CN1225501C - 具有改进性能的聚烯烃组合物 - Google Patents
具有改进性能的聚烯烃组合物 Download PDFInfo
- Publication number
- CN1225501C CN1225501C CNB018223273A CN01822327A CN1225501C CN 1225501 C CN1225501 C CN 1225501C CN B018223273 A CNB018223273 A CN B018223273A CN 01822327 A CN01822327 A CN 01822327A CN 1225501 C CN1225501 C CN 1225501C
- Authority
- CN
- China
- Prior art keywords
- alpha
- olefin
- polyolefin compositions
- ethylene
- propylene
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
-
- 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
- C08L23/06—Polyethene
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及具有良好冲击强度和透明性的聚烯烃组合物,其包含a)基于组合物总重85-98重量%的多相丙烯/α-烯烃共聚物,其包含具有0-15摩尔%α-烯烃的丙烯聚合物或与α-烯烃的共聚物作为母体聚合物和含20-80摩尔%α-烯烃的丙烯/α-烯烃橡胶共聚物。b)基于组合物总重15-2重量%的乙烯均聚物或乙烯/α-烯烃共聚物,乙烯共聚物中的α-烯烃具有4-10个碳原子,乙烯均聚物或共聚物的密度低于0.925g/cm3,生产这些组合物的方法及其用途。组合物特别有效地用于食品包装,尤其用于深冻应用。
Description
本发明涉及具有改进的冲击强度和改进的光学性能的聚烯烃组合物。更详细地,本发明涉及聚烯烃组合物,特别是在室温以下温度,特别地在0℃以下具有改进的冲击强度的聚丙烯组合物,其具有改进的光学性能,尤其是更高的透明性和更低的雾度。
本发明组合物特别适用于包装应用,尤其是应用于深冻应用食品包装。
发明背景
聚丙烯均聚物广泛地应用于包装应用中。聚丙烯均聚物具有均衡的性能,并且是便宜,易于分解的聚合物,但表现出透明度差及低冲击强度。
已建议通过添加成核剂和/或澄清剂改进聚丙烯均聚物差的光学性能和冲击强度。合适的成核剂有,例如滑石、二山梨糖醇、有机磷酸盐等。
然而,所想要的聚丙烯均聚物性能不能改进到希望的程度,即在低温下具有高冲击强度。
具有改进的冲击强度和改进的光学性能的组合物有,例如丙烯/α-烯烃无规共聚物,其中α-烯烃是乙烯或具有4-10个碳原子的α-烯烃。虽然在室温下透明性更高并且冲击强度得到显著改进,但冲击强度在更低的温度,即0℃及以下温度仍然不令人满意。丙烯/α-烯烃无规共聚物具有由韧性到脆性转变温度,根据单体含量的不同,在-5℃-5℃间,并且因此在更低的温度下冲击强度仍然很差。
为了改进更低温度下的冲击强度,已建议使用多相聚合物组合物。多相聚合物是具有基体相(相1)和第二相的聚合物。基体相通常是聚丙烯均聚物或聚丙烯/α-烯烃共聚物相,第二相通常是丙烯/α-烯烃橡胶聚合物。
第二相聚合物具有低玻璃化转变温度,通常低于-30℃。所以此多相体系的冲击强度令人相当满意,即使用于深冻应用。主要缺点是由在多相体系中的大橡胶颗粒引起的透明性差。
为改进多相聚合物体系的透明性已经进行了一些尝试。
EP-B0 373 660公开了具有改进冲击强度和改进透明性的多相聚合物体系,弹性丙烯/乙烯作为基体相,相2为丙烯/α-烯烃橡胶,其中相1和相2间的特性粘度比必须是确定的值,即0.2。所以,EP-BO373 660公开的多相体系限于非常特殊的相1和相2聚合物的组合。
EP-A0 814 127公开了基于丙烯均聚物或丙烯/α-烯烃共聚物和乙烯与丙烯或丁烯-1的弹性共聚物的耐脆聚烯烃组合物及其弹性制品。弹性共聚物增强了聚合物组合物的柔韧性且不影响其透明性,虽然这些组合物声称可用于生产医疗制品和食品包装材料,但至少用于包装应用不令人满意。
EP B0 593 221公开了含有确定MFR的聚丙烯和乙烯/α-烯烃共聚物的聚丙烯树脂组合物,具有良好冲击强度、刚性和高模塑性均衡性能,可用于汽车零件。这些组合物不具有良好的光学性能,特别是低透明性和高雾度。
发明目的
本发明的目的是提供在室温和低温具有改进冲击强度的用于包装应用的聚丙烯组合物,其具有改进的光学性能,尤其是良好的透明性和低雾度。
本发明的进一步目的是提供生产用于包装应用的在低温具有改进冲击强度和良好光学性能的聚丙烯组合物的方法。
本发明另外一个的目的是提供由这些聚丙烯组合物制备的制品,用于包装应用,尤其适用于深冻应用的食品包装。
发明简述
已经通过提供多相聚合物体系解决了本发明的目的,该多相聚合物体系用改性剂进行改性,具有改进的冲击强度以及改进的光学性能。
因此本发明涉及具有良好冲击强度和透明性的聚烯烃组合物,其包含
a)基于组合物总重85-98重量%的多相丙烯/α-烯烃共聚物,其包含具有0-15摩尔%α-烯烃的丙烯的聚合物或与α-烯烃的共聚物作为母体聚合物和含20-80摩尔%α-烯烃的丙烯/α-烯烃橡胶共聚物。
b)基于组合物总重15-2重量%的乙烯均聚物或乙烯/α-烯烃共聚物,乙烯共聚物中的α-烯烃具有4-10个碳原子,乙烯均聚物或共聚物的密度低于0.925g/cm3。
发明详述
组分a)优选为多相丙烯/α-烯烃共聚物,其包含具有0-15摩尔%α-烯烃的丙烯聚合物或共聚物作为母体聚合物(相1聚合物)和含20-80摩尔%α-烯烃的丙烯/α-烯烃橡胶共聚物。
优选地,丙烯/α-烯烃橡胶的分子量分别等于或小于丙烯均聚物和聚丙烯/α-烯烃共聚物的分子量。
组分a)多相聚合物可以使用传统催化剂通过聚丙烯或聚丙烯和α-烯烃的多级法聚合制备,例如本体聚合、气相聚合、淤浆聚合、溶液聚合及其组合。那些方法为本领域的技术人员所熟知。
优选的方法是本体淤浆环管反应器和气相反应器的组合。母体聚合物可以在环管反应器或环管和气相反应器的组合中制备。
以此法制备的聚合物转移到另一反应器并使丙烯/α-烯烃橡胶聚合。优选此聚合步骤以气相聚合完成。
