CN110564165A

CN110564165A - Preparation method of agricultural anti-aging and anti-wear plastic bowl body soft disc material

Info

Publication number: CN110564165A
Application number: CN201910752701.3A
Authority: CN
Inventors: 刘超; 曹成茂; 刘正元; 汪永武; 李梦龙; 王骏; 吴问天; 余飞; 端梦云
Original assignee: Anhui Hongxiang Cheerful Agriculture Machinery Corp
Current assignee: Anhui Hongxiang Cheerful Agriculture Machinery Corp
Priority date: 2019-08-15
Filing date: 2019-08-15
Publication date: 2019-12-13

Abstract

The invention discloses a preparation method of an agricultural anti-aging and anti-wear plastic bowl soft disc material, which belongs to the technical field of high polymer materials. The agricultural anti-aging and anti-wear plastic bowl body soft disc material disclosed by the invention is beneficial to reducing the labor cost, lightening the labor intensity, being reusable, strong in cold and heat resistance, reducing the production cost, having good thermal stability and aging resistance, simplifying the planting technology, providing a powerful measure for saving the cost of planting and increasing the yield and the efficiency, and having good comprehensive performance.

Description

Preparation method of agricultural anti-aging and anti-wear plastic bowl body soft disc material

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a preparation method of an agricultural anti-aging and anti-wear plastic bowl body floppy disk material.

Background

The plastic pot seedling transplanting technology is a new cultivation technology which is labor-saving, high-yield, stable in yield and remarkable in economic benefit. The method has the advantages of convenient centralized management, strong seedlings, less plant diseases and insect pests, no damage to roots, seedling cultivation and rejuvenation, high survival rate, seed saving, early maturity, staggered cross-selling, production peak period, yield improvement, income increase of more than 560 yuan, labor saving, time saving and the like, and is deeply welcomed by farmers. The forming and material of the bowl soft disc and the most suitable forming process for producing the bowl soft disc adopt plastic suction forming, perforation is easy to occur in the vacuum plastic suction forming process, the forming effect is influenced, the bottom of the bowl body is thinner, the bowl body does not meet the agricultural requirement, the production efficiency is also higher, and the production material is improved. The plastic bowl soft disks on the market at present are mostly made of polyethylene and polypropylene with poor weather resistance and polyvinyl chloride with poor heat resistance, and for the bowl plastic soft disks, the bowl plastic soft disks are prepared by adopting applicable and economical materials, but for being used as preservative films, the polyethylene and polypropylene bowl soft disks are slightly poor in toughness and strength compared with the PVC bowl soft disks and are easy to break. But the PVC pot-keeping body floppy disk is not suitable for cultivation of crops containing oil and fat, can not be heated at high temperature, and has the use limitation that the PVC material has poor heat resistance, can be decomposed and release hydrogen chloride gas when meeting high temperature, the plasticizers DEHP and DOP (dioctyl phthalate) and a small amount of heat stabilizer are usually added to reduce the processing temperature, the PVC material is a hard material, and can become soft and easy to bend after being added with the plasticizer, the plasticizers DEHP and DOP have hepatotoxicity, can cause the plasticizer represented by cancer, can be easily enriched in organisms, are generally colorless oily viscous liquid, the chemical structure determines the basic physicochemical properties of the PVC pot-keeping body floppy disk, the compounds have the characteristics of large liquidity, low water solubility, difficult volatilization, low freezing point and long residual time in the environment, have general toxicity and special toxicity, such as teratogenicity, mutagenicity or carcinogenic activity, especially, the most concerned about the abnormal reproductive function of human body, DOP has a mutagenic effect on the reproductive cells, plays a role of estrogen-like hormone in vivo, interferes with endocrine, and is classified as an environmental hormone. DEHP and DOP are listed as toxic pollutants for priority control by the EPA of the national environmental protection agency of America, DEP, DMP and DOP are also listed as black lists for environment priority control pollutants in China, and the materials are not wear-resistant, have poor low-temperature performance, are easy to tear, have short service life and increase the production cost. The existing plastic bowl body soft disk material cannot meet the use requirements of the existing production and life, and the technical personnel in the field need to develop an anti-aging plastic bowl body soft disk material with excellent comprehensive performance so as to meet the requirements of the vast agricultural production and life and application.

