CN101495568A - 具有改进的抗冲击性的聚乳酸组合物 - Google Patents

具有改进的抗冲击性的聚乳酸组合物 Download PDF

Info

Publication number
CN101495568A
CN101495568A CNA2007800279732A CN200780027973A CN101495568A CN 101495568 A CN101495568 A CN 101495568A CN A2007800279732 A CNA2007800279732 A CN A2007800279732A CN 200780027973 A CN200780027973 A CN 200780027973A CN 101495568 A CN101495568 A CN 101495568A
Authority
CN
China
Prior art keywords
composition
methyl
ethene
multipolymer
acrylate
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
CNA2007800279732A
Other languages
English (en)
Other versions
CN101495568B (zh
Inventor
托马斯·法恩
马利哈·库斯拉维
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.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of CN101495568A publication Critical patent/CN101495568A/zh
Application granted granted Critical
Publication of CN101495568B publication Critical patent/CN101495568B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • 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
    • 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
    • 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
    • B29C48/361—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die with the barrel or with a part thereof rotating
    • 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
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • 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
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0884—Epoxide containing esters
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31736—Next to polyester
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明涉及具有改进的抗冲击性的聚(乳酸)组合物，其按重量计包含：60％－97％的聚(乳酸)(PLA)、以及3％－40％的化合物A和B的混合物，其中，A是乙烯与含有至少一个环氧基或羧酸或羧酸酐官能团的不饱和单体、以及任选的(甲基)丙烯酸烷基酯的共聚物，B是乙烯与(甲基)丙烯酸烷基酯的共聚物，其中所述混合物的(A)重量％/(A+B)重量％之比为0.10－0.49。本发明还涉及使用这些组合物进行的部件或物品的制造。

