CN1174116A - 聚酯吹制膜 - Google Patents

聚酯吹制膜 Download PDF

Info

Publication number
CN1174116A
CN1174116A CN97117118A CN97117118A CN1174116A CN 1174116 A CN1174116 A CN 1174116A CN 97117118 A CN97117118 A CN 97117118A CN 97117118 A CN97117118 A CN 97117118A CN 1174116 A CN1174116 A CN 1174116A
Authority
CN
China
Prior art keywords
film
resin
mole
weight
dianhydride
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.)
Pending
Application number
CN97117118A
Other languages
English (en)
Inventor
H·艾尔·加提
S·科伯罗
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.)
Sinco Engineering SpA
Original Assignee
Sinco Engineering SpA
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 Sinco Engineering SpA filed Critical Sinco Engineering SpA
Publication of CN1174116A publication Critical patent/CN1174116A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • 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
    • 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.]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Wire Bonding (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

采用双泡法通过吹制由含有一种芳族四羧酸二酐的芳族聚酯树脂制取的薄膜,其厚度小于10微米。

Description

聚酯吹制膜
本发明涉及芳族聚酯树脂的低厚度吹制膜和它们的制备方法。
由于芳族聚酯树脂的高机械性能，它们适用于制备能够应用于各个领域的薄膜，这些领域主要的是食品包装、照相膜和电绝缘领域。
所用的薄膜绝大部分是单向和双向定向的。这些薄膜通常是使用“铸塑”技术制备的。由于聚酯树脂的熔融强度低，采用膜泡制的制备方法会产生困难。
铸塑薄膜的厚度通常在10-100微米之间。
在US-A-4 145 466中提议通过加入低百分含量的芳族四羧酸二酐(优选的是1，2，4，5-苯四酸酐)来增加聚酯树脂的熔融强度。这样改性的树脂用来制备吹塑瓶和采用膜泡技术制备薄膜。
然而所得到的薄膜仍然大于10微米。
这种制备采用单泡法吹膜和以PET为原料与1，2，4，5-苯四酸二酐在挤出机内混合然后直接进行成膜加工进行。
由于膜泡的不稳定性和其易燃烧的倾向，由加入1，2，4，5-苯四酸酐的聚酯树脂完成厚度小于10微米薄膜的制备是困难的。
采用膜泡法生产厚度小于10微米薄膜的可能性之所以有意义是在于能够获得高质量的薄膜，同时与采用铸塑法制膜相比费用减少。
已经令人意外地发现由在待吹制的熔融树脂中均匀分布熔融强度至少3～4cN的树脂采用单泡或双泡法吹制厚度小于10微米薄膜是可能的。
该熔融强度一般在3～15cN之间(在290℃)。
这种均匀的熔融强度是通过将熔融树脂与一种芳族四羧酸二酐混合、将该熔融树脂挤出和造粒获得的，然后再挤出用于成膜加工。
也可以通过使用在挤出机中足够长的滞留时间获得二酐的均匀分布从而保证达到所要求的熔融强度。滞留时间在5～10分钟之间。
1，2，4，5-苯四酸二酐是优选的化合物，其用量为0.01-2％重量。
其它可以使用的二酐类是3，3’-4，4二苯二酐、四羧酸、3，3’-4，4-苯并苯氧基四羧酸-双-(3，4-二羧苯基)醚、双-(3，4-二羧苯基)砜。
采用单泡法吹制获得的薄膜没有取向。
这些薄膜在例如食品包装领域很有用处。
双轴拉伸薄膜可以通过双泡吹制获得，其中在比该树脂的Tg高的温度下进一步吹制第一个泡。
