WO2019011152A1 - 一种增强增韧增透母粒及其制备方法和应用 - Google Patents

一种增强增韧增透母粒及其制备方法和应用 Download PDF

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Publication number
WO2019011152A1
WO2019011152A1 PCT/CN2018/094176 CN2018094176W WO2019011152A1 WO 2019011152 A1 WO2019011152 A1 WO 2019011152A1 CN 2018094176 W CN2018094176 W CN 2018094176W WO 2019011152 A1 WO2019011152 A1 WO 2019011152A1
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Prior art keywords
film
toughening
ultra
masterbatch
parts
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PCT/CN2018/094176
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English (en)
French (fr)
Inventor
米庆华
徐静
张坤
韩宾
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山东农业大学
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Priority claimed from CN201710572630.XA external-priority patent/CN107383796B/zh
Priority claimed from CN201710572629.7A external-priority patent/CN107365482B/zh
Priority claimed from CN201710572627.8A external-priority patent/CN107345053B/zh
Application filed by 山东农业大学 filed Critical 山东农业大学
Priority to JP2019563811A priority Critical patent/JP6942323B2/ja
Publication of WO2019011152A1 publication Critical patent/WO2019011152A1/zh
Priority to ZA2019/05793A priority patent/ZA201905793B/en

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    • 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
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the invention belongs to the field of materials, and particularly relates to a biodegradable plastic masterbatch, in particular to a reinforcing and toughening antireflective masterbatch and a preparation method and application thereof.
  • Plastic film and mulch film play an important role in daily life and industrial and agricultural production.
  • plastic film and film used at present are polyolefin film which is difficult to degrade in a short period of time or incomplete degradation of starch and photodegradation agent.
  • Polyolefin film The use of these thin film materials has caused "white pollution" of the environment, posing a safety hazard for human sustainable development.
  • the fully biodegradable film is made of fully biodegradable plastic by blow molding, casting or calendering. It can be completely decomposed by microorganisms.
  • the final products of its degradation are carbon dioxide and water, which can be completely eliminated by nature, so it is fully biodegraded.
  • the film replaces the current polyolefin products and is an important means to solve white pollution.
  • the whole biodegradable film is mainly composed of polylactic acid, polycaprolactone, aliphatic polyester, aliphatic polycarbonate, polyhydroxy ester, starch, etc., but due to the characteristics and defects of the above polymer, a single polymer is difficult to be used as a single polymer.
  • the current research mainly improves the comprehensive performance of the film through blending modification, copolymerization modification, plasticization modification and composite modification.
  • Patent CN103589124B discloses a fully biodegradable PLA/PBAT composite film and a preparation method thereof;
  • patent CN104744898A discloses a fully biodegradable film and a preparation method thereof, which are polylactic acid (PLA) and polypropylene carbonate ( PPC), poly(adipic acid)/butylene terephthalate (PBAT) and heat stabilizers, but these film products generally have a high thickness of 6um-50um, and the cost of film products is high, and the thickness is too high. High, which leads to poor light transmission and low thickness, leads to low strength, which makes it impossible to commercialize in a short period of time, so that the optimal functional balance cannot be achieved.
  • PLA polylactic acid
  • PPC polypropylene carbonate
  • PBAT poly(adipic acid)/butylene terephthalate
  • heat stabilizers heat stabilizers
  • the thinner the film product the better.
  • the ultra-thin film of less than 6 ⁇ m has difficulty in opening the bubble opening process, the tensile strength and tear strength are greatly reduced, and the haze is large, and the resin is used as a film during the field use due to illumination.
  • the toughness of the film is reduced and the brittleness is increased, and the film is easy to crack in advance; therefore, how to overcome the defects in the processing and performance of the existing ultra-thin fully biodegradable film products, and providing special enhanced toughening antireflective masterbatch has become an urgent need in the field. The problem.
  • the present invention provides a method for reinforcing and toughening antireflective masterbatch, and a preparation method and application thereof, which are made of polyadipate/terephthalate and enhanced by the prior art.
  • Toughening agent is prepared as the main raw material, which can process both film and film, maintain the smoothness of processing and mechanical, optical performance and stability of ultra-thin biodegradable film products, and greatly reduce the cost of film. .
  • the masterbatch production process is simple and easy to grasp, and the obtained masterbatch has stable properties, can be completely degraded and has good dispersibility, and a small amount of the masterbatch provided by the invention can be used in combination with a degradation resin (PBAT+PLA, etc.).
  • PBAT+PLA a degradation resin
  • Ultra-thin biodegradable film products with a thickness of less than 6 ⁇ m make the film easy to open in the ultra-thin film blowing process, improve processing stability and excellent mechanical properties. It can be widely used in film packaging, shopping bags, agricultural film, garbage sorting landfill. Composting and other fields.
  • a reinforced toughening antireflective masterbatch whose main components are in parts by weight:
  • the polyadipate/butylene terephthalate described therein as a carrier resin has a melt flow rate of 2 to 5 g/10 min and an acid value of less than 15.
  • the polyadipate/butylene terephthalate used in the invention is very important for the preparation and use performance of the special masterbatch for the ultra-thin fully degradable film, and it is necessary to fuse all the materials, and also to withstand high temperature without volatilization and decomposition.
  • the ultra-thin biodegradable film is prepared by the masterbatch of the present invention in the later stage, it has good compatibility with other biodegradable resins, and does not induce degradation of the film, so the inventor has many alternatives.
  • the resin is preferably used as a carrier resin for the master batch, and the specific amount thereof is defined as above, and the functions of the master batch are optimally balanced in the range of the amount.
  • the enhanced toughening and permeabilizing agent is one or more of an inorganic reinforcing and toughening agent and an organic reinforcing toughening agent: the inorganic reinforcing and toughening and permeating agent is selected from the group consisting of hydrophobic nano silica.
  • the hydrophobic nano-silica has a particle size of 5-25 nm;
  • the organic reinforcing toughening agent is an Acema AX-8900 or ADX-1200s resin compatibilizer or a Hangzhou Aike CE-AZ01 compatibilizer Species or several
  • the toughening and anti-reflecting agent is not more than 20 parts, which is to ensure that the powder loses less during the mixing with the resin, the distribution is uniform, and it is easy to granulate; at the same time, the compatibility of various resins in the post-film processing is improved, and Does not reduce the mechanical properties of the film due to the addition of too much compatibilizer;
  • the above-mentioned enhanced toughening and permeabilizing agent is selected, and has good blending compatibility with the carrier resin, and can obtain a high concentration of the masterbatch; in the later film processing, the nucleating agent and the compatibilizing effect can be obtained, which is beneficial to the ultra-thin film processing.
  • the stability is also used to enhance the mechanical properties of ultra-thin fully biodegradable films.
  • the inventors further provide a special enhanced toughening antireflective masterbatch for an ultra-thin fully biodegradable film, the main components of which are: by weight:
  • the lubricant described therein is one or both of polymer PMMA microspheres and silica microspheres.
