extract comprises the following steps:
r1 is prepared by soaking undaria pinnatifida in sodium citrate aqueous solution with the temperature of 40 ℃ and the concentration of 25wt.% for 20min, and adopting ultrasonic auxiliary treatment with the power of 330W and the frequency of 35 kHz; the bath ratio of the undaria pinnatifida to the sodium citrate aqueous solution is 1kg:4.2L;
r2 freezing the undaria pinnatifida treated by R1 at-45 ℃ for 5 hours, then crushing, and sieving with a 120-mesh sieve to obtain undaria pinnatifida powder;
r3, performing ethanol extraction treatment on the undaria pinnatifida powder to obtain the undaria pinnatifida extract.
The ethanol extraction steps are as follows:
h1 mixing the undaria pinnatifida powder and absolute ethyl alcohol according to a mass ratio of 1:4, and then performing ultrasonic treatment at 51 ℃ with power of 300W and frequency of 36kHz for 3 hours to obtain an alcohol extract;
evaporating the ethanol extract for 15H at 80deg.C under vacuum degree of-0.1 MPa to obtain Undaria pinnatifida extract.
Example 6
Substantially the same as in example 1, the only difference is that: a 'V' -shaped structure
The preparation method of the modified cashew seed oil comprises the following steps:
p1, mixing polyethylene glycol and 11wt.% sodium lactate aqueous solution according to a mass ratio of 9:20, and stirring at 80 ℃ for 80min at a rotating speed of 700rpm to obtain emulsion A;
p2, mixing the emulsion A and the synergist according to a mass ratio of 6:1.3, and homogenizing at a speed of 14000rpm for 5min at 50 ℃ to obtain modified emulsion;
p3, mixing the modified emulsion, cashew seed oil and tourmaline according to the mass ratio of 1:8:0.3, stirring at 65 ℃ for 480 minutes at the rotating speed of 500rpm, and filtering to obtain the modified cashew seed oil.
The synergistic agent is a mixture of undaria pinnatifida extract and C12-14 secondary alkanol polyether-8 in a mass ratio of 2:1.
The preparation method of the undaria pinnatifida extract comprises the following steps:
r1 is prepared by soaking undaria pinnatifida in sodium citrate aqueous solution with the temperature of 40 ℃ and the concentration of 25wt.% for 20min, and adopting ultrasonic auxiliary treatment with the power of 330W and the frequency of 35 kHz; the bath ratio of the undaria pinnatifida to the sodium citrate aqueous solution is 1kg:4.2L;
r2 freezing the undaria pinnatifida treated by R1 at-45 ℃ for 5 hours, then crushing, and sieving with a 120-mesh sieve to obtain undaria pinnatifida powder;
r3, carrying out carbon dioxide critical extraction treatment on the undaria pinnatifida powder to obtain an undaria pinnatifida extract; the technological parameters of the carbon dioxide critical extraction are that the extraction pressure is 26MPa, the extraction temperature is 51 ℃, the analysis pressure is 4MPa, the analysis temperature is 12 ℃, the flow of carbon dioxide is 4.3L/h, and the extraction time is 3h.
Example 7
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified cashew seed oil comprises the following steps:
p1, mixing cyclohexane phosphate, polyethylene glycol and 11wt.% sodium lactate aqueous solution at a mass ratio of 13:9:20, and stirring at 80 ℃ for 80min at a rotation speed of 700rpm to obtain emulsion A;
p2, mixing the emulsion A and the synergist according to a mass ratio of 6:1.3, and homogenizing at a speed of 14000rpm for 5min at 50 ℃ to obtain modified emulsion;
and P3, mixing the modified emulsion and cashew seed oil according to a mass ratio of 1:8, and stirring at 65 ℃ for 480 minutes at a rotating speed of 500rpm to obtain the modified cashew seed oil.
The synergistic agent is a mixture of undaria pinnatifida extract and C12-14 secondary alkanol polyether-8 in a mass ratio of 2:1.
