CN115058103A - 环氧腰果酚基扩链剂改性pbat-pla复合膜的制备 - Google Patents

环氧腰果酚基扩链剂改性pbat-pla复合膜的制备 Download PDF

Info

Publication number
CN115058103A
CN115058103A CN202210923288.4A CN202210923288A CN115058103A CN 115058103 A CN115058103 A CN 115058103A CN 202210923288 A CN202210923288 A CN 202210923288A CN 115058103 A CN115058103 A CN 115058103A
Authority
CN
China
Prior art keywords
epoxy
chain extender
cardanol
pbat
pla
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210923288.4A
Other languages
English (en)
Other versions
CN115058103B (zh
Inventor
张彩丽
翁云宣
杨洋
刁晓倩
宋鑫宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Technology and Business University
Original Assignee
Beijing Technology and Business University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Technology and Business University filed Critical Beijing Technology and Business University
Priority to CN202210923288.4A priority Critical patent/CN115058103B/zh
Publication of CN115058103A publication Critical patent/CN115058103A/zh
Application granted granted Critical
Publication of CN115058103B publication Critical patent/CN115058103B/zh
Priority to US18/320,312 priority patent/US11780959B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • 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
    • 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
    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9115—Cooling of hollow articles
    • B29C48/912—Cooling of hollow articles of tubular 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • 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
    • 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
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Epoxy Resins (AREA)

Abstract

本发明公开了一种环氧腰果酚基扩链剂改性PBAT‑PLA复合膜的制备，属于可生物降解薄膜加工技术领域。该改性PBAT‑PLA复合膜的原料包括：80‑85份PBAT、15‑20份PLA和环氧扩链剂0.5‑1.5份，所述环氧扩链剂为腰果酚基环氧扩链剂。制备方法包括以下步骤：将PBAT、PLA和环氧扩链剂混合，熔融挤出造粒，得到复合材料母粒；然后将所述复合材料母粒吹塑成膜，即可得到所述环氧腰果酚基扩链剂改性PBAT‑PLA复合膜。本发明通过腰果酚基环氧扩链剂对PBAT‑PLA复合膜进行扩链改性，从而提高PBAT‑PLA复合膜的界面结合力，使制备的改性PBAT‑PLA复合膜具有优异的力学性能。