  • the polymer microspheres have a particle diameter of 0.5-5 ⁇ m, and the silica microspheres have a particle diameter of 1-5 ⁇ m; all of which are commercially available directly from the market;
  • the above-mentioned lubricant mainly functions as a lubrication opening, which facilitates opening of the membrane during processing of the ultra-thin biodegradable film, and the particle diameter of the microspheres is less than 5 ⁇ m, thereby ensuring mechanical properties and light transmission of the ultra-thin fully biodegradable film in the later stage.
  • the dispersing agent of the present invention is selected from one or two selected from the group consisting of epoxy soybean oil and silicone type diffusing oil, and the dispersing agent can be used to better match the toughening and anti-reflecting agent. It is advantageous to enhance the dispersion of the toughening and permeabilizing agent in the carrier resin; in addition, the technical solution of the present invention can also disperse the system by using a conventional physical dispersion method instead of the addition of the dispersing agent and the organic solvent, but the effect may be It is weaker than the technical solution using a dispersant, and thus the above technical solution of adding a dispersant can be employed.
  • auxiliaries used in the above-mentioned invention are environmentally friendly reagents and materials which are capable of being completely degraded in nature.
  • step (3) Put the mixture of step (2) into a twin-screw extruder, extrude at 135-160 ° C, air-cool granulation, and obtain special enhanced and toughened ultra-thin biodegradable film. Antireflective masterbatch.
  • the inventor firstly uses carbon tetrachloride as a solvent to dissolve and disperse the toughening agent, and uniformly disperses the dispersant on the surface of the reinforcing toughening agent by a volatile solvent, which is beneficial to enhancing the toughening and permeabilizing agent.
  • the dispersion in the carrier resin is better than the conventional mixing method.
  • preparation method without adding a dispersing agent and an organic solvent may be employed as follows:
  • step (2) The mixed mixture of the step (1) is put into a twin-screw extruder, extruded at 135-160 ° C, and air-cooled granulated to obtain a special enhanced toughening antireflective masterbatch for the ultra-thin full biodegradable film.
  • the inventors further provide a specific application of the masterbatch, which is used for preparing an ultra-thin ultra-transparent fully biodegradable film blown film grade material.
  • the main components of the film blown film grade material are: by weight:
  • polyadipate/butylene terephthalate and polylactic acid are used as carrier resins, and the melt flow rate is 2-5 g/10 min, and the acid value is less than 15, and polyadipate/p-benzoic acid in the masterbatch material.
  • the specification of butylene formate is exactly the same; the polylactic acid melt flow rate is 2-5 g/10 min;
  • the corresponding preparation method of the blown film grade material is as follows:
  • the blown film grade material obtained by the above method can directly blow an ultrathin film having a thickness of 6 ⁇ m or less, and the tensile strength and elongation at break are superior to those of the same thickness polyethylene LLDPE, and can completely replace the application of the polyethylene PE product. At the same time, it has good processing performance and does not require special processing equipment for processing.
  • the inventors of the present invention further provide a special enhanced toughening antireflective masterbatch for ultra-thin fully biodegradable mulch film, the main components of which are: by weight:
  • polyadipate/butylene terephthalate 65-85 parts of polyadipate/butylene terephthalate, 1-20 parts of polylactic acid, 10-20 parts of toughening and toughening agent, 5-30 parts of lubricant, 1-5 parts of dispersant, stable 1-5 additives;
  • the polylactic acid used together with polyadipate/butylene terephthalate as a carrier resin has a melt flow rate of 2-5 g/10 min, an acid value of less than 15, and polyadipate/p-benzoic acid.
  • Butylene formate requires the same;
  • the lubricant and dispersant used above are the same as the film masterbatch candidate, and the inventors will not repeat them; and the stabilizer is one or both of an ultraviolet absorber and a UV stabilizer.
  • the UV absorber is a low volatility benzotriazole UV absorber Tinuvin 234;
  • the UV stabilizer is a sterically hindered amine stabilizer Uvinul ® 5050H, which can avoid and improve the ultra-thin biodegradable film processing and field use. The problem of photodegradation in the process and prolong its service life;
  • the corresponding inventors have also provided the preparation method of the above-mentioned reinforced film for strengthening and toughening antireflective masterbatch:
  • the above-mentioned masterbatch can also be dispersed by using a conventional physical dispersion method instead of the addition of a dispersant.
  • a conventional physical dispersion method instead of the addition of a dispersant.
  • the masterbatch provided by the invention is prepared by using polyadipate/butylene terephthalate and reinforcing toughening and permeabilizing agent as main raw materials, and can be used for processing film and processing film. It maintains the smoothness of processing and mechanical, optical properties and stability of ultra-thin biodegradable film products, while significantly reducing raw material costs.
  • the masterbatch production process is simple and easy to grasp, the obtained masterbatch is stable in nature, has no moisture, can be completely degraded, and has good dispersibility.
  • the addition of a small amount of the masterbatch provided by the invention can blow ultra-thin biodegradation below 6 ⁇ m.
  • the film product makes the film of the ultra-thin film blowing process easy to open, has improved processing stability and excellent mechanical properties, and can be widely used in the fields of film packaging, shopping bags, agricultural mulch, garbage bags and classified landfill composting.
  • Ultra-thin full biodegradable film special fortifying and toughening antireflective masterbatch including the following components by weight:
  • the masterbatch is used to prepare an ultra-thin ultra-transparent fully biodegradable film blown film grade material, the main components of which are: by weight:
  • the melt flow rate is 5g/10min, the acid value is less than 15; the polylactic acid melt flow rate is 2.5g/10min;
  • the preparation method of the ultra-thin ultra-transparent fully biodegradable film blown film grade material is as follows:
  • the ultra-thin ultra-transparent biodegradable film blown film material provided by the embodiment is blown into a 5 ⁇ 1 ⁇ m film product, and stored at room temperature and protected from light for 12 months, and the mechanical properties are not significantly changed; the tensile strength is 30 MPa, and the longitudinal and transverse fractures are stretched. The sum of the long rates is greater than 900%.
  • Ultra-thin full biodegradable film special fortifying and toughening antireflective masterbatch including the following components by weight:
  • hydrophobic nano silica, the epoxidized soybean oil, and the silicone diffusion oil are dissolved and dispersed in carbon tetrachloride, stirred uniformly, and carbon tetrachloride is distilled off to obtain a mixture 1; the mixture 1 and polyadipate are further /butylene terephthalate, Aike CE-AZ01, silica microspheres are sequentially put into a high-speed mixer 700 ⁇ 1000r / min for 10-30 minutes to obtain a mixture 2; the mixture 2 is put into a twin-screw extruder, Extrusion at 135-160 ° C, air-cooled granulation, to obtain ultra-thin full biodegradable film for enhanced toughening and anti-reflective masterbatch.
