US20060074171A1 - Use of polyolefin waxes in hot melt compositions - Google Patents
Use of polyolefin waxes in hot melt compositions Download PDFInfo
- Publication number
- US20060074171A1 US20060074171A1 US11/244,475 US24447505A US2006074171A1 US 20060074171 A1 US20060074171 A1 US 20060074171A1 US 24447505 A US24447505 A US 24447505A US 2006074171 A1 US2006074171 A1 US 2006074171A1
- Authority
- US
- United States
- Prior art keywords
- hot melt
- waxes
- melt composition
- weight
- polyolefin waxes
- 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.)
- Abandoned
Links
- 239000001993 wax Substances 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000012943 hotmelt Substances 0.000 title claims abstract description 46
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 42
- 239000004831 Hot glue Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 239000000155 melt Substances 0.000 claims abstract description 8
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229920001384 propylene homopolymer Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 15
- -1 hydrocarbon radical Chemical class 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 0 [1*]C([2*])([3*])[4*] Chemical compound [1*]C([2*])([3*])[4*] 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229920013640 amorphous poly alpha olefin Polymers 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229920003345 Elvax® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920006112 polar polymer Polymers 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- OSIHYASBAJHECK-UHFFFAOYSA-L 1,2-dimethylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound [Cl-].[Cl-].[Zr+4].CC1=C(C)[C-]=CC1.CC1=C(C)[C-]=CC1 OSIHYASBAJHECK-UHFFFAOYSA-L 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
- MALIONKMKPITBV-UHFFFAOYSA-N 2-(3-chloro-4-hydroxyphenyl)-n-[2-(4-sulfamoylphenyl)ethyl]acetamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1CCNC(=O)CC1=CC=C(O)C(Cl)=C1 MALIONKMKPITBV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BGGKSZPSSRGVTP-UHFFFAOYSA-L 2-methyl-1h-inden-1-ide;zirconium(4+);dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C1=CC=C2[CH-]C(C)=CC2=C1.C1=CC=C2[CH-]C(C)=CC2=C1 BGGKSZPSSRGVTP-UHFFFAOYSA-L 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 description 1
- AGKZDUBMFACJPR-UHFFFAOYSA-L C12=CC=CC=C2C2=CC=CC=C2C1[Zr](Cl)(Cl)(=C(C)C)C1C=CC=C1 Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1[Zr](Cl)(Cl)(=C(C)C)C1C=CC=C1 AGKZDUBMFACJPR-UHFFFAOYSA-L 0.000 description 1
- DPVGIVRTBGLKET-UHFFFAOYSA-L CC(C)=[Zr](C1C=CC=C1)C1C2=CC=CC=C2C=C1.C1=CC=CC1[Zr+2]C1C2=CC=CC=C2C=C1.[Cl-].[Cl-].Cl.Cl Chemical compound CC(C)=[Zr](C1C=CC=C1)C1C2=CC=CC=C2C=C1.C1=CC=CC1[Zr+2]C1C2=CC=CC=C2C=C1.[Cl-].[Cl-].Cl.Cl DPVGIVRTBGLKET-UHFFFAOYSA-L 0.000 description 1
- OXLXAPYJCPFBFT-UHFFFAOYSA-L CC1=CC(C)(C=C1)[Zr](Cl)(Cl)C1(C)C=CC(C)=C1 Chemical compound CC1=CC(C)(C=C1)[Zr](Cl)(Cl)C1(C)C=CC(C)=C1 OXLXAPYJCPFBFT-UHFFFAOYSA-L 0.000 description 1
- CKNXPIUXGGVRME-UHFFFAOYSA-L CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 Chemical compound CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 CKNXPIUXGGVRME-UHFFFAOYSA-L 0.000 description 1
- MPJLHVOQWLKMRN-UHFFFAOYSA-L C[SiH](C)[Zr](Cl)(Cl)(C1C=CC=C1)C1c2ccccc2-c2ccccc12 Chemical compound C[SiH](C)[Zr](Cl)(Cl)(C1C=CC=C1)C1c2ccccc2-c2ccccc12 MPJLHVOQWLKMRN-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- SVHPGKHHBXQFLQ-UHFFFAOYSA-L Cl[Zr](Cl)(C1C=CC=C1)(C1c2ccccc2-c2ccccc12)=C(c1ccccc1)c1ccccc1 Chemical compound Cl[Zr](Cl)(C1C=CC=C1)(C1c2ccccc2-c2ccccc12)=C(c1ccccc1)c1ccccc1 SVHPGKHHBXQFLQ-UHFFFAOYSA-L 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000006853 Ziegler synthesis reaction Methods 0.000 description 1
- KRWXNHYCEZBMTL-UHFFFAOYSA-L [Cl-].[Cl-].C(CCCCCCCCCCCCCCCCC)C1(C=CC=C1)[Zr+2]C1(C=CC=C1)CCCCCCCCCCCCCCCCCC Chemical compound [Cl-].[Cl-].C(CCCCCCCCCCCCCCCCC)C1(C=CC=C1)[Zr+2]C1(C=CC=C1)CCCCCCCCCCCCCCCCCC KRWXNHYCEZBMTL-UHFFFAOYSA-L 0.000 description 1
- JWCAYMSCCIFHCW-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC(C(=CC=C2)C)=C2C1[Zr+2]C1C(C=CC=C2C)=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC(C(=CC=C2)C)=C2C1[Zr+2]C1C(C=CC=C2C)=C2C=C1 JWCAYMSCCIFHCW-UHFFFAOYSA-L 0.000 description 1
- CUNNBZZJTYAIAL-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC(C)=CC=C2C1[Zr+2]C1C2=CC=C(C)C=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC(C)=CC=C2C1[Zr+2]C1C2=CC=C(C)C=C2C=C1 CUNNBZZJTYAIAL-UHFFFAOYSA-L 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 description 1
- JJQHEAPVGPSOKX-UHFFFAOYSA-L cyclopentyl(trimethyl)silane;dichlorozirconium Chemical compound Cl[Zr]Cl.C[Si](C)(C)[C]1[CH][CH][CH][CH]1.C[Si](C)(C)[C]1[CH][CH][CH][CH]1 JJQHEAPVGPSOKX-UHFFFAOYSA-L 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MIILMDFFARLWKZ-UHFFFAOYSA-L dichlorozirconium;1,2,3,4,5-pentamethylcyclopentane Chemical compound [Cl-].[Cl-].CC1=C(C)C(C)=C(C)C1(C)[Zr+2]C1(C)C(C)=C(C)C(C)=C1C MIILMDFFARLWKZ-UHFFFAOYSA-L 0.000 description 1
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 description 1
- LOKCKYUBKHNUCV-UHFFFAOYSA-L dichlorozirconium;methylcyclopentane Chemical compound Cl[Zr]Cl.C[C]1[CH][CH][CH][CH]1.C[C]1[CH][CH][CH][CH]1 LOKCKYUBKHNUCV-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000004407 fluoroaryl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
Definitions
- the invention relates to hot melt compositions comprising polyolefin waxes which have been prepared using metallocene catalysts.