Description

环氧腰果酚基扩链剂改性PBAT-PLA复合膜的制备
技术领域
本发明涉及环氧腰果酚基扩链剂改性PBAT-PLA复合膜的制备，属于可生物降解薄膜加工技术领域。
背景技术
农用地膜和包装膜占整个塑料制品的50％以上，因此膜类塑料制品多为造成塑料污染问题的主要来源。
目前，应用最广泛的可生物降解塑料分别为聚乳酸(PLA)和聚己二酸丁二醇酯(PBAT)，使用量分别为生物降解塑料的13.5％和18.8％。其中，PBAT是一种具有优异成膜性能的柔性可生物降解共聚酯，但缺点是强度较低，单独使用时力学强度无法满足膜袋类的要求。因为PLA的强度高，耐热性能较好，所以人们利用PLA较好的耐热性能和力学强度，结合PBAT良好的柔性，针对不同的应用调整PLA和PBAT的配比，从而制备得到满足不同应用领域的可生物降解PBAT-PLA复合改性膜。但由于PBAT和PLA的化学结构相差较大，导致相容性差。因此，要想制得分散性和界面结合力好的PBAT-PLA复合膜，需要添加相容剂。
目前，可生物降解材料制备过程中用到最多的一类扩链剂为环氧类的苯乙烯-甲基丙烯酸缩水甘油酯(ADR 4468)。ADR 4468为苯乙烯、丙烯酸酯和丙烯酸缩水甘油酯的共聚物，结构中含有5个环氧官能团，但是ADR 4468的单体均来自于石油单体，具有不可再生性，且所含的苯乙烯结构几乎不具备生物降解能力。因此，ADR 4468环氧扩链剂的添加量较高时，会影响PBAT-PLA复合改性膜的可生物降解性能。因此，需要对PBAT-PLA复合改性膜做进一步研究。
发明内容
为了解决上述技术问题，本发明提出了一种环氧腰果酚基扩链剂改性PBAT-PLA复合膜。
为实现上述目的，本发明提供了如下方案：
本发明提出了一种环氧腰果酚基扩链剂改性PBAT-PLA复合膜，按重量份数计，原料包括：80-85份聚己二酸丁二醇酯(PBAT)、15-20份聚乳酸(PLA)和环氧扩链剂0.5-1.5份，所述环氧扩链剂为腰果酚基环氧扩链剂，其中，所述PBAT和PLA的用量和为100份。
进一步地，按重量份数计，原料包括：85份聚己二酸丁二醇酯(PBAT)、15份聚乳酸(PLA)和环氧扩链剂1份，所述环氧扩链剂为环氧腰果酚缩水甘油醚(ECGE)或环氧腰果酚油酸酯(ECD-OA)。
进一步地，所述环氧腰果酚缩水甘油醚(ECGE)为腰果酚缩水甘油醚(CEG)经H2O2溶液在65℃下氧化反应3h制备得到。
更进一步地，所述环氧腰果酚缩水甘油醚(ECGE)的具体制备方法为：将腰果酚缩水甘油醚(CEG，Cardolite NC513)与质量浓度为30％的H2O2溶液、乙酸和浓硫酸按照摩尔比为1:20:3:0.01的比例混合，在65℃下反应3h，即可得到所述环氧腰果酚缩水甘油醚(ECGE)。
进一步地，所述环氧腰果酚油酸酯(ECD-OA)为腰果酚(CD)与油酸(OA)酯化反应得到的腰果酚油酸酯(CD-OA)，经H2O2溶液在65℃下氧化反应3h制备得到。
更进一步地，所述环氧腰果酚油酸酯(ECD-OA)的具体制备方法为：将腰果酚(CD)、油酸(OA)、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和4-二甲氨基吡啶按摩尔比为2:2:3:1混合，室温下反应5h得到腰果酚油酸酯(CD-OA)，将CD-OA与质量浓度为30％的H2O2溶液、乙酸和浓硫酸按照摩尔比为1:20:3:0.01的比例混合，在65℃下反应3h，即可得到所述环氧腰果酚油酸酯(ECD-OA)。
本发明还提出了一种上述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜的制备方法，包括以下步骤：
按所述重量份数称取各原料，将PBAT、PLA和环氧扩链剂混合，熔融挤出造粒，得到复合材料母粒；然后将所述复合材料母粒吹塑成膜，得到所述环氧腰果酚基扩链剂改性PBAT-PLA复合膜。
进一步地，所述熔融挤出造粒的温度为160-170℃。
进一步地，所述吹塑成膜的温度为160-165℃，牵引速率为3m/min。
本发明还提出了一种上述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜在农用地膜和包装膜中的应用。
增容是一种提高不相容和部分相容共混物性能的方法，是调节共混组分间界面张力的有效方法。热力学上不互溶的聚合物共混物可通过原位反应性增容法提高相容性。增容后，不相容共混物的粗糙形态转变为精细形态，有助于提高共混聚合物的性能。
