CN101652446A - The composition that is used for construction adhesive - Google Patents
The composition that is used for construction adhesive Download PDFInfo
- Publication number
- CN101652446A CN101652446A CN200880008781A CN200880008781A CN101652446A CN 101652446 A CN101652446 A CN 101652446A CN 200880008781 A CN200880008781 A CN 200880008781A CN 200880008781 A CN200880008781 A CN 200880008781A CN 101652446 A CN101652446 A CN 101652446A
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- Prior art keywords
- composition
- block copolymer
- styrene
- elastic block
- mixture
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 239000000853 adhesive Substances 0.000 title claims description 22
- 230000001070 adhesive effect Effects 0.000 title claims description 22
- 238000010276 construction Methods 0.000 title claims description 20
- 239000002245 particle Substances 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 26
- 229920001400 block copolymer Polymers 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 15
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 8
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 5
- 239000006254 rheological additive Substances 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 3
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920005570 flexible polymer Polymers 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- GJKZSOHUVOQISW-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 GJKZSOHUVOQISW-UHFFFAOYSA-N 0.000 claims 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical group CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 7
- 229920002633 Kraton (polymer) Polymers 0.000 description 24
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 19
- 239000011159 matrix material Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- -1 methacrylic acid 3-methyl cyclohexanol ester Chemical class 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- DFPOZTRSOAQFIK-UHFFFAOYSA-N S,S-dimethyl-beta-propiothetin Chemical compound C[S+](C)CCC([O-])=O DFPOZTRSOAQFIK-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920001084 poly(chloroprene) Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920013644 Chemigum Polymers 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- 229920013646 Hycar Polymers 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940102838 methylmethacrylate Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000003351 stiffener Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-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
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GILMNGUTRWPWSY-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(O)COC(=O)C=C GILMNGUTRWPWSY-UHFFFAOYSA-N 0.000 description 1
- RQAVKYPVSDCFJQ-UHFFFAOYSA-N 2-methyl-n-(2-methylpropoxy)prop-2-enamide Chemical compound CC(C)CONC(=O)C(C)=C RQAVKYPVSDCFJQ-UHFFFAOYSA-N 0.000 description 1
- VALXVSHDOMUUIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(O)=O VALXVSHDOMUUIC-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- 229910000547 2024-T3 aluminium alloy Inorganic materials 0.000 description 1
- ZRIMDWRLVGDUBW-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid phosphoric acid Chemical group P(=O)(O)(O)O.OCCC=C(C(=O)O)C ZRIMDWRLVGDUBW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000005340 bisphosphate group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to be used to comprise the composition of acrylic acid structure tackiness agent of the mixture of segmented copolymer, elastomerics and elastomeric polymer particle.
Description
The present invention relates to the field of acrylic acid structure tackiness agent (based on acrylate or methacrylic ester) and uses thereof.
Construction adhesive is that other will be attached to the good surrogate of one mechanical skill as two materials of metal or plastics.This is because and when using as comparing during the other technologies of riveted joint or welding, bonding (bonding) can produce better power distribution.In addition, use bonding often the permission to work faster, also have to provide and compare better and the isolated advantage of external factor (external elements) (dust, moisture) with mechanical skill.
Therefore, construction adhesive is applied in many industrial circles, although they have some shortcoming really.In fact, when essential excellent mechanical intensity, in curing (typing) process of tackiness agent, produce bonding often be inflexible.Therefore, if the elasticity deficiency of tackiness agent then when two parts that will be combined in stand to make the power that they separate, may be observed slight crack (fracture).Really have tackiness agent, but they often has low physical strength with favorable elasticity.
Therefore, need find and not only have good mechanical strength (particularly shearing resistance) but also have gratifying elastic construction adhesive.And at dissimilar materials, it is important particularly observing these character on metal and matrix material.At last, importantly, can on vertical or the surface of dangling, application can before being applied to the second surface that to adhere, not slide than length (greatlengths) or flow (flowingoff) thereby these tackiness agents have high viscosity.This phenomenon is horrible especially when must the farm labourer doing the time.
This sliding phenomenon has reduced for example purposes of acrylic based binders in the application that long article need be adhered to sheet material (panels).Attempt to use the fact of these tackiness agents can increase the construction time or make production process complicated.
The tackiness agent that exploitation is used for such purposes will make simplification need adhere two large-area methods, change building material and quicken these methods and become possibility.
The objective of the invention is by providing the binder composition that can be used in the construction adhesive to address the above problem, described construction adhesive has and is equal to or greater than 80% extension at break, has the tensile shear strength greater than 10 MPas on aluminium.In addition, tackiness agent according to the present invention has rheological, make and thickness might be 3-5 millimeter at least, preferred 6-8 millimeter at least according to adhesive application of the present invention to slick vertical metal surface, and in polymerization or solidify the described adhesive flow that can not occur in before finishing under the influence of gravity.
Tackiness agent according to the present invention is made up of composition according to the present invention and second component that contains polymerization starter (catalyzer).Composition according to the present invention mixes with second component on vertical surface, has observed the maximum ga(u)ge that gravity does not make tackiness agent collapse (collapse) before curing.
Generally speaking, the present invention can make the rheological of construction adhesive be conditioned and keep 80% minimum elongation simultaneously.
Construction adhesive is made up of two kinds of components, promptly is used for the catalyzer that polymerization or curing contain monomeric another kind of component.
Therefore, the present invention relates to be used for the composition of construction adhesive, it comprises:
(a) at least a methacrylate monomer;
(b) at least a vinylbenzene and at least a second monomeric elastic block copolymer of comprising;
(c) at least a elastomerics, described elastomerics is selected in the compatible mode of the hildebrand's solubility parameter of the segmented copolymer of its Xi Erde Blanc moral (Hildebrand) solubility parameter and use; And
(d) particle that forms by thermoplastic shell and elastic kernel.