  • the masterbatch is used to prepare an ultra-thin ultra-transparent fully biodegradable film blown film grade material, the main components of which are: by weight:
  • the melt flow rate is 5g/10min, the acid value is less than 15; the polylactic acid melt flow rate is 2.5g/10min;
  • the preparation method of the ultra-thin ultra-transparent fully biodegradable film blown film grade material is as follows:
  • the ultra-thin ultra-transparent fully biodegradable film blown film grade material provided by the embodiment is blown into a 5 ⁇ 1 ⁇ m film product, and stored at room temperature and protected from light for 12 months, and the mechanical properties are unchanged; the tensile strength is 35 MPa, and the longitudinal and transverse elongation at break The sum of the rates is greater than 800%.
  • the masterbatch is used to prepare an ultra-thin ultra-transparent fully biodegradable film blown film grade material, the main components of which are: by weight:
  • the preparation method of the ultra-thin ultra-transparent fully biodegradable film blown film grade material is as follows:
  • the ultra-thin ultra-transparent biodegradable film blown film grade material provided by the embodiment is blown into a 5 ⁇ 1 ⁇ m film product, and stored at room temperature and protected from light for 12 months, and the mechanical properties are unchanged; the tensile strength is 28 MPa, and the longitudinal and transverse elongation at break The sum of the rates is greater than 750%.
  • the ultra-thin full biodegradable film obtained in the above embodiment 1 is used for the application of the toughened antireflective masterbatch to the ultra-thin film blowing.
  • There are mainly two ways of adding one is to take the masterbatch according to the ultra-thin film component 1- 20% of the ratio is directly mixed with the blown film material, and added to the blown film machine for extrusion blow molding; the other is to mix the masterbatch with other components according to 1-20% of the ultra-thin film component, and then add it.
  • Film blower extrusion blow molding is mainly two ways of adding, one is to take the masterbatch according to the ultra-thin film component 1- 20% of the ratio is directly mixed with the blown film material, and added to the blown film machine for extrusion blow molding; the other is to mix the masterbatch with other components according to 1-20% of the ultra-thin film component, and then add it.
  • compositions and dosage are Composition and dosage (parts)
  • the ultra-thin full biodegradable film prepared in Example 1 is used for strengthening and toughening antireflective masterbatch 5
  • Preparation process Various raw materials were weighed according to the above formula and placed in a high speed mixer for 5 minutes. After uniform mixing, the mixture is granulated by twin-screw extrusion, and the mixture is placed in a hopper of an extrusion blown film machine, and extruded into a uniform cylindrical film (thickness of 4-6 ⁇ m), which is cut. , the volume is made into an ultra-thin full biodegradable film.
  • compositions and dosage are Composition and dosage (parts)
  • the ultrathin full biodegradable film prepared in Example 1 is used for strengthening and toughening antireflective masterbatch 3
  • Preparation process Various raw materials were weighed according to the above formula and placed in a high speed mixer for 5 minutes. After uniform mixing, the mixture is placed in a hopper of an extrusion blown film machine, and extruded into a uniform cylindrical film (thickness of 4-6 ⁇ m), which is cut and divided into ultra-thin Biodegradable film.
  • + The opening is smooth, continuous film
  • +- can open, easy to break the film
  • - difficult to open, easy to break the film.
  • the ultrathin full biodegradable film prepared by the invention is used for strengthening and toughening antireflective masterbatch, and the ultrathin whole biodegradable film is blown, and the light transmittance, tensile strength and elongation at break are superior to thickness. High biodegradable film with good processing properties.
  • the comparative example is a polyolefin LLDPE film of the same thickness.
  • Example 1 Example 2 Example 3 Comparative example thickness( Mm ) 5 5 5 5 5 Transmittance(%) 91 91 90 90 90 Tensile strength (MPa) 30 35 28 10 The sum of longitudinal and transverse elongation at break (%) 916 850 760 750 Right angle tear strength (N/mm) 117 119 116 85
  • the ultra-thin ultra-transparent biodegradable film blown by the blown film material prepared by the invention has good light transmittance, tensile strength and elongation at break superior to the same thickness polyethylene LLDPE, and can completely replace
  • the application of polyethylene PE products has good processing properties and does not require special processing equipment for processing.
  • the film product prepared by using the resin provided by the invention is stable at room temperature, has a light preservation period of 12 months, and has excellent mechanical properties, and can be widely used in the fields of film packaging, shopping bags, garbage sorting, landfill composting and the like.
  • Ultra-thin fully biodegradable mulch film for enhanced toughening and antireflective masterbatch, by weight including the following components:
  • Ultra-thin fully biodegradable mulch film for enhanced toughening and antireflective masterbatch, by weight including the following components:
  • UV absorber Tinuvin234 2.5 parts
  • the ultrathin full biodegradable mulch film special reinforcing and toughening antireflective masterbatch is applied to the blowing of the super mulch film, and there are mainly two ways of adding, one is to take the masterbatch according to the ratio of 1-5% of the super mulch component. Directly mixed with the blown film material, and added to the blown film machine for extrusion blow molding; the other is to mix the masterbatch with other components according to 1-5% of the super-film component, and then add it to the film blowing machine. Blowing out.
  • compositions and dosage are Composition and dosage (parts)
  • the ultrathin full biodegradable mulch film prepared in Example 7 is used for strengthening and toughening antireflective masterbatch 5 parts
  • Preparation process Various raw materials were weighed according to the above formula and placed in a high speed mixer for 5 minutes. After uniform mixing, the mixture is granulated by twin-screw extrusion, and the mixture is placed in a hopper of an extrusion blown film machine, and extruded into a uniform cylindrical film (the thickness of the film is 4-5 ⁇ m, and the width of the film is 90- 200cm can be), cut and divided into ultra-thin full biodegradable mulch film.
  • the ultrathin full biodegradable mulch film prepared in Example 7 is used for strengthening and toughening antireflective masterbatch.
  • Preparation process Various raw materials were weighed according to the above formula and placed in a high speed mixer for 5 minutes. After uniform mixing, the mixture is placed in a hopper of an extrusion blown film machine, and extruded into a uniform cylindrical film (the thickness of the film is 4-5 ⁇ m, the width of the film is 90-200 cm), and is cut. The sub-roll is made into an ultra-thin fully biodegradable mulch film.
  • the ultrathin full biodegradable mulch film prepared by the invention is used for reinforcing and toughening antireflective masterbatch, and the ultrathin full biodegradable mulch film is blown, and the light transmittance, tensile strength and elongation at break are better than thickness. High biodegradable mulch film with good processing properties.

