WO2019011153A1 - 一种可机械覆膜的全生物降解地膜 - Google Patents

一种可机械覆膜的全生物降解地膜 Download PDF

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WO2019011153A1
WO2019011153A1 PCT/CN2018/094195 CN2018094195W WO2019011153A1 WO 2019011153 A1 WO2019011153 A1 WO 2019011153A1 CN 2018094195 W CN2018094195 W CN 2018094195W WO 2019011153 A1 WO2019011153 A1 WO 2019011153A1
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Prior art keywords
film
parts
ultra
mechanically
fully biodegradable
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PCT/CN2018/094195
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English (en)
French (fr)
Inventor
徐静
米庆华
张坤
谭业明
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山东农业大学
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Priority claimed from CN201710572615.5A external-priority patent/CN107474494B/zh
Priority claimed from CN201710572626.3A external-priority patent/CN107418161B/zh
Application filed by 山东农业大学 filed Critical 山东农业大学
Priority to KR1020197030452A priority Critical patent/KR102331742B1/ko
Publication of WO2019011153A1 publication Critical patent/WO2019011153A1/zh

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    • 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
    • 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
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0256—Ground coverings
    • A01G13/0268—Mats or sheets, e.g. nets or fabrics
    • A01G13/0275—Films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • 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
    • 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
    • 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
    • C08K7/20—Glass
    • 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
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Definitions

  • the invention belongs to the field of agricultural materials, and in particular relates to a fully biodegradable mulch film which can be mechanically coated.
  • the mulch film plays a huge role in agricultural production.
  • plastic mulch films currently used are polyolefin mulch films which are difficult to degrade in a short period of time or incompletely degraded polyolefin mulch films which are added with starch and photodegradation agents.
  • the use of these mulch materials has caused "white pollution" of the environment, posing a safety hazard for the sustainable development of civilization.
  • the fully biodegradable mulch film is made of fully biodegradable plastic by blow molding or casting. It can be completely decomposed by microorganisms. The final products of its degradation are carbon dioxide and water, which can be completely absorbed by nature. Therefore, it is replaced by a fully biodegradable mulch film.
  • the current polyolefin products are an important means to solve white pollution in farmland and have important prospects for development and utilization.
  • the present invention provides a mechanically coated fully biodegradable mulch film, which is composed of a fully biodegradable resin, a reinforced and toughening auxiliaries and an easy processing aid, wherein the deficiencies of the prior art are provided.
  • the addition of enhanced toughening and anti-reflecting agent solves the problem that the mechanical strength of the ultra-thin film is poor, easy to break, and difficult to mechanically laminate;
  • the easy processing aid solves the problem of difficult opening of ultra-thin film processing and low processing efficiency;
  • the type of fully biodegradable resin, combined with functional additives, has developed an ultra-thin ultra-transparent and ultra-wide bio-controllable degradable film with a thickness of 4-6 ⁇ m.
  • the film has high transparency, light transmittance >90%, and haze ⁇ 13%;
  • the mechanical strength is high, and the tensile strength is >25 MPa, which satisfies the requirements of the filming strength of the ordinary laminating machine.
  • Tensile strength, elongation at break, and right-angle tear strength are all in accordance with PE film mechanical filming standards, and physical and mechanical properties are superior to or in accordance with GB13735-92.
  • a fully biodegradable mulch film which can be mechanically coated, characterized in that its main components are in parts by weight:
  • the whole biodegradable resin described therein is poly(adipic acid/butylene terephthalate), and one or more of polylactic acid and polypropylene carbonate;
  • polyadipate/butylene terephthalate as a main component, one or two of polylactic acid and polypropylene carbonate, wherein polybutylene adipate/butylene terephthalate accounts for 85-95% of biodegradable resin.
