CN102844394A - 粘合剂组合物 - Google Patents

粘合剂组合物 Download PDF

Info

Publication number
CN102844394A
CN102844394A CN2011800137579A CN201180013757A CN102844394A CN 102844394 A CN102844394 A CN 102844394A CN 2011800137579 A CN2011800137579 A CN 2011800137579A CN 201180013757 A CN201180013757 A CN 201180013757A CN 102844394 A CN102844394 A CN 102844394A
Authority
CN
China
Prior art keywords
styrene
compsn
copolymer
composition
elastomeric
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
CN2011800137579A
Other languages
English (en)
Inventor
M·G·博特罗斯
C·S·霍兰
S-H·郭
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.)
Equistar Chemicals LP
Original Assignee
Equistar Chemicals LP
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 Equistar Chemicals LP filed Critical Equistar Chemicals LP
Publication of CN102844394A publication Critical patent/CN102844394A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
    • B32B2274/00—Thermoplastic elastomer material
    • 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
    • B32B2307/702—Amorphous
    • 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
    • B32B2307/704—Crystalline
    • 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
    • B32B2439/00—Containers; Receptacles
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • 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
    • B32B2605/00—Vehicles
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y10T428/31917—Next to polyene polymer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

公开了一种粘合剂组合物。该粘合剂组合物包含30wt％至65wt％的聚烯烃、15wt％至65wt％的共轭二烯基弹性体、0.5wt％至15wt％的烯烃弹性体和0.5wt％至25wt％的马来酸化聚烯烃。烯烃弹性体与共轭二烯基弹性体的重量比在0.04至1的范围内。本发明的粘合剂组合物具有对苯乙烯类聚合物层、阻隔层和聚烯烃层改善的粘合性。其适用于挤出多层薄膜、片材和很多其它相关应用。

