CN104945724A - Allyl polymer composition as well as preparation method and steel-plastic complex thereof - Google Patents
Allyl polymer composition as well as preparation method and steel-plastic complex thereof Download PDFInfo
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- CN104945724A CN104945724A CN201410114509.9A CN201410114509A CN104945724A CN 104945724 A CN104945724 A CN 104945724A CN 201410114509 A CN201410114509 A CN 201410114509A CN 104945724 A CN104945724 A CN 104945724A
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- propenyl polymer
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- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 229920000642 polymer Polymers 0.000 title claims abstract description 42
- 239000004033 plastic Substances 0.000 title claims abstract description 19
- 229920003023 plastic Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title abstract 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 38
- -1 ethylene butylene Chemical group 0.000 claims description 34
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 33
- 239000003112 inhibitor Substances 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 229910000831 Steel Inorganic materials 0.000 claims description 22
- 239000010959 steel Substances 0.000 claims description 22
- 238000005453 pelletization Methods 0.000 claims description 18
- 238000004132 cross linking Methods 0.000 claims description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NJMGRJLQRLFQQX-HYXAFXHYSA-N 2-isopropylmaleic acid Chemical compound CC(C)C(\C(O)=O)=C\C(O)=O NJMGRJLQRLFQQX-HYXAFXHYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229940097413 isopropyl maleate Drugs 0.000 claims description 2
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 abstract 3
- 230000001070 adhesive effect Effects 0.000 description 31
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 24
- 238000002844 melting Methods 0.000 description 23
- 230000008018 melting Effects 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 12
- 235000019260 propionic acid Nutrition 0.000 description 12
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000004034 viscosity adjusting agent Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000003381 stabilizer Substances 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- 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
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/06—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules
-
- 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
- F16L9/14—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups
- F16L9/147—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups comprising only layers of metal and plastics with or without reinforcement
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an allyl polymer composition as well as a preparation method and a steel-plastic complex thereof. The composition is prepared by carrying out a grafting reaction on a mixture, wherein the mixture contains an allyl polymer and an elastomer, and by taking the total amount of the allyl polymer and the elastomer in the mixture as a reference, the content of the allyl polymer is greater than or equal to 25wt% and less than 80wt%, and the content of the elastomer is greater than or equal to 20wt% and less than 75wt%. The allyl polymer composition is suitable for the steel-plastic complex.
Description
Technical field
The present invention relates to a kind of propenyl polymer composition and method of making the same and steel plastic compount body.
Background technology
Steel-plastics composite pipe, with features such as its resistance to mesohigh, high structural strength, long service life, is used widely in municipal drainage, mine, chemical industry, oil-gas transportation field.But, steel, mould interface because thermally the delamination problems that causes of rate of expansion difference limits its development.Adopt polymer inner layer and the discontiguous hollow structure of steel layer can avoid the generation of delamination problems, double walls winding corrugated furnace disclosed in CN200810207973, the winding pipeline etc. with hollow interlayer disclosed in CN201210111828, but when malleation in the pipeline that polymer inner layer is born exceedes the compressive strength of its polymkeric substance own, inside easily deforms and caves in, and then affects fluids within pipes conveying.In addition, adopt special steel skeleton construction can strengthen steel, mould the cohesiveness at interface, the Steel Skeleton reinforcement be made up of crisscross steel wire disclosed in CN201110166413, the trapezoidal band reinforcement of steel disclosed in CN200910225151, the cylindrical metal reinforcement etc. with cellular structure disclosed in CN200510021225, although the complicacy of its structure to steel, mould interface debonding and have certain restriction, but improve difficulty and the cost of processing, and still there is possibility cohesive failure occurring or breaks in hot melt adhesive or tack coat simultaneously.Therefore, improve adhesive material to the holding capacity of being out of shape largely, allow steel, mould maintenance cohesive force while slippage occurs at interface, the generation of delamination problems can be reduced.
