CN111748180B - Biodegradable film raw material combination and biodegradable film material - Google Patents

Biodegradable film raw material combination and biodegradable film material Download PDF

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CN111748180B
CN111748180B CN202010614268.XA CN202010614268A CN111748180B CN 111748180 B CN111748180 B CN 111748180B CN 202010614268 A CN202010614268 A CN 202010614268A CN 111748180 B CN111748180 B CN 111748180B
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biodegradable film
poly
film
ppc
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CN111748180A (en
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赵阳
谢东
陈骏佳
李圆
刘海露
李发勇
龙碧波
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Guangdong Institute of Bioengineering Guangzhou Cane Sugar Industry Research Institute
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Guangdong Institute of Bioengineering Guangzhou Cane Sugar Industry Research Institute
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/02—Receptacles, e.g. flower-pots or boxes; Glasses for cultivating flowers
    • A01G9/029—Receptacles for seedlings
    • A01G9/0291—Planting receptacles specially adapted for remaining in the soil after planting
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2397/00—Characterised by the use of lignin-containing materials
    • C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/16—Biodegradable polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention belongs to the technical field of biodegradable materials, and particularly relates to a biodegradable film raw material composition and a biodegradable film material. The biodegradable film raw material composition consists of raw materials such as poly (adipic acid)/butylene terephthalate (PBT), poly (PPC) polyurethane, plant fibers, inorganic fillers and the like, wherein the PPC polyurethane can remarkably improve the compatibility of the filling material, reduce agglomeration and improve the mechanical property of the material and the flexibility of the film surface; the film material can keep higher mechanical property in early seedling raising by combining with other components, the mechanical property is reduced by more than 70% about 2 months under the soil temperature and humidity condition, the root rolling of root sockets of the root system of the seedling is avoided, and a better growth effect is achieved; the preparation method has the advantages of rich resources of all the components, environmental protection, degradability, low price, obvious reduction of production cost, reduction of environmental pollution, strong market competitiveness and wide application prospect.

Description

Biodegradable film raw material combination and biodegradable film material
Technical Field
The invention belongs to the technical field of biodegradable materials. More particularly, it relates to a biodegradable film material composition and a biodegradable film material.
Background
The container seedling raising is one advanced seedling producing technology, and is characterized by that various containers are filled into prepared matrix or nutrient soil, and seedling raising culture is implemented in greenhouse and other protecting facilities so as to create good growth condition and survival environment for seedling and implement industrial large-scale seedling raising. In addition, the seedling raising container has the advantages of short seedling raising period, easy control of seedling specification and quality, high nursery-out rate of the seedlings, seed saving, difficult damage of root systems in the seedling raising and conveying process, water saving, quick forestation, long period of forestation, no seedling recovering period, convenient mechanical planting, low cost, easy operation and the like, and is widely used at home and abroad. However, polyethylene films commonly used for container seedling raising in the market at present are not degradable, plant roots cannot penetrate and are easy to cause root rolling of nest roots, and the growth and development of seedlings are affected; and plastic recycling operation is complex, most of residual soil damages the soil structure, and serious negative effects are generated on the environment, so that the problem of white pollution is increasingly serious.
In order to solve the problem of white pollution, a degradable seedling raising bag is developed in the prior art for container seedling raising, for example, chinese patent application CN107828124A discloses a non-woven fabric environment-friendly degradable seedling raising bag which is mainly prepared from polylactic acid short fibers, bamboo fibers, aromatherapy oil, calcium oxide-poly-p-phenylene dibutyrate phenylbutanol ester, a degradation promoter, nano bentonite, an auxiliary agent and the like, and has the advantages of mosquito prevention, sterilization, high degradation speed, ageing resistance, good toughness, low production cost, degradability and the like; the Chinese patent application CN106496798A discloses a seedling raising bag which is mainly prepared from polypropylene, polyethylene, plant fibers, a filler, a degradation promoter, has the effects of high seedling raising survival rate, easiness in degradation, insect prevention, insect expelling and the like, is easy to obtain raw materials, is purely natural, and is safe and environment-friendly. However, the two degradation seedling bags still have high strength toughness or strength, are difficult to decompose within a period of time after being buried in soil, and still have the problem of root nesting and root rolling of plant roots; in addition, various added plant fibers or filling materials have poor compatibility with polylactic acid, polypropylene and other materials, and the problems that the plastic film cannot be formed by blow molding and the film is hard and brittle are solved, so that the plastic film cannot be used as a seedling raising bag.