本发明中可生物降解聚合物PBAT-PLA含有端羧基和端羟基，这两种活性基团容易与酸酐、环氧、恶唑啉和异氰酸酯等反应。在熔融共混过程中，腰果酚基环氧扩链剂的反应性官能团能够与共混组分的羟基、羧基反应，形成原位接枝和-或嵌段共聚物，从而实现增容。
本发明公开了以下技术效果：
本发明所用的腰果酚基环氧扩链剂均可以采用生物质来源的单体腰果酚为基础单元合成，从而实现对PBAT-PLA复合膜进行扩链改性。通过改变腰果酚基环氧扩链剂的分子结构和环氧官能团的位置，确定最优结构和最优比例的环氧腰果酚扩链剂，用于提高PBAT-PLA复合膜的界面结合力，利用本发明的环氧腰果酚扩链剂制备的PBAT-PLA改性复合塑料膜具有优异的力学性能及生物降解性能。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例2的吹膜过程图；
图2为实施例1、2和3以及对比例1、3和5制备得到的复合塑料膜纵向断面SEM对比图，其中(a)为对比例1，(b)为实施例1，(c)为实施例2，(d)为实施例3，(e)为对比例3，(f)为对比例5；
图3为实施例1、2和3以及对比例1、3和5制备得到的复合塑料膜横向断面SEM对比图，其中(a)为对比例1，(b)为实施例1，(c)为实施例2，(d)为实施例3，(e)为对比例3，(f)为对比例5。
图4为实施例2和对比例3的复合塑料膜分别在土壤中填埋30天前后降解的情况对比图，其中(a)为实施例2降解0天的形貌，(b)为实施例2降解30天的形貌，(c)为对比例3降解0天的形貌，(d)为对比例3降解30天的形貌。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和-或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
本发明提出了一种环氧腰果酚基扩链剂改性PBAT-PLA复合膜，按重量份数计，原料包括：80-85份聚己二酸丁二醇酯(PBAT)、15-20份聚乳酸(PLA)和环氧扩链剂0.5-1.5份，所述环氧扩链剂为腰果酚基环氧扩链剂，其中，所述PBAT和PLA的用量和为100份。
进一步地，按重量份数计，原料包括：85份聚己二酸丁二醇酯(PBAT)、15份聚乳酸(PLA)和环氧扩链剂1份，所述环氧扩链剂为环氧腰果酚缩水甘油醚(ECGE)或环氧腰果酚油酸酯(ECD-OA)。
进一步地，所述环氧腰果酚缩水甘油醚(ECGE)为腰果酚缩水甘油醚(CEG)经H2O2溶液在65℃下氧化反应3h制备得到。
进一步地，所述环氧腰果酚油酸酯(ECD-OA)为腰果酚(CD)与油酸(OA)酯化反应得到的腰果酚油酸酯(CD-OA)，经H2O2溶液在65℃下氧化反应3h制备得到。本发明还提出了一种上述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜的制备方法，包括以下步骤：
按所述重量份数称取各原料，将PBAT、PLA和环氧扩链剂混合，熔融挤出造粒，得到复合材料母粒；然后将所述复合材料母粒吹塑成膜，得到所述环氧腰果酚基扩链剂改性PBAT-PLA复合膜。
进一步地，所述熔融挤出造粒的温度为160-170℃。
进一步地，所述吹塑成膜的温度为160-165℃，牵引速率为3m/min。
本发明还提出了一种上述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜在农用地膜和包装膜中的应用。
本发明实施例中所用环氧腰果酚缩水甘油醚(ECGE)的具体制备方法为：将腰果酚缩水甘油醚(CEG)、质量浓度为30％的H2O2溶液、乙酸和质量浓度98％的浓硫酸按照摩尔比为1:20:3:0.01的比例混合，在65℃下反应3h，即可得到环氧腰果酚缩水甘油醚(ECGE)，具体反应过程为：
Figure BDA0003778587840000071
本发明实施例中所用环氧腰果酚油酸酯(ECD-OA)的具体制备方法为：将腰果酚(CD)、油酸(OA)、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐和4-二甲氨基吡啶按摩尔比为2:2:3:1混合，室温下反应5h得到腰果酚油酸酯(CD-OA)，之后将腰果酚油酸酯(CD-OA)、质量浓度为30％的H2O2溶液、乙酸和质量浓度98％的浓硫酸按照摩尔比为1:20:3:0.01的比例混合，在65℃下反应3h，即可得到环氧腰果酚油酸酯(ECD-OA)，具体反应过程为：