用于多相共聚物聚合的合适催化剂可以是任何用于丙烯聚合的立体定向催化剂,它能在40-110℃温度和10-100巴压力下聚合和共聚合丙烯和共聚单体。齐格勒纳塔催化剂及茂金属催化剂是合适的催化剂。
本领域技术人员知道生产这种多相体系的各种可能性,并能简单地发现生产用于本发明的合适的多相体系聚合物的适当方法。
组分a)多相聚合物的母体聚合物可以具有的母体聚合物(相1聚合物)与相2聚合物的比例约为97∶3-80∶20,优选为95∶5-90∶10。
多相聚合物的熔体流率根据ISO1133为约0.1-200g/10min,优选为0.2-50g/10min,更优选为0.3-20g/10min。母体聚合物的乙烯含量可至多7摩尔%并且组分a)多相聚合物总乙烯含量可以至多30摩尔%,优选至多15摩尔%。
组分a)聚合物优选弯曲模量高于500Mpa(DIN53457)。
组分b)为乙烯均聚物或乙烯/α-烯烃共聚物,其中α-烯烃具有4-10个碳原子。
例如,组分b)可以是低密度乙烯均聚物或乙烯与如乙酸乙烯酯或丙烯酸丁酯等的共聚物。组分b)的量为组合物总重的2-15重量%,优选为3-10重量%,最优选为4-7重量%。
优选低密度乙烯均聚物或共聚物(组分b))的密度按照ISO1183低于0.925g/cm3。更优选低密度乙烯均聚物或共聚物的密度低于0.920g/cm3。最优选密度为0.890-0.920g/cm3。
优选乙烯均聚物或共聚物(组分b))在熔融和共混条件下应比组分a)多相聚合物具有更高的熔体流率(MFR)(温度:190℃;负荷:2.16kg)。优选组分b)的熔体流率比组分a)的熔体流率至少高两倍,更优选至少高五倍。组分b)的熔体流率在190℃温度和2.16kg负荷下测定。组分a)的熔体流率在230℃温度和2.16kg负荷下测定。
那些乙烯均聚物或共聚物可以用高压管工艺或高压釜工艺制备。
作为选择,线性低密度型乙烯共聚物典型地可以用齐格勒型催化剂以低压工艺制备。另外组分b)聚合物可以用茂金属催化剂制备。采用茂金属催化剂制备的组分b)聚合物为典型的乙烯和丁烯或辛烷的弹性共聚物,密度优选为0.890-0.915g/cm3。
本发明组合物可进一步包含传统添加剂,例如抗氧剂、稳定剂、酸清除剂、澄清剂、着色剂、抗紫外剂、成核剂、抗静电剂、增润剂/脱模剂、填料、如纳米填料,等。典型地,这些添加剂每种以小于组合物总重的2重量%存在,更优选小于0.5重量%。
上述传统添加剂的实例包括Irganox 1010和Irgafos 168(可从Ciba Speciality Chemicals市购),硬脂酸钙和合成水滑石(例如Kyowa Chemical Industry的DHT-4A)和1,2:3,4-二(乙基苯亚甲基)山梨糖醇-EBDS(例如Mitsui Toatsu的NC-4)和1,3:2,4-双(3,4-二甲基苯亚甲基)山梨糖醇-DMBDS(例如Milliken Chemicals的Millad 3988)。
本发明的聚丙烯组合物优选进行澄清。澄清的聚丙烯可以通过例如添加澄清剂或成核剂制备,例如,如EDBS,MDBS(1,3:2,7-二(甲基苯亚甲基)山梨糖醇)和DMDBS的山梨糖醇衍生物,磷酸盐,例如2,2′-亚甲基双(4,6-二叔丁基苯基)磷酸钠,聚乙烯基环己烷等。典型地,上述澄清剂或成核剂在注塑后可使雾度水平低于60%,优选在2mm注塑片材中低于40%。
本发明的聚烯烃组合物通过混合组分a)多相聚合物和组分b)制备,任选地,添加传统的添加剂和/或稳定剂和/或填料。
优选地,通过在挤出机或另外一个熔融混合装置熔融混合进行掺混,优选使用双螺杆挤出机然后进行造粒。组分可以如上进行熔融混合,或者在过氧化物组分存在下进行熔融混合以增加组合物的熔体流率。然后,过氧化物与组分a)和b)一起加入到混合装置中或过氧化物可单独加入到熔融混合装置中,其中过氧化物优选为有机过氧化物,适合用于丙烯降解(减粘裂化)。
本发明的组合物具有改进的冲击强度,特别是在0℃以下,以及改进的光学性能,尤其是高透明性和低雾度。
本发明的聚丙烯组合物通过普通转化技术可进一步转化为终产品,例如注塑、压塑、吹塑(挤出或注射拉伸吹塑)、挤塑(薄膜、片材、管材、软管、型材挤塑)、薄膜吹塑、热成型等。优选终产品为通过注塑、吹塑或热成型制得的包装容器或通过薄膜挤塑制得的包装薄膜。
该产品特别适用于食品包装应用,尤其是用于深冻应用。
本发明的另外一个目的是提供具有良好冲击强度和良好光学性能,尤其是良好透明性和低雾度的新产品。使用含以下组分的聚烯烃组合物达到此目的,用于生产具有良好冲击强度和透明性的制品:
a)基于组合物总重85-98重量%的多相丙烯/α-烯烃共聚物,包含具有0-15摩尔%α-烯烃的丙烯聚合物或与α-烯烃的共聚物作为母体聚合物和含20-80摩尔%α-烯烃的丙烯/α-烯烃橡胶共聚物。
b)基于组合物总重15-2重量%的乙烯均聚物或乙烯/α-烯烃共聚物的组合物,乙烯共聚物中的α-烯烃具有4-10个碳原子,乙烯均聚物或共聚物的密度低于0.925g/cm3。
实施例:
多相聚合物:
多相聚合物以两步工艺制备。第一阶段使无规丙烯/乙烯共聚物聚合(在液相丙烯中聚合)和第二阶段使丙烯/乙烯橡胶聚合。丙烯/乙烯无规共聚物和丙烯/乙烯橡胶的比例为92∶8。
为使基本熔体流率减粘裂化至熔体流率为约10-15g/10min,使用二叔丁基过氧化物。
组合物和添加剂于250℃下在双螺杆挤出机中混合。在冷水中冷却线材并造粒。
多相聚合物的特性在表1中列出。
表1
MFR2 | XCS | C2 | MFR2 | XCS | C2 | i.v./XCS | C3/XCS | |
基体 | 基体 | 基体 | 总量 | 总量 | 总量 | |||
聚合物 | [g/10′] | [重量%] | [摩尔%] | [g/10′] | [重量%] | [摩尔%] | [ml/g] | [重量%] |
聚合物1 | 1.09 | 7.2 | 5.6 | 1.22 | 12.2 | 8.5 | 1.38 | 66.0 |
聚合物2 | 1.13 | 6.7 | 6.3 | 1.27 | 12.0 | 9.8 | 1.65 | 65.0 |
聚合物3 | 1.13 | 6.7 | 6.3 | 1.19 | 12.1 | 9.2 | 1.59 | 66.0 |
聚合物4 | 1.05 | 6.6 | 6.0 | 1.12 | 13.3 | 8.4 | 1.70 | 68.5 |
MFR2基体:根据ISO1133相1熔体流率
XCS基体:相1的冷二甲苯可溶部分
C2基体:相1的乙烯含量(无规结合)
MFR2总量:根据ISO1133测得的多相体系(相1+2)的熔体流率