- Hot melt compositions or hot melts are thermoplastic materials which are solid at ambient temperature and in the liquid melt state are applied layerwise to suitable substrate surfaces where, following solidification, they exert different functions. They are constructed preferably on the basis of resins, waxes, thermoplastics, and elastomers, and may include additions of fillers, pigments, and additives such as stabilizers, etc.
- hot melt compositions can be used as solvent-free adhesives for bonding.
- hot melt adhesives of this kind are increasingly being used in industries including those of packaging, furniture, textiles, and footwear as an economic and environment friendly alternative to conventional, solvent-based adhesives.
- Constituents of common hot melt adhesive formulas are polar or apolar polymers, generally ethylene-vinyl acetate copolymers, resins, and waxes.
- the polar or apolar polymers serve as scaffold material. They ensure the cohesion of the adhesive and at the same time contribute to adhesion to the substrate.
- the resin addition enhances the adhesion and may exert a compatibilizing effect on the various components of the adhesive.
- Waxes are used for modification in fractions, based on the hot melt adhesive compositions, of generally less than 10% by weight. They regulate important physical properties of the adhesives, such as hardness, melt viscosity, and softening point, and, in their effect on open time, adhesion, cohesion, etc., they decisively influence the performance characteristics. Wax used in amounts of more than 10% by weight has generally been found to date to be accompanied by a deterioration in the properties, particularly a reduction in the bond strength of the hot melt adhesive.
- Hot melt compositions are also used in road construction as thermoplastic binders for producing visual traffic guidance marks, such as “zebra stripes” at pedestrian crossings, center lines or boundary lines, or other signal indications for controlling traffic flow.
- the binders employed for this purpose may comprise thermoplastics, resins, and plasticizers.
- these binders are generally blended with fillers such as sand or lime, pigments such as titanium dioxide, and light-reflecting additions, e.g., glass beads.
- Waxes used to date in hot melt compositions have included macrocrystalline and microcrystalline paraffin waxes, Fischer-Tropsch waxes, and polyolefin waxes.
- polyolefin waxes here are meant low molecular mass polyolefins in the molar mass range between about 500 and 20 000 g/mol (number-average molar mass M n ) with MFR values, measured in accordance with ASTM D 1238-01, of more than 3000 g/10 min.
- Polyolefin waxes can be produced by thermal degradation of branched polyolefin high polymers or by direct polymerization of olefins.
- Suitable polymerization processes include, for example, high-pressure technologies, in which the olefins, generally ethylene, are reacted free-radically under high pressures and temperatures to form branched waxes, and also low-pressure or Ziegler processes, in which ethylene and/or higher 1-olefins are polymerized using organometallic catalysts under temperatures and pressures which are lower by comparison.
- organometallic catalysts used are metallocene compounds. These compounds contain titanium, zirconium or hafnium atoms as active species and are generally employed in combination with cocatalysts, examples being organoaluminum compounds or boron compounds, preferably aluminoxane compounds. Polymerization takes place where necessary in the presence of hydrogen as a molar mass regulator.
- metallocene processes is that, in comparison to the older Ziegler technology, it is possible to obtain waxes having a narrower molar mass distribution, more uniform incorporation of comonomer, lower melting points, and higher catalyst efficiency.
- hot melt compositions comprising polyolefin waxes which have been prepared using metallocene catalysts, have a dropping point or ring & ball softening point of between 80 and 165° C., have a melt viscosity, measured at a temperature of 170° C., of between 20 and 40 000 mPa ⁇ s, and have a glass transition temperature of not more than ⁇ 10° C., are suitable with particular advantage as hot melt adhesives.
- Hot melt adhesives of this kind display outstanding properties in respect of bond strength (substrate adhesion) and low-temperature flexibility.
- the invention accordingly provides hot melt compositions comprising one or more polyolefin waxes which have been prepared using metallocene catalysts, have a dropping point or ring & ball softening point of between 80 and 165° C., have a melt viscosity, measured at a temperature of 170° C., of between 20 and 40 000 mPa ⁇ s, and have a glass transition temperature of not more than ⁇ 10° C.
- the polyolefin waxes present in the hot melt compositions of the invention preferably have a dropping point or ring & ball softening point of between 90 and 160° C., a melt viscosity, measured at a temperature of 170° C., of between 50 and 30 000 mPa ⁇ s, and a glass transition temperature of not more than ⁇ 20° C.
- the polyolefin waxes present in the hot melt compositions of the invention preferably have a number-average molar mass M n of between 500 and 20 000 g/mol, more preferably between 800 and 10 000 g/mol, and with particular preference between 1000 and 5000 g/mol, and preferably a weight-average molar mass M w of between 1000 and 40 000 g/mol, more preferably between 1600 and 30 000 g/mol, and with particular preference between 2000 and 20 000 g/mol.
