An impact-resistant, crashworthy plastic container for chemical packaging and a method of making the same
By adding impact-resistant reinforcing agents and repair capsules to HDPE containers, the problem of poor impact resistance of HDPE containers has been solved, improving the impact resistance and safety of the containers and extending their service life.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HEQI (YIXING) PACKAGING MATERIALS CO LTD
- Filing Date
- 2026-04-17
- Publication Date
- 2026-06-05
Smart Images
Figure CN122145913A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of plastic containers, specifically to an impact-resistant and shockproof plastic container for chemical packaging and its preparation method. Background Technology
[0002] Chemical packaging containers, especially those used to hold corrosive, toxic, or flammable chemicals, have extremely high safety requirements. High-density polyethylene (HDPE) has become the mainstream material for such containers due to its excellent chemical resistance, processing performance, and cost advantages. However, pure HDPE containers have poor impact resistance, especially in terms of drop and impact resistance, which needs improvement. During transportation, storage, or use, they are prone to breakage due to accidental drops or collisions, posing a significant risk of chemical leakage and safety hazards.
[0003] Therefore, developing an impact-resistant and shockproof plastic container for chemical packaging and its preparation method has significant practical value. Summary of the Invention
[0004] In order to overcome the above-mentioned technical problems, the purpose of this invention is to provide an impact-resistant and anti-collision plastic container for chemical packaging and its preparation method, which solves the problem that the existing pure HDPE containers have poor impact resistance and are prone to breakage due to accidental drops or collisions, posing safety hazards.
[0005] The objective of this invention can be achieved through the following technical solutions:
[0006] In a first aspect, this application provides an impact-resistant and shockproof plastic container for chemical packaging, comprising the following components in parts by weight:
[0007] 80-90 parts high-density polyethylene resin, 1-6 parts ethylene-octene copolymer, 8-10 parts nano silica, 3-5 parts stearic acid, 1-3 parts antioxidant, 1-2 parts ultraviolet absorber, 0.5-8.5 parts impact enhancer, 1-5 parts repair capsule A component and 1-5 parts repair capsule B component;
[0008] The impact-resistant reinforcing agent is prepared by the following steps:
[0009] Step a1: Dimethyl 5-bromoisophthalate, 3,5-bis(methoxycarbonyl)phenylboronic acid pinacol ester, potassium carbonate solution, tetra(triphenylphosphine)palladium, anhydrous ethanol, and toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the reaction was stirred at 20-25℃ and a stirring rate of 300-400 r / min for 20-30 min. Then, the temperature was raised to 90-100℃ and the reaction was continued for 20-25 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a mixed solvent. After standing and separating the layers, the organic phase was dried with anhydrous sodium sulfate, then vacuum filtered, and the solvent was removed by rotary evaporation of the filtrate. Then, the filtrate was purified by silica gel column chromatography with eluent to obtain the polyester compound.
[0010] Step a2: Add the polyester compound, potassium hydroxide solution, tetrahydrofuran, and methanol to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 20-25℃ and a stirring rate of 300-400 r / min for 20-30 min. Then raise the temperature to 50-60℃ and continue stirring for 20-25 h. After the reaction is complete, cool the reaction product to room temperature, remove the solvent by rotary evaporation, add it to distilled water, and then filter under vacuum. Adjust the pH of the filtrate to 2-3 with hydrochloric acid solution, centrifuge, and place the precipitate in a vacuum drying oven at 40-50℃ for 3-4 h to obtain the polycarboxylic compound.
[0011] Step a3: Add the polycarboxylic acid compound, 12-hydroxystearic acid, half of the p-toluenesulfonic acid and toluene to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 20-25℃ and 300-400 r / min for 10-15 min. Then raise the temperature to 130-140℃ and continue stirring for 5-7 h. After that, add isooctanol and the remaining half of the p-toluenesulfonic acid and continue stirring for 4-5 h. After the reaction is completed, cool the reaction product to room temperature and wash it 2-3 times with sodium hydroxide solution, distilled water and saturated saline solution in sequence. Then dry with anhydrous sodium sulfate and filter under vacuum. Remove the solvent by rotary evaporation of the filtrate to obtain the impact-resistant reinforcing agent.
[0012] In a preferred embodiment of the present invention, the ratio of dimethyl 5-bromoisophthalate, 3,5-bis(methoxycarbonyl)phenylboronic acid pinacol ester, potassium carbonate solution, tetra(triphenylphosphine)palladium, anhydrous ethanol and toluene in step a1 is 10 mmol: 10 mmol: 10-15 mL: 0.6-0.8 g: 15-20 mL: 50-60 mL.
[0013] In a preferred embodiment of the present invention, the molar concentration of the potassium carbonate solution in step a1 is 2-3 mol / L; the mixed solvent is a mixture of dichloromethane and distilled water in a volume ratio of 1:2-3; and the eluent is a mixture of chloroform and methanol in a volume ratio of 20-25:1.
[0014] In a preferred embodiment of the present invention, the ratio of the polyester compound, potassium hydroxide solution, tetrahydrofuran and methanol in step a2 is 5 mmol: 10-15 mL: 10-15 mL: 40-50 mL.
[0015] In a preferred embodiment of the present invention, the molar concentration of the potassium hydroxide solution in step a2 is 5-6 mol / L; and the molar concentration of the hydrochloric acid solution is 1-1.5 mol / L.
[0016] In a preferred embodiment of the present invention, the ratio of the polycarboxylic acid compound, 12-hydroxystearic acid, p-toluenesulfonic acid, toluene and isooctyl alcohol in step a3 is 10 mmol: 40 mmol: 1-3 mmol: 80-90 mL: 40 mmol.