Description

粘合剂组合物
技术领域
本发明涉及一种粘合剂组合物。更具体地，本发明涉及一种具有对苯乙烯类聚合物(styrenic polymer)表面改善的粘合性的粘合剂组合物。
背景技术
多层薄膜和片材被广泛应用于食物包装应用。可以根据预期的应用来改变树脂层的数量、排布以及采用树脂的类型。由于食品接触和密封性，通常包括聚乙烯树脂作为其中一层。广泛采用乙烯-乙烯醇(EVOH)共聚物和聚酰胺(尼龙)作为氧气和水分阻隔层。通常包括苯乙烯类聚合物作为结构层，尤其为了热成型应用。含有橡胶的苯乙烯类聚合物，例如高抗冲聚苯乙烯(HIPS)是对于该目的特别有用的。然而，在多层薄膜和片材中粘合不相似的树脂层永远充满挑战性。虽然许多含有改性聚烯烃的复合薄膜粘结层(tie-layer)粘合剂组合物在粘合聚烯烃树脂层和阻隔树脂层中是有效的，但它们对苯乙烯类树脂层通常缺少足够的粘合力。
美国专利No.5709953公开了一种可挤出粘合剂组合物，用于将聚苯乙烯树脂粘结到例如含氧或含氮树脂的第二树脂，例如EVOH、聚酯和聚酰胺(尼龙)；或粘结到非极性树脂，例如聚乙烯。可挤出粘合剂组合物包含乙烯聚合物和苯乙烯/脂肪族/苯乙烯嵌段共聚物。该参考文献公开了乙烯聚合物组分的全部或部分可以与不饱和羧酸或酐进行接枝。类似地，美国专利No.6184298公开了一种粘合剂组合物，其基本上由聚乙烯聚合物和门尼粘度不可测的未改性的苯乙烯基弹性体组成。
对于在共挤出多层薄膜和片材中的苯乙烯类聚合物层提供改善粘合性的粘合剂组合物，具有持续的需求。
发明概述
本发明涉及一种粘合剂组合物。该粘合剂组合物包含：30wt％至65wt％的聚烯烃、15wt％至65wt％的共轭二烯基弹性体、0.5wt％至15wt％的烯烃弹性体和0.5wt％至25wt％的马来酸化聚烯烃(meleated polyolefin)。在粘合剂组合物中，烯烃弹性体与共轭二烯基弹性体的重量比在0.04至1的范围内。本发明的粘合剂具有对苯乙烯类聚合物表面改善的粘合性。其适用于挤出多层薄膜和片材以及很多其它应用。
发明详述
本发明的粘合剂组合物包含30wt％至65wt％，优选35wt％至65wt％，以及更优选45wt％至65wt％的聚烯烃。适合在本发明粘合剂组合物中使用的的聚烯烃包括由一种或多种C2至C10α-烯烃单体制备的那些。优选地，聚烯烃选自由聚乙烯、聚丙烯、聚丁烯等及其混合物组成的组。
合适的聚乙烯包括乙烯均聚物、乙烯与至少一种C3至C10α-烯烃的共聚物等及其混合物。它们包括高密度聚乙烯(HDPE，密度0.941g/cm3或以上)、低密度聚乙烯(LDPE，密度0.910g/cm3至0.925g/cm3)、中密度聚乙烯(MDPE，密度0.926g/cm3至0.940g/cm3)、线性低密度聚乙烯(LLDPE，密度0.910g/cm3至0.925g/cm3)等及其混合物。合适的聚乙烯的熔融指数(melt index)(MI2)(采用ASTM D-1238-01在190℃温度下、在2.16kg负载下测定)优选在0.01dg/min至150dg/min的范围内，更优选在0.01dg/min至10dg/min的范围内，且最优选在0.01dg/min至5dg/min的范围内。
合适的聚丙烯包括非晶聚丙烯、半结晶聚丙烯等及其混合物。优选地，半结晶聚丙烯选自由丙烯均聚物、丙烯与至少一种其它C2至C10α-烯烃的共聚物等及其混合物组成的组。丙烯的共聚物包括无规共聚物和抗冲共聚物。用于该共聚物的优选α-烯烃包括乙烯、1-丁烯、1-戊烯、1-己烯、甲基-1-丁烯、甲基-1-戊烯、1-辛烯、1-癸烯等及其混合物。这里使用的“半结晶”，意味着结晶度大于或等于40％，优选大于或等于55％，以及更优选大于或等于80％。优选地，半结晶聚丙烯的熔体流动速率(melt flow rate)(采用ASTM D-1238-01在230℃温度下、在2.16kg负载下测定)优选在0.001dg/min至500dg/min的范围内。优选地，半结晶聚丙烯的密度在0.897g/cm3至0.925g/cm3的范围内，并且重均分子量(Mw)在85000至900000的范围内。
合适的聚丁烯包括1-丁烯均聚物、1-丁烯与至少一种其它C2至C10α-烯烃的共聚物等及其混合物组成的组。用于该共聚物的优选α-烯烃包括乙烯、丙烯、1-戊烯、1-己烯、甲基-1-丁烯、甲基-1-戊烯、1-辛烯、1-癸烯等及其混合物。聚丁烯的熔融指数(采用ASTM D-1238，条件E下测定)优选在0.01dg/mm至1000dg/min的范围内，更优选在0.1dg/min至750dg/min的范围内。制备聚丁烯的方法是已知的。例如，参见美国专利6306996，其教导引入此处以作参考。