The preparation method of the undaria pinnatifida extract comprises the following steps:
r1 is prepared by soaking undaria pinnatifida in sodium citrate aqueous solution with the temperature of 40 ℃ and the concentration of 25wt.% for 20min, and adopting ultrasonic auxiliary treatment with the power of 330W and the frequency of 35 kHz; the bath ratio of the undaria pinnatifida to the sodium citrate aqueous solution is 1kg:4.2L;
r2 freezing the undaria pinnatifida treated by R1 at-45 ℃ for 5 hours, then crushing, and sieving with a 120-mesh sieve to obtain undaria pinnatifida powder;
r3, carrying out carbon dioxide critical extraction treatment on the undaria pinnatifida powder to obtain an undaria pinnatifida extract; the technological parameters of the carbon dioxide critical extraction are that the extraction pressure is 26MPa, the extraction temperature is 51 ℃, the analysis pressure is 4MPa, the analysis temperature is 12 ℃, the flow of carbon dioxide is 4.3L/h, and the extraction time is 3h.
Example 8
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified polystyrene comprises the following steps:
f1, mixing 75 parts by weight of polystyrene, 6 parts by weight of cashew seed oil, 3 parts by weight of a wetting agent, 4 parts by weight of 3-maleimidobenzoic acid succinimidyl ester and 5 parts by weight of a stabilizer, and stirring at 40 ℃ for 15min at a rotating speed of 600rpm to obtain a mixture;
f2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene; the temperature of a machine head in the double-screw extruder is 215 ℃, and the rotating speed of a screw is 350rpm; the size specification of the pellets was 1mm×1mm.
Example 9
Substantially the same as in example 8, the only difference is that:
the preparation method of the modified polystyrene comprises the following steps:
f1, 75 parts by weight of polystyrene, 6 parts by weight of castor oil, 3 parts by weight of a wetting agent, 4 parts by weight of 3-maleimide-based succinimide benzoate and 5 parts by weight of a stabilizer are mixed, and then stirred at 40 ℃ for 15 minutes at 600rpm to obtain a mixture;
f2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene; the temperature of a machine head in the double-screw extruder is 215 ℃, and the rotating speed of a screw is 350rpm; the size specification of the pellets was 1mm×1mm.
Example 10
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified polystyrene comprises the following steps:
f1, mixing 75 parts by weight of polystyrene, 6 parts by weight of modified cashew seed oil, 3 parts by weight of wetting agent and 5 parts by weight of stabilizer, and stirring at 40 ℃ for 15min at 600rpm to obtain a mixture;
f2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene; the temperature of a machine head in the double-screw extruder is 215 ℃, and the rotating speed of a screw is 350rpm; the size specification of the pellets was 1mm×1mm.
The wetting agent is a mixture of ethyl caproate, spermacetene and palmitoyl myristate in a mass ratio of 7:5:2.
The stabilizer is a mixture of distearyl pentaerythritol diphosphite and 4,4' -butylidenebis- (3-methyl-6-tertiary butylbenzene group) -tetra (tridecyl) diphosphite with the mass ratio of 1:4.
The preparation method of the modified cashew seed oil comprises the following steps:
p1, mixing cyclohexane phosphate, polyethylene glycol and 11wt.% sodium lactate aqueous solution at a mass ratio of 13:9:20, and stirring at 80 ℃ for 80min at a rotation speed of 700rpm to obtain emulsion A;
p2, mixing the emulsion A and the synergist according to a mass ratio of 6:1.3, and homogenizing at a speed of 14000rpm for 5min at 50 ℃ to obtain modified emulsion;
p3, mixing the modified emulsion, cashew seed oil and tourmaline according to the mass ratio of 1:8:0.3, stirring at 65 ℃ for 480 minutes at the rotating speed of 500rpm, and filtering to obtain the modified cashew seed oil.
The synergistic agent is a mixture of undaria pinnatifida extract and C12-14 secondary alkanol polyether-8 in a mass ratio of 2:1.
