CN104530532A - 用于通过热成形生产中空容器的聚乙烯模塑组合物及用其生产的燃料容器 - Google Patents
用于通过热成形生产中空容器的聚乙烯模塑组合物及用其生产的燃料容器 Download PDFInfo
- Publication number
- CN104530532A CN104530532A CN201410836333.8A CN201410836333A CN104530532A CN 104530532 A CN104530532 A CN 104530532A CN 201410836333 A CN201410836333 A CN 201410836333A CN 104530532 A CN104530532 A CN 104530532A
- Authority
- CN
- China
- Prior art keywords
- weight
- molding composition
- scope
- polyethylene molding
- polyethylene
- 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
Links
- -1 Polyethylene Polymers 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 30
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 30
- 238000000465 moulding Methods 0.000 title claims abstract description 23
- 239000000446 fuel Substances 0.000 title claims abstract description 18
- 238000003856 thermoforming Methods 0.000 title claims abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- 239000000206 moulding compound Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000005336 cracking Methods 0.000 claims description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- 230000002180 anti-stress Effects 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 4
- 238000012644 addition polymerization Methods 0.000 claims description 4
- 238000005829 trimerization reaction Methods 0.000 claims description 4
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000000691 measurement method Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 claims description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract 2
- 229920001038 ethylene copolymer Polymers 0.000 abstract 1
- 239000000725 suspension Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F10/02—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
- 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
-
- 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
- B29C51/02—Combined thermoforming and manufacture of the preform
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7172—Fuel tanks, jerry cans
