CN1231528C - 聚烯烃涂覆钢管 - Google Patents
聚烯烃涂覆钢管 Download PDFInfo
- Publication number
- CN1231528C CN1231528C CNB028142802A CN02814280A CN1231528C CN 1231528 C CN1231528 C CN 1231528C CN B028142802 A CNB028142802 A CN B028142802A CN 02814280 A CN02814280 A CN 02814280A CN 1231528 C CN1231528 C CN 1231528C
- Authority
- CN
- China
- Prior art keywords
- steel pipe
- polyolefin
- coating
- beta
- propylene copolymer
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 97
- 239000010959 steel Substances 0.000 title claims abstract description 97
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 79
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000000576 coating method Methods 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 73
- 229920001577 copolymer Polymers 0.000 claims abstract description 64
- 238000012360 testing method Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000004033 plastic Substances 0.000 claims abstract description 18
- 229920003023 plastic Polymers 0.000 claims abstract description 18
- 239000010779 crude oil Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- -1 organoaluminum Substances 0.000 claims description 46
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 19
- 229920001400 block copolymer Polymers 0.000 claims description 16
- 238000005482 strain hardening Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000012530 fluid Substances 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000035939 shock Effects 0.000 claims description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 6
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical group C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000003862 amino acid derivatives Chemical class 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 229940059260 amidate Drugs 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 238000009434 installation Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 47
- 229920001155 polypropylene Polymers 0.000 description 29
- 239000010410 layer Substances 0.000 description 22
- 238000009826 distribution Methods 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000012937 correction Methods 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 8
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- 235000013539 calcium stearate Nutrition 0.000 description 5
- 239000008116 calcium stearate Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
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- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
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- 239000011347 resin Substances 0.000 description 3
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical class O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 229920004449 Halon® Polymers 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- USYJXNNLQOTDLW-UHFFFAOYSA-L calcium;heptanedioate Chemical compound [Ca+2].[O-]C(=O)CCCCCC([O-])=O USYJXNNLQOTDLW-UHFFFAOYSA-L 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000012489 doughnuts Nutrition 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000009931 pascalization Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- BVXGBMBOZMRULW-UHFFFAOYSA-N 1-n,4-n-dicyclohexylbenzene-1,4-dicarboxamide Chemical compound C=1C=C(C(=O)NC2CCCCC2)C=CC=1C(=O)NC1CCCCC1 BVXGBMBOZMRULW-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- FPRSHRPBZCFRSF-UHFFFAOYSA-N 4-(cyclohexanecarbonylamino)-n-cyclohexylbenzamide Chemical compound C1CCCCC1C(=O)NC(C=C1)=CC=C1C(=O)NC1CCCCC1 FPRSHRPBZCFRSF-UHFFFAOYSA-N 0.000 description 1
- WJAWKGBMJMSKII-UHFFFAOYSA-N 4-n-cyclopentylbenzene-1,4-dicarboxamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)NC1CCCC1 WJAWKGBMJMSKII-UHFFFAOYSA-N 0.000 description 1
- KSLLMGLKCVSKFF-UHFFFAOYSA-N 5,12-dihydroquinolino[2,3-b]acridine-6,7,13,14-tetrone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C(=O)C(C(=O)C1=CC=CC=C1N1)=C1C2=O KSLLMGLKCVSKFF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SHVDIDLPIMYGTL-UHFFFAOYSA-N C(=O)N.C(=O)N.C1(CCCC1)C1=CC=C(C=C1)C1=CC=CC=C1 Chemical compound C(=O)N.C(=O)N.C1(CCCC1)C1=CC=C(C=C1)C1=CC=CC=C1 SHVDIDLPIMYGTL-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- JILYTPDQRCHWPA-UHFFFAOYSA-L calcium;octanedioate Chemical compound [Ca+2].[O-]C(=O)CCCCCCC([O-])=O JILYTPDQRCHWPA-UHFFFAOYSA-L 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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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
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/06—Protection of pipes or objects of similar shape against external or internal damage or wear against wear
-
- 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
- F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
- F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
- F16L58/04—Coatings characterised by the materials used
- F16L58/10—Coatings characterised by the materials used by rubber or plastics
- F16L58/1054—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe
- F16L58/109—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe the coating being an extruded layer
-
- 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
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Abstract
本发明公开了在安装操作过程中和在使用中钢管涂层具有高动态破裂韧性的聚烯烃涂覆钢,它由钢管芯、任选地中间发泡塑料材料、和β-成核化丙烯共聚物的聚烯烃涂层组成,其中由该β-成核化丙烯共聚物制成的试验聚烯烃管具有临界压力>25巴和动态破裂韧性>3.5MNm-3/2。该聚烯烃涂覆钢管适用于原油或气态产品的离岸运输或分区供暖。
Description
本发明的领域
本发明涉及由钢管芯、任选地中间发泡、填充或实心塑料材料、和聚烯烃涂层组成的在安装操作过程中和在使用中钢管涂层具有高动态破裂韧性的聚烯烃涂覆钢管,以及一种用于生产它们的方法。
本发明的背景
具有由线性低密度聚乙烯(JP 08,300,561)、丙烯聚合物和α-烯烃共聚物弹性体(JP 2000,44,909)或间同立构聚丙烯(JP 08,300,562)的共混物组成的聚烯烃涂层的聚烯烃涂覆钢管是已知的。这些聚烯烃钢涂层的缺点是由该涂覆材料制成的试验管的动态破裂韧性不足。高动态破裂韧性是涂覆钢管所需的,这样避免涂层在安装操作过程中和在使用中开裂。
本文所用的术语安装操作是指任何安装技术如现成管道的盘绕和伸展,焊接和其它连接技术和在海底用特殊设计船的离岸安装所进行的,最常见在数百米深度,以及在存在岩石冲击等危险的无常海底条件下的安装。涂覆钢管尤其是用于离岸场合的安装操作包括用于保护涂层的苛刻条件,包括在低和高温条件下以及在高静水压下的高应力,显著伸长率,表面损害,缺口,冲击事件等。涂层不仅是保护管道原样不受所述损害的层,而且它在高应力和/或高温和高压的阶段也起同样的作用,使得涂层对开裂最敏感,尤其与盘绕和伸展过程中所导致的应力相比。在涂覆管道的使用寿命期中,涂层必须保护管道在接近0℃,高静水压的条件下不受损害以及诱导应力和裂缝形成的影响,其中涂层中的小的损害或缺口可扩大成大的裂缝,使管道本身处于危险中。如果涂料具有高动态破裂韧性,该材料在安装操作过程中和在使用中将不会开裂。
本发明的目的
本发明的目的是提供在安装操作过程中和在使用中钢管涂层具有高动态破裂韧性的聚烯烃涂覆钢管。
本发明的简要描述
根据本发明,该目的通过在安装操作过程中和在使用中钢管涂层具有动态破裂韧性的,由钢管芯、任选地中间发泡塑料材料、和聚烯烃涂层组成的聚烯烃涂覆钢管而实现,其中聚烯烃涂层由在230℃/2.16kg下具有镕体指数0.1-8g/10min的90.0-99.9wt%丙烯和0.1-10.0wt%具有2或4-18个碳原子的α-烯烃的β-成核化丙烯共聚物组成,这样由该β-成核化丙烯共聚物制成的试验聚烯烃管在流体静力学小规模稳定态(流体静力学S4)试验中在3℃下具有临界压力>25巴和动态破裂韧性>3.5MNm-3/2。
本发明的详细描述
本文所用的术语安装操作是指任何安装技术如盘绕,伸展,焊接和其它连接技术。
β-成核化丙烯聚合物是由31螺旋构象的链组成的全同立构丙烯聚合物,所述螺旋构象具有由平行堆叠层的径向阵列组成的β-形式球粒的内微观结构。该微结构可通过加入β-成核剂至熔体中并随后结晶而实现。β-形式的存在可通过使用大角度X-射线衍射(Moore,J.,Polypropylene Hand-book,p.134-135,Hanser Publishers Munich1996)而检测。
根据有利的实施方案,聚烯烃涂层的β-成核化丙烯共聚物是具有IRτ≥0.97的β-成核化丙烯嵌段共聚物。更优选,β-成核化丙烯嵌段共聚物具有IRτ≥0.98,在+23℃下的拉伸模量≥1100MPa和使用切口试验试样在-20℃下的Charpy冲击强度≥6kJ/m2。β-成核化丙烯嵌段共聚物甚至更优选地具有IRτ≥0.985。IRτ是对异立构规整度的一种度量,在IRτ上0.005的差异包括在机械聚合物性能、尤其在刚度上的显著增加。
测定和计算丙烯聚合物的IRτ,例如描述于EP 0 277 514 A2第5页(栏7,行53-栏8,行11)。
用作根据本发明的钢管涂层的丙烯共聚物具有熔体指数0.1-8g/10min(在230℃/2.16kg下),优选0.2-5g/10min(在230℃/2.16kg下)。
根据进一步优选的实施方案,β-成核化聚丙烯嵌段共聚物具有拉伸模量优选≥1300MPa和最优选≥1500MPa(在+23℃下)。
使用切口试验试样时,β-成核化丙烯共聚物的Charpy冲击强度是≥6kJ/m2(在-20℃下),优选≥9kJ/m2(在-20℃下),最优选≥10kJ/m2(在-20℃下)。使用切口试验试样时最高至少60kJ/m2的Charpy冲击强度对共聚物是可能的。
试验压力管在流体静力学小规模稳定态(S4)试验中由临界压力计算的动态破裂韧性是在安装操作过程中和在使用中钢管的聚烯烃涂层具有高动态破裂韧性的钢管聚烯烃涂料所用的一个重要的安全参数。
确定动态破裂韧性的方法公开于Plastics,Rubber andComposites Processing and Applications,Vol.26,No.9,pp.387往下。
动态破裂韧性KD直接由流体静力学S4试验临界压力pc(在3℃下)根据以下等式计算:
KD=pc(πD/7)1/2·(D*-2),
其中pc是临界压力,D是试验管的直径,D*是D/t,t是试验管的壁厚度。
普通钢涂料的用于临界压力[巴]和动态破裂韧性[MNm-3/2]的比较值是约7.44/巴1.5MNm-3/2(对于丙烯-乙烯无规共聚物)。这些材料不适用作在盘绕、伸展、安装操作过程中和在使用中钢管涂层具有高破裂韧性的聚烯烃涂覆材料。对于丙烯-乙烯无规共聚物,动态破裂韧性不足以用于钢管涂层场合。
根据进一步的实施方案,丙烯均聚物嵌段的IRτ≥0.98的聚烯烃涂层的β-成核化丙烯嵌段共聚物是通过使用Ziegler-Natta催化剂体系的聚合反应而得到的丙烯共聚物,所述催化剂体系包括含钛的固体组分,有机铝(organoalumina),镁或钛化合物作为催化剂和下式的外给体
RxR′ySi(MeO)4-x-y,
其中R和R’是相同的或不同的、支化或环脂族或芳族烃残基,且y和x相互独立地是0或1,前提是x+y是1或2。
用于生产钢管聚烯烃涂层的β-成核化丙烯嵌段共聚物的Ziegler-Natta催化剂体系中的优选外给体是二环戊基二甲氧基硅烷。
根据有利的实施方案,聚烯烃涂层的β-成核化丙烯共聚物包含0.0001-2.0wt%的下列物质(基于所用的丙烯共聚物计)作为β-成核剂:
-来自C5-C8-环烷基单胺或C6-C12-芳族单胺和C5-C8-脂族、C5-C8-环脂族或C6-C12-芳族二羧酸的二羧酸衍生物型二酰胺化合物,和/或
-来自C5-C8-环烷基单羧酸或C6-C12-芳族单羧酸和C5-C8-环脂族或C6-C12-芳族二胺的二胺衍生物型二酰胺化合物,和/或
-来自C5-C8-烷基-、C5-C8-环烷基-或C6-C12-芳基氨基酸、C5-C8-烷基-、C5-C8-环烷基-或C6-C12-芳族单酰氯和C5-C8-烷基-、C5-C8-环烷基-或C6-C12-芳族单胺的酰胺化反应的氨基酸衍生物型二酰胺化合物,和/或
-喹吖啶酮化合物型的喹吖啶酮衍生物化合物,喹吖啶酮醌化合物,和/或二氢喹吖啶酮型化合物,和/或
-来自周期表的IIa族的金属的二羧酸盐和/或二羧酸和来自周期表的IIa族的金属的混合物,和/或
-来自周期表的IIa族的金属和下式亚氨基酸的盐
其中x=1-4;R=H,-COOH,C-C12-烷基,C5-C8-环烷基或C6-C12-芳基,Y=C1-C12-烷基,C5-C8-环烷基或C6-C12-芳基取代的二价C6-C12-芳族残基。
任选地包含在钢管聚烯烃涂层的β-成核化丙烯共聚物中的来自C5-C8-环烷基单胺或C6-C12-芳族单胺和C5-C8-脂族、C5-C8-环脂族或C6-C12-芳族二羧酸的二羧酸衍生物型二酰胺化合物的例子是:
-N,N′-二-C5-C8-环烷基-2,6-萘二甲酰胺化合物如
N,N′-二环己基-2,6-萘二甲酰胺和
N,N′-二环辛基-2,6-萘二甲酰胺,
-N,N′-二-C5-C8-环烷基-4,4-联苯二甲酰胺化合物如
N,N′-二环己基-4,4-联苯二甲酰胺和
N,N′-二环戊基-4,4-联苯二甲酰胺,
-N,N′-二-C5-C8-环烷基-对苯二甲酰胺化合物如
N,N′-二环己基对苯二甲酰胺和
N,N′-二环戊基对苯二甲酰胺,
-N,N′-二-C5-C8-环烷基-1,4-环己烷二甲酰胺化合物如
N,N′-二环己基-1,4-环己烷二甲酰胺和
N,N′-二环己基-1,4-环戊烷二甲酰胺。
任选地包含在钢管聚烯烃涂层的β-成核化丙烯共聚物中的来自的来自C5-C8-环烷基单羧酸或C6-C12-芳族单羧酸和C5-C8-环脂族或C6-C12-芳族二胺的二胺衍生物型二酰胺化合物的例子是
-N,N′-C6-C12-亚芳基-二-苯甲酰胺化合物如
N,N′-对亚苯基-二-苯甲酰胺和
N,N′-1,5-萘-二-苯甲酰胺,
-N,N′-C5-C8-环烷基-二-苯甲酰胺化合物如
N,N′-1,4-环戊烷-二-苯甲酰胺和
N,N′-1,4-环己烷-二-苯甲酰胺。
-N,N′-对C6-C12-亚芳基-二-C5-C8-环烷基甲酰胺化合物如
N,N′-1,5-萘-二-环己烷甲酰胺和
N,N′-1,4-亚苯基-二-环己烷甲酰胺。
-N,N′-C5-C8-环烷基-二-环己烷甲酰胺化合物如
N,N′-1,4-环戊烷-二-环己烷甲酰胺和
N,N′-1,4-环己烷-二-环己烷甲酰胺。
任选地包含在钢管聚烯烃涂层的β-成核化丙烯共聚物中的氨基酸衍生物型二酰胺化合物的例子是N-苯基-5-(N-苯甲酰基氨基)-戊烷酰胺和/或N-环己基-4-(N-环己基羰基氨基)-苯甲酰胺。
任选地包含在钢管聚烯烃涂层的β-成核化丙烯共聚物中的喹吖啶酮型化合物的例子是喹吖啶酮,二甲基喹吖啶酮和/或二甲氧基喹吖啶酮。
任选地包含在钢管聚烯烃涂层的β-成核化丙烯共聚物中的喹吖啶酮醌型化合物的例子是喹吖啶酮醌,如公开于EP-B 0 177 961的5,12-二氢(2,3b)吖啶-7,14-二酮与喹(2,3b)吖啶-6,7,13,14-(5H,12H)-四酮的一种混合晶体和/或二甲氧基喹吖啶酮醌。
任选地包含在钢管聚烯烃涂层的β-成核化丙烯共聚物中的二氢喹吖啶酮型化合物的例子是二氢喹吖啶酮,二甲氧基二氢喹吖啶酮和/或二苯并二氢喹吖啶酮。
任选地包含在钢管聚烯烃涂层的β-成核化丙烯共聚物中的周期表的IIa族的金属的二羧酸盐的例子是庚二酸钙盐和/或辛二酸钙盐。
任选地包含在钢管聚烯烃涂层的β-成核化丙烯共聚物中的周期表的IIa族的金属和下式亚氨基酸
的盐的例子是邻苯二甲酰甘氨酸、六氢邻苯二甲酰甘氨酸、N-邻苯二甲酰丙氨酸和/或N-4-甲基邻苯二甲酰甘氨酸的钙盐。
根据本发明的有利的特点,任选地***钢管和聚烯烃涂层之间的中间发泡塑料材料是一种具有应***化性质和熔体指数1.5-10g/10min(在230℃/2.16kg下)的发泡丙烯共聚物。
任选地***钢管和聚烯烃涂层之间,具有应***化性质的中间发泡塑料材料的丙烯共聚物可通过任何工艺,如通过将丙烯共聚物用热分解基团形成剂处理和/或通过用离子化辐射处理而制成,其中这两种处理可任选地伴随或继以使用双-或多官能不饱和单体,如丁二烯,异戊二烯,二甲基丁二烯或二乙烯基苯进行的处理。其它工艺可适用于生产具有应***化性质的丙烯共聚物,前提是所得丙烯共聚物满足应***化性质的特性。
任选地***钢管和聚烯烃涂层之间,具有应***化性质的中间发泡塑料材料的所述丙烯共聚物的例子是,尤其是:
通过聚丙烯与二马来酰亚氨基化合物在熔体中反应而改性的聚丙烯(EP-A-0 574 801;EP-A-0 574 804),
通过将聚丙烯用离子化辐射在固体相中处理而改性的聚丙烯(EP-A-0 190 889;EP-A-0 634 454),
通过将聚丙烯用过氧化物在固体相(EP-A-0-384 431)或在熔体(EP-A-0-142724)中处理而改性的聚丙烯,
通过将聚丙烯用多官能烯属不饱和单体在离子化辐射作用下处理而改性的聚丙烯(EP-A-0 678 527)
通过将聚丙烯用多官能烯属不饱和单体在存在过氧化物的情况下在熔体中处理而改性的聚丙烯(EP-A-0 688 817;EP-A-0 450 342)
本文所用的应***化性质根据图1和2定义。
图1给出了用于确定应***化的实验步骤的示意图。
聚合物的应***化性质通过Rheotens装置1(Gttfert的产品,Siemensstr.2,74711 Buchen,德国)而分析,其中熔体束2通过在规定的加速度下向下拉伸而延长。记录取决于下拉速度v的牵引力F。
Rheotens装置1与用于熔体束2的连续加料的挤出机/熔体泵3结合。挤塑温度是200℃;使用具有直径2mm和长度6mm的毛细管模头并且熔体束2下拉的加速度是120mm/sec2。
图1中的示意图以一种示例性方式说明牵引力F的测量增加(即″熔体强度″)对下拉速度v的增加(即″可拉伸性″)。
图2给出了有和没有应***化性质的聚合物样品的Rheotens测量记录曲线。在束破裂时的最大点(Fmax;Vmax)是该熔体的强度和可拉伸性的特性。
具有熔体指数0.3,2.0和3.0g/10min(在230℃/2.16kg下)的普通丙烯聚合物4,5,6具有非常低的熔体强度和低可拉伸性。它们没有应***化和因此在加工成挤塑泡沫材料时成问题。改性丙烯聚合物7(图中的样品的熔体指数是2-3g/10min,在230℃/2.16kg下)或未改性普通LDPE 8(图中的样品的熔体指数是0.7g/10min,在190℃/2.16kg下)具有完全不同的可拉伸性对熔体强度性质。随着增加下拉速度v,牵引力F增加至明显较高水平,与未改性普通丙烯聚合物4,5,6相比。曲线形状是应***化的特性。
本文所用的″具有应***化性质的丙烯共聚物″具有牵引力Fmax>15cN的增加的熔体强度和Vmax>150mm/s的增加的可拉伸性速度。
根据本发明进一步优选的实施方案,由β-成核化丙烯共聚物制成的试验聚烯烃管在流体静力学小规模稳定态(流体静力学S4)试验中在3℃下具有临界压力>30巴和动态破裂韧性>6.0MNm-3/2。
本发明进一步的主题是一种用于生产在安装操作过程中和在使用中钢管涂层具有高动态破裂韧性的聚烯烃涂覆钢管的方法,所述管由钢管芯、任选地中间发泡塑料材料、和通过涂层挤出机/旋转钢管技术、环模管涂布技术或注塑技术制成的聚烯烃涂层组成,特征在于聚烯烃涂层由在230℃/2.16kg下具有熔体指数0.1-8g/10min的90.0-99.9%重量丙烯和0.1-10.0%重量具有2或4-18个碳原子的α-烯烃的β-成核化丙烯共聚物组成,这样由该β-成核化丙烯共聚物制成的试验聚烯烃管在流体静力学小规模稳定态(流体静力学S4)试验中在3℃下具有临界压力>25巴和动态破裂韧性>3.5MNm-3/2。
用于钢管涂层的本发明丙烯嵌段共聚物可包含常规的辅助材料,如0.01-2.5wt%稳定剂和/或0.01-1wt%加工助剂,和/或0.1-1wt%抗静电剂和/或0.2-3wt%颜料,在每种情况下基于所用的丙烯共聚物计。
作为稳定剂,优选0.01-0.6wt%酚类抗氧化剂、0.01-0.6wt%3-芳基苯并呋喃酮、0.01-0.6wt%基于亚磷酸酯的加工稳定剂、0.01-0.6wt%基于二硫化物和硫醚的高温稳定剂和/或0.01-0.8wt%空间位阻胺(HALS)的混合物是合适的。
为获得钢管芯、任选地中间发泡塑料材料、或聚烯烃涂层之间的良好的层间粘附性,有利地使用环氧树脂涂覆的钢管和将相容层应用于环氧树脂涂覆钢管和聚烯烃层之间,由此,相容层由具有化学键接的烯属不饱和碳酸和/或碳酸酐,尤其丙烯酸,甲基丙烯酸和/或马来酸酐的丙烯共聚物或丙烯聚合物接枝共聚物组成。
用于熔化丙烯共聚物的常规挤出机适合本发明工艺。
如果通过涂层挤出机/旋转钢管技术生产聚烯烃涂覆钢管,将任选地涂有环氧树脂的预加热钢管在接连旋转下通过具有用于未发泡聚烯烃覆盖层以及相容剂和发泡塑料材料的任选的层的平膜模头的独立涂布挤出机熔体涂覆。
如果通过十字头模头管涂布技术生产聚烯烃涂覆钢管,优选使用通过挤出机加料的十字头用于未发泡聚烯烃外覆盖层和任选地用于相容剂和发泡塑料材料。钢管优选涂有环氧树脂层和在环氧树脂层上的相容层。优选钢管被预热至温度170-230℃,且在聚烯烃钢管涂装线中向十字头的环形模头加料的挤出机具有175-250℃的温度分布。任选的发泡熔体首先到达管上,随后是β-成核化丙烯共聚物的未发泡外层,随后涂覆管在校准套管中校准和冷却。优选的是钢管直径50-500mm。
用于生产聚烯烃涂覆钢管的注塑技术在安装接头处使用。安装接头涂布机器由两部分组成。注塑机使β-成核化丙烯共聚物在具有接头区的挤出机中熔化并随后将其注入受模具锁定部件控制的模具中。在该第二部分中,β-成核化丙烯共聚物通过油或水冷却至固态。挤出机的优选的温度分布是200-250℃且接头区是230-240℃。优选的模具温度是80-100℃。
如果任选地将中间发泡塑料材料施用到钢管上,使用优选的聚烯烃混合物,其中包含基于聚烯烃混合物1-12wt%的能分解出气体的化学发泡剂,或烃,卤化烃和/或气体作为发泡剂,这样钢管被预热至温度170-230℃且泡沫材料涂层挤出机具有温度分布175-250℃。
放出气体的合适的化学发泡剂的例于是碳酸氢钠,偶氮二甲酰胺和/或氰尿酸三酰肼。作为发泡剂的合适的烃是容易挥发性烃,如戊烷,异戊烷,丙烷和/或异丁烷。合适的卤化烃的例子是单氟三氯甲烷和/或二氟单氯甲烷。作为发泡剂的合适的气体是氮,氩和/或二氧化碳。
根据本发明的一个特征,在用于生产聚烯烃涂覆钢管的环模头管涂布技术中使用锥挤出机,这样成核化丙烯共聚物在环模头处的熔体温度是195-240℃且预加热钢管的温度是160-200℃。
聚烯烃涂覆钢管的优选应用是原油或气体产品的离岸运输或区域供暖应用。
如果作为聚烯烃涂覆钢管用于原油从海底至油船的离岸运输,其中发泡层的泡沫密度是600-800kg/m3的具有中间发泡丙烯共聚物材料的涂覆钢管是优选的。为了能够抽吸来自冷海区域中的沉积物的原油,该流体必须保持足够温暖。通过利用具有中间发泡丙烯共聚物基绝缘层的本发明涂覆钢管,可以避免过多地热损失至周围水,而且消除沿管线的昂贵的油加热装置。在水深度200-300m处,压力是相当可观的,因此需要高机械稳定性的发泡绝缘层。具有应***化性质的丙烯共聚物的泡沫塑料层具有突出的绝热效率和压缩强度之间的平衡。
实施例
以下试验使用根据ISO 1873制成的注塑试验试样进行
拉伸模量根据ISO 527(十字头速度1mm/min),在+23℃下进行
Charpy冲击强度使用切口试验试样根据ISO 179/1eA进行
快速裂缝传播试验根据ISO 13477在流体静力学条件下进行
动态破裂韧性根据Plastics,Rubber and Composites Processingand Applications,Vol.26,No.9,pp.387 ff进行。
压缩强度根据ASTM D 695-96,5%压缩进行
实施例1
1.1β-成核化丙烯共聚物的制备
以下物质的混合物在具有温度分布100/145/185/210/220/225/225/225/220/200/185℃的双螺杆挤出机中熔化,匀化,出料和造粒:
90wt%通过结合的本体和气相聚合反应使用具有二环戊基二甲氧基硅烷作为外给体的Ziegler-Natta催化剂体系而得到的,具有乙烯含量8.3wt%,丙烯均聚物嵌段的IRτ为0.985和在230℃/2.16kg下的熔体指数为0.30g/10min的丙烯嵌段共聚物,
10wt%母料,包含99重量份具有乙烯含量8.3%重量,丙烯均聚物嵌段的IRτ为0.985和在230℃/2.16kg下的熔体指数为0.30g/10min的丙烯嵌段共聚物,和1重量份庚二酸钙盐,以及0.1wt%硬脂酸钙,0.1wt%四[亚甲基(3,5-二-叔丁基羟基氢肉桂酸酯)]甲烷和0.1wt%亚磷酸三-(2,4-二-叔丁基苯基)酯,基于所用丙烯聚合物的总和计。
所得丙烯共聚物具有熔体指数0.32g/10min(在230℃/2.16kg下),拉伸模量1290MPa和在-20℃下的Charpy冲击强度(使用切口试验试样)39kJ/m2。
1.2丙烯共聚物试验管的制造
为了生产丙烯共聚物试验管,将1.1的β-成核化丙烯共聚物引入单螺杆挤出机(L/D=30,D=70mm,温度分布200/210/220/220/220/220/200℃,40rpm)中,熔化,挤出通过一个具有直径110mm的环形模头,在真空校准套管上取成直径110mm和壁厚度10mm的管,然后在6m水浴中在+20℃下冷却,其中取出速度是0.3m/min。
快速裂缝传播试验显示出临界压力31巴和动态破裂韧性19.60MNm-3/2。
1.3聚烯烃涂覆钢管的制造
试验性钢管涂装线由预加热单元,具有两个挤出机的十字头,真空校准套管,冷却单元和切割单元组成。
为了生产中间发泡塑料层,将包含以下物质的丙烯聚合物化合物与基于丙烯化合物计的2.2wt%的基于碳酸氢盐和柠檬酸的发泡剂的混合物干混并利用计量体系供给至具有螺杆直径90mm,L/D 35和温度分布200/230/240/230/230/230/230/230/230/230℃的第一单螺杆挤出机的加料漏斗:
-30wt%的用0.12%重量键接的丁二烯(通过IR光谱测定)改性和具有应***化性质,在230℃/2.16kg下的熔体指数0.45g/10min和结晶焓91J/g的丙烯均聚物,
-70wt%的具有乙烯含量8.3%重量,丙烯均聚物嵌段的IRτ为0.974,和在230℃/2.16kg下的熔体指数为0.30g/10min的丙烯嵌段共聚物,和0.1wt%硬脂酸钙,0.1wt%四[亚甲基(3,5-二-叔丁基羟基氢肉桂酸酯)]甲烷和0.1wt%亚磷酸三-(2,4-二-叔丁基苯基)酯,基于所用的丙烯聚合物的总和计。
起初,将混合物熔化和匀化和随后将分解的发泡气体在挤出机中增强混合并均匀分布。然后,熔体通过熔体泵转移到具有模头温度205℃的环形十字头上。
所述十字头通过一个具有螺杆直径60mm,L/D 35和温度分布200/230/240/220/220/220/220/220/220/220℃的第二单螺杆挤出机用1.1.的β-成核化丙烯共聚物加料。
涂有25μm环氧树脂层和马来酸酐接枝丙烯聚合物(0.20wt%马来酸酐)的30μm相容层,被预热至温度190℃的十字头钢管(Φ150mm)的内部在速度1.2m/min下驱动向前。十字头设计使得所形成的熔体首先加入到涂覆钢管上,随后是用于外层的未发泡丙烯聚合物的熔体,就在管进入被+20℃水冷却的真空校准套管之前。
将长度254mm的聚烯烃涂覆钢管试验试样机械切削。聚烯烃泡沫材料层具有厚度50mm和密度720kg/m3。未发泡覆盖层具有厚度8mm。涂覆钢管试验试样的压缩强度(ASTM D 695-96,5%压缩)是19MPa。
实施例2
2.1β-成核化丙烯共聚物的制备
将以下物质的混合物在具有温度分布100/145/190/215/225/230/230/215/205/190℃的双螺杆挤出机中熔化,匀化,出料和造粒:
94wt%通过结合的本体和气相聚合反应使用具有二环戊基二甲氧基硅烷作为外给体的Ziegler-Natta催化剂体系而得到的,具有乙烯含量8.3wt%,丙烯均聚物嵌段的IRτ为0.985,和在230℃/2.16kg下的熔体指数为0.30g/10min的丙烯嵌段共聚物,
6wt%的母料,包含99.8重量份具有乙烯含量8.3wt%,丙烯均聚物嵌段的IRτ为0.985,和在230℃/2.16kg下的熔体指数为0.30g/10min的丙烯嵌段共聚物,和0.2重量份的5,12-二氢(2,3b)吖啶-7,14-二酮与喹(2,3b)吖啶-6,7,13,14-(5H,12H)-四酮的混合晶体,以及0.05wt%硬脂酸钙,0.1wt%四[亚甲基(3,5-二-叔丁基羟基氢肉桂酸酯)]甲烷和0.1wt%亚磷酸三-(2,4-二-叔丁基-苯基)酯,基于所用丙烯聚合物的总和计。
所得聚丙烯聚合物具有在230℃/2.16kg下的熔体指数0.3g/10min,拉伸模量1450MPa和Charpy冲击强度(使用切口试验试样,在-20℃下)21kJ/m2。
2.2丙烯共聚物试验管的制造
为了生产丙烯共聚物试验管,将2.1的β-成核化丙烯共聚物引入单螺杆挤出机(L/D=30,D=70mm,温度分布200/210/225/225/225/225/205℃,40rpm)中,熔化,挤出通过一个具有直径110mm的环形模头,在真空校准套管上取成直径110mm和壁厚度10mm的管,然后在6m水浴中在+20℃下冷却,其中取出速度是0.35m/min。
快速裂缝传播试验显示出临界压力34巴和动态破裂韧性21.5MNm3/2
2.3聚烯烃涂覆钢管的制造
试验性钢管涂装线由预加热单元,具有两个挤出机的十字头,真空校准套管,冷却单元和切割单元组成。
为了生产中间发泡塑料层,将包含以下物质的丙烯聚合物化合物与基于丙烯化合物2.2wt%的基于碳酸氢盐和柠檬酸的发泡剂的混合物干混并利用计量体系供给至具有螺杆直径90mm,L/D 35和温度分布200/230/240/230/230/230/230/230/230/230℃的第一单螺杆挤出机的加料漏斗。
-20wt%具有乙烯量4.3wt%,用0.16%重量键接的二乙烯基苯改性(通过IR光谱测定),和具有应***化性质和在230℃/2.16kg下的熔体指数0.48g/10min的聚丙烯共聚物,
-80wt%的具有乙烯含量8.3wt%,丙烯嵌段的IRτ为0.974,和在230℃/2.16kg下的熔体指数为0.30g/10min的丙烯嵌段共聚物,以及基于所用丙烯聚合物的总和的0.1wt%硬脂酸钙,0.1wt%四[亚甲基(3,5-二-叔丁基羟基氢肉桂酸酯)]甲烷和0.1wt%亚磷酸三-(2,4-二-叔丁基苯基)酯。
起始,将混合物熔化和匀化和随后将分解的发泡气体在挤出机中增强混合并均匀分布。然后,熔体通过熔体泵转移到具有模头温度205℃的环形十字头上。
所述十字头通过一个具有螺杆直径60mm,L/D 35和温度分布200/230/240/220/220/220/220/220/220/220℃的第二单螺杆挤出机用2.1的β-成核化丙烯共聚物加料。
涂有25μm环氧树脂层和马来酸酐接枝丙烯聚合物(0.20wt%马来酸酐)的30μm相容层,被预热至温度190℃的十字头钢管(Φ150mm)的内部在速度1.2m/min下驱动向前。十字头设计使得所形成的熔体首先加入到涂覆钢管上,随后是用于外层的未发泡丙烯聚合物的熔体,就在管进入被+20℃水冷却的真空校准套管之前。
将长度254mm的聚烯烃涂覆钢管试验试样机械切削。聚烯烃泡沫材料层具有厚度55mm和密度700kg/m3。未发泡覆盖层具有厚度8mm。涂覆钢管试验试样的压缩强度(ASTM D 695-96,5%压缩)是17MPa。
实施例3
3.1β-成核化丙烯共聚物的制备
以下物质的混合物在具有温度分布100/145/185/210/220/225/225/200/185℃的双螺杆挤出机中熔化,匀化,出料和造粒:
75wt%的通过结合的本体和气相聚合反应使用具有二环戊基二甲氧基硅烷作为外给体的Ziegler-Natta催化剂体系而得到的,具有乙烯含量8.3wt%,丙烯均聚物嵌段的IRτ为0.985,和在230℃/2.16kg下的熔体指数为0.30g/10min的丙烯嵌段共聚物,
25wt%的母料,包含99.5重量份具有乙烯含量8.3wt%,丙烯均聚物嵌段的IRτ为0.985,和在230℃/2.16kg下的熔体指数为0.30g/10min的丙烯嵌段共聚物,和0.5重量份六氢邻苯二甲酰甘氨酸钙盐,以及基于所用丙烯共聚物的总和的0.1wt%硬脂酸钙,0.1wt%四[亚甲基(3,5-二-叔丁基羟基氢肉桂酸酯)]甲烷和0.1wt%亚磷酸三-(2,4-二-叔丁基苯基)酯。
所得丙烯共聚物具有熔体指数0.32g/10min(在230℃/2.16kg下),拉伸模量1310MPa和Charpy冲击强度(使用缺口试验试样,在-20℃下)37kJ/m2。
3.2丙烯共聚物试验管的制造
为了生产丙烯共聚物试验管,将3.1的β-成核化丙烯共聚物引入单螺杆挤出机(L/D=30,D=70mm,温度分布200/210/220/220/220/220/200℃,40rpm)中,熔化,挤出通过一个具有直径110mm的环形模头,在真空校准套管上取成直径110mm和壁厚度10mm的管,然后在6m水浴中在+20℃下冷却,其中取出速度是0.3m/min。
快速裂缝传播试验显示出临界压力31巴和动态破裂韧性19.60MNm-3/2。
3.3聚烯烃涂覆钢管的制造
试验性钢管涂装线由预加热单元,具有挤出机的十字头,真空校准套管,冷却单元和切割单元组成。
十字头通过一个具有螺杆直径60mm,L/D 35和温度分布200/230/240/220/220/220/220/220/220/220℃的单螺杆挤出机用3.1的β-成核化丙烯共聚物加料。
涂有25μm环氧树脂层和马来酸酐接枝丙烯聚合物(0.20wt%马来酸酐)的30μm相容层,被预热至温度190℃的十字头钢管(Φ150mm)的内部在速度1.2m/min下驱动向前。十字头设计使得β-成核化丙烯共聚物的熔体刚好在管进入被+20℃水冷却的真空校准套管之前加入到涂覆钢管上。
聚烯烃涂层具有厚度7.5mm。
Claims (11)
1.在安装操作过程中和在使用中钢管涂层具有高动态破裂韧性的聚烯烃涂覆钢管,由钢管芯和聚烯烃涂层组成,特征在于所述聚烯烃涂层由在230℃/2.16kg下熔体指数为0.1-8g/10min的90.0-99.9wt%丙烯和0.1-10.0wt%具有2或4至18个碳原子的α-烯烃的β-成核化丙烯共聚物组成,这样由该β-成核化丙烯共聚物制成的试验聚烯烃管具有根据ISO 13477在流体静力学小规模稳定态试验中在3℃下的临界压力>25巴和动态破裂韧性>3.5MNm-3/2。
2.根据权利要求1的聚烯烃涂覆钢管,其中β-成核化丙烯共聚物是丙烯均聚物嵌段的IRτ≥0.98、23℃时的拉伸模量≥1100MPa和使用切口试验试样在-20℃下的Charpy冲击强度≥6kJ/m2的β-成核化丙烯嵌段共聚物。
3.根据权利要求2的聚烯烃涂覆钢管,其中β-成核化丙烯嵌段共聚物是通过用Ziegler-Natta催化剂体系进行聚合反应而得到的丙烯共聚物,所述催化剂体系包括含钛的固体组分、有机铝、镁或钛化合物作为催化剂和根据下式的外给体
RxR′ySi(MeO)4-x-y,
其中R和R′是相同的或不同的,并且是支化或环脂族或芳族烃残基,并且y和x相互独立地是0或1,前提是x+y是1或2。
4.根据权利要求3的聚烯烃涂覆钢管,其中外给体是二环戊基二甲氧基硅烷。
5.根据权利要求1-4之一的聚烯烃涂覆钢管,其中β-成核化丙烯共聚物包含基于所用的丙烯共聚物计0.0001-2.0wt%的下列物质作为β-成核剂:
-来自C5-C8-环烷基单胺或C6-C12-芳族单胺和C5-C8-脂族、C5-C8-环脂族或C6-C12-芳族二羧酸的二羧酸衍生物型二酰胺化合物,和/或
-来自C5-C8-环烷基单羧酸或C6-C12-芳族单羧酸和C5-C8-环脂族或C6-C12-芳族二胺的二胺衍生物型二酰胺化合物,和/或
-来自C5-C8-烷基-、C5-C8-环烷基-或C6-C12-芳基氨基酸,C5-C8-烷基-、C5-C8-环烷基-或C6-C12-芳族单酰氯和C5-C8-烷基-、C5-C8-环烷基-或C6-C12-芳族单胺的酰胺化反应的氨基酸衍生物型二酰胺化合物,和/或
-喹吖啶酮化合物型、喹吖啶酮醌化合物型和/或二氢喹吖啶酮化合物型的喹吖啶酮衍生物化合物,和/或
-来自周期表IIa族的金属的二羧酸盐和/或
-二羧酸和周期表IIa族的金属的混合物,和/或
-周期表IIa族的金属和下式亚氨基酸的盐
其中x=1-4;R=H、-COOH、C1-C12-烷基、C5-C8-环烷基或C6-C12-芳基,Y=C1-C12-烷基、C5-C8-环烷基或C6-C12-芳基取代的二价C6-C12-芳族残基。
6.根据权利要求1-4之一的聚烯烃涂覆钢管,其中中间发泡塑料材料是具有应***化性质和在230℃/2.16kg下的熔体指数为1.5-10g/10min的发泡丙烯共聚物。
7.根据权利要求1的聚烯烃涂覆钢管,其在钢管芯和聚烯烃涂层之间具有中间发泡塑料材料。
8.一种用于生产在安装操作过程中和在使用中钢管涂层具有高动态破裂韧性的聚烯烃涂覆钢管的方法,所述钢管由钢管芯和通过涂层挤出机/旋转钢管技术、十字头模头管涂布技术或注塑技术制成的聚烯烃涂层组成,特征在于聚烯烃涂层由在230℃/2.16kg下具有熔体指数为0.1-8g/10min的90.0-99.9%重量丙烯和0.1-10.0%重量具有2或4至18个碳原子的α-烯烃的β-成核化丙烯共聚物组成,这样由该β-成核化丙烯共聚物制成的试验聚烯烃管具有根据ISO 13477在流体静力学小规模稳定态试验中在3℃下的临界压力>25巴和动态破裂韧性>3.5MNm-3/2。
9.根据权利要求8的用于生产聚烯烃涂覆钢管的方法,其中在十字模头管涂布技术中使用锥挤出机,这样成核化丙烯共聚物的熔体在十字模头处的湿度是195-240℃且预加热钢管的温度是160-200℃。
10.根据权利要求8的用于生产聚烯烃涂覆钢管的方法,其中所述管在钢管芯和聚烯烃涂层之间具有中间发泡塑料材料。
11.根据权利要求1-5之一的聚烯烃涂覆钢管用于原油或气态产品的离岸运输或分区供暖的应用。
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EP01112369A EP1260547A1 (en) | 2001-05-21 | 2001-05-21 | Polyolefin coated steel pipes |
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-
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BR0209871B1 (pt) | 2011-05-31 |
DE60237283D1 (de) | 2010-09-23 |
RU2279352C2 (ru) | 2006-07-10 |
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BR0209871A (pt) | 2004-07-13 |
ATE477295T1 (de) | 2010-08-15 |
EP1260547A1 (en) | 2002-11-27 |
EP1401936A1 (en) | 2004-03-31 |
EP1401936B1 (en) | 2010-08-11 |
MXPA03010690A (es) | 2005-03-07 |
US20050025922A1 (en) | 2005-02-03 |
WO2002094922A1 (en) | 2002-11-28 |
US8415447B2 (en) | 2013-04-09 |
RU2003136747A (ru) | 2005-05-20 |
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