[0017] In a preferred embodiment of the present invention, the molar concentration of the sodium hydroxide solution in step a3 is 2-3 mol / L.
[0018] In a preferred embodiment of the present invention, the repair capsule component A is prepared by the following steps:
[0019] Ammonium chloride, sodium dodecylbenzenesulfonate, resorcinol, and deionized water were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred for 10-15 minutes at 20-25°C and a stirring rate of 300-400 r / min. The temperature was then raised to 40-50°C, and the stirring continued for 20-30 minutes. Then, diglycidyl 4,5-epoxytetrahydrophthalic acid was added, and the reaction was continued for 30-60 minutes to obtain a core material emulsion. The shell material solution was added to the core material emulsion, and the pH was adjusted to 3-4 with citric acid solution. The temperature was then raised to 60-70°C, and the reaction continued for 3-5 hours. After the reaction, the product was cooled to room temperature and then vacuum filtered. The filter cake was washed 2-3 times with distilled water and then placed in a vacuum drying oven at 40-50°C for 5-7 hours to obtain component A of the repair capsule.
[0020] In a preferred embodiment of the present invention, the ratio of the amount of ammonium chloride, sodium dodecylbenzenesulfonate, resorcinol, deionized water, diglycidyl 4,5-epoxytetrahydrophthalic acid and shell material solution is 1g:1g:1g:400mL:30-40mL:40-50mL.
[0021] In a preferred embodiment of the present invention, the shell material solution is prepared by mixing urea and formaldehyde solution at a mass ratio of 1:6-6.5, and then adjusting the pH to 8.5-9 with triethylamine; the mass fraction of the formaldehyde solution is 33-35%; and the mass fraction of the citric acid solution is 10-15%.
[0022] In a preferred embodiment of the present invention, the repair capsule component B is prepared by the following steps:
[0023] Ammonium chloride, sodium dodecylbenzenesulfonate, resorcinol, and deionized water were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred for 10-15 minutes at a temperature of 20-25℃ and a stirring rate of 300-400 r / min. The temperature was then raised to 40-50℃ and the stirring was continued for 10-20 minutes. The solidifying material was then added and the mixture was stirred for another 20-30 minutes to obtain a core material emulsion. The shell material solution was added to the core material emulsion, and the pH was adjusted to 3-4 with citric acid solution. The temperature was then raised to 60-70℃ and the stirring was continued for 3-5 hours. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed 2-3 times with distilled water and then placed in a vacuum drying oven and dried at 40-50℃ for 5-7 hours to obtain component B of the repair capsule.
[0024] In a preferred embodiment of the present invention, the ratio of the amount of ammonium chloride, sodium dodecylbenzenesulfonate, resorcinol, deionized water, curing substance and shell material solution is 1g:1g:1g:400mL:25-35g:40-50mL.
[0025] In a preferred embodiment of the present invention, the solidifying substance is a mixture of pentaerythritol tetrakis(3-mercaptopropionic acid) and N,N-dimethylbenzylamine in a mass ratio of 10-12:1; the shell material solution is prepared by mixing urea and formaldehyde solution in a mass ratio of 1:6-6.5, and then adjusting the pH to 8.5-9 with triethylamine; the mass fraction of the formaldehyde solution is 33-35%; and the mass fraction of the citric acid solution is 10-15%.
[0026] Secondly, this application provides a method for preparing an impact-resistant and shock-proof plastic container for chemical packaging, comprising the following steps:
[0027] Step 1: Weigh out 80-90 parts by weight of high-density polyethylene resin, 1-6 parts by weight of ethylene-octene copolymer, 8-10 parts by weight of nano-silica, 3-5 parts by weight of stearic acid, 1-3 parts by weight of antioxidant, 1-2 parts by weight of ultraviolet absorber, 0.5-8.5 parts by weight of impact enhancer, 1-5 parts by weight of repair capsule component A and 1-5 parts by weight of repair capsule component B, and set aside.
[0028] Step 2: Mix high-density polyethylene resin, ethylene-octene copolymer, nano silica, stearic acid, antioxidant, ultraviolet absorber, impact enhancer, repair capsule component A and repair capsule component B evenly, and then melt extrusion and blow molding to obtain impact-resistant and shockproof plastic containers for chemical packaging.
[0029] In a preferred embodiment of the present invention, the high-density polyethylene resin is HDPE M200056.
[0030] In a preferred embodiment of the present invention, the ethylene-octene copolymer is POE 8540.
[0031] In a preferred embodiment of the present invention, the average particle size of the nano-silica is 30 nm.
[0032] In a preferred embodiment of the present invention, the antioxidant is antioxidant 3114.
[0033] In a preferred embodiment of the present invention, the ultraviolet absorber is ultraviolet absorber UV-571.
[0034] The beneficial effects of this invention are:
[0035] This invention discloses an impact-resistant and shock-proof plastic container for chemical packaging and its preparation method. The method involves uniformly mixing high-density polyethylene resin, ethylene-octene copolymer, nano-silica, stearic acid, antioxidant, ultraviolet absorber, impact enhancer, repair capsule component A, and repair capsule component B, followed by melt extrusion and blow molding to obtain the impact-resistant and shock-proof plastic container for chemical packaging. The high-density polyethylene resin serves as the base material. Adding the impact enhancer strengthens the base material's toughness, allowing it to undergo plastic deformation under external impact, effectively absorbing impact energy and improving its impact resistance. Adding repair capsule components A and B imparts repair capabilities, enabling the repair of internal micro-cracks and further enhancing its impact resistance. The resulting plastic container exhibits excellent impact resistance and shock protection, improving safety during use, enhancing protection of the packaged contents, and extending the container's service life.