Therefore, will use with curing catalysts according to composition of the present invention.
Preferably, segmented copolymer (b) is selected from the segmented copolymer that comprises vinylbenzene and isoprene, the elastic block copolymer that comprises vinylbenzene and divinyl or ethene or its mixture.
In preferred specific embodiments, ester monomer (a) is a methacrylate monomer.Preferably select alcohol moiety to have the methacrylate monomer of short straight chain (promptly having one or two carbon atom).Therefore, preferred monomers according to the present invention is methyl methacrylate and Jia Jibingxisuanyizhi.
In another embodiment, alcohol moiety has at least one ring, and it can be substituted or not be substituted.Therefore, in this specific embodiments, monomer can be selected from especially: methacrylic acid tetrahydro furfuryl ester, methacrylic acid phenoxy ethyl, isobornyl methacrylate, methyl propenoic acid glycidyl base ether-ether, benzyl methacrylate, cyclohexyl methacrylate or methacrylic acid 3-methyl cyclohexanol ester.
Also can use the mixture of these esters.The weight percent of methacrylic ester is preferably 20-80% in the composition, 30-65% more preferably, even 42-58% more preferably, promptly about 50%.
In a special specific embodiments, composition comprises that also at least a alcohol moiety has the acrylate monomer of the straight chain of at least 6 carbon atoms (e) (long-chain monomer).Therefore, preferably use lauryl methacrylate(LMA), methacrylic acid 2-ethylhexyl, 2-EHA, based on the ester of polyoxyethylene glycol or the mixture of these esters.It is maximum 10% that composition preferably includes, and preferred maximum 8% or even these acrylate long-chain monomers of maximum 5% gross weights.In a special specific embodiments, composition comprises two kinds of monomeric mixtures of acrylate long-chain ester.Preferably, when composition only comprised a kind of acrylate monomer (e), preferably this monomeric amount was 8 weight % or still less, although when composition comprises the mixture of these esters (e), acceptable amount is 8-10%.In this case, preferably the amount of each ester mostly is 5% most.
Composition also can comprise other monomers, as vinyl cyanide, methacrylonitrile or vinylbenzene.
Also comprise the segmented copolymer that one or more are different according to composition of the present invention.Therefore, it can comprise styrene isoprene styrene block copolymer (SIS) (SIS), comprises the block polymer of vinylbenzene and divinyl or ethene or their mixture.
When composition comprises the segmented copolymer that comprises vinylbenzene and divinyl, it may be styrene-butadiene-styrene multipolymer (SBS) or styrene/isoprene-butadiene/styrene copolymers (SIBS), as Kraton MD6455 (from the Kraton Polymers of company), its by people such as Donn doctor DuBois 9-12 day in October, 2005 in Louisville, the meeting of KY " tackiness agent; (the Adhesives ﹠amp of sealing agent executive session; Sealants CouncilMeeting) " go up description.
When composition comprised the block polymer that comprises vinylbenzene and ethene, it can be SEBS (styrene/ethylene-butadiene/styrene copolymers) or SEPS (styrene/ethylene-propylene/styrene multipolymer).These compounds can be available from Kraton G range (from KratonPolymers).
Preferably, vinylbenzene is with the 15-50% of SBS multipolymer weight, 22-40% more preferably, even more preferably approximately the ratio of 28-33% exist.With 12-24%, more preferably approximately the weight ratio of 18-19% exists in SIS or SIBS multipolymer for it.
When composition comprised the mixture of two kinds of segmented copolymers (as SIS and SIBS), the SIS/SIBS relative proportion was preferably in 4/1 (weight ratio of the composition) ratio vary to 1.5/1.Preferred SIS is about 3/1 or 3.3/1 with respect to the ratio of second segmented copolymer.Yet, also may use the SIS/SIBS mixture with the relative proportion identical with the SIS/SIBS mixture.Also may use the mixture of SIS, SIBS and SBS.Another segmented copolymer also can be added to one of them in these mixtures.
Spendable segmented copolymer SIS, SBS or SIBS are known to those skilled in the art according to the present invention.Especially, they are by Kraton Polymers company (Houston, Texas, USA) preparation.Therefore, might use disclosed SIS KratonD1160 or Kraton D1161 in US 20050238603, the SBS Kraton D1102 and SIBS Kraton MD6455 or the Kraton MD 6460 that in US 5106917, describe.
How to those skilled in the art will know that from those existence, particularly according to they in the monomer that uses solubleness or select to be used for other SIS, SIBS and SBS segmented copolymer according to their tensile strength according to composition of the present invention.
Preferably, composition according to the present invention comprises 5-30% by weight, preferred 12-25%, the more preferably elastic block copolymer of 15-25%.
In a special specific embodiments, composition according to the present invention comprises elastic block copolymer and at least a elastic block copolymer that comprises vinylbenzene and divinyl that comprises vinylbenzene and isoprene, i.e. SIS/SIBS mixture, SIS/SBS mixture or SIS/SIBS/SBS mixture.
In another embodiment, only comprise a kind of elastic block copolymer that comprises vinylbenzene and isoprene, i.e. SIS according to composition of the present invention.
According to another specific embodiments, only comprise a kind of elastic block copolymer that comprises vinylbenzene and divinyl according to composition of the present invention, it is selected from SIBS or SBS.
Also comprise at least a elastomerics according to composition of the present invention, described elastomerics is selected in its mode compatible with the segmented copolymer that uses in solution.If necessary, its (functionalized) (having two keys, particularly methacrylate functional at its end combines with monomeric with improvement) that be functionalized.Preferably, select liquid elastomer.Preferred separately or to use at least a functionalized elastomeric body with the form of mixtures of at least a non-functionalized elastomeric body.