Abstract

本发明是属于生物降解高分子材料领域，尤其涉及一种增强增韧增透母粒，该母粒以聚己二酸/对苯二甲酸丁二酯和增强增韧增透剂为主要原料制备而成，既能加工薄膜又可加工地膜，保持了超薄全生物降解膜产品的加工顺畅性以及力学、光学性能和使用稳定性，同时能大幅度降低薄膜成本。该母粒生产过程简单，容易掌握，所获得的母粒性质稳定，可完全降解、分散性好，添加少量本发明所提供的母粒与降解树脂（PBAT+PLA等）配合使用，即可吹制6μm以下的超薄生物降解薄膜制品，使得超薄薄膜吹制过程膜片易开口，加工稳定性提高，机械性能优异，可广泛应用于薄膜类包装、购物袋、农用地膜、垃圾袋及分类填埋堆肥处理等领域。

Description

一种增强增韧增透母粒及其制备方法和应用
本发明属于材料领域，具体涉及一种生物降解塑料母粒，特别是一种增强增韧增透母粒及其制备方法和应用。
塑料薄膜和地膜在日常生活和工农业生产中起到巨大作用，然而目前所采用的塑料薄膜和地膜绝大多数为难以短时期降解的聚烯烃类薄膜或者添加了淀粉和光降解剂的不完全降解聚烯烃类薄膜。这些薄膜材料的使用，造成环境的“白色污染”，为人类可持续发展带来了安全隐患。全生物降解薄膜是由完全生物降解塑料通过吹塑、流延或者压延加工而成，能被微生物完全分解，其降解的最终产物为二氧化碳和水，可完全由自然界消纳，因此以全生物降解薄膜代替目前的聚烯烃类产品，是解决白色污染的重要手段。
目前全生物降解薄膜主要由聚乳酸、聚己内酯、脂肪族聚酯、脂肪族聚碳酸酯、聚羟基酯类、淀粉等，但是由于上述聚合物的自身特点和缺陷，单一聚合物难以作为薄膜材料使用。目前的研究主要是通过共混改性、共聚改性、增塑改性以及复合改性来改善薄膜的综合性能。专利CN103589124B公开了一种全生物降解PLA/PBAT复合薄膜及其制备方法；专利CN104744898A公开了一种全生物降解薄膜及其制备方法，该薄膜是有聚乳酸（PLA）、聚碳酸亚丙酯（PPC）、聚己二酸/对苯二甲酸丁二酯（PBAT）和热稳定剂组成，但是上述这些薄膜制品普遍厚度偏高，为6um-50um，薄膜制品的成本居高不下，而厚度过高又会导致透光性差、厚度过低又会导致强度低，导致短期内无法商业化推广，因此无法达到最佳的功能平衡。不同于难以降解的聚烯烃类薄膜，对于全生物降解薄膜，只要加工方便、性能优良，薄膜制品越薄越好。然而我们通过试验发现，低于6μm的超薄薄膜存在加工过程膜泡开口困难、拉伸强度和撕裂强度大幅下降、雾度大等问题，而作为地膜使用时田间使用过程中由于光照引发树脂分子断链交联，地膜韧性降低脆性增加，地膜易提前发生开裂；因此如何克服现有超薄全生物降解薄膜制品的加工及性能缺陷，提供专用增强增韧增透母粒成为本领域急需解决的问题。
发明内容
本发明针对现有技术存在的诸多不足之处，提供了一种增强增韧增透母粒及其制备方法和应用，该母粒以聚己二酸/对苯二甲酸丁二酯和增强增韧增透剂为主要原料制备而成，既能加工薄膜又可加工地膜，保持了超薄全生物降解膜产品的加工顺畅性以及力学、光学性能和使用稳定性，同时能大幅度降低薄膜成本。该母粒生产过程简单，容易掌握，所获得的母粒性质稳定，可完全降解、分散性好，添加少量本发明所提供的母粒与降解树脂（PBAT+PLA等）配合使用，即可吹制6μm以下的超薄生物降解薄膜制品，使得超薄薄膜吹制过程膜片易开口，加工稳定性提高，机械性能优异，可广泛应用于薄膜类包装、购物袋、农用地膜、垃圾分类填埋堆肥处理等领域。
本发明的具体技术方案是：
一种增强增韧增透母粒，其主要组分按重量份计为：
聚己二酸/对苯二甲酸丁二酯65-88份、增强增韧增透剂10-20份；
其中所述的聚己二酸/对苯二甲酸丁二酯作为载体树脂，其熔体流动速率为2-5g/10min，酸值小于15。本发明使用的聚己二酸/对苯二甲酸丁二酯对超薄全降解薄膜专用母粒的制备和使用性能非常重要，既要融合所有物料，而且还要耐受高温不发生挥发和分解，在后期以本发明所述母粒制备超薄全生物降解薄膜时，还要与其他全生物降解树脂有较好的相容性，且不会诱发薄膜的降解，因此发明人在众多备选树脂中优选采用了该树脂作为母粒的载体树脂，且限定了其具体的用量如上，在该用量范围下母粒的各项功能达到最佳平衡。
所述的增强增韧增透剂为无机增强增韧增透剂、有机增强增韧剂的一种或几种：所述的无机增强增韧增透剂，选自疏水型纳米二氧化硅，所述疏水型纳米二氧化硅粒径为5-25nm；所述的有机增强增韧剂为阿克玛AX-8900或ADX-1200s树脂相容剂或杭州爱克CE-AZ01增容剂的一种或几种；
增强增韧增透剂不超过20份，是为了保证粉体在与树脂混合过程中损失少，分布均匀，且便于造粒；同时还提高了后期薄膜加工中的多种树脂相容性，又不会因为过多增容剂的添加而降低薄膜的机械性能；
选择上述增强增韧增透剂，与载体树脂具有良好的共混相容性，可制得高浓度母粒；在后期薄膜加工过程中，可以起成核剂和增容作用，利于超薄膜加工的稳定性，同时用于增强超薄全生物降解薄膜的力学性能。
除此之外根据用途的不同还可以在上述组方的基础上添加其他助剂成分：
更为具体的，发明人进一步提供了一种超薄全生物降解薄膜专用增强增韧增透母粒，其主要组分按重量份计为：
聚己二酸/对苯二甲酸丁二酯65-88份、增强增韧增透剂10-20份、润滑剂0.5-30份、分散剂1-5份；
其中所述的润滑剂为聚合物PMMA微球、二氧化硅微球中的一种或两种。所述的聚合物微球粒径为0.5-5μm，所述的二氧化硅微球粒径为1-5μm；均可以从市场上直接购得；
上述润滑剂在本发明中主要起润滑开口作用，利于超薄全生物降解薄膜加工时膜片开口，同时微球粒径均小于5μm，保证后期制备超薄全生物降解薄膜的机械性能和透光性；
本发明所述的分散剂选自所述的选自环氧大豆油、有机硅类扩散油的一种或两种，选用上述分散剂后，可以更好的与增强增韧增透剂配合，利于增强增韧增透剂在载体树脂中的分散；除此之外，本发明的技术方案还可以采用常规的物理分散方法代替分散剂和有机溶剂的加入而对体系进行分散，但是效果可能要弱于采用分散剂的技术方案，因此可采用上述添加分散剂的技术方案。
本发明上述所用的所有助剂均为环境友好试剂和材料，能够在自然界全部降解。
对应的上述超薄全生物降解薄膜专用增强增韧增透母粒的制备方法，包括以下步骤：（1）将组方量的增强增韧增透剂、分散剂溶解分散在四氯化碳中，搅拌均匀后，蒸馏出四氯化碳得混合物；（2）将步骤（1）得到的混合物、聚己二酸/对苯二甲酸丁二酯、润滑剂依次按重量份投入高速搅拌机，混炼10-30分钟；（3）将步骤（2）混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解薄膜专用增强增韧增透母粒。
