WO2018028513A1 - Film mince de polyester biodégradable et son procédé de préparation - Google Patents

Film mince de polyester biodégradable et son procédé de préparation Download PDF

Info

Publication number
WO2018028513A1
WO2018028513A1 PCT/CN2017/095942 CN2017095942W WO2018028513A1 WO 2018028513 A1 WO2018028513 A1 WO 2018028513A1 CN 2017095942 W CN2017095942 W CN 2017095942W WO 2018028513 A1 WO2018028513 A1 WO 2018028513A1
Authority
WO
WIPO (PCT)
Prior art keywords
biodegradable polyester
polyester film
film
longitudinal
tear strength
Prior art date
Application number
PCT/CN2017/095942
Other languages
English (en)
Chinese (zh)
Inventor
熊凯
袁志敏
蔡彤旻
黄险波
曾祥斌
焦健
苑仁旭
钟宇科
卢昌利
杨晖
麦开锦
董学腾
Original Assignee
金发科技股份有限公司
珠海万通化工有限公司
天津金发新材料有限公司
上海金发科技发展有限公司
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 金发科技股份有限公司, 珠海万通化工有限公司, 天津金发新材料有限公司, 上海金发科技发展有限公司 filed Critical 金发科技股份有限公司
Publication of WO2018028513A1 publication Critical patent/WO2018028513A1/fr