In the prior art, the polypropene composition adopting polar monomer graft is compare the method commonly used as the binding agent between metal with polypropylene, employing grafted polyethylene disclosed in US4409364, high density polyethylene(HDPE) and polypropene blended adhesion resin, itself and polyacrylic stripping strength are 7.1 pounds per inch (being roughly equal to 32N/25mm); Bonded polyolefine resin composition disclosed in CN200610080836, the cohesive strength of itself and metal is roughly equal to 200N/25mm more than 80N/10mm(); Polypropylene disclosed in CN1443823A, metal hotmelt, with polypropylene, grafted monomer, initiator, tackifying resin and mineral filler for raw material, reaction extrusion process is adopted to have also been obtained the higher polypropene composition of cohesive strength, but, the elongation at break of major part adhesive composition is less than 100%, and does not all report the elastic recovery rate of its adhesive composition.In sum, the polypropylene-base adhesive composition simultaneously with higher metal adhesion, elongation at break, tensile strength and deformation-recovery rate not yet sees prior art.
Summary of the invention
The object of this invention is to provide a kind of propenyl polymer composition simultaneously with higher metal adhesion, elongation at break, tensile strength and deformation-recovery rate.
To achieve these goals, the invention provides a kind of propenyl polymer composition, obtain by a kind of mixture is carried out graft reaction, described mixture contains propenyl polymer and elastomerics, with propenyl polymer in described mixture and elastomeric total amount for benchmark, the content of propenyl polymer is for being more than or equal to 25 % by weight and being less than 80 % by weight, and elastomeric content is for being greater than 20 % by weight and being less than or equal to 75 % by weight; The content of preferred propylene-based polymers is for being greater than 30 % by weight and being less than 70 % by weight, and elastomeric content is for being greater than 30 % by weight and being less than or equal to 70 % by weight.
Preferably, composition of the present invention is by carrying out graft reaction by the propenyl polymer in this amount ranges and elastomerics, and propenyl polymer and elastomerics cografting form two-arch tunnel at least partly.
Preferably, by the 5A type batten in the international standard ISO527.2 obtained under the pressure condition of the temperature of 190 DEG C and 150 bar of said composition, there is following character:
(1) stripping strength measured according to standard GB/T/T1040-1992 is more than 50N/25mm;
(2) elongation at break measured according to standard GB/T/T1040-1992 is more than 100%, tensile break strength is more than 20MPa;
(3) 100% tensile deformation response rates are more than 45%.
In composition provided by the invention, propenyl polymer and elastomerics cografting, and composition has above-mentioned character, is suitable for steel-plastics composite pipe.
Described graft reaction can by carrying out extruding pelletization by described mixture and realizing in an extruder.Described forcing machine can be single screw extrusion machine and/or twin screw extruder, is preferably twin screw extruder.Preferably, the service temperature of twin screw extruder is 160-230 DEG C, and the residence time of mixture in twin screw extruder is 0.5-10min.
Described propenyl polymer can be the various propenyl polymers for steel plastic compount body, such as, can be polypropylene and/or propylene copolymer.
Described propylene copolymer can be segmented copolymer or random copolymers.Described propylene copolymer can be the multipolymer of propylene and ethene or C4-C12 alpha-olefin.Described C
4-C
12the example of alpha-olefin includes but not limited to butylene, amylene, hexene, heptene, octene, nonene and decene.
The homopolymer of propylene and multipolymer can such as use the polymerization catalyst such as Ziegler-Natta catalyst or metallocene, and the melting index under 230 DEG C and 2.16kg is 0.1 ~ 50g/10min, are preferably 0.1 ~ 8g/10min.
Described thermoplastic elastomer can be the various thermoplastic elastomers for steel plastic compount body, such as comprise without polar monomer graft thermoplastic elastomer and/or be grafted with the thermoplastic elastomer of polar monomer.The example of described thermoplastic elastomer includes but not limited to ethylene-propylene rubber, Ethylene-Propylene-Diene rubber, ethylene butylene rubber, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymers, ethylene-hexene co-polymers, ethene-methylpentene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer, the ethylene-octene copolymer of maleic anhydride graft, ethylene-acrylic acid copolymer and salt (iolon) thereof, one or more of ethylene-vinyl acetate copolymer etc.Described thermoplastic elastomer is preferably the ethylene-octene copolymer adopting metallocene catalyst polymerisation, and the melting index under 190 DEG C and 2.16kg is 0.1 ~ 10g/10min, is more preferably 0.5 ~ 5g/10min.