聚乙烯是本发明的粘合剂组成物中使用的优选聚烯烃。LLDPE是更优选的。合适的LLDPE包括乙烯与一种或多种C3至C10α-烯烃的共聚物。合适的α-烯烃包括1-丁烯、1-己烯、1-辛烯等及其混合物。LLDPE的密度优选在0.865至0.925g/cm3的范围内。LLDPE是商业可得的，例如来自Equistar Chemicals，LP的GA502
Figure BPA00001624608400031
、GA602
Figure BPA00001624608400032
和GA616
Figure BPA00001624608400033
LLDPE。合适的LLDPE可以采用Ziegler-Natta、单活性中心催化剂、或任何其它烯烃聚合催化剂制备。特别优选的一种LLDPE树脂是1-丁烯含量在2至20wt％范围内的乙烯与1-丁烯的共聚物。乙烯-1-丁烯共聚物优选密度为0.912至0.925g/cm3，以及更优选地为0.915至0.92g/cm3。乙烯-1-丁烯共聚物的熔融指数(MI2)优选在0.5至15g/10min的范围内，更优选地为1至10g/10min。在本发明一个特别有用的实施方案中，乙烯-1-丁烯共聚物的MI2为1.5至5g/10min，且密度为0.916至0.919g/cm3。密度和MI2是分别按照ASTM 1505和1238(条件190/2.16)测定的。
本发明的粘合剂组合物包含15wt％至65wt％，优选25wt％至55wt％，更优选25wt％至45wt％，以及最优选27wt％至35wt％的共轭二烯基弹性体。
通过“共轭二烯基弹性体”，我们意指任何含共轭二烯的聚合物和共聚物，其玻璃化转变温度(Tg)低于室温(25℃)。换言之，含共轭二烯的聚合物和共聚物在室温下是呈弹性或橡胶态的。共轭二烯基弹性体的例子包括聚丁二烯、聚异戊二烯、丁二烯-乙烯基芳族无规和嵌段共聚物、异戊二烯-乙烯基芳族无规和嵌段共聚物、氢化丁二烯-乙烯基芳族嵌段共聚物、氢化异戊二烯-乙烯基芳族嵌段共聚物等及其混合物。优选地，共轭二烯基弹性体选自由丁二烯-苯乙烯嵌段共聚物、异戊二烯-苯乙烯嵌段共聚物、氢化丁二烯-苯乙烯嵌段共聚物、氢化异戊二烯-苯乙烯嵌段共聚物等及其混合物组成的组。更优选地，共轭二烯基弹性体选自由苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯三嵌段共聚物(SIS)等及其混合物组成的组。SBS是特别优选的。
粘合剂组合物包含0.5wt％至15wt％，优选1wt％至10wt％，以及更优选1.5wt％至7.5wt％的烯烃弹性体。
通过“烯烃弹性体”，我们意指具有弹性体特性的任何烯烃聚合物或共聚物。合适的聚烯烃弹性体包括乙烯-丙烯橡胶、乙烯-丙烯酸酯橡胶、乙烯-1-丁烯橡胶、乙烯-丙烯-二烯橡胶(EPDM)、聚乙烯塑性体、弹塑性聚丙烯或抗冲聚丙烯等及其混合物。优选地，聚烯烃弹性体选自由乙烯-丙烯橡胶、乙烯-1-丁烯橡胶、EPDM等及其混合物组成的组。特别优选乙烯-丙烯橡胶。
乙烯-丙烯橡胶优选包含35wt％至75wt％的乙烯和25wt至65wt％的丙烯，以及更优选45wt％至75wt％的乙烯和25wt％至55wt％的丙烯。乙烯-丙烯橡胶可以任选地包含其它共聚单体。其它合适的共聚单体包括1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-辛烯、丁二烯、异戊二烯等及其混合物。合适的乙烯-1-丁烯基橡胶优选包括35wt％至65wt％的乙烯和35wt％至65wt％的1-丁烯，以及更优选45wt％至55wt％的乙烯和45wt％至55wt％的1-丁烯。乙烯-1-丁烯基橡胶可任选地包含其它共聚单体。其它合适的共聚单体包括丙烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-辛烯、丁二烯、异戊二烯等及其混合物。合适的EPDM优选包含35wt％至75wt％的乙烯、25wt％至55wt％的丙烯和2wt％至10wt％的二烯单体。用于制备EPDM的合适的二烯单体优选选自二环戊二烯、乙叉降冰片烯和乙烯基降冰片烯。
以可有效提高粘合剂对苯乙烯类聚合物表面粘合力的量使用烯烃弹性体。烯烃弹性体/共轭二烯基弹性体以0.04至1，优选0.05至1，更优选0.05至0.25，最优选0.05至0.20，并特别优选0.05至0.15的的重量比使用。
