Woody grease-based PVC printing film and preparation method thereof

Abstract

The invention discloses a woody grease-based PVC printing film and a preparation method thereof, and relates to the technical field of PVC film materials. When the woody grease-based PVC printing film is prepared, rubber seed oil is esterified with 2-bis (phenyl) phosphoric acid ethanol and then epoxidized to prepare modified rubber seed oil; the preparation method comprises the following steps: sequentially reacting polyvinyl chloride with sodium azide and propynyl cardamonin to prepare modified polyvinyl chloride; the pre-modified calcium carbonate and 4-aminomethyl-2, 2, 6, 6-tetramethylpiperidine are subjected to a reaction, and modified calcium carbonate is prepared; and uniformly mixing the modified polyvinyl chloride, the modified calcium carbonate, the modified rubber seed oil, diisononyl phthalate and a barium-zinc heat stabilizer, and carrying out hot press molding to obtain the woody grease-based PVC printing film. The woody grease-based PVC printing film prepared by the preparation method disclosed by the invention has excellent flame retardance and ageing resistance.

Description

Technical Field

[0001] This invention relates to the field of PVC film technology, specifically to a woody oil-based PVC printing film and its preparation method. Background Technology

[0002] PVC printed film is a functional film made from polyvinyl chloride (PVC) resin as the main base material, with the addition of fillers, plasticizers, stabilizers, and other additives, through calendering or blow molding processes. This film allows for customized patterns using gravure printing, UV printing, and other technologies, and features long-lasting color, making it widely used in packaging (such as food labels), building materials decoration, and advertising. However, when PVC printed film is applied outdoors (such as on outdoor billboards), its structure is easily affected by ultraviolet light from sunlight, causing aging and ultimately leading to the loss of performance. While PVC resin itself is not easily flammable, a large amount of plasticizer is usually added during the preparation of PVC products such as PVC printed film to improve the material's plasticity. These plasticizers are often flammable, significantly increasing the flammability of PVC products. Therefore, it is necessary to develop an aging-resistant and flame-retardant PVC printed film.

[0003] Most PVC plasticizers currently on the market are phthalate-based. However, these plasticizers are questioned for their persistent reproductive toxicity, posing potential threats to the environment and health. They are explicitly banned in many countries for use in the electronics, food, daily necessities, and toy industries. Developing environmentally friendly and green plasticizers has become a research hotspot. Rubber seed oil is a tropical woody plant oilseed with considerable yield, but its comprehensive development and utilization are not high. Its fatty acid composition contains over 80% unsaturated fatty acids, making it an ideal raw material for synthesizing non-toxic and environmentally friendly plasticizers. Using rubber seed oil as a raw material to prepare PVC plasticizers, partially or completely replacing traditional phthalate-based plasticizers, can improve the high-value utilization of natural resources, resulting in significant social and economic benefits. Summary of the Invention

[0004] The purpose of this invention is to provide a woody oil-based PVC printing film and its preparation method, so as to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A woody oil-based PVC printing film, by weight parts, comprises: 70 parts modified polyvinyl chloride, 8-10 parts modified calcium carbonate, 20-22 parts modified rubber seed oil, 10-12 parts diisononyl phthalate, and 3-4 parts barium zinc heat stabilizer. The modified polyvinyl chloride is prepared by reacting polyvinyl chloride sequentially with sodium azide and propyne-based cardamom. The propynyl cardamomine is prepared by reacting cardamomine and 3-bromopropyne. The modified calcium carbonate is prepared by reacting pre-modified calcium carbonate with 4-aminomethyl-2,2,6,6-tetramethylpiperidine. The pre-modified calcium carbonate is prepared by polymerizing and growing 1,1,3,3,5,5-hexamethyltrisiloxane and 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione on pretreated calcium carbonate. The pretreated calcium carbonate is prepared by reacting calcium carbonate with allyltriethoxysilane. The modified rubber seed oil is obtained by esterification of rubber seed oil and ethanol 2-di(phenyl)phosphoethanol followed by epoxidation.