[0036] In the process of preparing plastic containers, an impact-resistant reinforcing agent was first prepared. This was achieved through the reaction of dimethyl 5-bromoisophthalate and 3,5-bis(methoxycarbonyl)phenylboronic acid phenanthol ester. The bromine atom on dimethyl 5-bromoisophthalate reacts with the borate phenanthol ester structure on 3,5-bis(methoxycarbonyl)phenylboronic acid phenanthol ester to form a polyester compound containing multiple ester groups. Subsequently, the ester groups on the polyester compound are hydrolyzed to form carboxyl groups, yielding a polycarboxyl compound. Then, the carboxyl groups on the polycarboxyl compound react with the hydroxyl groups on 12-hydroxystearic acid to introduce long carbon chains containing carboxyl groups. Finally, the carboxyl groups on this compound react with the hydroxyl groups on isooctanol to further introduce long carbon chains, resulting in the impact-resistant reinforcing agent. This impact-resistant reinforcing agent contains a large number of long carbon chains in its molecular structure. These long carbon chains possess excellent flexibility and, through intramolecular entanglement and physical cross-linking, can construct a stable flexible network, endowing it with excellent impact resistance and significantly improving the impact resistance and anti-collision effect of plastic containers.
[0037] In the process of preparing plastic containers, a repair capsule component A and a repair capsule component B were also prepared. Urea and formaldehyde were used as raw materials to form a urea-formaldehyde resin shell, and 4,5-epoxytetrahydrophthalic acid diglycidyl ester and a curing substance were used as the core materials to prepare repair capsule components A and B, respectively. These components were added to the substrate. When the substrate is subjected to impact and microcracks are generated, there are two large numbers of repair capsules at the microcrack locations. During the microcrack formation process, the repair capsules are torn open, and the two core materials in the repair capsules flow into the microcrack gaps through capillary action. Then, a curing reaction occurs, filling the cracks and thus significantly improving the impact resistance of the plastic container. Attached Figure Description
[0038] The invention will now be further described with reference to the accompanying drawings.
[0039] Figure 1 This is a schematic diagram showing the performance test results of the impact-resistant and collision-proof plastic container for chemical packaging in this invention. Detailed Implementation
[0040] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0041] Example 1:
[0042] This embodiment describes a method for preparing an impact-resistant and shock-proof plastic container for chemical packaging, comprising the following steps:
[0043] Step S1: 10 mmol of dimethyl 5-bromoisophthalate, 10 mmol of 3,5-bis(methoxycarbonyl)phenylboronic acid pinacol ester, 10 mL of potassium carbonate solution with a molar concentration of 2 mol / L, 0.6 g of tetra(triphenylphosphine)palladium, 15 mL of anhydrous ethanol, and 50 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 20 °C and a stirring rate of 300 r / min for 20 min. Then, the temperature was raised to 90 °C and the stirring was continued for 20 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a mixed solvent of dichloromethane and distilled water in a volume ratio of 1:2. After standing and separating the layers, the organic phase was dried with anhydrous sodium sulfate and then filtered under vacuum. The filtrate was evaporated by rotary evaporation to remove the solvent. Then, the filtrate was purified by silica gel column chromatography using a mixture of trichloromethane and methanol in a volume ratio of 20:1 to obtain the polyester compound.
[0044] Step S2: Add 5 mmol of the polyester compound, 10 mL of 5 mol / L potassium hydroxide solution, 10 mL of tetrahydrofuran, and 40 mL of methanol to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 20 °C and 300 r / min for 20 min. Then raise the temperature to 50 °C and continue stirring for 20 h. After the reaction is complete, cool the reaction product to room temperature, remove the solvent by rotary evaporation, add it to distilled water, and then filter under vacuum. Adjust the pH of the filtrate to 2 with 1 mol / L hydrochloric acid solution, centrifuge, and place the precipitate in a vacuum drying oven to dry at 40 °C for 3 h to obtain the polycarboxylic acid compound.
[0045] Step S3: 10 mmol of polycarboxylic acid compound, 40 mmol of 12-hydroxystearic acid, 0.5 mmol of p-toluenesulfonic acid and 80 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 20 °C and 300 r / min for 10 min. Then the temperature was raised to 130 °C and the mixture was stirred for 5 h. Then 40 mmol of isooctyl alcohol and 0.5 mmol of p-toluenesulfonic acid were added and the mixture was stirred for 4 h. After the reaction was completed, the reaction product was cooled to room temperature and then washed twice with sodium hydroxide solution with a molar concentration of 2 mol / L, distilled water and saturated saline solution, respectively. The product was then dried with anhydrous sodium sulfate and vacuum filtered. The filtrate was then evaporated by rotary evaporation to remove the solvent to obtain the impact-resistant reinforcing agent.
[0046] Step S4: Add 1g ammonium chloride, 1g sodium dodecylbenzenesulfonate, 1g resorcinol, and 400mL deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 20℃ and 300r / min for 10min. Then raise the temperature to 40℃ and continue stirring for 20min. Add 30mL of 4,5-epoxytetrahydrophthalic acid diglycidyl ester and continue stirring for 30min to obtain the core material emulsion. Add 40m... L-urea and 33% formaldehyde solution were mixed at a mass ratio of 1:6. The resulting shell material solution was then adjusted to pH 8.5 with triethylamine and added to the core material emulsion. The pH was then adjusted to 3 with 10% citric acid solution. The mixture was then heated to 60°C and stirred for 3 hours. After the reaction was completed, the product was cooled to room temperature and then vacuum filtered. The filter cake was washed twice with distilled water and then placed in a vacuum drying oven and dried at 40°C for 5 hours to obtain component A of the repair capsule.