  • the polyadipate/butylene terephthalate has a melt flow rate of 1-2 g/10 min and an acid value of less than 15; wherein the polylactic acid melt flow rate is 2-5 g/10 min, and the acid value Less than 15; wherein the polypropylene carbonate has a melt flow rate of 1-2 g/10 min and an acid value of less than 15.
  • 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 2-25 nm; and the organic reinforcing toughening agent is an Acme AX-8900 or ADX-1200s resin compatibilizer.
  • the easy processing aid is one or two of polymer PMMA microspheres and silica microspheres.
  • the polymer microspheres have a particle size of 1-5 ⁇ m.
  • the silica microspheres have a particle size of 1-5 ⁇ m;
  • the inventors used polyadipate/butylene terephthalate as the main fully biodegradable resin, and controlled the melt flow rate to be 1-2 g/10 min, and the acid value was less than 15; The toughness is complemented by other resins to achieve better film formation and processability.
  • the inventors further provide an ultra-thin, ultra-transparent, fully biodegradable mulch film which can be mechanically coated, the main components of which are: by weight:
  • the inventors increased the amount of the fully biodegradable resin, thereby improving its mechanical properties and light transmission properties.
  • the whole biodegradable resin, the strengthening and toughening antireflective agent and the easy processing aid are mixed by a high-speed mixer for 5-8 min, mixed into a twin-screw extruder, and extruded at 135-160 ° C for granulation.
  • the whole biodegradable mulch film blowing material is obtained; then the whole biodegradable mulch film blowing material is blown on the film blowing machine to obtain an ultra-thin film having a film thickness of 4-6 ⁇ m, wherein the inflation ratio is 1.6-3.6.
  • the die gap is 0.8-1.8, and the width of the film is adjustable from 600-4000mm. The above parameters further limit the die gap and the blow ratio, thereby ensuring better performance of the film.
  • the film thickness is only 4-6 ⁇ m, and the thinned film reduces the cost per unit area of the fully biodegradable film.
  • the mulch film adopts the enhanced toughening and anti-reflecting agent, which not only improves the mechanical properties (tensile strength is higher than 25MPa, meets the requirements of mechanical coating standard), but also improves the light transmittance (light transmittance >90%, haze). ⁇ 13%).
  • the mulch film adopts microsphere type easy processing aid to make the blown film processing stable, and the film opening is smooth and easy to process.
  • the film can be completely degraded and the product is free from pollution.
  • the inventors also provide a mechanically laminable ultra-thin weather-resistant fully biodegradable mulch film based on the basic composition, the main components of which are: by weight:
  • one or both of the stability aid ultraviolet light stabilizer and the ultraviolet light absorber, and further the ultraviolet absorber is a low-volatility benzotriazole ultraviolet absorber Tinuvin 234;
  • the UV stabilizer is a hindered amine stabilizer Uvinul ® 5050H.
  • the method for preparing the above-mentioned mechanically coated ultra-thin weather-resistant fully biodegradable mulch film has the following specific steps:
  • the film thickness is only 4-6 ⁇ m, and the thinned film reduces the cost per unit area of the fully biodegradable film.
  • the mulch film adopts the enhanced toughening and anti-reflecting agent, which not only improves the mechanical properties (tensile strength is higher than 25MPa, meets the requirements of mechanical coating standard), but also improves the light transmittance (light transmittance >90%, haze). ⁇ 13%).
  • the mulch film adopts microsphere type processing type auxiliary agent to make the blown film processing stable, and the film opening is smooth and easy to process.
  • the mulch film is compounded with a full biodegradable resin and functional additives, combined with different thicknesses to improve the weather resistance of the film.
  • the film degradation cycle is controllable for 2-6 months and can be completely degraded without any pollution.
