CN107921764B - 包含丙烯-乙烯-1-丁烯三元共聚物的组合物 - Google Patents
包含丙烯-乙烯-1-丁烯三元共聚物的组合物 Download PDFInfo
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- CN107921764B CN107921764B CN201680045884.XA CN201680045884A CN107921764B CN 107921764 B CN107921764 B CN 107921764B CN 201680045884 A CN201680045884 A CN 201680045884A CN 107921764 B CN107921764 B CN 107921764B
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- Prior art keywords
- ethylene
- derived units
- propylene
- polyolefin composition
- butene
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- -1 propylene-ethylene -1- butene Chemical class 0.000 title claims abstract description 22
- 229920001897 terpolymer Polymers 0.000 title claims abstract description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000005977 Ethylene Substances 0.000 claims abstract description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000098 polyolefin Polymers 0.000 claims abstract description 28
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims description 9
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
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- 239000001257 hydrogen Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical compound CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 description 2
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- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
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- MXEYWRZVLWMSTE-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl(dimethoxy)silane Chemical compound CO[SiH](OC)C(C)(C)C(C)C MXEYWRZVLWMSTE-UHFFFAOYSA-N 0.000 description 1
- UVGKQRAGAYVWQV-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C(C)C UVGKQRAGAYVWQV-UHFFFAOYSA-N 0.000 description 1
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 1
- QWJUMUXQFFWLIF-UHFFFAOYSA-N 9,9-dimethoxyfluorene Chemical class C1=CC=C2C(OC)(OC)C3=CC=CC=C3C2=C1 QWJUMUXQFFWLIF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
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- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
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- TXLMBPWQZULYHP-UHFFFAOYSA-N tert-butyl(dimethoxy)silane Chemical compound CO[SiH](OC)C(C)(C)C TXLMBPWQZULYHP-UHFFFAOYSA-N 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