Especially, described elastomerics is selected in the compatible mode of the hildebrand's solubility parameter of the segmented copolymer of its hildebrand's solubility parameter and use.Hildebrand's solubility parameter is that the square root known and cohesive energy density(CED) (cohesive energydensity) by compound is calculated.Especially, elastomeric hildebrand's solubility parameter is 8-9.Therefore, (polyhutadiene is preferably liquid and functionalized to the elastomerics of preferred use polyhutadiene type, for example has the vinyl terminal group, contain ester group, as derive from EmeraldPerformance Materials (EPM), (Cuyahoga Falls, Ohio, Hycar VTB 2000x168 USA) or derive from the Ricacryl 3801 of Sartomer) or polyisoprene type.(Neoprene AD10 comes from DuPont, USA) also can to use sovprene.These elastomericss can use separately or use (therefore with form of mixtures, especially, might use sovprene/(functionalized poly divinyl) mixture or (functionalized poly divinyl)/(non-functionalized poly divinyl such as Hycar CTB 2000x162 (EPM)) mixture.
The amount of this component (c) advantageously is according to the 4-20% of the weight of composition of the present invention, is preferably 6-15%, more preferably is about 8-12%.
In composition, the relative weight ratio of segmented copolymer/elastomer blends is 4/1-0.5/1, is preferably about 2/1.Yet, also may have the relative proportion of about 0.5/1 rank (order).
Also comprise the elastomeric polymer particle according to composition of the present invention.These particles are called " nuclear-shell (core-shell) " particle in English, it is known to those skilled in the art, and by " firmly " thermoplastic shell, preferably, often form with elastic kernel styrene copolymerized or acrylic based on poly methyl methacrylate (PMMA) and by being generally butadienyl.For implementing the present invention, acrylonitrile-butadiene-styrene (ABS) (ABS), methacrylic ester-butadiene-styrene (MBS) and methacrylic ester-acrylonitrile-butadiene-styrene (ABS) (MABS) polymkeric substance and their mixture have been mentioned especially.
These particles comprise the crosslinked elastic kernel that is surrounded by thermoplastic shell, often are methyl-methacrylate polymers (PMMA).Patent US 3 985 703, US 4 304 709, US 6 433 091, and EP 1 256 615 and US 6 869 497 have described such particle especially, so it is known to those skilled in the art.
Especially, preferred impact-resistant modified particle, particularly MBS impact modifier.In preferred specific embodiments, these MBS have the lightly crosslinked of the polymkeric substance that forms nuclear.In addition, these MBS except their shock strength, also preferably have the splitting resistance of (shock-induced) of impact induced.
Can obtain nuclear-shell (core-shell) polymkeric substance from many companies.Therefore, GEPlastics and Arkema (Paris, FRA) have also been mentioned.Particularly preferred particle is Clearstrength C301, C303H, C223, C350, C351, E920 or the C859 type that comes from Arkema, preferred C301 and C303H MBS.Also can use the DurastrengthD300 or the D340 that derive from Arkema, it has the vinylformic acid nuclear that is surrounded by the PMMA shell.Similarly, also may use the MBS, particularly Paraloid that develops by Rohm and Haas (Philadelphia, PA, the U.S.)
TMBTA 753.
These particles can use separately or use with form of mixtures.Therefore, in a special specific embodiments of the present invention, used MBS (C303H or C301 especially) particle and had the PMMA shell and the mixture of the particle (D340 particle especially) of vinyl cyanide nuclear.
Preferably, the amount of these particles in composition accounts for the 2-20% of composition weight, preferred 5-15%.
Also can comprise acid mono according to composition of the present invention, if can be by the acid mono of unsaturated carboxylic acid radical polymerization, well known in the art, toxilic acid, Ba Dousuan, m-phthalic acid and Boletic acid type.Also may add isobornyl acrylate (IBXA), methacrylic acid 2-hydroxyl ethyl ester (HEMA), methacrylic acid 2-hydroxypropyl acrylate (HPMA), vinylformic acid 2-(perfluoro octyl) ethyl ester (POA), vinylformic acid tetrahydro furfuryl ester (THFA) or isobutoxy Methacrylamide (IBMA).The mixture that can add these compounds, particularly HEMA/HPMA mixture.Preferable methyl vinylformic acid or vinylformic acid.This compound that adds 2-10%, preferred 3-5%.
As above finding also can comprise other elastomericss according to composition of the present invention, as sovprene, (comes from Dupont, USA) as Neoprene AD10.
In its preferred specific embodiments, also can comprise at least a additional compounds according to composition of the present invention, it is selected from curing catalyst, rheology modifier or adhesion promotor.
When adding catalyzer, curing catalyst is used to promote the polymerization and the curing of tackiness agent.It is a tertiary amine, is preferably arylamine, for example dimethyl right-Tolylamine and/or 2,2 '-(right-the tolyl imido grpup) di-alcohol.
Rheology modifier is used to improve the desirable viscosity according to composition of the present invention, makes it be easy to be applied to and treat on the bonded surface.Can use polyamide-based, as Disparlon 6200 or Disparlon 6500 (coming from Kusumoto Chemicals Ltd, Japan).The normally used amount of this rheology modifier is no more than 2% or 3% of composition weight.
In the context according to composition of the present invention, preferably, phosphate-based adhesion promotor is by methacrylated (methacrylated).Especially, use the phosphoric acid ester adhesion promotor, wherein ester is a 2-hydroxyethyl methacrylic acid phosphoric acid ester.Especially, it can obtain by title Genorad 40 (Rahn AG, Zurich, Switzerland).Such adhesion promotor is being known in the art, and is disclosed in especially among the US 4223115.Therefore; mentioned following substances: phosphoric acid 2-methacryloyl ethoxy ester (2-methacryloyloxyethyl phosphate); two-(phosphoric acid 2-methacryloyl ethoxy ester); phosphoric acid 2-acryl ethoxy ester; two-(phosphoric acid 2-acryl ethoxy ester); methyl-(phosphoric acid 2-methacryloyl ethoxy ester); ethyl-(phosphoric acid 2-methacryloyl ethoxy ester); (particularly known name is called T-Mulz 1228 (Harcros Organics for the phosplate of methacrylic acid 2-hydroxyl ethyl ester and the mixture of bisphosphate; Kansas City, US) a kind of) and similar compound or derivative.
