CN109575536B - Modified polyglycolic acid biodegradable mulching film and preparation method thereof - Google Patents
Modified polyglycolic acid biodegradable mulching film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a mulching film, in particular to a modified polyglycolic acid biodegradable mulching film and a preparation method thereof. The modified polyglycolic acid biodegradable mulching film is prepared from the following raw materials in parts by weight: 15-45 parts of polyglycolic acid, 40-80 parts of poly butylene succinate-co-terephthalate, 5-15 parts of compatilizer, 0.5-1.5 parts of slipping agent, 0.5-1 part of hydrolysis resistant agent, 0.1-0.5 part of antioxidant, 0.1-0.5 part of light aging resistant agent, 0.5-1 part of antibacterial agent and 5-20 parts of lightweight modified composite material; the lightweight modified composite material is prepared from 0.1-0.5 part of epoxy chloropropane, 1-2 parts of beta-cyclodextrin, 1-2 parts of potassium aluminum silicate and 5-10 parts of mesoporous silicon dioxide. The invention has excellent heat preservation and soil moisture preservation performance and obvious light weight effect. The preparation method is simple and easy to implement and is easy to realize.
Description
Technical Field
The invention relates to a mulching film, in particular to a modified polyglycolic acid biodegradable mulching film and a preparation method thereof.
Background
The mulching film has a great effect, can improve the ground temperature, retain water, soil and fertilizer, and has certain weeding function. In the 60 s of the 20 th century, the technology of mulching film was developed in japan, europe, and the united states, and gradually popularized. Since 1978, the agricultural film mulching cultivation technology is widely popularized in China, the mulching area of agricultural films is only 2.5 ten thousand mu in 1980, 1.35 hundred million mu in 2005, more than 4 hundred million mu in 2017, and more than 150 million tons of mulching films are used, so that the agricultural film mulching cultivation technology is the country with the most amount of mulching films in the world.
However, in order to reduce costs, the thickness of the mulching film is becoming thinner and thinner, and as the amount of the mulching film used increases year by year, the recycling of the mulching film becomes more and more difficult. A large amount of waste agricultural films are accumulated in soil year after year, are extremely difficult to degrade under natural conditions, and the harm of the waste agricultural films is increasingly highlighted. On the one hand, the residual agricultural film in the cultivated land is continuously increased, the original structure of the soil is damaged, and the soil fertility level is reduced along with the damage. Meanwhile, the residual film directly influences the growth and uniform distribution of the root system of the crop, and hinders the absorption of the crop on water and nutrients, so that the yield of the crop is reduced. On the other hand, the residual films on the edges and the ground are abandoned at will and blown away by wind, which affects the natural landscape and the environmental sanitation of the countryside. The residual film is mixed with the straw and the pasture, the disease and even death can be caused after the residual film is eaten by livestock by mistake, and the residual film can be randomly stacked or burnt to cause secondary pollution. The residual pollution of the waste agricultural film becomes a serious threat to the sustainable development of agriculture, so that the white pollution of the farmland can be effectively prevented and controlled.
In recent years, the wide application of biodegradable materials brings opportunities to the mulching film industry. The biodegradable material is used for completely replacing the traditional material PE, and is one of effective ways for solving the problem of mulching film pollution. At present, biodegradable materials which have been industrially produced include polyglycolic acid (PGA), polylactic acid (PLA), poly (butylene adipate/terephthalate) (PBAT), poly (butylene succinate) (PBS), poly (butylene succinate-adipate-butylene succinate) (PBSA), poly (butylene succinate-co-terephthalate) (PBST), Polycaprolactone (PCL), Polyhydroxyalkanoates (PHAs), polypropylene carbonate (PPC), and the like.
The materials of the degradable mulching films disclosed by the inventions of CN103819794A, CN106336567A, CN105001568A and the like all contain polyethylene, but the polyethylene cannot be biodegraded, so the degradable mulching films in the patents are not completely biodegraded.
The degradable mulching films disclosed by the inventions of CN104109359A, CN106117622A and the like contain polyvinyl alcohol, the main chain of a polyvinyl alcohol molecule is a carbon-carbon chain, the polyvinyl alcohol molecule is the same as polyethylene and cannot be biodegraded, and the polyvinyl alcohol is a water-soluble material, so that the polyvinyl alcohol is not suitable for being used as the mulching film because the polyvinyl alcohol is a risk of dissolving and breaking holes when encountering rainwater.