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明涉及一种聚乙烯模塑组合物，所述聚乙烯模塑组合物具有多峰摩尔质量分布并特别适于热成形生产容量在20-200l范围内的燃料容器。所述模塑组合物在温度23℃下的密度在0.948-0.953g/cm3范围内，MFR190/21.6在4.5-6g/10min范围内。所述聚乙烯模塑组合物包含40-50％重量的低分子量乙烯均聚物A、35-45％重量的高分子量的乙烯与含4-8个碳原子的另一烯烃的共聚物B和10-25％重量的超高分子量乙烯共聚物C。
Description
本申请是申请日为2008年3月28日、申请号为200880010868.2、发明名称为“用于通过热成形生产中空容器的聚乙烯模塑组合物及用其生产的燃料容器”的发明专利申请的分案申请。
本发明涉及一种聚乙烯模塑组合物，其具有多峰摩尔质量分布并特别适合于容量在20-200 l范围内的汽车用燃料容器的热成形。本发明也涉及在包含Ziegler催化剂和助催化剂的催化体系的存在下通过在由逐次液相聚合组成的多级反应序列中聚合制备该模塑组合物的方法。本发明还涉及自所述模塑组合物通过热成形生产的燃料容器。
聚乙烯被广泛用来生产需要材料具有特别高的力学强度、高的耐腐蚀性和绝对可靠的长期稳定性的各种类型模制品。此外，聚乙烯也具有耐化学性好和固有重量轻的特定优势。
EP-A-603,935已描述了一种基于聚乙烯的模塑组合物，该模塑组合物具有双峰摩尔质量分布并适合于生产具有良好力学性质的模制品。
一种具有更宽摩尔质量分布的材料见述于美国专利5,338,589中并用高活性催化剂生产，所述高活性催化剂从WO 91/18934已知且在其制备中以凝胶样悬浮体使用醇镁。已意外地发现，该材料在模制品特别是管中的使用使一方面刚性和蠕变倾向及另一方面抗应力开裂性和韧性的同时改进成为可能，而在部分结晶热塑性塑料中这两个方面常常是背道而驰的。
但已知的双峰产品具有熔体强度较低的缺点，这使这类模塑组合物的挤出加工困难得多。固化过程中将不时发生熔融态模制品的撕裂并因此导致挤出方法中不希望有的不稳定性。此外，观察到由固化前熔体从上部区域向下流到下部区域引起的壁厚的不均匀性，特别是在厚壁模制品的生产中。另外，特别是在热成形中，由于加工机器设置成会产生这种情形，因此需要达到模塑组合物的特定膨胀度。
最后，燃料容器自身需要具有平衡的刚性/冲击韧性比率以满意地用于其预期用途。
因此本发明的目的是开发一种聚乙烯模塑组合物，用所述模塑组合物可比所有已知材料更好地通过热成形方法加工生产燃料容器。特别地，所述模塑组合物应因其特别高的熔体强度而使长时间稳定的热成形方法成为可能并因其特别设定的膨胀度而可实现最佳壁厚控制。此外，所述模塑组合物在加工后的冷态需要具有足够高的刚性和良好的冲击韧性，以便自其制备的燃料容器的寿命可长于机动车辆的平均使用寿命而不损坏。
该目的通过起先提到的类型的模塑组合物达到，所述模塑组合物包含40-50％重量的第一低分子量乙烯均聚物A、35-45％重量的第二高分子量的乙烯与含4-8个碳原子的另一烯烃的共聚物B和10-25％重量的第三超高分子量乙烯共聚物C，所有百分数均基于模塑组合物的总重量计算。
本发明还提供了一种在级联悬浮聚合中制备所述模塑组合物的方法及容量在20-200 l范围内、由该模塑组合物制成并具有优异的力学强度性质的燃料容器。
本发明的聚乙烯模塑组合物在温度23℃下的密度在0.948-0.953g/cm3范围内并具有宽的三峰摩尔质量分布。所述第二高分子量共聚物B包含小比例即0.4-0.8％重量的含4-8个碳原子的其他烯烃单体单元。这类共聚单体的实例有1-丁烯、1-戊烯、1-己烯、1-辛烯和4-甲基-1-戊烯。所述第三超高分子量乙烯共聚物C同样包含量在1.5-3.0％重量范围内的一种或多种上述共聚单体。
此外，本发明的模塑组合物以MFR190/21.6表示的熔体流动指数(按ISO 1133)在4.5-6g/10min范围内，优选4.8-5.6g/10min，按ISO 1628-3在萘烷中于135℃的温度下测得的粘数VNtot在400-480ml/g范围内，特别是420-460ml/g。
作为三个单独的摩尔质量分布的重心位置的量度，所述三峰可用逐次聚合步骤中形成的聚合物的粘数VN(按ISO 1628-3)描述。这里需提到各反应步骤中形成的聚合物的如下带宽：
对第一聚合步骤后的聚合物测得的粘数VN1与所述第一低分子量聚乙烯A的粘数VNA相同，根据本发明，在160-200ml/g范围内。
对第二聚合步骤后的聚合物测得的粘数VN2不与第二聚合步骤中形成的较高分子量的聚乙烯B的VNB(在本制备方法中，其仅可用算术方法确定)对应，而是代表聚合物A加聚合物B的混合物的粘数VN2。根据本发明，VN2在250-300ml/g范围内。
对第三聚合步骤后的聚合物测得的粘数VN3不与第三聚合步骤中形成的第三超高分子量共聚物C的VNC(其同样仅可用算术方法确定)对应，而是代表聚合物A、聚合物B加聚合物C的混合物的粘数VN3。根据本发明，VN3在400-480ml/g范围内，特别是420-460ml/g。
所述聚乙烯通过在悬浮体中于60-90℃的温度、2-10巴的压力及由过渡金属化合物和有机铝化合物组成的高活性且氢敏感的Ziegler催化剂的存在下将单体聚合获得。所述聚合分三个逐次步骤进行，各步骤中通过加入氢来调节摩尔质量。