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- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
- C08F4/6421—Titanium tetrahalides with organo-aluminium compounds
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6491—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon
- C08F4/6492—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon containing aliphatic unsaturation
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Abstract
一种聚烯烃组合物，其包含：A)19wt％到50wt％的丙烯‑乙烯共聚物，其具有1.5wt％到6.0wt％的乙烯衍生单元含量；B)50wt％到81wt％的丙烯‑乙烯‑1‑丁烯三元共聚物，其具有1.5wt％到6.0wt％的乙烯衍生单元含量和4.8wt％与12.4wt％之间的1‑丁烯衍生单元含量；组分A)和组分B)的量的和为100；组合物的特征在于以下特性：‑C2wt％/C4wt％的比例包含在0.22和3.0之间，其中C2wt％为乙烯衍生单元的重量百分比，C4wt％为1‑丁烯衍生单元的重量百分比；‑25℃下的二甲苯可溶部分的含量包含在2wt％和15wt％之间；‑以Mw/Mn表示的分子量分布(MWD)大于4.0；‑200℃下的可恢复柔量在800秒与1200秒之间具有低于65x10‑5Pa‑1的最大值。
Description
技术领域
本公开涉及包含丙烯-乙烯共聚物和丙烯-乙烯-1-丁烯三元共聚物的聚烯烃组合物，其适合得到薄膜，特别是双轴取向薄膜，并且在电晕处理后具有改进的表面张力方面的特性。
背景技术
由丙烯共聚物或三元共聚物制成的薄膜在本领域是已知的。
之所以使用丙烯共聚物或三元共聚物，是由于与丙烯均聚物相比，其具有更好的冲击性能、更低的刚性和更好的透明性。但是在一些情况下，难以在那些特性之间找到可接受的平衡，特别是当所期望的各种特性彼此相冲突时。例如，当期望一定的柔软度时，其通常在较高量的二甲苯可溶部分的存在下得到，这会使得它们不适合于食品接触应用。
美国专利号6,221,984公开了丙烯与乙烯和至少一种C4-C10α-烯烃的无规共聚物，以及用来制备此类无规共聚物的工艺，其可用于薄膜、纤维或模制品。特别地，通过本说明书中公开的工艺获得的三元共聚物特别适合于食品包装薄膜，这是由于它们的二甲苯可溶聚合物颗粒的比例较低(实例1-3)。另一方面，当二甲苯可溶部分增加时，密封起始温度和光学特性便会变得不令人满意。
WO2009/019169涉及在包含两个相互连接的聚合区的气相反应器中制备的丙烯/乙烯/1-丁烯三元共聚物。除了其它特征之外，所述三元共聚物的乙烯的量(wt％)与1-丁烯的量(wt％)之间的比例为0.1到0.8，并且25℃下的二甲苯可溶部分高于9wt％。
WO2013/174778涉及包含0.5wt％到2.2wt％的乙烯衍生单元和6.0wt％到20.0wt％的1-丁烯衍生单元的丙烯-乙烯-1-丁烯三元共聚物，其中特别地25℃下的二甲苯可溶部分低于15.0wt％，最小值为5.0。同样在这种情况下，二甲苯可溶部分与SIT之间的平衡可被进一步改进。
本领域中同样已知的是，与其它材料相比聚烯烃薄膜润湿性差，可印刷性差，并且粘合性差。这些特性与基于聚烯烃的聚合物的低表面张力以及它们对许多化学品和溶剂的高抗性相关。通常，丙烯薄膜的表面张力在27mN/m到30mN/m的范围内。
为了增加表面张力以便使得薄膜接受敷金属、涂料、印刷油墨、层压等或其组合，对表面的几种处理在本领域是已知的，包括电晕放电处理、火焰处理、等离子处理、化学处理或者通过极化火焰方式的处理。
这些步骤的共同之处在于，通过曝露于所产生的反应性物质，聚合物表面部分地和暂时地被极性基团改性，从而使得表面更容易印刷。
发明内容
现已令人惊讶地发现，包含丙烯-乙烯共聚物和丙烯-乙烯-1-丁烯三元共聚物的聚烯烃组合物可有利地用来获得薄膜，特别是双轴取向薄膜(BOPP)，其在电晕处理后具有较高的表面张力。
因此，本公开涉及一种聚烯烃组合物，其包含：
A)19wt％到50wt％的丙烯-乙烯共聚物，其具有1.5wt％到6.0wt％的乙烯衍生单元含量；
B)50wt％到81wt％的丙烯-乙烯-1-丁烯三元共聚物，其具有1.5wt％到6.0wt％的乙烯衍生单元含量和4.8wt％与12.4wt％之间的1-丁烯衍生单元含量；
组分A)和组分B)的量的和为100；
所述组合物的特征在于以下特性：
-C2wt％/C4wt％比在0.22与3.0之间，其中C2wt％为乙烯衍生单元的重量百分比，C4wt％为1-丁烯衍生单元的重量百分比；
-25℃下的二甲苯可溶部分包含在2wt％与15wt％之间；
-以Mw/Mn表示的分子量分布(MWD)大于4.0；
-根据在表征部分中记录的步骤在200℃下测量的可恢复柔量在800秒与1200秒之间具有低于65x10-5Pa-1的最大值。
附图说明