双向定向的薄膜具有显著的机械性能和屏障特性，这些特性比未定向薄膜的超出很多。
已经发现构成了本发明的另一个方面，即添加有芳族四羧酸二酐和小于5％重量的液晶(LCP)和/或1～20％重量的聚酰胺的聚酯树脂所得到的薄膜，具有优于只加入二酐得到的薄膜的氧阻隔性。
还发现高机械性能的薄膜也能够由添加有芳族四羧酸二酐的树脂获得，其中所述二酐是与聚碳酸酯树脂以母料的形式提供的。该母料通常含有低于20％重量的二酐。
特别有意义的结果也由对苯二酸乙二醇酯共聚物获得，其中，最多15％由对苯二酸衍生的单元由从间苯二酸和2，6-萘-二羧酸衍生的单元所取代，这里间苯二酸衍生单元与萘二羧酸衍生单元之比是1∶3-3∶1。
可用于制备本发明的薄膜的芳族聚酯树脂是一种芳族二羧酸或它的一种烷基醇二酯——尤其是二甲醇二酯——与一种带有2～12个碳原子的脂族二元醇——特别是乙二醇、1，4-丁二醇和1，4-二羟甲基-环己烷--的缩聚反应产物。
当以二甲基酯类为原料时，上述缩聚反应和脂基转移反应按照已知的方法进行。
特别适合用于饮料听内层的双向定向薄膜制备的树脂由聚对苯二甲酸乙二醇酯获得，它有至少85％摩尔从乙二醇衍生的和30～10％摩尔从二乙二醇衍生的重复单元，其中从乙二醇和二乙二醇衍生总的重复单元至少是90％摩尔。
特别适用的薄膜是由其中从二乙二醇衍生的重复单元在15～25％摩尔的树脂获得的。
制备这些薄膜所用的聚酯树脂的特性粘度一般在0.5-0.8dl/g之间。
采用单泡或双泡吹制制备薄膜按照已知的方法进行。
挤出聚合物并传到一个吹制机头，后者一般按垂直于挤出的方向设置，从该吹制机头得到一个用空气吹胀的管状产品。
空气被限制在一端是挤出机头另一端是收拢线之间的泡中。当熔融物料从挤出机头出来并开始冷却时，该管状物的直径膨胀若干倍并且被压扁而形成扁平的管状膜，然后收集在管状卷筒上或切断。
在挤出机出口的管状产品在冷空气流下被冷却。
空气的温度和在泡的外表面的接触点根据所要求的薄膜的性质而变化。
为了能够形成泡，要保持尽可能低的挤出机头的速度(在实施例中所述的条件下为1kg/h)，要调整空气流的压力以便允许该泡获得最大的膨胀(挤出机环孔直径的约6～9倍)。
在双泡吹制的情形中，第一泡以高于该树脂的Tg的温度再次被吹制。
测量和分析性质
特性粘度的测量是通过将0.5g树脂溶解于100ml 60/40(重量)苯酚和四氯乙烷的混合物在25℃ 按照ASTM 4063-8G操作进行的。
熔融强度的测量是通过在290℃用设置有2mm直径毛细管的Goettfert流变仪进行，挤出单丝的柱塞的速度是0.2mm/s。
该单丝被夹在齿轮之间，该齿轮所施加的圆周加速度是60mm/s2。
所施加的拉力是在最高速度(1000mm/s)时单丝施加给齿轮的力。
测量按照ASTM D 4440进行。
下面的实施例用来具体说明本发明而不是限制本发明。
实施例1
颗粒状的PET晶体(IV＝0.6dl/g)和1，2，4，5-苯四酸二酐PMDA(0.3％重量)的混合物在真空下以140℃干燥10小时后，以10kg/h的流量往一个在下列条件的反向啮合双螺杆挤出机中供料：
螺杆速度：              150rpm
螺筒温度：              170℃
颗粒供料速度：          10kg/h
机头的形式：            环形-直径3mm
PMDA供料速度：          0.03kg/h
在挤出机中的滞留时间：  1min
挤出物的IV：          0.607dl/g
挤出物的熔融强度：    3.5-4cN
然后所得到的颗粒或聚合物使用Brabender单螺杆挤出机(在280℃操作，设置有一个直径3cm的环形机头和Haake吹膜机头)挤出生产吹制薄膜。
在吹膜机头的流量是1kg/h。
在Brabender挤出机中的滞留时间是1.5分钟。在吹膜机头出口管状物以室温的空气吹胀。
在泡表面上流过的冷却空气的温度是23℃。
调整吹胀压力以使泡获得最大的吹胀(20～25cm直径)。
薄膜的收卷速度是3微米，薄膜的IV是0.65dl/g。
该吹制薄膜的屏障特性例如二氧化碳透气率是750(ml/day/cm2)。
实施例2
重复实施例1的制备工作，不同之处是使用下列的混合物：95％重量的PET，4.4％重量的液晶Vectra A 950(来自Hoechst Celanese)和0.3％重量的PMDA。
得到的薄膜的厚度是4微米。
二氧化碳的透气率是550ml/day/m2。
实施例3
重复实施例1的制备工作，不同之处是使用95％重量的PET，4.5％重量的尼龙6和0.3％重量的PMDA的混合物。
薄膜的厚度是2.5-3微米。
二氧化碳的透气率是450ml/day/m2。
使用一种在23℃操作的Mocon Permatron的设备测量二氧化碳的透气率。