除所述聚乙烯外，本发明的聚乙烯模塑组合物可还包含添加剂。这类添加剂有例如量为0-10％重量(优选0-5％重量)的热稳定剂、抗氧化剂、UV吸收剂、光稳定剂、金属钝化剂、破坏过氧化物的化合物、基本的助稳定剂，以及总量占混合物总重量的0-50％重量的填料、增强材料、增塑剂、润滑剂、乳化剂、颜料、荧光增白剂、阻燃剂、抗静电剂、发泡剂或其组合。
本发明的模塑组合物特别适于通过热成形方法生产燃料容器。这里，聚乙烯模塑组合物先在挤出机中于200-250℃的温度下塑化，随后挤出通过模头而产生坯件，坯件再在热态下三维成形并随后冷却。
本发明的模塑组合物可特别易于通过热成形方法加工生产燃料容器，因为其具有170-210％范围内的膨胀度。因此，燃料容器的壁厚可在0.8-15mm范围内最佳地设定。由于本发明的模塑组合物在-30℃下的缺口冲击韧性(DIN)在37-47kJ/m2范围内且抗应力开裂性(FNCT＝全缺口蠕变试验)在30-60h范围内，故这样生产的燃料容器具有特别高的力学强度。
缺口冲击韧性(DIN)按DINEN ISO 179于23和-30℃下测定。试样的尺寸为10×4×80mm，并在试样中切出角度为45°、深度为2mm、缺口底部半径为0.25mm的V-型缺口。
本发明的模塑组合物的抗应力开裂性通过室内测定法测定，单位为小时(h)。该实验室方法在M.Fleiβner,Kunststoffe 77(1987),p.45 ff中有述，其对应于已开始实行的ISO/CD 16770。该出版物表明，周向缺口试条上蠕变试验中裂纹缓慢生长的确定与按ISO 1167的长期内压试验的脆性分枝间存在关系。失效时间的缩短通过借助缺口(1.6mm/刀片)在作为促进应力开裂的乙二醇介质中于80℃的温度和4MPa的拉伸应力下缩短开裂开始时间达到。试样通过从10mm厚的压板锯下三个尺寸为10×10×90mm的试样产生。用室内为此目的构建的开缺口装置中的刀片在试样的中部周向地开缺口(参见出版物中图5)。缺口深度为1.6mm。
实施例1
乙烯的聚合在三个串联连接的反应器中以连续方法进行。以5.2mmol/h的量向第一反应器中进给按WO 91/18934实施例2的方法制备并已经过该专利中编号2.2的操作的Ziegler催化剂；此外进给足够的悬浮介质(己烷)、乙烯和氢。乙烯的量(＝45kg/h)和氢的量(＝17.6g/h)设定为使第一反应器的气体空间中测得的乙烯的体积百分数为44％、氢的体积百分数为44％；余下的为惰性气体(氮气)、乙烷和气化的悬浮介质的混合物。
第一反应器中的聚合在70℃的温度下进行。
随后将来自第一反应器的悬浮体转移到第二反应器中，在其中，气体空间中氢的百分数降至10％体积，并一起向其中引入量为38kg/h的乙烯和量为150g/h的1-丁烯。氢的量的减少通过H2的中间减压达到。第二反应器的气体空间中测得74％体积的乙烯、10％体积的氢和0.60％体积的1-丁烯；余下的为惰性气体(氮气)、乙烷和气化的悬浮介质的混合物。
第二反应器中的聚合在85℃的温度下进行。
经过H2的再次中间减压将来自第二反应器的悬浮体转移到第三反应器中，通过中间减压，第三反应器中氢的量被设定为0.0％体积。
一起向第三反应器中引入量为17kg/h的乙烯和量为300g/h的1-丁烯。第三反应器的气体空间中测得的乙烯的百分数为79％体积、氢的百分数为0％体积、1-丁烯的百分数为1.9％体积；余下的为惰性气体(氮气)、乙烷和气化的悬浮介质的混合物。
第三反应器中的聚合在82℃的温度下进行。
上述级联操作模式所需聚合催化剂的长期活性由专门开发的具有上面提到的WO出版物中指出的组成的Ziegler催化剂保证。该催化剂的适宜性的量度是其特别高的氢敏感性和其在1-8小时的长时间内保持恒定的高活性。
从离开第三反应器的聚合物悬浮体中分离出悬浮介质，将粉干燥并送造粒。
实施例1中产生的多峰聚乙烯模塑组合物的粘数及聚合物A、B和C的比例WA、WB和WC在下表1中给出。
表1A–对粉测得的值
| 实施例 | (1) |
| WA[％重量] | 45 |
| WB[％重量] | 38 |
| WC[％重量] | 17 |
| VN1[ml/g] | 181 |
| VN2[ml/g] | 278 |
| VNtot[ml/g] | 440 |
| MI21.6(粉) | 5.2g/10min |
表1B–对粒测得的值
| VN(粒)[ml/g] | 420 |
| MFR21.6 | 4.2g/10min |
| MFR5 | 0.21g/10min |
| FRR21.6/5 | 20.4 |
| SD | 202％ |
| FNCT(4MPa/80℃) | 50h |
| NITDIN-30℃ | 41kJ/m2 |
表1中物理性质的缩写具有如下含义：
-MFR21.6(＝熔体流动速率)按ISO 1133于190℃的温度和21.6kg的负荷下测定。
-MFR5(＝熔体流动速率)按ISO 1133于190℃的温度和5kg的负荷下测定。