  • An ultra-thin, ultra-transparent, fully biodegradable mulch film that can be mechanically coated, and its raw material composition is in parts by weight:
  • Step 1 the above components are placed in a high-speed mixer for mixing and mixing, without heating, the high-speed mixer is stirred for 5-8 min;
  • Step 2 the mixed materials in step 1 are extruded through a twin-screw granulator at 135-160 ° C, and air-cooled granulation to obtain a blown film material for the whole biodegradable mulch film;
  • step 3 the film blowing material of step 2 is blown on a film blowing machine with a blow ratio of 3.6 and a die gap of 1.0 mm.
  • the thickness is 0.004 mm and the width is 4000 mm.
  • An ultra-thin, ultra-transparent, fully biodegradable mulch film that can be mechanically coated, and its raw material composition is in parts by weight:
  • Step 1 the above components are placed in a high-speed mixer for mixing and mixing, without heating, the high-speed mixer is stirred for 5-8 min;
  • Step 2 the mixed materials in step 1 are extruded through a twin-screw granulator at 135-160 ° C, and air-cooled granulation to obtain a blown film material for the whole biodegradable mulch film;
  • step 3 the film blowing material of step 2 is blown on a film blowing machine with a blow ratio of 2.3 and a die gap of 1.0 mm.
  • the thickness is 0.006 mm and the width is 900 mm.
  • An ultra-thin, ultra-transparent, fully biodegradable mulch film that can be mechanically coated, and its raw material composition is in parts by weight:
  • Step 1 the above components are placed in a high-speed mixer for mixing and mixing, without heating, the high-speed mixer is stirred for 5-8 min;
  • Step 2 the mixed materials in step 1 are extruded through a twin-screw granulator at 135-160 ° C, air-cooled granulation to obtain a fully biodegradable film blowing material;
  • step 3 the film blowing material of step 2 is blown on a film blowing machine with a blow ratio of 1.6 and a die gap of 0.8 mm.
  • the thickness is 0.005 mm and the width is 900 mm.
  • the tensile rate is 200mm/min.
  • the properties of the obtained ultra-thin super-ultra-transparent fully biodegradable mulch film are shown in the following table.
  • Example 1 Example 2 Example 3 thickness( Mm ) 4 6 5 Transmittance(%) 91.9 90.5 90.0 Haze 11.0 12.4 12.6 Tensile strength (MPa) 28 28 26 The sum of longitudinal and transverse elongation at break (%) 900 856 820 Right angle tear strength (N/mm) 120 115 109 Blown bubble opening Smooth opening, continuous film Smooth opening, continuous film Smooth opening, continuous film
  • the ultra-thin ultra-high-transparent and fully biodegradable mulch film degradability verification test It can be seen that the ultra-thin super-transparent biodegradable mulch film having a thickness of 4-6 ⁇ m prepared by the invention has high transparency, light transmittance of >90% and haze of ⁇ 13%. High mechanical strength, tensile strength >25MPa, can be machined using a common laminating machine. Overwintering garlic mulching cultivation can meet the needs of garlic for 6 months, and the mulch can be completely degraded.
  • An ultra-thin weather-resistant fully biodegradable mulch film which can be mechanically coated, and its raw material composition is in parts by weight:
  • Step 1 The above components are placed in a high-speed mixer for stirring and mixing, without heating, the high-speed mixer is stirred for 5-8 min;
  • Step 2 the mixed materials in the step 1 are extruded through a twin-screw granulator at 135-160 ° C, and air-cooled and granulated to obtain a special blown film material for the biodegradable mulch film;
  • Step 3 The blown film of the step 2 was blown on a film blowing machine with a blow ratio of 3.6 and a die gap of 0.8 mm.
  • the thickness is 0.004 mm and the width is 2000 mm.
  • An ultra-thin weather-resistant fully biodegradable mulch film which can be mechanically coated, and its raw material composition is in parts by weight:
  • UV stabilizer Uvinul ® 5050H 0.5 parts
  • UV absorber Tinuvin234 0.5 parts
  • Step 1 The above components are placed in a high-speed mixer for stirring and mixing, without heating, the high-speed mixer is stirred for 5-8 min;
  • Step 2 the mixed materials in the step 1 are extruded through a twin-screw granulator at 135-160 ° C, and air-cooled and granulated to obtain a special blown film material for the biodegradable mulch film;
  • Step 3 The blown film of the step 2 was blown on a film blowing machine with a blow ratio of 2.3 and a die gap of 1.0 mm.