Therefore, there is an urgent need to provide a biodegradable film material composition for preparing biodegradable film materials of seedling bags, which improves the compatibility of filling components, improves the filling quantity, reduces the production cost, can maintain higher mechanical properties in early seedling, and can reduce the mechanical property to root system tearing and puncturing after soil burying for a period of time in the later stage, thereby avoiding the occurrence of root rolling phenomenon of nest roots.
Disclosure of Invention
The invention aims to solve the technical problems that the toughness or strength of the existing biodegradable seedling bag material is high, and root nesting and root rolling are easy to cause; the filling material has the defects of poor compatibility, incapability of blow molding and hard and brittle film, and provides a biodegradable film material composition for preparing biodegradable film materials of seedling bags, which improves the compatibility of filling components, improves the filling quantity, reduces the production cost, can maintain higher mechanical property in early seedling, and can reduce the mechanical property to root system tearing and puncturing after soil is buried for a period of time in the later period, thereby avoiding the occurrence of root rolling phenomenon of nest roots.
The invention aims to provide a biodegradable film raw material combination.
The invention also aims to provide application of the biodegradable film raw material combination in preparation of biodegradable film materials.
Another object of the present invention is to provide a biodegradable film material for use in a seedling bag.
The invention also aims to provide a preparation method of the biodegradable film material for the seedling bag.
The invention also aims to provide a seedling raising bag prepared from the biodegradable film material.
The above object of the present invention is achieved by the following technical scheme:
the biodegradable film raw material composition comprises the following raw materials in parts by weight: 100 parts of poly (adipic acid)/butylene terephthalate, 30-50 parts of PPC type polyurethane, 50-100 parts of plant fiber and 50-100 parts of inorganic filler.
Preferably, the material comprises the following raw materials in parts by weight: 100 parts of poly (adipic acid)/butylene terephthalate, 30-45 parts of PPC polyurethane, 50-70 parts of plant fiber and 50-70 parts of inorganic filler.
The application of the raw material combination in preparing the biodegradable film material is within the protection scope of the invention.
Meanwhile, the invention also provides a biodegradable film material for the seedling bag, which comprises the following raw materials in parts by weight:
100 parts of poly (adipic acid)/butylene terephthalate, 5-15 parts of polylactic acid, 30-50 parts of PPC polyurethane, 50-100 parts of plant fiber, 50-100 parts of inorganic filler, 5-10 parts of plasticizer and 1-3 parts of coupling agent.
Preferably, the material comprises the following raw materials in parts by weight:
100 parts of poly (adipic acid)/butylene terephthalate, 5-10 parts of polylactic acid, 30-45 parts of PPC polyurethane, 50-70 parts of plant fiber, 50-70 parts of inorganic filler, 5-8 parts of plasticizer and 1-3 parts of coupling agent.
The poly (adipic acid)/butylene terephthalate has good flexibility and similar mechanical properties as a film and a polyethylene film, but the poly (adipic acid)/butylene terephthalate has the problems of higher cost and difficult processing caused by higher melt strength, and modified materials are needed to be added to reduce the cost and improve the processing property. The polylactic acid has good plasticity, and can reduce the melt strength of the material and improve the processing and forming properties of the material. Plant fiber powder such as wood powder, bamboo powder and the like, and inorganic powder such as talcum powder, calcium carbonate and the like are commonly used as filling materials, but the materials are easy to agglomerate when the filling amount is too high, the materials are difficult to process and the performance is reduced, and the plant fiber is used as a natural high polymer material, and the molecular chain contains a large number of hydrogen bonds, cannot be melted at high temperature and can only be distributed in a polymer matrix in the form of powder. Coupling agents are a class of additives that improve the compatibility of inorganic fillers with polymer matrices, but excessive amounts increase cost and tend to cause crosslinking that reduces material properties.