[0047] Step S5: Add 1g ammonium chloride, 1g sodium dodecylbenzenesulfonate, 1g resorcinol, and 400mL deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 20℃ and 300r / min for 10min. Then, raise the temperature to 40℃ and continue stirring for 10min. Next, add 25g pentaerythritol tetrakis(3-mercaptopropionic acid) and N,N-dimethylbenzylamine in a mass ratio of 10:1 to form a solidified substance, and continue stirring for 20min. The core material emulsion was obtained. 40 mL of urea and 33% formaldehyde solution were mixed at a mass ratio of 1:6. The shell material solution prepared by adjusting the pH to 8.5 with triethylamine was added to the core material emulsion. The pH was adjusted to 3 with 10% citric acid solution. The mixture was then heated to 60°C and stirred for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed twice with distilled water and then placed in a vacuum drying oven and dried at 40°C for 5 hours to obtain component B of the repair capsule.
[0048] Step S6: Weigh out 80 parts by weight of high-density polyethylene resin, 1 part of ethylene-octene copolymer, 8 parts of nano-silica, 3 parts of stearic acid, 1 part of antioxidant, 1 part of ultraviolet absorber, 0.5 parts of impact enhancer, 1 part of repair capsule component A, and 1 part of repair capsule component B, and set aside for later use; the high-density polyethylene resin is HDPE M200056; the ethylene-octene copolymer is POE 8540; the average particle size of the nano-silica is 30nm; the antioxidant is antioxidant 3114; and the ultraviolet absorber is ultraviolet absorber UV-571.
[0049] Step S7: Mix high-density polyethylene resin, ethylene-octene copolymer, nano silica, stearic acid, antioxidant, ultraviolet absorber, impact enhancer, repair capsule A component and repair capsule B component evenly, and then melt extrusion and blow molding to obtain impact-resistant and shockproof plastic containers for chemical packaging.
[0050] Example 2:
[0051] This embodiment describes a method for preparing an impact-resistant and shock-proof plastic container for chemical packaging, comprising the following steps:
[0052] Step S1: 10 mmol of dimethyl 5-bromoisophthalate, 10 mmol of 3,5-bis(methoxycarbonyl)phenylboronic acid pinacol ester, 12 mL of potassium carbonate solution with a molar concentration of 2.5 mol / L, 0.7 g of tetra(triphenylphosphine)palladium, 18 mL of anhydrous ethanol, and 55 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the reaction was stirred at 22 °C and a stirring rate of 350 r / min for 2 seconds. After 5 minutes, the temperature was raised to 95°C and the reaction was stirred for 22 hours. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a mixed solvent of dichloromethane and distilled water in a volume ratio of 1:2.5. The mixture was then allowed to stand and separate into layers. The organic phase was dried with anhydrous sodium sulfate and then filtered under vacuum. The filtrate was evaporated by rotary evaporation to remove the solvent. The filtrate was then purified by silica gel column chromatography using a mixture of chloroform and methanol in a volume ratio of 22:1 to obtain the polyester compound.
[0053] Step S2: 5 mmol of the polyester compound, 12 mL of 5.5 mol / L potassium hydroxide solution, 12 mL of tetrahydrofuran, and 45 mL of methanol were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 22 °C and 350 r / min for 25 min. The temperature was then increased to 55 °C and the stirring was continued for 22 h. After the reaction was completed, the reaction product was cooled to room temperature, and the solvent was removed by rotary evaporation. The product was then added to distilled water and vacuum filtered. The filtrate was adjusted to pH 2.5 with 1.3 mol / L hydrochloric acid solution, centrifuged, and the precipitate was placed in a vacuum drying oven and dried at 45 °C for 3.5 h to obtain the polycarboxylic acid compound.
[0054] Step S3: 10 mmol of polycarboxylic acid compound, 40 mmol of 12-hydroxystearic acid, 1 mmol of p-toluenesulfonic acid and 85 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 22 °C and 350 r / min for 12 min. Then the temperature was raised to 135 °C and the mixture was stirred for 6 h. Then 40 mmol of isooctyl alcohol and 1 mmol of p-toluenesulfonic acid were added and the mixture was stirred for 4.5 h. After the reaction was completed, the reaction product was cooled to room temperature and then washed twice with sodium hydroxide solution with a molar concentration of 2.5 mol / L, distilled water and saturated saline solution, respectively. The product was then dried with anhydrous sodium sulfate and vacuum filtered. The filtrate was then evaporated by rotary evaporation to remove the solvent to obtain the impact-resistant reinforcing agent.
[0055] Step S4: Add 1g ammonium chloride, 1g sodium dodecylbenzenesulfonate, 1g resorcinol, and 400mL deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 22℃ and 350r / min for 12min. Then raise the temperature to 45℃ and continue stirring for 25min. Add 35mL of 4,5-epoxytetrahydrophthalic acid diglycidyl ester and continue stirring for 45min to obtain the core material emulsion. Add 45mL of urine... A shell material solution containing 34% formaldehyde was mixed at a mass ratio of 1:6.2 and then adjusted to pH 8.5 with triethylamine. This shell material solution was added to the core material emulsion and adjusted to pH 3.5 with 12% citric acid solution. The mixture was then heated to 65°C and stirred for 4 hours. After the reaction was completed, the product was cooled to room temperature and then vacuum filtered. The filter cake was washed twice with distilled water and then placed in a vacuum drying oven and dried at 45°C for 6 hours to obtain component A of the repair capsule.