The biodegradable mulching films disclosed by the inventions of CN106221165A, CN106046725A and the like are respectively added with plasticizers with different contents, and the mulching films are very thin and have large specific surface area, so that the plasticizers are easy to migrate out when being used in an outdoor natural environment and are not beneficial to the stability of the mulching films.
The invention discloses a full-biodegradable mulching film such as CN106084700A, CN103709687A, CN103709695A and the like, which is respectively added with 20-50% of calcium carbonate, 5-40% of modified talcum powder and 0.1-5% of modified talcum powder. Due to the addition of the talcum powder or the calcium carbonate, the density of the material is further increased, the cost of the mulching film is increased, and the popularization is not facilitated.
In addition, the density of the traditional PE material is 0.92-0.95g/cm3The density of the biodegradable material is 1.25-1.30g/cm3Approximately 1.3 times the density of conventional PE materials. The unit price of the traditional PE material is about 10000 yuan/ton, while the unit price of the biodegradable material is 20000- & lt 40000 yuan/ton, which is about 2 times of the unit price of the traditional PE material.
In conclusion, the market competitiveness can be improved only by reducing the cost of the biodegradable mulching film. The most effective means for reducing the cost is the light weight of the biodegradable mulching film, and the pure pursuit of light weight inevitably affects the heat preservation and soil moisture preservation performance of the biodegradable mulching film, so that the improvement of the heat preservation and soil moisture preservation performance of the biodegradable mulching film on the basis of reducing the density of the biodegradable mulching film is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a modified polyglycolic acid biodegradable mulching film with low density and excellent heat preservation and soil moisture preservation performance; the invention also provides a preparation method thereof.
The invention relates to a modified polyglycolic acid biodegradable mulching film which is prepared from the following raw materials in parts by weight: 15-45 parts of polyglycolic acid, 40-80 parts of poly butylene succinate-co-terephthalate, 5-15 parts of compatilizer, 0.5-1.5 parts of slipping agent, 0.5-1 part of hydrolysis resistant agent, 0.1-0.5 part of antioxidant, 0.1-0.5 part of light aging resistant agent, 0.5-1 part of antibacterial agent and 5-20 parts of lightweight modified composite material; the lightweight modified composite material is prepared from 0.1-0.5 part of epoxy chloropropane, 1-2 parts of beta-cyclodextrin, 1-2 parts of potassium aluminum silicate and 5-10 parts of mesoporous silicon dioxide.
Wherein:
the preparation method of the lightweight modified composite material comprises the steps of carrying out crosslinking reaction on epoxy chloropropane and beta-cyclodextrin to prepare epoxy chloropropane crosslinked-beta-cyclodextrin, and sequentially introducing aluminum potassium silicate and mesoporous silicon dioxide in the crosslinking reaction process.
The specific preparation process of the lightweight modified composite material is as follows: sodium hydroxide is used as a catalyst, and 1 to 2 parts of beta-cyclodextrin and 0.1 to 0.5 part of epichlorohydrin are subjected to crosslinking reaction for 1.5 to 2.5 hours at the temperature of between 60 and 70 ℃ to obtain the beta-cyclodextrin. Wherein, 1-2 parts of potassium aluminum silicate and 5-10 parts of mesoporous silicon dioxide are sequentially introduced when the reaction is carried out for 1-1.2 hours.
The mesh number of the aluminum potassium silicate is 4000-6000 meshes.
The aperture of the mesoporous silica is 5-30nm, and the mesh number is 4000-6000 meshes.
The melting point of the polyglycolic acid is 160-; the melting point of the poly (butylene succinate) -co-terephthalate is 115 ℃ and 130 ℃, and the melt index is less than or equal to 5.0g/10min (190 ℃, 2.16 kg).
The compatilizer is a glycolic acid-succinic acid butanediol ester copolymer, the mass ratio of glycolic acid to succinic acid butanediol ester is 1:2-3, the melting point is 120-140 ℃, and the melt index is less than or equal to 10.0g/10 min.
The slipping agent is polyethylene wax grafted glycidyl methacrylate, the melting point is 105 ℃ and 125 ℃, and the grafting rate is 0.5-1.5%.
The hydrolysis resisting agent is dicyclohexylcarbodiimide or N, N' -diisopropylcarbodiimide.