The inventor has found through a great deal of creative labor that PPC polyurethane is a biodegradable thermoplastic elastomer, has excellent mechanical properties, processability and the like, has good compatibility with polyester biodegradable materials, can improve the flexibility and compatibility of other materials such as filling materials, can further improve the filler content of film materials, especially improve the content of plant fiber powder, and can remarkably improve the dispersion of organic/inorganic powder (plant fiber powder and inorganic filler) in a polymer matrix and reduce aggregation. The principle is that a large number of urethane bonds and terminal hydroxyl groups on PPC polyurethane molecular chain segments can interact with a large number of hydroxyl groups on organic/inorganic filling powder; on the other hand, the PPC type polyurethane is a cut-sensitive polymer, is sheared and thinned under the stronger shearing action of a continuous internal mixer, is fully contacted with organic/inorganic filling powder with rough surface, fully wraps and winds the powder, can reduce the agglomeration among the filling powder and improve the dispersion performance of the filling powder in a matrix, thereby achieving the effects of reducing the agglomeration of the filling material and improving the compatibility and the addition amount of the filling material. The film has the advantages that the film is combined with other materials to act together, the mechanical property of the film and the flexibility of the surface of the film are further improved, the film can also keep good tensile strength and elongation after being stored for 2 months, the original film state can be kept after the soil of 2 months is contacted and buried, but the mechanical property of the film is obviously reduced, and the root system of the nursery stock can easily tear the film and grow normally.
Further, the PPC polyurethane is a thermoplastic elastomer of a polypropylene carbonate diol and a diisocyanate, the molar ratio of the polypropylene carbonate diol to the diisocyanate being 1: (1.0-1.1).
Preferably, the polypropylene carbonate diol has a number average molecular weight of 1000 to 5000Da.
Further, the plant fiber is powder with the granularity of 100-600 meshes. The preferred particle sizes are 100 mesh, 200 mesh, 300 mesh, 400 mesh.
Further, the plant fiber is selected from one or more of sugarcane slag powder, wood powder, bamboo powder, straw powder, grass fiber and microcrystalline cellulose.
Further, the inorganic filler is selected from one or more of talcum powder, calcium carbonate, montmorillonite and white carbon black.
Preferably, the particle size of the inorganic filler is below 1000 mesh. More preferably, the inorganic filler is 2000 mesh talc or calcium carbonate.
Further, the plasticizer is polyethylene glycol with the number average molecular weight of 600-5000 Da. Preferred number average molecular weights are 1000Da, 2000Da, 3000Da.
Further, the coupling agent is a silane coupling agent.
Further, the melt index of the poly (adipic acid)/butylene terephthalate is lower than 8.0g/10min. The test condition of the melt finger is 190 ℃ and 2.16kg.
Preferably, the type of the poly (butylene adipate/terephthalate) comprises C1200, A400, TH801T.
Further, the polylactic acid is a film blowing grade or injection molding grade polylactic acid.
Preferably, the types of the polylactic acid comprise 4032D, 4043D, L175 and LX175.
In addition, the invention also provides a preparation method of the biodegradable film material, which comprises the following steps:
the raw materials are continuously banburying and granulating at 170-190 ℃, blow molding is carried out at 150-180 ℃, and the blow ratio is 1.5-3.0, thus obtaining the film.
The raw materials are mixed by the continuous internal mixer, the uniform dispersion of the filler in the polymer in the blending process is promoted by the continuous high-shear and high-temperature effects, the filler with higher content is achieved, the mixing time of the continuous internal mixer is shorter than that of a double-screw extruder, and the thermal decomposition of the biodegradable material in the processing process is reduced.
The mixed granules obtained by the invention are suitable for blow molding, including single-layer blow molding and multi-layer coextrusion blow molding, and are also suitable for other extrusion molding processes for preparing sheets, pipes and the like.
In addition, the invention also provides a seedling raising bag which is prepared from the biodegradable film material.