Disclosure of Invention

the invention aims to solve the existing problems and provides a preparation method of an agricultural anti-aging and anti-wear plastic bowl body floppy disk material.

A preparation method of agricultural anti-aging and anti-wear plastic bowl body floppy disk material comprises the following steps:

the method comprises the steps of firstly, adding 100 ~ 113 parts of soybean oil, 20.2 ~ 22.3 parts of glycerol triacetate and 0.5 ~ 0.9 part of dibutyltin maleate into a reaction kettle with a stirring device, a thermometer and a reflux condenser in sequence, introducing nitrogen, stirring and heating, adding 2.1 ~ 2.4 parts of sodium hydroxide when the temperature reaches 130 ~ 140 ℃, carrying out heat preservation and stirring reaction for 1 ~ 2 hours at 180 ~ 200 ℃ to obtain a champagne yellow product, secondly, adding 275 ~ 313 parts of the champagne yellow product, 19 ~ 22 parts of acetic acid into a reaction kettle with a stirring device, a thermometer, a dropping funnel and a reflux condenser, heating to 50 ~ 55 ℃ under stirring, slowly dropping 10 ~ 23 parts of 20 ~ 25% hydrogen peroxide by volume fraction, 0.5 ~ 0.7 part of 98% by mass fraction, reacting for 3 ~ 4 hours at 75 ~ 80 ℃ after completion of extrusion, separating a lower layer, washing upper layer with vinyl ester, pressing to neutral water, filtering, modifying, adding modified epoxy resin, stirring, a polypropylene resin, a polypropylene.

further, the modified filler is modified sericite powder, and the specific modification method comprises the steps of adjusting the pH value of 1 ~ 2.5 parts of a coupling agent KH ~ 560 and 28 ~ 30 parts of absolute ethanol to 4 ~ 5 by using a hydrochloric acid solution with the mass fraction of 15 ~ 17%, stirring and hydrolyzing at room temperature, then adjusting 100 parts of sericite powder by using absolute ethanol, dispersing, then adding the hydrolyzed coupling agent, stirring for 10 ~ 20min at 50 ~ 55 ℃, then filtering at room temperature, and drying for 10 ~ 12h at 70 ~ 80 ℃ to obtain the modified filler.

further, the vinyl acetate ~ vinyl chloride ~ vinyl acetate copolymer is vinyl acetate ~ vinyl chloride ~ vinyl acetate copolymer with the content of 20 ~ 24% and the K value of 47 ~ 58.

furthermore, the ethylene ~ vinyl acetate copolymer has a vinyl acetate content of 19 ~ 23% and a melt index of 1.5 ~ 2.0g/10 min.

Further, the lubricant is one of boronized succinimide, polyisobutylene succinate and melamine cyanurate; the dispersant is selected from one of sodium stearate, dioctyl sebacate and acetyl tri-n-butyl citrate.

Further, the anti-aging agent is one or more of diphenyl octyl phosphite, dimethyl methylphosphonate, zinc diisobutyl dithiophosphate and molybdenum diisobutyl dithiocarbamate.

The invention has the beneficial effects that:

The method prepares the epoxidized soybean oil resin through esterification reaction and epoxidation reaction, takes the epoxidized soybean oil resin as a modified component, namely plasticized vinyl chloride-vinyl acetate resin and ethylene-vinyl acetate copolymer, not only plays a role of plasticizing the vinyl chloride-vinyl acetate resin, but also has good plasticizing effect on the vinyl chloride-vinyl acetate resin because of an epoxy group and a resin structure forming a high-molecular long chain, reduces the use of the plasticizer, avoids the migration of the plasticizer, has wide cyclic regeneration sources of the soybean oil, greatly reduces the production cost, and can further play the internal plasticizing role of the vinyl chloride-vinyl acetate resin, so that the method does not add a large amount of plasticizer like the prior art, only depends on 'internal plasticization' to realize the service performance and the molding of the plastic bowl body floppy disc, has convenient molding and processing, simple process and greatly reduces the production cost, is obviously different from the prior preparation technology of the plastic bowl body floppy disc added with the liquid plasticizer, the prepared epoxy soybean oil resin has epoxy groups which can generate a synergistic effect with components such as an anti-aging agent, a lubricant and the like to play a role of a synergistic stabilizer, further, due to the existence of vinyl acetate blocks, the system has good compatibility and cannot generate micro-phase separation, the epoxy soybean oil resin is used as a compatilizer to further promote the compatibility of the epoxy soybean oil resin and the lubricant, the coupling modification of the modified filler is carried out to improve the hydrophobicity and lipophilicity of the filler, the wrapping effect of a resin matrix on filler powder is improved, the agglomeration of the powder is reduced, the epoxy soybean oil resin is uniformly dispersed in a plastic matrix to play a good reinforcing effect, the sericite powder has wide sources, the cost is low, the modification treatment mode is simple, the aim is to improve the lipophilicity of the filler and improve the lipophilicity of the filler, and the epoxy soybean oil resin has a good combination effect with the epoxy soybean oil resin, the function capability of the epoxidized soybean oil resin which can play multiple roles is indirectly improved, so that the epoxidized soybean oil resin has the strength which cannot be achieved independently, and the dispersion capability of the epoxidized soybean oil resin is further improved. The invention uses the dispersant and the lubricant to uniformly disperse the components, has good forming capability, and the obtained sheet has average mechanical property and better heat resistance and low temperature resistance.

Compared with the prior art, the invention has the following advantages:

the present invention relates to a plastic pot soft disc, which is characterized in that a plastic pot soft disc is used as a plastic pot seedling transplanting machine, and the plastic pot soft disc is used as a plastic pot seedling transplanting machine, so that the plastic pot seedling transplanting machine has the advantages of good heat resistance, good seedling transplanting efficiency, and the like.

Detailed Description

The invention is illustrated by the following specific examples, which are not intended to be limiting.

Example 1

Firstly, adding 113 parts of soybean oil, 22.3 parts of glycerol triacetate and 0.9 part of dibutyltin maleate into a reaction kettle with a stirring device, a thermometer and a reflux condenser in sequence, introducing nitrogen, stirring and heating, adding 22.4 parts of sodium hydroxide when the temperature reaches 140 ℃, keeping the temperature and stirring for reaction for 2 hours at 200 ℃, and finishing the reaction to obtain a champagne yellow product; secondly, adding 313 parts of the champagne yellow product and 22 parts of acetic acid in the step one into a reaction kettle with a stirring device, a thermometer, a dropping funnel and a reflux condenser, raising the temperature to 55 ℃ under stirring, slowly dropping 23 parts of hydrogen peroxide with the volume fraction of 25% and 0.7 part of concentrated sulfuric acid with the mass fraction of 98%, reacting for 4 hours at 80 ℃ after the addition is finished, separating acid water on the lower layer, washing the oil ester on the upper layer with alkaline water and water to be neutral, distilling under pressure to remove water and filtering to obtain modified epoxy soybean oil resin; mixing 40 parts of sebacic acid, 110 parts of hydroquinone and 4 parts of dimethylaminopyridine for 5 minutes at 1200 ℃, sequentially adding the mixture into a high-speed mixer, mechanically stirring the mixture for 5 minutes at the rotating speed of 300 revolutions per minute, then adding 63 parts of ethylene-vinyl acetate copolymer, 56 parts of vinyl chloride-vinyl acetate resin, 226.5 parts of dispersing agent, 0.4 part of lubricating agent and 20 parts of modified filler, fully stirring the mixture for 15 minutes at the rotating speed of 1000 revolutions per minute and at the temperature of 70 ℃, adding 0.4 part of anti-aging agent and 0.4 part of ultramarine blue, extruding the mixture into sheets to obtain the plastic bowl body flexible disk sheet, wherein the process of extruding the sheets is a double-screw extruder, the screw diameter is 100mm, the L/D =30 and the epsilon =4, and the temperature of the extruder is set as follows: the setting temperature of the charging barrel is 140 ℃, 150 ℃, 155 ℃, 155 ℃, the filter, the die head and the material temperature of the machine head is 155 ℃ in sequence; fourthly, controlling the molding temperature of the plastic bowl body floppy disk sheet obtained in the third step to 148 ℃, controlling the heating rate to be 35 ℃/min, controlling the heating time of the whole molding process to be 15s, immediately conveying the softened sheet after heating and softening molding into a plastic suction mold in a vacuum plastic suction molding machine, starting a vacuum machine, moving the mold upwards and vacuumizing, stretching and deforming the plastic suction sheet under the action of the air pressure difference formed between the upper surface and the lower surface, so that the softened material is adsorbed on the surface of the mold, the vacuum degree is-0.3 MPa, the vacuumizing time is 5 seconds, the pressure maintaining time is 1 minute, soaking the molded sheet into cold water at 10 ℃ for cooling for 2 minutes, and cutting to obtain the agricultural anti-aging and anti-wear plastic bowl body floppy disk material.