Description

具有改进的抗冲击性的聚乳酸组合物
技术领域
本发明涉及具有改进的冲击强度的聚乳酸组合物。
背景技术
聚乳酸(PLA)是由来源于植物的单体合成的聚酯。其由于其可生物降解性和可再生性质而受到较多关注。然而，其是需要增强抗冲击性的特别脆性的单体。
在本领域的当前情况中，JP H09-316310描述了含有用聚苯乙烯或聚二甲基丙烯酸酯接枝的乙烯-甲基丙烯酸缩水甘油酯共聚物、或者用马来酸酐接枝的聚烯烃的PLA组合物。
最近，WO 2005/059031描述了已经用含有至少50％的乙烯-(甲基)丙烯酸烷基酯-(甲基)丙烯酸缩水甘油酯共聚物和乙烯-(甲基)丙烯酸烷基酯共聚物的混合物进行了抗冲改性的PLA树脂。
这些组合物的确具有改进的冲击强度，然而，该强度不是完全令人满意的，特别是在低温下。
而且，这些组合物的流动性显著地低于PLA的流动性。这种流动性的显著降低不利于其实施，尤其是大尺寸的、薄的注射成型部件的实施。
本发明的目的是提出一种既具有良好的冲击强度(特别是在低温下)又具有良好的流动性的PLA组合物。
发明内容
本发明涉及一种聚乳酸组合物，其按重量计包含：
-60％-97％的聚乳酸(PLA)，和
-3％-40％的化合物A和B的混合物，其中：
○A是乙烯与含有至少一个环氧基或羧酸或羧酸酐官能团的不饱和单体、以及任选的(甲基)丙烯酸烷基酯的共聚物，
○B是乙烯与(甲基)丙烯酸烷基酯的共聚物，
所述混合物的(A)重量％/(A+B)重量％之比为0.10-0.49。
本发明人惊讶地发现，在混合物A+B中主要含有乙烯-(甲基)丙烯酸烷基酯共聚物的PLA组合物赋予从这些组合物获得的部件在室温下尤其是在低温下的改进的冲击强度。该冲击强度高于富含乙烯-(甲基)丙烯酸烷基酯-(甲基)丙烯酸缩水甘油酯共聚物的组合物的冲击强度。
另外，这些组合物显示出在冲击强度和粘度之间的良好的平衡(compromise)。
根据本发明的一个变型，化合物A是可通过乙烯与不饱和环氧化物的共聚或者通过将不饱和环氧化物接枝到聚乙烯上而获得的乙烯与不饱和环氧化物的共聚物。该接枝可在溶剂相中进行或者在过氧化物的存在下在聚乙烯熔体上进行。这些接枝技术本身是已知的。对于乙烯和不饱和环氧化物的共聚，可使用通常在200-2500巴的压力下进行的自由基聚合工艺。
可提及的不饱和环氧化物的实例包括：
-脂肪族缩水甘油酯和醚，例如烯丙基缩水甘油醚、乙烯基缩水甘油醚、马来酸缩水甘油酯和衣康酸缩水甘油酯、或(甲基)丙烯酸缩水甘油酯，和
-脂环族缩水甘油酯和醚，例如2-环己烯1-缩水甘油醚、环己烯-4，5-二缩水甘油基羧酸酯、环己烯-4-缩水甘油基羧酸酯、5-降冰片烯-2-甲基-2-缩水甘油基羧酸酯和内顺式(endo-cis)-双环(2，2，1)-5-己烯-2，3-二缩水甘油基二羧酸酯。
乙烯与不饱和环氧化物的共聚物还可包含其它单体，这些单体可选自例如：
-α-烯烃，例如丙烯、1-丁烯、己烯等，
-饱和羧酸的乙烯基酯，例如乙酸乙烯酯或丙酸乙烯酯，
-饱和羧酸酯，例如可能含有最高达24个碳的(甲基)丙烯酸烷基酯。
例如，该不饱和环氧化物可接枝到下列聚合物上：
-聚乙烯，乙烯与α-烯烃的共聚物，聚乙烯类例如VLDPE(极低密度聚乙烯)、ULDPE(超低密度聚乙烯)或茂金属催化聚乙烯；
-乙烯与至少一种饱和羧酸的乙烯基酯(如乙酸乙烯酯或丙酸乙烯酯)的共聚物；
-乙烯与至少一种不饱和羧酸酯的共聚物，例如可能含有最高达24个碳的(甲基)丙烯酸烷基酯；
-EPR弹性体(二元乙丙橡胶)或EPDM弹性体(乙烯/丙烯/二烯)；
-选自上述的聚合物的混合物。
本发明的化合物A有利地为乙烯/(甲基)丙烯酸烷基酯/不饱和环氧化物共聚物。
有利地，本发明的化合物A可含有最高达40重量％的(甲基)丙烯酸烷基酯。
该环氧化物有利地为(甲基)丙烯酸缩水甘油酯。
有利地，该(甲基)丙烯酸烷基酯选自(甲基)丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸正辛酯和丙烯酸2-乙基己酯。
(甲基)丙烯酸烷基酯的量有利地为20-35％。
A的熔体流动指数(MFI)有利地为2-40且优选为5-20(190℃，2.16kg)。
该共聚物可通过单体的自由基聚合获得。
根据另一变型，化合物A是乙烯与不饱和羧酸酐的共聚物。
A是乙烯与不饱和羧酸酐的共聚物、或者用不饱和羧酸酐接枝的聚烯烃。
该聚烯烃可选自可用上述不饱和环氧化物接枝的聚烯烃。
可用作A的组成的不饱和二羧酸酐的实例特别是马来酸酐、衣康酸酐、柠康酸酐和四氢邻苯二甲酸酐。
可提及的实例包括乙烯、(甲基)丙烯酸烷基酯、不饱和羧酸酐的共聚物和乙烯、饱和羧酸的乙烯基酯和不饱和羧酸酐的共聚物。
不饱和羧酸酐的量可最高达共聚物的15重量％且乙烯的量至少为50重量％。
有利地，A是乙烯、(甲基)丙烯酸烷基酯和不饱和羧酸酐的共聚物。优选地，(甲基)丙烯酸烷基酯的烷基含有2-10个碳原子。
(甲基)丙烯酸烷基酯可选自上述的那些。
A的MFI可为例如0.1-50(克/10分钟，在190℃、2.16kg下)。
根据本发明，化合物B是乙烯与(甲基)丙烯酸烷基酯的共聚物。(甲基)丙烯酸烷基酯可有利地选自(甲基)丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸正辛酯和丙烯酸2-乙基己酯。
(甲基)丙烯酸烷基酯的量优选为20-40％。