Preferably, said composition is also simultaneously containing polar monomer and common monomer.Described polar monomer is more than one in MALEIC ANHYDRIDE, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride, alkenyl succinic anhydride, vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, methyl methacrylate and glycidyl base propyl ester.Described altogether monomer is more than one in vinylbenzene, Vinylstyrene, glycidyl methacrylate and isopropyl maleate.According to this preferred implementation, the metal adhesion of composition can be improved further.
Relative to the propenyl polymer of 100 weight parts, the content of polar monomer can be 0.1-15 weight part, is preferably 0.5-5 weight part, and the content of monomer can be 0.1-10 weight part altogether, is preferably 0.5-3 weight part.
Preferably, described mixture is also containing initiator, and relative to the propenyl polymer of 100 weight parts, the content of initiator can be 0.1 ~ 5 weight part.
Described initiator can be one or more in alkyl peroxide, aryl peroxides, acyl peroxide and ketone peroxide; be preferably dicumyl peroxide, benzoyl peroxide, 2; one or more in 5-bis(t-butylperoxy)-2,5-dimethylhexane.
Described mixture can also contain crosslinking coagent.Relative to the propenyl polymer of 100 weight parts, the content of crosslinking coagent can be 0.01-10 weight part, is preferably 0.05-5 weight part.Described crosslinking coagent be preferably in 1,2-polyhutadiene, triallyl cyanate, triallyl isocyanate, Phthalic acid, diallyl ester, tetramethyl-thiuram disulfide one or more.
Described mixture can also contain oxidation inhibitor, tackifying resin, viscosity modifier and other auxiliary agent.The content of auxiliary agent can be its respective conventional content, relative to the propenyl polymer of 100 weight parts, the content of oxidation inhibitor can be 0.1-5 weight part, the content of tackifying resin can be 0.1-5 weight part, the content of viscosity modifier can be 0.1-5 weight part, and the content of other auxiliary agent can be 0.1-5 weight part.
Described oxidation inhibitor can be selected from Irganox1010, Irganox168, Irganox1076, Irganox1098, Irganox1330, one or more in tertiary butyl Pyrogentisinic Acid, quinhydrones, the two octadecyl of thio-2 acid, Tyox B.Be preferably Irganox1010 and Irganox168.
Described tackifying resin can be one or more in amorphous state polypropylene, petroleum resin, Gum Rosin, terpine resin and p-tert-butylphenol-polyacetylene resin.
Described viscosity modifier can be one or more in paraffin, microcrystalline wax and polyethylene wax.
The example of other auxiliary agents described includes but not limited to processing aid (not comprising mineral oil and other softening agent), anti-light aging agent, thermo-stabilizer, anti-dripping agent, rheological additives, releasing agent, antiblocking/antiseize paste, nucleator.
Present invention also offers the preparation method of described propenyl polymer composition, said composition is by obtaining a kind of mixture extruding pelletization, described mixture contains propenyl polymer and elastomerics, with propenyl polymer in described mixture and elastomeric total amount for benchmark, the content of propenyl polymer is for being more than or equal to 25 % by weight and being less than 80 % by weight, and elastomeric content is for being greater than 20 % by weight and being less than or equal to 75 % by weight.
In the present invention, preferred forcing machine carries out described extruding pelletization.Utilize twin screw extruder to carry out described extruding pelletization, the service temperature of twin screw extruder can be 160-230 DEG C, and the residence time of mixture in twin screw extruder can be 0.5-10min.
The component of described mixture elaborates hereinbefore, does not repeat them here.Described mixture can by being obtained by mixing various component.
Composition of the present invention, has good deformation-recovery rate and tensile strength, has stronger metal bonding power simultaneously.Distortion largely and do not break (cohesive failure) should be born, be applicable to as using polypropylene as the tack coat of the steel-plastics composite pipe of plastic layer.Preferably, described polypropylene-base adhesive composition has the cohesive strength higher with metallic surface, and its stripping strength is more than or equal to 50N/25mm; Have higher elongation at break, its numerical value is more than or equal to 100%; Have higher tensile strength, its tensile break stress is more than or equal to 20MP; Have higher deformation-recovery rate, its 100% tensile deformation response rate is more than or equal to 45%.