- suitable polyolefin waxes present in the hot melt compositions of the invention include homopolymers of propylene or of higher 1-olefins or copolymers of propylene with ethylene or with higher 1-olefins, or copolymers thereof with one another.
- Higher 1-olefins used are preferably linear or branched olefins having 4 to 20 carbon atoms and preferably having 4 to 6 carbon atoms. These olefins may have an aromatic substitution which is in conjugation with the olefinic double bond. Examples thereof are 1-butene, 1-hexene, 1-octene or 1-octadecene, and styrene.
- the copolymers are composed preferably of 70% to 99.9% and more preferably of 80% to 99% by weight of one kind of olefin. Preference is additionally given to copolymers of propylene with 0.1% to 30%, preferably 1% to 20%, by weight of ethylene.
- polyolefin waxes present in the hot melt compositions are propylene homopolymer waxes.
- the polyolefin waxes present in the hot melt compositions are copolymer waxes of propylene and one or more further monomers selected from ethylene and branched or unbranched 1-alkenes having 4 to 20 carbon atoms, the amount of structural units originating from propylene in the copolymer waxes being from 70% to 99.9% by weight.
- copolymer waxes it is also possible to use a variety of the 1-alkenes stated.
- the polyolefin waxes present in the hot melt compositions are copolymer waxes of ethylene and at least one branched or unbranched 1-alkene having 3 to 20 carbon atoms, the amount of structural units originating from the one or more 1-alkenes in the copolymer waxes being from 0.1% to 30% by weight.
- the polyolefin waxes present in the hot melt compositions are copolymer waxes of propylene and one or more further monomers selected from ethylene and branched or unbranched 1-alkenes having 4 to 20 carbon atoms, the amount of structural units originating from ethylene in the copolymer waxes being from 0.1% to 30% by weight and the amount of structural units originating from the one or more 1-alkenes in the copolymer waxes being from 0.1% to 50% by weight.
- the olefin homopolymer and copolymer waxes used in the hot melt compositions may have undergone polar modification.
- the hot melt compositions of the invention may further comprise polyolefin polymers, resins, waxes, plasticizers, polar or apolar polymers, pigments, fillers, stabilizers and/or antioxidants.
- polyolefin waxes used in accordance with the invention are prepared using metallocene compounds of the formula I.
- M 1 is a metal from group IVb, Vb or VIb of the periodic system, examples being titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten, preferably titanium, zirconium or hafnium.
- R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 , preferably C 1 -C 3 alkyl group, especially methyl, a C 1 -C 10 , preferably C 1 -C 3 alkoxy group, a C 6 -C 10 , preferably C 6 -C 8 aryl group, a C 6 -C 10 , preferably C 6 -C 8 aryloxy group, a C 2 -C 10 , preferably C 2 -C 4 alkenyl group, a C 7 -C 40 , preferably C 7 -C 10 arylalkyl group, a C 7 -C 40 , preferably C 7 -C 12 alkylaryl group, a C 8 -C 40 , preferably C 8 -C 12 arylalkenyl group, or a halogen atom, preferably chlorine atom.
- R 3 and R 4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which together with the central atom M 1 may form a sandwich structure.
- R 3 and R 4 are cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl, it being possible for the parent structures to carry additional substituents or to be bridged with one another.
- one of the radicals R 3 and R 4 to be a substituted nitrogen atom, with R 24 having the definition of R 17 and being preferably methyl, tert-butyl or cyclohexyl.
- R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C 1 -C 10 , preferably C 1 -C 4 alkyl group, a C 6 -C 10 , preferably C 6 -C 8 aryl group, a C 1 -C 10 , preferably C 1 -C 3 alkoxy group, a radical —NR 16 2 —, —SR 16 —, —OSiR 16 3 —, —SiR 16 3 — or —PR 16 2 —, in which R 16 is a C 1 -C 10 , preferably C 1 -C 3 alkyl group or C 6 -C 10 , preferably C 6 -C 8 aryl group or else, in the case of radicals containing Si or P, is a halogen atom, preferably chlorine atom, or pairs of
- M 2 is silicon, germanium or tin, preferably silicon and germanium.
- R 13 is preferably ⁇ CR 17 R 18 , ⁇ SiR 17 R 18 , ⁇ GeR 17 R 18 , —O—, —S—, ⁇ SO, ⁇ PR 17 or ⁇ P(O)R 17 .
- R 11 and R 12 are identical or different and have the definition stated for R 17 .
- m and n are identical or different and denote zero, 1 or 2, preferably zero or 1, with m plus n being zero, 1 or 2, preferably zero or 1.
- R 14 and R 15 have the definition of R 17 and R 18 .
- the single-center catalyst systems are activated using suitable cocatalysts.
- suitable cocatalysts for metallocenes of the formula I are organoaluminum compounds, especially aluminoxanes or else aluminum-free systems such as R 20 x NH 4-x BR 21 4 , R 20 x PH 4-x BR 21 4 , R 20 3 CBR 21 4 or BR 21 3 .
- x is a number from 1 to 4, the radicals R 20 are identical or different, preferably identical, and are C 1 -C 10 alkyl or C 6 -C 18 aryl, or two radicals R 20 form a ring together with the atom connecting them, and the radicals R 21 are identical or different, preferably identical, and are C 6 -C 18 aryl which may be substituted by alkyl, haloalkyl or fluorine.
- R 20 is ethyl, propyl, butyl or phenyl and R 21 is phenyl, pentafluorophenyl, 3,5-bistrifluoro-methylphenyl, mesityl, xylyl or tolyl.
- organoaluminum compounds such as triethylaluminum, tributylaluminum, etc., and also mixtures.