根据本发明的第一个方面，该组合物的(A)重量％/(A+B)重量％之比为0.15-0.40，且优选为0.20-0.30。
本发明还涉及通过挤出制备上述组合物的方法。该方法可根据两种具体实施方式进行：
-通过同时混合PLA、A和B，或者
-通过相继进行下列两个步骤：
a)混合A和B，然后
b)将从a)获得的产物与PLA混合。
另外，本发明涉及这些组合物的用途，并且还涉及从这些组合物制造的部件或物品。
可非限制性地提及下列物品的制造：注射成型部件、挤出并任选地热成型的膜和片材、通过挤出吹塑成型形成的空心体、容器(如盘子)等。
由此获得的部件或物品可经历退火步骤以控制结晶度。
该控制还可以通过将成核剂加入根据本发明的组合物或PLA而获得。
本发明还涉及多层结构，其包含对应于本发明的组合物的层和至少一个热塑性塑料层，该热塑性塑料选自聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚酰胺(PA)和乙烯/乙烯醇(EVOH)共聚物。
现在将通过下面描述的具体生产实施例说明本发明。应指出这些实施例绝非意图限制本发明的范围。
实施例
所使用的材料：
由Natureworks以标号PLA 2002D出售的聚乳酸或PLA。
使用的化合物A是乙烯(68重量％)、丙烯酸甲酯(MeA)(24重量％)和甲基丙烯酸缩水甘油酯(GMA)(8重量％)的具有等于6的MFI的三元共聚物。该三元共聚物由Arkema France以标号
Figure A20078002797300061
AX8900出售。
使用的化合物B是乙烯(70重量％)和丙烯酸丁酯(30重量％)的具有1.5-2.5的MFI的共聚物。该共聚物由Arkema France以标号
Figure A20078002797300062
30BA02出售。
所测试的组合物的特征：
○参照组合物：试验1：100％PLA
○对比组合物：试验2和6-8
试验2：80％PLA+20％B
试验6：80％PLA+10％A+10％B，即A％/(A+B)％＝0.5
试验7：80％PLA+15％A+5％B，A％/(A+B)％＝0.75
试验8：80％PLA+20％A+5％B，A％/(A+B)％＝1
○根据本发明的组合物：试验3-5
试验3：80％PLA+2％A+18％B，即A％/(A+B)％＝0.1
试验4：80％PLA+4％A+16％B，即A％/(A+B)％＝0.2
试验5：80％PLA+6％A+14％B，即A％/(A+B)％＝0.3
制备各种组合物的方法：
配混：
通过在产量为15kg且螺杆转速为280rpm的装配有脱气系统和挤出物切割器的L/D 30双螺杆挤出机上配混而获得各组合物。使用的温度分布是从170℃到200℃递增的温度分布。材料温度为220℃。
在配混之后，将PLA在70℃下干燥4小时。
Figure A20078002797300072
样品的成型：
将粒料干燥然后在标准注塑压机上在下列条件下进行成型：
■塑化筒温度：180/200℃
■模塑温度：30℃
■注射压力：1200巴
■保持压力：700巴
将由此获得的标准化试样(80×10×4mm3)在100℃、轻负载下退火30分钟。
组合物的评价：
-根据ISO 179 931Ae在23℃和-40℃下Charpy(简支梁)型预先带有缺口的(prenotched)试样上的冲击强度。
-根据标准ISO 1133-1981-F在190℃的温度和2.16kg的重量下测量的熔体流动指数(MFI)。
试验结果总结于下表1中。
表1
  试验   1(参照)   2(对比) 3(本发明)   4(本发明)   5(本发明)   6(对比)   7(对比)   8(对比)
  PLA％   100   80   80   80   80   80   80   80
  A％   0   0   2   4   6   10   15   20
  B％   0   20   18   16   14   10   5   0
  A％/(A+B)％   -   -   0.1   0.2   0.3   0.5   0.75   1
  23℃下的Charpy冲击强度(kJ/m2)   3.8   6.5   16.1   20.9   21.4   24.5   20.7   16.6
  -40℃下的Charpy冲击强度(kJ/m2)   3.7   5   5.1   5.6   5   3.8   3.9   3.2
  MFI   2.9   2.4   1.9   1.9   1.7   1.05   1.4   1.0
Figure A20078002797300081
试验1清楚地显示PLA是需要增强抗冲击性的脆性材料。其作为参照。
Figure A20078002797300082
试验2显示，没有化合物A，增强的水平仍然低，特别是在23℃下。
Figure A20078002797300083
对比试验6-8对应于WO 2005/059031中公开的发明。这样的主要含有化合物A的组合物在23℃下给出令人满意的抗冲击增强。另一方面，在-40℃下没有观察到冲击强度的改善，或者当单独使用化合物A时甚至观察到轻微的脆裂。
Figure A20078002797300084
试验3、4和5对应于本发明。这样的在混合物A+B中含有多于50％的化合物B的组合物在23℃以及-40℃下给出优异的冲击强度结果。而且，这些组合物可以保持良好的流动性。