-SD(＝膨胀度)，单位为[％]，在高压毛细管流变仪上具有圆锥形入口(角度＝15°)的2/2圆孔模头中于190℃的温度和14401/s的剪切速率下测得。
-FNCT＝抗应力开裂性(全缺口蠕变试验)，通过M.Fleiβner的室内测定法在4MPa的载荷和80℃的温度下测定，单位为[h]。
-NITDIN＝缺口冲击韧性，按DINEN ISO 179于23和-30℃的温度下测定，单位为[kJ/m2]。
实施例2(对比例)
用与实施例1中相同的催化剂在与实施例1中相同的条件下进行三级聚合。但第一反应器中乙烯的量设定为38kg/h，氢的量设定为19.3g/h。在第二反应器中，进给量为34kg/h的乙烯而无另外的1-丁烯，并设定气体空间中氢的体积浓度为18％。在第三反应器中，设定乙烯的量为28kg/h，而氢的量减至零，1-丁烯的量增至451g/h。
从离开第三反应器的聚合物悬浮体中分离出悬浮介质，将粉干燥并送造粒。
实施例2中产生的多峰聚乙烯模塑组合物的粘数及聚合物A、B和C的比例WA、WB和WC在下表2中给出。
表2中物理性质的缩写具有与上表1中相同的含义。
表2A–对粉测得的值
| 实施例 | (2) |
| WA[％重量] | 38 |
| WB[％重量] | 34 |
| WC[％重量] | 28 |
| VN1[ml/g] | 173 |
| VN2[ml/g] | 230 |
| VNtot[ml/g] | 438 |
| MI21.6(粉) | 5.3g/10min |
表2B–对粒测得的值
| VN(粒)[ml/g] | 425 |
| MFR21.5 | 4.0g/10min |
| MFR5 | 0.18g/10min |
| FRR21.6/5 | 23 |
| SD | 194％ |
| FNCT(4MPa/80℃) | 17h |
| NITISO-30℃ | 37kJ/m2 |
与实施例1结果的比较清楚地表明了本发明的意外好处。在对比例中，具有不同摩尔质量的各部分A、B和C的比率中仅设定了小的偏差。此外，虽然共聚单体的总量保持451g/h，但全部共聚单体被加到第三聚合步骤。虽然此改变带来了聚合物的可加工性，其膨胀度及其缺口冲击韧性保持不变，但抗应力开裂性(FNCT)显著降低，这是特别意外的。很明显，为用作机动车辆中的燃料箱的模塑组合物，仅可以可靠地在非常窄的选择范围中设定所需所有物理性质的“总图(overall picture)”。
Claims (10)
1.一种聚乙烯模塑组合物，所述聚乙烯模塑组合物具有多峰摩尔质量分布，在温度23℃下的密度在0.948-0.953g/cm3范围内，MFI190/21.6在4.5-6dg/min范围内，包含40-50%重量的第一低分子量乙烯均聚物A、35-45%重量的第二高分子量的乙烯与含4-8个碳原子的另一烯烃的共聚物B和10-25%重量的第三超高分子量乙烯共聚物C，所有百分数均基于所述模塑组合物的总重量计算，其中所述高分子量共聚物B包含占共聚物B的重量的0.4-0.8%重量的小比例的含4-8个碳原子的共聚单体，所述聚乙烯模塑组合物按ISO 1628-3在萘烷中于135℃的温度下测得的粘数VNtot在420-460ml/g范围内，其中所述超高分子量乙烯共聚物C包含占共聚物C的重量的1.5-3.0%重量的共聚单体。
2.根据权利要求1的聚乙烯模塑组合物，其中MFI190/21.6在4.8-5.6dg/min范围内。
3.根据权利要求1的聚乙烯模塑组合物，所述聚乙烯模塑组合物包含1-丁烯、1-戊烯、1-己烯、1-辛烯、4-甲基-1-戊烯或其混合物作为共聚单体。
4. 根据权利要求1的聚乙烯模塑组合物，所述聚乙烯模塑组合物的膨胀度在170-210%范围内，抗应力开裂性(FNCT)在30-60h范围内，其中膨胀度单位为[%]，在高压毛细管流变仪上具有圆锥形入口(角度=15o)的2/2圆孔模头中于190℃的温度和1440 1/s的剪切速率下测得，其中抗应力开裂性通过M. Flei?ner的室内测定法在4MPa的载荷和80℃的温度下测定，单位为[h]。
5. 一种制备根据权利要求1-4中任一项的聚乙烯模塑组合物的方法，在所述方法中，单体的聚合在悬浮体中于60-90℃的温度、2-10巴的压力及由过渡金属化合物和有机铝化合物组成的高活性Ziegler催化剂的存在下进行，其中所述聚合分三个步骤进行，各步骤中制得的聚乙烯的摩尔质量通过氢来调节。
6. 根据权利要求5的方法，其中第一聚合步骤中的氢浓度设定为使所述低分子量聚乙烯A的粘数VN1在160-200ml/g范围内。
7. 根据权利要求5或6的方法，其中第二聚合步骤中的氢浓度设定为使聚合物A加聚合物B的混合物的粘数VN2在250-300ml/g范围内。
8. 根据权利要求5或6的方法，其中第三聚合步骤中的氢浓度设定为使聚合物A、聚合物B加聚合物C的混合物的粘数VN3在420-460ml/g范围内。