- catalyst systems in which the residues of support material and cocatalyst do not exceed a concentration of 100 ppm in the product.
- polyolefin metallocene waxes in unmodified form or in polar-modified form.
- Polar-modified waxes are prepared in conventional manner from a polar raw materials by oxidation with oxygenous gases, air for example, or by free-radical grafting reaction with polar monomers, examples being ⁇ , ⁇ -unsaturated carboxylic acids or derivatives thereof, such as acrylic acid, maleic acid or maleic anhydride, or unsaturated organosilane compounds such as trialkoxyvinylsilanes.
- the invention further provides for the use of the hot melt compositions of the invention as hot melt adhesives.
- the polyolefin waxes are present preferably with a weight fraction of greater than or equal to 50%, more preferably between 50% and 99%, and with particular preference between 60% and 90% by weight.
- Further possible constituents are resins, waxes, and apolar or polar polymers such as ethylene-vinyl acetate copolymers, atactic poly- ⁇ -olefins (APAO), polyisobutylene, styrene-butadiene-styrene block polymers or styrene-isoprene-styrene block polymers, and, for particularly heavy-duty bonds, polyamides or polyesters.
- APAO atactic poly- ⁇ -olefins
- resin components which may be present include rosins and their derivatives or hydrocarbon resins, while possible waxes are hydrocarbon waxes such as Fischer-Tropsch paraffins, and polyolefin waxes not prepared using metallocene catalysts, it being possible for said waxes to have undergone apolar or polar modification, by means, for example, of oxidation or of grafting with polar monomers such as maleic anhydride.
- the hot melt adhesive compositions may further comprise fillers or auxiliaries such as plasticizers, pigments, and stabilizers such as antioxidants or light stabilizers.
- the invention further provides for the use of the hot melt compositions of the invention as binders for producing roadmarkings.
- the polyolefin waxes are present preferably with a weight fraction of between 5% and 99% by weight.
- the polyolefin waxes are present in the hot melt compositions used as binders for roadmarking with a weight fraction of between 20% and 90% by weight.
- the polyolefin waxes are present in the hot melt compositions used as binders for roadmarking with a weight fraction of between 50% and 99% by weight.
- the polyolefin waxes are present very preferably with a weight fraction of between 60% and 90% by weight.
- binder is generally blended with further components such as fillers, e.g., sand or lime, and also pigments, e.g., titanium dioxide, and light-reflecting adjuvants such as glass beads, for example.
- fillers e.g., sand or lime
- pigments e.g., titanium dioxide
- light-reflecting adjuvants such as glass beads, for example.
- the melt viscosities were determined in accordance with DIN 53019 using a rotational viscometer, the dropping points in accordance with DIN 51801/2, the ring & ball softening points in accordance with DIN EN 1427, and the glass transition temperatures by means of differential thermoanalysis in accordance with DIN 51700.
- the weight-average molar mass M w , the number-average molar mass M n , and the resulting quotient M w /M n were determined by gel permeation chromatography at 135° C. in 1,2-dichlorobenzene.
- the metallocene polyolefin waxes used in accordance with the invention and listed in Table 1 were prepared by the process specified in EP-A-0 571 882. TABLE 1 Polyolefin waxes used Softening point/ Viscosity at dropping point 170° C.
- Product type [° C.] [mPa ⁇ s] Wax 1 propylene-ethylene 88 6300 (inventive) copolymer wax (metallocene) Wax 2 propylene 143 60 (inventive) homopolymer wax (metallocene) Licowax ® propylene 158 700 PP 220 homopolymer wax (Ziegler)
- the waxes listed in Table 1 were used to prepare hot melt adhesive compositions in accordance with the mixing proportions set out in Table 2. The components were jointly melted and stirred at 180° C. for 1 h.
- Examples 1 to 3 are inventive.
- Examples 4 to 9, in contrast, are comparative examples.
- Examples 1 to 3 in comparison with Examples 4 to 6, show that by increasing the wax fraction to more than 50% by weight it is possible to achieve a distinct improvement in cohesion and also a reduction in the glass transition temperature and an increase in the low-temperature flexibility.
- Hot melt adhesive compositions formulated conventionally with ethylene-vinyl acetate copolymer and conventional wax exhibit not only higher melt viscosities but also, by comparison, poorer cohesion and in some cases poorer low-temperature flexibility (Examples 7 to 9).
- Vestoplast® 708 (APAO, Degussa AG), 40 parts by weight of Regalite® 1125 (hydrocarbon resin, Eastman), 4 parts by weight of liquid paraffin, 12 parts by weight of Licowax® PP 230 (Ziegler PP wax from Clariant AG) and 4 parts by weight of Licomont® AR 504 (PP wax grafted with maleic anhydride, for improving adhesion, Clariant AG) were mixed homogeneously at 180° C. 50 g of the melt obtained were spread over a sample plate of asphalt road covering measuring 10 cm ⁇ 10 cm. After cooling, the coated plate was stored at ⁇ 15° C. for 24 h.
- APAO Degussa AG
- Regalite® 1125 hydrocarbon resin, Eastman
- Licowax® PP 230 Ziegler PP wax from Clariant AG
- Licomont® AR 504 PP wax grafted with maleic anhydride, for improving adhesion, Clariant AG
- the coated plate was again stored at ⁇ 15° C. for 24 h.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
- The present invention is described in the German priority application No. 102004048536.4, filed Jun. 10, 2004, which is hereby incorporated by reference as is fully disclosed herein.
- The invention relates to hot melt compositions comprising polyolefin waxes which have been prepared using metallocene catalysts.
- Hot melt compositions or hot melts are thermoplastic materials which are solid at ambient temperature and in the liquid melt state are applied layerwise to suitable substrate surfaces where, following solidification, they exert different functions. They are constructed preferably on the basis of resins, waxes, thermoplastics, and elastomers, and may include additions of fillers, pigments, and additives such as stabilizers, etc.