[0006] A method for preparing a woody oil-based PVC printing film, the method comprising the following steps: (1) Esterified rubber seed oil, formic acid, and ethyl acetate are mixed evenly in a mass ratio of 1:(0.1~0.12):(0.3~0.4). The mixture is stirred at 50~60℃ and 300~500r / min for 10~20min. Hydrogen peroxide with a mass fraction of 30% (0.2~0.22 times the mass of esterified rubber seed oil) and concentrated sulfuric acid with a mass fraction of 0.02~0.04 (0.02~0.04 times the mass of esterified rubber seed oil) are added. The reaction is continued for 5~6h. The mixture is allowed to stand and separate into layers. The oil phase is taken and washed 5 times each with sodium bicarbonate aqueous solution with a mass fraction of 10% (60℃) and deionized water. The mixture is then evaporated under reduced pressure to obtain modified rubber seed oil. (2) Polyvinyl chloride, sodium azide, and N,N-dimethylformamide are mixed evenly at a mass ratio of 1:(1.2~1.3):(30~40), and stirred at 30~40℃ and 100~120r / min for 20~24h. Precipitation is carried out using a mixed solvent of methanol and deionized water at a volume ratio of 2:1. After filtration, the mixture is dried at 30~40℃ for 18~22h under vacuum to obtain pre-modified polyvinyl chloride. Under nitrogen protection, the pre-modified polyvinyl chloride and propyne-based cardamom are mixed... Mix 2,2'-bipyridine, copper bromide, and N,N-dimethylformamide in a mass ratio of 1:(1.6~1.8):(2~3):(1.3~1.5):(28~32) until homogeneous. Stir at 100~120 r / min for 20~24 h at room temperature. Filter the mixture and add 200~300 times the mass of methanol of the pre-modified polyvinyl chloride to the filtrate for precipitation. Filter the filtrate and dry it at 40~50℃ under vacuum for 18~22 h to obtain modified polyvinyl chloride. (3) Add 1,1,3,3,5,5-hexamethyltrisiloxane and 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione at a molar ratio of 1:(0.7~0.8) to N,N-dimethylformamide at a mass ratio of 18~20 times that of 1,1,3,3,5,5-hexamethyltrisiloxane to prepare a polymerization reaction solution; mix chloroplatinic acid and N,N-dimethylformamide at a mass ratio of 1:(4~5) to prepare a catalyst solution; weigh pretreated calcium carbonate, catalyst solution and polymerization reaction solution at a mass ratio of 1:(3~4):(10~12); add pretreated calcium carbonate, 1 / 3 part of polymerization reaction solution and 1 / 3 part of catalyst... The solutions were mixed and stirred at 70-80℃ and 300-400 r / min for 20-30 min. The remaining polymerizable reaction solution and catalyst solution were added dropwise at a uniform rate over 20 min. The reaction was continued with stirring for 2-3 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 40-50℃ for 18-22 h under vacuum to obtain pre-modified calcium carbonate. Pre-modified calcium carbonate, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:(4-5):(18-20). The mixture was stirred at 50-60℃ and 300-500 r / min for 5-6 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 40-50℃ for 18-22 h under vacuum to obtain modified calcium carbonate. (4) Mix the modified polyvinyl chloride, modified calcium carbonate, modified rubber seed oil, diisononyl phthalate and barium zinc heat stabilizer evenly, place them in a rheometer and stir at 180℃ and 40~50r / min for 4~5min, place them in a flat vulcanizing machine, hot press them into shape, and cool them naturally to room temperature to obtain woody oil-based PVC printing film.

[0007] As an optimization, the preparation method of the esterified rubber seed oil in step (1) is as follows: rubber seed oil, 2-bis(phenyl)phosphoethanol and p-toluenesulfonic acid are mixed in a mass ratio of 1:(0.3~0.4):(0.03~0.05), stirred at 80~90℃ and 300~500r / min for 4~5h, filtered, and the filtrate is dried at 60~70℃ under vacuum for 5~6h to obtain esterified rubber seed oil.

[0008] As an optimization, the CAS number of the 2-bis(phenyl)phosphoethanol is 887-21-8; the structural formula is:

[0009] As an optimization, the preparation method of propyne-based cardamom in step (2) is as follows: cardamom and 3-bromopropyne are added to acetone at a molar ratio of 1:1, which is 13 to 15 times the mass of cardamom. Potassium carbonate is added at a mass of 0.1 to 0.12 times the mass of cardamom. The mixture is stirred and refluxed at 200 to 300 r / min for 16 to 18 hours at 56°C. After filtration, the filtrate is dried at 40 to 50°C under vacuum for 8 to 10 hours to obtain propyne-based cardamom. The reaction process is as follows:

[0010] As an optimization, the preparation method of the pretreated calcium carbonate in step (3) is as follows: calcium carbonate, allyltriethoxysilane and anhydrous ethanol are mixed in a mass ratio of 1:(3~4):(20~30), ultrasonically dispersed for 30~40 min, and 3~4 times the mass of calcium carbonate is added to an ammonia solution with a mass fraction of 15%. The mixture is stirred at 50℃ and 300~500 r / min for 4~5 h, filtered, washed 3 times each with anhydrous ethanol and deionized water, and dried at 50~60℃ for 12~14 h to obtain pretreated calcium carbonate.

[0011] As an optimization, the CAS number of the 1-epoxyethylenemethyl-3,5-bis-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione described in step (3) is 20395-16-8; the structural formula is:

[0012] As an optimization, the amounts of modified polyvinyl chloride, modified calcium carbonate, modified rubber seed oil, diisononyl phthalate, and barium zinc heat stabilizer in step (4) are as follows: by mass parts, 70 parts of modified polyvinyl chloride, 8-10 parts of modified calcium carbonate, 20-22 parts of modified rubber seed oil, 10-12 parts of diisononyl phthalate, and 3-4 parts of barium zinc heat stabilizer.

[0013] As an optimization, the hot pressing process parameters in step (4) are: hot pressing at 165~175℃, 6~7MPa for 5~6min, and hot pressing at 12~14MPa for 2~3min.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: In preparing woody oil-based PVC printing film, this invention first reacts rubber seed oil with ethanol 2-di(phenyl)phosphophosphate to obtain esterified rubber seed oil, and then epoxidizes the esterified rubber seed oil to obtain modified rubber seed oil. Phosphorus and epoxy groups are introduced into the modified rubber seed oil. The introduction of phosphorus can improve the flame retardant properties of the woody oil-based PVC printing film, and the unsaturated carbon-carbon double bonds in the rubber seed oil are transformed into epoxy groups, allowing the modified rubber seed oil to be used as a plasticizer for PVC, replacing some traditional PVC plasticizers.