上述制备方法中，发明人首先选用四氯化碳作为溶剂对增强增韧剂进行溶解分散，并通过挥发溶剂使分散剂均匀包覆于增强增韧剂表面，有利于增强增韧增透剂在载体树脂中的分散，较之现在常规的混合方式效果更好。
除此之外，还可以采用不加分散剂和有机溶剂的制备方法如下：
（1）将组方量的增强增韧增透剂、聚己二酸/对苯二甲酸丁二酯、润滑剂依次按重量份投入高速搅拌机，混炼10-30分钟；
（2）将步骤（1）混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解薄膜专用增强增韧增透母粒。
获得了上述的超薄全生物降解薄膜专用增强增韧增透母粒之后，发明人进一步提供了所述母粒的具体应用，将其用于制备超薄超透明全生物降解薄膜吹膜级材料，该薄膜吹膜级材料主要组分按重量份计为：
聚己二酸/对苯二甲酸丁二酯80～90份，聚乳酸0.5～20份，超薄全生物降解薄膜专用增强增韧增透母粒1～5份；
其中聚己二酸/对苯二甲酸丁二酯和聚乳酸作为载体树脂，其熔体流动速率为2-5g/10min，酸值小于15，与母粒材料中聚己二酸/对苯二甲酸丁二酯的规格完全相同；所述聚乳酸熔体流动速率为2-5g/10min；
对应的该吹膜级材料的制备方法如下：
（1）聚己二酸/对苯二甲酸丁二酯、聚乳酸、超薄超透明全生物降解薄膜专用增强增韧增透母粒投入高速搅拌机，搅拌5-8分钟，搅拌速度700～1000r/min；
（2）将上述混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒即得。
通过上述方法获得的吹膜级材料，可以直接吹制厚度6μm以下的超薄薄膜，其拉伸强度及断裂伸长率优于同等厚度聚乙烯LLDPE的效果，可完全替代聚乙烯PE产品的应用，同时具有良好的加工性能，且不需要特殊的加工设备进行处理。
除了上述薄膜专用母粒外，本发明的发明人还进一步提供了一种超薄全生物降解地膜专用增强增韧增透母粒，其主要组分按重量份计为：
聚己二酸/对苯二甲酸丁二酯65-85份、聚乳酸1-20份、增强增韧增透剂10-20份、润滑剂5-30份、分散剂1-5份、稳定性助剂1-5份；
其中所采用的聚乳酸与聚己二酸/对苯二甲酸丁二酯一起作为载体树脂，其熔体流动速率为2-5g/10min，酸值小于15，与聚己二酸/对苯二甲酸丁二酯要求相同；
上述所采用的润滑剂和分散剂与薄膜母粒备选物质相同，发明人不再赘述；而所述的稳定性助剂为紫外线吸收剂、紫外线稳定剂的一种或两种，所述的紫外线吸收剂为低挥发性苯并三唑类紫外吸收剂Tinuvin234；所述的紫外线稳定剂为空间位阻胺类稳定剂Uvinul®5050H，可避免和改善超薄全生物降解地膜加工过程和田间使用过程中的光降解问题，延长其使用寿命；
对应的发明人也提供了上述地膜专用增强增韧增透母粒的制备方法如下：
（1）将组方量的增强增韧增透剂、分散剂溶解分散在四氯化碳中，搅拌均匀后，蒸馏出四氯化碳得混合物；（2）将步骤（1）得到的混合物、聚己二酸/对苯二甲酸丁二酯和聚乳酸、稳定性助剂、润滑剂依次按重量份投入高速搅拌机，700～1000r/min搅拌混炼10-30分钟；（3）将步骤（2）混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解地膜专用增强增韧增透母粒。
同样的，上述母粒也可以采用常规的物理分散方法代替分散剂的加入而对体系进行分散，具体方法可参考上述超薄全生物降解薄膜专用增强增韧增透母粒的制备方法。
综上所述，本发明所提供的母粒以聚己二酸/对苯二甲酸丁二酯和增强增韧增透剂为主要原料制备而成，既能用于加工薄膜又可加工地膜，保持了超薄全生物降解膜产品的加工顺畅性以及力学、光学性能和使用稳定性，同时能大幅度降低原材料成本。该母粒生产过程简单，容易掌握，所获得的母粒性质稳定，无任何水分，可完全降解、分散性好，添加少量本发明所提供的母粒即可吹制6μm以下的超薄生物降解薄膜制品，使得超薄薄膜吹制过程膜片易开口，加工稳定性提高，机械性能优异，可广泛应用于薄膜类包装、购物袋、农用地膜、垃圾袋及分类填埋堆肥处理等领域。
具体实施方式
实施例1
超薄全生物降解薄膜专用增强增韧增透母粒，按照重量份计，包括以下组分：
聚己二酸/对苯二甲酸丁二酯 75份
疏水型纳米二氧化硅（粒径5-10nm） 20份
聚合物PMMA微球（粒径2-3μm） 30份
环氧大豆油 1份
按照下述步骤制备而成：
将疏水型纳米二氧化硅、环氧大豆油溶解分散于四氯化碳中，搅拌均匀，蒸馏出四氯化碳，得混合物1；再将该混合物1、聚己二酸/对苯二甲酸丁二酯、聚合物PMMA微球依次投入高速搅拌机700～1000r/min混炼10-30分钟，得混合物2；混合物2投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解薄膜专用增强增韧增透母粒；
应用该母粒制备超薄超透明全生物降解薄膜吹膜级材料，其主要组分按重量份计为：
聚己二酸/对苯二甲酸丁二酯87份，聚乳酸10份，超薄超透明全生物降解薄膜专用增强增韧增透母粒3份；
其中所述的聚己二酸/对苯二甲酸丁二酯作为载体树脂，其熔体流动速率为5g/10min，酸值小于15；所述聚乳酸熔体流动速率为2.5g/10min；
所述超薄超透明全生物降解薄膜吹膜级材料的制备方法如下：
聚己二酸/对苯二甲酸丁二酯、聚乳酸、超薄超透明全生物降解薄膜专用增强增韧增透母粒投入高速搅拌机，搅拌速度700～1000r/min搅拌5-8分钟；将上述混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到一种超薄超透明全生物降解薄膜吹膜级材料。
采用本实施例提供的超薄超透明全生物降解薄膜吹膜级材料吹制成5±1μm薄膜制品，常温避光储存12个月，机械性能无明显变化；拉伸强度30MPa，纵横向断裂伸长率之和大于900%。
实施例2
超薄全生物降解薄膜专用增强增韧增透母粒，按照重量份计，包括以下组分：
聚己二酸/对苯二甲酸丁二酯 69份
疏水型纳米二氧化硅（粒径5-10nm） 10份
爱克CE-AZ01 10份
二氧化硅微球（粒径2-3μm） 10份
环氧大豆油 0.5份
有机硅扩散油 0.5份
按照下述步骤制备而成：