Other components are as mineral filler (TiO
2, CaCO
3, Al
2O
3, zinc phosphate), ultra-violet stabilizer (as come from Ciba-Geigy 2-hydroxyphenyl three azines, Tinuvin 400), paraffin (paraffin) and glass microballon also can be added to according in the composition of the present invention.Radical polymerization inhibitor also can be added into to increase the life-span of composition as BHT or benzoquinones class such as naphthoquinones, quinhydrones or ethyl quinhydrones.
Be known that construction adhesive is formed by two components, described two components are to solidify and the catalyzer of the tackiness agent of finalizing the design according to composition of the present invention and being used to.These two components are kept in two different compartments (compartments) and when adhesive application and mix.Such tackiness agent also is a theme of the present invention.
This catalyzer is a radical polymerization initiator, especially, is peroxide-based initiator, and is well known in the art.What can select especially is Benzoyl Peroxide, tert-butyl peroxy benzoate or hydrogen peroxide cumene.When catalyzer comprises the superoxide of 5-40 weight %, especially, during the superoxide of about 20 weight %, it is preferred.Used the thickener that comprises about 20% Benzoyl Peroxide especially.
With with respect to second component 1/1 to 1/30, preferred 1/5 to 1/30, even more preferably about 1/10 ratio uses catalyzer, described second component is according to composition of the present invention.
Therefore, the present invention is based on the following fact, be that elastic block copolymer (is selected from the segmented copolymer that comprises vinylbenzene and isoprene, comprise the elastic block copolymer of vinylbenzene and divinyl or ethene or their mixture), functionalized liquid elastomer (described elastomerics is selected in the compatible mode of the hildebrand's solubility parameter of its hildebrand's solubility parameter and described elastic block copolymer) and make the composition to obtain to be used for construction adhesive based on being used in combination of divinyl and cinnamic flexible polymer particle, described construction adhesive has and is equal to or greater than 80%, more preferably 100% extension at break is equal to or greater than 10 MPas, the tensile shear strength and the high viscosity of 15 MPas even 17 MPas (on aluminium).This shearing resistance can be regulated by the aforesaid adhesion promotor or the acid mono of addition.
This result is all beyond one's expectations, because this tackiness agent has the character that is far superior to those tackiness agents described in the prior thus.Therefore, patent US 6 433 091 suggestions are used core-shell polymer and have been mentioned MABS, MBS and abs polymer in construction adhesive.Yet the composition of describing in this patent does not all comprise all components according to composition of the present invention.
Similarly, EP 1 256 615 is the shearing resistance of the tackiness agent of not mentioned description also, and unique data are inferior to the character according to composition of the present invention far away.
And when using on matrix material, this tackiness agent also has fabulous physical strength.What in fact, find usually is can not obtain repetition on matrix material at viewed mechanical strength value on the metal.
Therefore, use makes that according to composition of the present invention metal, plastics and matrix material might be bonded to matrix material therefore also can be applied in silo, boat or truck trailer (trucktrailer) the structure field especially.It also can be used on automobile construction field or railway territory.
Therefore, said composition can make a kind of material cohesive bond to another kind of material, and one or another kind of material is metal, plastics, timber or matrix material especially.Therefore, composition can be used in one or more following application: metal/metal, metal/matrix material, metal/plastic, metal/timber, timber/plastics, timber/matrix material, timber/timber, plastics/matrix material, plastic/plastic or matrix material/matrix material are bonding.
Therefore, when material must be bonded to matrix material, useful especially according to composition of the present invention.
The flexible metacrylic acid ester structure tackiness agent impact with high-mechanical property and the vibration that obtain with composition according to the present invention have recuperability (resilient) and resistibility.They make might may produce bonding joint (adhesive joints) at the storeroom with identical or different chemical property, and described material for example is a concrete, timber, pottery, glass, ferrite, aluminium, anodized aluminum, steel, galvinized steel, stainless steel, lacquer painting metal (painted metal), steel, copper, zinc, ABS, PVC, polyester, esters of acrylic acid, polystyrene, gel coat (gel-coat) polyester or epoxide, matrix material, glass-fiber composite, laminating material, polynuclear plane and any mopping or the painted material.
They also can fill big gap between the substrate (substrates) with different or variable thickness, roughness or planeness with better stress distribution.This character is owing to the rheological according to composition of the present invention increases.
Hardness according to composition of the present invention is derived from the principle measurement that cone (cones) diameter is 4.5 centimetres slump cone (slump cones) (being also referred to as a Abrams cone) principle by use.Abrams cone method (Abrams cone method) is used especially in cement and mortar field, makes the slump (slump) that might measure the concrete cone under the influence of himself weight.This slump is big more, then thinks concrete mobile more (fluid).
The slump of having observed according to preparation of the present invention is slight, and promptly they are combined in one under the influence of their own wts.Therefore, can think, by the similar mortar of binder performance of composition acquisition according to the present invention because they have pasty consistency.Because their pasty state character, these tackiness agents can be used as cement or mortar filling two gaps between part and to allow not directly bonding between two parts of contact, and still keep the character of thermoplastic binder, that is, the elasticity that do not have of mortar especially.
Therefore, may produce the big area molectron with big especially gap, it is combined in one and do not occur collapsing after surpassing one hour the assembling of long shaping time relatively at several minutes.Especially, this (deck-on-shell) molectron or fillet welding on preparation deck-shell are favourable separator is combined in one shipbuilding n. camber.