粘合剂组合物包含0.5wt％至25wt％，优选5wt％至20wt％，并更优选5wt％至15wt％的马来酸化聚烯烃。用在本发明中的合适的马来酸化聚烯烃包括马来酸化HDPE、LDPE、LLDPE、丙烯均聚物、丙烯无规共聚物、丙烯抗冲共聚物等及其混合物。聚烯烃马来酸化的方法是已知的。例如，美国专利No.6716928，教导了马来酸化丙烯抗冲共聚物，其教导引入此处以作参考。优选地，马来酸化聚烯烃为马来酸化HDPE。用来制备马来酸化HDPE的合适的HDPE包括乙烯均聚物和乙烯与一种或多种C3-C10α-烯烃的共聚物。合适的α-烯烃包括1-丁烯、1-己烯和1-辛烯等及其混合物。优选地，HDPE包含低于5wt％的C3-C10α-烯烃。HDPE的密度优选在0.932g/cm3至0.965g/cm3的范围内，且更优选0.952g/cm3至0.965g/cm3的范围内。马来酸化聚烯烃优选含有0.1wt％至10wt％，更优选0.5wt％至5wt％，且最优选1wt％至2.5wt％的接枝马来酸酐。
本发明的粘合剂组合物任选包含其它添加剂、填料和改性剂。合适的添加剂包括发泡剂、交联剂、成核剂、阻燃剂、加工助剂、抗静电剂、润滑剂、光学增亮剂、颜料、分散剂、堵水剂(water-blocking agent)、UV吸收剂和光稳定剂等及其混合物。添加剂和填料优选以相对粘合剂组合物0.05wt％至35wt％，更优选0.05wt％至15wt％的量使用。
本发明的粘合剂组合物可以通过混合各组分来制备。可以使用工业已知的任何合适的混合方法。熔体共混(melt blending)是优选的方法。优选通过挤出进行熔体混合(melt mixing)。
本发明包括一种包含该粘合剂组合物的制品，包括多层薄膜和片材、管材、土工膜、容器、汽车部件以及电线和电缆绝缘和护套层，其中该粘合剂组合物用作粘合剂层。通过“多层”，我们意指制品除了粘合剂层外、还具有至少两个层。粘合剂层将其它层粘合起来。多层薄膜的一个例子是五层薄膜，其具有苯乙烯聚合物/粘合剂层/EVOH/粘合剂层/聚乙烯的结构。采用乙烯-乙烯醇共聚物(EVOH)层作为隔氧层。用在多层薄膜和片材中的合适的聚乙烯如上所述。合适的苯乙烯类聚合物包括聚苯乙烯、高抗冲聚苯乙烯、苯乙烯-丙烯腈共聚物、苯乙烯-丁二烯-丙烯腈共聚物、苯乙烯-烯烃共聚物、苯乙烯-马来酸酐共聚物、苯乙烯-丙烯酸酯共聚物等及其混合物。本发明的制品可以通过多种方法或工艺来制备。例如，本发明的多层薄膜或片材可以通过共挤出、涂覆和其它层压工艺制备。
下面的实施例仅仅例示本发明。本领域技术人员认可在本发明的精神和权利要求的范围内的多种改变。
对比例1
通过熔体共混59.8重量份的具有0.918g/cm3的密度和2g/10min的MI2的LLDPE、30重量份的具有44wt％的苯乙烯和56wt％的丁二烯的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)、10重量份的接枝1.9wt％马来酸酐的HDPE和0.2重量份的受阻酚类稳定剂制备本发明的粘合剂组合物。粘合剂与苯乙烯类聚合物(聚苯乙烯与高抗冲聚苯乙烯50/50的共混物)和具有32mol％乙烯的EVOH树脂共挤出来制备多层共挤出薄膜，其具有5mils的总厚度和下面的结构以及各组分的重量百分比：
41％苯乙烯类聚合物|3％粘合剂层|12％EVOH|3％粘合剂层|41％苯乙烯类聚合物
在苯乙烯类聚合物/粘合界面上的粘合强度为0.06磅每线性英寸(P/LI)，按照ASTM D 1876-93测定。
对比例2
按照对比例1的一般步骤，除了使用29重量份的SBS和1重量份的乙烯-丙烯橡胶EPR(EPR/SBS比例：0.03)。EPR含有72wt％的乙烯重复单元和28wt％的丙烯重复单元，并具有1.0g/10min的熔融指数。在苯乙烯类聚合物/粘合界面上的粘合强度为0.06P/LI。
实施例3-5
遵照对比例2的一般步骤，除了EPR/SBS的比例在实施例3、4和5中分别为0.05、0.1和0.2。在苯乙烯类聚合物/粘合界面上的粘合强度在实施例3中为0.08P/LI，在实施例4中为0.13P/LI，在实施例5中为0.07P/LI。
实施例6-8
遵照对比例1的一般步骤。在实施例6-8中，使用了30重量份的SBS和变量的EPR。各组分的量及粘合结果列在表1中。
对比例9
遵照对比例1的一般步骤，除了用对比例C2中的EPR代替SBS。在苯乙烯类聚合物/粘合界面上的粘合强度为0.02P/LI。
Figure BPA00001624608400071