The antioxidant is calcium dodecahydroxystearate, zinc dodecahydroxystearate or magnesium dodecahydroxystearate.
The anti-light aging agent is poly (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate.
The antibacterial agent is piroctone.
The preparation method of the modified polyglycolic acid biodegradable mulching film comprises the steps of firstly carrying out crosslinking reaction on epoxy chloropropane and beta-cyclodextrin to prepare epoxy chloropropane crosslinked-beta-cyclodextrin, sequentially introducing aluminum potassium silicate and mesoporous silica in the crosslinking reaction process to prepare a lightweight modified composite material, and then blending, extruding and blow-molding the lightweight modified composite material, polyglycolic acid, polybutylene succinate-co-butylene terephthalate, a compatilizer, a slipping agent, an anti-hydrolysis agent, an antioxidant, an anti-light aging agent and an antibacterial agent to prepare the modified polyglycolic acid biodegradable mulching film.
The most important functions of the mulching film are heat preservation and soil moisture preservation. According to the invention, the mesoporous material is added into the mulching film for the first time, namely, hollow structures are introduced into the microstructure of the mulching film, and the hollow structures are contributed by the mesoporous material, so that the gram weight of the mulching film with the same thickness in unit area is reduced, namely, the density of the mulching film is obviously reduced, and the purpose of reducing the cost of the mulching film is realized. Meanwhile, due to the introduction of the mesoporous silica, the mulching film can be reinforced to a certain extent, and the microporous structure of the mesoporous silica can improve the heat preservation effect of the mulching film.
Although the introduction of the mesoporous silica plays a role in heat preservation to a certain extent, the role of preserving soil moisture is weaker. The outside of the beta-cyclodextrin is hydrophilic and does not have the function of preserving soil moisture, but when the beta-cyclodextrin and epoxy chloropropane are crosslinked to form a hydrophobic cavity structure, water drops or water vapor adsorbed on the inner surface of the mulching film can be blocked in the mulching film, so that the function of preserving soil moisture is realized. Moreover, after the beta-cyclodextrin is crosslinked with the epichlorohydrin, the strength is greatly increased.
Meanwhile, a hydrophobic cavity structure formed after the beta-cyclodextrin and the epichlorohydrin are crosslinked can also cooperate with micropores of the mesoporous silica to play a heat preservation function. The potassium aluminosilicate has a layered structure, and after the mesoporous silica is added, the mesoporous silica can be loaded in the layered structure of the potassium aluminosilicate, so that the stability of the mesoporous silica in the lightweight modified composite material is improved, and the mesoporous silica is not easy to separate from the lightweight modified composite material.
In addition, the mesoporous silica and the potassium aluminum silicate both form a hydrogen bond effect with hydroxyl of the epichlorohydrin crosslinked-beta-cyclodextrin, and the stability of the mesoporous silica in the lightweight modified composite material is also improved. Due to the existence of the mesoporous silica micropores and the hydrophobic cavity structure, the lightweight of the mulching film can be synergistically promoted while the heat preservation and soil moisture preservation effects are improved.
Because the density of the biodegradable material is generally higher than that of PE by more than 30%, the cost of the biodegradable mulching film is increased invisibly, and the biodegradable mulching film is not beneficial to popularization and application. Therefore, the density of the mulching film is reduced and the cost of the biodegradable mulching film is reduced while the heat preservation and soil moisture preservation functions of the mulching film are ensured, so that the market competitiveness of the mulching film can be improved, and a foundation is laid for the popularization and application of the biodegradable mulching film.
In order to solve the compatibility of PGA and PBST, a glycolic acid-succinic acid butanediol ester copolymer (PGA-co-BS) is introduced into a system, and the micro interface compatibility of the PGA and the PBST is greatly improved by utilizing the principle of similar compatibility, so that the mechanical property of the material is improved.
The PGA-co-BS copolymer is prepared by reacting low molecular weight PGA (molecular weight 1-5 ten thousand) and low molecular weight BS (molecular weight 2-5 ten thousand) in a mass ratio of 1:3 under the chain extension of isocyanate MDI, and the molecular weight is 5-10 ten thousand.