- By way of example, hot melt compositions can be used as solvent-free adhesives for bonding. On account of their multifarious advantages, hot melt adhesives of this kind are increasingly being used in industries including those of packaging, furniture, textiles, and footwear as an economic and environment friendly alternative to conventional, solvent-based adhesives. Constituents of common hot melt adhesive formulas are polar or apolar polymers, generally ethylene-vinyl acetate copolymers, resins, and waxes.
- The polar or apolar polymers serve as scaffold material. They ensure the cohesion of the adhesive and at the same time contribute to adhesion to the substrate. The resin addition enhances the adhesion and may exert a compatibilizing effect on the various components of the adhesive. Waxes are used for modification in fractions, based on the hot melt adhesive compositions, of generally less than 10% by weight. They regulate important physical properties of the adhesives, such as hardness, melt viscosity, and softening point, and, in their effect on open time, adhesion, cohesion, etc., they decisively influence the performance characteristics. Wax used in amounts of more than 10% by weight has generally been found to date to be accompanied by a deterioration in the properties, particularly a reduction in the bond strength of the hot melt adhesive.
- Hot melt compositions are also used in road construction as thermoplastic binders for producing visual traffic guidance marks, such as “zebra stripes” at pedestrian crossings, center lines or boundary lines, or other signal indications for controlling traffic flow. Besides waxes, the binders employed for this purpose may comprise thermoplastics, resins, and plasticizers. For roadmarking application these binders are generally blended with fillers such as sand or lime, pigments such as titanium dioxide, and light-reflecting additions, e.g., glass beads.
- Waxes used to date in hot melt compositions have included macrocrystalline and microcrystalline paraffin waxes, Fischer-Tropsch waxes, and polyolefin waxes. By polyolefin waxes here are meant low molecular mass polyolefins in the molar mass range between about 500 and 20 000 g/mol (number-average molar mass Mn) with MFR values, measured in accordance with ASTM D 1238-01, of more than 3000 g/10 min.
- Polyolefin waxes can be produced by thermal degradation of branched polyolefin high polymers or by direct polymerization of olefins. Suitable polymerization processes include, for example, high-pressure technologies, in which the olefins, generally ethylene, are reacted free-radically under high pressures and temperatures to form branched waxes, and also low-pressure or Ziegler processes, in which ethylene and/or higher 1-olefins are polymerized using organometallic catalysts under temperatures and pressures which are lower by comparison.
- A variant of the low-pressure process which has been disclosed more recently is a procedure in which the organometallic catalysts used are metallocene compounds. These compounds contain titanium, zirconium or hafnium atoms as active species and are generally employed in combination with cocatalysts, examples being organoaluminum compounds or boron compounds, preferably aluminoxane compounds. Polymerization takes place where necessary in the presence of hydrogen as a molar mass regulator. A feature of metallocene processes is that, in comparison to the older Ziegler technology, it is possible to obtain waxes having a narrower molar mass distribution, more uniform incorporation of comonomer, lower melting points, and higher catalyst efficiency.
- Surprisingly it has now been found that hot melt compositions comprising polyolefin waxes which have been prepared using metallocene catalysts, have a dropping point or ring & ball softening point of between 80 and 165° C., have a melt viscosity, measured at a temperature of 170° C., of between 20 and 40 000 mPa·s, and have a glass transition temperature of not more than −10° C., are suitable with particular advantage as hot melt adhesives. Hot melt adhesives of this kind display outstanding properties in respect of bond strength (substrate adhesion) and low-temperature flexibility.
- Additionally it has been found that the stated hot melt compositions are outstandingly suitable as a constituent of roadmarking materials. Marking materials of this kind possess, in particular, improved adhesion to the road.
- The invention accordingly provides hot melt compositions comprising one or more polyolefin waxes which have been prepared using metallocene catalysts, have a dropping point or ring & ball softening point of between 80 and 165° C., have a melt viscosity, measured at a temperature of 170° C., of between 20 and 40 000 mPa·s, and have a glass transition temperature of not more than −10° C.
- The polyolefin waxes present in the hot melt compositions of the invention preferably have a dropping point or ring & ball softening point of between 90 and 160° C., a melt viscosity, measured at a temperature of 170° C., of between 50 and 30 000 mPa·s, and a glass transition temperature of not more than −20° C.
- The polyolefin waxes present in the hot melt compositions of the invention preferably have a number-average molar mass Mn of between 500 and 20 000 g/mol, more preferably between 800 and 10 000 g/mol, and with particular preference between 1000 and 5000 g/mol, and preferably a weight-average molar mass Mw of between 1000 and 40 000 g/mol, more preferably between 1600 and 30 000 g/mol, and with particular preference between 2000 and 20 000 g/mol.
- Examples of suitable polyolefin waxes present in the hot melt compositions of the invention include homopolymers of propylene or of higher 1-olefins or copolymers of propylene with ethylene or with higher 1-olefins, or copolymers thereof with one another. Higher 1-olefins used are preferably linear or branched olefins having 4 to 20 carbon atoms and preferably having 4 to 6 carbon atoms. These olefins may have an aromatic substitution which is in conjugation with the olefinic double bond. Examples thereof are 1-butene, 1-hexene, 1-octene or 1-octadecene, and styrene. The copolymers are composed preferably of 70% to 99.9% and more preferably of 80% to 99% by weight of one kind of olefin. Preference is additionally given to copolymers of propylene with 0.1% to 30%, preferably 1% to 20%, by weight of ethylene.
- In one preferred embodiment of the invention the polyolefin waxes present in the hot melt compositions are propylene homopolymer waxes.
- In a further preferred embodiment of the invention the polyolefin waxes present in the hot melt compositions are copolymer waxes of propylene and one or more further monomers selected from ethylene and branched or unbranched 1-alkenes having 4 to 20 carbon atoms, the amount of structural units originating from propylene in the copolymer waxes being from 70% to 99.9% by weight. To prepare these copolymer waxes it is also possible to use a variety of the 1-alkenes stated.