9. 根据权利要求1-4中的任一项的聚乙烯模塑组合物用于生产容量在20-200 l范围内的燃料容器的用途，其中所述聚乙烯模塑组合物先在挤出机中于200-250℃的温度下塑化，随后挤出通过模头而产生坯件，所述坯件再在热态下三维成形并随后冷却。
10. 一种自根据权利要求1-4中任一项的聚乙烯模塑组合物通过挤出和随后热成形生产的用于机动车辆的燃料容器，其中所述燃料容器的壁厚在0.8-15mm范围内。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007016348.9 | 2007-04-03 | ||
| DE102007016348A DE102007016348A1 (de) | 2007-04-03 | 2007-04-03 | Polyethylen Formmasse zum Herstellen von Hohlkörpern durch Thermoformen und damit hergestellte Kraftstoffbehälter |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880010868A Division CN101679695A (zh) | 2007-04-03 | 2008-03-28 | 用于通过热成形生产中空容器的聚乙烯模塑组合物及用其生产的燃料容器 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104530532A true CN104530532A (zh) | 2015-04-22 |
Family
ID=39736179
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880010868A Pending CN101679695A (zh) | 2007-04-03 | 2008-03-28 | 用于通过热成形生产中空容器的聚乙烯模塑组合物及用其生产的燃料容器 |
| CN201410836333.8A Pending CN104530532A (zh) | 2007-04-03 | 2008-03-28 | 用于通过热成形生产中空容器的聚乙烯模塑组合物及用其生产的燃料容器 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880010868A Pending CN101679695A (zh) | 2007-04-03 | 2008-03-28 | 用于通过热成形生产中空容器的聚乙烯模塑组合物及用其生产的燃料容器 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20100301054A1 (zh) |
| EP (1) | EP2129721B1 (zh) |
| JP (1) | JP5562828B2 (zh) |
| CN (2) | CN101679695A (zh) |
| DE (1) | DE102007016348A1 (zh) |
| WO (1) | WO2008119504A1 (zh) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2498936A (en) * | 2012-01-31 | 2013-08-07 | Norner Innovation As | Polyethylene with multi-modal molecular weight distribution |
| BR112014023559B1 (pt) | 2012-03-28 | 2021-11-30 | Borealis Ag | Copolímero de etileno multimodal, seu processo de preparação, composto, filme e fibra |
| EP2799487B1 (en) * | 2013-05-01 | 2015-11-04 | Borealis AG | Composition |
| GB201313937D0 (en) | 2013-08-05 | 2013-09-18 | Ineos Europe Ag | Polymerisation process |
| CN105295159A (zh) * | 2014-07-24 | 2016-02-03 | 中国石化扬子石油化工有限公司 | 用于生产散装容器桶的聚乙烯吹塑组合物 |
| HUE047424T2 (hu) | 2016-09-12 | 2020-04-28 | Thai Polyethylene Co Ltd | Multimodális polietilén vékony film |
| EP3293206B1 (en) | 2016-09-12 | 2019-10-23 | Thai Polyethylene Co., Ltd. | Multimodal polyethylene pipe |