Present invention also offers a kind of steel plastic compount body, comprise steel main body and the plastic layer being attached to steel body surfaces, it is characterized in that, described plastic layer is made up of composition of the present invention.
Described steel main body can be conventional steel main body, such as, be steel pipe, and described composition forms protective layer by ordinary method (such as thermoplastic shaping) on steel pipe inner wall.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is deformation-recovery rate definition schematic diagram.
Fig. 2 is the deformation-load curve figure of the composition cyclic tension of embodiment 4.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Embodiment 1
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 29.4 weight parts, 65.2 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.5 weight part dicumyl peroxide, 0.2 part of triallyl isocyanate, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor (Irganox1010), 0.1 weight part tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester) oxidation inhibitor (Irganox168).Superoxide, crosslinking coagent, polar monomer and common monomer fully mix with polymkeric substance in advance.The mixture twin screw extruder extruding pelletization of all said components, its operational condition temperature is 170 DEG C, the residence time of mixture in twin screw extruder is 1.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.
Definition and the testing method of deformation-recovery rate are as follows:
To have after batten made by certain elastic polymer materials adopts universal testing machine to carry out cyclic tension test, and can obtain take Fig. 1 as deformation (strain)-load (stress) curve (its STRESS VARIATION by figure 1 → 2 → 3 shown in) of Typical Representative.Definition deformation-recovery rate ε=(1-L2/L1) * 100%.Concrete testing method is the dimensions according to 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.The rate of extension of batten is 50mm/min, circulates 5 times, and adopts the data of the 5th by calculating 100% tensile deformation response rate.In Fig. 1, L1 is 100% of batten gauge length, (batten gauge length is 21mm), and L2 tests for reality and obtains.
The deformation recovery rate score recorded is 67.5%.
Embodiment 2
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 33.1 weight parts, 61.5 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.5 weight part 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 0.1 part of triallyl isocyanate, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer fully mix with polymkeric substance in advance.The mixture twin screw extruder extruding pelletization of all said components, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 1.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 71.4%.
Embodiment 3
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 37.8 weight parts, 56.8 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.5 weight part dicumyl peroxide, 0.2 part 1,2-polyhutadiene, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer fully mix with polymkeric substance in advance.The mixture twin screw extruder extruding pelletization of all said components, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 2.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 59.4%.
Embodiment 4
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 47.3 weight parts, 47.3 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.5 weight part 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 0.2 part of triallyl isocyanate, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer fully mix with polymkeric substance in advance.The mixture twin screw extruder extruding pelletization of all said components, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 1.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 57.1%.
Embodiment 5
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 58.1 weight parts, 38 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.5 weight part 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 0.2 part 1, 2-polyhutadiene, 2 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer fully mix with polymkeric substance in advance.The mixture twin screw extruder extruding pelletization of all said components, its service temperature is 190 DEG C, the residence time of mixture in twin screw extruder is 1.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 61.2%.
Embodiment 6
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 66.5 weight parts, 29.1 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.5 weight part dicumyl peroxide, 0.1 part of triallyl isocyanate, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer fully mix with polymkeric substance in advance.The mixture twin screw extruder extruding pelletization of all said components, its service temperature is 170 DEG C, the residence time of mixture in twin screw extruder is 3min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 47.6%.
Embodiment 7
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 56.7 weight parts, (trade mark is Primacor5980 to 37.9 parts by weight of ethylene-acrylic copolymer, acrylic acid content is 20%, Dow Chemical), 0.5 weight part 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 0.2 part of triallyl isocyanate, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer fully mix with polymkeric substance in advance.The mixture twin screw extruder extruding pelletization of all said components, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 1.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 53%.
Embodiment 8
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 33 weight parts, (trade mark is Affinity GR-216 to 61.6 parts by weight maleic anhydride grafted ethene-octene copolymers, Dow Chemical), 0.5 weight part 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 0.2 part of triallyl isocyanate, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer fully mix with polymkeric substance in advance.The mixture twin screw extruder extruding pelletization of all said components, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 2min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 67.7%.
Reference examples 1
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 23.6 weight parts, 71.0 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.5 weight part 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 0.2 part of triallyl isocyanate, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer need fully mix with polymkeric substance in advance.Mixture twin screw extruder (lower same) extruding pelletization of all said components, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 1.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 73.8%.