  • the thickness is 0.006 mm and the width is 900 mm.
  • An ultra-thin weather-resistant fully biodegradable mulch film which can be mechanically coated, and its raw material composition is in parts by weight:
  • UV stabilizer Uvinul ® 5050H 0.5 parts
  • UV absorber Tinuvin234 0.5 parts
  • Step 1 The above components are placed in a high-speed mixer for stirring and mixing, without heating, the high-speed mixer is stirred for 5-8 min;
  • Step 2 the mixed materials in step 1 are extruded through a twin-screw granulator at 135-160 ° C, and air-cooled granulation to obtain a fully biodegradable film blowing material;
  • Step 3 The blown film of the step 2 was blown on a film blowing machine with a blow ratio of 1.6 and a die gap of 0.8.
  • the thickness is 0.005 mm and the width is 900 mm.
  • the tensile rate is 200 mm/min.
  • the properties of the obtained mechanically laminable ultra-thin weather-resistant fully biodegradable mulch film are shown in the following table.
  • Example 4 Example 5 Example 6 thickness( Mm ) 4 6 5 Transmittance(%) 91.5 90.2 90.8 Haze 11.7 12.5 12.0 Tensile strength (MPa) 28 26 26 The sum of longitudinal and transverse elongation at break (%) 900 854 800 Right angle tear strength (N/mm) 110 107 99 Blown bubble opening Smooth opening, continuous film Smooth opening, continuous film Smooth opening, continuous film
  • Ultra-thin ultra-high-transparent and fully biodegradable mulch film degradability verification test It can be seen that the ultra-thin weather-resistant biodegradable mulch film with a thickness of 4-6 ⁇ m prepared by the invention has high transparency, light transmittance of >90%, and fog. Degree ⁇ 13%; high mechanical strength, tensile strength > 25MPa, can be machined using a common laminating machine. Overwintering garlic mulching cultivation can meet the needs of garlic for 6 months, and the mulch can be completely degraded.