- In another preferred embodiment of the invention the polyolefin waxes present in the hot melt compositions are copolymer waxes of ethylene and at least one branched or unbranched 1-alkene having 3 to 20 carbon atoms, the amount of structural units originating from the one or more 1-alkenes in the copolymer waxes being from 0.1% to 30% by weight.
- In yet another preferred embodiment of the invention the polyolefin waxes present in the hot melt compositions are copolymer waxes of propylene and one or more further monomers selected from ethylene and branched or unbranched 1-alkenes having 4 to 20 carbon atoms, the amount of structural units originating from ethylene in the copolymer waxes being from 0.1% to 30% by weight and the amount of structural units originating from the one or more 1-alkenes in the copolymer waxes being from 0.1% to 50% by weight.
- The olefin homopolymer and copolymer waxes used in the hot melt compositions may have undergone polar modification.
- The hot melt compositions of the invention may further comprise polyolefin polymers, resins, waxes, plasticizers, polar or apolar polymers, pigments, fillers, stabilizers and/or antioxidants.
-
-
-
- of the formula Ib
- and of the formula Ic
- of the formula Ib
- In formulae I, Ia and Ib, M1 is a metal from group IVb, Vb or VIb of the periodic system, examples being titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten, preferably titanium, zirconium or hafnium.
- R1 and R2 are identical or different and are a hydrogen atom, a C1-C10, preferably C1-C3 alkyl group, especially methyl, a C1-C10, preferably C1-C3 alkoxy group, a C6-C10, preferably C6-C8 aryl group, a C6-C10, preferably C6-C8 aryloxy group, a C2-C10, preferably C2-C4 alkenyl group, a C7-C40, preferably C7-C10 arylalkyl group, a C7-C40, preferably C7-C12 alkylaryl group, a C8-C40, preferably C8-C12 arylalkenyl group, or a halogen atom, preferably chlorine atom.
- R3 and R4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which together with the central atom M1 may form a sandwich structure. Preferably R3 and R4 are cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl, it being possible for the parent structures to carry additional substituents or to be bridged with one another. It is also possible for one of the radicals R3 and R4 to be a substituted nitrogen atom, with R24 having the definition of R17 and being preferably methyl, tert-butyl or cyclohexyl.
- R5, R6, R7, R8, R9, and R10 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C1-C10, preferably C1-C4 alkyl group, a C6-C10, preferably C6-C8 aryl group, a C1-C10, preferably C1-C3 alkoxy group, a radical —NR16 2—, —SR16—, —OSiR16 3—, —SiR16 3— or —PR16 2—, in which R16 is a C1-C10, preferably C1-C3 alkyl group or C6-C10, preferably C6-C8 aryl group or else, in the case of radicals containing Si or P, is a halogen atom, preferably chlorine atom, or pairs of adjacent radicals R5, R6, R7, R8, R9, or R10 form a ring with the carbon atoms connecting them. Particularly preferred ligands are the substituted compounds of the parent structures cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl.
-
- R13 is
- ═BR17, ═AlR17, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO2, ═NR17, ═CO, ═PR17 or ═P(O)R17, R17, R18, and R19 being identical or different and being a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C1-C30, preferably C1-C4 alkyl, especially methyl, group, a C1-C10 fluoroalkyl, preferably CF3 group, a C6-C10 fluoroaryl, preferably pentafluorophenyl group, a C6-C10, preferably C6-C8 aryl group, a C1-C10, preferably C1-C4 alkoxy, especially methoxy group, a C2-C10, preferably C2-C4 alkenyl group, a C7-C40, preferably C7-C10 aralkyl group, a C8-C40, preferably C8-C12 arylalkenyl group or a C7-C40, preferably C7-C12 alkylaryl group, or R17 and R18, or R17 and R19, each form a ring together with the atoms connecting them.
- R13 is
- M2 is silicon, germanium or tin, preferably silicon and germanium. R13 is preferably ═CR17R18, ═SiR17R18, ═GeR17R18, —O—, —S—, ═SO, ═PR17 or ═P(O)R17.
- R11 and R12 are identical or different and have the definition stated for R17. m and n are identical or different and denote zero, 1 or 2, preferably zero or 1, with m plus n being zero, 1 or 2, preferably zero or 1.
- R14 and R15 have the definition of R17 and R18.