Although the lubricating effect of the common slipping agent is good, the migration speed of the common slipping agent is too high due to poor compatibility with biodegradable materials, and a layer of precipitate is easily formed on the surface layer of the mulching film to influence the transparency of the mulching film. The selected slipping agent is polyethylene wax grafted glycidyl methacrylate (PE-g-GMA), and the GMA is grafted on the polyethylene wax, so that an epoxy group on the GMA can react with terminal hydroxyl groups on molecular chains of PGA and PBST, thereby greatly improving the compatibility of the slipping agent and the biodegradable material and reducing the migration speed.
The preparation process of the polyethylene wax grafted glycidyl methacrylate comprises the following steps: 0.001 part of dicumyl peroxide (DCP) and 100 parts of polyethylene wax are uniformly mixed, then the mixture is added into a double-screw extruder with the length-diameter ratio of 48:1, and simultaneously 1-2 parts of GMA is quantitatively added into a screw through a liquid injection pump at the front end of the screw, so that PE-g-GMA with the melting point of 105-125 ℃ and the grafting rate of 0.5-1.5% is obtained.
In a natural environment, the mulching film can be hydrolyzed, oxidized and degraded, photodegraded and biodegraded under the action of water, air, illumination and microorganisms, in order to inhibit various degradations and prolong the service life of the mulching film, a hydrolysis resistant agent, an antioxidant, a light aging resistant agent and an antibacterial agent are correspondingly added into a system, and the using effect of the degradable mulching film is ensured through the adjustment of various auxiliary agents.
The invention has the following beneficial effects:
the mesoporous silica introduced into the system plays a role in lightening and strengthening the mulching film, and the microporous structure of the mesoporous silica can also improve the heat preservation effect of the mulching film; after the beta-cyclodextrin and the epoxy chloropropane are crosslinked to form a hydrophobic cavity structure, water drops or water vapor adsorbed on the inner surface of the mulching film can be blocked in the mulching film, so that the function of preserving soil moisture is realized; and after the beta-cyclodextrin is crosslinked with the epichlorohydrin, the strength is greatly increased. Meanwhile, a hydrophobic cavity structure formed after the beta-cyclodextrin and the epichlorohydrin are crosslinked can also cooperate with micropores of the mesoporous silica to play a heat preservation function; the potassium aluminosilicate has a layered structure, and mesoporous silica can be loaded in the layered structure of the potassium aluminosilicate, so that the mesoporous silica is not easy to separate from the lightweight modified composite material; the mesoporous silicon dioxide and the potassium aluminum silicate both form a hydrogen bond with hydroxyl of the epichlorohydrin crosslinked-beta-cyclodextrin, so that the stability of the mesoporous silicon dioxide in the lightweight modified composite material is improved.
The slipping agent introduced in the system is polyethylene wax grafted glycidyl methacrylate, and an epoxy group on GMA reacts with terminal hydroxyl groups on PGA and PBST molecular chains, so that the compatibility of the slipping agent and a biodegradable material is greatly improved, and the migration speed of the slipping agent is reduced. In addition, terminal hydroxyl groups on molecular chains of PGA and PBST, mesoporous silicon dioxide and potassium aluminum silicate can also form hydrogen bonds, so that the stability of the lightweight modified composite material in the biodegradable mulching film is improved.
The glycolic acid-succinic acid butanediol ester copolymer introduced into the system greatly improves the micro interface compatibility of PGA and PBST, thereby improving the mechanical property of the material.
The invention has excellent heat preservation and soil moisture preservation performance and obvious light weight effect. The preparation method is simple and easy to implement and is easy to realize.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
Using NaOH as a catalyst, and carrying out crosslinking reaction on 1 part of beta-cyclodextrin and 0.1 part of epichlorohydrin for 1.5 hours at the temperature of 60 ℃. When the reaction is carried out for 1 hour, 1 part of potassium aluminum silicate (mesh number 4000) and 5 parts of mesoporous silica (aperture 30nm, mesh number 6000) are sequentially introduced to obtain the lightweight modified composite material.
Adding 5 parts of lightweight modified composite material, 15 parts of PGA (melting point 180 ℃, melt index 5.0), 80 parts of PBST (melting point 115 ℃, melt index 4.0), 5 parts of PGA-co-BS (melting point 120 ℃, melt index 10.0), 0.5 part of PE-g-GMA (melting point 125 ℃, graft ratio 1.5%), 0.5 part of dicyclohexylcarbodiimide, 0.1 part of calcium dodecahydroxystearate, 0.5 part of polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester and 0.5 part of piroctone into a mixer in sequence, mixing uniformly, adding into a double-screw extruder for extrusion and granulation, adding the obtained particles into a film blowing machine for blow molding, and obtaining the biodegradable mulching film.