The preparation method of the undaria pinnatifida extract comprises the following steps:
r1 is prepared by soaking undaria pinnatifida in sodium citrate aqueous solution with the temperature of 40 ℃ and the concentration of 25wt.% for 20min, and adopting ultrasonic auxiliary treatment with the power of 330W and the frequency of 35 kHz; the bath ratio of the undaria pinnatifida to the sodium citrate aqueous solution is 1kg:4.2L;
r2 freezing the undaria pinnatifida treated by R1 at-45 ℃ for 5 hours, then crushing, and sieving with a 120-mesh sieve to obtain undaria pinnatifida powder;
r3, carrying out carbon dioxide critical extraction treatment on the undaria pinnatifida powder to obtain an undaria pinnatifida extract; the technological parameters of the carbon dioxide critical extraction are that the extraction pressure is 26MPa, the extraction temperature is 51 ℃, the analysis pressure is 4MPa, the analysis temperature is 12 ℃, the flow of carbon dioxide is 4.3L/h, and the extraction time is 3h.
Example 11
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified polystyrene comprises the following steps:
f1, mixing 75 parts by weight of polystyrene, 6 parts by weight of modified cashew seed oil, 3 parts by weight of a wetting agent, 4 parts by weight of 3-maleimidobenzoic acid succinimidyl ester and 5 parts by weight of a stabilizer, and stirring at 40 ℃ for 15min at a rotating speed of 600rpm to obtain a mixture;
f2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene; the temperature of a machine head in the double-screw extruder is 215 ℃, and the rotating speed of a screw is 350rpm; the size specification of the pellets was 1mm×1mm.
The wetting agent is a mixture of ethyl caproate and palmitoyl myristate in a mass ratio of 7:2.
The stabilizer is a mixture of distearyl pentaerythritol diphosphite and 4,4' -butylidenebis- (3-methyl-6-tertiary butylbenzene group) -tetra (tridecyl) diphosphite with the mass ratio of 1:4.
The preparation method of the modified cashew seed oil comprises the following steps:
p1, mixing cyclohexane phosphate, polyethylene glycol and 11wt.% sodium lactate aqueous solution at a mass ratio of 13:9:20, and stirring at 80 ℃ for 80min at a rotation speed of 700rpm to obtain emulsion A;
p2, mixing the emulsion A and the synergist according to a mass ratio of 6:1.3, and homogenizing at a speed of 14000rpm for 5min at 50 ℃ to obtain modified emulsion;
p3, mixing the modified emulsion, cashew seed oil and tourmaline according to the mass ratio of 1:8:0.3, stirring at 65 ℃ for 480 minutes at the rotating speed of 500rpm, and filtering to obtain the modified cashew seed oil.
The synergistic agent is a mixture of undaria pinnatifida extract and C12-14 secondary alkanol polyether-8 in a mass ratio of 2:1.
The preparation method of the undaria pinnatifida extract comprises the following steps:
r1 is prepared by soaking undaria pinnatifida in sodium citrate aqueous solution with the temperature of 40 ℃ and the concentration of 25wt.% for 20min, and adopting ultrasonic auxiliary treatment with the power of 330W and the frequency of 35 kHz; the bath ratio of the undaria pinnatifida to the sodium citrate aqueous solution is 1kg:4.2L;
r2 freezing the undaria pinnatifida treated by R1 at-45 ℃ for 5 hours, then crushing, and sieving with a 120-mesh sieve to obtain undaria pinnatifida powder;
r3, carrying out carbon dioxide critical extraction treatment on the undaria pinnatifida powder to obtain an undaria pinnatifida extract; the technological parameters of the carbon dioxide critical extraction are that the extraction pressure is 26MPa, the extraction temperature is 51 ℃, the analysis pressure is 4MPa, the analysis temperature is 12 ℃, the flow of carbon dioxide is 4.3L/h, and the extraction time is 3h.
Example 12
A sanitary, safe and environment-friendly food packaging box comprises an inner box and an outer box; the upper surface of the outer box has the size of 17cm, and the bottom has the size of 10cm; the height was 7cm. The upper surface of the inner box has the size of 15cm x 15cm, and the bottom has the size of 9cm x 9cm; the height is 5cm.
The material of the outer box is antibacterial PP.
The inner box is made of commercially available polystyrene.
Test example 1
Impact strength test: the impact strength of the modified polystyrene obtained in each embodiment of the invention was tested according to GB/T21189-2007 test of a pendulum impact tester for Plastic simple beams, cantilever beams and tensile impact test. The modified polystyrene and the commercially available polystyrene obtained in each example were prepared into a long sample having a specification of 60mm×10mm×3mm, respectively; and adopting a simple beam impact tester to perform impact test. The impact energy is calculated according to the falling height of the impact head when the sample breaks, and the unit is kJ/m 2 . Test environmentThe temperature of (2) was 23℃and the relative humidity was 65%. Each example was subjected to 5 parallel experiments, and the results of the experiments were averaged.