Reference examples 2
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 75.7 weight parts, 18.9 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.5 weight part 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 0.2 part of triallyl isocyanate, 3.5 weight part MALEIC ANHYDRIDE, 1 parts by weight of styrene, 0.1 weight part four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer need fully mix with polymkeric substance in advance.Mixture twin screw extruder (lower same) extruding pelletization of all said components, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 1.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 38.1%.
Reference examples 3
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 34.8 weight parts, 65.0 parts by weight of ethylene-octene copolymer (melting index under 190 DEG C and 2.16kg is 5g/10min), 0.1 weight part four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Mixture adopts twin screw extruder (lower same) extruding pelletization, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 1.5min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample is very poor, can ignore, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 78.9%.
Reference examples 4
The alfon (melting index under 230 DEG C and 2.16kg is 3.0g/10min) of 33.5 weight parts, (trade mark is Affinity GR-216 to 64.6 parts by weight maleic anhydride grafted ethene-octene copolymers, Dow Chemical), 0.5 weight part 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, 0.2 part of triallyl isocyanate, 1 parts by weight of styrene, 0.1 weight part four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor, 0.1 weight part tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) oxidation inhibitor.Superoxide, crosslinking coagent, polar monomer and common monomer need fully mix with polymkeric substance in advance.Mixture twin screw extruder (lower same) extruding pelletization of all said components, its service temperature is 180 DEG C, the residence time of mixture in twin screw extruder is 2min, and according to the dimensions of 5A type batten in international standard ISO527.2, by the polypropylene-base adhesive composition particle through extruding at 190 DEG C, hot-forming under 150bar pressure.Namely required test batten is obtained.The stripping strength (adhesive property) of sample measures according to standard GB/T/T2791-1995, and tensile property measures according to standard GB/T/T1040-1992, and the results are shown in Table 1.Measure 100% tensile deformation response rate according to the method identical with embodiment 1, its numerical value is 69.0%.
As can be seen from table 1 and Fig. 2, polypropylene-base adhesive composition in the embodiment of the present invention has good 100% tensile deformation response rate and tensile strength simultaneously, there is stronger metal bonding power simultaneously, therefore can bear and be out of shape and do not break (cohesive failure) largely, be applicable to the tack coat of the steel-plastics composite pipe as plastic layer.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
The term that this specification sheets is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its integral part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary, those of ordinary skill in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (14)
1. a propenyl polymer composition, wherein, said composition obtains by a kind of mixture is carried out graft reaction, described mixture contains propenyl polymer and elastomerics, with propenyl polymer in described mixture and elastomeric total amount for benchmark, the content of propenyl polymer is for being more than or equal to 25 % by weight and being less than 80 % by weight, and elastomeric content is for being greater than 20 % by weight and being less than or equal to 75 % by weight.
2. composition according to claim 1, wherein, described propenyl polymer is alfon and/or propylene copolymer.
3. composition according to claim 1 and 2, wherein, described elastomerics is one or more in ethylene-propylene rubber, Ethylene-Propylene-Diene rubber, ethylene butylene rubber, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymers, ethylene-hexene co-polymers, ethene-methylpentene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer, the ethylene-octene copolymer of maleic anhydride graft, ethylene-acrylic acid copolymer and salt thereof, ethylene-vinyl acetate copolymer.
4. the composition according to any one of claim 1-3, wherein, the 5A type batten in the international standard ISO527.2 obtained under the pressure condition of the temperature of 190 DEG C and 150 bar by said composition has following character:
(1) stripping strength measured according to standard GB/T/T1040-1992 is more than 50N/25mm;
(2) elongation at break measured according to standard GB/T/T1040-1992 is more than 100%, tensile break strength is more than 20MPa;
(3) 100% tensile deformation response rates are more than 45%.
5. the composition according to any one of claim 1-4, wherein, described mixture is also containing polar monomer and common monomer.
6. composition according to claim 5, wherein, described polar monomer is selected from one or more in MALEIC ANHYDRIDE, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride, alkenyl succinic anhydride, vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, methyl methacrylate and glycidyl base propyl ester; Described altogether monomer be selected from vinylbenzene, Vinylstyrene, glycidyl methacrylate and isopropyl maleate one or more.