将疏水型纳米二氧化硅、环氧大豆油、有机硅扩散油溶解分散于四氯化碳中，搅拌均匀，蒸馏出四氯化碳，得混合物1；再将该混合物1、聚己二酸/对苯二甲酸丁二酯、爱克CE-AZ01、二氧化硅微球依次投入高速搅拌机700～1000r/min混炼10-30分钟，得混合物2；混合物2投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解薄膜专用增强增韧增透母粒。
应用该母粒制备超薄超透明全生物降解薄膜吹膜级材料，其主要组分按重量份计为：
聚己二酸/对苯二甲酸丁二酯85份，聚乳酸10份，超薄超透明全生物降解薄膜专用增强增韧增透母粒5份；
其中所述的聚己二酸/对苯二甲酸丁二酯作为载体树脂，其熔体流动速率为5g/10min，酸值小于15；所述聚乳酸熔体流动速率为2.5g/10min；
所述超薄超透明全生物降解薄膜吹膜级材料的制备方法如下：
聚己二酸/对苯二甲酸丁二酯、聚乳酸、超薄超透明全生物降解薄膜专用增强增韧增透母粒投入高速搅拌机，搅拌速度700～1000r/min搅拌5-8分钟；将上述混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到一种超薄超透明全生物降解薄膜吹膜级材料。
采用本实施例提供的超薄超透明全生物降解薄膜吹膜级材料吹制成5±1μm薄膜制品，常温避光储存12个月，机械性能无变化；拉伸强度35MPa，纵横向断裂伸长率之和大于800%。
实施例3
超薄全生物降解薄膜专用增强增韧增透母粒，按照重量百分比计，包括以下组分：
聚己二酸/对苯二甲酸丁二酯 68份
疏水型纳米二氧化硅（粒径10-20nm） 15份
阿克玛AX-8900 5份
二氧化硅微球（粒径1μm） 5份
有机硅扩散油 2份
按照下述步骤制备而成：
将疏水型纳米二氧化硅、有机硅扩散油溶解分散于四氯化碳中，搅拌均匀，蒸馏出四氯化碳，得混合物1；再将该混合物1、聚己二酸/对苯二甲酸丁二酯、阿克玛AX-8900、二氧化硅微球依次投入高速搅拌机700～1000r/min混炼10-30分钟，得混合物2；混合物2投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解薄膜专用增强增韧增透母粒。
应用该母粒制备超薄超透明全生物降解薄膜吹膜级材料，其主要组分按重量份计为：
聚己二酸/对苯二甲酸丁二酯90份，聚乳酸5份，超薄超透明全生物降解薄膜专用增强增韧增透母粒5份；
其中所述的聚己二酸/对苯二甲酸丁二酯作为载体树脂，其熔体流动速率为5g/10min；所述聚乳酸熔体流动速率为2.5g/10min；
所述超薄超透明全生物降解薄膜吹膜级材料的制备方法如下：
聚己二酸/对苯二甲酸丁二酯、聚乳酸、超薄超透明全生物降解薄膜专用增强增韧增透母粒投入高速搅拌机，搅拌速度700～1000r/min搅拌5-8分钟；将上述混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到一种超薄超透明全生物降解薄膜吹膜级材料。
采用本实施例提供的超薄超透明全生物降解薄膜吹膜级材料吹制成5±1μm薄膜制品，常温避光储存12个月，机械性能无变化；拉伸强度28MPa，纵横向断裂伸长率之和大于750%。
实施例4
上述实施例1获得的超薄全生物降解薄膜专用增强增韧增透母粒应用到超薄膜的吹制中，主要有两种加入方式，一种是将母粒按照超薄膜组分的1-20%的比例与吹膜料直接混合，加入吹膜机挤出吹塑；另一种是将母粒按照超薄膜组分的1-20%与其他组分一起再经混合造粒后，加入吹膜机挤出吹塑。
应用实例1
组分及用量（份数）
PBAT 90
PLA 5
实施例1制备的超薄全生物降解薄膜专用增强增韧增透母粒 5
制备工艺：按上述配方将各种原料称重，并置于高速混合机中搅拌5分钟。经均匀混合后，通过双螺杆挤出造粒，将混合料置于挤出吹膜机的料斗中，挤出吹塑成均匀筒状薄膜（薄膜厚度为4-6μm均可），经裁切、分卷制成超薄全生物降解薄膜。
应用实例2
组分及用量（份数）
PBAT 92
PPC 5
实施例1制备的超薄全生物降解薄膜专用增强增韧增透母粒 3
制备工艺：按上述配方将各种原料称重，并置于高速混合机中搅拌5分钟。经均匀混合后，将混合料置于挤出吹膜机的料斗中，挤出吹塑成均匀筒状薄膜（薄膜厚度为4-6μm均可），经裁切、分卷制成超薄全生物降解薄膜。
按照GB/T1040.3塑料拉伸性能的测定第3部分：薄膜和薄片的试验条件，拉伸速率200mm/min。所得薄膜各性能如下表所示。对比例为采用同等树脂，未加入超薄全生物降解薄膜专用增强增韧增透母粒的薄膜。
应用实例1 对比例1 应用实例2 对比例2
树脂 PBAT、PLA PBAT、PLA PBAT、PPC PBAT、PPC
厚度（ μm ） 5 8 5 8
透光率（%） 91 90 88 85
拉伸强度（MPa） 30 25 23 17
纵横向断裂伸长率之和（%） 916 850 660 590
直角撕裂强度（N/mm） 115 98 87 85
降解性 全降解 全降解 全降解 全降解
吹塑膜泡开口性 + - + +-
+：开口顺滑，不断膜，+-：能开口，易断膜，-：难以开口，易断膜。
可见采用本发明所制备的超薄全生物降解薄膜专用增强增韧增透母粒，吹制超薄全生物降解薄膜，其透光率、拉伸强度及断裂伸长率等均优于厚度较高的全生物降解薄膜，同时具有良好的加工性能。
实施例5
按照GB/T1040.3塑料拉伸性能的测定第3部分：薄膜和薄片的试验条件，拉伸速率200mm/min。实施例1-3中吹膜级材料所得薄膜各性能如下表所示。
对比例为同等厚度的聚烯烃LLDPE薄膜。
实施例1 实施例2 实施例3 对比例
厚度（ μm ） 5 5 5 5
透光率（%） 91 91 90 90
拉伸强度（MPa） 30 35 28 10
纵横向断裂伸长率之和（%） 916 850 760 750
直角撕裂强度（N/mm） 117 119 116 85
可见采用本发明所制备的吹膜材料吹制的超薄超透明全生物降解薄膜，其透光性好，拉伸强度及断裂伸长率优于同能厚度聚乙烯LLDPE的效果，可完全替代聚乙烯PE产品的应用，同时具有良好的加工性能，且不需要特殊的加工设备进行处理。采用本发明提供的树脂制得的薄膜制品常温稳定，避光保存期12个月，机械性能优异，可广泛应用于薄膜类包装、购物袋、垃圾分类填埋堆肥处理等领域。
实施例7
超薄全生物降解地膜专用增强增韧增透母粒，按照重量份计，包括以下组分：
聚己二酸/对苯二甲酸丁二酯 67份
聚乳酸 1份
疏水型纳米二氧化硅（粒径5-10nm） 20份
聚合物PMMA微球（粒径2-3μm） 10份
环氧大豆油 2份