Figure BDA0003778587840000081
本发明实施例所用到的环氧腰果酚低聚物(Cardolite NC514)来自于卡德莱公司，具体结构式为：
Figure BDA0003778587840000082
苯乙烯–甲基丙烯酸缩水甘油酯(Joncryl ADR 4468)来自于巴斯夫公司，具体结构式为：
Figure BDA0003778587840000091
式中R1-R5为H或CH3。
本发明中所有实施例和对比例制备的第一步均为在双螺杆中进行熔融挤出、冷却、造粒，得到的混合复合材料母粒用于第二步的吹膜。
本发明所用PLA来自于NatureWorks，牌号为4032D，结构式为：
Figure BDA0003778587840000092
本发明所用PBAT来自于山西金晖兆隆FP-0325，结构式为：
Figure BDA0003778587840000093
本发明实施例与对比例中所用“份”若无特殊说明均为重量份数。
本发明中可生物降解聚合物PBAT-PLA含有端羧基和端羟基，这两种活性基团容易与酸酐、环氧、恶唑啉和异氰酸酯等反应。在熔融共混过程中，腰果酚基环氧扩链剂的反应性官能团能够与共混组分的羟基、羧基反应，形成原位接枝和/或嵌段共聚物，从而实现增容，结构为：
Figure BDA0003778587840000101
本发明实施例中术语“等量”指的是等质量。
以下通过实施例对本发明的技术方案做进一步说明。
实施例1
按重量份数称取85份PBAT、15份PLA和0.5份ECGE，将PBAT、PLA和ECGE混合后用双螺杆熔融挤出造粒得到复合材料母粒，挤出机从加料区到机头区五段的温度依次为160℃、165℃、165℃、168℃、170℃，接着使用吹塑机将所得复合材料母粒吹塑成型，吹塑成膜从加料区到机头的温度依次为160℃、160℃、165℃、165℃，牵引速率为3m/min，得到环氧腰果酚基扩链剂改性PBAT-PLA复合膜(85PBAT-15PLA-0.5ECGE)。
实施例2
同实施例1，区别仅在于添加1.0份的ECGE，得到环氧腰果酚基扩链剂改性PBAT-PLA复合膜(85PBAT-15PLA-1.0ECGE)，吹膜过程见图1。
实施例3
同实施例1，区别仅在于添加1.5份的ECGE，得到环氧腰果酚基扩链剂改性PBAT-PLA复合膜(85PBAT-15PLA-1.5ECGE)。
实施例4
同实施例1，区别仅在于将0.5份的ECGE替换为1.0份的ECD-OA，得到环氧腰果酚基扩链剂改性PBAT-PLA复合膜(85PBAT-15PLA-1.0ECD-OA)。
实施例5
同实施例2，区别仅在于按重量份数称取80份PBAT和20份PLA，得到环氧腰果酚基扩链剂改性PBAT-PLA复合膜(80PBAT-20PLA-1.0ECGE)。
对比例1
同实施例1，区别仅在于不加任何扩链剂，为空白对比样，得到PBAT-PLA复合膜(85PBAT-15PLA)。
对比例2
同实施例1，区别仅在于将0.5份ECGE等量替换为0.5份的ADR 4468，得到改性PBAT-PLA复合膜(85PBAT-15PLA-0.5ADR)。
对比例3
同实施例1，区别仅在于将0.5份ECGE替换为1.0份的ADR 4468，得到改性PBAT-PLA复合膜(85PBAT-15PLA-1.0ADR)。
对比例4
同实施例1，区别仅在于将0.5份ECGE等量替换为0.5份的NC514，得到改性PBAT-PLA复合膜(85PBAT-15PLA-0.5NC514)。
对比例5
同实施例1，区别仅在于将0.5份ECGE替换为1.0份的NC514，得到改性PBAT-PLA复合膜(85PBAT-15PLA-1.0NC514)。
实施例1-5与对比例1-5制备过程中各原料用量对比见表1。
表1实施例与对比例原料用量对比
Figure BDA0003778587840000121
性能测试
一、分子量测试
扩链反应前后分子量的变化是最能直接反应扩链效率的参数，采用凝胶渗透色谱法对实施例1-5与对比例1-5制备的改性PBAT-PLA复合膜的数均分子量Mn、重均分子量Mw和分布指数Mw/Mn进行测试，流动相为四氢呋喃，测定结果见表2。
表2实施例与对比例的分子量
Figure BDA0003778587840000122
Figure BDA0003778587840000131