Claims (10)

1.一种聚乳酸组合物，其按重量计包含：
-60％-97％的聚乳酸(PLA)，和
-3％-40％的化合物A和B的混合物，其中：
○A是乙烯与含有至少一个环氧基或羧酸或羧酸酐官能团的不饱和单体、以及任选的(甲基)丙烯酸烷基酯的共聚物，
○B是乙烯与(甲基)丙烯酸烷基酯的共聚物，
所述混合物的(A)重量％/(A+B)重量％之比为0.10-0.49。
2.权利要求1的组合物，其特征在于A选自乙烯-(甲基)丙烯酸烷基酯-马来酸酐三元共聚物和乙烯-(甲基)丙烯酸烷基酯-甲基丙烯酸缩水甘油酯三元共聚物。
3.权利要求1或2的组合物，其特征在于A是乙烯、丙烯酸甲酯和甲基丙烯酸缩水甘油酯的共聚物。
4.权利要求1-3中任一项的组合物，其特征在于B是乙烯与丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸正辛酯或丙烯酸2-乙基己酯的共聚物。
5.权利要求1-4中任一项的组合物，其特征在于所述混合物的(A)重量％/(A+B)重量％之比为0.15-0.40，且优选为0.20-0.30。
6.制备权利要求1-5中任一项的组合物的方法，其中通过挤出进行PLA、A和B的同时混合。
7.制备权利要求1-5中任一项的组合物的方法，其中通过挤出进行下列步骤：
-在第一步中，通过A和B的挤出进行混合，然后
-在第二步中，通过由所述第一步获得的产物和PLA的挤出进行混合。
8.由权利要求1-5中任一项的组合物获得的部件或物品，其特征在于所述部件或物品通过选自模塑、挤出和热成型的方法制备。
9.权利要求8的部件或物品，其制备还包括退火步骤。
10.一种多层结构，其包含权利要求1-5中任一项的组合物的层和至少一个热塑性塑料层，该热塑性塑料选自聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚酰胺(PA)和乙烯/乙烯醇(EVOH)共聚物。
CN2007800279732A 2006-06-16 2007-06-11 具有改进的抗冲击性的聚乳酸组合物 Expired - Fee Related CN101495568B (zh)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR0652160A FR2902434B1 (fr) 2006-06-16 2006-06-16 Composition d'acide polylactique presentant une resistance aux chocs amelioree
FR0652160 2006-06-16
US81986206P 2006-07-11 2006-07-11
US60/819,862 2006-07-11
PCT/FR2007/051403 WO2007144529A1 (fr) 2006-06-16 2007-06-11 Composition de polyacide lactique presentant une resistance aux chocs amelioree

Publications (2)

Publication Number Publication Date
CN101495568A true CN101495568A (zh) 2009-07-29
CN101495568B CN101495568B (zh) 2012-02-29

Family

ID=37667525

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007800279732A Expired - Fee Related CN101495568B (zh) 2006-06-16 2007-06-11 具有改进的抗冲击性的聚乳酸组合物

Country Status (11)

Country Link
US (1) US9512311B2 (zh)
EP (1) EP2032649B1 (zh)
JP (1) JP5174017B2 (zh)
KR (1) KR101332990B1 (zh)
CN (1) CN101495568B (zh)
AT (1) ATE518912T1 (zh)
DK (1) DK2032649T3 (zh)
ES (1) ES2368093T3 (zh)
FR (1) FR2902434B1 (zh)
PL (1) PL2032649T3 (zh)
WO (1) WO2007144529A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8859690B2 (en) 2011-06-23 2014-10-14 China Petroleum & Chemical Corporation Biodegradable composite, the preparation process thereof, and a disposable article made therefrom
CN105694401A (zh) * 2016-03-15 2016-06-22 江苏永盛三维打印新材料有限公司 一种可用于快速成型的增韧聚乳酸及其制备方法
CN109825048A (zh) * 2019-02-20 2019-05-31 华南理工大学 一种pla/pbat复合材料及其制备方法
CN113943406A (zh) * 2021-05-08 2022-01-18 天津科技大学 一种智能温控可逆透光材料的制备方法