在图1中记录了根据在表征部分中记录的步骤在200℃下测量的实例1和对比例2的恢复柔量相对于时间。
具体实施方式
一种聚烯烃组合物，其包含：
A)19wt％到50wt％、优选25wt％到42wt％、更优选31wt％到38wt％的丙烯-乙烯共聚物，其具有1.5wt％到6.0wt％、优选2.6wt％到5.2wt％、更优选3.1wt％到4.3wt％的乙烯衍生单元含量；
B)50wt％到81wt％、优选58wt％到75wt％、更优选62wt％到69wt％的丙烯-乙烯-1-丁烯三元共聚物，其具有1.5wt％到6.0wt％、优选1.9wt％到4.8wt％、更优选2.1wt％到3.7wt％的乙烯衍生单元含量，以及在4.8wt％与12.4wt％之间、优选5.1wt％到10.5wt％、更优选6.8wt％到10.0wt％的1-丁烯衍生单元含量；
组分A)和组分B)的量的和为100；
所述组合物的特征在于以下特性：
-C2wt％/C4wt％比在0.22与3.0之间，优选在0.30与2.3之间，更优选从0.35到1.3，其中C2wt％为乙烯衍生单元的重量百分比，C4wt％为1-丁烯衍生单元的重量百分比；
-25℃下的二甲苯可溶部分包含在2wt％与15wt％之间，优选在5wt％与13wt％之间，更优选在7wt％与11.5wt％之间；
-以Mw/Mn表示的分子量分布(MWD)高于4.0，优选低于10.0；
-根据在表征部分中记录的步骤在200℃下测量的可恢复柔量在800秒与1200秒之间具有低于65x10-5 Pa-1的最大值。
优选地，涉及作为反应器级别的聚烯烃组合物(即未进行化学或物理减粘裂化的共聚物)的熔体流动速率(MFR 230℃2.16Kg)为0.5g/10min到75g/10min，优选为1.0g/10min到25.0g/10min，更优选为3.0g/10min到20.0g/10min，甚至更优选为4.0g/10min到18.0g/10min。
特别地，聚烯烃组合物优选具有低于140℃的熔融温度，更优选低于136.8℃。
优选地，聚烯烃组合物具有包含在90℃与109℃之间的密封起始温度(SIT)。
丙烯-乙烯共聚物定义为仅包含丙烯和乙烯共聚单体，丙烯-乙烯-1-丁烯三元共聚物定义为仅包含丙烯、乙烯和1-丁烯共聚单体。
聚烯烃组合物特别适合生产薄膜，特别是双轴取向(BOPP)薄膜。使用聚烯烃组合物获得的BOPP薄膜在电晕处理后具有较高的表面张力。
本文公开的聚烯烃组合物可通过包含以下的工艺来制备：在包含以下物质之间的反应产物的催化剂的存在下将丙烯与乙烯聚合，以及将丙烯与乙烯和1-丁烯聚合：
(i)包含Ti、Mg、Cl和电子供体化合物(内部供体)的固体催化剂组分；
(ii)烷基铝化合物，以及，
(iii)电子供体化合物(外部供体)。
固体组分颗粒具有基本上球形的形态以及在5μm与150μm之间、优选20μm到100μm、更优选30μm到90μm的平均直径。作为具有基本上球形的形态的颗粒，那些颗粒意思是其中较长的轴与较短的轴之间的比例等于或低于1.5，优选低于1.3。
通常，Mg的量优选为8到30％，更优选为10wt％到25wt％。
通常，Ti的量为0.5wt％到5wt％，更优选为0.7wy％到3wt％。
内部电子供体化合物为具有以下化学式的1，3-二醚：
其中RI和RII相同或不同，并且是C1-C18烷基、C3-C18环烷基或C7-C18芳基；RIII和RIV相同或不同，并且是C1-C4烷基；或者是这样的1，3-二醚：其中2位碳原子属于一环状结构或多环结构，所述环状结构或多环结构由5个、6个或7个碳原子构成，或者由5-n个或6-n′个碳原子，以及相应的n个氮原子和n′个选自由N、O、S和Si组成的群组的杂原子构成，其中n为1或2，n′为1、2或3，所述结构包含两个或更多个不饱和基团(环多烯烃结构)，并且任选地与其它环状结构稠和，或者被选自由直链或支链烷基、环烷基、芳基、芳烷基、烷芳基和卤素组成的群组的一个或多个取代基取代，或者与其它环状结构稠和并且被一个或多个以上所述取代基(其也可以与稠和的环状结构连接)取代；以上所述烷基、环烷基、芳基、芳烷基或烷芳基中的一个或多个以及稠和的环状结构任选地包含一个或多个杂原子作为碳原子或氢原子，或者两者的替代。
在公布的欧洲专利申请361493和728769中描述了这一类型的醚。
所述二醚的代表性实例为2-甲基-2-异丙基-1，3-二甲氧基丙烷、2，2-二异丁基-1，3-二甲氧基丙烷、2-异丙基-2-环戊基-1，3-二甲氧基丙烷、2-异丙基-2-异戊基-1，3-二甲氧基丙烷、9，9-双(甲氧基甲基)芴。
Mg/Ti摩尔比优选等于或高于13，优选在14-40的范围内，更优选为15到40。相应地，Mg/供体摩尔比优选高于16，更优选高于17，通常为18到50。
固体催化剂组分的制备可根据几种方法进行。
根据一种方法，固体催化剂组分可通过将化学式为Ti(OR)q-yXy(其中q为钛的化合价，y为1与q之间的数值，优选为TiCl4)的钛化合物与衍生自化学式为MgCl2·pROH(其中p为0.1与6之间的数值，优选为2到3.5，R为具有1-18个碳原子的烃)的加成物的氯化镁反应来制备。所述加成物可通过在搅拌条件下在加成物的熔融温度下(100-130℃)操作将醇与氯化镁混合适当地制备成球形。然后，将加成物跟与加成物不互溶的惰性烃混合，从而产生乳状液，其迅速被淬灭，导致加成物以球形颗粒形式固化。在USP4,399,054和USP4,469,648中描述了根据该步骤制备的球形加成物的实例。如此获得的加成物可直接与Ti化合物反应，或者它可预先进行热控脱醇(80-130℃)，以便获得其中醇的摩尔数通常低于3、优选在0.1和2.5之间的加成物。与Ti化合物的反应可通过将加成物(经脱醇或照原样)悬浮在冷的TiCl4(通常为0℃)中来进行；将该混合物加热至80-130℃并在此温度下保持0.5-2小时。用TiCl4所进行的处理可进行一次或多次。在用TiCl4进行处理的过程中可以期望的比例添加内部电子供体化合物。