Links

Classifications

    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a biodegradable polyester film and a preparation method thereof.
  • Polylactic acid is completely biodegradable and derived from renewable resources such as plants. Its properties are similar to those of general-purpose plastic polypropylene, such as high modulus, high tensile strength and good processability. However, the brittleness of polylactic acid is severe, which severely limits its wide application. It is the main technical means to improve the toughness of polylactic acid by multi-component blending modification.
  • Polyterephthalic acid-adipate-1,4-butanediol terpolymer (PBAT) is also a fully biodegradable material with both PBA segment flexibility and PBT segments. The heat resistance and impact resistance, so the blending of PBAT and polylactic acid can effectively improve the performance of polylactic acid.
  • Patent Application No.: 201080050600.9 discloses a method of producing a shrink film comprising: A) 20-90% by weight biodegradable aliphatic-aromatic polyester; B) 10-80% by weight polylactic acid and C) 0- 2% by weight of compatibilizer, but no vertical and horizontal balance of the tear strength of the film was mentioned.
  • Light transmittance is the percentage of the luminous flux through the film and its incident light flux, which is usually one of the important parameters for characterizing the transparency of the film.
  • the crystallinity, crystal size and preparation process of the film material may cause different microstructures of the film molecules, thereby obtaining films of different light transmittance.
  • the invention discovers unexpectedly that when the light transmittance of the polyester film is controlled within the range of 80% to 90%, the longitudinal and lateral unbalance of the tear strength of the film material when the polyester film is used can be effectively improved.
  • the problem is that the prepared film has a high stiffness and a good longitudinal and lateral balance of the tear strength.
  • An object of the present invention is to provide a biodegradable polyester film having a good longitudinal and lateral balance of tear strength in order to overcome the deficiencies of the above-mentioned conventional film.
  • a biodegradable polyester film comprising, by weight, the following components:
  • the biodegradable polyester film has a light transmittance of 80% to 90% in a film thickness of 20 to 35 ⁇ m, preferably 83% to 88%, the light transmittance is measured according to GB/T 2410-2008.
  • the invention finds that when the light transmittance of the biodegradable polyester film is in the range of 80% to 90%, the crystallinity of the film material in the light transmittance range is low due to the difference in molecular microstructure. Therefore, the problem of the longitudinal and lateral unbalance of the tear strength of the film when the polyester film is used can be effectively improved, and the prepared film has a high stiffness and a good longitudinal and lateral balance of the tear strength.
  • the light transmittance of the biodegradable polyester film of the present invention is preferably in the range of 80% to 90%.
  • the biodegradable polyester film comprises, by weight, the following components:
  • the ratio of the longitudinal and transverse tear strength of the biodegradable polyester film with a film thickness of 20-35 ⁇ m is 1:1 to 1:2, indicating that the longitudinal and transverse balance of the film tear strength is good, and the longitudinal and transverse tear strength is good.
  • Ratio longitudinal tear strength / transverse tear strength, wherein the longitudinal and transverse tear strength is determined according to GB/T 16578.2.
  • the biodegradable polyester film has a film thickness of 20-35 ⁇ m according to GB/T 1040.3, and a longitudinal 10% modulus is between 4 and 10 N, and a lateral 10% modulus is between 2 and 5 N.
  • the polylactic acid has a melt flow rate of 2-5 g/10 min at a temperature of 190 ° C and a load of 2.16 kg;
  • the polyadipate/butylene terephthalate had a melt flow rate of 2-5 g/10 min at a temperature of 190 ° C under a load of 2.16 kg.
  • the biodegradable polyester film of the present invention further comprises (c) an epoxy copolymer of 0 to 2 parts, (d) talc and/or calcium carbonate in an amount of from 0 to 8 parts by weight.
  • the epoxy-based copolymer is an epoxy-based copolymer having 2 to 15 epoxy groups in the structure, and the compatibilizing agent can react with terminal groups of PBAT and PLA such as a hydroxyl group or a carboxyl group to increase compatibility. .
  • the preparation method of the biodegradable polyester film of the invention comprises the following steps:
  • the biodegradable polyester mixture is blown on a double-air ring blown film machine to obtain a film having a film thickness of 20-35 ⁇ m, wherein the air volume of the inner and outer air rings is 1:1 to 1:3.
  • the inflation ratio is between 2.5 and 4.0.
  • the invention has the following beneficial effects:
  • the invention can effectively improve the polyester film by blending polyadipate/butylene terephthalate with polylactic acid and controlling the transmittance of the polyester film to be in the range of 80% to 90%.
  • Vertical and horizontal unevenness of the tear strength of the film when it is used The problem of balance is that the prepared film has a high stiffness and a good vertical and horizontal balance of tear strength.
  • the raw materials used in the present invention are as follows:
  • PBAT BASF, Germany, trade name Ecoflex@, MFR is 3g/10min (190°C/2.16kg);
  • PLA purchased from Natureworks, USA, MFR is 3g/10min (190 ° C / 2.16kg);
  • Talc powder and calcium carbonate are commercially available
  • Epoxy copolymer 9 epoxy groups in the structure, BASF, Germany, trade name ADR-4370;
  • the detection method or standard used in the present invention is:
  • the obtained biodegradable polyester composition is blown on a double air ring blown film machine with a film thickness of 25 ⁇ m, and the air volume of the inner and outer air rings is controlled between 1:1 and 1:3, and the blow ratio is 2.5 to 4.0.
  • the properties of the obtained film are shown in Table 1.
  • Comparative Example 1 The air volume of the inner and outer air rings was controlled to be 1:3.5, and the inflation ratio was 4.0. The rest were the same as in the examples.
  • Comparative Example 2 The air volume of the inner and outer air rings was controlled to be 1:0.8, and the inflation ratio was 4.0. The rest were the same as in the examples.
  • Comparative Example 3 The air volume of the inner and outer air rings was controlled to be 1:4, and the inflation ratio was 2.0. The rest were the same as in the examples.
  • the present invention is modified by blending poly(adipic acid)/butylene terephthalate with polylactic acid, and by controlling the light transmission of the polyester film.
  • the rate is in the range of 80%-90%, which can effectively improve the longitudinal and lateral imbalance of the tear strength of the film when the polyester film is used, and the prepared film has high stiffness and vertical and horizontal tear strength. Balance is good.