[0056] Step S5: Add 1g ammonium chloride, 1g sodium dodecylbenzenesulfonate, 1g resorcinol, and 400mL deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 22℃ and 350r / min for 12min. Then, raise the temperature to 45℃ and continue stirring for 15min. Next, add 30g pentaerythritol tetrakis(3-mercaptopropionic acid) and N,N-dimethylbenzylamine in a mass ratio of 11:1 to form a solidified substance. Continue stirring for 25min to obtain the desired product. For the core material emulsion, 45 mL of urea and 34% formaldehyde solution were mixed at a mass ratio of 1:6.2, and then the pH was adjusted to 8.5 with triethylamine. The resulting shell material solution was added to the core material emulsion, and the pH was adjusted to 3.5 with 12% citric acid solution. The mixture was then heated to 65°C and stirred for 4 hours. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed twice with distilled water and then placed in a vacuum drying oven and dried at 45°C for 6 hours to obtain component B of the repair capsule.
[0057] Step S6: Weigh out 85 parts by weight of high-density polyethylene resin, 3.5 parts by weight of ethylene-octene copolymer, 9 parts by weight of nano-silica, 4 parts by weight of stearic acid, 2 parts by weight of antioxidant, 1.5 parts by weight of ultraviolet absorber, 4.5 parts by weight of impact enhancer, 3 parts by weight of repair capsule component A, and 3 parts by weight of repair capsule component B, and set aside for later use; the high-density polyethylene resin is HDPE M200056; the ethylene-octene copolymer is POE 8540; the average particle size of the nano-silica is 30nm; the antioxidant is antioxidant 3114; the ultraviolet absorber is ultraviolet absorber UV-571.
[0058] Step S7: Mix high-density polyethylene resin, ethylene-octene copolymer, nano silica, stearic acid, antioxidant, ultraviolet absorber, impact enhancer, repair capsule A component and repair capsule B component evenly, and then melt extrusion and blow molding to obtain impact-resistant and shockproof plastic containers for chemical packaging.
[0059] Example 3:
[0060] This embodiment describes a method for preparing an impact-resistant and shock-proof plastic container for chemical packaging, comprising the following steps:
[0061] Step S1: 10 mmol of dimethyl 5-bromoisophthalate, 10 mmol of 3,5-bis(methoxycarbonyl)phenylboronic acid pinacol ester, 15 mL of potassium carbonate solution with a molar concentration of 3 mol / L, 0.8 g of tetra(triphenylphosphine)palladium, 20 mL of anhydrous ethanol, and 60 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25 °C and a stirring rate of 400 r / min for 30 min. Then, the temperature was raised to 100 °C and the stirring was continued for 25 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a mixed solvent of dichloromethane and distilled water in a volume ratio of 1:3. After standing and separating the layers, the organic phase was dried with anhydrous sodium sulfate and then filtered under vacuum. The filtrate was evaporated by rotary evaporation to remove the solvent. Then, the filtrate was purified by silica gel column chromatography using a mixture of chloroform and methanol in a volume ratio of 25:1 to obtain the polyester compound.
[0062] Step S2: Add 5 mmol of the polyester compound, 15 mL of potassium hydroxide solution with a molar concentration of 6 mol / L, 15 mL of tetrahydrofuran, and 50 mL of methanol to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25 °C and a stirring rate of 400 r / min for 30 min. Then raise the temperature to 60 °C and continue stirring for 25 h. After the reaction is complete, cool the reaction product to room temperature, remove the solvent by rotary evaporation, add it to distilled water, and then filter under vacuum. Adjust the pH of the filtrate to 3 with hydrochloric acid solution with a molar concentration of 1.5 mol / L, centrifuge, and place the precipitate in a vacuum drying oven and dry at 50 °C for 4 h to obtain the polycarboxylic acid compound.
[0063] Step S3: 10 mmol of polycarboxylic acid compound, 40 mmol of 12-hydroxystearic acid, 1.5 mmol of p-toluenesulfonic acid and 90 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 25 °C and 400 r / min for 15 min. Then the temperature was raised to 140 °C and the mixture was stirred for 7 h. Then 40 mmol of isooctyl alcohol and 1.5 mmol of p-toluenesulfonic acid were added and the mixture was stirred for 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then washed three times with sodium hydroxide solution with a molar concentration of 3 mol / L, distilled water and saturated saline solution. The product was then dried with anhydrous sodium sulfate and vacuum filtered. The filtrate was then evaporated by rotary evaporation to remove the solvent to obtain the impact-resistant reinforcing agent.
[0064] Step S4: Add 1g ammonium chloride, 1g sodium dodecylbenzenesulfonate, 1g resorcinol, and 400mL deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 400r / min for 15min. Then raise the temperature to 50℃ and continue stirring for 30min. Add 40mL of 4,5-epoxytetrahydrophthalic acid diglycidyl ester and continue stirring for 60min to obtain the core material emulsion. Then, add 50m... L-urea and 35% formaldehyde solution were mixed at a mass ratio of 1:6.5. The resulting shell material solution was then adjusted to pH 9 with triethylamine and added to the core material emulsion. The pH was then adjusted to pH 4 with 15% citric acid solution. The mixture was then heated to 70°C and stirred for 5 hours. After the reaction was completed, the product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times with distilled water and then placed in a vacuum drying oven and dried at 50°C for 7 hours to obtain component A of the repair capsule.