烷基铝化合物(ii)优选选自像(例如)三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝这样的三烷基铝化合物。还可以使用烷基铝卤化物、烷基铝氢化物或烷基铝倍半氯化物，例如AlEt2Cl和Al2Et3Cl3，可能在与以上所述三烷基铝的混合物中。Al/Ti比高于1，通常包含在50与2000之间。
合适的外部电子供体化合物包括硅化合物、醚、酯、胺、杂环化合物(特别是2，2，6，6-四甲基哌啶)和酮。
优选的一类外部供体化合物是化学式为(R6)a(R7)bSi(OR8)c的硅化合物，其中a和b为0到2的整数，c为1到4的整数，并且(a+b+c)的和为4；R6、R7和R8为具有1-18个碳原子且任选地包含杂原子的烷基、环烷基或芳基。特别优选的是这样的硅化合物：其中a为1，b为1，c为2，R6和R7中的至少一个选自具有3-10个碳原子且任选地包含杂原子的支链烷基、环烷基或芳基，并且R8为C1-C10烷基，特别是甲基。此类优选硅化合物的实例为甲基环己基二甲氧基硅烷(C供体)、二苯基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷、二环戊基二甲氧基硅烷(D供体)、二异丙基二甲氧基硅烷、(2-乙基哌啶基)叔丁基二甲氧基硅烷、(2-乙基哌啶基)(1，1，2-三甲基-丙基)二甲氧基硅烷、(3，3，3-三氟正丙基)-(2-乙基哌啶基)-二甲氧基硅烷、甲基(3，3，3-三氟正丙基)二甲氧基硅烷。此外，其中a为0、c为3、R7为任选地包含杂原子的支链烷基或环烷基并且R8为甲基的硅化合物也是优选的。此类优选硅化合物的实例为环己基三甲氧基硅烷、叔丁基三甲氧基硅烷和(1，1，2-三甲基-丙基)三甲氧基硅烷。
电子供体化合物(iii)以可以给出的有机铝化合物与所述电子供体化合物(iii)之间的摩尔比为0.1到500、优选1到300、更优选3到100的量使用。
聚合工艺可根据已知的技术进行，例如使用惰性烃溶剂作为稀释剂的浆液聚合，或者使用液体单体(例如丙烯)作为反应介质的本体聚合。另外，聚合工艺可以在在一个或多个流化床或机械搅拌床反应器中操作的气相中进行。
聚合通常在20℃到120℃、优选40℃到80℃的温度下进行。当聚合在气相中进行时，操作压力通常在0.5Mpa与5Mpa之间，优选在1Mpa与4Mpa之间。在本体聚合中，操作压力通常在1Mpa与8Mpa之间，优选在1.5Mpa与5 Mpa之间。通常使用氢气作为分子量调节剂。
本公开的聚烯烃组合物还可包含通常用于薄膜制造的添加剂，例如抗氧化剂、工艺稳定剂、增滑剂、抗静电剂、抗粘连剂。
聚烯烃组合物可根据众所周知的工艺和技术用来制备单层或多层薄膜。
特别地，可以使用挤压工艺。
在挤压工艺中，待用聚合物材料在挤压机中融熔并挤压通过窄的模缝。离开模头后，可对所述材料进行冷却、加热以及任选地以几种方式进行取向，或组合进行。
此类工艺的实例为流延、吹塑、挤压涂覆、单轴取向、同时双轴取向以及依次双轴取向薄膜工艺。
此类工艺的特定实例为吹塑薄膜和BOPP工艺。
给出以下实例以更好地说明本公开，但绝不意在以任何方式对其进行限制。
实例
表征
二甲苯可溶部分的测定
将2.5g聚合物和250mL邻二甲苯加入配有致冷器和磁力搅拌器的玻璃烧瓶中。将温度在30分钟内升高到溶剂沸点。然后将如此获得的溶液保持回流并继续搅拌30分钟。然后将密封烧瓶在冰水浴中保持30分钟，并在电热恒温浴中在25℃下也保持30分钟。将如此获得的固体在快速滤纸上过滤，并将100mL滤液倒入预先称量好的铝容器中，其在氮气流下在加热板上加热，以通过蒸发除去溶剂。然后将容器置于80℃和真空下的烘箱中，直到获得恒定重量。称量残留物以确定二甲苯可溶聚合物的百分比。
分子量分布MWD(Mw/Mn)
分子量和分子量分布使用配有4个粒径为13μm的混合床柱PLgel Olexis的WatersAlliance GPCV/2000仪器在150℃下测量。各柱的尺寸为300×7.8mm。所用流动相为真空蒸馏的1，2，4-三氯苯(TCB)，流动速率保持在1.0mL/min。样品溶液通过将样品在搅拌下在150℃下在TCB中加热1到2小时来制备。浓度为1mg/mL。为了防止降解，加入0.1g/l的2，6-二叔丁基对甲酚。将300μl(标称值)溶液注入柱组中。使用10个分子量为580到7500000Da的聚苯乙烯标准样品(安捷伦的EasiCal试剂盒)得到校正曲线。假定马克-霍温克关系的K值为：
对于聚苯乙烯标准物，K＝1.21×10-4dl/g，a＝0.706，
对于实验样品，K＝1.90×10-4dl/g，a＝0.725。
使用三次多项式拟合***实验数据并获得校准曲线。数据的获取和处理通过使用带有GPC选项的Waters Empowers 3色谱数据软件来进行。
熔体流动速率(MFR)