The invention has the following beneficial effects:
the biodegradable film raw material composition provided by the invention is composed of raw materials such as poly (adipic acid)/butylene terephthalate (PBT), poly (PPC) polyurethane, plant fibers, inorganic fillers and the like, wherein the PPC polyurethane can obviously improve the compatibility of the filler, reduce agglomeration and improve the mechanical property of the material and the flexibility of the film surface; the film material can keep higher mechanical property in early seedling raising by combining with other components, and can be degraded gradually under the soil temperature and humidity condition, the mechanical property is reduced by more than 70% about 2 months, when the root system of the seedling touches the film, the film can be easily torn and penetrated, the root is not rolled up by the root nest, and a better growth effect is achieved; the preparation method has the advantages of rich resources of all the components, environmental protection, degradability, low price, obvious reduction of production cost, reduction of environmental pollution, strong market competitiveness and wide application prospect.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Wherein, the mole ratio of the polypropylene carbonate glycol to the diisocyanate used in the examples is 1: (1.0-1.1), wherein the number average molecular weight of the polypropylene carbonate dihydric alcohol is 1000-5000 Da, the poly (adipic acid)/butylene terephthalate) C1200 is purchased from Basiff corporation, the poly (adipic acid)/butylene terephthalate) A400 is purchased from Jinfa technology Co., ltd, and the poly (adipic acid)/butylene terephthalate) TH801T is purchased from Xinjiang blue mountain river chemical Co., ltd; polylactic acids 4032D, 4043D were purchased from nature, usa and polylactic acids L175, LX175 were purchased from the company of the trade company of the sciences of the bien (Shanghai).
The remaining reagents and materials used in the examples below are all commercially available unless otherwise specified.
Example 1A biodegradable film Material for use in seedling bags
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/poly (butylene terephthalate), 5 parts of polylactic acid, 30 parts of PPC type polyurethane, 50 parts of plant fiber, 50 parts of inorganic filler, 5 parts of plasticizer and 1 part of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is C1200, the type of the poly (lactic acid) is 4043D, the plant fiber is 200-mesh sugarcane slag powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 5000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 180 ℃, continuous internal mixing granulation is carried out, blow molding is carried out at the temperature of 175 ℃ to form a film, the blow ratio is 2.8+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Example 2A biodegradable film Material for use in seedling bags
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/butylene terephthalate, 10 parts of polylactic acid, 40 parts of PPC type polyurethane, 50 parts of plant fiber, 100 parts of inorganic filler, 8 parts of plasticizer and 3 parts of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is A400, the type of the poly (lactic acid) is 4032D, the plant fiber is 400-mesh bamboo powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 5000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 190 ℃, continuous internal mixing granulation is carried out, the film is formed by blow molding under the condition of 180 ℃, the blow-up ratio is 2.5+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Example 3 biodegradable film Material for seedling bag
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/butylene terephthalate, 10 parts of polylactic acid, 50 parts of PPC type polyurethane, 100 parts of plant fiber, 50 parts of inorganic filler, 10 parts of plasticizer and 2 parts of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is C1200, the type of the poly (lactic acid) is 4043D, the plant fiber is 400-mesh bamboo powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 2000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to 175 ℃, continuous internal mixing granulation is carried out, blow molding is carried out at the temperature of 175 ℃ to form a film, the blow ratio is 1.8+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Example 4A biodegradable film Material for use in seedling bags
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/poly (butylene terephthalate), 15 parts of polylactic acid, 50 parts of PPC type polyurethane, 80 parts of plant fiber, 80 parts of inorganic filler, 10 parts of plasticizer and 3 parts of coupling agent;
the model of the poly (adipic acid)/butylene terephthalate is TH801T, the model of the poly (lactic acid) is LX175, the plant fiber is 600-mesh bamboo powder, the inorganic filler is 3000-mesh calcium carbonate, the plasticizer is polyethylene glycol with the number average molecular weight of 3000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 180 ℃, continuous internal mixing granulation is carried out, blow molding is carried out at the temperature of 175 ℃ to form a film, the blow ratio is 2.2+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Example 5A biodegradable film Material for use in seedling bags