Claims (10)

1、薄膜，从含有芳族四羧酸二酐的芳族聚酯树脂通过双泡吹制法制取，厚度小于10微米。
2、根据权利要求1的薄膜，其中所述的树脂选自聚对苯二酸乙二醇酯、聚对苯二酸丁二醇酯、对苯二酸乙二醇酯共聚物，在后者中最多15％摩尔的对苯二酸乙二醇酯单元由选自间苯二酸和/或萘二羧酸的芳族二羧酸衍生单元所取代。
3、根据权利要求1的薄膜，其中所述的树脂是聚对苯二酸乙二醇酯，其中的重复单元由至少85％摩尔的乙二醇和至少10～30％摩尔二乙二醇衍生的，并且其中由乙二醇和二乙二醇衍生的重复单元的总量是至少90％摩尔。
4、根据权利要求1、2和3中任意一项的薄膜，其中所述的二酐是1，2，4，5-苯四酸二酐，用量为0.01至2％重量。
5、根据权利要求4的薄膜，其中所述1，2，4，5-苯四酸二酐使与聚碳酸酯以母料的形式与聚酯树脂熔融混合的。
6、根据权利要求1、2、3、4或5中任意一项的薄膜，其中所述的树脂含有最多5％重量的一种液晶。
7、根据权利要求1至6中任意一项的薄膜，其中所述的聚酯树脂加有1～20％重量的一种聚酰胺。
8、根据权利要求1至7中任意一项的薄膜，其厚度小于5微米。
9、双向定向的薄膜，根据上述权利要求1至8获得。
10、根据上述各权利要求的薄膜，其熔融强度值为至少3～4cN。
CN97117118A 1996-07-15 1997-07-14 聚酯吹制膜 Pending CN1174116A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI96A001461 1996-07-15
IT96MI001461A IT1283160B1 (it) 1996-07-15 1996-07-15 Film poliestere soffiato

Publications (1)

Publication Number Publication Date
CN1174116A true CN1174116A (zh) 1998-02-25

Family

ID=11374584

Family Applications (1)

Application Number Title Priority Date Filing Date
CN97117118A Pending CN1174116A (zh) 1996-07-15 1997-07-14 聚酯吹制膜

Country Status (10)

Country Link
US (1) US6013360A (zh)
EP (1) EP0819728B1 (zh)
JP (1) JPH1087852A (zh)
KR (1) KR980009343A (zh)
CN (1) CN1174116A (zh)
AT (1) ATE230775T1 (zh)
CA (1) CA2209733A1 (zh)
DE (1) DE69718251T2 (zh)
ES (1) ES2186825T3 (zh)
IT (1) IT1283160B1 (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1283160B1 (it) * 1996-07-15 1998-04-07 Sinco Eng Spa Film poliestere soffiato
IT1291706B1 (it) * 1997-05-09 1999-01-21 L M P Impianti S R L Procedimento di produzione di poliestere, in particolare pet, espanso.
NZ506974A (en) * 1998-03-30 2002-10-25 Sealed Air Corp Production of reduced gas-permeable polyalkylene terephthalate films by strain induced crystallization
IT1301690B1 (it) * 1998-06-11 2000-07-07 Sinco Ricerche Spa Miscele di resine poliestere aventi elevate proprieta' di barriera aigas.
EP1607426B1 (en) * 2003-03-19 2016-08-24 Toyo Seikan Group Holdings, Ltd. Film for laminate and laminate comprising the same
CN100387633C (zh) * 2003-03-19 2008-05-14 东洋制罐株式会社 层压用薄膜及使用该薄膜的层压材料