Example 2
Using NaOH as a catalyst, and carrying out crosslinking reaction on 2 parts of beta-cyclodextrin and 0.5 part of epichlorohydrin for 2.5 hours at 70 ℃. When the reaction is carried out for 1.2 hours, 2 parts of potassium aluminum silicate (mesh number of 6000) and 10 parts of mesoporous silica (aperture of 10nm, mesh number of 4000) are sequentially introduced to obtain the lightweight modified composite material.
Adding 20 parts of lightweight modified composite material, 45 parts of PGA (melting point 160 ℃, melt index 4.0), 40 parts of PBST (melting point 130 ℃, melt index 5.0), 15 parts of PGA-co-BS (melting point 140 ℃, melt index 5.0), 1.5 parts of PE-g-GMA (melting point 105 ℃, graft ratio 0.5%), 1 part of dicyclohexylcarbodiimide, 0.5 part of zinc dodecahydroxystearate, 0.1 part of polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester and 1 part of piroctone into a mixer in sequence, uniformly mixing, adding into a double-screw extruder for extrusion granulation, adding the obtained particles into a film blowing machine for blow molding, and obtaining the biodegradable mulching film.
Example 3
Using NaOH as a catalyst, and carrying out crosslinking reaction on 1.5 parts of beta-cyclodextrin and 0.2 part of epichlorohydrin for 2 hours at 65 ℃. When the reaction is carried out for 1 hour, 1.5 parts of potassium aluminum silicate (with the mesh number of 5000) and 8 parts of mesoporous silica (with the aperture of 20nm and the mesh number of 5000) are sequentially introduced to obtain the lightweight modified composite material.
Adding 10 parts of lightweight modified composite material, 25 parts of PGA (melting point 170 ℃, melt index 3.0), 65 parts of PBST (melting point 120 ℃, melt index 4.5), 10 parts of PGA-co-BS (melting point 130 ℃, melt index 7.0), 1 part of PE-g-GMA (melting point 115 ℃, graft ratio 1%), 0.7 part of N, N' -diisopropylcarbodiimide, 0.3 part of calcium dodecahydroxystearate, 0.3 part of poly (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate and 0.8 part of piroctone into a mixer in sequence, mixing uniformly, adding into a double-screw extruder for extrusion and granulation, adding the obtained particles into a film blowing machine for blow molding, and obtaining the biodegradable mulching film.
Example 4
Using NaOH as a catalyst, and carrying out crosslinking reaction on 2 parts of beta-cyclodextrin and 0.1 part of epichlorohydrin for 2.3 hours at 63 ℃. When the reaction is carried out for 1.1 hour, 1.3 parts of potassium aluminum silicate (with a mesh size of 5500 meshes) and 7 parts of mesoporous silica (with a pore diameter of 5nm and a mesh size of 4500 meshes) are sequentially introduced to obtain the lightweight modified composite material.
Adding 15 parts of lightweight modified composite material, 35 parts of PGA (melting point 165 ℃, melt index 3.5), 58 parts of PBST (melting point 120 ℃, melt index 5.0), 7 parts of PGA-co-BS (melting point 125 ℃, melt index 4.0), 0.8 part of PE-g-GMA (melting point 120 ℃, graft ratio 1.2%), 0.6 part of dicyclohexylcarbodiimide, 0.4 part of zinc dodecahydroxystearate, 0.4 part of polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester and 0.7 part of piroctone into a mixer in sequence, mixing uniformly, adding into a double-screw extruder for extrusion and granulation, adding the obtained particles into a film blowing machine for blow molding, and obtaining the biodegradable mulching film.
Example 5
Using NaOH as a catalyst, and carrying out crosslinking reaction on 1.8 parts of beta-cyclodextrin and 0.2 part of epichlorohydrin for 2 hours at 61 ℃. When the reaction is carried out for 1 hour, 1.2 parts of potassium aluminum silicate (with the mesh number of 5000) and 10 parts of mesoporous silica (with the aperture of 15nm and the mesh number of 5000) are sequentially introduced to obtain the lightweight modified composite material.