Also has low shr (shrinkage) according to composition of the present invention, particularly after thermoplastics is engaged to polyester composite.Therefore, the observed shr of composition according to the present invention is lower than 2%, and prior art combinations generally has the shr of 5-7%.
Therefore, denseness and their the low shr according to composition of the present invention makes them be used to obtain king-sized bonding joint easily together.
In addition, the snappiness of said composition make treat difference bulging force (differential expansion force) between the bonded substrate spread all over several meters than length (great lengths), and reduce simultaneously or eliminate (angle, roughness, planeness) defective how much.
In addition, composition according to the present invention has low exothermicity in solidification process.This also is favourable because too high exothermicity,, can apply force to ABS and on matrix material, produce in conjunction with strain particularly when in conjunction with ABS thermoplastics (can be used as stiffener) during to the polyester based composite bodies, its mopping week after date be visible.
Application that relates to and moving part (activity sectors) comprising:
The combination of stiffener, railing, skeleton construction, beam, strengthening rib, sheet material, separator, fastening piece, upholder, body composition (body components), hog frame, inset, cylinder shape assembly and conical assembly, hinge, framework etc.; The combination that combines (lamination take-up on partitions) with stratiform thing on the separator with combining of weighting material, needs high mechanical strength; Particularly in conjunction with any bonded structure or the mechanical component in following field: shipbuilding, car industry, railway (and Infrastructure), air system, aerospace industry, electronics industry, dynamo-electric and household electrical appliances are equipped, military fabrication (military structures), indication (and advertisement) signal and panel, city furniture, outdoor woodwork (window, glaze post (glazed bays), window, entrance door and garage door), wind energy conversion system (wind machines), freight container (containers), engineering structure and Infrastructure (suspension bridge, off-lying sea oil platform and hangarage etc.), building and fastening piece, curtain wall and solar panel.
Instruction provided by the invention might change according to the viscosity of composition of the present invention those skilled in the art and keeps mechanical property for example extension at break (greater than 80%) or shearing resistance simultaneously.
For example, following two types composition falls into scope of the present invention, and those skilled in the art can regulate the relative proportion of various components.
Therefore, can use following composite preparation:
(a) methacrylate monomer (MMA): be equal to or greater than 40%;
(b) elastic block copolymer (separately or with form of mixtures): 15-21%;
(c) elastomerics (functionalized poly divinyl (VTB)): 8-10%; And
(d) core-shell particles: 2-15%.
The acid mono of Disparlon, 1-4% of monomer (e), 0-3% of following substances: 5-10% amount and the Genorad of 0-3% have also been added.
Also might use following composite preparation:
(a) methacrylate monomer (MMA): be equal to or greater than 40%;
(b) elastic block copolymer (separately or with form of mixtures): 2-15%;
(c) the functionalized poly divinyl (VTB) of 8-10%, the sovprene of optional and 3-10%, or butadiene/acrylonitrile copolymer is mixed; And
(d) core-shell particles: 10-25%.
Also can add the acid mono of Disparlon, 1-4% of monomer (e), 0-3% of following substances: 5-10% amount and the Genorad of 0-3%.
Embodiment
Following embodiment for example understands the present invention, but does not limit the scope of the invention.
Embodiment 1: the raw material of use and method
Used following component:
Methacrylate monomer (a): methyl methacrylate (MMA);
Acrylate monomer (e): lauryl methacrylate(LMA) (LauMA) and/or 2-EHA (2EHA);
SIS multipolymer (b): Kraton D1160 (Kraton Polymers);
SBS multipolymer (b): Kraton D1102 (Kraton Polymers); Or
SIBS multipolymer (b): Kraton MD6455 (Kraton Polymers);
Functionalized liquid elastomer (c):
VTB 2000x168 (Noveon, USA) (functionalized poly divinyl);
Flexible polymer particle (d): Clearstrength C301 (Arkema), ClearstrengthC303H, Durastrength D340 (Arkema), Paraloid BTA 753 (Rohm and Haas);
Acid mono: methacrylic acid (MAA);
Adhesion promotor: methacrylic acid phosphoric acid ester Genorad 40 (Rahn AG);
Curing catalyst: dimethyl-right-Tolylamine (DMPT) and/or dihydroxy ethyl-right-Tolylamine (DHEPT);
Rheology modifier: Disparlon 6200, Disparlon 6500 (KusumotoChemicals);
Catalyzer: 20% Benzoyl Peroxide ADERIS 1003 (Jacret, France);
And
Nitrile/butadiene elastomer: Chemigum P83 (Eliokem, France).
Carried out test according to following experimental program:
The test that-use ISO 527 standards are measured tensile strength TS, extension at break EB and Young's modulus or Young's modulus YM.
-to use to well known to a person skilled in the art the method observation elongation of particularly in ISO 527 standards, describing, the rate (pull rate) of drawing of tackiness agent is constant 50 mm/min;
-according to ISO 4587 canonical measure tensile shear strengths (SS).In brief, use and to be measured as 100 * 25 * 1.6 millimeters (2024T3 aluminium test specimens of L * W * T).Two test specimens are bonded to each other, and the overlapping region is 25 * 12 millimeters (300 square millimeters), has the bonding bond thickness of about 200-400 micron.Then by drawing two test specimens to measure the required power of the bonding joint of fracture; And
-according to ISO 14173 standard evaluation stretch release intensity (PS).Use is measured as 100 * 25 * 1.5 millimeters aluminium test specimen or is measured as 100 * 25 * 0.8 millimeter galvinized steel test specimen, and these test specimens carry out combination with overlapping and about 500 microns bonding bond thickness of 75 * 25 millimeters.