XCS总量:多相体系(相1+2)的冷二甲苯可溶部分
C2总量:多相体系(相1+2)的乙烯含量
i.v./XCS:冷二甲苯可溶部分的特性粘度(表明丙烯/乙烯橡胶-相2的分子量)
C3/XCS:冷二甲苯可溶部分丙烯含量
聚合物和传统添加剂(0.05% Irgafos 168,0.05% Irganox 1010,0.1硬脂酸钙,0.06%甘油单硬脂酸酯,0.18%Millad 3988)在强力混炼机(Henschel mixer)中混合20秒。
实施例1-4
表1聚合物1-4(组分a))与5% Exact 2M048混合,(一种商品化基于茂金属催化剂的聚乙烯等级,MFR(190℃,2.16kg)10g/10min,密度0.902g/cm3);加入DexPlastomers(组分b))。
为使基本熔体流率减粘裂化至熔体流率为约10-15g/10min,使用二叔丁基过氧化物。
组合物和添加剂250℃下在双螺杆挤出机中混合。在冷水中冷却线材并造粒。
制备注塑试验样条并测定根据ISO179的缺口冲击强度。
为测定光学性能,尤其是透明性和雾度,制备注塑板(60×60×2mm)。根据ASTM D-1003-92测定光学性能。
比较例1-4:
使用表1的多相聚合物作为比较化合物。
按所述方法测定冲击强度和光学性能。
结果列于表2。
表2
MFR | NIS/+23℃ | IS/-20℃ | 雾度 | |||
实施例 | 聚合物 | 改性剂 | [g/10′] | 1791eA/+23℃ | 1791eU/-20℃ | [%] |
[kJ/m2] | [kJ/m2] | |||||
实施例1 | 聚合物1 | 5%Exact2M048 | 12.7 | 11.6 | 77.5 | 28.0 |
实施例2 | 聚合物2 | 5%Exact2M048 | 12.4 | 13.2 | 131.7 | 39.4 |
实施例3 | 聚合物3 | 5%Exact2M048 | 12.5 | 11.8 | 125.9 | 38.5 |
实施例4 | 聚合物4 | 5%Exact2M048 | 12.0 | 11.1 | 130.3 | 43.5 |
比较例1 | 聚合物1 | 13.8 | 9.4 | 62.9 | 36.0 | |
比较例2 | 聚合物2 | 13.6 | 10.5 | 88.9 | 54.0 | |
比较例3 | 聚合物3 | 13.4 | 9.3 | 75.8 | 53.6 | |
比较例4 | 聚合物4 | 13.0 | 8.8 | 70.4 | 60.6 |
实施例5-6
将选定的表1多相聚合物(组分a))与5%Borealis CA9150(可市购的LDPE等级,MFR(190℃,2.16kg)15g/10min,密度0.915g/cm3(组分b))混合。
不加入组分b)制备比较例5和6。
组合物按上述方法处理,冲击强度和光学性能按上述方法测定。
结果列于表3。
表3
MFR | NIS/+23℃ | IS/-20℃ | 雾度 | |||
实施例 | 聚合物 | 改性剂 | [g/10′] | 1791eA/+23℃ | 1791eU/-20℃ | [%] |
[kJ/m2] | [kJ/m2] | |||||
实施例5 | 聚合物2 | 5%Borealis CA9150 | 13.5 | 10.5 | 108.3 | 40.8 |
实施例6 | 聚合物4 | 5%Borealis CA9150 | 12.5 | 10.0 | 115.8 | 44.2 |
Claims (15)
1.具有良好冲击强度和透明性的聚烯烃组合物,包含
a)基于组合物总重85-98重量%的多相丙烯/α-烯烃共聚物,其包含具有0-15摩尔%α-烯烃的丙烯聚合物或与α-烯烃的共聚物作为母体聚合物和含20-80摩尔%α-烯烃的丙烯/α-烯烃橡胶共聚物,和
b)基于组合物总重15-2重量%乙烯均聚物或乙烯/α-烯烃共聚物,乙烯共聚物中的α-烯烃具有4-10个碳原子,乙烯均聚物或共聚物的密度低于0.925g/cm3,
其中在190℃、2.16kg负荷下测定的组分b)的熔体流率比在230℃、2.16kg负荷下测定的组分a)的熔体流率高至少两倍。
2.根据权利要求1的聚烯烃组合物,包含
a)90-97重量%的多相丙烯/α-烯烃共聚物和
b)10-3重量%的乙烯均聚物或乙烯/α-烯烃共聚物。
3.根据权利要求1的聚烯烃组合物,其中多相聚丙烯/α-烯烃共聚物母体聚合物是丙烯/乙烯共聚物,丙烯/α-烯烃橡胶聚合物是丙烯/乙烯橡胶。
4.根据权利要求1的聚烯烃组合物,其中母体聚合物与丙烯/α-烯烃橡胶共聚物的重量比为97∶3-80∶20。
5.根据权利要求1的聚烯烃组合物,其中组分b)是以高压管工艺或高压釜工艺制备的乙烯均聚或共聚物。
6.根据权利要求1的聚烯烃组合物,其中组分b)是使用齐格勒型催化剂以低压工艺制备的线性低密度乙烯共聚物。
7.根据权利要求1的聚烯烃组合物,其中组分b)使用茂金属催化剂制备。
8.根据权利要求1的聚烯烃组合物,其中聚烯烃组合物中乙烯含量至多15摩尔%。
9.根据权利要求1的聚烯烃组合物,其中在230℃下测定的聚合物组合物的熔体流率为0.1-200g/min。
10.根据权利要求1的聚烯烃组合物,其中组分b)的熔体流率比组分a)的熔体流率高至少五倍。
11.根据权利要求1的聚烯烃组合物,进一步包含传统的添加剂和/或稳定剂和/或填料。
12.一种制备权利要求1至11中任一项的聚烯烃组合物的方法,其中组分a)多相聚合物通过多级方法制备并和乙烯均聚物或乙烯/α-烯烃共聚物混合。
13.根据权利要求12的方法,其中组分a)和b)可在存在或不存在过氧化物的情况下经熔融混合而掺混。
14.权利要求1至11中任一项的聚烯烃组合物在生产用于包装应用的产品中的用途,其中采用注塑、压塑、吹塑、薄膜挤塑、片材挤塑、管材挤塑、软管挤塑、型材挤塑、薄膜吹塑和热成型方法。
15.包含以下组分的聚烯烃组合物在生产具有良好冲击强度和良好透明性的制品中的用途,
a)基于组合物总重85-98重量%的多相丙烯/α-烯烃共聚物,其包含具有0-15摩尔%α-烯烃的丙烯聚合物或与α-烯烃的共聚物作为母体聚合物和含20-80摩尔%α-烯烃的丙烯/α-烯烃橡胶共聚物,和
b)基于组合物总重15-2重量%的乙烯均聚物或乙烯/α-烯烃共聚物,乙烯共聚物中的α-烯烃具有4-10个碳原子,乙烯均聚物或共聚物的密度低于0.925g/cm3,