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/butylene terephthalate, 10 parts of polylactic acid, 30 parts of PPC type polyurethane, 80 parts of plant fiber, 50 parts of inorganic filler, 7 parts of plasticizer and 2 parts of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is C1200, the type of the poly (lactic acid) is LX175, the plant fiber is 400-mesh wood powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 3000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 180 ℃, continuous internal mixing granulation is carried out, blow molding is carried out at the temperature of 175 ℃ to form a film, the blow ratio is 2.0+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Example 6A biodegradable film Material for use in seedling bags
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/poly (butylene terephthalate), 15 parts of polylactic acid, 40 parts of PPC type polyurethane, 50 parts of plant fiber, 80 parts of inorganic filler, 8 parts of plasticizer and 2 parts of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is C1200, the type of the poly (lactic acid) is 4043D, the plant fiber is 400-mesh bamboo powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 3000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 180 ℃, continuous internal mixing granulation is carried out, the film is formed by blow molding under the condition of 180 ℃, the blow-up ratio is 2.0+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Example 7A biodegradable film Material for use in seedling bags
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/poly (butylene terephthalate), 5 parts of polylactic acid, 50 parts of PPC type polyurethane, 100 parts of plant fiber, 50 parts of inorganic filler, 10 parts of plasticizer and 3 parts of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is C1200, the type of the poly (lactic acid) is 4043D, the plant fiber is 400-mesh bamboo powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 3000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to 175 ℃, continuous internal mixing granulation is carried out, blow molding is carried out at the temperature of 175 ℃ to form a film, the blow ratio is 1.8+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Comparative example 1A film Material
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/poly (butylene terephthalate), 5 parts of polylactic acid, 50 parts of plant fiber, 50 parts of inorganic filler, 5 parts of plasticizer and 1 part of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is C1200, the type of the poly (lactic acid) is 4043D, the plant fiber is 200-mesh sugarcane slag powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 5000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 180 ℃, continuous internal mixing granulation is carried out, blow molding is carried out at the temperature of 175 ℃ to form a film, the blow ratio is 2.8+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Comparative example 2A film Material
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/butylene terephthalate, 10 parts of polylactic acid, 40 parts of PPC type polyurethane, 50 parts of plant fiber, 150 parts of inorganic filler, 8 parts of plasticizer and 3 parts of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is A400, the type of the poly (lactic acid) is 4032D, the plant fiber is 400-mesh bamboo powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 5000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 190 ℃, continuous internal mixing granulation is carried out, the film is formed by blow molding under the condition of 180 ℃, the blow-up ratio is 2.5+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Comparative example 3A film Material
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/poly (butylene terephthalate), 10 parts of polylactic acid, 40 parts of maleic anhydride grafted polypropylene carbonate (PPC-MA), 50 parts of plant fiber, 100 parts of inorganic filler, 8 parts of plasticizer and 3 parts of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is A400, the type of the poly (lactic acid) is 4032D, the poly (propylene carbonate) (PPC-MA) grafted by maleic anhydride is a melt blend of poly (crown poly (number average molecular weight) 70000Da in Henan) and 1% of maleic anhydride by weight, the plant fiber is 400-mesh bamboo powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 5000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 190 ℃, continuous internal mixing granulation is carried out, the film is formed by blow molding under the condition of 180 ℃, the blow-up ratio is 2.5+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Comparative example 4A film Material
The biodegradable film material for the seedling bag is prepared from the following raw materials in parts by weight:
100 parts of poly (adipic acid)/butylene terephthalate, 10 parts of polylactic acid, 40 parts of maleic anhydride grafted poly (adipic acid)/butylene terephthalate (PBAT-MA), 50 parts of plant fiber, 100 parts of inorganic filler, 8 parts of plasticizer and 3 parts of coupling agent;
the type of the poly (adipic acid)/butylene terephthalate is A400, the type of the poly (lactic acid) is 4032D, the poly (adipic acid)/butylene terephthalate (PBAT-MA) grafted by maleic anhydride is a melt blend of poly (adipic acid)/butylene terephthalate) (Pasteur C1200) and 1% of maleic anhydride by weight, the plant fiber is 400-mesh bamboo powder, the inorganic filler is 2000-mesh talcum powder, the plasticizer is polyethylene glycol with the number average molecular weight of 5000Da, and the coupling agent is silane coupling agent KH-570.
The preparation method comprises the following steps:
the raw materials are manually mixed and then put into a continuous internal mixer, the highest temperature is set to be 190 ℃, continuous internal mixing granulation is carried out, the film is formed by blow molding under the condition of 180 ℃, the blow-up ratio is 2.5+/-0.2, and the film thickness is controlled to be about 40 mu m, thus obtaining the film.