由表2数据可以看出，采用三种基于腰果酚的环氧扩链剂ECGE、ECD-OA、NC514和一种ADR 4468对PBAT-PLA复合材料进行扩链后，对添加相同份数(1.0份)扩链剂的实施例2、实施例4、对比例3以及对比例5的改性PBAT-PLA复合膜的数均分子量进行对比发现：实施例2>实施例4>对比例5>对比例3，即为ECGE>ECD-OA>NC514>ADR 4468。因此添加三种基于腰果酚的环氧扩链剂具有更好的分子扩链效果，能更好地提高分子量。
二、力学性能测试
通过力学性能测试得出扩链剂对相界面增容改性的能力，力学上不互溶的聚合物共混物可通过原位反应性增容法提高相容性。增容后，不相容共混物的粗糙形态转变为精细形态，有助于提高共混聚合物的性能。根据GB/T 10004-2008对实施例1-5与对比例1-5制备得到的改性PBAT-PLA复合膜进行拉伸性能测试，测试结果见表3。
表3实施例与对比例的拉伸测试结果
Figure BDA0003778587840000132
Figure BDA0003778587840000141
由表3数据可以看出，对添加相同份数(1.0份)扩链剂的实施例2、实施例4、对比例3以及对比例5的改性PBAT-PLA复合膜的断裂伸长率进行对比发现：实施例2>实施例4>对比例5>对比例3，即为ECGE>ECD-OA>NC514>ADR 4468，其中添加1.0份ECGE的实施例2的断裂伸长率是对比例1的2.4倍，是对比例3的1.84倍。实施例1与实施例2随着ECGE的添加量从0.5份增加到1.5份时，力学性能出现增大的现象，断裂伸长率基本接近，拉伸强度出现明显下降，这主要是由于过量的ECGE未与聚合物发生反应，在聚合物中起到增塑润滑的作用，导致复合膜拉伸强度的明细降低，因此环氧扩链剂的最优添加量为1.0份。
添加ECGE后可有效提高PBAT-PLA两相相界面的结合力，增强两相的相容性，这是力学性能提高的主要原因。ECD-OA较ECGE扩链效果差的原因主要在于ECD-OA的脂肪链较长，环氧官能团会被柔性的脂肪链包覆，与环氧基团连接在端基的ECGE相比，ECD-OA的环氧基团接触聚酯端基的概率降低，因此扩链效果没有ECGE好。此外，同样具有两个端环氧基团的NC514的扩链效果确不如ECD-OA好的原因为NC514分子结构中含有两个苯环，分子的刚性和空间位阻较强，扩链剂分子在扩散进入PBAT-PLA相界面时有一定的阻力，所以扩链效果没有含有一个苯环的ECGE和ECD-OA效果好。
本发明中三种基于腰果酚的扩链剂，ECGE、ECD-OA和NC514的扩链效果均优于ADR4468的原因在于前三者的分子量较小(小于1000)，属于小分子，而ADR 4468的分子量为6800，在添加相同质量的情况下，前三者的摩尔数较后者高出很多倍，因此环氧官能团的个数也较之后两者高出很多，具有更高的反应几率；此外，小分子扩散进入相界面的几率更大，因此在相界面发生扩链增容反应的几率也更大。以上原因是基于腰果酚的环氧扩链剂比ADR具有更好扩链增容效果的主要原因。
三、SEM测试
将实施例1、2和3以及对比例1、3和5制备得到的改性PBAT-PLA复合膜进行断面SEM扫描并对比，图2为纵向断面SEM对比图，图中(a)为对比例1，(b)为实施例1，(c)为实施例2，(d)为实施例3，(e)为对比例3，(f)为对比例5。图3为横向断面SEM对比图，图中(a)为对比例1，(b)为实施例1，(c)为实施例2，(d)为实施例3，(e)为对比例3，(f)为对比例5。与对比例1相比，添加ECGE的复合塑料膜中，PLA在PBAT中的相界面减少，实施例2中的断面中只有少量的PLA分散相。
四、土壤填埋降解测试
将实施例2和对比例3在土壤中填埋30天，观察复合塑料膜在土壤中填埋30天前后降解的情况，图4为实施例2和对比例3分别在土壤中填埋30天后降解的情况，其中(a)为实施例2降解0天的形貌，(b)为实施例2降解30天的形貌，(c)为对比例3降解0天的形貌，(d)为对比例3降解30天的形貌。由图4可以看出，与对比例3相比，实施例2中添加ECGE的复合膜质量损失为65％，对比例3中添加ADR的复合膜质量损失为32％。
本发明所制备的氧化腰果酚缩水甘油醚的低聚物扩链剂加入PBAT-PLA中，可使其具有优异的力学性能，由于扩链剂原料均来自于生物质，具有无毒绿色的特点，可用于农用地膜和包装膜中，还可用于食品包装膜领域。
以上所述的实施例仅是对本发明的优选方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。