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2700999A1 (en) * 2007-10-01 2009-04-09 Arkema Inc. Blends of biodegradable polymers and acrylic copolymers
EP2110407A1 (en) * 2008-04-16 2009-10-21 Total Petrochemicals Research Feluy Blends of polar low density ethylene copolymers and poly(hydroxy carboxylic acid)s
JP5177748B2 (ja) * 2008-09-02 2013-04-10 独立行政法人産業技術総合研究所 脂肪族ポリエステル組成物およびその製造方法
CN101402786B (zh) * 2008-11-14 2011-05-18 上海宝利纳材料科技有限公司 一种增韧聚乙烯-聚乳酸组合物
US8729156B2 (en) 2009-07-17 2014-05-20 Arkema France Polyhydroxyalkanoate composition exhibiting improved impact resistance at low levels of impact modifier
FR2956405B1 (fr) * 2010-02-15 2012-03-16 Arkema France Composition de polyhydroxyalcanoate presentant une resistance au choc amelioree
EP2454063A1 (fr) * 2009-07-17 2012-05-23 Arkema France Procede de fabrication de composition polyester aux proprietes choc ameliorees
JP5373569B2 (ja) * 2009-07-24 2013-12-18 三菱樹脂株式会社 フィルムカッター
US10753023B2 (en) 2010-08-13 2020-08-25 Kimberly-Clark Worldwide, Inc. Toughened polylactic acid fibers
US8936740B2 (en) * 2010-08-13 2015-01-20 Kimberly-Clark Worldwide, Inc. Modified polylactic acid fibers
DE102011011173A1 (de) 2011-02-14 2012-08-16 Martin Schwemmer Formteil mit Carbonfasern
KR101734561B1 (ko) 2011-03-25 2017-05-11 현대자동차주식회사 폴리유산 복합재료 조성물의 제조방법
DE102011017126A1 (de) 2011-04-14 2012-10-18 Martin Schwemmer Formteil mit Carbonfasern
US10858762B2 (en) 2012-02-10 2020-12-08 Kimberly-Clark Worldwide, Inc. Renewable polyester fibers having a low density
US8637130B2 (en) 2012-02-10 2014-01-28 Kimberly-Clark Worldwide, Inc. Molded parts containing a polylactic acid composition
US9040598B2 (en) 2012-02-10 2015-05-26 Kimberly-Clark Worldwide, Inc. Renewable polyester compositions having a low density
US8975305B2 (en) 2012-02-10 2015-03-10 Kimberly-Clark Worldwide, Inc. Rigid renewable polyester compositions having a high impact strength and tensile elongation
US8980964B2 (en) 2012-02-10 2015-03-17 Kimberly-Clark Worldwide, Inc. Renewable polyester film having a low modulus and high tensile elongation
BR102013013965B1 (pt) 2013-06-06 2020-12-15 Petróleo Brasileiro S/A - Petrobras blendas de poliestireno e poli ácido lático
BR112016002594B1 (pt) 2013-08-09 2021-08-17 Kimberly-Clark Worldwide, Inc. Método para controlar seletivamente o grau de porosidade em um material polimérico, e, material polimérico
AU2014304179B2 (en) 2013-08-09 2017-08-17 Kimberly-Clark Worldwide, Inc. Anisotropic polymeric material
US9228044B2 (en) 2014-04-02 2016-01-05 International Business Machines Corporation Versatile, facile and scalable route to polylactic acid-backbone graft and bottlebrush copolymers
US9458268B2 (en) 2014-04-02 2016-10-04 International Business Machines Corporation Lactide-functionalized polymer
US9187597B1 (en) 2014-10-21 2015-11-17 International Business Machines Corporation Flame-retardant polylactic acid (PLA) by grafting through of phosphorus-containing polymers directly to PLA backbone
US9505858B2 (en) 2014-10-21 2016-11-29 International Business Machines Corporation Polylactic acid (PLA) with low moisture vapor transmission rates by grafting through of hydrophobic polymers directly to PLA backbone
US9193818B1 (en) 2014-10-29 2015-11-24 International Business Machines Corporation Toughened polylactic acid (PLA) by grafting through of impact-modifying polymers directly to PLA backbone
WO2016085712A1 (en) 2014-11-26 2016-06-02 Kimberly-Clark Worldwide, Inc. Annealed porous polyolefin material
FR3065738B1 (fr) * 2017-04-26 2020-03-13 Decathlon Filament ou fibre absorbant les gaz acides et/ou basiques, procede de fabrication d'un tel filament ou d'une telle fibre, article textile comprenant un tel filament ou une telle fibre