7. composition according to claim 5, wherein, relative to the propenyl polymer of 100 weight parts, the content of polar monomer is 0.1-15 weight part, is preferably 0.5-5 weight part; Altogether monomer content be 0.1-10 weight part, be preferably 0.5-3 weight part.
8. the composition according to any one of claim 1-7, wherein, described mixture is also containing initiator, and relative to the propenyl polymer of 100 weight parts, the content of initiator is 0.1 ~ 5 weight part.
9. composition according to claim 8, wherein, described initiator is one or more in alkyl peroxide, aryl peroxides, acyl peroxide and ketone peroxide; Be preferably dicumyl peroxide, benzoyl peroxide, one or more in 2,5-bis(t-butylperoxy)-2,5-dimethylhexane.
10. the composition according to any one of claim 1-9, wherein, described mixture also contains crosslinking coagent and/or oxidation inhibitor, relative to the propenyl polymer of 100 weight parts, the content of crosslinking coagent is 0.01 ~ 10 weight part, and the content of oxidation inhibitor is 0.1 ~ 5 weight part.
11. compositions according to claim 10, wherein, described oxidation inhibitor is one or more in Irganox1010, Irganox168, Irganox1076, Irganox1098, Irganox1330, tertiary butyl Pyrogentisinic Acid, quinhydrones, the two octadecyl of thio-2 acid, Tyox B; Described crosslinking coagent is one or more in 1,2-polyhutadiene, triallyl cyanate, triallyl isocyanate, Phthalic acid, diallyl ester, tetramethyl-thiuram disulfide.
12. 1 kinds of preparation methods preparing the propenyl polymer composition according to any one of claim 1-11, the method comprises a kind of mixture extruding pelletization, thus obtained described propenyl polymer composition, described mixture contains propenyl polymer and elastomerics, with propenyl polymer in described mixture and elastomeric total amount for benchmark, the content of propenyl polymer is for being more than or equal to 25 % by weight and being less than 80 % by weight, and elastomeric content is for being greater than 20 % by weight and being less than or equal to 75 % by weight.
13. methods according to claim 12, wherein, utilize twin screw extruder to carry out described extruding pelletization, and the service temperature of twin screw extruder is 160-230 DEG C, and the residence time of mixture in twin screw extruder is 0.5-10min.
14. 1 kinds of steel plastic compount bodies, comprise steel main body and the plastic layer being attached to steel body surfaces, it is characterized in that, described plastic layer is made up of the composition in claim 1-11 described in any one.
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| CN201410114509.9A Pending CN104945724A (en) | 2014-03-25 | 2014-03-25 | Allyl polymer composition as well as preparation method and steel-plastic complex thereof |
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| US6426388B1 (en) * | 1999-11-18 | 2002-07-30 | Nippon Paper Industries Co., Ltd. | Modified polyolefin composition and uses thereof |
| CN1443823A (en) * | 2003-04-09 | 2003-09-24 | 广州市鹿山化工材料有限公司 | Hot-melt adhesive for polypropylene and metal |
| CN101423733A (en) * | 2008-11-18 | 2009-05-06 | 广州市鹿山化工材料有限公司 | Method for preparing transparent hot melt adhesive for PP-R plastic-aluminum steady state tube |
| CN101454363A (en) * | 2006-05-25 | 2009-06-10 | 科聚亚公司 | Grafted polyolefins useful as metal adhesion promoters |
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| US6426388B1 (en) * | 1999-11-18 | 2002-07-30 | Nippon Paper Industries Co., Ltd. | Modified polyolefin composition and uses thereof |
| CN1443823A (en) * | 2003-04-09 | 2003-09-24 | 广州市鹿山化工材料有限公司 | Hot-melt adhesive for polypropylene and metal |
| CN101454363A (en) * | 2006-05-25 | 2009-06-10 | 科聚亚公司 | Grafted polyolefins useful as metal adhesion promoters |
| CN101423733A (en) * | 2008-11-18 | 2009-05-06 | 广州市鹿山化工材料有限公司 | Method for preparing transparent hot melt adhesive for PP-R plastic-aluminum steady state tube |
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