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145466A (en) * 1977-09-02 1979-03-20 Rohm And Haas Company Melt strength improvement of PET
US4837115A (en) * 1986-07-30 1989-06-06 Toyo Seikan Kaisha, Ltd. Thermoplastic polyester composition having improved flavor-retaining property and vessel formed therefrom
JP2621262B2 (ja) * 1987-12-16 1997-06-18 東ソー株式会社 複合樹脂の製造方法
JP3090222B2 (ja) * 1991-05-22 2000-09-18 東洋紡績株式会社 粗面化ポリエステルフイルム
IT1251953B (it) * 1991-10-18 1995-05-27 M & G Ricerche Spa Procedimento per la produzione di resine poliestere ad elevato peso molecolare.
US5670584A (en) * 1993-05-07 1997-09-23 Sinco Engineering S.P.A. Polyester compositions suitable for the manufacture of fibres and films with high elastic modulus
JPH0753737A (ja) * 1993-08-18 1995-02-28 Kanebo Ltd ポリエステル系シュリンクフィルム
IL110514A0 (en) * 1993-10-04 1994-10-21 Eastman Chem Co Concentrates for improving polyester compositions and a method for preparing such compositions
IT1283590B1 (it) * 1996-04-12 1998-04-22 Sinco Eng Spa Resine poliesteri aventi migliorate proprieta' reologiche (mg-18)
IT1283160B1 (it) * 1996-07-15 1998-04-07 Sinco Eng Spa Film poliestere soffiato

Also Published As

Publication number Publication date
EP0819728A2 (en) 1998-01-21
ES2186825T3 (es) 2003-05-16
DE69718251D1 (de) 2003-02-13
KR980009343A (ko) 1998-04-30
CA2209733A1 (en) 1998-01-15
DE69718251T2 (de) 2003-08-28
ITMI961461A0 (zh) 1996-07-15
MX9705328A (es) 1998-08-30
EP0819728A3 (en) 1998-02-04
ITMI961461A1 (it) 1998-01-15
US6013360A (en) 2000-01-11
EP0819728B1 (en) 2003-01-08
JPH1087852A (ja) 1998-04-07
IT1283160B1 (it) 1998-04-07
ATE230775T1 (de) 2003-01-15

Similar Documents

Publication Publication Date Title
EP0964031B1 (en) Polyester resin blends with high-level gas barrier properties
CN100336865C (zh) 聚乙醇酸树脂组合物及其成型物
JP2000302952A (ja) ポリエステル樹脂組成物
CN1771281A (zh) 可生物降解的树脂膜或片及其制造方法
CN1174209A (zh) 生产聚酯树脂的改进方法
CN104908329A (zh) 一种高结晶度双向高力学强度的聚乳酸薄膜的制备方法
CN1276287A (zh) 单轴或双轴拉伸的聚酯树脂发泡片材和膜
CN1174116A (zh) 聚酯吹制膜
CN115627057A (zh) 一种吸管及其制备方法
US5670584A (en) Polyester compositions suitable for the manufacture of fibres and films with high elastic modulus
CN1165835A (zh) 具有改善流变性质的聚酯树脂
CN1101831C (zh) 聚酯组合物
CN100480326C (zh) 一种聚酯薄膜及其生产方法
CN1772792A (zh) 由固相聚合制备聚对苯二甲酸乙二酯和二元醇的共聚物的方法
US6441104B1 (en) Process for producing high molecular weight thermoplastic resin composition and its use
CN1266860A (zh) 聚酯树脂的透明物件
CN117984643B (zh) 一种pet与二氧化碳共聚物的多层共挤材料及其制备方法
US3825516A (en) Glass fiber-reinforced,terephthalic acid-containing polyamide molding compounds
CN1744981A (zh) 挤坯吹塑制品
JP3181270B2 (ja) 回収ペットボトル粉砕物及びペット樹脂を原料とするペットパイプの押出成形法
JP2004155968A (ja) 回収ポリエステル樹脂の製造方法および設備
MXPA97005328A (en) Blown poly film
CN114055877A (zh) 耐热、低水蒸气透过率且可生物降解的纸塑复合材料及其制备方法和应用
CN116003982A (zh) 一种3d打印用玻璃纤维复合聚碳酸酯改性材料及其制备方法和打印丝材
CN118374133A (zh) 一种高性能生物可降解薄膜及其制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
AD01 Patent right deemed abandoned
C20 Patent right or utility model deemed to be abandoned or is abandoned
REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1047605

Country of ref document: HK