聚合物组合物的熔体流动速率MFR根据ISO 1133(230℃，2.16Kg)测定。
共聚单体含量的测定
共聚单体的含量通过红外光谱测定-通过使用傅里叶变换红外光谱仪(FTIR)收集样品相对于空气背景的IR光谱；仪器的数据获取参数为：
-清除时间：最短30秒
-收集时间：最短3分钟
-变迹：Happ-Genzel
-分辨率：2cm-1。
样品制备：
使用液压机，通过在两个铝箔之间按压约g1样品来获得厚板。如果均匀性有问题，建议最少按压2次。从该板上切割下一小部分来模制薄膜。建议薄膜厚度在0.02cm与0.05cm(8-20密耳)之间。
按压温度为180±10℃(356°F)，压力为约10kg/cm2(142.2PSI)。
约1分钟后，释放压力，并且从液压机上去除样品并将其冷却至室温。
按压后的聚合物薄膜的光谱以吸收相对于波数(cm-1)记录。使用以下测量值来计算乙烯和1-丁烯的含量：
-在4482cm-1与3950cm-1之间的组合吸收谱带的面积(At)用于薄膜厚度的光谱测定标准化。
-AC2为如下恰当地连续进行两次光谱扣除之后750-700cm-1之间的吸收谱带的面积：扣除全同立构未加添加剂的聚丙烯光谱，然后扣除在800-690cm-1范围内的1-丁烯-丙烯无规共聚物的参考光谱。
-DC4为如下恰当地连续进行两次光谱扣除之后在769cm-1(最大值)处的吸收谱带的高度：扣除全同立构未加添加剂的聚丙烯光谱，然后扣除在800-690cm-1范围内的乙烯-丙烯无规共聚物的参考光谱。
为了计算乙烯和1-丁烯的含量，需要通过使用已知量的乙烯和1-丁烯的样品获得的乙烯和1-丁烯的校准直线。
乙烯的校准：
通过AC2/At相对于乙烯摩尔百分比(％C2m)进行绘制获得校准直线GC2。通过线性回归计算GC2的斜率。
1-丁烯的校准：
通过DC4/At相对于1-丁烯摩尔百分比(％C4m)进行绘制获得校准直线GC4。通过线性回归计算GC4的斜率。
记录未知样品的光谱，然后计算未知样品的(At)、(AC2)和(DC4)。样品的乙烯含量(％摩尔分数C2m)如下计算：
样品的1-丁烯含量(％摩尔分数C4m)如下计算：
丙烯含量(摩尔分数C3m)如下计算：
C3m＝100-％C4m-％C2m
乙烯、1-丁烯以重量计的含量如下计算：
通过差示扫描量热法(DSC)的熔融温度
在Perkin Elmer DSC-1量热器上通过差示扫描量热法(D.S.C.)并根据2009年的ISO 11357-1和2011年的11357-3以20℃/min测量聚合物的熔融温度(Tm)，所述PerkinElmer DSC-1量热器预先通过铟的熔点进行校准。每个DSC坩埚中的样品重量保持在6.0±0.5mg。
为了得到熔点，将称量好的样品密封在铝盘中并以20℃/分钟的速度加热到200℃。将样品在200℃下保持2分钟，以容许所有微晶完全熔融，然后以20℃/分钟冷却到5℃。在5℃下保持2分钟后，第二次以20℃/min将样品加热到200℃。在该第二次加热过程中，采用峰值温度(Tp，m)作为熔融温度。
雾度的测定
使用通过在单螺杆Collin挤压机(螺杆的长度/直径比为1∶25)中在7m/min的薄膜牵引速度和210-250℃的熔融温度下挤压每种测试组合物制备的约5x5em的50μm厚的薄膜样本。雾度值使用与UX-10型雾度计或具有带滤光器“C”的G.E.1209光源的等同仪器连接的Gardner光度装置测量。使用已知雾度的参考样品来校准仪器。
表面张力的测定
表面张力的测定根据ASTMD2578-09测量。
密封起始温度(SIT)
薄膜样本的制备：
本公开的聚烯烃组合物被用来生产A/B/C多层薄膜，其中A层为实例1的聚合物，B层为由利安德巴塞尔工业公司(Lyondellbasell)销售的丙烯均聚物MOPLEN HP522H，C层为对比例2的聚合物。加工参数列于表1中。
表1
将多层薄膜以5.1∶1的比例拉伸。
为了对比，还制造了C/B/C多层薄膜，其中C层为对比例2的聚合物，B层为由利安德巴塞尔工业公司销售的丙烯均聚物MOPLEN HP522H。加工参数列于表2中
表2
SIT的测定：
对于每次测试，将两个以上样本对齐叠加，相邻层为特定的测试组合物层。使用HSG-ETK745型Brugger Feinmechanik密封器沿着2cm侧面中的一个将叠加的样本密封。密封时间在0.1N/mm2的压力下为5秒。从低于测试组合物的熔融温度的约30℃开始，每次密封将密封温度增加1℃。将密封的样品放置冷却，然后将其未密封端连接到Instron机器，在该Instron机器中以50mm/min的牵引速度对它们进行测试。
SIT为当在所述测试条件下施加至少2牛顿的负载时密封不会断裂的最低密封温度。
可恢复柔量的测定
可恢复柔量由使用具有半径为25mm的锥板(cone plate)几何形状和1.992°度的测量锥角(锥板在顶部)的Physica MCR301流变仪得到的蠕变和恢复测试测量值确定。测试温度为200℃。
蠕变时间的测定
在100rad/s到0.01rad/s的扫频测试中以5％的恒定应变测定复数粘度，并选择0.01rad/s的频率处的值来计算蠕变时间(未设置时间参数)。然后使用以下公式计算蠕变时间：
蠕变时间＝0.01rad/s下的复数粘度/100；[1]
其中100为以帕斯卡计的所施加的应力，。
恢复时间的测定
根据以下公式计算恢复时间：
恢复时间＝蠕变时间*7[2]
蠕变和恢复测试
a)蠕变