| HUE045071T2 (hu) | 2016-09-12 | 2019-12-30 | Thai Polyethylene Co Ltd | Multimodális polietilén film |
| EP3293207B1 (en) | 2016-09-12 | 2019-08-07 | Thai Polyethylene Co., Ltd. | Multimodal polyethylene pipe |
| PL3293214T3 (pl) | 2016-09-12 | 2020-07-27 | Thai Polyethylene Co., Ltd. | Wielomodalny polietylen o ultradużej masie cząsteczkowej o wysokich parametrach |
| RU2759904C2 (ru) | 2016-09-12 | 2021-11-18 | Тай Полиэтилен Ко., Лтд. | Бимодальная полиэтиленовая композиция и содержащая ее труба |
| PT3293205T (pt) | 2016-09-12 | 2019-10-31 | Scg Chemicals Co Ltd | Processo para a preparação de polietileno multimodal |
| HUE046743T2 (hu) | 2016-09-12 | 2020-03-30 | Thai Polyethylene Co Ltd | Multimodális polietilén tartály |
| HUE045763T2 (hu) | 2016-09-12 | 2020-01-28 | Thai Polyethylene Co Ltd | Multimodális polietilén csavaros kupak |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729247A (zh) * | 2002-12-24 | 2006-02-01 | 巴塞尔聚烯烃有限公司 | 用于生产大型容器的聚乙烯吹塑组合物 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4017661A1 (de) | 1990-06-01 | 1991-12-05 | Hoechst Ag | Verfahren zur herstellung eines poly-1-olefins |
| US5338589A (en) | 1991-06-05 | 1994-08-16 | Hoechst Aktiengesellschaft | Polyethylene molding composition |
| BE1006439A3 (fr) | 1992-12-21 | 1994-08-30 | Solvay Societe Annonyme | Procede de preparation d'une composition de polymeres d'ethylene, composition de polymeres d'ethylene et son utilisation. |
| JP3564548B2 (ja) * | 1995-09-22 | 2004-09-15 | 新日本石油化学株式会社 | エチレン／α−オレフィン共重合体の連続多段重合法 |
| DE19945980A1 (de) * | 1999-09-24 | 2001-03-29 | Elenac Gmbh | Polyethylen Formmasse mit verbesserter ESCR-Steifigkeitsrelation und Schwellrate, Verfahren zu ihrer Herstellung und daraus hergestellte Hohlkörper |
| CA2349939C (en) * | 2000-06-30 | 2008-04-15 | Kuraray Co., Ltd. | A method of producing a shaped article having excellent barrier properties |
| WO2004058878A1 (en) * | 2002-12-24 | 2004-07-15 | Basell Polyolefine Gmbh | Polyethylene blow molding composition for producing large containers |
-
2007
- 2007-04-03 DE DE102007016348A patent/DE102007016348A1/de not_active Withdrawn
-
2008