Further, the modified filler is modified sericite powder, and the specific modification method comprises the steps of adjusting the pH value of 2.5 parts of a coupling agent KH-560 and 30 parts of absolute ethanol to 5 by using a hydrochloric acid solution with the mass fraction of 17%, stirring and hydrolyzing at room temperature, then, mixing 100 parts of sericite powder with absolute ethanol, dispersing, then, adding the hydrolyzed coupling agent, stirring for 20min at the temperature of 55 ℃, then, filtering at room temperature, and drying for 12h at the temperature of 80 ℃ to obtain the modified filler.

further, the vinyl acetate-vinyl chloride copolymer resin is vinyl acetate-vinyl chloride copolymer resin with the content of 24% and the K value of 58.

Further, the ethylene-vinyl acetate copolymer has a vinyl acetate content of 23% and a melt index of 2.0g/10 min.

further, the lubricant is melamine cyanurate; the dioctyl sebacate.

Further, the anti-aging agent is molybdenum diisobutyl dithiocarbamate.

Example 2

Firstly, sequentially adding 100 parts of soybean oil, 20.2 parts of glycerol triacetate and 0.5 part of dibutyltin maleate into a reaction kettle with a stirring device, a thermometer and a reflux condenser, introducing nitrogen, stirring and heating, adding 2.1 parts of sodium hydroxide when the temperature reaches 130 ℃, preserving heat at 180 ℃, stirring and reacting for 1 hour, and finishing the reaction to obtain a champagne yellow product; adding 275 parts of the champagne yellow product obtained in the step one and 19 parts of acetic acid into a reaction kettle with a stirring device, a thermometer, a dropping funnel and a reflux condenser, heating to 50 ℃ under stirring, slowly dropping 10 parts of hydrogen peroxide with the volume fraction of 20% and 0.5 part of concentrated sulfuric acid with the mass fraction of 98%, reacting for 3 hours at 75 ℃ after the addition is finished, separating acid water at the lower layer, washing the oil ester at the upper layer with alkaline water and water to be neutral, distilling under pressure to remove water, and filtering to obtain modified epoxy soybean oil resin; thirdly, mixing 30 parts of sebacic acid, 100 parts of hydroquinone and 2 parts of dimethylaminopyridine for 5 minutes at 180 ℃, sequentially adding the mixture into a high-speed mixer, mechanically stirring the mixture for 4 minutes at the rotating speed of 100 revolutions per minute, then adding 49 parts of ethylene-vinyl acetate copolymer, 45 parts of vinyl chloride-vinyl acetate resin, 25.2 parts of dispersing agent, 0.3 part of lubricating agent and 15 parts of modified filler, fully stirring the mixture for 5 minutes at the rotating speed of 1000 revolutions per minute and the temperature of 65 ℃, adding 0.2 part of anti-aging agent and 0.2 part of ultramarine blue, extruding the mixture into sheets to obtain the plastic bowl body flexible disk sheet, wherein the process of extruding the sheets is a double-screw extruder, the screw diameter is 100mm, the L/D =25, and the epsilon =3.5, and the temperature of the extruder is set as follows: the setting temperature of the charging barrel is 130 ℃, 140 ℃, 150 ℃, 155 ℃, 155 ℃, 155 ℃, the filter, the die head and the material temperature at the machine head are 155 ℃ in sequence; fourthly, controlling the molding temperature of the plastic bowl body floppy disk sheet obtained in the third step to 148 ℃, controlling the heating rate to be 35 ℃/min, controlling the heating time of the whole molding process to be 15s, immediately conveying the softened sheet after heating and softening molding into a plastic suction mold in a vacuum plastic suction molding machine, starting a vacuum machine, moving the mold upwards and vacuumizing, stretching and deforming the plastic suction sheet under the action of the air pressure difference formed between the upper surface and the lower surface, so that the softened material is adsorbed on the surface of the mold, the vacuum degree is-0.3 MPa, the vacuumizing time is 5 seconds, the pressure maintaining time is 1 minute, soaking the molded sheet into cold water at 10 ℃ for cooling for 2 minutes, and cutting to obtain the agricultural anti-aging and anti-wear plastic bowl body floppy disk material.