Claims (15)

1.一种粘合剂组合物，其包含，基于组合物重量，30％至65％的聚烯烃、15％至65％的共轭二烯基弹性体、0.5％至15％的烯烃弹性体和0.5％至25％的马来酸化聚烯烃，其中该组合物的烯烃弹性体/共轭二烯基弹性体的重量比在0.04至1的范围内。
2.根据权利要求1的组合物，其中烯烃弹性体/共轭二烯基弹性体的重量比在0.05至1的范围内。
3.根据权利要求2的组合物，其中烯烃弹性体/共轭二烯基弹性体的重量比在0.05至0.20的范围内。
4.根据权利要求3的组合物，其中烯烃弹性体/共轭二烯基弹性体的重量比在0.05至0.15的范围内。
5.根据权利要求1的组合物，其中聚烯烃选自由聚乙烯、聚丙烯、聚丁烯及其混合物组成的组。
6.根据权利要求1的组合物，其中烯烃弹性体选自由乙烯-丙烯橡胶、乙烯-丙烯-二烯单体橡胶、弹性聚丙烯、聚乙烯塑性体及其混合物组成的组。
7.根据权利要求1的组合物，其中烯烃弹性体是乙烯-丙烯橡胶。
8.根据权利要求1的组合物，其中共轭二烯基弹性体选自由聚丁二烯、聚异戊二烯、丁二烯-苯乙烯无规和嵌段共聚物、异戊二烯-苯乙烯无规和嵌段共聚物、氢化丁二烯-苯乙烯嵌段共聚物、氢化异戊二烯-苯乙烯嵌段共聚物及其混合物组成的组。
9.根据权利要求1的组合物，其中共轭二烯基弹性体选自由丁二烯-苯乙烯嵌段共聚物、异戊二烯-苯乙烯嵌段共聚物、氢化丁二烯-苯乙烯嵌段共聚物、氢化异戊二烯-苯乙烯嵌段共聚物及其混合物组成的组。
10.根据权利要求1的组合物，其中共轭二烯基弹性体为苯乙烯-丁二烯-苯乙烯三嵌段共聚物。
11.一种多层薄膜或片材，其包括权利要求1的组合物的粘合剂层。
12.根据权利要求11的多层薄膜或片材，其包括粘合到粘合剂层的苯乙烯类聚合物层。
13.根据权利要求12的多层薄膜或片材，其中苯乙烯类聚合物选自由聚苯乙烯、高抗冲聚苯乙烯、苯乙烯-丙烯腈共聚物、苯乙烯-丁二烯-丙烯腈共聚物、苯乙烯-烯烃共聚物、苯乙烯-马来酸酐共聚物、苯乙烯-丙烯酸酯共聚物及其混合物组成的组。
14.根据权利要求12的多层薄膜或片材，其中苯乙烯类聚合物选自由聚苯乙烯、高抗冲聚苯乙烯及其混合物组成的组。
15.根据权利要求12的多层薄膜或片材，其进一步包括聚烯烃层，其中粘合剂层粘合到聚烯烃层和苯乙烯类聚合物层上。
CN2011800137579A 2010-03-12 2011-03-10 粘合剂组合物 Pending CN102844394A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US12/661,209 US8378025B2 (en) 2010-03-12 2010-03-12 Adhesive composition
US12/661209 2010-03-12
PCT/US2011/027856 WO2011112790A1 (en) 2010-03-12 2011-03-10 Adhesive composition