- 2008-03-28 WO PCT/EP2008/002446 patent/WO2008119504A1/en active Application Filing
- 2008-03-28 CN CN200880010868A patent/CN101679695A/zh active Pending
- 2008-03-28 JP JP2010501412A patent/JP5562828B2/ja active Active
- 2008-03-28 EP EP08734824.9A patent/EP2129721B1/en active Active
- 2008-03-28 CN CN201410836333.8A patent/CN104530532A/zh active Pending
- 2008-03-28 US US12/450,050 patent/US20100301054A1/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729247A (zh) * | 2002-12-24 | 2006-02-01 | 巴塞尔聚烯烃有限公司 | 用于生产大型容器的聚乙烯吹塑组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2129721A1 (en) | 2009-12-09 |
| CN101679695A (zh) | 2010-03-24 |
| JP2010523744A (ja) | 2010-07-15 |
| US20100301054A1 (en) | 2010-12-02 |
| DE102007016348A1 (de) | 2008-10-09 |
| WO2008119504A1 (en) | 2008-10-09 |
| EP2129721B1 (en) | 2016-09-07 |
| JP5562828B2 (ja) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104530532A (zh) | 用于通过热成形生产中空容器的聚乙烯模塑组合物及用其生产的燃料容器 | |
| US7427649B2 (en) | Polyethylene blow molding composition for producing small containers | |
| EP1576049B1 (en) | Polyethylene composition for producing l-ring drums | |
| EP1578862B1 (en) | Polyethylene blow moulding composition for producing jerry cans | |
| EP2167578B1 (en) | Pe molding composition for blow-molding of small low-density blow moldings | |
| EP2231773B1 (en) | Pe moulding composition for producing injection-molded screw cap closures and high-strenght screw cap closure for carbonated beverages produced therewith | |
| EP3464456B1 (en) | Hinged component comprising polyethylene composition | |
| EP1576048B1 (en) | Polyethylene blow molding composition for producing large containers | |
| KR20030004297A (ko) | Ｅｓｃｒ-강성 관계와 팽윤비가 개선된 폴리에틸렌 성형배합물, 이의 제조방법 및 이의 용도 | |
| CN1926185B (zh) | 聚合物组合物 | |
| CN100487034C (zh) | 用于生产大型容器的聚乙烯吹塑组合物 | |
| CN100363413C (zh) | 用于生产简便油桶的聚乙烯吹塑组合物 | |
| CN100363414C (zh) | 用于生产l-环形鼓的聚乙烯组合物 | |
| CN101688034B (zh) | 用于吹塑小的低密度吹塑品的pe模塑组合物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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: 20150422 |
|
| RJ01 | Rejection of invention patent application after publication |