[0015] Secondly, propynyl cardamom is prepared by reacting cardamom with 3-bromopropyne; pre-modified PVC is prepared by reacting polyvinyl chloride with sodium azide, and azide groups are introduced onto the side chains of the pre-modified PVC molecule; the azide groups on the pre-modified PVC are then reacted with the alkynyl groups on the propynyl cardamom to prepare modified PVC; cardamom is then grafted onto the side chains of the modified PVC molecule. Cardamom is a natural chalcone-type compound with a main skeleton structure of 1,3-stilbene ketone, which has an alternating single and double bond structure. It can easily relax energy through a non-adiabatic pathway. The hydroxyl groups in the structure and the adjacent carbonyl groups can form intramolecular hydrogen bonds, further promoting the absorption of ultraviolet light and endowing the woody oil-based PVC printing film with excellent anti-aging properties.

[0016] Finally, pretreated calcium carbonate was prepared by reacting calcium carbonate with allyltriethoxysilane, introducing C=C double bonds onto the pretreated calcium carbonate. Pre-modified calcium carbonate was then prepared by polymerizing 1,1,3,3,5,5-hexamethyltrisiloxane and 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione onto the pretreated calcium carbonate via hydrosilylation, introducing triazine, siloxane, and epoxy groups onto the pre-modified calcium carbonate. The introduction of the triazine and siloxane structures further enhances the flame retardant properties. Modified calcium carbonate was prepared by reacting the epoxy groups on the pre-modified calcium carbonate with the amino group on 4-aminomethyl-2,2,6,6-tetramethylpiperidine. Hindered amine structures were then grafted onto the modified calcium carbonate, further improving the excellent anti-aging properties of woody oil-based PVC printing films. Detailed Implementation

[0017] 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.

[0018] In the following examples and comparative examples, the polyvinyl chloride used was SG-3, purchased from Jinan Xiangfeng Weiye Chemical Co., Ltd.; the calcium carbonate used had a particle size of 1500 mesh, purchased from Hebei Houkang Mineral Products Co., Ltd.; the rubber seed oil used was purchased from Wuhan Beileye Biomedical Technology Co., Ltd.; and the barium zinc heat stabilizer used was purchased from Shandong Sancheng New Material Technology Co., Ltd. Example 1:

[0019] A method for preparing a woody oil-based PVC printing film, comprising the following preparation steps: (1) Rubber seed oil, 2-di(phenyl)phosphoethanol and p-toluenesulfonic acid were mixed in a mass ratio of 1:0.3:0.03 and stirred at 300 r / min for 5 h at 80 °C. The mixture was filtered and the filtrate was dried at 60 °C under vacuum for 6 h to obtain esterified rubber seed oil. Esterified rubber seed oil, formic acid and ethyl acetate were mixed evenly in a mass ratio of 1:0.1:0.3 and stirred at 300 r / min for 20 min at 50 °C. Hydrogen peroxide with a mass fraction of 20% (0.2 times the mass of esterified rubber seed oil) and concentrated sulfuric acid with a mass fraction of 0.02 (0.02 times the mass of esterified rubber seed oil) were added and the mixture was stirred for 6 h. The mixture was allowed to stand and separate into layers. The oil phase was taken and washed 5 times each with sodium bicarbonate aqueous solution with a mass fraction of 10% (at 60 °C) and deionized water. The mixture was then evaporated under reduced pressure to obtain modified rubber seed oil. (2) Cardamom and 3-bromopropyne were added to acetone at a molar ratio of 1:1, which was 13 times the mass of cardamom. Potassium carbonate at a mass of 0.1 times the mass of cardamom was added. The mixture was stirred and refluxed at 200 r / min for 16 h at 56 °C. The mixture was then filtered, and the filtrate was dried at 40 °C under vacuum for 10 h to obtain propyne-based cardamom. Polyvinyl chloride, sodium azide, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.2:30. The mixture was stirred and reacted at 100 r / min for 24 h at 30 °C. The mixture was then mixed with methanol and deionized water at a volume ratio of 2:1. Pre-modified polyvinyl chloride (PVC) was obtained by precipitating the PVC in a solvent, filtering, and drying at 30°C for 22 hours under vacuum. Pre-modified PVC, propyne-based cardamom, 2,2'-bipyridine, copper bromide, and N,N-dimethylformamide were mixed uniformly at a mass ratio of 1:1.6:2:1.3:28 under nitrogen protection and stirred at 100 r / min for 24 hours at room temperature. After filtration, methanol (200 times the mass of the pre-modified PVC) was added to the filtrate for precipitation. After filtration, the PVC was dried at 40°C for 22 hours under vacuum to obtain modified PVC. (3) Calcium carbonate, allyltriethoxysilane, and anhydrous ethanol were mixed in a mass ratio of 1:3:20 and ultrasonically dispersed for 30 min. Ammonia solution with a mass fraction of 15% was added, which was three times the mass of calcium carbonate. The mixture was stirred at 50 °C and 300 r / min for 4 h. After filtration, the mixture was washed three times each with anhydrous ethanol and deionized water and dried at 50 °C for 14 h to obtain pretreated calcium carbonate. 1,1,3,3,5,5-hexamethyltrisiloxane, 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione was added in a molar ratio of 1:0.7 to N,N-dimethylformamide, which was 18 times the mass of 1,1,3,3,5,5-hexamethyltrisiloxane, to prepare a polymerizable reaction solution. Chloroplatinic acid and N,N-dimethylformamide were mixed in a mass ratio of 1:4. The pretreated calcium carbonate, catalyst solution, and polymerizable reaction solution were weighed in a mass ratio of 1:3:10. The pretreated calcium carbonate, 1 / 3 of the polymerizable reaction solution, and 1 / 3 of the catalyst solution were mixed and stirred at 70℃ and 300 r / min for 30 min. The remaining polymerizable reaction solution and catalyst solution were added dropwise at a uniform rate over 20 min, and the reaction was continued with stirring for 3 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 40℃ for 22 h under vacuum to obtain pre-modified calcium carbonate. The pre-modified calcium carbonate, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, and N,N-dimethylformamide were mixed in a mass ratio of 1:4:18 and stirred at 50℃ and 300 r / min for 6 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 40℃ for 22 h under vacuum to obtain modified calcium carbonate. (4) Weigh 70 parts of modified polyvinyl chloride, 8 parts of modified calcium carbonate, 20 parts of modified rubber seed oil, 10 parts of diisononyl phthalate, and 3 parts of barium zinc heat stabilizer by mass. Mix the modified polyvinyl chloride, modified calcium carbonate, modified rubber seed oil, diisononyl phthalate, and barium zinc heat stabilizer evenly, place them in a rheometer and stir at 180°C and 40 r / min for 4 min. Place them in a flat vulcanizing machine and hot press at 165°C and 6 MPa for 6 min, then hot press at 12 MPa for 3 min. Allow them to cool naturally to room temperature to obtain a woody oil-based PVC printing film. Example 2:

[0020] A method for preparing a woody oil-based PVC printing film, comprising the following preparation steps: (1) Rubber seed oil, 2-di(phenyl)phosphoethanol and p-toluenesulfonic acid were mixed in a mass ratio of 1:0.35:0.04 and stirred at 85℃ and 400r / min for 4.5h. The mixture was filtered and the filtrate was dried at 65℃ under vacuum for 5.5h to obtain esterified rubber seed oil. Esterified rubber seed oil, formic acid and ethyl acetate were mixed evenly in a mass ratio of 1:0.11:0.35 and stirred at 55℃ and 400r / min for 15min. Hydrogen peroxide with a mass fraction of 20% and concentrated sulfuric acid with a mass fraction of 0.21 times that of esterified rubber seed oil were added and the reaction was continued for 5.5h. The mixture was allowed to stand and separate into layers. The oil phase was taken and washed 5 times each with sodium bicarbonate aqueous solution with a mass fraction of 10% at 60℃ and deionized water. The mixture was then evaporated under reduced pressure to obtain modified rubber seed oil. (2) Cardamom and 3-bromopropyne were added to acetone at a molar ratio of 1:1, which was 14 times the mass of cardamom. Potassium carbonate was added at a molar ratio of 0.11 times the mass of cardamom. The mixture was stirred and refluxed at 250 r / min for 17 h at 56 °C. The mixture was then filtered, and the filtrate was dried at 45 °C under vacuum for 9 h to obtain propyne-based cardamom. Polyvinyl chloride, sodium azide, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.25:35. The mixture was stirred and reacted at 110 r / min for 22 h at 35 °C. The mixture was then mixed with methanol and deionized water at a volume ratio of 2:1. The solvent was used to precipitate the polyvinyl chloride (PVC), which was then filtered and dried at 35°C for 20 hours under vacuum to obtain pre-modified PVC. Under nitrogen protection, the pre-modified PVC, propyne-based cardamom, 2,2'-bipyridine, copper bromide, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:1.7:2.5:1.4:30. The mixture was stirred at 110 r / min for 22 hours at room temperature, filtered, and methanol (250 times the mass of the pre-modified PVC) was added to the filtrate for precipitation. The mixture was then filtered and dried at 45°C for 20 hours under vacuum to obtain modified PVC. (3) Calcium carbonate, allyltriethoxysilane, and anhydrous ethanol were mixed in a mass ratio of 1:3.5:25 and ultrasonically dispersed for 35 min. Then, 3.5 times the mass of calcium carbonate and a 15% ammonia solution were added. The mixture was stirred at 50°C and 400 r / min for 4.5 h. After filtration, the mixture was washed three times each with anhydrous ethanol and deionized water, and dried at 55°C for 13 h to obtain pretreated calcium carbonate. (The remaining text appears to be a fragmented and nonsensical string of characters.) -Hexamethyltrisiloxane and 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione were added to N,N-dimethylformamide at a molar ratio of 1:0.75 to prepare a polymerization reaction solution; chloroplatinic acid and N,N-dimethylformamide were mixed at a mass ratio of 1:4.5. The pretreated calcium carbonate, catalyst solution, and polymerizable reaction solution were weighed in a mass ratio of 1:3.5:11. The pretreated calcium carbonate, 1 / 3 of the polymerizable reaction solution, and 1 / 3 of the catalyst solution were mixed and stirred at 75℃ and 350 r / min for 25 min. The remaining polymerizable reaction solution and catalyst solution were added dropwise at a uniform rate over 20 min, and the reaction was continued with stirring for 2.5 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 45℃ under vacuum for 20 h to obtain pre-modified calcium carbonate. The pre-modified calcium carbonate, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, and N,N-dimethylformamide were mixed in a mass ratio of 1:4.5:19 and stirred at 55℃ and 400 r / min for 5.5 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 45℃ under vacuum for 20 h to obtain modified calcium carbonate. (4) Weigh 70 parts of modified polyvinyl chloride, 9 parts of modified calcium carbonate, 21 parts of modified rubber seed oil, 11 parts of diisononyl phthalate, and 3.5 parts of barium zinc heat stabilizer by mass. Mix the modified polyvinyl chloride, modified calcium carbonate, modified rubber seed oil, diisononyl phthalate, and barium zinc heat stabilizer evenly, place them in a rheometer and stir at 180℃ and 45r / min for 4.5min. Place them in a flat vulcanizing machine and hot press at 170℃ and 6.5MPa for 5.5min, then hot press at 13MPa for 2.5min. Allow to cool naturally to room temperature to obtain woody oil-based PVC printing film. Example 3:

[0021] A method for preparing a woody oil-based PVC printing film, comprising the following preparation steps: (1) Rubber seed oil, 2-di(phenyl)phosphoethanol and p-toluenesulfonic acid were mixed in a mass ratio of 1:0.4:0.05 and stirred at 90℃ and 500r / min for 4h. After filtration, the filtrate was dried at 70℃ under vacuum for 5h to obtain esterified rubber seed oil. Esterified rubber seed oil, formic acid and ethyl acetate were mixed evenly in a mass ratio of 1:0.12:0.4 and stirred at 60℃ and 500r / min for 10min. Hydrogen peroxide with a mass fraction of 20% (0.22 times the mass of esterified rubber seed oil) and concentrated sulfuric acid with a mass fraction of 0.04 (0.04 times the mass of esterified rubber seed oil) were added and the reaction was continued for 5h. After standing and separation, the oil phase was taken and washed 5 times each with sodium bicarbonate aqueous solution with a mass fraction of 10% (60℃) and deionized water. The modified rubber seed oil was obtained by rotary evaporation under reduced pressure. (2) Cardamom and 3-bromopropyne were added to acetone at a molar ratio of 1:1, which was 15 times the mass of cardamom. Potassium carbonate was added at a mass ratio of 0.12 times the mass of cardamom. The mixture was stirred and refluxed at 300 r / min for 18 h at 56 °C. After filtration, the filtrate was dried at 50 °C under vacuum for 8 h to obtain propyne-based cardamom. Polyvinyl chloride, sodium azide, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:1.3:40. The mixture was stirred and reacted at 120 r / min for 20 h at 40 °C. The mixture was then mixed with methanol and deionized water at a volume ratio of 2:1. Pre-modified polyvinyl chloride (PVC) was obtained by precipitating the PVC in a solvent, filtering, and drying at 40°C for 18 hours under vacuum. Pre-modified PVC, propyne-based cardamom, 2,2'-bipyridine, copper bromide, and N,N-dimethylformamide were mixed uniformly at a mass ratio of 1:1.8:3:1.5:32 under nitrogen protection and stirred at 120 r / min for 24 hours at room temperature. After filtration, methanol (300 times the mass of the pre-modified PVC) was added to the filtrate for precipitation. After filtration, the PVC was dried at 50°C for 18 hours under vacuum to obtain modified PVC. (3) Calcium carbonate, allyltriethoxysilane, and anhydrous ethanol were mixed in a mass ratio of 1:4:30 and ultrasonically dispersed for 40 min. Four times the mass of calcium carbonate and a 15% ammonia solution were added. The mixture was stirred at 500 r / min for 4 h at 50 °C. After filtration, the mixture was washed three times each with anhydrous ethanol and deionized water and dried at 60 °C for 12 h to obtain pretreated calcium carbonate. 1,1,3,3,5,5-hexamethyltrisiloxane, 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione were added in a molar ratio of 1:0.8 to N,N-dimethylformamide in a mass ratio of 20 times that of 1,1,3,3,5,5-hexamethyltrisiloxane to prepare a polymerizable reaction solution. Chloroplatinic acid and N,N-dimethylformamide were mixed in a mass ratio of 1:5. The pretreated calcium carbonate, catalyst solution, and polymerizable reaction solution were weighed in a mass ratio of 1:4:12. The pretreated calcium carbonate, 1 / 3 of the polymerizable reaction solution, and 1 / 3 of the catalyst solution were mixed and stirred at 80℃ and 400 r / min for 20 min. The remaining polymerizable reaction solution and catalyst solution were added dropwise at a uniform rate within 20 min, and the reaction was continued with stirring for 2 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 50℃ for 18 h under vacuum to obtain pre-modified calcium carbonate. The pre-modified calcium carbonate, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, and N,N-dimethylformamide were mixed in a mass ratio of 1:5:20 and stirred at 60℃ and 500 r / min for 5 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 50℃ for 18 h under vacuum to obtain modified calcium carbonate. (4) Weigh 70 parts of modified polyvinyl chloride, 10 parts of modified calcium carbonate, 22 parts of modified rubber seed oil, 12 parts of diisononyl phthalate, and 4 parts of barium zinc heat stabilizer by mass. Mix the modified polyvinyl chloride, modified calcium carbonate, modified rubber seed oil, diisononyl phthalate, and barium zinc heat stabilizer evenly, place them in a rheometer and stir at 180°C and 50 r / min for 5 min. Place them in a flat vulcanizing machine and hot press at 175°C and 7 MPa for 5 min, then hot press at 14 MPa for 2 min. Allow them to cool naturally to room temperature to obtain a woody oil-based PVC printing film.