其中在190℃、2.16kg负荷下测定的组分b)的熔体流率比在230℃、2.16kg负荷下测定的组分a)的熔体流率高至少两倍。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00126051A EP1211289A1 (en) | 2000-11-29 | 2000-11-29 | Polyolefin compositions with improved properties |
EP00126051.2 | 2000-11-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1487973A CN1487973A (zh) | 2004-04-07 |
CN1225501C true CN1225501C (zh) | 2005-11-02 |
Family
ID=8170523
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB018223273A Expired - Fee Related CN1225501C (zh) | 2000-11-29 | 2001-11-26 | 具有改进性能的聚烯烃组合物 |
Country Status (11)
Country | Link |
---|---|
US (1) | US6930149B2 (zh) |
EP (3) | EP1211289A1 (zh) |
JP (2) | JP2004520455A (zh) |
KR (1) | KR100822656B1 (zh) |
CN (1) | CN1225501C (zh) |
AT (2) | ATE478118T1 (zh) |
AU (2) | AU2368502A (zh) |
DE (2) | DE60131460T2 (zh) |
DK (1) | DK1358266T3 (zh) |
ES (2) | ES2296832T3 (zh) |
WO (1) | WO2002044272A1 (zh) |
Families Citing this family (67)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10212654B4 (de) * | 2001-03-30 | 2012-06-14 | Jnc Corporation | Propylenpolymerzusammensetzung und geschäumte Formlinge daraus |
AU2003263188A1 (en) | 2002-07-24 | 2004-02-16 | Basell Polyolefine Gmbh | At least two-stage process for preparing propylene polymer compositions |
EP1428853A1 (en) * | 2002-12-09 | 2004-06-16 | Borealis Technology OY | Propylene polymer composition with improved balance of mechanical and optical properties |
EP1428854A1 (en) * | 2002-12-09 | 2004-06-16 | Borealis Technology OY | Propylene polymer composition with improved balance of mechanical and optical properties |
DE60335346D1 (de) * | 2003-05-15 | 2011-01-27 | Borealis Tech Oy | Polyolefin-Zusammensetzung |
EP1510547A1 (en) * | 2003-08-13 | 2005-03-02 | Borealis Technology OY | Novel polypropylene compositions with improved resistance to stress whitening |
US7452919B2 (en) | 2004-05-27 | 2008-11-18 | Sunoco, Inc. (R&M) | Clarity, low haze polymer |
EP1619217B1 (en) * | 2004-07-20 | 2010-09-15 | Borealis Technology Oy | Cable with thermoplastic insulation |
US20070010626A1 (en) * | 2005-07-11 | 2007-01-11 | Shankernarayanan Manivakkam J | Polyethylene compositions |
DK1849826T3 (da) * | 2006-04-26 | 2013-04-22 | Borealis Tech Oy | Transparent polyolefingenstand, der er blevet udsat for varmebehandling |
ATE456618T1 (de) * | 2006-05-26 | 2010-02-15 | Borealis Tech Oy | Eine polyolefinzusammensetzung mit verbessertem weissbruchwiderstand |
EP1873203B1 (en) * | 2006-06-30 | 2015-10-28 | Borealis Technology Oy | Polyolefin composition suitable for bottles with high-impact strength and transparency |
EP1884539A1 (en) | 2006-07-31 | 2008-02-06 | Total Petrochemicals Research Feluy | Polyolefin composition for injection stretch blow moulding |