Adding 12 parts of lightweight modified composite material, 20 parts of PGA (melting point 170 ℃, melt index 4.2), 70 parts of PBST (melting point 125 ℃, melt index 4.0), 10 parts of PGA-co-BS (melting point 130 ℃, melt index 3.0), 1 part of PE-g-GMA (melting point 110 ℃, graft ratio 0.9%), 1 part of N, N' -diisopropylcarbodiimide, 0.5 part of magnesium dodecahydroxy stearate, 0.5 part of polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester and 0.5 part of piroctone into a mixer in sequence, mixing uniformly, adding into a double-screw extruder for extrusion and granulation, adding the obtained particles into a film blowing machine for blow molding, and obtaining the biodegradable mulching film.
Comparative example 1
The thickness of the PE mulching film is 0.01 mm.
Comparative example 2
20 parts of PGA with the thickness of 0.01mm and without various additives, 70 parts of PBST and 10 parts of PGA-co-BS mulching film.
Comparative example 3
Example 1 was followed except that the lightweight modified composite material was not added.
Comparative example 4
Example 2 was followed except that the lightweight modified composite material was not added.
The PGA-co-BS copolymers in the examples and comparative examples were prepared by reacting low molecular weight PGA (molecular weight 2 ten thousand) and low molecular weight BS (molecular weight 3 ten thousand) in a mass ratio of 1:3 under chain extension of isocyanate MDI, and had a molecular weight of 6 ten thousand.
PE-g-GMA was prepared as follows: 0.001 part of DCP and 100 parts of polyethylene wax are uniformly mixed, then the mixture is added into a double-screw extruder with the length-diameter ratio of 48:1, and simultaneously 2 parts of GMA is quantitatively added into a screw through a liquid injection pump at the front end of the screw to prepare PE-g-GMA.
In the invention, for comparison, the thicknesses of the PE mulching film and the biodegradable mulching film are unified to be 0.01 mm; the density of the mulch is expressed in grams per square meter; the heat preservation performance is represented by the temperature of 10cm deep soil after 24 hours of film laying; the soil moisture preservation performance is represented by the water vapor transmission rate of the mulching film; the melt index test conditions are unified at 190 ℃, 2.16kg and the unit of the melt index is g/10 min.
| Examples | The depth of soil is 10cm and the temperature is lower | Water vapor transmission rate g/m2*24h | Gram weight per square meter g |
| Example 1 | 17.8 | 105 | 9.9 |
| Example 2 | 19.5 | 98 | 9.1 |
| Example 3 | 18.2 | 90 | 9.8 |
| Example 4 | 18.9 | 97 | 9.5 |
| Example 5 | 19.1 | 100 | 9.7 |
| Comparative example 1 | 15.7 | 92 | 9.5 |
| Comparative example 2 | 13.5 | 956 | 12.6 |
| Comparative example 3 | 13.8 | 850 | 12.9 |
| Comparative example 4 | 12.9 | 848 | 12.7 |
In conclusion, after the modified polyglycolic acid biodegradable mulching film is paved for 24 hours, the temperature of the soil with the depth of 10cm is higher than 17.8 ℃, the heat preservation effect is greatly improved, and the water vapor transmission rate is lower than 105g/m224h, the soil moisture preservation effect is ensured, the weight per square meter is not more than 9.9g, and the cost is reduced. Compared with the existing mulching film, the mulching film has excellent effect and can be popularized and used.
Claims (9)
1. The modified polyglycolic acid biodegradable mulching film is characterized by being prepared from the following raw materials in parts by weight: 15-45 parts of polyglycolic acid, 40-80 parts of poly butylene succinate-co-terephthalate, 5-15 parts of compatilizer, 0.5-1.5 parts of slipping agent, 0.5-1 part of hydrolysis resistant agent, 0.1-0.5 part of antioxidant, 0.1-0.5 part of light aging resistant agent, 0.5-1 part of antibacterial agent and 5-20 parts of lightweight modified composite material; wherein the lightweight modified composite material is prepared from 0.1-0.5 part of epoxy chloropropane, 1-2 parts of beta-cyclodextrin, 1-2 parts of potassium aluminum silicate and 5-10 parts of mesoporous silicon dioxide;
the preparation method of the lightweight modified composite material comprises the steps of carrying out crosslinking reaction on epoxy chloropropane and beta-cyclodextrin to prepare epoxy chloropropane crosslinked-beta-cyclodextrin, and sequentially introducing potassium aluminum silicate and mesoporous silicon dioxide in the crosslinking reaction process.