further, the vinyl acetate-vinyl chloride copolymer resin is vinyl acetate-vinyl chloride copolymer resin with the content of 20% and the K value of 58.

Further, the ethylene-vinyl acetate copolymer has a vinyl acetate content of 19% and a melt index of 1.5g/10 min.

Further, the lubricant is boronized succinimide; the dispersant is acetyl tri-n-butyl citrate.

Further, the anti-aging agent is one or more of zinc diisobutyl dithiophosphate and molybdenum diisobutyl dithiocarbamate.

Comparative example 1

In this comparative example, compared with example 2, in the third step, the vinyl chloride-vinyl acetate resin component was omitted, except that the process steps were the same.

Comparative example 2

In this comparative example, compared with example 2, in step three, the modified filler component was omitted except that the process steps were the same.

Comparative example 3

This comparative example is compared to example 2, with the exception that step one and step two are omitted, except that the process steps are otherwise identical.

Comparative example 4

This comparative example compares to example 2 in step three, the sebacic acid was omitted except that the process steps were the same.

Comparative example 5

This comparative example compares to example 2 in step three, the dispersant is omitted except that the process steps are otherwise the same.

Comparative example 6

This comparative example compares with example 2 in step three, the ethylene-vinyl acetate copolymer component is omitted except that the process steps are the same.

TABLE 1 Performance test results of agricultural anti-aging and anti-wear plastic bowl floppy disk material

Note: adjusting the state of the sample in a standard environment with the relative humidity of 50% at 23 ℃ for not less than 4h, and performing the test under the environment condition; folding resistance: the two sides of the plastic bowl body soft disc in the length direction are respectively folded by 90 degrees towards the front and the back, which is the condition that any part of the seedling raising tray is broken after being folded for 30 times; the breaking force is tested by a tensile testing machine; low temperature resistance: placing the soft test pot body disc into a cold box at the temperature of minus 25 ℃ for storage for 72 hours, and respectively folding two sides of the soft plastic pot body disc in the length direction by 90 degrees towards the front side and the back side, wherein the soft test pot body disc is unqualified if any part of the seedling raising disc is broken after being folded for 30 times; randomly extracting 10 samples/sleeving a flexible disk into a clamp, stretching at the speed of 200mm/min until the flexible disk is broken, recording the tension force during breaking, calculating the average value of 10 tensile breaking forces, wherein the unit is N, and measuring the folding endurance times; measurement of pressure resistance: placing a plastic pot body soft disk between two paper boards with flat surfaces, placing a weight 2lkg stably at the center and at a distance of 50m from four corners on the paper boards respectively, discharging the plastic pot body soft disk after continuously lmin, and inspecting by using an visual inspection method; the glass transition temperature was measured using DMAQ 800; testing the tensile strength of the high temperature resistance for 72 hours at 100 ℃; ultraviolet aging GB/T16422.3-2014 Plastic laboratory light Source Exposure test method part 3: fluorescent uv lamp UVB72h, tensile force was tested.