The test results are shown in Table 1.
TABLE 1 impact Strength of modified polystyrene
Test example 2
Tensile strength test: determination of tensile Properties of plastics according to GB/T1040.3-2006 section 3: test conditions for films and sheets the tensile strength of the modified polystyrene obtained in each example of the present invention was tested. The test temperature was 23℃and the humidity was 65%. A type 2 sample is adopted, the width of the sample is 10mm, the thickness of the sample is 0.8mm, the gauge length is 50mm, and the idle speed of the test is 500mm/min. Each example was subjected to 5 parallel experiments, and the results of the experiments were averaged.
The test results are shown in Table 2.
TABLE 2 tensile Strength of modified polystyrene
Test example 3
Photo aging resistance test: according to GB/T16422.3-2014, section 3 of the Plastic laboratory light Source Exposure test method: method A in fluorescent ultraviolet lamp was used to test the tensile strength of the modified polystyrene obtained in each example of the present invention. A type 1A (UVA-340) fluorescent ultraviolet lamp is adopted; the test conditions were a temperature of 25℃and a relative humidity of 70%. The yellowing index DeltaYI of the above-mentioned sample treated with a fluorescent ultraviolet lamp was measured according to HG/T3862-2006 test method for Plastic yellow index. Each example was subjected to 6 parallel experiments and the results averaged.
The test results are shown in Table 3.
TABLE 3 yellowing index of modified polystyrene
Cashew nut seed oil is widely applied to the fields of motor vehicles, machine tools, ships, wood furniture, home decoration, rubber, PVC, metal and plastic products, chemical equipment, various anti-corrosion paints, coatings and the like; the cashew nut seed oil modified resin material has the advantages of high impact strength, stable friction coefficient, good recovery, low cost and the like. However, if the cashew seed oil is directly applied to polystyrene, the final product is softened, cracked and other adverse phenomena occur under the long-time service state, so in the technical scheme of the invention, the raw materials such as the inositol phosphate, the polyethylene glycol and the like, namely the multi-cashew seed oil, are used for preparing the modified polystyrene after being modified, and then are used for preparing the sanitary, safe and environment-friendly food packaging box. The undaria pinnatifida is rich in polysaccharide such as alginic acid, algin and the like and fucoidan, is environment-friendly, safe and nontoxic, and has the advantages of wide sources, low cost, high safety and strong reliability when being applied to the food packaging industry; the extraction capacity of the carbon dioxide supercritical extraction technology for the effective substances is obviously superior to that of the traditional extraction means including ethanol extraction. Therefore, the extract obtained by supercritical carbon dioxide extraction of undaria pinnatifida is added into the modification process of cashew nut seed oil, so that the modified cashew nut seed oil which is higher in service reliability and capable of remarkably improving the mechanical strength of the polystyrene is obtained. The phosphorus element in the inositol phosphate has a charge attraction effect on alginic acid, polysaccharide such as algal polysaccharide and fucoidan in the undaria pinnatifida extract, can enhance the compatibility between the modified cashew seed oil and the polystyrene matrix, and avoids the occurrence of brittle failure and damage of the polystyrene possibly occurring after long-time service; and the polyethylene glycol treated by sodium lactate has a more complex chain structure, and can cooperate with the inositol phosphate to enhance the toughness improvement effect of the modified cashew seed oil on polystyrene. The compatibility of the nonpolar group in the C12-14 secondary alkanol polyether-8 to the polystyrene matrix ensures that the mechanical strength of the modified polystyrene can be further enhanced when the undaria pinnatifida extract prepared by the specific method is compounded and used; and also improves the resistance of the polystyrene to photo aging, unexpected technical effects are obtained, which are presumably related to the polyether structure in C12-14 secondary alkanol polyether-8 and L-fucoidan-4-sulfate in Undaria pinnatifida extract. According to the invention, the negative ions released by tourmaline are utilized to promote the grafting and crosslinking reaction between the modified milk and the cashew seed oil to a sufficient degree, so that the modified cashew seed oil with better quality is obtained. The special relative alignment of two nitrogen-containing five-membered heterocyclic rings and aldehyde groups in the 3-maleimide succinimidyl benzoate can enhance the toughness of the modified polystyrene when the modified polystyrene is used in the modification process of the polystyrene, thereby enhancing the macroscopic mechanical strength of the modified polystyrene; and, 3-maleimidobenzoic acid succinimidyl ester can synergistically enhance the photo-aging resistance of the modified polystyrene with undaria pinnatifida extract and C12-14 secondary alkanol polyether-8, which is presumably related to their electron cloud energy distribution, and can effectively eliminate free radicals generated by illumination. The spermacetene in the wetting agent system adopted by the invention contains one carbon-carbon double bond, so that the distribution uniformity degree of the modified cashew seed oil in the polystyrene can be effectively enhanced, and the destructive phenomena such as cracking and the like of the modified polystyrene possibly occurring under long-time service are avoided; and pi bonds in spermaceti may enhance the capture of free radicals by the 3-maleimidobenzoate.