KR101273049B1 (ko) * | 2006-12-29 | 2013-06-10 | 주식회사 효성 | 폴리올레핀계 수지조성물 및 이를 포함하는 다층 필름 |
US20090186999A1 (en) * | 2008-01-22 | 2009-07-23 | Fina Technology, Inc. | Low melt flow rate (MFR) propylene based polymers for injection stretch blow molding |
US9090000B2 (en) * | 2009-03-26 | 2015-07-28 | Fina Technology, Inc. | Injection stretch blow molded articles and random copolymers for use therein |
US20100249354A1 (en) * | 2009-03-26 | 2010-09-30 | Fina Technology, Inc. | Injection stretch blow molded articles and syndiotactic polymers for use therein |
EP2251375A1 (en) * | 2009-05-07 | 2010-11-17 | Borealis AG | Thermoplastic polyolefin compounds with decreased flaming sensitivity |
US20120070601A1 (en) * | 2009-05-19 | 2012-03-22 | Polyone Corporation | Thermoplastic elastomers exhibiting superior food contact compliance |
EP2275485B1 (en) * | 2009-06-22 | 2011-06-08 | Borealis AG | Heterophasic polypropylene copolymer composition |
WO2011057928A1 (en) | 2009-11-11 | 2011-05-19 | Borealis Ag | Crosslinkable polymer composition and cable with advantageous electrical properties |
ES2758129T3 (es) | 2009-11-11 | 2020-05-04 | Borealis Ag | Un cable y procedimiento de producción del mismo |
EP2499175B2 (en) | 2009-11-11 | 2022-08-17 | Borealis AG | A polymer composition and a power cable comprising the polymer composition |
EP2499176B2 (en) | 2009-11-11 | 2022-08-10 | Borealis AG | Power cable comprising a polymer composition comprising a polyolefin produced in a high pressure process |
EP2431416B1 (en) * | 2010-09-16 | 2012-10-31 | Borealis AG | High flow and stiff polymer material with good transparency and impact properties |
EP2450910B1 (en) | 2010-11-03 | 2019-09-25 | Borealis AG | A polymer composition and a power cable comprising the polymer composition |
ES2620135T3 (es) | 2010-12-06 | 2017-06-27 | Borealis Ag | Polipropileno heterofásico con rigidez y transparencia mejoradas y resistencia al impacto aceptable |
EP2492309A1 (en) * | 2011-02-28 | 2012-08-29 | Borealis AG | Heterophasic polyolefin composition having improved flowability and impact strength |
ES2610140T3 (es) * | 2011-02-28 | 2017-04-26 | Borealis Ag | Composición de poliolefina heterofásica que tiene mejor fluidez y resistencia al impacto |
EP2508562B1 (en) * | 2011-03-28 | 2018-06-13 | Borealis AG | Polypropylene composition for extrusion blown molded bottles |
CA2834812A1 (en) | 2011-05-04 | 2012-11-08 | Borealis Ag | Polymer composition for electrical devices |
CN103649192A (zh) | 2011-05-04 | 2014-03-19 | 博里利斯股份公司 | 用于电气装置的聚合物组合物 |
JP6255337B2 (ja) * | 2011-05-04 | 2017-12-27 | ボレアリス エージー | 電気デバイスのためのポリマー組成物 |
ES2524190T3 (es) * | 2011-12-05 | 2014-12-04 | Borealis Ag | Aumento del rendimiento de un proceso de extrusión de películas |
CN102632600B (zh) * | 2012-04-25 | 2014-11-19 | 昆明东方塑纸包装有限公司 | 应用高分子材料制造低温保鲜袋的方法 |