Publications (1)

Publication Number Publication Date
CN102844394A true CN102844394A (zh) 2012-12-26

Family

ID=43856057

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011800137579A Pending CN102844394A (zh) 2010-03-12 2011-03-10 粘合剂组合物

Country Status (6)

Country Link
US (1) US8378025B2 (zh)
EP (1) EP2545131B1 (zh)
CN (1) CN102844394A (zh)
BR (1) BR112012023029B1 (zh)
ES (1) ES2643215T3 (zh)
WO (1) WO2011112790A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107603534A (zh) * 2017-09-21 2018-01-19 杭州汉高新材料科技有限公司 一种聚烯烃嵌段共聚物热熔胶及其制造方法
CN110678527A (zh) * 2017-04-28 2020-01-10 陶氏环球技术有限责任公司 具有粘着剂层的物品
CN114456748A (zh) * 2022-02-23 2022-05-10 张家港康得新光电材料有限公司 一种粘着组合物及自粘保护膜
CN114854332A (zh) * 2021-02-04 2022-08-05 厦门内加湖新材料科技有限公司 粘合剂组合物、锂电池包材以及锂电池

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9650548B2 (en) * 2014-08-06 2017-05-16 Equistar Chemicals, Lp Polyolefin-based compositions, adhesives, and related multi-layered structures prepared therefrom
RU2716019C2 (ru) * 2015-02-13 2020-03-05 Эквистар Кемикалз, Лп Составы на основе полиолефина, клейкие вещества и получаемые многослойные структуры
FR3078009B1 (fr) * 2018-02-22 2021-11-19 Sealynx Int Piece d'habillage ou d'etancheite hybride avec une partie plastique - elastomere pour vehicule automobile.
EP3781873A1 (en) * 2018-04-19 2021-02-24 Flamco B.V. Single layer expansion tank membrane
WO2019203648A1 (en) 2018-04-19 2019-10-24 Flamco B.V. Single layer expansion tank membrane
CN114133676B (zh) * 2021-09-29 2023-05-05 天津金发新材料有限公司 一种低光泽、低密度、耐低温asa复合材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5591792A (en) * 1994-01-25 1997-01-07 Mitsubishi Chemical Corporation Adhesive resin composition
CN1378579A (zh) * 1999-09-03 2002-11-06 纳幕尔杜邦公司 具有高剥离强度和内聚破坏的低活化温度的粘合剂组合物
WO2007040667A1 (en) * 2005-09-29 2007-04-12 Equistar Chemicals, Lp Adhesive blends for styrene polymers and articles
US20070167569A1 (en) * 2006-01-17 2007-07-19 Botros Maged G Tie-layer adhesive compositions for styrene polymers and articles
WO2008018949A1 (en) * 2006-08-03 2008-02-14 Equistar Chemicals, Lp Propylene elastomer-containing adhesive blends