紫外线吸收剂Tinuvin234 1份
按照下述步骤制备而成：
将疏水型纳米二氧化硅、环氧大豆油溶解分散于四氯化碳中，搅拌均匀，蒸馏出四氯化碳，得混合物1；再将该混合物1、聚己二酸/对苯二甲酸丁二酯、聚乳酸、紫外线吸收剂Tinuvin234、聚合物PMMA微球依次投入高速搅拌机700～1000r/min搅拌，混炼10-30分钟，得混合物2；混合物2投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解地膜专用增强增韧增透母粒。
实施例8
超薄全生物降解地膜专用增强增韧增透母粒，按照重量份计，包括以下组分：
聚己二酸/对苯二甲酸丁二酯 69份
聚乳酸 10份
疏水型纳米二氧化硅（粒径15-25nm） 10份
爱克CE-AZ01 10份
二氧化硅微球（粒径2-3μm） 5份
有机硅扩散油 1份
紫外线吸收剂Tinuvin234 2.5份
紫外线稳定剂Uvinul®5050H 2.5份
按照下述步骤制备而成：
将疏水型纳米二氧化硅、有机硅扩散油溶解分散于四氯化碳中，搅拌均匀，蒸馏出四氯化碳，得混合物1；再将该混合物、聚己二酸/对苯二甲酸丁二酯、聚乳酸、爱克CE-AZ01、紫外线吸收剂Tinuvin234、紫外线稳定剂Uvinul®5050H、二氧化硅微球依次投入高速搅拌机700～1000r/min搅拌混炼10-30分钟，得混合物2；混合物2投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解地膜专用增强增韧增透母粒。
实施例9
超薄全生物降解地膜专用增强增韧增透母粒，按照重量百分比计，包括以下组分：
聚己二酸/对苯二甲酸丁二酯 85份
聚乳酸 20份
疏水型纳米二氧化硅（粒径10-20nm） 10份
阿克玛AX-8900 10份
二氧化硅微球（粒径1μm） 1份
紫外线稳定剂Uvinul®5050H 2.5份
有机硅扩散油 1.5份
按照下述步骤制备而成：
将疏水型纳米二氧化硅、有机硅扩散油溶解分散于四氯化碳中，搅拌均匀，蒸馏出四氯化碳，得混合物1；再将该混合物、聚己二酸/对苯二甲酸丁二酯、紫外线稳定剂Uvinul®5050H、阿克玛AX-8900、二氧化硅微球依次投入高速搅拌机700～1000r/min搅拌混炼10-30分钟，得混合物2；混合物2投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解地膜专用增强增韧增透母粒。
实施例10
本发明超薄全生物降解地膜专用增强增韧增透母粒应用到超地膜的吹制中，主要有两种加入方式，一种是将母粒按照超地膜组分的1-5%的比例与吹膜料直接混合，加入吹膜机挤出吹塑；另一种是将母粒按照超地膜组分的1-5%与其他组分一起再经混合造粒后，加入吹膜机挤出吹塑。
应用实例3
组分及用量（份数）
PBAT 90份
PLA 5份
实施例7制备的超薄全生物降解地膜专用增强增韧增透母粒 5份
制备工艺：按上述配方将各种原料称重，并置于高速混合机中搅拌5分钟。经均匀混合后，通过双螺杆挤出造粒，将混合料置于挤出吹膜机的料斗中，挤出吹塑成均匀筒状地膜（地膜厚度为4-5μm均可，地膜宽度90-200cm均可），经裁切、分卷制成超薄全生物降解地膜。
应用实例4
PBAT 92份
PPC 5份
实施例7制备的超薄全生物降解地膜专用增强增韧增透母粒 3份
制备工艺：按上述配方将各种原料称重，并置于高速混合机中搅拌5分钟。经均匀混合后，将混合料置于挤出吹膜机的料斗中，挤出吹塑成均匀筒状地膜（地膜厚度为4-5μm均可，地膜宽度90-200cm均可），经裁切、分卷制成超薄全生物降解地膜。
按照GB/T1040.3塑料拉伸性能的测定第3部分：薄膜和薄片的试验条件，拉伸速率200mm/min。所得地膜各性能如下表所示。对比例为采用同等树脂，未加入超薄全生物降解地膜专用增强增韧增透母粒的地膜。
应用实例3 对比例1 应用实例4 对比例2
树脂 PBAT、PLA PBAT、PLA PBAT、PPC PBAT、PPC
厚度（ μm ） 5 8 5 8
透光率（%） 90 88 88 85
拉伸强度（MPa） 28 25 23 17
纵横向断裂伸长率之和（%） 910 850 670 590
直角撕裂强度（N/mm） 108 108 93 85
降解性 全降解 全降解 全降解 全降解
吹塑膜泡开口性 + - + +-
+：开口顺滑，不断膜，+-：能开口，易断膜，-：难以开口，易断膜
可见采用本发明所制备的超薄全生物降解地膜专用增强增韧增透母粒，吹制超薄全生物降解地膜，其透光率、拉伸强度及断裂伸长率等均优于厚度较高的全生物降解地膜，同时具有良好的加工性能。

Claims (10)

1、一种增强增韧增透母粒，其特征在于：其主要组分按重量份计为：聚己二酸/对苯二甲酸丁二酯65-88份、增强增韧增透剂10-20份。
2、根据权利要求1所述的增强增韧增透母粒，其特征在于：所述的聚己二酸/对苯二甲酸丁二酯熔体流动速率为2-5g/10min，酸值小于15；所述的增强增韧增透剂为无机增强增韧增透剂和有机增强增韧剂的一种或几种。
3、根据权利要求1所述的增强增韧增透母粒，其特征在于：所述的无机增强增韧增透剂，选自疏水型纳米二氧化硅，所述疏水型纳米二氧化硅粒径为5-25nm；所述的有机增强增韧剂为阿克玛AX-8900或ADX-1200s树脂相容剂或杭州爱克CE-AZ01增容剂中的一种或几种。
4、一种超薄全生物降解薄膜专用增强增韧增透母粒，其特征在于：其主要组分按重量份计为：聚己二酸/对苯二甲酸丁二酯65-88份、增强增韧增透剂10-20份、润滑剂0.5-30份、分散剂1-5份；其中所述的聚己二酸/对苯二甲酸丁二酯熔体流动速率为2-5g/10min，酸值小于15；所述的润滑剂为聚合物PMMA微球或二氧化硅微球中的一种或两种；所述的分散剂选自环氧大豆油或有机硅类扩散油的一种或两种。
5、一种超薄全生物降解薄膜专用增强增韧增透母粒的制备方法，其特征在于：具体步骤如下：（1）将组方量的增强增韧增透剂、分散剂溶解分散在四氯化碳中，搅拌均匀后，蒸馏出四氯化碳得混合物；（2）将步骤（1）得到的混合物、聚己二酸/对苯二甲酸丁二酯、润滑剂依次按重量份投入高速搅拌机，混炼10-30分钟；（3）将步骤（2）混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解薄膜专用增强增韧增透母粒。