Claims (8)
1. The preparation method of the modified cashew seed oil is characterized by comprising the following steps of:
p1, mixing and stirring cyclohexane hexaol phosphate, polyethylene glycol and 8-12wt.% sodium lactate aqueous solution according to the mass ratio of (11-14): (8-10): (19-23) to obtain emulsion A;
p2, mixing the emulsion A with a synergist according to a mass ratio of 6 (0.7-1.3), and homogenizing to obtain a modified emulsion;
p3, mixing the modified emulsion, cashew seed oil and tourmaline according to the mass ratio of (0.8-1.2) (7-9) (0.1-0.3), stirring, and filtering to obtain the modified cashew seed oil;
the synergistic agent is undaria pinnatifida extract and/or C12-14 secondary alkanol polyether-8;
the preparation method of the undaria pinnatifida extract comprises the following steps:
r1, soaking undaria pinnatifida in a sodium citrate aqueous solution and adopting ultrasonic auxiliary treatment; the bath ratio of the undaria pinnatifida to the sodium citrate aqueous solution is 1kg (4-4.6) L;
r2, freezing the undaria pinnatifida subjected to R1, crushing, and sieving to obtain undaria pinnatifida powder;
r3, carrying out carbon dioxide critical extraction treatment on the undaria pinnatifida powder to obtain the undaria pinnatifida extract.
2. The modified cashew seed oil is characterized in that: the modified cashew seed oil is obtained by adopting the preparation method of the modified cashew seed oil in claim 1.
3. The preparation method of the modified polystyrene is characterized by comprising the following steps of:
f1, mixing 72-78 parts by weight of polystyrene, 5-7 parts by weight of the modified cashew nut seed oil of claim 2, 3-4 parts by weight of a wetting agent, 2-5 parts by weight of 3-maleimidobenzoic acid succinimidyl ester and 4-5 parts by weight of a stabilizer, and stirring to obtain a mixture;
and F2, putting the mixture into a double-screw extruder, carrying out melt extrusion through the extruder, and cooling and granulating to obtain the modified polystyrene.
4. A process for preparing a modified polystyrene as defined in claim 3, wherein: the wetting agent is at least one of ethyl caproate, spermacetene and palmitoyl myristate.
5. A process for preparing a modified polystyrene as defined in claim 3, wherein: the stabilizer is dioctadecyl pentaerythritol diphosphite and/or 4,4' -butylene-bis- (3-methyl-6-tertiary butylbenzene) -tetra (tridecyl) diphosphite.
6. A modified polystyrene, characterized in that: obtained by the process for producing a modified polystyrene according to any one of claims 3 to 5.
7. The production method of the sanitary, safe and environment-friendly food packaging box is characterized by comprising the following steps of: the antibacterial PP is prepared into an outer box according to a conventional food packaging box production process, the modified polystyrene according to claim 6 is prepared into an inner box according to a conventional food packaging box production process, and the inner box is placed in the outer box, so that the sanitary, safe and environment-friendly food packaging box is obtained.
8. Sanitary, safe and environment-friendly food packaging box is characterized in that: is obtained by the production method of the sanitary, safe and environment-friendly food packaging box of claim 7.
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