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5709953A (en) * 1996-02-21 1998-01-20 Morton International, Inc. Extrudable resin for polystyrene and laminate
ES2205795T5 (es) * 1998-03-05 2009-11-24 Basell Poliolefine Italia S.R.L. (co)polimeros de polibuteno-1 y procedimiento para su preparacion.
US6184298B1 (en) * 1998-06-19 2001-02-06 E. I. Du Pont De Nemours And Company Adhesive compositions based on blends of grafted polyethylenes and non-grafted polyethylenes and styrene container rubber
US6855432B1 (en) * 1999-09-03 2005-02-15 E. I. Du Pont De Nemours And Company Low activation temperature adhesive composition with high peel strength and cohesive failure
US6716928B2 (en) * 2002-08-16 2004-04-06 Equistar Chemicals, Lp Grafted propylene copolymers and adhesive blends

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5591792A (en) * 1994-01-25 1997-01-07 Mitsubishi Chemical Corporation Adhesive resin composition
CN1378579A (zh) * 1999-09-03 2002-11-06 纳幕尔杜邦公司 具有高剥离强度和内聚破坏的低活化温度的粘合剂组合物
WO2007040667A1 (en) * 2005-09-29 2007-04-12 Equistar Chemicals, Lp Adhesive blends for styrene polymers and articles
US20070167569A1 (en) * 2006-01-17 2007-07-19 Botros Maged G Tie-layer adhesive compositions for styrene polymers and articles
WO2008018949A1 (en) * 2006-08-03 2008-02-14 Equistar Chemicals, Lp Propylene elastomer-containing adhesive blends

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110678527A (zh) * 2017-04-28 2020-01-10 陶氏环球技术有限责任公司 具有粘着剂层的物品
CN107603534A (zh) * 2017-09-21 2018-01-19 杭州汉高新材料科技有限公司 一种聚烯烃嵌段共聚物热熔胶及其制造方法
CN114854332A (zh) * 2021-02-04 2022-08-05 厦门内加湖新材料科技有限公司 粘合剂组合物、锂电池包材以及锂电池
CN114456748A (zh) * 2022-02-23 2022-05-10 张家港康得新光电材料有限公司 一种粘着组合物及自粘保护膜

Also Published As

Publication number Publication date
WO2011112790A1 (en) 2011-09-15
US20110223439A1 (en) 2011-09-15
BR112012023029A2 (pt) 2016-05-31
US8378025B2 (en) 2013-02-19
EP2545131B1 (en) 2017-08-16
EP2545131A1 (en) 2013-01-16
ES2643215T3 (es) 2017-11-21
BR112012023029B1 (pt) 2020-01-21

Similar Documents

Publication Publication Date Title
CN102844394A (zh) 粘合剂组合物
CN101027374B (zh) 衍生自官能化的乙烯共聚物的粘合剂组合物
US8637159B2 (en) Graft composition for improved tie layers
EP1144531B1 (en) Adhesive compositions based on blends of grafted polyethylenes and non-grafted polyethylenes and styrene containing rubber
US6838520B2 (en) Adhesives for fluoropolymer films and structures containing same
CN102575135B (zh) 改进的粘合剂组合物
CN102725370B (zh) 含丁烯共聚物的粘合剂共混物
EP3099758B1 (en) Polyolefin-based compositions, adhesives, and related multi-layered structures prepared therefrom
CN102725371B (zh) 改进的粘合剂组合物
EP3058030B1 (en) Compositions with a grafted polyolefin copolymer having constituents of an unsaturated monomer, an olefin elastomer, and a long-chain branched polyolefin
WO2016022581A1 (en) Polyolefin-based compositions, adhesives, and related multi-layered structures prepared therefrom
CA2942661C (en) Polyolefin-based compositions, adhesives, and related multi-layered structures prepared therefrom
CN103328563B (zh) 形成含金属层的多层结构的方法
CN110050050B (zh) 粘合性树脂组合物、氟类树脂粘合用膜、层叠体及层叠体的制造方法
EP0791640B1 (en) Extrudable resin for polystyrene and laminate
JPH07178873A (ja) 高周波シールが可能な積層体及びその製造方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20121226

RJ01 Rejection of invention patent application after publication