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1985003718A1 (en) * 1984-02-24 1985-08-29 E. I. Du Pont De Nemours And Company Toughened thermoplastic polyester compositions
CN1033517C (zh) * 1988-08-08 1996-12-11 巴特尔纪念研究院 可生物降的组合物及其制备方法
JPH03122158A (ja) * 1989-10-06 1991-05-24 Nippon Petrochem Co Ltd ポリエステル樹脂組成物
JP3070982B2 (ja) * 1991-07-18 2000-07-31 日本ジーイープラスチックス株式会社 耐衝撃性ポリエステル系樹脂組成物
US5371423A (en) * 1992-12-14 1994-12-06 Siemens Aktiengesellschaft Tri-state-capable driver circuit
US5714573A (en) * 1995-01-19 1998-02-03 Cargill, Incorporated Impact modified melt-stable lactide polymer compositions and processes for manufacture thereof
JP3693756B2 (ja) * 1996-05-27 2005-09-07 カネボウ株式会社 ポリ乳酸樹脂組成物
US6020414A (en) * 1996-10-23 2000-02-01 Hoechst Celanese Corporation Method and compositions for toughening polyester resins
JP2001347622A (ja) * 2000-06-09 2001-12-18 Asahi Kasei Corp 多層密着性耐熱ラップフィルム
JP2002212406A (ja) * 2001-01-17 2002-07-31 Sumitomo Chem Co Ltd 樹脂組成物
ITTO20010062A1 (it) * 2001-01-25 2002-07-25 Novamont Spa Miscele binarie di poliesteri alifatici biodegradabili e prodotti da queste ottenuti.
ITTO20010060A1 (it) * 2001-01-25 2002-07-25 Novamont Spa Miscele ternartie di poliesteri alifatici biodegradabili e prodotti da queste ottenuti.
KR100620471B1 (ko) * 2002-03-29 2006-09-13 미쯔이가가꾸가부시끼가이샤 락트산계 수지 조성물
DE60228195D1 (de) * 2002-04-12 2008-09-25 Procter & Gamble Flüssigkeitsdichte, wasserdampfdurchlässige Folien und Schichten mit thermoplastischen hydrophilen Polymerzusammensetzungen die verbesserte Festigkeit aufweisen
FR2841254B1 (fr) * 2002-06-24 2004-09-03 Atofina Compositions ignifugees a base de polyamide et de polyolefine
US6844077B2 (en) * 2003-03-26 2005-01-18 Exxonmobil Oil Corporation High barrier metallized film with mirror-like appearance
US6943214B2 (en) * 2003-05-13 2005-09-13 E. I. Du Pont De Nemours And Company Toughened polyoxymethylene-poly(lactic acid) compositions
JP4809233B2 (ja) * 2003-05-13 2011-11-09 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 強化されたポリオキシメチレン−ポリ乳酸組成物
JP2005298797A (ja) * 2003-10-08 2005-10-27 Asahi Kasei Chemicals Corp 脂肪族ポリエステル系樹脂組成物成形体
US7514503B2 (en) * 2003-10-08 2009-04-07 Asahi Kasei Chemicals Corporation Molded article produced from aliphatic polyester resin composition
US7354973B2 (en) * 2003-12-12 2008-04-08 E.I. Du Pont De Nemours And Company Toughened poly(lactic acid) compositions
US7381772B2 (en) * 2003-12-12 2008-06-03 E. I. Du Pont De Nemours And Company Toughened poly(lactic acid) compositions
CN100506912C (zh) * 2004-03-05 2009-07-01 三菱丽阳株式会社 热塑性树脂组合物以及使用该组合物的成型品
CN100475860C (zh) * 2004-03-26 2009-04-08 三井化学株式会社 新型树脂改性剂和含有其的含极性基团的聚合物组合物
JP2006328117A (ja) * 2005-05-23 2006-12-07 National Institute Of Advanced Industrial & Technology 耐衝撃性環境素材とその製造方法及び成形体
US9163141B2 (en) * 2006-04-27 2015-10-20 Cryovac, Inc. Polymeric blend comprising polylactic acid
FR2902433A1 (fr) * 2006-06-16 2007-12-21 Arkema France Materiau composite a base d'acide polylactique et de polyamide presentant une resistance aux chocs amelioree, son procede de fabrication et utilisation
US7951438B2 (en) * 2007-12-10 2011-05-31 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with high barrier