ES2625403T3 (es) * | 2012-09-19 | 2017-07-19 | Saudi Basic Industries Corporation | Proceso para la preparación de una composición que comprende un copolímero de propileno heterofásico y talco |
BR112015012240A2 (pt) * | 2012-12-12 | 2017-07-11 | Borealis Ag | frascos moldados por sopro via extrusão |
EP2746295A1 (en) * | 2012-12-21 | 2014-06-25 | Borealis AG | Transparent thin wall packaging material with improved stiffness and flowability |
US8871868B2 (en) | 2013-01-09 | 2014-10-28 | Braskem America, Inc. | Propylene impact copolymers having good optical properties |
US9115279B2 (en) | 2013-03-15 | 2015-08-25 | Asahi Kasei Plastics North America, Inc. | Polypropylene compounds with high impact performance and improved stress whitening resistance |
EP2824141B1 (en) * | 2013-07-09 | 2016-06-22 | Borealis AG | Use of a polyolefin composition to reduce sink marks |
US9376559B2 (en) | 2013-11-22 | 2016-06-28 | Exxonmobil Chemical Patents Inc. | Reverse staged impact copolymers |
WO2015076987A1 (en) * | 2013-11-22 | 2015-05-28 | Exxonmobil Chemical Patents Inc. | Reverse staged impact copolymers |
BR112016020830B1 (pt) * | 2014-03-14 | 2021-08-17 | Milliken & Company | Composição de poliolefina heterofásica modificada e método de preparação |
EP3015503A1 (en) | 2014-10-27 | 2016-05-04 | Borealis AG | Heterophasic polypropylene with improved stiffness/impact balance |
CN115505192A (zh) * | 2014-10-27 | 2022-12-23 | 北欧化工股份公司 | 具有优越电性能的用于电缆应用的聚合物组合物 |
US10822478B2 (en) * | 2014-10-27 | 2020-11-03 | Borealis Ag | Polymer composition and cable with advantageous electrical properties |
CN107207658B (zh) * | 2014-12-19 | 2022-11-01 | 博里利斯股份公司 | 用于w&c应用的具有有利电性能的聚合物组合物 |
WO2016160228A1 (en) * | 2015-03-31 | 2016-10-06 | Dow Global Technologies Llc | Spray dried polyolefin elastomer powder for rotational molding processes |
CN107667140B (zh) * | 2015-05-29 | 2020-12-04 | 博里利斯股份公司 | 丙烯共聚物组合物 |
WO2017025268A1 (en) * | 2015-08-10 | 2017-02-16 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
US10113058B2 (en) | 2015-12-30 | 2018-10-30 | Braskem America, Inc. | Clear and impact resistant polymer composition and fabricated article |
US10519306B2 (en) | 2016-05-18 | 2019-12-31 | Borealis Ag | Soft polypropylene composition |
EP3246358A1 (en) * | 2016-05-18 | 2017-11-22 | Borealis AG | Soft and transparent propylene copolymers |
CN107880405A (zh) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | 一种低拉伸断裂伸长率抗冲聚丙烯树脂 |
ES2958562T3 (es) | 2017-02-03 | 2024-02-09 | Borealis Ag | Uso de una composición polimérica para la producción de artículos con capacidad de pintado y apariencia superficial mejoradas |
US11377543B2 (en) | 2017-06-26 | 2022-07-05 | Borealis Ag | Polypropylene composition with excellent surface appearance |