[0065] Step S5: Add 1g ammonium chloride, 1g sodium dodecylbenzenesulfonate, 1g resorcinol, and 400mL deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 400r / min for 15min. Then, raise the temperature to 50℃ and continue stirring for 20min. Next, add 35g pentaerythritol tetrakis(3-mercaptopropionic acid) and N,N-dimethylbenzylamine in a mass ratio of 12:1 to form a solidified substance, and continue stirring for 30min. The core material emulsion was obtained. 50 mL of urea and 35% formaldehyde solution were mixed at a mass ratio of 1:6.5. The shell material solution prepared by adjusting the pH to 9 with triethylamine was added to the core material emulsion. The pH was adjusted to 4 with 15% citric acid solution. The mixture was then heated to 70°C and stirred for 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times with distilled water and then placed in a vacuum drying oven and dried at 50°C for 7 h to obtain component B of the repair capsule.
[0066] Step S6: Weigh out 90 parts by weight of high-density polyethylene resin, 6 parts by weight of ethylene-octene copolymer, 10 parts by weight of nano-silica, 5 parts by weight of stearic acid, 3 parts by weight of antioxidant, 2 parts by weight of ultraviolet absorber, 8.5 parts by weight of impact enhancer, 5 parts by weight of repair capsule component A, and 5 parts by weight of repair capsule component B, and set aside for later use; the high-density polyethylene resin is HDPE M200056; the ethylene-octene copolymer is POE 8540; the average particle size of the nano-silica is 30nm; the antioxidant is antioxidant 3114; the ultraviolet absorber is ultraviolet absorber UV-571.
[0067] Step S7: Mix high-density polyethylene resin, ethylene-octene copolymer, nano silica, stearic acid, antioxidant, ultraviolet absorber, impact enhancer, repair capsule A component and repair capsule B component evenly, and then melt extrusion and blow molding to obtain impact-resistant and shockproof plastic containers for chemical packaging.
[0068] Comparative Example 1:
[0069] This comparative example illustrates a method for preparing an impact-resistant and shock-proof plastic container for chemical packaging, comprising the following steps:
[0070] Step S1: Weigh out 90 parts by weight of high-density polyethylene resin, 6 parts by weight of ethylene-octene copolymer, 10 parts by weight of nano-silica, 5 parts by weight of stearic acid, 3 parts by weight of antioxidant, and 2 parts by weight of ultraviolet absorber, and set aside; the high-density polyethylene resin is HDPE M200056; the ethylene-octene copolymer is POE 8540; the average particle size of the nano-silica is 30nm; the antioxidant is antioxidant 3114; and the ultraviolet absorber is ultraviolet absorber UV-571.
[0071] Step S2: Mix high-density polyethylene resin, ethylene-octene copolymer, nano silica, stearic acid, antioxidant and ultraviolet absorber evenly, then melt extrusion and blow molding to obtain impact-resistant and shockproof plastic containers for chemical packaging.
[0072] Comparative Example 2:
[0073] This comparative example illustrates a method for preparing an impact-resistant and shock-proof plastic container for chemical packaging, comprising the following steps:
[0074] Step S1: 10 mmol of dimethyl 5-bromoisophthalate, 10 mmol of 3,5-bis(methoxycarbonyl)phenylboronic acid pinacol ester, 15 mL of potassium carbonate solution with a molar concentration of 3 mol / L, 0.8 g of tetra(triphenylphosphine)palladium, 20 mL of anhydrous ethanol, and 60 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25 °C and a stirring rate of 400 r / min for 30 min. Then, the temperature was raised to 100 °C and the stirring was continued for 25 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a mixed solvent of dichloromethane and distilled water in a volume ratio of 1:3. After standing and separating the layers, the organic phase was dried with anhydrous sodium sulfate and then filtered under vacuum. The filtrate was evaporated by rotary evaporation to remove the solvent. Then, the filtrate was purified by silica gel column chromatography using a mixture of chloroform and methanol in a volume ratio of 25:1 to obtain the polyester compound.
[0075] Step S2: Add 5 mmol of the polyester compound, 15 mL of potassium hydroxide solution with a molar concentration of 6 mol / L, 15 mL of tetrahydrofuran, and 50 mL of methanol to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25 °C and a stirring rate of 400 r / min for 30 min. Then raise the temperature to 60 °C and continue stirring for 25 h. After the reaction is complete, cool the reaction product to room temperature, remove the solvent by rotary evaporation, add it to distilled water, and then filter under vacuum. Adjust the pH of the filtrate to 3 with hydrochloric acid solution with a molar concentration of 1.5 mol / L, centrifuge, and place the precipitate in a vacuum drying oven and dry at 50 °C for 4 h to obtain the polycarboxylic acid compound.
[0076] Step S3: 10 mmol of polycarboxylic acid compound, 40 mmol of 12-hydroxystearic acid, 1.5 mmol of p-toluenesulfonic acid and 90 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 25 °C and 400 r / min for 15 min. Then the temperature was raised to 140 °C and the mixture was stirred for 7 h. Then 40 mmol of isooctyl alcohol and 1.5 mmol of p-toluenesulfonic acid were added and the mixture was stirred for 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then washed three times with sodium hydroxide solution with a molar concentration of 3 mol / L, distilled water and saturated saline solution. The product was then dried with anhydrous sodium sulfate and vacuum filtered. The filtrate was then evaporated by rotary evaporation to remove the solvent to obtain the impact-resistant reinforcing agent.
[0077] Step S4: Weigh out 90 parts by weight of high-density polyethylene resin, 6 parts by weight of ethylene-octene copolymer, 10 parts by weight of nano-silica, 5 parts by weight of stearic acid, 3 parts by weight of antioxidant, 2 parts by weight of ultraviolet absorber, and 8.5 parts by weight of impact-resistant reinforcing agent, and set aside; the high-density polyethylene resin is HDPE M200056; the ethylene-octene copolymer is POE 8540; the average particle size of the nano-silica is 30nm; the antioxidant is antioxidant 3114; and the ultraviolet absorber is ultraviolet absorber UV-571.