The viscosity of tackiness agent is not observed the thickness of the tackiness agent of downward landing (downward slip) and is estimated by being applied to vertical surface.
Be bonded to matrix material: carry out the combination test by galvinized steel being bonded to the polyester gel coat.Estimate bonding quality according to following agreement:
++=very good; +=medium;-=a little less than
The result
Tested the sample of the mixture that comprises two kinds of elastic block copolymers (b) and elastomerics (c) that has or do not have particle (d).
| Sample | ??1 | ??2 | ??3 | ??6 | ??5 | ??4 |
| ??MMA | ??50.2 | ??46.2 | ??51 | ??46 | ??54 | ??50 |
| ??Kraton??D1160 | ??16 | ??16 | ??16 | ??15 | ??16 | ??16 |
| ??Kraton??MD6455 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 |
| ??VTB??2000x168 | ?10 | ??10 | ??10 | ??10 | ??10 | ??10 |
| ??C301 | ??- | ??5 | ??- | ??5 | ??- | ??4 |
| ??2EHA | ??8.8 | ??8.8 | ??8 | ??9 | ??5 | ??5 |
| ??MAA | ??5 | ??4 | ??4 | ??4 | ??4 | ??4 |
| ??Genorad?40 | ??3 | ??3 | ??3 | ??3 | ??3 | ??3 |
| ??DMPT | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| ??Disparlon??6500 | ??1 | ??1 | ??2 | ??2 | ??2 | ??2 |
| Amount to (weight) | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
The result who obtains is as follows:
| Sample | ??1 | ??2 | ??3 | ??6 | ??5 | ??4 |
| SS (MPa) is on aluminium | ??20.5 | ??18.7 | ??19.2 | ??18.3 | ??n.c.o. | ??20.5 |
| PS (Newton/millimeter) is on aluminium | ??17.3 | ??15.4 | ??14.3 | ??13 | ??n.c.o. | ??15.5 |
| PS (Newton/millimeter) is on galvinized steel | ??17.5 | ??16.7 | ??19.6 | ??15 | ??n.c.o. | ??15.3 |
| TS (MPa) | ??9.6 | ??10.1 | ??9.8 | ??9.6 | ??11.1 | ??10.5 |
| ??EB(％) | ??251 | ??189.8 | ??156.3 | ??202 | ??84.6 | ??151.1 |
| YM (MPa) | ??95.7 | ??118.5 | ??150 | ??104.6 | ??201.8 | ??164.4 |
| Thickness (millimeter) | ??1-2 | ??3-5 | ??2-4 | ??6-9 | ??2-4 | ??8-11 |
| Gel coat is bonding | ??+ | ??++ | ??n.c.o. | ??++ | ??++ | ??+ |
N.c.o.: do not carry out.
These results prove, the existence of elastic particle (d) makes might increase the viscosity (not having the thickness of mobile layer to measure by being employed) of tackiness agent, and the reduction that do not perceive of shearing resistance or extension at break.
When mixing other segmented copolymers (SIS+SBS), observed similar result.
Also tested the compound that comprises a kind of (a single) segmented copolymer (b):
| Sample | ??8 | ??9 | ??10 | ??11 | ??12 | ??13 | ??14 |
| ??MMA | ??54 | ??50 | ??50 | ??54 | ??50 | ??54 | ??50 |
| ??Kraton??D1102 | ??- | ??- | ??- | ??21 | ??21 | ??- | ??- |
| ??Kraton??D1160 | ??- | ??- | ??- | ??- | ??- | ??21 | ??21 |
| ??Kraton??MD6455 | ??21 | ??21 | ??21 | ??- | ??- | ??- | ??- |
| ??VTB??2000x168 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 |
| ??C301 | ??- | ??5 | ??4 | ??- | ??4 | ??- | ??4 |
| ??2EHA | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 |
| ??MAA | ??4 | ??4 | ??4 | ??5 | ??4 | ??5 | ??4 |
| ??Genorad?40 | ??3 | ??3 | ??3 | ??3 | ??3 | ??3 | ??3 |
| ??DMPT | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| ??Disparlon??6500 | ??2 | ??1 | ??2 | ??1 | ??2 | ??1 | ??2 |
| Amount to (weight) | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
The result who obtains is as follows:
| Sample | ??8 | ??9 | ??10 | ??11 | ??12 | ??13 | ??14 |
| SS (MPa) is on aluminium | ??22 | ??20 | ??22.2 | ??22 | ??21.4 | ??21.1 | ??n.c.o. |
| PS (Newton/millimeter) is on aluminium | ??16.7 | ??13 | ??16.6 | ??12.4 | ??14.9 | ??20.5 | ??n.c.o. |
| PS (Newton/millimeter) is on galvinized steel | ??13.1 | ??13.5 | ??16.8 | ??8.9 | ??18.7 | ??17.2 | ??n.c.o. |
| TS (MPa) | ??10.5 | ??10.9 | ??11 | ??12.4 | ??12.4 | ??9.4 | ??11.5 |
| ??EB(％) | ??86.5 | ??128.8 | ??140.4 | ??43.2 | ??146.3 | ??50.2 | ??87.3 |
| YM (MPa) | ??178.6 | ??175.6 | ??177.8 | ??268 | ??228.3 | ??173.8 | ??210.2 |
| Thickness (millimeter) | ??2-4 | ??3-5 | ??6-9 | ??1-2 | ??6-9 | ??1-2 | ??6-9 |
| Gel coat is bonding | ??++ | ??++ | ??++ | ??+ | ??++ | ??+ | ??n.c.o. |
Obviously, component (b), (c) and the existence of combination (d) make the tensile shear strength that might keep fabulous to improve extension at break (elasticity) and to increase viscosity.It should be noted that also observed stripping strength and tensile strength result have obtained maintenance.