[0022] Comparative Example 1: The difference between the preparation method of woody oil-based PVC printing film in Comparative Example 1 and Example 2 lies in the different steps (1). Step (1) is modified as follows: Rubber seed oil, n-propanol, and p-toluenesulfonic acid are mixed in a mass ratio of 1:0.35:0.04 and stirred at 85°C and 400 r / min for 4.5 h. After filtration, the filtrate is dried at 65°C under vacuum for 5.5 h to obtain esterified rubber seed oil. Esterified rubber seed oil, formic acid, and ethyl acetate are mixed evenly in a mass ratio of 1:0.11:0.35 and stirred at 55°C and 400 r / min for 15 min. Hydrogen peroxide with a mass fraction of 20% and concentrated sulfuric acid with a mass fraction of 0.21 times that of esterified rubber seed oil are added. The reaction is continued for 5.5 h. After standing and separation, the oil phase is taken and washed 5 times each with sodium bicarbonate aqueous solution with a mass fraction of 10% at 60°C and deionized water. The modified rubber seed oil is obtained by rotary evaporation under reduced pressure. The remaining steps are the same as in Example 2.

[0023] Comparative Example 2: The preparation method of the woody oil-based PVC printing film in Comparative Example 2 differs from that in Example 2 in that step (2) is omitted, and step (4) is modified as follows: Weigh 70 parts of polyvinyl chloride, 9 parts of modified calcium carbonate, 21 parts of modified rubber seed oil, 11 parts of diisononyl phthalate, and 3.5 parts of barium zinc heat stabilizer by mass. Mix the polyvinyl chloride, modified calcium carbonate, modified rubber seed oil, diisononyl phthalate, and barium zinc heat stabilizer evenly, place them in a rheometer and stir at 180°C and 45 r / min for 4.5 min. Place them in a flat vulcanizing machine and hot press at 170°C and 6.5 MPa for 5.5 min, then hot press at 13 MPa for 2.5 min. Allow to cool naturally to room temperature to obtain the woody oil-based PVC printing film. The remaining steps are the same as in Example 2.

[0024] Comparative Example 3: The preparation method of the woody oil-based PVC printing film in Comparative Example 3 differs from that in Example 2 only in step (3). Step (3) is modified as follows: calcium carbonate, allyltriethoxysilane, and anhydrous ethanol are mixed in a mass ratio of 1:3.5:25, ultrasonically dispersed for 35 min, and 3.5 times the mass of calcium carbonate in a 15% ammonia solution is added. The mixture is stirred at 50°C and 400 r / min for 4.5 h, filtered, washed three times each with anhydrous ethanol and deionized water, and dried at 55°C for 13 h to obtain pretreated calcium carbonate. 1,1,3,3,5,5-hexamethyltrisiloxane, 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are mixed in a molar ratio of... A polymerizable reaction solution was prepared by adding N,N-dimethylformamide in a ratio of 1:0.75 to 1,1,3,3,5,5-hexamethyltrisiloxane at a mass ratio of 1:4.5. A catalyst solution was prepared by mixing chloroplatinic acid and N,N-dimethylformamide at a mass ratio of 1:4.5. Pretreated calcium carbonate, the catalyst solution, and the polymerizable reaction solution were weighed in a mass ratio of 1:3.5:11. The pretreated calcium carbonate, 1 / 3 of the polymerizable reaction solution, and 1 / 3 of the catalyst solution were mixed and stirred at 75°C and 350 rpm for 25 min. The remaining polymerizable reaction solution and catalyst solution were added dropwise at a uniform rate over 20 min, and the reaction was continued with stirring for 2.5 h. The mixture was filtered, washed three times with anhydrous ethanol, and dried at 45°C under vacuum for 20 h to obtain modified calcium carbonate. The remaining steps were the same as in Example 2.

[0025] Comparative Example 4: The preparation method of the woody oil-based PVC printing film in Comparative Example 4 differs from that in Example 2 only in step (3). Step (3) is modified as follows: calcium carbonate, allyltriethoxysilane, and anhydrous ethanol are mixed in a mass ratio of 1:3.5:25, ultrasonically dispersed for 35 min, and 3.5 times the mass of calcium carbonate in a 15% ammonia solution is added. The mixture is stirred at 50°C and 400 r / min for 4.5 h, filtered, washed three times each with anhydrous ethanol and deionized water, and dried at 55°C for 13 h to obtain modified calcium carbonate. The remaining steps are the same as in Example 2.

[0026] Test Example 1 Flame retardant performance testing Test method: The examples and comparative examples were processed into 125mm×50mm×3mm specimens. The limiting oxygen index of the specimens was determined using a limiting oxygen index meter according to GB / T2406.2 standard. The results are shown in Table 1.

[0027] Table 1 Limiting oxygen index (%) Limiting oxygen index (%) Example 1 32.37 Comparative Example 1 28.21 Example 2 33.45 Comparative Example 2 32.04 Example 3 33.18 Comparative Example 3 32.17 Comparative Example 4 27.41 A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-4 in Table 1 reveals that the woody oil-based PVC printing film prepared by this invention has good flame-retardant properties.