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  • Engineering & Computer Science (AREA)
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  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明是属于生物降解高分子材料领域，尤其涉及一种可机械覆膜的全生物降解地膜，该地膜以全生物降解树脂、增强增韧增透助剂和易加工助剂组成，其中增强增韧增透助剂的加入解决了超薄地膜机械强度差、易断裂，难以机械覆膜的难题；易加工助剂解决了超薄地膜加工难开口、加工效率低的难题；并通过优选全生物降解树脂的种类，结合功能性助剂开发出厚度4-6μm的超薄超透明超强全生物可控降解地膜，地膜透明性高，透光率＞90%，雾度＜13%；机械强度高，拉伸强度＞25MPa，满足普通覆膜机对地膜强度要求。拉伸强度、断裂伸长率、直角撕裂强度均符合PE地膜机械铺膜标准，物理机械性能优于或符合GB13735-92规定。

Description

一种可机械覆膜的全生物降解地膜
本发明属于农业材料领域，具体涉及一种可机械覆膜的全生物降解地膜。
地膜在农业生产中，起到巨大作用，然而目前所采用的塑料地膜绝大多数为难以短时期降解的聚烯烃类地膜或者添加了淀粉和光降解剂的不完全降解聚烯烃类地膜。这些地膜材料的使用，造成环境的“白色污染”，为人类可持续发展带来了安全隐患。全生物降解地膜是由完全生物降解塑料通过吹塑或者流延加工而成，能被微生物完全分解，其降解的最终产物为二氧化碳和水，可完全为自然界消纳，因此以全生物降解地膜代替目前的聚烯烃类产品，是解决农田白色污染的重要手段，有着重要的开发利用前景。
目前德国巴斯夫、日本三菱、法国利马格兰集团以及国内的广东金发、山东意可曼、杭州鑫富药业等都有该类地膜的生产，并在在玉米、棉花、花生、烟草、大蒜、马铃薯、草莓等作物上进行了试验。但是普遍存在地膜厚度高，成本居高不下；减薄后加工稳定性差，难开口；力学性能差，无法机械覆膜；耐候性差，强光照下易变脆，降解周期过快等问题，严重制约了全生物降解地膜的推广和应用。
发明内容
本发明针对现有技术存在的诸多不足之处，提供了一种可机械覆膜的全生物降解地膜，该地膜以全生物降解树脂、增强增韧增透助剂和易加工助剂组成，其中增强增韧增透助剂的加入解决了超薄地膜机械强度差、易断裂，难以机械覆膜的难题；易加工助剂解决了超薄地膜加工难开口、加工效率低的难题；并通过优选全生物降解树脂的种类，结合功能性助剂开发出厚度4-6μm的超薄超透明超强全生物可控降解地膜，地膜透明性高，透光率＞90%，雾度＜13%；机械强度高，拉伸强度＞25MPa，满足普通覆膜机对地膜强度要求。拉伸强度、断裂伸长率、直角撕裂强度均符合PE地膜机械铺膜标准，物理机械性能优于或符合GB13735-92规定。
本发明的主要具体技术方案是：
一种可机械覆膜的全生物降解地膜，其特征在于：其主要组分按重量份计为：
全生物降解树脂70-98份、增强增韧增透助剂1-8份、易加工助剂1-3份；
其中所述的全生物降解树脂为聚己二酸/对苯二甲酸丁二酯，以及聚乳酸、聚碳酸亚丙酯的一种或几种；
其中，聚己二酸/对苯二甲酸丁二酯作为主要组分，配合聚乳酸、聚碳酸亚丙酯的一种或两种，其中聚己二酸/对苯二甲酸丁二酯占全生物降解树脂的85-95%。
所述的聚己二酸/对苯二甲酸丁二酯熔体流动速率为1-2g/10min，酸值小于15；其中所述的聚乳酸熔体流动速率为2-5g/10min，酸值小于15；其中所述的聚碳酸亚丙酯熔体流动速率为1-2g/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、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2-25nm；所述的有机增强增韧剂，为阿克玛AX-8900或ADX-1200s树脂相容剂。
所述的易加工助剂为聚合物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1-5μm。所述的二氧化硅微球粒径为1-5μm；