Also tested different elasticity core-shell particles:
| Sample | ??15 | ??16 | ??17 |
| ??MMA | ??46 | ??46 | ??45.1 |
| ??Kraton?MD6455 | ??21 | ??21 | ??18.9 |
| ??Kraton?D1160 | ??- | ??- | ??- |
| ??VTB?2000x168 | ??10 | ??10 | ??9 |
| ??Neoprene?AD10 | ??- | ??- | ??- |
| ??C303H | ??- | ??10 | ??- |
| ??D340 | ??10 | ??- | ??14 |
| ??BTA753 | ??- | ??- | ??- |
| ??2EHA | ??5 | ??5 | ??5 |
| ??Lauryl?MA | ??- | ??- | ??- |
| ??MAA | ??4 | ??4 | ??4 |
| ??Genorad?40 | ??3 | ??3 | ??3 |
| ??DMPT | ??1 | ??1 | ??1 |
| ??Disparlon?6500 | ??0 | ??0 | ??0 |
| Amount to (weight) | ??100 | ??100 | ??100 |
Obtained following result:
| Sample | ??15 | ??16 | ??17 |
| SS (MPa) is on aluminium | ??22.1 | ??23.5 | ??20.0 |
| TS (MPa) | ??9.7 | ??10 | ??9.9 |
| ??EB(％) | ??127.9 | ??97.0 | ??97.2 |
| YM (MPa) | ??200.1 | ??165.6 | ??170.2 |
| Thickness (millimeter) | ??8-11 | ??14-18 | ??18-20 |
| Gel coat is bonding | ??++ | ??++ | ??++ |
Also test other and comprised the preparation of the mixture of segmented copolymer (b).
| Sample | ??19 | ??20 | ??21 | ??22 | ??23 | ??24 | ??25 |
| ??MMA | ??53.72 | ??55 | ??43.3 | ??40.3 | ??40.3 | ??44.3 | ??44.3 |
| ??Kraton??D1160 | ??- | ??5 | ??15 | ??15 | ??15 | ??16 | ??16 |
| ??Kraton??MD6455 | ??7.14 | ??15 | ??5 | ??5 | ??5 | ??5 | ??5 |
| ??VTB??2000x168 | ??8.2 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 |
| ??2EHA | ??4.1 | ??- | ??5 | ??5 | ??5 | ??5 | ??5 |
| ??Lauryl?MA | ??5.1 | ??1 | ??5 | ??5 | ??5 | ??5 | ??5 |
| ??C303H | ??15.3 | ??10 | ??- | ??15 | ??- | ??- | ??- |
| ??D340 | ??- | ??- | ??15 | ??- | ??- | ??10 | ??- |
| ??BTA753 | ??- | ??- | ??- | ??- | ??15 | ??- | ??- |
| ??MAA | ??2 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| ??DHEPT | ??- | ??- | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 |
| ??DMPT | ??0.3 | ??1 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| ??Neoprene??AD10 | ??4.14 | ??- | ??- | ??- | ??- | ??- | ??- |
| ??Chemigum??P83 | ??- | ??- | ??- | ??- | ??- | ??- | ??10 |
| ??Disparlon??6500 | ??- | ??2 | ??- | ??3 | ??3 | ??3 | ??3 |
| Amount to (weight) | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
Obtained following result:
| Sample | ??19 | ??20 | ??21 | ??22 | ??23 | ??24 | ??25 |
| TS (MPa) | ??7.2 | ??5.5 | ??6.4 | ??7 | ??6.1 | ??6.2 | ??3.2 |
| ??EB(％) | ??132.8 | ??103.5 | ??180.2 | ??291 | ??210.3 | ??199.8 | ??130.3 |
| YM (MPa) | ??108.1 | ??54.3 | ??111.6 | ??102.3 | ??78.9 | ??116.9 | ??35.5 |
| Thickness (millimeter) | ??15-20 | ??12-16 | ??20-25 | ??20-25 | ??20-25 | ??20-25 | ??10-15 |
Effective these results' demonstrations, the particle (d) that use NBR uses in the context of the invention.
All these results prove, by blending ingredients (a) and (b), (c) and (d), and the tackiness agent that might obtain to have high viscosity and keep good extension at break simultaneously.
Claims (16)
1, a kind of composition that is used in the construction adhesive, it comprises:
(a) at least a methacrylate monomer;
(b) at least a cinnamic elastic block copolymer and at least a second monomer of comprising;
(c) at least a elastomerics, described elastomerics is selected in the compatible mode of the hildebrand's solubility parameter of the segmented copolymer of its hildebrand's solubility parameter and use; And
(d) particle that forms by thermoplastic shell and elastic kernel.
2, composition according to claim 1 is characterized in that second monomer of described elastic block copolymer (b) is selected from isoprene, divinyl or ethene.
3, composition according to claim 2 is characterized in that described elastic block copolymer is selected from styrene-isoprene-phenylethene (SIS), styrene-butadiene-styrene (SBS) or styrene-isoprene-butadiene-styrene (SIBS) multipolymer or its mixture.
4,, it is characterized in that it comprises the described elastic block copolymer (b) of 5-30 weight % or the mixture of elastic block copolymer (b) according to each described composition of claim 1 to 3.
5,, it is characterized in that described elastomerics (c) is selected from the mixture of functionalized or not functionalized polyhutadiene, polyisoprene or these components according to each described composition of claim 1 to 4.
6,, it is characterized in that it comprises the described elastomerics (c) of 4-20 weight % according to each described composition of claim 1 to 5.
7,, it is characterized in that described particle (d) is selected from acrylonitrile-butadiene-styrene (ABS), methacrylic ester-butadiene-styrene, methacrylic ester-acrylonitrile-butadiene-styrene (ABS) or methacrylic ester-vinyl cyanide particle or their mixture according to each described composition of claim 1 to 6.