蠕变每秒测量一次，测量时间为根据[1]中计算的蠕变时间的最大秒数。所施加的剪切应力为100Pa；
b)恢复
恢复每秒测量一次，测量时间为根据[2]中计算的恢复时间的最大秒数。所施加的剪切应力为0Pa。
在测试结束时通过软件计算以Pa-1测量的可恢复柔量相对于以秒测量的时间。
实例1
球形加合物的制备步骤
微球状MgCl2.2.1C2H5OH加成物根据欧洲专利申请728769的实例1制备。
固体催化剂组分的制备步骤
固体催化剂组分根据欧洲专利申请728769的实例1制备。
预聚合处理
在将以上所述固体催化剂组分加入聚合反应器中之前，将其以表2中所列比例与三乙基铝(TEAL)和二环戊基二甲氧基硅烷(DCPMS，D供体)接触。
然后，所得混合物在将其加入第一聚合反应器中之前通过将其在20℃下在液体丙烯中的悬浮液中保持约5分钟进行预聚合。
聚合
通过供应预聚合的催化剂***、氢(当用作分子量调节剂时)、丙烯和乙烯的气态连续流和恒定流在第一气相聚合反应器中产生丙烯-乙烯共聚物。
清除未反应单体之后，第一反应器中产生的聚合物以连续流排出，并与数量上恒定的氢(当使用时)、1-丁烯、乙烯和丙烯的气态流一起以连续流引入第二气相聚合反应器中。
离开第二反应器的聚合物颗粒进行蒸气处理，以除去反应性单体和挥发性物质，然后干燥。
主要聚合条件列于表3中。聚合物特征列于表4中。
表3
C2＝乙烯；C3＝丙烯；C4＝1-丁烯；H2＝氢
对比例2为由利安德巴塞尔工业公司销售的商业产品，其具有表4所列特征，并使用由邻苯二甲酸二异丁基酯而不是9，9-双(甲氧基甲基)芴作为内部供体的催化剂产生。
实例1和对比例2两者的恢复柔量曲线示于图1中。两个曲线在800秒与1200秒之间的最大值列于表4中。
表4
将所得薄膜的样品进行电晕处理，然后在不同时间测量表面张力。各结果列于表4中。
表4
从表4结果明显看出，本公开的聚烯烃组合物相对于对比例2显示更高的表面张力。
Claims (11)
1.一种聚烯烃组合物，其包含：
A)19wt％到50wt％的丙烯-乙烯共聚物，其具有1.5wt％到6.0wt％的乙烯衍生单元含量；
B)50wt％到81wt％的丙烯-乙烯-1-丁烯三元共聚物，其具有1.5wt％到6.0wt％的乙烯衍生单元含量和4.8wt％与12.4wt％之间的1-丁烯衍生单元含量；
组分A)和组分B)的量的和为100；
所述组合物的特征在于以下特性：
-C2wt％/C4wt％比包含在0.22和3.0之间，其中C2wt％为乙烯衍生单元的重量百分比，C4wt％为1-丁烯衍生单元的重量百分比；
-25℃下的二甲苯可溶部分的含量包含在2wt％和15wt％之间；
-以Mw/Mn表示的分子量分布(MWD)大于4.0；
-200℃下的可恢复柔量在800秒与1200秒之间具有低于65x10-5Pa-1的最大值。
2.根据权利要求1所述的聚烯烃组合物，其中组分A)为25wt％到42wt％，且组分B)为58wt％到75wt％。
3.根据权利要求1所述的聚烯烃组合物，其中组分A)中的所述乙烯衍生单元含量为2.6wt％到5.2wt％。
4.根据权利要求1所述的聚烯烃组合物，其中组分B)中的所述乙烯衍生单元含量为1.9wt％到4.8wt％，且所述1-丁烯衍生单元含量为5.1wt％到10.5wt％。
5.根据权利要求1所述的聚烯烃组合物，其中200℃下的所述可恢复柔量在800秒与1200秒之间具有低于60x10-5Pa-1的最大值。
6.根据权利要求1所述的聚烯烃组合物，其中所述乙烯衍生单元含量为2.5wt％到3.9wt％。
7.根据权利要求1所述的聚烯烃组合物，其中所述1-丁烯衍生单元含量为5.3wt％到6.9wt％。
8.根据权利要求1所述的聚烯烃组合物，其中熔融温度低于136.8℃。
9.根据权利要求1所述的聚烯烃组合物，其中密封起始温度(SIT)包含在90℃与109℃之间。
10.一种薄膜，其包含根据权利要求1-9中任一项所述的聚烯烃组合物。
11.一种双轴取向(BOPP)薄膜，其包含根据权利要求1-9中任一项所述的聚烯烃组合物。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15180040.6 | 2015-08-06 | ||
| EP15180040 | 2015-08-06 | ||
| PCT/EP2016/067144 WO2017021138A1 (en) | 2015-08-06 | 2016-07-19 | Composition comprising propylene-ethylene-1-butene terpolymers |
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| Publication Number | Publication Date |
|---|---|
| CN107921764A CN107921764A (zh) | 2018-04-17 |
| CN107921764B true CN107921764B (zh) | 2019-07-26 |
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| CN (1) | CN107921764B (zh) |
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| PL (1) | PL3331703T3 (zh) |