本发明中，发明人将聚己二酸/对苯二甲酸丁二酯作为主要的全生物降解树脂，控制其熔体流动速率为1-2g/10min，酸值小于15；主要利用了其良好的韧性，配合其他树脂实现了性能互补，使其具有较好的成膜性和加工性。
在上述基础组方的基础上，发明人进一步提供了一种可机械覆膜的超薄超强超透明全生物降解地膜，其主要组分按重量份计为：
全生物降解树脂89-98份、增强增韧增透助剂1-8份、易加工助剂1-3份。
在上述组方中发明人提高了全生物降解树脂的用量，从而提高了其力学性能和透光性能。
其对应的制备方法，具体步骤如下：
将全生物降解树脂、增强增韧增透剂、易加工助剂按重量份配比高速混合机搅拌5-8min混匀后投入双螺杆挤出机中，于135-160℃挤出、造粒，得到全生物降解地膜专用吹膜料；然后将全生物降解地膜吹膜料在吹膜机上进行吹膜，得到膜厚为4-6μm的超薄地膜，其中，吹胀比为1.6-3.6，模口间隙为0.8-1.8，地膜幅宽为600-4000mm可调。上述参数中进一步限制了模口间隙和吹胀比，从而确保地膜的性能更佳。
与现有技术相比，上述可机械覆膜的超薄超强超透明全生物降解地膜的优点在于：
1.该地膜厚度仅为4-6μm，减薄后的地膜降低了全生物降解地膜的单位面积成本。
2.该地膜采用增强增韧增透助剂，不仅力学性能得到改善（拉伸强度高于25MPa，满足机械覆膜标准要求），透光率也明显提高（透光率＞90%，雾度＜13%）。
3.该地膜采用微球型易加工助剂，使吹膜加工稳定，膜片开口顺滑易加工。
4.该地膜可完全降解，产物无污染。
除此之外，发明人在基础组方的基础上还提供了一种可机械覆膜的超薄耐候全生物降解地膜，其主要组分按重量份计为：
全生物降解树脂70-90份、增强增韧增透助剂1-8份、易加工助剂1-3份，稳定性助剂1-2份。
其中，所述的稳定性助剂紫外光稳定剂、紫外光吸收剂的一种或两种，更进一步的所述的紫外线吸收剂为低挥发性苯并***类紫外吸收剂Tinuvin234；所述的紫外线稳定剂为受阻胺类稳定剂Uvinul®5050H。
本发明中所采用的各种主料辅料除特殊说明外均可以从市场上直接购得。
上述可机械覆膜的超薄耐候全生物降解地膜的制备方法，具体步骤如下：
（1）将全生物降解树脂、增强增韧增透助剂、稳定性助剂、易加工助剂按重量份配比高速混合机搅拌5-8min混匀后投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
（2）将全生物降解地膜专用吹膜料投入吹膜机进行吹膜，得到膜厚为4-6μm的超薄地膜，其中，吹胀比为1.6-3.6，模口间隙为0.8-1.8。
上述可机械覆膜的超薄耐候全生物降解地膜与现有技术相比，优点在于：
1.该地膜厚度仅为4-6μm，减薄后的地膜降低了全生物降解地膜的单位面积成本。
2.该地膜采用增强增韧增透助剂，不仅力学性能得到改善（拉伸强度高于25MPa，满足机械覆膜标准要求），透光率也明显提高（透光率＞90%，雾度＜13%）。
3.该地膜采用微球型加工型助剂，使吹膜加工稳定，膜片开口顺滑易加工。
4.该地膜采用全生物降解树脂与功能性助剂复配，结合不同厚度，提高地膜耐候性，地膜降解周期2-6个月可控且可以完全降解，完全没有任何污染。
具体实施方式
实施例1
一种可机械覆膜的超薄超强超透明全生物降解地膜，其原料组成按照重量份计为：
聚己二酸/对苯二甲酸丁二酯 90份
聚乳酸 5份
疏水型纳米二氧化硅（粒径2-25nm） 2份
二氧化硅微球（粒径1-4μm） 3份
按照下述步骤制备而成：
步骤1，将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2，将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
步骤3，将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为3.6，模口间隙为1.0mm。厚度为0.004mm，幅宽4000mm。
实施例2
一种可机械覆膜的超薄超强超透明全生物降解地膜，其原料组成按照重量份计为：
聚己二酸/对苯二甲酸丁二酯 89份
聚碳酸亚丙酯 5份
疏水型纳米二氧化硅（粒径2-25nm） 4份
二氧化硅微球（粒径2-3μm） 1份
聚合物PMMA微球（粒径2-3μm） 1份
按照下述步骤制备而成：