6、一种超薄全生物降解地膜专用增强增韧增透母粒，其特征在于：其主要组分按重量份计为：聚己二酸/对苯二甲酸丁二酯65-85份、聚乳酸1-20份、增强增韧增透剂10-20份、润滑剂0.5-30份、分散剂1-5份、稳定性助剂1-5份；其中所述的聚己二酸/对苯二甲酸丁二酯熔体流动速率为2-5g/10min，酸值小于15；其中所述的聚乳酸，其熔体流动速率为2-5g/10min，酸值小于15；所述的润滑剂为聚合物PMMA微球或二氧化硅微球中的一种或两种；所述的分散剂选自环氧大豆油或有机硅类扩散油的一种或两种；所述的稳定性助剂为紫外线吸收剂或紫外线稳定剂的一种或两种。
7、根据权利要求6所述的超薄全生物降解地膜专用增强增韧增透母粒，其特征在于：所述的紫外线吸收剂为低挥发性苯并三唑类紫外吸收剂Tinuvin234；所述的紫外线稳定剂为空间位阻胺类稳定剂Uvinul®5050H。
8、一种超薄全生物降解地膜专用增强增韧增透母粒的制备方法，其特征在于：具体步骤如下：（1）将组方量的增强增韧增透剂、分散剂溶解分散在四氯化碳中，搅拌均匀后，蒸馏出四氯化碳得混合物；（2）将步骤（1）得到的混合物、聚己二酸/对苯二甲酸丁二酯、聚乳酸、稳定性助剂、润滑剂依次按重量份投入高速搅拌机，700～1000r/min搅拌混炼10-30分钟；（3）将步骤（2）混合均匀的混合物投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到超薄全生物降解地膜专用增强增韧增透母粒。
9、一种应用超薄全生物降解薄膜专用增强增韧增透母粒制备的超薄超透明全生物降解薄膜吹膜级材料，其特征在于：主要组分按重量份计为：聚己二酸/对苯二甲酸丁二酯80～90份，聚乳酸0.5～20份，超薄全生物降解薄膜专用增强增韧增透母粒1～5份；其中所述聚己二酸/对苯二甲酸丁二酯作为载体树脂，其熔体流动速率为2～5g/10min，酸值小于15；所述聚乳酸熔体流动速率为2～5g/10min。
10、一种应用超薄全生物降解薄膜专用增强增韧增透母粒制备的超薄超透明全生物降解薄膜吹膜级材料的方法，其特征在于：具体步骤如下：（1）聚己二酸/对苯二甲酸丁二酯、聚乳酸、超薄超透明全生物降解薄膜专用增强增韧增透母粒投入高速搅拌机，700～1000r/min搅拌5～8分钟；（2）将上述混合均匀的混合物投入双螺杆挤出机中，于135～160℃挤出、风冷造粒即得。
PCT/CN2018/094176 2017-07-13 2018-07-03 一种增强增韧增透母粒及其制备方法和应用 WO2019011152A1 (zh)

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CN111138812A (zh) * 2019-12-31 2020-05-12 中国科学院理化技术研究所 一种甜菜专用超薄降解地膜及其制备方法
CN111534066A (zh) * 2020-05-13 2020-08-14 江西广源新材料有限公司 一种用于增强增韧聚乳酸纤维的功能母粒及其制备方法和增强增韧聚乳酸材料
CN111647183A (zh) * 2020-06-22 2020-09-11 浙江理工大学 一种无机微粉/pbat全降解复合薄膜的制备方法
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CN115322533A (zh) * 2022-08-23 2022-11-11 康辉新材料科技有限公司 一种mlcc离型膜专用聚酯母粒及其制备方法
CN116239874A (zh) * 2023-02-24 2023-06-09 大禾科技发展(南京)有限公司 一种水稻专用具有疏水性的生物降解农用地膜及其制备方法与应用
CN116253911A (zh) * 2023-04-21 2023-06-13 海南师范大学 一种超薄高强度高透光生物可降解食品内包装膜的制备方法

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CN110964298A (zh) * 2019-12-20 2020-04-07 深圳市祥鸿辉科技有限公司 一种生物降解改性材料及其制备方法
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CN111534066A (zh) * 2020-05-13 2020-08-14 江西广源新材料有限公司 一种用于增强增韧聚乳酸纤维的功能母粒及其制备方法和增强增韧聚乳酸材料
CN111647183A (zh) * 2020-06-22 2020-09-11 浙江理工大学 一种无机微粉/pbat全降解复合薄膜的制备方法
CN112662147A (zh) * 2020-12-23 2021-04-16 青岛润兴塑料新材料有限公司 一种高性能三元复配生物降解薄膜
CN112900149A (zh) * 2021-01-16 2021-06-04 北京金印联国际供应链管理有限公司 食品包装白卡纸及其生产工艺
CN113843999B (zh) * 2021-09-26 2023-07-04 中国科学技术大学先进技术研究院 一种聚己二酸/对苯二甲酸丁二醇酯薄膜的制备方法
CN113843999A (zh) * 2021-09-26 2021-12-28 中国科学技术大学先进技术研究院 一种聚己二酸/对苯二甲酸丁二醇酯薄膜的制备方法
CN114031904A (zh) * 2021-12-03 2022-02-11 辽宁东盛塑业有限公司 一种抑菌气调保鲜降解水果网套及其制备方法
CN114381100A (zh) * 2021-12-24 2022-04-22 贵州省材料产业技术研究院 一种阻燃增韧改性聚乳酸复合材料及其制备方法
CN115322533A (zh) * 2022-08-23 2022-11-11 康辉新材料科技有限公司 一种mlcc离型膜专用聚酯母粒及其制备方法
CN116239874A (zh) * 2023-02-24 2023-06-09 大禾科技发展(南京)有限公司 一种水稻专用具有疏水性的生物降解农用地膜及其制备方法与应用
CN116239874B (zh) * 2023-02-24 2024-01-23 大禾科技发展(南京)有限公司 一种水稻专用具有疏水性的生物降解农用地膜及其制备方法与应用
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