2. The modified polyglycolic acid biodegradable mulch film according to claim 1, wherein: the mesh number of the potassium aluminum silicate is 4000-6000 meshes.
3. The modified polyglycolic acid biodegradable mulch film according to claim 1, wherein: the aperture of the mesoporous silica is 5-30nm, and the mesh number is 4000-6000 meshes.
4. The modified polyglycolic acid biodegradable mulch film according to claim 1, wherein: the melting point of polyglycolic acid is 160-; the melting point of the poly (butylene succinate) -co-butylene terephthalate) is 115 ℃ and 130 ℃, and the melt index is less than or equal to 5.0g/10 min.
5. The modified polyglycolic acid biodegradable mulch film according to claim 1, wherein: the compatilizer is glycolic acid-succinic acid butanediol ester copolymer, the mass ratio of the glycolic acid to the succinic acid butanediol ester is 1:2-3, the melting point is 120-140 ℃, and the melt index is less than or equal to 10.0g/10 min.
6. The modified polyglycolic acid biodegradable mulch film according to claim 1, wherein: the slipping agent is polyethylene wax grafted glycidyl methacrylate, the melting point is 105 ℃ and 125 ℃, and the grafting rate is 0.5-1.5%.
7. The modified polyglycolic acid biodegradable mulch film according to claim 1, wherein: the hydrolysis resisting agent is dicyclohexylcarbodiimide or N, N' -diisopropylcarbodiimide.
8. The modified polyglycolic acid biodegradable mulch film according to claim 1, wherein: the light aging resistant agent is poly (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate; the antibacterial agent is piroctone.
9. A method for preparing the modified polyglycolic acid biodegradable mulch film according to any one of claims 1 to 8, which is characterized in that: the method comprises the steps of firstly carrying out a crosslinking reaction on epoxy chloropropane and beta-cyclodextrin to prepare epoxy chloropropane crosslinking-beta-cyclodextrin, sequentially introducing aluminum potassium silicate and mesoporous silica in the crosslinking reaction process to prepare a lightweight modified composite material, and then blending, extruding and blow molding the lightweight modified composite material, polyglycolic acid, poly butylene succinate-co-butylene terephthalate, a compatilizer, a slipping agent, a hydrolysis resistance agent, an antioxidant, a light aging resistance agent and an antibacterial agent to prepare the modified polyglycolic acid biodegradable mulching film.
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| CN109054309A (en) * | 2018-07-12 | 2018-12-21 | 安徽聚美生物科技有限公司 | A kind of preparation method of PLA high-barrier mulch |
| CN110016216B (en) * | 2019-04-28 | 2021-08-27 | 睿泊(中国)环保科技有限公司 | Fully-degradable polyglycolic acid composite packaging material and preparation method thereof |
| CN111117263A (en) * | 2019-12-30 | 2020-05-08 | 武汉华星光电半导体显示技术有限公司 | Polyimide composite, preparation method and application thereof |
| CN112679927A (en) * | 2020-12-24 | 2021-04-20 | 海南赛诺实业有限公司 | Modified PGA material with higher shelf life and preparation method thereof |
| CN112759907A (en) * | 2020-12-24 | 2021-05-07 | 海南赛高新材料有限公司 | Modified PGA material with long shelf life and preparation method thereof |
| CN113278269B (en) * | 2021-04-15 | 2022-08-02 | 江南大学 | Preparation method of durable polyglycolic acid-based material |
| CN113278268B (en) * | 2021-04-15 | 2022-08-09 | 江南大学 | High-toughness polyester composite material and preparation method thereof |
| CN113583255A (en) * | 2021-08-03 | 2021-11-02 | 海南赛诺实业有限公司 | Polyglycolic acid emulsion and preparation method thereof |
| CN115746514B (en) * | 2022-11-16 | 2024-01-30 | 中国石油化工股份有限公司 | Polyglycolic acid resin composition and film, and preparation method and application thereof |
| CN116178921B (en) * | 2023-04-26 | 2023-06-27 | 中联融鑫(北京)科技开发有限公司 | Degradation auxiliary agent for degrading PP and PE |
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