Claims (8)

1.环氧腰果酚基扩链剂改性PBAT-PLA复合膜，其特征在于，按重量份数计，原料包括：80-85份PBAT、15-20份PLA和环氧扩链剂0.5-1.5份，所述环氧扩链剂为腰果酚基环氧扩链剂。
2.根据权利要求1所述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜，其特征在于，按重量份数计，原料包括：85份PBAT、15份PLA和环氧扩链剂1份，所述环氧扩链剂为环氧腰果酚缩水甘油醚或环氧腰果酚油酸酯。
3.根据权利要求2所述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜，其特征在于，所述环氧腰果酚缩水甘油醚为腰果酚缩水甘油醚经H2O2溶液在65℃下氧化反应3h制备得到。
4.根据权利要求2所述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜，其特征在于，所述环氧腰果酚油酸酯为腰果酚与油酸酯化反应得到的腰果酚油酸酯，经H2O2溶液在65℃下氧化反应3h制备得到。
5.一种权利要求1-4任一项所述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜的制备方法，其特征在于，包括以下步骤：
按所述重量份数称取各原料，将PBAT、PLA和环氧扩链剂混合，熔融挤出造粒，得到复合材料母粒；然后将所述复合材料母粒吹塑成膜，得到所述环氧腰果酚基扩链剂改性PBAT-PLA复合膜。
6.根据权利要求5所述的制备方法，其特征在于，所述熔融挤出造粒的温度为160-170℃。
7.根据权利要求5所述的制备方法，其特征在于，所述吹塑成膜的温度为160-165℃，牵引速率为3m/min。
8.权利要求1-4任一项所述的环氧腰果酚基扩链剂改性PBAT-PLA复合膜在农用地膜和包装膜中的应用。
CN202210923288.4A 2022-08-02 2022-08-02 环氧腰果酚基扩链剂改性pbat-pla复合膜的制备 Active CN115058103B (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202210923288.4A CN115058103B (zh) 2022-08-02 2022-08-02 环氧腰果酚基扩链剂改性pbat-pla复合膜的制备
US18/320,312 US11780959B1 (en) 2022-08-02 2023-05-19 Preparation method of polybutylene adipate terephthalate-polylactic acid blend films modified by epoxidized cardanol-based chain extender