8,, it is characterized in that it comprises the described particle (d) of 2-20 weight % according to each described composition of claim 1 to 7.
9, according to each described composition of claim 1 to 8, it is characterized in that it also comprises at least a acrylate monomer (e), wherein alcohol moiety has the straight chain that at least one contains at least 6 carbon atoms.
10, composition according to claim 9 is characterized in that described a kind of acrylate monomer (e) is methacrylic ester or acrylate monomer.
11,, it is characterized in that it comprises the mixture of two kinds of acrylate monomers (e) according to each described composition in claim 9 and 10.
12,, it is characterized in that it comprises acrylate monomer (e) less than 10 weight % according to each described composition of claim 9 to 11.
13,, it is characterized in that it also comprises sovprene according to each described composition of claim 1 to 12.
14,, it is characterized in that it also comprises at least a additional compounds that is selected from curing catalyst, rheology modifier, adhesion promotor or acid mono according to each described composition of claim 1 to 13.
15, elastic block copolymer, functionalized liquid elastomer and flexible polymer particle are preparing as the combined use in the composition of construction adhesive, described elastic block copolymer is selected from the segmented copolymer that comprises vinylbenzene and isoprene, comprise the vinylbenzene and the second monomeric elastic block copolymer, described functionalized liquid elastomer is selected in the compatible mode of the hildebrand's solubility parameter of its hildebrand's solubility parameter and described elastic block copolymer, and described construction adhesive has and is equal to or greater than 80% extension at break and makes thickness not have rheological in the influence of gravity current downflow at least 3 to 5 millimeters described composition is applied to vertical surface.
16, be used for a kind of material is adhered to the purposes of another kind of material according to each described composition of claim 1 to 14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410340350.2A CN104212366B (en) | 2007-04-05 | 2008-04-04 | Composition for structural adhesive |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0702485A FR2914651B1 (en) | 2007-04-05 | 2007-04-05 | COMPOSITION FOR STRUCTURAL ADHESIVE |
| FR07/02485 | 2007-04-05 | ||
| FR0705492 | 2007-07-26 | ||
| FR07/05492 | 2007-07-26 | ||
| PCT/EP2008/054097 WO2008125521A1 (en) | 2007-04-05 | 2008-04-04 | Composition for structural adhesive |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410340350.2A Division CN104212366B (en) | 2007-04-05 | 2008-04-04 | Composition for structural adhesive |
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| Publication Number | Publication Date |
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| CN101652446A true CN101652446A (en) | 2010-02-17 |
| CN101652446B CN101652446B (en) | 2014-08-27 |
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| Country | Link |
|---|---|
| CN (1) | CN101652446B (en) |
| FR (1) | FR2914651B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103619975A (en) * | 2011-03-25 | 2014-03-05 | 胶合剂与复合材料聚合物公司 | Structural adhesives, process for the preparation thereof, and application thereof |
| CN105593325A (en) * | 2014-02-20 | 2016-05-18 | 乐金华奥斯有限公司 | Rubber-based adhesive composition and rubber-based adhesive tape for automobile using same |
| CN109196066A (en) * | 2016-04-01 | 2019-01-11 | 汉高知识产权控股有限责任公司 | (methyl) acrylate composition of anaerobically curable |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2936956B1 (en) * | 2008-10-10 | 2010-11-12 | Saint Gobain Ct Recherches | PARTICLE FILTRATION DEVICE |
| FR2988397B1 (en) * | 2012-03-26 | 2015-02-20 | Adhesifs Et Composites Polymers | APPLICATION OF STRUCTURAL ADHESIVES FOR CALFASTING |
| FR3039560B1 (en) * | 2015-07-28 | 2019-04-05 | Arkema France | ADDITIVE COMPOSITION FOR USE IN A STRUCTURAL ADHESIVE |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6433091B1 (en) * | 2001-05-10 | 2002-08-13 | Henkel Loctite Corporation | Adhesive composition |
| CN1629243A (en) * | 2002-12-19 | 2005-06-22 | 伊利诺斯工具公司 | Heat-resistant and impact-resistant acrylic/epoxy adhesive |
-
2007
- 2007-04-05 FR FR0702485A patent/FR2914651B1/en active Active
-
2008
- 2008-04-04 CN CN200880008781.1A patent/CN101652446B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6433091B1 (en) * | 2001-05-10 | 2002-08-13 | Henkel Loctite Corporation | Adhesive composition |
| CN1629243A (en) * | 2002-12-19 | 2005-06-22 | 伊利诺斯工具公司 | Heat-resistant and impact-resistant acrylic/epoxy adhesive |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103619975A (en) * | 2011-03-25 | 2014-03-05 | 胶合剂与复合材料聚合物公司 | Structural adhesives, process for the preparation thereof, and application thereof |
| CN105593325A (en) * | 2014-02-20 | 2016-05-18 | 乐金华奥斯有限公司 | Rubber-based adhesive composition and rubber-based adhesive tape for automobile using same |
| US9988561B2 (en) | 2014-02-20 | 2018-06-05 | Lg Chem, Ltd. | Rubber-based adhesive composition and rubber-based adhesive tape for automobile using the same |
| CN105593325B (en) * | 2014-02-20 | 2019-09-13 | 株式会社Lg化学 | Rubber adhesive composition and the automobile rubber adhesive tape for utilizing it |
| CN109196066A (en) * | 2016-04-01 | 2019-01-11 | 汉高知识产权控股有限责任公司 | (methyl) acrylate composition of anaerobically curable |
| CN109196066B (en) * | 2016-04-01 | 2021-08-24 | 汉高知识产权控股有限责任公司 | Anaerobically curable (meth) acrylate compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2914651B1 (en) | 2012-08-31 |
| CN101652446B (en) | 2014-08-27 |
| FR2914651A1 (en) | 2008-10-10 |
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