[0028] By comparison, the limiting oxygen index of Examples 1-3 is greater than that of Comparative Example 1, indicating that esterified rubber seed oil is prepared by reacting rubber seed oil with ethanol 2-bis(phenyl)phosphophosphate, and modified rubber seed oil is prepared by epoxidizing the esterified rubber seed oil; phosphorus element is introduced into the modified rubber seed oil, and the introduction of phosphorus element can improve the flame retardant properties of woody oil-based PVC printing film.

[0029] By comparison, the limiting oxygen index of Examples 1-3 is greater than that of Comparative Example 4, indicating that pretreated calcium carbonate is prepared by reacting calcium carbonate with allyltriethoxysilane, introducing C=C double bonds into the pretreated calcium carbonate; premodified calcium carbonate is prepared by polymerizing 1,1,3,3,5,5-hexamethyltrisiloxane and 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione on the pretreated calcium carbonate via hydrosilylation reaction, introducing triazine structure, siloxane structure and epoxy group into the premodified calcium carbonate; the introduction of triazine structure and siloxane structure can further improve flame retardant performance.

[0030] Test Example 2 Anti-aging performance test Test method: In accordance with the relevant provisions of GB / T1040.2-2006, dumbbell-shaped type II standard specimens were prepared from the examples and comparative examples. The tensile strength M of the standard specimens was tested at a tensile rate of 100 m / min. The standard specimens were placed in an ultraviolet aging test chamber with a 500W straight-tube ultraviolet high-pressure mercury lamp at a distance of 45 cm from the specimen and an intensity of 1500 μW / cm. 2 The temperature was 40℃, and the irradiation time was 7 days. After the irradiation, the tensile strength N of the standard sample was tested. The performance retention rate of the standard sample before and after aging was calculated as N / M×100%. The results are shown in Table 2.

[0031] Table 2 Performance retention rate (%) Performance retention rate (%) Example 1 88.48 Comparative Example 1 88.32 Example 2 90.21 Comparative Example 2 70.41 Example 3 89.75 Comparative Example 3 76.91 Comparative Example 4 74.23 A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-4 in Table 2 reveals that the woody oil-based PVC printing film prepared by this invention has good anti-aging properties.

[0032] By comparison, the performance retention rates of Examples 1-3 were greater than those of Comparative Example 2, indicating that the reaction of cardamom and 3-bromopropyne yielded propynyl cardamom; the reaction of polyvinyl chloride and sodium azide yielded pre-modified polyvinyl chloride, and azide groups were introduced onto the side chains of the pre-modified polyvinyl chloride molecule; the azide groups on the pre-modified polyvinyl chloride were subjected to a click reaction with the alkynyl groups on the propynyl cardamom to obtain modified polyvinyl chloride; and cardamom was grafted onto the side chains of the modified polyvinyl chloride molecule. Cardamom is a natural chalcone-type compound with a main skeleton structure of 1,3-stilbene ketone, possessing an alternating single and double bond structure. It easily relaxes energy through a non-adiabatic pathway, and the hydroxyl groups and adjacent carbonyl groups in the structure can form intramolecular hydrogen bonds, further promoting the absorption of ultraviolet light and endowing the woody oil-based PVC printing film with excellent anti-aging properties.

[0033] By comparison, the performance retention rates of Examples 1-3 were greater than those of Comparative Examples 3-4, indicating that pretreated calcium carbonate was prepared by reacting calcium carbonate with allyltriethoxysilane, introducing C=C double bonds onto the pretreated calcium carbonate; pre-modified calcium carbonate was prepared by polymerizing 1,1,3,3,5,5-hexamethyltrisiloxane and 1-epoxyethylenemethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione onto the pretreated calcium carbonate via hydrosilylation, introducing epoxy groups onto the pre-modified calcium carbonate; modified calcium carbonate was prepared by reacting the epoxy groups on the pre-modified calcium carbonate with the amino group on 4-aminomethyl-2,2,6,6-tetramethylpiperidine, and grafting hindered amine structures onto the modified calcium carbonate. The introduction of hindered amine structures can further improve the excellent anti-aging properties of woody oil-based PVC printing films.

[0034] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A wood oil-based PVC printing film, characterized by, By mass fraction, including: modified polyvinyl chloride 70 parts, modified calcium carbonate 8~10 parts, modified rubber seed oil 20~22 parts, diisononyl phthalate 10~12 parts, barium zinc heat stabilizer 3~4 parts; The modified polyvinyl chloride is prepared by sequentially reacting polyvinyl chloride with sodium azide and propargyl myristicin; The propargyl myristicin is prepared by reacting myristicin and 3-bromopropargyl; The modified calcium carbonate is prepared by reacting pre-modified calcium carbonate and 4-aminomethyl-2,2,6,6-tetramethylpiperidine; The pre-modified calcium carbonate is prepared by polymerizing 1,1,3,3,5,5-hexamethyltrisiloxane and 1-oxiranylmethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione on pre-treated calcium carbonate; The pre-treated calcium carbonate is prepared by reacting calcium carbonate and allyl triethoxysilane; The modified rubber seed oil is prepared by esterification and epoxidation of rubber seed oil and 2-di(phenyl)phosphoric acid ethanol.

