CN106661291A - 用于管道的丙烯基共聚物组合物 - Google Patents
用于管道的丙烯基共聚物组合物 Download PDFInfo
- Publication number
- CN106661291A CN106661291A CN201580039211.9A CN201580039211A CN106661291A CN 106661291 A CN106661291 A CN 106661291A CN 201580039211 A CN201580039211 A CN 201580039211A CN 106661291 A CN106661291 A CN 106661291A
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- Prior art keywords
- 10min
- ethylene
- propylene
- polyolefin composition
- mfr
- 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.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims abstract description 9
- 239000000155 melt Substances 0.000 claims abstract description 4
- 239000008096 xylene Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 229920005606 polypropylene copolymer Polymers 0.000 abstract 1
- -1 polypropylene Polymers 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 20
- 238000000034 method Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 10
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- 239000003054 catalyst Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
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- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
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- 238000005243 fluidization Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
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- 229920001384 propylene homopolymer Polymers 0.000 description 2
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- 150000003377 silicon compounds Chemical class 0.000 description 2
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- 235000012222 talc Nutrition 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical class COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 description 1
- IJBYVSUZCRXTOD-UHFFFAOYSA-N 1-methoxy-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(OC)=CC=C2 IJBYVSUZCRXTOD-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920005621 immiscible polymer blend Polymers 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000013849 propane Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
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- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
一种聚烯烃组合物,其包括:A)90.0wt%至99.0wt%的丙烯与乙烯的共聚物,其中:i)乙烯衍生单元的含量包括在1.0wt%和8.0wt%之间;(ii)熔融温度范围为135℃至155℃;(iii)熔体流动速率(230℃/5kg,ISO 1133)为0.2g/10min至3.5g/10min;(iv)25℃的二甲苯可溶物的范围为10.0wt%至4.0wt%;(v)多分散性PI的范围为3.0至7.0;B)1.0wt%至10.0wt%的丙烯‑乙烯共聚物,含有8.0wt%至20.0wt%的乙烯;所述共聚物具有包括在0.5g/10min和5.0g/10min之间的MFR(在190℃下在2.16kg负荷下测量),其中所得的聚烯烃组合物具有的熔体流动速率为0.2g/10min至4.0g/10min(230℃/5kg,ISO 1133);A+B的和为100。
Description
技术领域
本发明涉及一种包含丙烯-乙烯共聚物和多相丙烯-乙烯共聚物的组合物,其特别适用于生产尤其适合于在低温下使用的压力管道。
发明背景
丙烯-乙烯共聚物在本领域中已知用于生产管道。
例如,根据国际专利申请WO 97/33117,可以获得用具有高抗蠕变性、长期高耐压性、改善的刚度和针对快速裂纹扩展的刚性和抵抗性的聚丙烯塑料材料制成的管道。根据所述文献,当管道由多层不同的聚丙烯塑料材料制成时,避免了聚丙烯塑料管道的突发故障,其中至少一层由提供高抗蠕变性的宽分子量分布(MWD)聚丙烯组成,以及至少一层由改善冲击强度的弹性体改性的聚丙烯组成。所述宽MWD聚丙烯是具有1-10wt%的乙烯或高级α-烯烃重复单元的极高分子量丙烯无规共聚物及具有低(高达1wt%)或零共聚单体的低分子量丙烯聚合物的混合物。
特别是当需要小直径管道时,重要的是具有有限的管道壁厚度。这允许获得包含较少材料的管道,以及由于较高的内径首先是要改进管道在进料方面的效率。然而,当壁厚变小时,管道可能变脆,因此需要使用具有高抗冲击性的材料,尤其是在低温下。
申请人发现可以向丙烯-乙烯共聚物中加入少量具有某些特征的多相共聚物以改善用于小直径管道的冲击性能。
发明内容
因此,本发明的目的是聚烯烃组合物,其包含:
A)90.0wt%至99.0wt%的丙烯与乙烯的共聚物,其中:
i)乙烯衍生单元的含量包括在1.0wt%和8.0wt%之间;
(ii)熔融温度范围为135℃至155℃;
(iii)熔体流动速率为0.2g/10min至3.5g/10min(230℃/5kg,ISO1133);
(iv)25℃的二甲苯可溶物的范围为10.0wt%至4.0wt%;
(v)多分散性P1的范围为3.0至7.0;
B)1.0wt%至10.0wt%的丙烯-乙烯共聚物含有8.0wt%至20.0wt%的乙烯衍生单元;所述共聚物具有包括在0.5g/10min和5.0g/10min之间的MFR(在190℃下在2.16kg负荷下测量);
其中所得的聚烯烃组合物具有熔体流动速率为0.2g/10min至4.0g/10min(ISO1133(230℃,5kg)。
A+B的和为100。
具体实施方式
因此,本发明的目的是聚烯烃组合物,其包括:
A)90.0wt%至99.0wt%,优选92.0wt%至98.0wt%,更优选94.0wt%至97.0wt%,甚至更优选94.5wt%至97.5wt%的丙烯与乙烯的共聚物,其中:
i)乙烯衍生单元的含量包括在1.0wt%和8.0wt%,优选2.0wt%至6.0wt%,更优选3.0wt%至5.0wt%之间。
(ii)熔融温度范围为135℃至155℃;优选137℃至148℃;
(iii)熔体流动速率(230℃/5kg,ISO 1133)为0.2g/10min至3.5g/10min,优选0.6g/10min至2.0g/10min;
(iv)25℃的二甲苯可溶物的范围为10.0wt%至4.0wt%;优选9.0wt%至6.0wt%;
(v)多分散性P1的范围为3.0至7.0;优选为3.5至6.0,更优选为4.0至5.5;
B)MFR(在190℃下在2.16kg负荷下测量)在1.0wt%至10.0wt%,优选2.0wt%至8.0wt%;更优选3.0wt%至6.0wt%,甚至更优选2.5wt%至5.5wt%的丙烯-乙烯共聚物含有8.0wt%至20.0wt%,优选11wt%至19wt%,更优选13wt%至18wt%的乙烯衍生单元;所述共聚物具有包括在0.5g/10min和5.0g/10min,优选0.8g/10min至3.0g/10min之间;
其中所得的聚烯烃组合物具有的熔体流动速率(ISO 1133(230℃,5kg)为0.2g/10min至4.0g/10min,优选0.4g/10min至3.0g/10min,更优选0.5g/10min至2g/10min。A+B的和为100。
术语共聚物是指含有两种单体、丙烯和另一共聚单体,优选为乙烯的聚合物。
组分B)具有一个或多个以下特征:
i)断裂拉伸强度(ASTM D638)高于4MPa;
ii)断裂伸长率(ASTM D638)高于1500%,优选高于2000%;
iii)弯曲模量(ASTM D 790)为5MPa至30MPa,优选6MPa至17MPa,甚至更优选8MPa至19MPa。
iv)肖氏A硬度(ASTM 2240)为40至90,优选50至80,甚至更优选55至75。
对于本发明的聚烯烃组合物,可以获得管道,特别是适合即使在压力下使用的具有特别小的壁厚的小直径管道。
因此,本发明的另一个目的是包括本发明的组合物的管道。
本文所使用的术语“管道”还包括例如热水管道系统通常需要的管道配件、阀门和所有部件。还包括在此定义范围内的是单层和多层管道,其中例如一个或多个层是金属层并且可以包括粘合剂层。
这种制品可以通过本领域公知的各种工业方法制造,例如模制、挤出等。
在本发明的另一个实施例中,本发明的组合物还包含相对于所述组合物的100重量份计0.5至60重量份的无机填充剂。这种填充剂的典型实例是碳酸钙、硫酸钡、生物氧化钛和滑石。滑石和碳酸钙是优选的。许多填充剂也可以具有成核效果,例如也是成核剂的滑石。成核剂的量相对于聚合物量通常是0.2wt%至5wt%。
本发明的组合物还适于提供具有除了具有光滑内表面和外表面外的任何构造的壁的管道。实例是具有夹层状管壁的管道、具有纵向延伸的空腔的中空壁构造的管道、具有螺旋空腔的中空壁构造的管道、具有光滑内表面和紧凑或中空、螺旋形或环形肋状的外表面的管道,不取决于相应管端的构造。
根据本发明的制品、压力管道和相关配件而以本身已知的方式,例如,(共)挤出或模制而制造。
可以使用不同类型的用于聚烯烃的挤出机,例如单或双螺杆挤出机来挤出制品。
本发明的另一个实施例是其中将所述组合物模制成所述制品的方法。
当管道是多层时,至少一层由上述三元共聚物制成。另外的层优选是由R-CH=CH2烯烃的无定形或结晶聚合物(例如均聚物和共聚物或三元共聚物)制成,其中R是氢原子或C1-C6烷基。特别优选的是以下聚合物:
全同立构或主要是全同立构丙烯均聚物;
丙烯与乙烯和/或C4-C8α-烯烃的无规共聚物和三元共聚物,诸如1-丁烯、1-己烯、1-辛烯、4-甲基-1-戊烯,其中总的聚单体含量范围是0.05wt%至20wt%,或所述聚合物与全同立构或主要全同立构丙烯均聚物的混合物;
多相聚合物共混物包含(a)丙烯均聚物和/或第(2)项的共聚物和三元共聚物之一,并且弹性部分(b)包含具有丙烯和/或C4-C8α-烯烃的乙烯的共聚物和三元聚物,任选地包含少量的二烯烃,与针对聚合物(2)(a)所公开的相同;和
无定形聚合物,例如氟化聚合物、聚偏二氟乙烯(PVDF)。
在多层管道中,管道的层可以具有相同或不同的厚度。
本发明的组合物可以通过共混组分A)和B)来制备。
A)的聚合可以在齐格勒-纳塔催化剂的存在下进行。所述催化剂的主要组分是固体催化剂组分,其包含具有至少一个钛-卤键的钛化合物和电子给体化合物,二者以活性形式负载在卤化镁上。另一种主要组分(助催化剂)是有机铝化合物,例如烷基铝化合物。
任选地加入外给体。
通常用于本发明方法的催化剂能够产生具有在环境温度下大于90%,优选大于95%的二甲苯不溶性值的聚丙烯。
具有上述特征的催化剂在专利文献中是总所周知的;尤其有利的是美国专利4,399,054和欧洲专利45977中记载的催化剂。可以在美国专利4,472,524中找到其它实例。
用于所述催化剂中的固体催化剂组分包含选自由醚、酮、内酯、含有N、P和/或S原子以及单羧酸和二羧酸组成的群组的化合物作为电子给体(内部给体)。
特别合适的电子给体化合物是下式的邻苯二甲酸和1,3-二醚的酯:
其中RI和RII相同或不同,并且为C1-C18烷基、C3-C18环烷基或C7-C18烷芳基;RIII和RIV相同或不同,并且为C1-C4烷基;或是其中2位碳原子属于由5、6或7个碳原子或5-n或6-n'碳原子组成的环状或多环结构的1,3-二醚,并且n个氮原子和n'个杂原子分别选自由N、O、S和Si组成的群组,其中n为1或2、n'为1、2或3,所述结构含有两个或三个不饱和度(环多烯结构),并任选与其它环状结构缩合,或被一个或多个选自由以下组成的群组的取代基所取代:直链或支链烷基、环烷基、芳基、芳烷基、烷芳基和卤素,或者与其它环状结构缩合并且被一个或多个也可以与缩合的环状结构键合的上述取代基所取代;一个或多个上述烷基、环烷基、芳基、芳烷基或烷芳基以及缩合的环状结构任选地含有一个或多个杂原子作为碳或氢原子或二者的取代基。
这种类型的醚在公开的欧洲专利申请361493和728769中有记载。
所述二醚的代表性实例是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。
其它合适的电子给体化合物是邻苯二甲酸酯,例如邻苯二甲酸二异丁酯、二辛酯、二苯酯和苄基丁酯。
上述催化剂组分的制备根据各种方法进行。
例如,MgCl2·nROH加合物(特别是以球形颗粒形式存在),其中n通常为1至3,并且ROH为乙醇、丁醇或异丁醇,该MgCl2nROH加合物与过量的包含电子给体化合物的TiCl4反应。反应温度通常为80℃至120℃。然后分离固体,并在存在或不存在电子给体化合物的情况下再次与TiCl4反应,之后将其分离并用等分的烃洗涤,直到所有氯离子消失为止。
在固体催化剂组分中,表示为Ti的钛化合物通常以0.5wt%至10wt%的量存在。保持固定在固体催化剂组分上的电子给体化合物的量通常相对于二卤化镁为5摩尔%至20摩尔%。
可用于制备固体催化剂组分的钛化合物是钛的卤化物和卤化醇化物。四氯化钛是优选的化合物。
上述反应导致以活性形式存在的卤化镁的形成。其它反应在文献中是已知的,其导致以活性形式存在的卤化镁的形成,由除卤化物之外的镁化合物(诸如羧酸镁)开始。
用作助催化剂的Al-烷基铝化合物包括三烷基铝,诸如三乙基铝、三异丁基铝、三正丁基铝以及含有通过O或N原子或SO4或SO3基团彼此键合的两个或多个Al原子的直链或环状烷基铝化合物。
烷基铝化合物通常以Al/Ti比为1至1000的量使用。
可用作外给电子体的电子给体化合物包括芳族酸酯,诸如烷基苯甲酸酯,并且特别是含有至少一个Si-OR键的硅化合物,其中R是烃基。
硅化合物的实例是(叔丁基)2Si(OCH3)2、(环己基)(甲基)Si(OCH3)2、(环戊基)2Si(OCH3)2和(苯基)2Si(OCH3)2以及(1,1,2-三甲基丙基)Si(OCH3)3。
也可以有利地使用具有上述式的1,3-二醚。如果内部供体是这些二醚的其中之一,则可以省略外部供体。
特别地,即使先前所述的催化剂组分的许多其它组合可允许获得根据本发明的组合物,然而优选通过使用含有邻苯二甲酸酯作为内部给体和(环戊基)2Si(OCH3)2作为外部供体,或所述1,3-二醚作为内部供体来制备组分A)。
可用于制备本发明的丙烯聚合物的另一种齐格勒-纳塔催化剂是一种固体催化剂组分,其包含卤化镁、如上所述的具有至少一个Ti-卤素键的钛化合物和至少两种电子给体化合物,一种选自琥珀酸酯,而另一种选自1,3-二醚。
组分A)用EP申请1012195中所述的聚合方法制备。
详细地说,所述方法包括在反应条件下在催化剂存在下将单体进料至所述聚合区并从所述聚合区收集聚合物产物。在所述方法中,生长的聚合物颗粒在快速流化条件下向上流过所述聚合区(上升管)中的一个(第一),离开所述上升管并进入另一个(第二)聚合区(下降管),生成的聚合物颗粒通过它们以致密化形式在重力的作用下向下流动,离开所述下降管并再进入上升管中,从而在上升管和下降管之间建立聚合物的循环。
在下降管中,达到了接近聚合物的堆积密度的高固体密度值。因此可以沿着流动方向获得压力的正增大,使得可以在不借助特殊的机械装置的情况下将聚合物再次引入到上升管中。由此建立了“回路”循环,其通过在两个聚合区域之间的压力平衡和通过被引入到系统中的压头损失进行限定。
通常,上升管中的快速流化的条件通过将包含相关单体的气体混合物进料至所述上升管而建立。优选的是通过在合适的地方使用气体分配器装置,将气体混合物在聚合物的再引入点处下方进料至所述上升管中。输送气体进入上升管的速度高于操作条件下的输送速度,优选为2-15m/s。
通常,离开上升管的聚合物和气体混合物被传送到固体/气体分离区。固体/气体分离可以通过使用常规的分离装置来实现。聚合物从分离区进入下降管。如果合适,添加补充单体和/或分子量调节剂,离开分离区的气体混合物被压缩、冷却并输送到上升管。可以通过用于气体混合物的再循环管线来实现输送。
可以通过使用适于控制固体流的装置(例如机械阀)来计量离开下降管的聚合物的量而控制在两个聚合区之间循环的聚合物。
在烯烃聚合方法中常用的操作参数,例如温度,例如在50℃至120℃之间。
该第一阶段方法可以在0.5至10MPa,优选1.5至6MPa之间的操作压力下进行。
有利的是,聚合区内维持一种或多种这种量的惰性气体以使惰性气体的分压总和优选为气体总压的5%至80%。例如,惰性气体可以是氮气或丙烷。
在所述上升管的任何点处将各种催化剂向上进料至上升管。然而,也可以在下降管的任何点处进料。催化剂可以处于任何物理状态,因此可以使用固体或液体状态的催化剂。
可以通过使用上述催化剂系统或通过使用基于催化剂系统的茂金属来制备组分B)。可以通过使用气相聚合方法、淤浆聚合方法或溶液聚合方法来获得组分B)。
给出以下实施例以举例说明而并非限制本发明。
实施例
表征方法
熔融温度和结晶温度:通过差示扫描量热法(DSC)测量。
加重6±1mg,以20℃/min的速率加热至220±1℃,并在氮气流中在220±1℃下保持2分钟,其后以20℃/min的速率冷却至40±2℃,从而在该温度下保持2分钟以使样品结晶。然后,以20℃/min的升温速率再次将样品熔融至220℃±1。记录熔化扫描,获得热谱图,由此读取熔融温度和结晶温度。
熔体流动速率:根据ISO 1133方法(230℃,5kg)测定。
二甲苯中的溶解度:按如下测定。
将2.5g聚合物和250ml二甲苯引入装配有冰箱和磁力搅拌器的玻璃烧瓶中。将温度在30分钟内提升到溶剂的沸点。将如此获得的透明溶液保持回流,并进一步搅拌30分钟。然后将封闭的烧瓶在冰和水浴中保持30分钟,并在25℃的恒温水浴中保持30分钟。在快速滤纸上过滤如此形成的固体。100ml的滤液倾注于预先称重的铝容器,其在氮气流中在加热板上进行加热,以通过蒸发除去溶剂。然后将容器在真空下保持在80℃的烘箱中直至获得恒重。然后计算在室温下可溶于二甲苯的聚合物的重量百分比。
通过FT-IR光谱法测定乙烯含量(C2含量)。根据ASTM D5576-00(2013)制备压膜的样品。
聚合物的压膜的光谱记录在吸光度相对波数(cm-1)中。以下测量用于计算C2含量:
a)4482和3950cm-1之间的组合吸收带的面积(At)用于膜厚度的光谱分析标准化。
b)在等规聚丙烯(IPP)参考光谱的合适的数字减法之后由于亚甲基序列(CH2摇摆振动)产生的吸收带的面积(AC2)。范围660至790cm-1。
屈服伸长率:根据ISO 527测量。
断裂伸长率:根据ISO 527测量。
断裂应力:根据ISO 527测量。
冲击试验:ISO 180
用于机械分析的样品
除了已经使用ISO 3167的弯曲模量之外,根据ISO 1873-2:2007获得样品。
弯曲模量
根据ISO 178测定。
拉伸模量
根据ISO 527测定。
多分散指数(PI):通过使用由RHEOMETRICS(USA)出售的RMS-800型平行板流变仪在200℃的温度下测定,在从0.1r/s增加至100r/s的振荡频率下操作。可以通过以下等式从交叉模量得到P.I.:
P.I.=105/Gc
其中Gc是交叉模量,其定义为G’=G”时的值(以Pa表示),其中G’是储能模量,G”是损耗模量。
对于组分B),已在表2中报道了所用的方法。
组分A)
组分A是由LyondellBasell出售的商业无规丙烯-乙烯共聚物。已在表1中报道了共聚物的性质:
表1
组分B)
组分B)是市售的丙烯-乙烯弹性体。所述共聚物的特性报道在表2中。
表2
丙烯含量 | wt% | 84 |
乙烯含量 | wt% | 16 |
MFR(190℃,2.16Kg) | g/10’ | 1.4 |
断裂拉伸强度(ASTM D 638) | MPa | >6.9 |
断裂伸长率(ASTM D 638) | % | >2000 |
肖氏A硬度(ASTM D 2240) | - | 66 |
弯曲模量(ASTM D790) | MPa | 12.3 |
*C2=乙烯衍生单元
组分A和B已以各种百分比共混在一起,已经分析了所得共混物。已在表3中报道了结果:
表3
*剩余量是组分A
C1是单独的组分A
从表3清楚地得出所得共混物的冲击性能得到高度改进,而其它性能基本上保持相同。
Claims (7)
1.一种聚烯烃组合物,其包括:
A)90.0wt%至99.0wt%的丙烯与乙烯的共聚物,其中:
i)乙烯衍生单元的含量包括在1.0wt%和8.0wt%之间;
(ii)熔融温度范围为135℃至155℃;
(iii)熔体流动速率为0.2g/10min至3.5g/10min(230℃/5kg,ISO1133);
(iv)25℃的二甲苯可溶物的范围为10.0wt%至4.0wt%;
(v)多分散性P1的范围为3.0至7.0;
B)1.0wt%至10.0wt%的丙烯-乙烯共聚物,其含有8.0wt%至20.0wt%的乙烯衍生单元;所述共聚物具有包括在0.5g/10min和5.0g/10min之间的MFR(在190℃下在2.16kg负荷下测量),
其中所得的聚烯烃组合物具有的熔体流动速率为0.2g/10min至4.0g/10min(230℃/5kg,ISO 1133);A+B的和为100。
2.根据权利要求1所述的聚烯烃组合物,其中组分A)中所述乙烯衍生单元的含量的范围为2.0wt%至8.0wt%。
3.根据权利要求1-2中任一项所述的聚烯烃组合物,其中在组分B)中,所述乙烯衍生单元的含量的范围为11wt%至19wt%。
4.根据权利要求1-3中任一项所述的聚烯烃组合物,其中所述熔体流动速率(MFR)(ISO1133230℃,5kg)的范围为0.4g/10min至3.0g/10min;
5.包含根据权利要求1至4所述的聚烯烃组合物的管道系统和片材。
6.根据权利要求5所述的压力管道系统。
7.单层或多层管材和片材,其中至少一层包括根据权利要求1所述的聚烯烃组合物。
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CN110546199A (zh) * | 2017-05-04 | 2019-12-06 | 巴塞尔聚烯烃意大利有限公司 | 丙烯基聚合物组合物 |
CN111492005A (zh) * | 2017-12-22 | 2020-08-04 | Sabic环球技术有限责任公司 | 用于非加压管道的聚丙烯组合物 |
CN111836855A (zh) * | 2018-03-14 | 2020-10-27 | 住友化学株式会社 | 多相丙烯聚合材料 |
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WO2023198642A1 (en) | 2022-04-12 | 2023-10-19 | Basell Poliolefine Italia S.R.L. | Propylene-based copolymer composition |
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CN110546199B (zh) * | 2017-05-04 | 2020-11-06 | 巴塞尔聚烯烃意大利有限公司 | 丙烯基聚合物组合物 |
CN111492005A (zh) * | 2017-12-22 | 2020-08-04 | Sabic环球技术有限责任公司 | 用于非加压管道的聚丙烯组合物 |
CN111836855A (zh) * | 2018-03-14 | 2020-10-27 | 住友化学株式会社 | 多相丙烯聚合材料 |
CN111836855B (zh) * | 2018-03-14 | 2023-09-22 | 住友化学株式会社 | 多相丙烯聚合材料 |
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EP3172278B1 (en) | 2018-07-18 |
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BR112017000729B1 (pt) | 2021-08-31 |
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