[0078] Step S5: Mix high-density polyethylene resin, ethylene-octene copolymer, nano silica, stearic acid, antioxidant, ultraviolet absorber and impact enhancer evenly, then melt extrusion and blow molding to obtain impact-resistant and shockproof plastic containers for chemical packaging.
[0079] Comparative Example 3:
[0080] This comparative example illustrates a method for preparing an impact-resistant and shock-proof plastic container for chemical packaging, comprising the following steps:
[0081] Step S1: Add 1g ammonium chloride, 1g sodium dodecylbenzenesulfonate, 1g resorcinol, and 400mL deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 400r / min for 15min. Then raise the temperature to 50℃ and continue stirring for 30min. Add 40mL of 4,5-epoxytetrahydrophthalic acid diglycidyl ester and continue stirring for 60min to obtain the core material emulsion. Then, add 50m... L-urea and 35% formaldehyde solution were mixed at a mass ratio of 1:6.5. The resulting shell material solution was then adjusted to pH 9 with triethylamine and added to the core material emulsion. The pH was then adjusted to pH 4 with 15% citric acid solution. The mixture was then heated to 70°C and stirred for 5 hours. After the reaction was completed, the product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times with distilled water and then placed in a vacuum drying oven and dried at 50°C for 7 hours to obtain component A of the repair capsule.
[0082] Step S2: Add 1g ammonium chloride, 1g sodium dodecylbenzenesulfonate, 1g resorcinol, and 400mL deionized water to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 400r / min for 15min. Then, raise the temperature to 50℃ and continue stirring for 20min. Next, add 35g pentaerythritol tetrakis(3-mercaptopropionic acid) and N,N-dimethylbenzylamine in a mass ratio of 12:1 to form a solidified substance, and continue stirring for 30min. The core material emulsion was obtained. 50 mL of urea and 35% formaldehyde solution were mixed at a mass ratio of 1:6.5. The shell material solution prepared by adjusting the pH to 9 with triethylamine was added to the core material emulsion. The pH was adjusted to 4 with 15% citric acid solution. The mixture was then heated to 70°C and stirred for 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times with distilled water and then placed in a vacuum drying oven and dried at 50°C for 7 h to obtain component B of the repair capsule.
[0083] Step S3: Weigh out 90 parts by weight of high-density polyethylene resin, 6 parts by weight of ethylene-octene copolymer, 10 parts by weight of nano-silica, 5 parts by weight of stearic acid, 3 parts by weight of antioxidant, 2 parts by weight of ultraviolet absorber, 5 parts by weight of repair capsule component A, and 5 parts by weight of repair capsule component B, and set aside for later use; the high-density polyethylene resin is HDPE M200056; the ethylene-octene copolymer is POE 8540; the average particle size of the nano-silica is 30nm; the antioxidant is antioxidant 3114; and the ultraviolet absorber is ultraviolet absorber UV-571.
[0084] Step S4: Mix high-density polyethylene resin, ethylene-octene copolymer, nano silica, stearic acid, antioxidant, ultraviolet absorber, repair capsule A component and repair capsule B component evenly, and then melt extrusion and blow molding to obtain impact-resistant and shockproof plastic containers for chemical packaging.
[0085] The impact-resistant and shockproof plastic containers for chemical packaging in Examples 1-3 and Comparative Examples 1-3 were subjected to notched impact strength tests at room temperature using a Jinjian XJUD-5.5 cantilever beam impact testing machine. The test results are as follows: Figure 1 As shown.
[0086] See Figure 1 The data shows that, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that adding impact enhancer and repair capsule A component and repair capsule B component can significantly improve the notched impact strength of plastic containers. Under the synergistic effect of the three, the impact resistance and anti-collision performance of plastic containers can be significantly improved.
[0087] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0088] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.
Claims
1. An impact-resistant and shockproof plastic container for chemical packaging, characterized in that, Includes the following components by weight: 80-90 parts high-density polyethylene resin, 1-6 parts ethylene-octene copolymer, 8-10 parts nano silica, 3-5 parts stearic acid, 1-3 parts antioxidant, 1-2 parts ultraviolet absorber, 0.5-8.5 parts impact enhancer, 1-5 parts repair capsule A component and 1-5 parts repair capsule B component; The impact-resistant reinforcing agent is prepared by the following steps: Step a1: Dimethyl 5-bromoisophthalate, 3,5-bis(methoxycarbonyl)phenylboronic acid pinacol ester, potassium carbonate solution, tetra(triphenylphosphine)palladium, anhydrous ethanol and toluene were stirred and reacted. After the reaction was completed, the reaction product was cooled and then poured into a mixed solvent. After standing and separating the layers, the organic phase was dried and then filtered under vacuum. The filtrate was evaporated by rotary evaporation and then purified by silica gel column chromatography with eluent to obtain the polyester compound. Step a2: The polyester compound, potassium hydroxide solution, tetrahydrofuran and methanol were stirred and reacted. After the reaction was completed, the reaction product was cooled, then evaporated by rotary evaporation, then added to distilled water, then filtered under vacuum, the pH of the filtrate was adjusted with hydrochloric acid solution, then centrifuged, and the precipitate was dried to obtain the polycarboxylic compound. Step a3: The polycarboxylic acid compound, 12-hydroxystearic acid, 1 / 2 p-toluenesulfonic acid and toluene are stirred and reacted. Then isooctyl alcohol and the remaining 1 / 2 p-toluenesulfonic acid are added and the reaction is continued. After the reaction is completed, the reaction product is cooled, washed and dried, then vacuum filtered, and the filtrate is evaporated by rotary evaporation to obtain the impact resistance enhancer.