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8859690B2 (en) 2011-06-23 2014-10-14 China Petroleum & Chemical Corporation Biodegradable composite, the preparation process thereof, and a disposable article made therefrom
CN105694401A (zh) * 2016-03-15 2016-06-22 江苏永盛三维打印新材料有限公司 一种可用于快速成型的增韧聚乳酸及其制备方法
CN109825048A (zh) * 2019-02-20 2019-05-31 华南理工大学 一种pla/pbat复合材料及其制备方法
CN109825048B (zh) * 2019-02-20 2021-03-30 华南理工大学 一种pla/pbat复合材料及其制备方法
CN113943406A (zh) * 2021-05-08 2022-01-18 天津科技大学 一种智能温控可逆透光材料的制备方法

Also Published As

Publication number Publication date
KR20090024709A (ko) 2009-03-09
EP2032649A1 (fr) 2009-03-11
ATE518912T1 (de) 2011-08-15
KR101332990B1 (ko) 2013-11-25
EP2032649B1 (fr) 2011-08-03
FR2902434A1 (fr) 2007-12-21
FR2902434B1 (fr) 2008-08-01
JP5174017B2 (ja) 2013-04-03
US9512311B2 (en) 2016-12-06
US20100112357A1 (en) 2010-05-06
JP2009540088A (ja) 2009-11-19
WO2007144529A1 (fr) 2007-12-21
PL2032649T3 (pl) 2012-01-31
CN101495568B (zh) 2012-02-29
DK2032649T3 (da) 2011-10-17
ES2368093T3 (es) 2011-11-14

Similar Documents

Publication Publication Date Title
CN101495568B (zh) 具有改进的抗冲击性的聚乳酸组合物
KR101111368B1 (ko) 개선된 내충격성을 지니는, 폴리락트산 및 폴리아미드 기재의 조합물, 이의 제조 방법 및 용도
CA1337306C (en) Thermoplastic elastomeric compositions
JP2014051661A (ja) ポリ乳酸樹脂含有ポリプロピレン系樹脂組成物
JP2017522442A (ja) オレフィン−無水マレイン酸コポリマーを用いたエンジニアリングプラスチックの改質
CN101817966B (zh) 一种汽车用abs挤出板材材料及其制备方法
CN101724129A (zh) 具有极好的低光泽特性的耐候性热塑性树脂及其制备方法
WO2020153303A1 (ja) 樹脂組成物およびその樹脂組成物を用いた成形品
US8658739B2 (en) Polyolefin-based resin composition and molded article
CN103917566A (zh) 基于接枝聚烯烃的聚合物
CN111936576B (zh) 热塑性树脂组合物及由其制造的模制产品
US9279049B2 (en) Low-gloss thermoplastic resin composition having excellent heat resistance and weather resistance
JP2008143988A (ja) 再生ｐｅｔを含む押出成形用熱可塑性樹脂組成物および成形品
JPH02155944A (ja) 熱可塑性樹脂組成物
KR101279974B1 (ko) 저광 특성과 치수안정성 및 면충격성이 우수한 내후성 열가소성 수지 조성물
US20170183490A1 (en) Polyvinylchloride/polyolefin composition
JPH06248159A (ja) 熱可塑性樹脂組成物
JPS6137836A (ja) 艶消し熱可塑性樹脂組成物
JP2009114401A (ja) ポリエステル樹脂組成物
CN117659664A (zh) 一种耐溶剂pc/abs复合材料及其制备方法和应用
CN113286847A (zh) 树脂组合物及使用该树脂组合物的成型品
JP2009114400A (ja) 熱可塑性樹脂組成物及び該組成物を用いるエンジニアリングプラスチックの改質方法
JP2005041964A (ja) 再生ｐｅｔを用いた熱可塑性樹脂組成物
JPH0234654A (ja) 繊維強化熱可塑性樹脂組成物
JP2007063506A (ja) 熱可塑性樹脂組成物、及び成形品

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120229

Termination date: 20170611

CF01 Termination of patent right due to non-payment of annual fee