Abstract

L'invention concerne un film mince de polyester biodégradable et un procédé pour sa préparation. Le film mince de polyester biodégradable comprend les constituants suivants : (a) 20 à 50 parties de poly(acide lactique); (b) 50 à 80 parties de poly(adipate/téréphtalate de butylène), le facteur de transmission lumineuse du film mince de polyester biodégradable étant de 80 à 90 pourcents pour une épaisseur du film de 20 à 35 µm. Après mélange et modification du poly(adipate/téréphtalate de butylène) et du poly(acide lactique), et réglage du facteur de transmission lumineuse du film mince de polyester à une valeur de 80 à 90 pourcents, il est possible, lors de l'utilisation du film mince de polyester, d'améliorer efficacement les problèmes que présente le matériau du film de polyester, à savoir une faible uniformité de la résistance à la déchirure longitudinale et transversale, et une faible transparence. Le film mince ainsi préparé présente une grande rigidité du film et une bonne uniformité de la résistance à la déchirure longitudinale et transversale.
PCT/CN2017/095942 2016-08-12 2017-08-04 Film mince de polyester biodégradable et son procédé de préparation WO2018028513A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610658569.6 2016-08-12
CN201610658569.6A CN106280307A (zh) 2016-08-12 2016-08-12 一种可生物降解聚酯薄膜及其制备方法

Publications (1)

Publication Number Publication Date
WO2018028513A1 true WO2018028513A1 (fr) 2018-02-15

Family

ID=57669560

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/095942 WO2018028513A1 (fr) 2016-08-12 2017-08-04 Film mince de polyester biodégradable et son procédé de préparation

Country Status (2)

Country Link
CN (1) CN106280307A (fr)
WO (1) WO2018028513A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112210197A (zh) * 2020-10-10 2021-01-12 莱涤新材料(宁波)有限公司 一种可生物降解聚乳酸薄膜及其制备方法
CN113234304A (zh) * 2021-05-11 2021-08-10 贵州省材料产业技术研究院 一种生物可降解薄膜材料及薄膜的制备方法
CN113683869A (zh) * 2021-09-01 2021-11-23 海南赛诺实业有限公司 一种完全可生物降解耐用型农业地膜及其制备方法
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
CN114656886A (zh) * 2022-03-29 2022-06-24 湖北正宇环保材料科技有限公司 一种全生物降解缠绕膜及其制备方法
CN115521588A (zh) * 2022-09-30 2022-12-27 新疆蓝山屯河高端新材料工程技术研究中心有限公司 一种全生物降解薄膜及其制备方法和在地膜中的应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106280307A (zh) * 2016-08-12 2017-01-04 金发科技股份有限公司 一种可生物降解聚酯薄膜及其制备方法
CN107345053B (zh) * 2017-07-13 2019-11-05 山东农业大学 一种超薄超透明全生物降解薄膜吹膜级材料及其制备方法
CN109810476A (zh) * 2017-11-20 2019-05-28 武汉华丽生物股份有限公司 可完全生物降解膜袋材料及膜袋制备方法
CN108359223B (zh) * 2017-12-27 2020-07-14 杨红梅 一种生物可降解的聚酯组合物及其应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702696A (zh) * 2012-06-20 2012-10-03 浙江华夏包装有限公司 全降解生物材料及其制品
CN104559087A (zh) * 2015-01-21 2015-04-29 江苏科技大学 一种可控生物基全降解地膜
CN104744898A (zh) * 2015-03-26 2015-07-01 南通龙达生物新材料科技有限公司 一种全生物降解薄膜及其制备方法
CN105086395A (zh) * 2015-09-02 2015-11-25 深圳王子新材料股份有限公司 生物降解复合材料及其制备方法
CN106280307A (zh) * 2016-08-12 2017-01-04 金发科技股份有限公司 一种可生物降解聚酯薄膜及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702696A (zh) * 2012-06-20 2012-10-03 浙江华夏包装有限公司 全降解生物材料及其制品
CN104559087A (zh) * 2015-01-21 2015-04-29 江苏科技大学 一种可控生物基全降解地膜
CN104744898A (zh) * 2015-03-26 2015-07-01 南通龙达生物新材料科技有限公司 一种全生物降解薄膜及其制备方法
CN105086395A (zh) * 2015-09-02 2015-11-25 深圳王子新材料股份有限公司 生物降解复合材料及其制备方法
CN106280307A (zh) * 2016-08-12 2017-01-04 金发科技股份有限公司 一种可生物降解聚酯薄膜及其制备方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112210197A (zh) * 2020-10-10 2021-01-12 莱涤新材料(宁波)有限公司 一种可生物降解聚乳酸薄膜及其制备方法
CN113234304A (zh) * 2021-05-11 2021-08-10 贵州省材料产业技术研究院 一种生物可降解薄膜材料及薄膜的制备方法
CN113683869A (zh) * 2021-09-01 2021-11-23 海南赛诺实业有限公司 一种完全可生物降解耐用型农业地膜及其制备方法
CN113683869B (zh) * 2021-09-01 2022-12-30 海南赛诺实业有限公司 一种完全可生物降解耐用型农业地膜及其制备方法
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
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
CN114656886A (zh) * 2022-03-29 2022-06-24 湖北正宇环保材料科技有限公司 一种全生物降解缠绕膜及其制备方法
CN115521588A (zh) * 2022-09-30 2022-12-27 新疆蓝山屯河高端新材料工程技术研究中心有限公司 一种全生物降解薄膜及其制备方法和在地膜中的应用