Claims

1. A preparation method of an agricultural anti ~ aging and anti ~ wear plastic bowl body soft disk material is characterized by comprising the steps of firstly, adding 100 ~ 113 parts of soybean oil, 20.2 ~ 22.3 parts of glyceryl triacetate and 0.5 ~ 0.9 part of dibutyltin maleate into a reaction kettle with a stirring device, a thermometer and a reflux condenser tube in sequence, introducing nitrogen, stirring and heating up, when the temperature reaches 130 ~ 140 ℃, adding 2.1 ~ 2.4 parts of sodium hydroxide, carrying out heat preservation stirring reaction for 1 ~ 2 hours at 180 ~ 200 ℃, finishing the reaction to obtain a champagne yellow product, secondly, adding 275 ~ 313 parts of champagne yellow product, 19 ~ 22 parts of acetic acid into a reaction kettle with a stirring device, a dropping funnel and a reflux condenser tube, stirring and heating to 50 ~ 55 ℃, slowly dropping 10 ~ 23 parts of hydrogen peroxide with a volume fraction of 20 ~ 25% under stirring, a plastic suction molding process with a vacuum degree of 20 ~ 7 parts of 98 ~ 0.5 ℃ to 0.7 parts of a plastic bowl body soft disk material, adding vinyl ester, a vacuum forming soft resin, a plastic bowl body soft disk material with a vacuum distillation speed of 150 ~ 2.1 ~ 2.4.4 ~ 150 ~ 140 ℃ of an epoxy resin, stirring machine, heating a plastic bowl body soft disk, a plastic bowl body soft molding machine with a vacuum distillation machine head for 20 ~ 2.1 ~ 2.4.4.4.4 ~ 2min, a vacuum distillation speed, a vacuum distillation machine head for 20 ~ 150 ~ 140 ℃ of a vacuum distillation machine, a vacuum distillation machine head for 20 ~ 150 ~ 140 ℃ to 150 ~ 150 mm thick film forming machine, stirring machine, stirring, removing a vacuum ~ 150.

2. the preparation method of the plastic bowl body floppy disk material particles according to claim 1, characterized in that the modified filler is modified sericite powder, and the specific modification method is that 1 ~ 2.5 parts of coupling agent KH ~ 560 and 28 ~ 30 parts of absolute ethyl alcohol are adjusted to pH 4 ~ 5 with 15 ~ 17% by mass of hydrochloric acid solution, stirred and hydrolyzed at room temperature, then 100 parts of sericite powder is mixed and dispersed with absolute ethyl alcohol, then the hydrolyzed coupling agent is added, stirred at 50 ~ 55 ℃ for 10 ~ 20min, filtered at room temperature, and dried at 70 ~ 80 ℃ for 10 ~ 12h to obtain the modified filler.

3. the method for preparing plastic bowl body floppy disk material particles according to claim 1, characterized in that said vinyl chloride ~ vinyl acetate resin is vinyl acetate with a content of 20 ~ 24% and a K value of 47 ~ 58.

4. the method for making plastic bowl body floppy disk material particles according to claim 1, characterized in that the ethylene ~ vinyl acetate copolymer has a vinyl acetate content of 19 ~ 23% and a melt index of 1.5 ~ 2.0g/10 min.

5. The method of claim 1 wherein the lubricant is one of a succinimide boride, a polyisobutylene succinate, and a melamine cyanurate; the dispersant is selected from one of sodium stearate, dioctyl sebacate and acetyl tri-n-butyl citrate.

6. The method of making plastic bowl body floppy disk material pellets in accordance with claim 1 wherein the anti-aging agent is one or more of diphenyl octyl phosphite, dimethyl methylphosphonate, zinc diisobutyl dithiophosphate, molybdenum diisobutyl dithiocarbamate.