- Examples of suitable metallocenes are:
- bis(1,2,3-trimethylcyclopentadienyl)zirconium dichloride,
- bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride,
- bis(1,2-dimethylcyclopentadienyl)zirconium dichloride,
- bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,
- bis(1-methylindenyl)zirconium dichloride,
- bis(1-n-butyl-3-methylcyclopentadienyl)zirconium dichloride,
- bis(2-methyl-4,6-diisopropylindenyl)zirconium dichloride,
- bis(2-methylindenyl)zirconium dichloride,
- bis(4-methylindenyl)zirconium dichloride,
- bis(5-methylindenyl)zirconium dichloride,
- bis(alkylcyclopentadienyl)zirconium dichloride,
- bis(alkylindenyl)zirconium dichloride,
- bis(cyclopentadienyl)zirconium dichloride,
- bis(indenyl)zirconium dichloride,
- bis(methylcyclopentadienyl)zirconium dichloride,
- bis(n-butylcyclopentadienyl)zirconium dichloride,
- bis(octadecylcyclopentadienyl)zirconium dichloride,
- bis(pentamethylcyclopentadienyl)zirconium dichloride,
- bis(trimethylsilylcyclopentadienyl)zirconium dichloride,
- biscyclopentadienylzirconium dibenzyl,
- biscyclopentadienylzirconium dimethyl,
- bistetrahydroindenylzirconium dichloride,
- dimethylsilyl-9-fluorenylcyclopentadienylzirconium dichloride,
- dimethylsilylbis-1-(2,3,5-trimethylcyclopentadienyl)zirconium dichloride,
- dimethylsilylbis-1-(2,4-dimethylcyclopentadienyl)zirconium dichloride,
- dimethylsilylbis-1-(2-methyl-4,5-benzoindenyl)zirconium dichloride,
- dimethylsilylbis-1-(2-methyl-4-ethylindenyl)zirconium dichloride,
- dimethylsilylbis-1-(2-methyl-4-isopropylindenyl)zirconium dichloride,
- dimethylsilylbis-1-(2-methyl-4-phenylindenyl)zirconium dichloride,
- dimethylsilylbis-1-(2-methylindenyl)zirconium dichloride,
- dimethylsilylbis-1-(2-methyltetrahydroindenyl)zirconium dichloride,
- dimethylsilylbis-1-indenylzirconium dichloride,
- dimethylsilylbis-1-indenylzirconium dimethyl,
- dimethylsilylbis-1-tetrahydroindenylzirconium dichloride,
- diphenylmethylene-9-fluorenylcyclopentadienylzirconium dichloride,
- diphenylsilylbis-1-indenylzirconium dichloride,
- ethylenebis-1-(2-methyl-4,5-benzoindenyl)zirconium dichloride,
- ethylenebis-1-(2-methyl-4-phenylindenyl)zirconium dichloride,
- ethylenbis-1-(2-methyltetrahydroindenyl)zirconium dichloride,
- ethylenebis-1-(4,7-dimethylindenyl)zirconium dichloride,
- ethylenebis-1-indenylzirconium dichloride,
- ethylenebis-1-tetrahydroindenylzirconium dichloride,
- indenylcyclopentadienylzirconium dichloride isopropylidene(1-indenyl)(cyclopentadienyl)zirconium dichloride,
- isopropylidene(9-fluorenyl)(cyclopentadienyl)zirconium dichloride,
- phenylmethylsilylbis-1-(2-methylindenyl)zirconium dichloride,
- and the alkyl or aryl derivatives of each of these metallocene dichlorides.
- The single-center catalyst systems are activated using suitable cocatalysts. Suitable cocatalysts for metallocenes of the formula I are organoaluminum compounds, especially aluminoxanes or else aluminum-free systems such as R20 xNH4-xBR21 4, R20 xPH4-xBR21 4, R20 3CBR21 4 or BR21 3. In these formulae x is a number from 1 to 4, the radicals R20 are identical or different, preferably identical, and are C1-C10 alkyl or C6-C18 aryl, or two radicals R20 form a ring together with the atom connecting them, and the radicals R21 are identical or different, preferably identical, and are C6-C18 aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular R20 is ethyl, propyl, butyl or phenyl and R21 is phenyl, pentafluorophenyl, 3,5-bistrifluoro-methylphenyl, mesityl, xylyl or tolyl.
- Additionally a third component is often necessary in order to maintain protection against polar catalyst poisons. Suitable for this purpose are organoaluminum compounds such as triethylaluminum, tributylaluminum, etc., and also mixtures.
- Depending on process it is also possible for supported single-center catalysts to be used. Preference is given to catalyst systems in which the residues of support material and cocatalyst do not exceed a concentration of 100 ppm in the product.
- To prepare the hot melt compositions of the invention it is possible to use polyolefin metallocene waxes in unmodified form or in polar-modified form. Polar-modified waxes are prepared in conventional manner from a polar raw materials by oxidation with oxygenous gases, air for example, or by free-radical grafting reaction with polar monomers, examples being α,β-unsaturated carboxylic acids or derivatives thereof, such as acrylic acid, maleic acid or maleic anhydride, or unsaturated organosilane compounds such as trialkoxyvinylsilanes. The polar modification of metallocene polyolefin waxes by oxidation with air is described for example in EP 0 890 583, modification by grafting for example in U.S. Pat. No. 5,998,547 or JP 54-145785.
- The invention further provides for the use of the hot melt compositions of the invention as hot melt adhesives.
- In the hot melt compositions used as hot melt adhesives the polyolefin waxes are present preferably with a weight fraction of greater than or equal to 50%, more preferably between 50% and 99%, and with particular preference between 60% and 90% by weight. Further possible constituents are resins, waxes, and apolar or polar polymers such as ethylene-vinyl acetate copolymers, atactic poly-α-olefins (APAO), polyisobutylene, styrene-butadiene-styrene block polymers or styrene-isoprene-styrene block polymers, and, for particularly heavy-duty bonds, polyamides or polyesters. Examples of resin components which may be present include rosins and their derivatives or hydrocarbon resins, while possible waxes are hydrocarbon waxes such as Fischer-Tropsch paraffins, and polyolefin waxes not prepared using metallocene catalysts, it being possible for said waxes to have undergone apolar or polar modification, by means, for example, of oxidation or of grafting with polar monomers such as maleic anhydride. The hot melt adhesive compositions may further comprise fillers or auxiliaries such as plasticizers, pigments, and stabilizers such as antioxidants or light stabilizers.
- The invention further provides for the use of the hot melt compositions of the invention as binders for producing roadmarkings.
- In the hot melt compositions used as binders for roadmarking the polyolefin waxes are present preferably with a weight fraction of between 5% and 99% by weight.
- In one particularly preferred embodiment of the invention, the polyolefin waxes are present in the hot melt compositions used as binders for roadmarking with a weight fraction of between 20% and 90% by weight.
- In a further particularly preferred embodiment of the invention, the polyolefin waxes are present in the hot melt compositions used as binders for roadmarking with a weight fraction of between 50% and 99% by weight.
- In the hot melt compositions used as binders for roadmarking the polyolefin waxes are present very preferably with a weight fraction of between 60% and 90% by weight.