Table 1 examples 1 to 7 and comparative examples 1 to 4 were prepared from the raw materials in parts by weight
Figure GDA0004057099710000091
Figure GDA0004057099710000101
Experimental example 1 influence of mechanical Properties of thin film Material after soil burying
The mechanical properties such as tensile strength and elongation of the film materials of examples 1 to 7 and comparative examples 1 to 4 were measured, and the mechanical properties were measured after the film materials were buried in soil or stored in a warehouse for 2 months, respectively, and the results are shown in Table 2.
TABLE 2 influence of mechanical Properties of film Material and Strength after soil burying
Figure GDA0004057099710000102
Note that: the symbol "/" in Table 2 indicates that the material could not be formed or tested under this process.
As can be seen from Table 2, the films with certain mechanical strength can be prepared in the embodiments 1-7 of the invention, the original film state can be maintained after the soil is contacted and buried for 2 months, but the mechanical property of the material of the film is obviously reduced, the root system of the nursery stock can easily tear the film for normal growth, and the tensile strength, the elongation and the like of the nursery stock are not obviously changed after the nursery stock is stored for 2 months; however, the polyurethane of comparative example 1 which does not contain PPC cannot be blow molded at all, and the inorganic filler of comparative example 2 is too high, so that the film is hard and brittle, each performance is poor, and the film is broken within one week after soil burying and cannot be used normally; comparative examples 3 and 4 use other materials instead of PPC type polyurethane, the film performance is lowered and the morphology cannot be stably maintained in use.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (8)

1. The biodegradable film raw material composition is characterized by comprising the following raw materials in parts by weight: 100 parts of poly (adipic acid)/butylene terephthalate, 30-50 parts of PPC type polyurethane, 50-100 parts of plant fiber, 50-100 parts of inorganic filler and 5-15 parts of polylactic acid;
the PPC polyurethane is a thermoplastic elastomer of polypropylene carbonate glycol and diisocyanate, and the molar ratio of the polypropylene carbonate glycol to the diisocyanate is 1: (1.0-1.1), wherein the number average molecular weight of the polypropylene carbonate dihydric alcohol is 1000-5000 Da.
2. The biodegradable film raw material composition according to claim 1, characterized by comprising the following raw materials in parts by weight: 100 parts of poly (adipic acid)/butylene terephthalate, 30-45 parts of PPC type polyurethane, 50-70 parts of plant fiber, 50-70 parts of inorganic filler and 5-10 parts of polylactic acid.
3. The biodegradable film raw material composition according to claim 1 or 2, characterized in that said plant fiber is selected from one or more of the group consisting of sugar cane slag powder, wood powder, bamboo powder, straw powder, grass fiber, microcrystalline cellulose.
4. The biodegradable film raw material composition according to claim 1 or 2, characterized in that said inorganic filler is selected from one or more of talc, calcium carbonate, montmorillonite, white carbon black.
5. Use of the biodegradable film raw material composition according to any one of claims 1 to 4 for preparing a biodegradable film material.
6. The biodegradable film material for the seedling bag is characterized by comprising the following raw materials in parts by weight:
100 parts of poly (adipic acid)/butylene terephthalate, 5-15 parts of polylactic acid, 30-50 parts of PPC polyurethane, 50-100 parts of plant fiber, 50-100 parts of inorganic filler, 5-10 parts of plasticizer and 1-3 parts of coupling agent;
the PPC polyurethane is a thermoplastic elastomer of polypropylene carbonate glycol and diisocyanate, and the molar ratio of the polypropylene carbonate glycol to the diisocyanate is 1: (1.0-1.1), wherein the number average molecular weight of the polypropylene carbonate dihydric alcohol is 1000-5000 Da.
7. The method for preparing the biodegradable film material according to claim 6, comprising the steps of:
the raw materials are continuously banburying and granulating at 170-190 ℃, blow molding is carried out at 150-180 ℃, and the blow ratio is 1.5-3.0, thus obtaining the film.
8. A seedling bag, characterized in that the seedling bag is prepared by the biodegradable film material according to claim 6.
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CN107523080A (en) * 2017-09-06 2017-12-29 中国科学院长春应用化学研究所 A kind of increased surface covering and preparation method thereof

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