步骤1，将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2，将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
步骤3，将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为2.3，模口间隙为1.0mm。厚度为0.006mm，幅宽900mm。
实施例3
一种可机械覆膜的超薄超强超透明全生物降解地膜，其原料组成按照重量份计为：
聚己二酸/对苯二甲酸丁二酯 85份
聚乳酸 5份
聚碳酸亚丙酯 5份
疏水型纳米二氧化硅（粒径2-25nm） 2份
二氧化硅微球（粒径2-3μm） 3份
按照下述步骤制备而成：
步骤1，将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2，将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜吹膜料；
步骤3，将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为1.6，模口间隙为0.8mm。厚度为0.005mm，幅宽900mm。
实验例1
按照GB13735-92塑料拉伸性能的测定，拉伸速率200mm/min。所得超薄超强超透明全生物降解地膜各性能如下表所示。
实施例1 实施例2 实施例3
厚度（ μm ） 4 6 5
透光率（%） 91.9 90.5 90.0
雾度 11.0 12.4 12.6
拉伸强度（MPa） 28 28 26
纵横向断裂伸长率之和（%） 900 856 820
直角撕裂强度（N/mm） 120 115 109
吹塑膜泡开口性 开口顺滑，不断膜 开口顺滑，不断膜 开口顺滑，不断膜
通过超薄超强超透明全生物降解地膜降解性验证试验：可知本发明所制备的厚度4-6μm超薄超强超透明全生物降解地膜，地膜透明性高，透光率＞90%，雾度＜13%；机械强度高，拉伸强度＞25MPa，可以使用普通覆膜机进行机铺。越冬大蒜覆膜栽培可以满足大蒜6个月生长期需求，地膜可以完全降解。
实施例4
一种可机械覆膜的超薄耐候全生物降解地膜，其原料组成按照重量份计为：
聚己二酸/对苯二甲酸丁二酯 88.7份
聚乳酸 5份
疏水型纳米二氧化硅（粒径2-25nm） 2份
二氧化硅微球（粒径1μm） 3份
紫外线吸收剂Tinuvin234 1.5份
按照下述步骤制备而成：
步骤1将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
步骤3将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为3.6，模口间隙为0.8mm。厚度为0.004mm，幅宽2000mm。
实施例5
一种可机械覆膜的超薄耐候全生物降解地膜，其原料组成按照重量份计为：
聚己二酸/对苯二甲酸丁二酯 88.2份
聚碳酸亚丙酯 5份
疏水型纳米二氧化硅（粒径2-25nm） 4份
二氧化硅微球（粒径2-3μm） 1份
聚合物PMMA微球（粒径2-3μm） 1份
紫外线稳定剂Uvinul®5050H 0.5份
紫外线吸收剂Tinuvin234 0.5份
按照下述步骤制备而成：
步骤1将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
步骤3将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为2.3，模口间隙为1.0mm。厚度为0.006mm，幅宽900mm。
实施例6
一种可机械覆膜的超薄耐候全生物降解地膜，其原料组成按照重量份计为：
聚己二酸/对苯二甲酸丁二酯 84.2份
聚乳酸 5份
聚碳酸亚丙酯 5份
疏水型纳米二氧化硅（粒径2-25nm） 2份
二氧化硅微球（粒径2-3μm） 3份
紫外线稳定剂Uvinul®5050H 0.5份
紫外线吸收剂Tinuvin234 0.5份
按照下述步骤制备而成：
步骤1将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜吹膜料；
步骤3将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为1.6，模口间隙为0.8。厚度为0.005mm，幅宽900mm。
实验例2