| RU (1) | RU2679259C1 (zh) |
| TR (1) | TR201910968T4 (zh) |
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| KR102173594B1 (ko) * | 2020-07-16 | 2020-11-04 | 최용제 | 단열 및 차열성능이 우수한 비닐 하우스용 시트 |
| EP4259700A1 (en) * | 2020-12-09 | 2023-10-18 | Basell Poliolefine Italia S.r.l. | Propylene polymer composition |
| WO2024028042A1 (en) * | 2022-08-03 | 2024-02-08 | Basell Poliolefine Italia S.R.L. | Polypropylene composition for heat sealable films |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3539352C2 (de) * | 1984-11-09 | 1994-12-22 | Mitsubishi Yuka Badische | Polypropylenschaumteilchen sowie deren Verwendung |
| CN1112144A (zh) * | 1994-03-24 | 1995-11-22 | 希蒙特公司 | 具有低密封温度和良好油墨粘附性的晶体丙烯共聚物组合物 |
| EP1332179A2 (en) * | 2000-10-24 | 2003-08-06 | Union Carbide Chemicals & Plastics Technology Corporation | High-speed processable cellular insulation material with enhanced foamability |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2735550A1 (de) | 1977-08-06 | 1979-02-08 | Guenther O Prof Dr Schenck | Mehrkammer-photoreaktor |
| IT1096661B (it) | 1978-06-13 | 1985-08-26 | Montedison Spa | Procedimento per la preparazione di prodotti in forma sferoidale solidi a temperatura ambiente |
| IT1098272B (it) | 1978-08-22 | 1985-09-07 | Montedison Spa | Componenti,di catalizzatori e catalizzatori per la polimerizzazione delle alfa-olefine |
| JPS61248740A (ja) * | 1985-04-26 | 1986-11-06 | 住友化学工業株式会社 | ポリプロピレン多層フイルム |
| IT1227260B (it) | 1988-09-30 | 1991-03-28 | Himont Inc | Dieteri utilizzabili nella preparazione di catalizzatori ziegler-natta |
| IL117114A (en) | 1995-02-21 | 2000-02-17 | Montell North America Inc | Components and catalysts for the polymerization ofolefins |
| US7049377B1 (en) | 1995-02-21 | 2006-05-23 | Basell Poliolefine Italia S.R.L. | 1,3-diethers and components and catalysts for the polymerization of olefins, containing said diethers |
| DE19722569A1 (de) | 1997-05-28 | 1998-12-03 | Basf Ag | Statistische Propylencopolymerisate |
| US7351478B2 (en) * | 2001-03-16 | 2008-04-01 | Fina Technology, Inc. | Heat-seal films and method of manufacture |
| EP2173471B1 (en) | 2007-08-03 | 2011-12-14 | Basell Poliolefine Italia S.r.l. | Process for producing propylene terpolymers |