- Further possible constituents are apolar or polar polymers, resins, and waxes of the type described above, and also plasticizers, such as liquid paraffin, and antioxidants. For roadmarking use the binder is generally blended with further components such as fillers, e.g., sand or lime, and also pigments, e.g., titanium dioxide, and light-reflecting adjuvants such as glass beads, for example.
- The examples which follow are intended to illustrate the invention but not to restrict it to them.
- The melt viscosities were determined in accordance with DIN 53019 using a rotational viscometer, the dropping points in accordance with DIN 51801/2, the ring & ball softening points in accordance with DIN EN 1427, and the glass transition temperatures by means of differential thermoanalysis in accordance with DIN 51700. The weight-average molar mass Mw, the number-average molar mass Mn, and the resulting quotient Mw/Mn were determined by gel permeation chromatography at 135° C. in 1,2-dichlorobenzene.
- The metallocene polyolefin waxes used in accordance with the invention and listed in Table 1 were prepared by the process specified in EP-A-0 571 882.
TABLE 1 Polyolefin waxes used Softening point/ Viscosity at dropping point 170° C. Product type [° C.] [mPa · s] Wax 1 propylene-ethylene 88 6300 (inventive) copolymer wax (metallocene) Wax 2 propylene 143 60 (inventive) homopolymer wax (metallocene) Licowax ® propylene 158 700 PP 220 homopolymer wax (Ziegler) - Results of Performance Testing
- A. Use in Hot Melt Adhesive Formulas
- The waxes listed in Table 1 were used to prepare hot melt adhesive compositions in accordance with the mixing proportions set out in Table 2. The components were jointly melted and stirred at 180° C. for 1 h.
- To test the cohesion, moldings were cast from the mixtures in accordance with DIN 53455 and their mechanical stability was tested in a tensile test.
- To determine the low-temperature flexibility, test specimens measuring 250 mm×10 mm were produced and bent over a mandrel. The temperature was lowered in steps of 10, beginning at 0° C. The measurement parameter used was the temperature at which the test specimen fractures.
TABLE 2 Properties of the formula mixtures and performance results Licowax ® PP Regalite ® Low- Wax 1 Wax 2 Elvax ® 220 220 1140 Melting Melt Glass transition temperature [parts by [parts by [parts by [parts by [parts by point viscosity temperature flexibility Cohesion Example weight] weight] weight] weight] weight] [° C.] [mPas] [° C.] [° C.] [N/mm2] 1 36 45 19 148 936 −16 −17 3.2 2 56 30 14 140 2100 −22 −23 3.9 3 71 21 8 136 3370 −24 −26 3.8 4 (Comp.) 10 30 60 144 960 16 18 1.4 5 (Comp.) 14 21 65 138 2186 18 19 1.2 6 (Comp.) 7 14 79 134 3130 35 35 0.8 7 (Comp.) 48 5 47 158 23500 −14 −16 1.2 8 (Comp.) 10 5 85 156 14720 12 11 0.6 9 (Comp.) 66 5 29 140 32920 −22 −23 1.2
Elvax ® 220: ethylene-vinyl acetate copolymer, manufacturer: DuPont AG
Licowax ® PP 220: polypropylene wax from Ziegler synthesis, manufacturer: Clariant AG
Regalite ® 1140: hydrocarbon resin, manufacturer: Eastman
- Examples 1 to 3 are inventive. Examples 4 to 9, in contrast, are comparative examples.
- Examples 1 to 3, in comparison with Examples 4 to 6, show that by increasing the wax fraction to more than 50% by weight it is possible to achieve a distinct improvement in cohesion and also a reduction in the glass transition temperature and an increase in the low-temperature flexibility. Hot melt adhesive compositions formulated conventionally with ethylene-vinyl acetate copolymer and conventional wax exhibit not only higher melt viscosities but also, by comparison, poorer cohesion and in some cases poorer low-temperature flexibility (Examples 7 to 9).
- B. Use as Binder Component for Roadmarking
- 40 parts by weight of Vestoplast® 708 (APAO, Degussa AG), 40 parts by weight of Regalite® 1125 (hydrocarbon resin, Eastman), 4 parts by weight of liquid paraffin, 12 parts by weight of Licowax® PP 230 (Ziegler PP wax from Clariant AG) and 4 parts by weight of Licomont® AR 504 (PP wax grafted with maleic anhydride, for improving adhesion, Clariant AG) were mixed homogeneously at 180° C. 50 g of the melt obtained were spread over a sample plate of asphalt road covering measuring 10 cm×10 cm. After cooling, the coated plate was stored at −15° C. for 24 h.
- A melt mixture homogenized at 180° C. and composed of 39 parts by weight of the wax 1 specified in Table 1 and 9 parts by weight of the wax 2 specified in Table 1, 40 parts by weight of Regalite® 1125 and 12 parts by weight of Licowax® PP 230 was used to produce a test coat in the manner described in Example 10. The coated plate was again stored at −15° C. for 24 h.
- After the end of low-temperature storage, the plates were removed from the refrigeration cabinet. From an attempt to detach the test coat by hand from the substrate it was apparent that the mixture from Example 11 exhibited significantly better adhesion than the comparative mixture from Example 10.
Claims (18)
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Also Published As
Publication number | Publication date |
---|---|
ES2334035T3 (en) | 2010-03-04 |
EP1645608A1 (en) | 2006-04-12 |
DE502005008522D1 (en) | 2009-12-31 |
EP1645608B1 (en) | 2009-11-18 |
DE102004048536A1 (en) | 2006-04-13 |
DE102004048536B4 (en) | 2008-09-18 |
JP2006104472A (en) | 2006-04-20 |
JP5144008B2 (en) | 2013-02-13 |
US7825186B2 (en) | 2010-11-02 |
US20080262148A1 (en) | 2008-10-23 |
DE502005008522C5 (en) | 2016-10-13 |
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