2. A method of preparing a wood oil based PVC printing film, characterized by, The preparation method of the woody oil-based PVC printing film comprises the following preparation steps: (1) uniformly mix esterified rubber seed oil, formic acid and ethyl acetate, stir at 50~60℃ for 10~20min, add 0.2~0.22 times the mass of the esterified rubber seed oil of hydrogen peroxide and 0.02~0.04 times the mass of the esterified rubber seed oil of concentrated sulfuric acid, continue to react for 5~6h, stand for layering, take the oil phase, wash with 10% sodium bicarbonate aqueous solution and deionized water at a temperature of 60℃ for 5 times respectively, and prepare modified rubber seed oil by rotary evaporation under reduced pressure; (2) uniformly mix polyvinyl chloride, sodium azide and N,N-dimethylformamide, stir and react at 30~40℃ for 20~24h, precipitate with a mixed solvent of methanol and deionized water in a volume ratio of 2:1, filter, dry, and prepare pre-modified polyvinyl chloride; uniformly mix pre-modified polyvinyl chloride, propargyl myristicin, 2,2'-dipyridyl, copper bromide and N,N-dimethylformamide under nitrogen protection, stir and react at room temperature for 20~24h, filter, add methanol to the filtrate to precipitate, filter, dry, and prepare modified polyvinyl chloride; (3) take pre-treated calcium carbonate, catalyst solution and polymerizable reaction liquid in a mass ratio of 1:(3~4):(10~12); mix pre-treated calcium carbonate, 1 / 3 of the polymerizable reaction liquid and 1 / 3 of the catalyst solution, react at 70~80℃ for 20~30min, uniformly drop the remaining polymerizable reaction liquid and catalyst solution within 20min, continue to stir and react for 2~3h, filter, wash and dry, and prepare pre-modified calcium carbonate; uniformly mix pre-modified calcium carbonate, 4-aminomethyl-2,2,6,6-tetramethylpiperidine and N,N-dimethylformamide, react at 50~60℃ for 5~6h, filter, wash and dry, and prepare modified calcium carbonate; (4) mixing modified polyvinyl chloride, modified calcium carbonate, modified rubber seed oil, diisononyl phthalate, barium-zinc heat stabilizer uniformly, placing in a rheometer, stirring at 180℃, 40~50r / min for 4~5min, placing in a flat vulcanizing machine, hot-pressing forming, naturally cooling to room temperature, to obtain a woody oil-based PVC printing film.

3. A method of preparing a wood-based oil-based PVC printing film according to claim 2, characterized in that, The mass fraction of the hydrogen peroxide in step (1) is 20%.

4. A method of preparing a wood-based oil-based PVC printing film according to claim 2, characterized in that, The preparation method of the esterified rubber seed oil in step (1) is as follows: mixing rubber seed oil, 2-di(phenyl)phosphoric acid ethanol, p-toluene sulfonic acid, reacting at 80~90℃ for 4~5h, filtering, drying the filtrate, to obtain the esterified rubber seed oil.

5. A method of preparing a wood-based oil-based PVC printing film according to claim 2, characterized in that, The preparation method of the propargyl cardamomine in step (2) is as follows: adding cardamomine and 3-bromopropargyl to acetone, adding potassium carbonate, stirring at 56℃ under reflux for 16~18h, filtering, drying the filtrate, to obtain the propargyl cardamomine.

6. A method of preparing a wood-based oil-based PVC printing film according to claim 2, characterized in that, The preparation method of the pretreated calcium carbonate in step (3) is as follows: mixing calcium carbonate, allyl triethoxysilane, anhydrous ethanol, ultrasonic dispersion, adding an ammonia water solution with a mass of 3~4 times that of the calcium carbonate, reacting at 50℃ for 4~5h, filtering, washing and drying, to obtain the pretreated calcium carbonate.

7. A method of preparing a wood-based oil-based PVC printing film according to claim 2, characterized in that, The preparation method of the polymerizable reaction liquid in step (3) is as follows: mixing 1,1,3,3,5,5-hexamethyltrisiloxane and 1-oxiranylmethyl-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione in a molar ratio of 1:(0.7~0.8) in N,N-dimethylformamide, to obtain the polymerizable reaction liquid.

8. A method of preparing a wood-based oil-based PVC printing film according to claim 2, characterized in that, The preparation method of the catalyst solution in step (3) is as follows: mixing chloroplatinic acid and N,N-dimethylformamide uniformly, to obtain the catalyst solution.

9. A method of preparing a wood-based oil-based PVC printing film according to claim 2, characterized in that, The dosages of the modified polyvinyl chloride, modified calcium carbonate, modified rubber seed oil, diisononyl phthalate and barium-zinc heat stabilizer in step (4) are as follows: 70 parts of modified polyvinyl chloride, 8~10 parts of modified calcium carbonate, 20~22 parts of modified rubber seed oil, 10~12 parts of diisononyl phthalate, and 3~4 parts of barium-zinc heat stabilizer.

10. A method of preparing a wood-based oil-based PVC printing film according to claim 2, characterized in that, The process parameters of the hot-pressing forming in step (4) are as follows: hot-pressing at 165~175℃, 6~7MPa for 5~6min, and hot-pressing at 12~14MPa for 2~3min.

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