CN109135067A (zh) * | 2017-06-27 | 2019-01-04 | 阿布扎比聚合物有限责任公司(博禄) | 用于制造高压管的聚丙烯组合物 |
EP3502177B1 (en) * | 2017-12-20 | 2020-02-12 | Borealis AG | Polypropylene composition |
WO2019119392A1 (en) * | 2017-12-22 | 2019-06-27 | Borouge Compounding Shanghai Co., Ltd. | Soft polyolefin composition |
US20210363314A1 (en) | 2018-11-07 | 2021-11-25 | Borealis Ag | Polyolefin composition with improved impact and whitening resistance |
US20220017733A1 (en) | 2018-11-23 | 2022-01-20 | Borealis Ag | Polypropylene composition with improved optical properties and whitening resistance |
EP3770211A4 (en) * | 2018-12-05 | 2022-03-23 | Guangdong Tianan New Material Co., Ltd | POLYPROPYLENE FILM AND POLYPROPYLENE COMPOSITE FILM |
EP3953401A1 (en) | 2019-04-12 | 2022-02-16 | Borealis AG | Low stress whitening polypropylene composition |
CN114423817B (zh) | 2019-09-20 | 2023-09-12 | 北欧化工公司 | 性能特征改善的多相丙烯聚合物组合物 |
EP4038138A1 (en) | 2019-10-02 | 2022-08-10 | Borealis AG | Polymer composition suitable for making blown films |
KR102528749B1 (ko) * | 2019-11-28 | 2023-05-03 | 롯데케미칼 주식회사 | 폴리올레핀계 수지 조성물 및 이로부터 제조된 의료용 호스 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1227893B (it) | 1988-12-14 | 1991-05-14 | Himont Inc Centerville Road Ne | Composizioni polipropileniche aventi buona trasparenza e migliorata resistenza all'urto |
DE69320135T2 (de) * | 1992-10-15 | 1998-12-10 | Mitsubishi Chemical Corp., Tokio/Tokyo | Polypropylen Zusammensetzungen |
US5331047A (en) * | 1993-02-17 | 1994-07-19 | Himont Incorporated | Olefin polymer films |
CA2162946C (en) * | 1994-11-21 | 2004-01-06 | Kazuyuki Watanabe | Propylene block copolymer and process for producing the same |
US5929147A (en) | 1996-06-18 | 1999-07-27 | Montell North America Inc. | Embrittlement-resistant polyolefin composition and flexible articles therefrom |
JP3347958B2 (ja) * | 1996-11-26 | 2002-11-20 | 日本ポリケム株式会社 | プロピレン系樹脂組成物 |
GB0008690D0 (en) * | 2000-04-07 | 2000-05-31 | Borealis Polymers Oy | Process |
WO2002053374A1 (en) * | 2001-01-02 | 2002-07-11 | Dow Global Technologies Inc. | Peelable seal and method of making and using same |
-
2000
- 2000-11-29 EP EP00126051A patent/EP1211289A1/en not_active Withdrawn
-
2001
- 2001-11-26 DK DK01998593T patent/DK1358266T3/da active
- 2001-11-26 DE DE60131460T patent/DE60131460T2/de not_active Expired - Lifetime
- 2001-11-26 AU AU2368502A patent/AU2368502A/xx active Pending
- 2001-11-26 EP EP06113874A patent/EP1702956B1/en not_active Expired - Lifetime
- 2001-11-26 AT AT06113874T patent/ATE478118T1/de not_active IP Right Cessation
- 2001-11-26 JP JP2002546627A patent/JP2004520455A/ja active Pending
- 2001-11-26 EP EP01998593A patent/EP1358266B1/en not_active Expired - Lifetime