按照GB 13735-92塑料拉伸性能的测定，拉伸速率200mm/min。所得可机械覆膜的超薄耐候全生物降解地膜各性能如下表所示。
实施例4 实施例5 实施例6
厚度（ μm ） 4 6 5
透光率（%） 91.5 90.2 90.8
雾度 11.7 12.5 12.0
拉伸强度（MPa） 28 26 26
纵横向断裂伸长率之和（%） 900 854 800
直角撕裂强度（N/mm） 110 107 99
吹塑膜泡开口性 开口顺滑，不断膜 开口顺滑，不断膜 开口顺滑，不断膜
通过超薄超强超透明全生物降解地膜降解性验证试验：可知本发明所制备的厚度4-6μm可机械覆膜的超薄耐候全生物降解地膜，地膜透明性高，透光率＞90%，雾度＜13%；机械强度高，拉伸强度＞25MPa，可以使用普通覆膜机进行机铺。越冬大蒜覆膜栽培可以满足大蒜6个月生长期需求，地膜可以完全降解。

Claims (10)

1、一种可机械覆膜的全生物降解地膜，其特征在于：其主要组分按重量份计为：全生物降解树脂70-98份、增强增韧增透助剂1-8份、易加工助剂1-3份；其中所述的全生物降解树脂为聚己二酸/对苯二甲酸丁二酯，以及聚乳酸、聚碳酸亚丙酯中的一种或两种，其中聚己二酸/对苯二甲酸丁二酯占全生物降解树脂的85-95wt%；所述的增强增韧增透剂为无机增强增韧增透剂或有机增强增韧剂的一种或几种；所述的易加工助剂为聚合物PMMA微球或二氧化硅微球中的一种或两种。
2、根据权利要求1所述的可机械覆膜的全生物降解地膜，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2-25nm；所述的有机增强增韧剂为阿克玛AX-8900或ADX-1200s树脂相容剂。
3、根据权利要求1所述的可机械覆膜的全生物降解地膜，其特征在于：所述的聚合物微球粒径为1-5μm；所述的二氧化硅微球粒径为1-5μm。
4、根据权利要求1所述的可机械覆膜的全生物降解地膜，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1-2g/10min，酸值小于15；其中所述的聚乳酸熔体流动速率为2-5g/10min，酸值小于15；其中所述的聚碳酸亚丙酯熔体流动速率为1-2g/10min，酸值小于15。
5、一种可机械覆膜的超薄超强超透明全生物降解地膜，其特征在于：其主要组分按重量份计为：全生物降解树脂89-98份、增强增韧增透助剂1-8份、易加工助剂1-3份。
6、权利要求5所述可机械覆膜的超薄超强超透明全生物降解地膜的制备方法，其特征在于：具体步骤如下：将全生物降解树脂、增强增韧增透剂、易加工助剂按重量份配比高速混合机搅拌5-8min混匀后投入双螺杆挤出机中，于135-160℃挤出、造粒，得到全生物降解地膜专用吹膜料；然后将全生物降解地膜吹膜料在吹膜机上进行吹膜，得到膜厚为4-6μm的超薄地膜，其中，吹胀比为1.6-3.6，模口间隙为0.8-1.8，地膜幅宽为600-4000mm可调。
7、一种可机械覆膜的超薄耐候全生物降解地膜，其特征在于：其主要组分按重量份计为：全生物降解树脂70-90份、增强增韧增透助剂1-8份、易加工助剂1-3份，稳定性助剂1-2份。
8、根据权利要求7所述的可机械覆膜的超薄耐候全生物降解地膜，其特征在于：所述的稳定性助剂为紫外光稳定剂或紫外光吸收剂的一种或两种。
9、根据权利要求8所述的可机械覆膜的超薄耐候全生物降解地膜，其特征在于：所述的紫外线吸收剂为低挥发性苯并***类紫外吸收剂Tinuvin234；所述的紫外线稳定剂为受阻胺类稳定剂Uvinul®5050H。
10、权利要求7所述可机械覆膜的超薄耐候全生物降解地膜的制备方法，其特征在于：具体步骤如下：（1）将全生物降解树脂、增强增韧增透助剂、稳定性助剂、易加工助剂按重量份配比高速混合机搅拌5-8min混匀后投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；（2）将全生物降解地膜专用吹膜料投入吹膜机进行吹膜，得到膜厚为4-6μm的超薄地膜，其中，吹胀比为1.6-3.6，模口间隙为0.8-1.8。
PCT/CN2018/094195 2017-07-13 2018-07-03 一种可机械覆膜的全生物降解地膜 WO2019011153A1 (zh)

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