2. The impact-resistant and shockproof plastic container for chemical packaging according to claim 1, characterized in that, In step a1, the ratio of dimethyl 5-bromoisophthalate, 3,5-bis(methoxycarbonyl)phenylboronic acid pinacol ester, potassium carbonate solution, tetra(triphenylphosphine)palladium, anhydrous ethanol, and toluene is 10 mmol: 10 mmol: 10-15 mL: 0.6-0.8 g: 15-20 mL: 50-60 mL; the molar concentration of the potassium carbonate solution is 2-3 mol / L; the mixed solvent is a mixture of dichloromethane and distilled water in a volume ratio of 1:2-3; and the eluent is a mixture of chloroform and methanol in a volume ratio of 20-25:
1.
3. The impact-resistant and shockproof plastic container for chemical packaging according to claim 1, characterized in that, In step a2, the ratio of the polyester compound, potassium hydroxide solution, tetrahydrofuran, and methanol is 5 mmol: 10-15 mL: 10-15 mL: 40-50 mL; the molar concentration of the potassium hydroxide solution is 5-6 mol / L; and the molar concentration of the hydrochloric acid solution is 1-1.5 mol / L.
4. The impact-resistant and shockproof plastic container for chemical packaging according to claim 1, characterized in that, The ratio of the polycarboxylic acid compound, 12-hydroxystearic acid, p-toluenesulfonic acid, toluene, and isooctyl alcohol in step a3 is 10 mmol: 40 mmol: 1-3 mmol: 80-90 mL: 40 mmol.
5. The impact-resistant and shockproof plastic container for chemical packaging according to claim 1, characterized in that, The repair capsule component A is prepared by the following steps: Ammonium chloride, sodium dodecylbenzenesulfonate, resorcinol, and deionized water were stirred and reacted. Then, diglycidyl 4,5-epoxytetrahydrophthalic acid was added and the reaction was continued with stirring to obtain a core material emulsion. The shell material solution was added to the core material emulsion, and the pH was adjusted with citric acid solution. The reaction was then continued with stirring. After the reaction was completed, the reaction product was cooled and then vacuum filtered. The filter cake was washed and dried to obtain component A of the repair capsule.
6. The impact-resistant and shockproof plastic container for chemical packaging according to claim 5, characterized in that, The ratio of ammonium chloride, sodium dodecylbenzenesulfonate, resorcinol, deionized water, diglycidyl 4,5-epoxytetrahydrophthalic acid, and shell material solution is 1g:1g:1g:400mL:30-40mL:40-50mL; the shell material solution is prepared by mixing urea and formaldehyde solution at a mass ratio of 1:6-6.5, and then adjusting the pH to 8.5-9 with triethylamine; the mass fraction of the formaldehyde solution is 33-35%; and the mass fraction of the citric acid solution is 10-15%.
7. The impact-resistant and shockproof plastic container for chemical packaging according to claim 1, characterized in that, The repair capsule component B is prepared by the following steps: Ammonium chloride, sodium dodecylbenzenesulfonate, resorcinol, and deionized water were stirred and reacted. Then, a solidifying agent was added and the reaction was continued with stirring to obtain a core material emulsion. The shell material solution was added to the core material emulsion, and the pH was adjusted with citric acid solution. The reaction was then continued with stirring. After the reaction was completed, the reaction product was cooled and then vacuum filtered. The filter cake was washed and dried to obtain component B of the repair capsule.
8. The impact-resistant and shockproof plastic container for chemical packaging according to claim 7, characterized in that, The ratio of ammonium chloride, sodium dodecylbenzenesulfonate, resorcinol, deionized water, curing agent, and shell material solution is 1g:1g:1g:400mL:25-35g:40-50mL; the curing agent is a mixture of pentaerythritol tetrakis(3-mercaptopropionic acid) and N,N-dimethylbenzylamine in a mass ratio of 10-12:1; the shell material solution is prepared by mixing urea and formaldehyde solution in a mass ratio of 1:6-6.5, and then adjusting the pH to 8.5-9 with triethylamine; the mass fraction of the formaldehyde solution is 33-35%; and the mass fraction of the citric acid solution is 10-15%.
9. A method for preparing an impact-resistant and shock-proof plastic container for chemical packaging as described in any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Weigh out 80-90 parts by weight of high-density polyethylene resin, 1-6 parts by weight of ethylene-octene copolymer, 8-10 parts by weight of nano-silica, 3-5 parts by weight of stearic acid, 1-3 parts by weight of antioxidant, 1-2 parts by weight of ultraviolet absorber, 0.5-8.5 parts by weight of impact enhancer, 1-5 parts by weight of repair capsule component A and 1-5 parts by weight of repair capsule component B, and set aside. Step 2: Mix high-density polyethylene resin, ethylene-octene copolymer, nano silica, stearic acid, antioxidant, ultraviolet absorber, impact enhancer, repair capsule component A and repair capsule component B evenly, and then melt extrusion and blow molding to obtain impact-resistant and shockproof plastic containers for chemical packaging.
10. The method for preparing an impact-resistant and shock-proof plastic container for chemical packaging according to claim 9, characterized in that, The high-density polyethylene resin is HDPE M200056; The ethylene-octene copolymer is POE 8540; The average particle size of the nano-silica is 30 nm. The antioxidant is antioxidant 3114; The ultraviolet absorber is ultraviolet absorber UV-571.