- 2001-11-26 DE DE60142860T patent/DE60142860D1/de not_active Expired - Lifetime
- 2001-11-26 KR KR1020037007169A patent/KR100822656B1/ko active IP Right Grant
- 2001-11-26 ES ES01998593T patent/ES2296832T3/es not_active Expired - Lifetime
- 2001-11-26 US US10/433,202 patent/US6930149B2/en not_active Expired - Lifetime
- 2001-11-26 WO PCT/EP2001/013717 patent/WO2002044272A1/en active IP Right Grant
- 2001-11-26 CN CNB018223273A patent/CN1225501C/zh not_active Expired - Fee Related
- 2001-11-26 AU AU2002223685A patent/AU2002223685B2/en not_active Ceased
- 2001-11-26 ES ES06113874T patent/ES2348383T3/es not_active Expired - Lifetime
- 2001-11-26 AT AT01998593T patent/ATE378377T1/de not_active IP Right Cessation
-
2008
- 2008-03-05 JP JP2008055487A patent/JP2008138222A/ja not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
DE60131460T2 (de) | 2008-09-04 |
KR20030066685A (ko) | 2003-08-09 |
ES2296832T3 (es) | 2008-05-01 |
AU2002223685B2 (en) | 2006-06-08 |
EP1358266B1 (en) | 2007-11-14 |
EP1211289A1 (en) | 2002-06-05 |
DE60142860D1 (de) | 2010-09-30 |
EP1702956A3 (en) | 2006-11-22 |
US6930149B2 (en) | 2005-08-16 |
EP1702956A2 (en) | 2006-09-20 |
ATE378377T1 (de) | 2007-11-15 |
ES2348383T3 (es) | 2010-12-03 |
ATE478118T1 (de) | 2010-09-15 |
EP1702956B1 (en) | 2010-08-18 |
CN1487973A (zh) | 2004-04-07 |
JP2008138222A (ja) | 2008-06-19 |
EP1358266A1 (en) | 2003-11-05 |
KR100822656B1 (ko) | 2008-04-17 |
JP2004520455A (ja) | 2004-07-08 |
DK1358266T3 (da) | 2008-03-10 |
AU2368502A (en) | 2002-06-11 |
US20040210002A1 (en) | 2004-10-21 |
DE60131460D1 (de) | 2007-12-27 |
WO2002044272A1 (en) | 2002-06-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1225501C (zh) | 具有改进性能的聚烯烃组合物 | |
CN102099415B (zh) | 高刚度的多相聚合物组合物 | |
AU2002223685A1 (en) | Polyolefin compositions with improved properties | |
EP2527593B1 (en) | Random propylene copolymer with high stiffness and low haze | |
CN104995215B (zh) | 具有改善的刚度和流动性的透明薄壁包装材料 | |
EP2989160B1 (en) | Propylene random copolymer composition for pipe applications | |
JP2004520455A5 (zh) | ||
CN1946792A (zh) | 适于注射模塑的聚烯烃母料和组合物 | |
CA3003227C (en) | High flow tpo composition with excellent tensile strain at break and low powder stickiness | |
KR101780751B1 (ko) | 파이프용 프로필렌 랜덤 코폴리머 조성물 | |
CN101484522A (zh) | 具有高冲击强度和透明度的适用于瓶子的聚烯烃组合物 | |
EP2254945B1 (en) | Clarified polypropylene and ethylene alpha olefin blend | |
EP3625273B1 (en) | Heterophasic polyolefin composition with excellent optical properties | |
CN1446829A (zh) | 丙烯基聚合物及由其制造的注塑成型制品 | |
EP3665224A1 (en) | Composition comprising heterophasic propylene copolymer | |
EP1672021A1 (en) | Polypropylene compositions |
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: 20051102 Termination date: 20191126 |
|
CF01 | Termination of patent right due to non-payment of annual fee |