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210923288.4A CN115058103B (zh) 2022-08-02 2022-08-02 环氧腰果酚基扩链剂改性pbat-pla复合膜的制备

Publications (2)

Publication Number Publication Date
CN115058103A true CN115058103A (zh) 2022-09-16
CN115058103B CN115058103B (zh) 2023-03-31

Family

ID=83207533

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210923288.4A Active CN115058103B (zh) 2022-08-02 2022-08-02 环氧腰果酚基扩链剂改性pbat-pla复合膜的制备

Country Status (2)

Country Link
US (1) US11780959B1 (zh)
CN (1) CN115058103B (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115537964A (zh) * 2022-11-09 2022-12-30 福建师范大学泉港石化研究院 一种改性电气石聚乳酸熔喷料及其制备方法和应用
CN115948033A (zh) * 2022-12-31 2023-04-11 浙江工业大学 一种pbat吹膜用环氧类扩链剂母粒及其制备方法和应用
CN116693471A (zh) * 2023-06-07 2023-09-05 北京工商大学 一种生物基环氧扩链剂及其制备方法与应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114479398A (zh) * 2022-03-24 2022-05-13 北京工商大学 一种可生物降解材料及其制备方法和应用

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114479398A (zh) * 2022-03-24 2022-05-13 北京工商大学 一种可生物降解材料及其制备方法和应用

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115537964A (zh) * 2022-11-09 2022-12-30 福建师范大学泉港石化研究院 一种改性电气石聚乳酸熔喷料及其制备方法和应用
CN115537964B (zh) * 2022-11-09 2023-09-15 福建师范大学泉港石化研究院 一种改性电气石聚乳酸熔喷料及其制备方法和应用
CN115948033A (zh) * 2022-12-31 2023-04-11 浙江工业大学 一种pbat吹膜用环氧类扩链剂母粒及其制备方法和应用
CN115948033B (zh) * 2022-12-31 2024-06-11 浙江工业大学 一种pbat吹膜用环氧类扩链剂母粒及其制备方法和应用
CN116693471A (zh) * 2023-06-07 2023-09-05 北京工商大学 一种生物基环氧扩链剂及其制备方法与应用
CN116693471B (zh) * 2023-06-07 2023-11-03 北京工商大学 一种生物基环氧扩链剂及其制备方法与应用

Also Published As

Publication number Publication date
CN115058103B (zh) 2023-03-31
US11780959B1 (en) 2023-10-10

Similar Documents

Publication Publication Date Title
CN115058103B (zh) 环氧腰果酚基扩链剂改性pbat-pla复合膜的制备
CN105623214B (zh) 一种增塑可生物降解聚酯薄膜及其制备方法
Imre et al. Compatibilization in bio-based and biodegradable polymer blends
Singh et al. Thermal properties and degradation characteristics of polylactide, linear low density polyethylene, and their blends
CN103265798B (zh) 聚乳酸(pla)与乙烯-醋酸乙烯酯共聚物(eva)共混组合物及其成型制品
CN104144967A (zh) 由2，5-呋喃二甲酸制备聚(2，5-呋喃二甲酸乙二醇酯)的方法及其用途，聚酯化合物及其混合物
US9217056B2 (en) Polymers, the process for the synthesis thereof and compositions comprising same
CN106674923B (zh) 一种降解可控pbat/pla复合膜及其制备方法
CN103571158A (zh) 一种高界面相容性的pla/pbat共混物及制备方法
CN112094488A (zh) 一种高韧高耐热聚乳酸复合材料及其制备方法
CN111978687B (zh) 全生物降解复合高分子材料及其制备方法和应用
CN108017887A (zh) 一种pla-pbsa吹塑薄膜及其制备方法
Doganci Effects of star-shaped PCL having different numbers of arms on the mechanical, morphological, and thermal properties of PLA/PCL blends
AU2019213590B2 (en) Hyperbranched polylactide resin compositions
CN112961472B (zh) 一种改性聚呋喃二甲酸乙二醇酯及其制备方法及应用
CN114573965A (zh) 一种高阻隔生物可降解材料及其制备方法和应用
CN106751568B (zh) 一种抗菌pbat/pla复合膜及其制备方法
CN112409769A (zh) 一种pla-pbat共混改性可降解材料
CN111234484B (zh) 一种全生物基可降解聚乳酸/淀粉复合材料及其制备方法
CN111675854A (zh) 一种聚氨酯增韧聚丙烯复合材料及其制备与检测方法
CN111944291A (zh) 一种聚乳酸树脂组合物及其制备方法
Cui et al. Preparation of chlorinated poly (propylene carbonate) and its effects on the mechanical properties of poly (propylene carbonate)/starch blends as a compatibilizer
US20230303829A1 (en) Biodegradable material, preparation method and application thereof
CN103980685B (zh) 一种抗冲击生物可降解聚酯组合物及其制备方法
CN112662147A (zh) 一种高性能三元复配生物降解薄膜

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant