CN1906022A - 冷却剂管道 - Google Patents
冷却剂管道 Download PDFInfo
- Publication number
- CN1906022A CN1906022A CNA2005800014639A CN200580001463A CN1906022A CN 1906022 A CN1906022 A CN 1906022A CN A2005800014639 A CNA2005800014639 A CN A2005800014639A CN 200580001463 A CN200580001463 A CN 200580001463A CN 1906022 A CN1906022 A CN 1906022A
- Authority
- CN
- China
- Prior art keywords
- layer
- ooling channel
- weight
- internal layer
- polypropylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 239000004760 aramid Substances 0.000 claims description 5
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- 229910052615 phyllosilicate Inorganic materials 0.000 description 7
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- 238000002360 preparation method Methods 0.000 description 6
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
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- 239000000654 additive Substances 0.000 description 3
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
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- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
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- 239000012809 cooling fluid Substances 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
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- 238000006460 hydrolysis reaction Methods 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- MRERMGPPCLQIPD-NBVRZTHBSA-N (3beta,5alpha,9alpha,22E,24R)-3,5,9-Trihydroxy-23-methylergosta-7,22-dien-6-one Chemical compound C1C(O)CCC2(C)C(CCC3(C(C(C)/C=C(\C)C(C)C(C)C)CCC33)C)(O)C3=CC(=O)C21O MRERMGPPCLQIPD-NBVRZTHBSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- JHXVRRJXCDAINK-UHFFFAOYSA-N NC(=O)N.N#CC#N Chemical compound NC(=O)N.N#CC#N JHXVRRJXCDAINK-UHFFFAOYSA-N 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
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- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- LTHCSWBWNVGEFE-UHFFFAOYSA-N octanamide Chemical compound CCCCCCCC(N)=O LTHCSWBWNVGEFE-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006396 polyamide 1012 Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 150000003504 terephthalic acids Chemical class 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
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/18—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side
- B32B3/20—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side of hollow pieces, e.g. tubes; of pieces with channels or cavities
-
- 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
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
- Y10T428/1317—Multilayer [continuous layer]
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Abstract
本发明涉及一种冷却剂管道,其含下列的层:I.由聚酰胺模塑组合物制成的外层,和II.内层,其含聚丙烯以及至少0.02重量%的热稳定剂,该冷却剂管道具有高的耐热老化性和高的脆裂强度。
Description
本发明涉及一种多层冷却剂管道,其包含由聚酰胺模塑组合物制成的外层和由经稳定化的聚烯烃模塑组合物制成的内层。
近年来在汽车的冷却剂管道领域对水/乙二醇内接触以及管道系统的高运行温度方面的长期稳定性提出越来越高的要求。在高于约100℃的高温下所需的优良机械性能包括所需的脆裂强度是通过聚酰胺提供的。纯聚烯烃管道在这种高温范围中的脆裂强度不足;其耐油脂性也是有限的。
但是由聚酰胺制成的单层管道没有足够的耐水解性;由于在冷却液中的膨胀行为也使其机械强度下降。
为此,在现有技术中已知一种具有聚烯烃内层和聚酰胺外层的多层冷却剂管道。内层起防水层作用,并防止聚酰胺外层受到水解分解。
特别是由于提高的功率密度而越来越高的发动机温度或发动机腔的温度,要求特别是具有下列特性的管道:
·在130℃以上的温度下的高脆裂强度;
·甚至在热老化后的足够的冷冲击韧性,可在约130℃以上通过水/乙二醇循环泵试验超过至少1000小时或通过在高温如150℃下的热存放来证实;
·甚至在长期负荷后的足够的层粘附性;
·使用已知的共挤出工艺进行低成本制备。
EP-A-0436923描述了一种由聚烯烃内层和聚酰胺外层制成的部分呈波纹状的多层冷却剂管道,需要时经粘附剂层相互粘结。
EP-A-1362890描述了一种具有至少一层软的TPE内层与基于聚酰胺的外层相组合的多层受压流体管道。
EP-A-0671582描述了一种由多层制成的冷却液管道,它具有经纵向肋改性的波纹形以减少纵向膨胀。
DE-A-4428236描述了一种具有由改性的热塑性弹性体制成的内层的三层波纹管作为冷却水软管。
WO 01/42005描述了一种具有弹性体内层和聚酰胺外层的冷却液管道。
WO 01/42701描述了一种冷却液管道,其具有作为粘附剂的由聚酰胺和聚丙烯的混合物制成的层、TPE内层和外聚酰胺层。
DE-A-3715251描述了一种具有薄的聚烯烃内层的双层管。
但所述文献未表明如何达到耐高温、在所述运行温度下的脆裂强度和长期的机械强度(特别是冲击韧性)的方法。
这类管的弱点是聚烯烃内层。已表明,正是聚丙烯在所述运行温度下会较快脆化。一个原因可能是在冷却系统中溶解的氧或通过聚合物层由外向内扩散的氧;存在的痕量金属也会在这方面起作用。当为实现足够的防水层以保护外置的聚酰胺层而使聚烯烃内层较厚以减弱聚酰胺外层时,该问题更为明显。已表明,为此聚烯烃层的层厚应为至少约0.3mm,但优选至少0.4mm。
内层脆化的结果常是形成微裂纹,并且冷却液经微裂纹到达聚酰胺外层。然后发生的水解导致脆裂强度明显下降,并最后导致管失效。
因此,本发明的目的是避免这些缺点,并提供具有更长期稳定性的冷却剂管道。
该目的是通过含下列各层的冷却剂管道实现的:
I.由聚酰胺模塑组合物制成的外层,和
II.内层,其含聚丙烯以及至少0.02重量%,优选至少0.1重量%,特别优选至少0.2重量%,尤其优选至少0.3重量%,更特别优选至少0.4重量%的热稳定剂。
在一种可能的实施方案中,内层的材料是经粘附改性的,如通过加入酸酐基改性。合适的方法是现有技术,并且可市购相应的产品。内层的材料也可作为未改性的聚丙烯型与改性的聚丙烯型的混合形式存在。
在第二种可能的实施方案中,内层由两层组成,其中邻接聚酰胺层的一层经粘附改性,并且其中另一层不需经粘附改性。除所述粘附改性外,还可使用不同的聚丙烯模塑组合物作为层材料。
在另一种可能的实施方案中,在层I和II之间存在具有其它组成的粘附层。为此由现有技术已知例如聚酰胺/聚丙烯混合物,其中至少部分聚丙烯成分是经粘附改性的。
作为聚酰胺可首先考虑脂族均缩聚物和共缩聚物,例如PA 46、PA66、PA 68、PA 610、PA 612、PA 410、PA 810、PA 1010、PA 412、PA1012、PA 1212、PA 6、PA 7、PA8、PA 9、PA 10、PA 11和PA 12。(这些聚酰胺的标号相应于国际标准,前面的数表示原始二胺的C原子数,后面的数表示二羧酸的C原子数。如果仅一个数,则意指以α,ω-氨基羧酸或从其衍生的内酰胺作为原料;此外还可参考H.Domininghaus,Die Kunststoffe und ihre Eigenschaften,第272页以下,VDI-Verlag,1976)。
使用PA 612是优选的,因为该聚酰胺一方面在高使用温度下有高的脆裂强度,另一方面在湿的气氛中具有足够的尺寸稳定性。
如果使用共聚酰胺,其可含例如己二酸、癸二酸、辛二酸、间苯二酸、对苯二酸、萘-2,6-二羧酸等作为共酸以及二(4-氨基环己基)甲烷、三甲基六亚甲基二胺、1,6-己二胺或类似物作为共二胺。内酰胺如己内酰胺或月桂内酰胺和氨基羧酸如ω-氨基十一酸也可作为共成分加入。
这些聚酰胺的制备是已知的(如D.B.Lacobs,J.Zimmermann,Polymerization Processes,第424-467页,Interscience Publishers,Newyork,1977;DE-AS 2152194)。
此外,混合的脂族/芳族缩聚物也可适合作为聚酰胺,如其描述于例如US-PSS 2071250、2071251、2130523、2130948、2241322、2312966、2512606和3392210以及Kirk-Othmer,Encyclopedia of ChemicalTechnology,3.Aufl.,Vol.18,第328页以下和第435页以下,Wiley&Sons,1982。
所述聚酰胺模塑组合物可含这些聚酰胺中的一种或含多种作为混合物。此外,可含达50重量%的其它热塑性塑料(只要这些塑料不干扰粘合性),特别是增加冲击韧性的橡胶如乙烯/丙烯共聚物或乙烯/丙烯/二烯共聚物、聚烯烃(EP-0731308A)、聚戊烯、聚辛烯、由链烯基芳族化合物与脂族烯烃或二烯组成的无规或嵌段结构的共聚物(EP-A-0261748)或具有由玻璃化温度Tg<-10℃的(甲基)丙烯酸酯橡胶、丁二烯橡胶或苯乙烯/丁二烯橡胶组成的粘弹性芯的芯/壳橡胶,其中该芯可以是交联的,而壳可由苯乙烯和/或甲基丙烯酸甲酯和/或其它不饱和单体构成(DE-OSS 2144528、3728685)。
聚酰胺优选具有过量的氨端基,这一过量通常是由于在制备时作为分子量调节剂使用了二胺。氨端基的过量也可通过贫氨基的聚酰胺和富氨基的聚酰胺的混合来调节。氨端基与羧端基之比应至少为51∶49,优选至少55∶45,特别优选至少60∶40,尤其优选70∶30。
此外,所述聚酰胺模塑组合物还可含少量为调节某些特性所需的添加剂。其实例是颜料或填料如炭黑、二氧化钛、硫化锌、硅酸盐或碳酸盐;加工助剂如蜡、硬脂酸锌或硬脂酸钙;防火剂如氢氧化镁、氢氧化铝或氰脲酸密胺;玻璃纤维;抗氧化剂、UV稳定剂以及赋予产物抗静电特性或导电特性的添加剂如碳纤维、石墨原纤维、由不锈钢或导电炭黑制成的纤维。
在一具体实施方案中,该模塑组合物含1-25重量%增塑剂,特别优选2-20重量%,尤其优选3-15量重%。
在聚酰胺中的增塑剂和其使用是已知的。适用于聚酰胺的增塑剂的概述可参阅Gchter/Müller,Kunststoffadditive,C.Hanser Verlag,第二版,第296页。
适合作为增塑剂的通常的化合物是例如在醇组分中具有2-20个C原子的对羟基苯甲酸的酯或在胺组分中具有2-12个C原子的芳基磺酸的酰胺。
作为增塑剂可使用对羟基苯甲酸乙酯、对羟基苯甲酸辛酯、对羟基苯甲酸异十六酯、甲苯磺酸正辛酰胺、苯磺酸正丁酰胺或苯磺酸-2-乙基己酰胺。
内层的聚丙烯模塑组合物基本上可含各种市售的聚丙烯型物,例如全同立构的或间同立构的均聚丙烯、丙烯和乙烯和/或丁烯-1的无规共聚物、乙烯-丙烯嵌段共聚物、基于聚丙烯的热塑性弹性体和类似物。聚丙烯可按各种现有技术制备,例如按Ziegler-Natta法或借助于金属茂催化剂制备。还可含冲击韧性成分如EPM橡胶或EPDM橡胶或SEBS。此外,也可含通常的助剂和添加剂,例如颜料或填料如炭黑、二氧化钛、硫酸锌、硅酸盐或碳酸盐或加工助剂如蜡、硬脂酸锌或硬脂酸钙。在模塑组合物中聚丙烯的通常含量例如是至少50重量%,至少60重量%,至少70重量%,至少80重量%或至少90重量%。
在一个优选实施方案中,最内层中所用的聚丙烯的熔体流动速率(MFR)按ISO 1133(230℃/2.16kg)为0.1-3g/10min,特别优选为0.15-2g/10min,更特别优选为0.18-1.5g/10min,尤其是0.2-1g/10min。这类管具有特别高的耐老化性。
在另一个优选实施方案中,最内层的聚丙烯是所谓的丙烯-乙烯嵌段共聚物,常也称为非均相共聚物。这类非均相共聚物例如可在两相工艺中制备,该工艺大致如下进行:首先例如用Ziegler-Natta催化剂制备高全同立构的聚丙烯,有时也可存在少量乙烯,从而产生无规聚合物。这种材料作为非均相共聚物的基质起作用。在第二反应步骤(视需要在另一反应器中)中,视需要可加入第二催化剂例如金属茂催化剂。这时发生乙烯和丙烯的共聚合反应,该聚合仅应在第一聚合物的空腔中发生。由此在那里引入第二聚合物。
在一个优选实施方案中,该嵌段共聚物或非均相共聚物含有至少0.5重量%,至少0.6重量%,至少0.7重量%,至少0.8重量%或至少0.9重量%,以及最大20重量%,最大15重量%,最大12重量%,最大10重量%或最大8重量%的呈共聚合形式的乙烯。此外还可含达15重量%的呈共聚合形式的1-丁烯。
在一个优选实施方案中,内层的模塑组合物或内次层之一的模塑组合物可含0.1-50重量%,优选0.5-40重量%,特别优选1-30重量%的纳米级填料。该填料例如是改性形层状硅酸盐。其纵横比(横向尺寸和层厚之比)通常至少为20,优选至少30,特别优选至少50,层厚为0.5-50nm,优选1-35nm,特别优选1-20nm。由亲有机物化的层状硅酸盐和聚合物制成的聚合物纳米复合物首次描述于US-PS 2531396中。层状硅酸盐的亲有机物化例如也可由US-PSS 2531472、2996506、4105578、4412018、4434075、4434076、4450095和4874728已知。关于层状硅酸盐的概述可参阅Lehrbuch der Anorganischen Chemie,Arnold F.Holleman,Niels Wiberg,91.-100.Auflage,Verlag Walter deGruyter,Berlin-New York,1985,第764-786页。
有机改性的层状硅酸盐由各公司提供,例如Süedchemie AG(商品名:Nanofil),Southern Clay Products(商品名:Cloisite),Rheox GmbH(商品名:Bentone),Laporte(商品名:Laponite),COOP Chemical(商品名:Somasif)和TOP(商品名:Planomer)。
特别合适的纳米级填料是层状硅酸盐中的蒙脱石、锂蒙脱石、滑石以及合成的层状硅酸盐。
所述的热稳定剂例如是位阻酚或硫化合物,如硫代丙酸的二烷基酯或硫代二亚乙基二酯。这类化合物是市售的;当然也可使用不同的热稳定剂的混合物。
此外,内层的聚丙烯模塑组合物或内次层之一、优选最内层的聚丙烯模塑组合物可含金属去活化剂,例如含量至少为0.01重量%,0.03重量%,0.06重量%,0.1重量%或0.15重量%,其中可使用常用于聚烯烃的各种金属去活化剂;例如可用酰肼。
例如金属去活化剂即受阻酚和硫代增效剂的组合是有利的。
聚丙烯内层II优选的厚度为至少0.3mm,特别优选至少0.4mm。管的总壁厚优选为0.8-2.5mm,特别优选0.9-2mm,尤其是1-1.5mm;管的外径优选8-50mm,特别优选10-40mm,尤其是12-30mm。
本发明的冷却剂管道可呈平滑形或波纹形或仅在部分段呈波纹形。该管道可以一步或多步通过注塑、共挤压、顺序共挤压、共挤压吹塑或包层法制备。此外,该管道还可用所谓的Conex法制备。这是一种共挤压法,其中各层用特定的挤压机(锥形转子和定子)相互叠置(WO 97/28949)。
此外,本发明的冷却剂管道也可借助于用于制备多层空心体的特殊注塑法来制备。这里的实例是由夹层注塑(制备含表层/芯体结构的多层注塑模制件)和接着的流体注入(气体注入或水注入)的组合来制备在这种注塑部件中的用于液体输送的空心通道。
一些改进的方法原理上也是基于半壳工艺,即通过热塑法加工多层的膜半成品/板半成品,并将该半体熔接成具有用于液体输送的空腔的模制件。
在一个优选的实施方案中,该波纹管具有平滑的内层。外层呈波纹状(需要时还含粘附剂层),并在波谷中与内层粘合。其优点是流阻低、壁厚均匀和特别是与通常的波纹管相比无局部的过度拉伸变形;此外,由此避免其中可形成淀积的皱折。这种管描述于WO 03/064910和WO 03/064911中。
本发明的冷却剂管道依其聚酰胺外层材料不同可短时耐受如在发动机附近出现的达150℃的峰荷,并且具有高的耐热老化性和优良的脆裂强度。由于该按权利要求的聚烯烃内层,该管道也可在达约135℃的温度下耐受作为冷却液体用的乙二醇-水混合物。
本发明以下列实施例阐明。
在实施例中应用下列模塑组合物:
外层(层I):
聚酰胺1:热稳定的PA12
聚酰胺2:热稳定的PA612
内层(层II):
聚丙烯1:基于丙烯的非均相共聚物,乙烯含量为4.1重量%(以13C-NMR测定),按ISO 1133的MFR 230/2.16为2cm3/10min。
聚丙烯2:基于丙烯的非均相共聚物,乙烯含量为2.4重量%(以13C-NMR测定),按ISO 1133的MFR 230/2.16为0.4cm3/10min。
聚丙烯3:由99.2重量%的聚丙烯2和下列化合物组成的混合物:
0.2重量%IRGANOXMD 1024,一种基于酚的金属去活化剂,
0.2重量%IRGANOX1010,一种基于受阻酚的热稳定剂
0.4重量%IRGANOXPS802FL,一种基于硫的热稳定剂。
粘附剂:ADMERQB520E,一种以马来酸酐官能化的聚丙烯。
实施例1-5:
在装备有两个45mm的挤压机和三个30mm的挤压机的5层装置中以挤出速度约为12m/min制备尺寸为8×1mm的管。
实施例 | 外层=层I | 粘附剂 | 层IIa | 层IIb | 层IIc |
1 | 0.45mm聚酰胺1 | 0.1mm | 0.15mm聚丙烯3 | 0.15mm聚丙烯3 | 0.15mm聚丙烯3 |
2 | 0.45mm聚酰胺2 | 0.1mm | 0.15mm聚丙烯3 | 0.15mm聚丙烯3 | 0.15mm聚丙烯3 |
3*) | 0.45mm聚酰胺1 | 0.1mm | 0.15mm聚丙烯1 | 0.15mm聚丙烯1 | 0.15mm聚丙烯1 |
4*) | 0.45mm聚酰胺1 | 0.1mm | 0.15mm聚丙烯2 | 0.15mm聚丙烯2 | 0.15mm聚丙烯2 |
5 | 0.70mm聚酰胺1 | 0,1mm | 0.05mm聚丙烯3 | 0.05mm聚丙烯3 | 0.10mm聚丙烯3 |
*)非本发明
由于聚丙烯的高粘度,在此情况下的内层用3个挤压机制备。
管的特性:
在实施例1-5的管中,在粘附剂内层或聚丙烯内层与聚酰胺层之间的粘附不仅在新挤压时而且在存放后(在130℃下与乙二醇/水内接触1300小时)均是如此高,以致该复合体有时不可能被分离,但总是达超过3N/mm的高值。
在应用非本发明的内层聚丙烯(实施例3和4)时,经内接触存放后的冲击韧性比本发明的实施例1和2的要差。
对实施例5,由于其较薄的内层而不能与其余实施例直接比较,但其内接触存放后的冲击韧性与本发的实施例1和2相比是降低了。
Claims (13)
1.一种冷却剂管道,其含下列的层:
I.由聚酰胺模塑组合物制成的外层,和
II.内层,其含聚丙烯以及至少0.02重量%的热稳定剂。
2.权利要求1的冷却剂管道,其特征在于,所述层I和层II通过粘附剂层互相粘结。
3.权利要求1的冷却剂管道,其特征在于,所述内层的材料是经粘附改性的。
4.权利要求1的冷却剂管道,其特征在于,所述内层由两个次层组成,其中邻接聚酰胺层的一层是经粘附改性的。
5.上述权利要求之一的冷却剂管道,其特征在于,所述热稳定剂是位阻酚或硫化合物。
6.上述权利要求之一的冷却剂管道,其特征在于,所述内层或内次层之一的模塑组合物含0.1-50重量%的纳米级填料。
7.上述权利要求之一的冷却剂管道,其特征在于,所述内层或内次层之一的模塑组合物含金属去活化剂。
8.上述权利要求之一的冷却剂管道,其特征在于,所述层II的聚丙烯的按ISO 1133(230℃/2.16)的熔体流动速率(MFR)为0.1-3g/min。
9.上述权利要求之一的冷却剂管道,其特征在于,所述层II的聚丙烯是丙烯和己烯的非均相共聚物。
10.权利要求9的冷却剂管道,其特征在于,所述非均相共聚物含至少0.5重量%和最大20重量%的呈共聚合物形式的乙烯。
11.上述权利要求之一的冷却剂管道,其特征在于,所述层II的厚度为至少0.3mm。
12.上述权利要求之一的冷却剂管道,其特征在于,该管道部分段或全部呈波纹形。
13.权利要求12的冷却剂管道,其特征在于,该管道构型为具有光滑内层的波纹管。
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- 2005-07-21 US US10/580,194 patent/US7939151B2/en active Active
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Publication number | Priority date | Publication date | Assignee | Title |
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CN102686926A (zh) * | 2010-10-08 | 2012-09-19 | 东海橡塑工业株式会社 | 制冷剂输送用软管 |
CN102686926B (zh) * | 2010-10-08 | 2014-09-03 | 东海橡塑工业株式会社 | 制冷剂输送用软管 |
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BRPI0513764B1 (pt) | 2016-02-10 |
CN102582134A (zh) | 2012-07-18 |
WO2006010736A1 (de) | 2006-02-02 |
KR20070033446A (ko) | 2007-03-26 |
KR100886582B1 (ko) | 2009-03-05 |
RU2403486C2 (ru) | 2010-11-10 |
RU2007106492A (ru) | 2008-09-10 |
JP4909267B2 (ja) | 2012-04-04 |
US20070148388A1 (en) | 2007-06-28 |
EP1771298B1 (de) | 2017-04-05 |
JP2008507436A (ja) | 2008-03-13 |
DE102004036179A1 (de) | 2006-03-23 |
US7939151B2 (en) | 2011-05-10 |
EP1771298A1 (de) | 2007-04-11 |
BRPI0513764A (pt) | 2008-05-20 |
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