| EP2283072B2 (en) | 2008-04-24 | 2018-07-18 | Borealis AG | Process for producing high purity heterophasic propylene copolymers |
| EP2666793A1 (en) | 2012-05-21 | 2013-11-27 | Basell Poliolefine Italia S.r.l. | Propylene based terpolymer |
| EP2743307A1 (en) | 2012-12-12 | 2014-06-18 | Basell Poliolefine Italia S.r.l. | Polyolefin composition |
| KR101349929B1 (ko) | 2013-05-14 | 2014-01-14 | 두지산업 주식회사 | 리본형 직물 |
| EP2810773A1 (en) * | 2013-06-05 | 2014-12-10 | Basell Poliolefine Italia S.r.l. | Butene-1 copolymer tie layer in multilayer film structures having a low seal temperature and improved hot tack |
-
2016
- 2016-07-19 WO PCT/EP2016/067144 patent/WO2017021138A1/en active Application Filing
- 2016-07-19 PL PL16766855T patent/PL3331703T3/pl unknown
- 2016-07-19 ES ES16766855T patent/ES2731357T3/es active Active
- 2016-07-19 RU RU2018105006A patent/RU2679259C1/ru active
- 2016-07-19 CN CN201680045884.XA patent/CN107921764B/zh active Active
- 2016-07-19 JP JP2018506284A patent/JP6491792B2/ja active Active
- 2016-07-19 TR TR2019/10968T patent/TR201910968T4/tr unknown
- 2016-07-19 US US15/750,772 patent/US10577492B2/en active Active
- 2016-07-19 KR KR1020187004230A patent/KR101917069B1/ko active IP Right Grant
- 2016-07-19 EP EP16766855.7A patent/EP3331703B1/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3539352C2 (de) * | 1984-11-09 | 1994-12-22 | Mitsubishi Yuka Badische | Polypropylenschaumteilchen sowie deren Verwendung |
| CN1112144A (zh) * | 1994-03-24 | 1995-11-22 | 希蒙特公司 | 具有低密封温度和良好油墨粘附性的晶体丙烯共聚物组合物 |
| EP1332179A2 (en) * | 2000-10-24 | 2003-08-06 | Union Carbide Chemicals & Plastics Technology Corporation | High-speed processable cellular insulation material with enhanced foamability |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017021138A1 (en) | 2017-02-09 |
| US20180237623A1 (en) | 2018-08-23 |
| EP3331703B1 (en) | 2019-05-29 |
| RU2679259C1 (ru) | 2019-02-06 |
| PL3331703T3 (pl) | 2019-11-29 |
| EP3331703A1 (en) | 2018-06-13 |
| JP2018525488A (ja) | 2018-09-06 |
| KR101917069B1 (ko) | 2018-11-08 |
| KR20180025974A (ko) | 2018-03-09 |
| CN107921764A (zh) | 2018-04-17 |
| ES2731357T3 (es) | 2019-11-15 |
| JP6491792B2 (ja) | 2019-03-27 |
| US10577492B2 (en) | 2020-03-03 |
| BR112018002393A2 (pt) | 2018-09-18 |
| TR201910968T4 (tr) | 2019-08-21 |
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