Also Published As

Publication number Publication date
CN106280307A (zh) 2017-01-04

Similar Documents

Publication Publication Date Title
WO2018028513A1 (fr) Film mince de polyester biodégradable et son procédé de préparation
CN109796734B (zh) 一种聚乳酸全生物降解复合材料
US20200291225A1 (en) Low cost bio-based full degradable film and preparation method thereof
US9228066B2 (en) Polymer material and method for the production thereof
JP5616451B2 (ja) ポリマー／熱可塑性デンプン組成物
CN108822514B (zh) 一种完全生物降解聚乳酸基吹塑薄膜及其制备方法
JP5587194B2 (ja) ポリマー材料およびその生産のための方法
US20160060451A1 (en) Polymer composition
BRPI0715054A2 (pt) mÉtodo para preparar uma composiÇço de polÍmero biodegradÁvel, mistura padrço, mÉtodo para preparar a mesma, e, composiÇço de polÍmero biodegradÁvel
KR20110095293A (ko) 생분해성 폴리머 조성물
JP2008088417A (ja) 樹脂組成物及び成形体
JP2016524645A (ja) ポリマー組成物
CN105062024B (zh) 高透明高耐温聚乳酸复合材料及其制备方法
US11732058B2 (en) Thermoplastic starch and starch-based biodegradable film
WO2013021772A1 (fr) Film biodégradable
CN111978691B (zh) 一种可生物降解地膜及其制备方法
CN108017887A (zh) 一种pla-pbsa吹塑薄膜及其制备方法
US20180327589A1 (en) Composition comprising a mixture of polyesters and thermoplastic starch, having improved film-forming ability
CN111907031B (zh) 一种pla/pbat薄膜及制备方法与应用
JP2009013271A (ja) ポリ乳酸系シートまたはフィルム、およびその製造方法。
JP2013067812A (ja) 極性低密度エチレンコポリマーとポリ（ヒドロキシカルボン酸）との混合物
JP2018204005A (ja) 樹脂組成物、フィルム、多層フィルム、延伸フィルム及び包装材
WO2020088215A1 (fr) Résine ppc/pbat modifiée par pha et procédé de préparation associé
CN103013071B (zh) 一种生物降解pha透气膜及其制备方法
KR20200061929A (ko) 접착성이 우수한 방수 시트용 수지 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17838643

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17838643

Country of ref document: EP

Kind code of ref document: A1