AU2012322689B2 - Controlled architecture polymers - Google Patents
Controlled architecture polymersInfo
- Publication number
- AU2012322689B2 AU2012322689B2 AU2012322689A AU2012322689A AU2012322689B2 AU 2012322689 B2 AU2012322689 B2 AU 2012322689B2 AU 2012322689 A AU2012322689 A AU 2012322689A AU 2012322689 A AU2012322689 A AU 2012322689A AU 2012322689 B2 AU2012322689 B2 AU 2012322689B2
- Authority
- AU
- Australia
- Prior art keywords
- reactive
- segment
- functional group
- polymer
- acrylic polymer
- 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.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims description 112
- 125000000524 functional group Chemical group 0.000 claims description 87
- 229920000058 polyacrylate Polymers 0.000 claims description 76
- 230000001070 adhesive Effects 0.000 claims description 65
- 239000000853 adhesive Substances 0.000 claims description 63
- 239000002253 acid Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 44
- -1 alkoxymethylol Chemical class 0.000 claims description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 41
- 239000004593 Epoxy Substances 0.000 claims description 38
- 125000003700 epoxy group Chemical group 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 33
- 229920001577 copolymer Polymers 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000004132 cross linking Methods 0.000 claims description 19
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- 150000004756 silanes Chemical class 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000003573 thiols Chemical class 0.000 claims description 6
- 230000000379 polymerizing Effects 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- 230000000111 anti-oxidant Effects 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (Z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 93
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 28
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 27
- 239000003153 chemical reaction reagent Substances 0.000 description 21
- 206010028154 Multi-organ failure Diseases 0.000 description 19
- 230000001143 conditioned Effects 0.000 description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 241000283725 Bos Species 0.000 description 16
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000010926 purge Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000010526 radical polymerization reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 11
- 125000004432 carbon atoms Chemical group C* 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 229920002799 BoPET Polymers 0.000 description 10
- 239000005041 Mylar™ Substances 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- UCTWMZQNUQWSLP-VIFPVBQESA-N Epinephrine Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 230000002441 reversible Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-VAWYXSNFSA-N Azobisisobutyronitrile Chemical compound N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 230000000996 additive Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000875 corresponding Effects 0.000 description 5
- 230000000977 initiatory Effects 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 229950010765 Pivalate Drugs 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000001902 propagating Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 4
- VUNGHBJEVBKTME-UHFFFAOYSA-N [NH-]C=C Chemical class [NH-]C=C VUNGHBJEVBKTME-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- LAKYXBYUROTWBI-UHFFFAOYSA-N bis(benzylsulfanyl)methanethione Chemical compound C=1C=CC=CC=1CSC(=S)SCC1=CC=CC=C1 LAKYXBYUROTWBI-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000001404 mediated Effects 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- XMGQYMWWDOXHJM-UHFFFAOYSA-N (+-)-(RS)-limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-Aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylazacyclopropane Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 241000411998 Gliricidia Species 0.000 description 2
- 235000009664 Gliricidia sepium Nutrition 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N Glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229940119545 Isobornyl methacrylate Drugs 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N Itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N Methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-Bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N Titanium isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229920001567 Vinyl ester Polymers 0.000 description 2
- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1R,3R,4R)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001541 aziridines Chemical class 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000001808 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000002427 irreversible Effects 0.000 description 2
- 229930007650 limonene Natural products 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- 239000008601 oleoresin Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HPEPIADELDNCED-UHFFFAOYSA-N triethoxysilylmethanol Chemical compound CCO[Si](CO)(OCC)OCC HPEPIADELDNCED-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- CRPUJAZIXJMDBK-DTWKUNHWSA-N (+)-camphene Chemical compound C1C[C@@H]2C(=C)C(C)(C)[C@H]1C2 CRPUJAZIXJMDBK-DTWKUNHWSA-N 0.000 description 1
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (N-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-Dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
- UQAIMZSFWBGBTN-UHFFFAOYSA-L 1,2-xylene;dicyanate Chemical compound [O-]C#N.[O-]C#N.CC1=CC=CC=C1C UQAIMZSFWBGBTN-UHFFFAOYSA-L 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- RPKDVZHXJRQCTN-UHFFFAOYSA-N 1,6-bis(2-ethylaziridin-1-yl)-2,2,4-trimethylhexane-1,6-dione Chemical compound CCC1CN1C(=O)CC(C)CC(C)(C)C(=O)N1C(CC)C1 RPKDVZHXJRQCTN-UHFFFAOYSA-N 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- SKTBRSPTURENNM-UHFFFAOYSA-N aziridine;phosphoric acid Chemical class C1CN1.OP(O)(O)=O SKTBRSPTURENNM-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 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
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229930006739 camphene Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- NRLCNVYHWRDHTJ-UHFFFAOYSA-L cobalt(2+);naphthalene-1-carboxylate Chemical compound [Co+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 NRLCNVYHWRDHTJ-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- KRJIBMFDBVWHBJ-UHFFFAOYSA-N cycloheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCCC1 KRJIBMFDBVWHBJ-UHFFFAOYSA-N 0.000 description 1
- VLIHGIDKOZKVBS-UHFFFAOYSA-N cycloheptyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCCC1 VLIHGIDKOZKVBS-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
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- GUOJYIXWHMJFDM-UHFFFAOYSA-N decan-2-yl prop-2-enoate Chemical compound CCCCCCCCC(C)OC(=O)C=C GUOJYIXWHMJFDM-UHFFFAOYSA-N 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- IBWXKMBLEOLOLY-UHFFFAOYSA-N dimethoxy(prop-2-enyl)silicon Chemical compound CO[Si](OC)CC=C IBWXKMBLEOLOLY-UHFFFAOYSA-N 0.000 description 1
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- 125000005022 dithioester group Chemical group 0.000 description 1
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- PBOSTUDLECTMNL-UHFFFAOYSA-N dodecyl prop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
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- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
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- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
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- 239000010433 feldspar Substances 0.000 description 1
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- 238000005755 formation reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- KLGZELKXQMTEMM-UHFFFAOYSA-N hydride Chemical compound [H-] KLGZELKXQMTEMM-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- CFBXDFZIDLWOSO-UHFFFAOYSA-N icosyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCOC(=O)C(C)=C CFBXDFZIDLWOSO-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009114 investigational therapy Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M isothiocyanate Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- ORDSZCXGICENNU-UHFFFAOYSA-L lead(2+) dihydride;octanoate Chemical compound [PbH2+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O ORDSZCXGICENNU-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- JLIDVCMBCGBIEY-UHFFFAOYSA-N pent-1-en-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- OEUAEFQARUZYLW-UHFFFAOYSA-N prop-1-en-2-olate Chemical group [CH2+]C([O-])=C OEUAEFQARUZYLW-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052904 quartz Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229940086735 succinate Drugs 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 1
- XSIGLRIVXRKQRA-UHFFFAOYSA-N triethoxysilylmethanethiol Chemical compound CCO[Si](CS)(OCC)OCC XSIGLRIVXRKQRA-UHFFFAOYSA-N 0.000 description 1
- ARKBFSWVHXKMSD-UHFFFAOYSA-N trimethoxysilylmethanamine Chemical compound CO[Si](CN)(OC)OC ARKBFSWVHXKMSD-UHFFFAOYSA-N 0.000 description 1
- QJOOZNCPHALTKK-UHFFFAOYSA-N trimethoxysilylmethanethiol Chemical compound CO[Si](CS)(OC)OC QJOOZNCPHALTKK-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
Description
CONTROLLED ARCHITECTURE POLYMERS
CROSS REFERENCES TO RELATED APPLICATIONS [0001] The present application claims the benefit of U.S. Provisional Patent Application No. 61/547,481 filed October 14, 2011, which is incorporated herein by reference in its entirety.
BACKGROUND [0001] The subject matter relates to acrylic polymers, and in particular, to acrylic copolymers that include controlled placement of reactive functional groups within the polymer structure. The copolymers are useful in the manufacture of adhesives and elastomers.
[0002] (Meth)acrylic (co)polymers have been studied and used industrially for more than 50 years. Due to a wide range of monomers, (meth)acrylic (co)polymers display a significant array of viscoelastic properties that lend themselves well to applications in adhesives and elastomers. When compared to other copolymers that are used for similar purposes as (meth)acrylics, several significant advantages of (meth)acrylics become apparent. For example, relative to natural rubber and styrene block copolymers (meth)acrylic copolymers have superior optical clarity, UV stability, and temperature and oxidative resistance. State of the art (meth)acrylic copolymers meet many performance characteristics by virtue of their high molecular weight and crosslinking reactions. Because of the wide array of copolymerizable monomers, (meth)acrylic polymers have tailorable polarity and the ability to undergo a variety of crosslinking reactions. Typically high performance (meth)acrylic copolymers are processed with large amounts of organic solvents.
[0003] Increasingly, there are significant economic and regulatory pressures for producers of solvent acrylic polymers to reduce the use of organic solvents in their processes. In particular, it is common for solvent acrylic polymers in adhesive applications to be coated from solutions averaging only 30-40% polymer. The solvent has to be evaporated and then either collected or incinerated, all of which are energy intensive and costly operations. Additionally, removal of solvent from thick adhesive films may produce defects in the dry adhesive film.
[0004] Control of polymer architecture is often the subject of intensive research with the
WO 2013/055978
PCT/US2012/059849 goal of improving performance for ever increasingly challenging applications. Architectures that acrylic polymers are known to possess include block copolymers, telechelic polymers, and random polymers of controlled molecular weight. Even though advances in controlling architecture have occurred with many benefits, each of these particular architectural types has disadvantages. For example, block copolymers have high melt viscosities which require high processing temperatures, making it difficult to control reactivity of functional groups. The production of telechelic polymers often involves multiple steps. Telechelics involve the placement of a reactive functional group exclusively on the end terminus of a polymer and not elsewhere in the polymer backbone. Functional groups placed at the end termini of polymers serve solely to increase the linear molecular weight in a manner in which free polymer chain ends are eliminated. As a result, telechelic polymers can yield high strength materials but do not provide the viscoelastic properties critical to adhesives and some elastomer applications. Random polymers of controlled molecular weight require high amounts of crosslinking to attain network formation.
[0005] In the past 15-20 years a variety of controlled radical polymerization techniques have been developed to afford good architectural control of (meth)acrylic monomers. These techniques typically are tolerant to a wide variety of monomers and functional groups as opposed to previous techniques like anionic or group transfer polymerization. A substantial amount of fundamental research has been performed to understand these types of polymerization and a thorough review has been edited by Matyjewski. Reversible addition fragmentation chain transfer (RAFT) polymerization is one such technique that has been shown to work exceedingly well with a wide variety of (meth)acrylic monomers yielding excellent control of molecular weight and polydispersity. The RAFT mechanism for controlled polymerization is well understood and reported extensively. While some examples of controlled architecture acrylic PSAs have been reported, very little work has been done to explore the influence of reactive functional group placement.
SUMMARY [0006] The present subject matter addresses problems associated with previously known architectured polymers by placement of crosslinkable monomers into segments of the polymer of controlled molecular weight and position. The overall molecular weight is low which yields desirable low viscosity, high solids solutions and melts. In conjunction with good processability, high performance elastomers and adhesives are obtained upon crosslinking. In particular, the crosslinkable monomers are placed in specific segments of the polymer backbone so that the crosslink density is controlled for optimal performance. The compositions of the present subject matter contain no undesired heterogeneity prior to crosslinking. A further benefit is that in all embodiments of the subject matter,
WO 2013/055978
PCT/US2012/059849 the polymer chain ends are preserved to yield desired visco-elastic and surface properties. To control the placement of crosslinkable monomers, it is preferred to employ a controlled free radical polymerization technique. In contrast with standard free radical processes it is now possible to control the placement of crosslinkable monomers.
[0007] In one aspect, the present subject matter provides an acrylic polymer comprising a first reactive segment that includes at least one monomer having a self reactive functional group. The acrylic polymer also comprises a second reactive segment that includes at least one monomer having a reactive functional group.
[0008] In another aspect, the present subject matter provides a crosslinkable composition comprising an acrylic polymer including a first reactive segment that includes at least one monomer having a self reactive functional group, and a second reactive segment that includes at least one monomer having a reactive functional group.
[0009] In yet another aspect, the present subject matter provides a method of preparing a crosslinkable composition comprising polymerizing at least one monomer having a self reactive functional group to thereby form a first reactive segment. The method also comprises polymerizing at least one monomer having a reactive functional group to thereby form a second reactive segment. At least one of the first reactive segment and the second reactive segment includes an acrylate group. The method also comprises forming an acrylic polymer from the first reactive segment and the second reactive segment.
BRIEF DESCRIPTION OF DRAWINGS [0010] Figure 1 is a graph of viscosity as a function of solids content for high glass transition temperature polymeric samples described herein.
[0011] Figure 2 is a graph of viscosity as a function of solids content for low glass transition temperature polymeric samples described herein.
DETAILED DESCRIPTION [0012] Acrylic copolymers prepared by sequential polymerization of polymer segments from various monomers are provided. The preferred embodiment copolymers contain a first reactive segment preferably at a polymer chain end and at least one other or a second reactive segment preferably at another polymer chain end. The first reactive segment includes at least one functional group that is capable of undergoing a crosslinking reaction. Preferably, the second reactive segment also includes at least one functional group that is capable of undergoing a crosslinking reaction. The reactive segments have controlled size and placement for tailored properties. For example, by
WO 2013/055978
PCT/US2012/059849 selectively placing functional groups in desirable positions on a polymer molecule, polymers that yield pressure sensitive adhesives that exhibit enhanced balance between cohesion and adhesion can be produced. In certain embodiments the polymers also include a third segment which is located between the first reactive segment and the second reactive segment. The third segment preferably includes at least one reactive functionality and/or a nonreactive segment. Also provided are adhesive compositions based upon the various polymers, and methods of preparing the polymers.
[0013] High modulus elastomers and high strength adhesives typically display a constant modulus as a function of temperature. Conversely, highly extensible, tough elastomers, and high tack and peel adhesives often have a degree of viscous liquid character. One route to this behavior is through control of crosslink density via placement of reactive functionalities in specific segments of the polymer. Placing reactive functionalities in segments adjacent to the polymer end groups yields high modulus and high strength. Placing the reactive functionalities in the central segment(s) of the polymer yields significant viscous liquid character. As described herein, the present subject matter provides strategies for controlling the structure and architecture of polymers and thereby enabling production of compositions having specific and desired characteristics.
Polymers and Crosslinkable Compositions [0014] Generally, the present subject matter provides an acrylic polymer having a first reactive segment that includes at least one monomer having a self reactive functional group, and a second reactive segment that includes at least one monomer having a reactive functional group. The reactive functionalities in the first reactive segment and the second reactive segment may be the same or different from one another. A wide array of reactive functionalities can be included in the first and second reactive segments. In certain embodiments, the reactive functional group of the second reactive segment is a self reactive functional group as in the first reactive segment. The self reactive functional group in the second reactive segment may be the same or different than the self reactive functional group of the first reactive segment. And, in certain embodiments, the second reactive segment is free of a self reactive functional group.
[0015] The term reactive functional group refers to a functional group that is capable of reacting with another functional group. The term self reactive functional group refers to a functional group that is capable of reacting with (i) an identical second self reactive functional group, (ii) with a different second self reactive functional group and/or (iii) with a reactive functional group. That is, the self reactive functional group can react with another identical self reactive functional group, with another self reactive functional group that is different, and/or with a reactive functional group. Self reactive functional groups are capable of polymerizing with themselves. Preferably, the self reactive
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PCT/US2012/059849 functional group is selected from anhydrides, epoxies, alkoxymethylols, and cyclic ethers. Non-limiting examples of reactive functional groups are provided herein, however preferably include acids, hydroxyls, amines, and mercapto (thiols).
[0016] In another embodiment of the subject matter, there is provided a crosslinkable composition comprising at least one acrylic copolymer having a first reactive segment of controlled size and position and at least one other or second reactive segment of controlled size and position. The first reactive segment comprises at least one monomer having a self reactive functional group as described herein. The other or second reactive segment comprises at least one monomer having a reactive functional group and is preferably reactive with the self reactive functional group of the first reactive segment. The second reactive segment may contain a group that is capable of undergoing crosslinking while remaining reactive with the reactive segment. The acrylic copolymer of the crosslinkable composition may in certain embodiments also preferably comprise a third polymeric segment. The third polymeric segment preferably includes a reactive functionality and/or a nonreactive segment. Additional aspects as described in conjunction with the previously described preferred embodiment acrylic copolymers are included in the examples described herein.
[0017] In certain embodiments, the acrylic copolymers preferably include at least one nonreactive segment. The nonreactive segments of the acrylic polymer may be derived from acrylates, methacrylates, or mixtures thereof. The acrylates include Cx to about C20 alkyl, aryl or cyclic acrylates such as methyl acrylate, ethyl acrylate, phenyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate, isobornyl acrylate, 2-propyl heptyl acrylate, isodecyl acrylate, isostearyl acrylate and the like. These moieties typically contain from about 3 to about 20 carbon atoms, and in one embodiment about 3 to about 8 carbon atoms. The methacrylates include Ci to about C2o alkyl, aryl or cyclic methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, isobornyl methacrylate, isooctyl methacrylate, and the like. These moeties typically contain from about 4 to about 20 carbon atoms, and in one embodiment about 3 to about 10 carbon atoms.
[0018] The preferred embodiment polymers exhibit relatively narrow ranges of molecular weight and thus have relatively low polydispersity values. Typically, the preferred embodiment polymers exhibit polydispersity (Pdi) values of less than 4.0, preferably less than 3.5, more preferably less than 3.0, more preferably less than 2.5, and most preferably less than 2.0. In certain embodiments, the preferred embodiment polymers exhibit polydispersities of less than 1.5, and as low as about 1.4. The preferred embodiment polymers typically have a number average molecular weight (Mn) of from about 40,000 to about 150,000, and preferably about 50,000 to about 110,000. However, it will be appreciated that the subject matter includes polymers having molecular weights and/or polydispersity
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Reactive Segments [0019] The reactive segments of the acrylic polymer may be a copolymer derived from one or more of the monomers of a nonreactive segment and at least one polymerizable comonomer having crosslinkable functionality. In one embodiment, the reactive segment comprises at least one monomer having the formula (I):
R
H2C=C--X (I) where R is H or CH3 and X represents or contains a functional group capable of crosslinking. The crosslinkable functional group of the reactive segment of the acrylic polymer is not particularly restricted, but may include one or more crosslinkable silyl, hydroxyl, carboxyl, carbonyl, carbonate ester, isocyanate, epoxy, vinyl, amine, amide, imide, anhydride, mercapto (thiol), acid, acrylamide, acetoacetyl groups, alkoxymethylol, and cyclic ether groups. As previously noted, the functional group of at least one reactive segment is a self reactive functional group and most preferably is selected from the previously noted collection of self reactive functional groups.
[0020] Hydroxy functional monomers include, for example, hydroxy ethyl (meth)acrylate, hydroxy isopropyl (meth)acylate, hydroxy butyl (meth)acrylate and the like.
[0021] Epoxy functional monomers include, for example, glycidyl methacrylate and glycidal acrylate. In certain embodiments, a particularly preferred epoxy functional monomer is commercially available under the designation S-100 from Synasia. That monomer is 3, 4 epoxycydohexylmethyl methacrylate, [CAS 82428-30-6], having a chemical formula CuHi6O3 and a molecular weight of 196.2.
[0022] The acid containing monomers include, for example, unsaturated carboxylic acids containing from 3 to about 20 carbon atoms. The unsaturated carboxylic acids include, among others, acrylic acid, methacrylic acid, itaconic acid, beta carboxy ethyl acrylate, mono-2-acroyloxypropyl succinate, and the like. It is contemplated that phosphoric acids may be used.
[0023] Anhydride containing monomers include, for example, maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
[0024] The acrylamides include, for example, acrylamide and its derivatives including the Nsubstituted alkyl and aryl derivatives thereof. These include N-methyl acrylamide, N,N-dimethyl acrylamide, t-octyl acrylamide and the like. The methacrylamides include methacrylamide and its derivatives including the N-substituted alkyl and aryl derivatives thereof.
[0025] Vinyl groups include, for example, vinyl esters, vinyl ethers, vinyl amides, and vinyl
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PCT/US2012/059849 ketones. The vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl versitate, vinyl isobutyrate and the like. The vinyl ethers include vinyl ethers having 1 to about 8 carbon atoms including ethylvinyl ether, butylvinyl ether, 2-ethylhexylvinyl ether and the like. The vinyl amides include vinyl amides having 1 to about 8 carbon atoms including vinyl pyrrolidone, and the like. The vinyl ketones include vinyl ketones having 1 to about 8 carbon atoms including ethylvinyl ketone, butylvinyl ketone, and the like.
[0026] Silyl groups include, for example, polymerizable silanes. The polymerizable silanes include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxy-silane, vinylmethyldipropoxysilane, γ-methacryloxypropyl-trimethoxysilane, γmethacryloxypropyltriethoxysilane, γ-methacryloxypropyl-tripropoxysilane, ymethacryloxydimethoxysilane, γ-methacryloxypropyl-methyldimethoxysilane, ymethacryloxypropylmethyldiethoxysilane, y-methacryl-oxypropylmethyldipropoxysilane, ymethacryloxymethyl-dimethoxysilane, γ-methacryloxymethyltrimethoxysilane, y-methacryloxymethyltriethoxy-silane, (methacryloxymethyl) methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, γ-methacryloxypropyltriacetoxysilane, γ-acryloxypropyltrimethoxy-silane, yacryloxypropyltriethoxy-silane, y-methacryl-oxymethyldiethoxysilane, y-acryloxypropyltripropoxy-silane, y-acryloxypropyl-methyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, y-acryloxypropylmethyldipropoxysilane, and the like.
[0027] In addition to the monomer having functional group(s), the reactive segment may include at least one monomer having the formula (II):
R3 ο
H2C=C—c—or4 (ii) where R3 is H or CH3 and R4 is a branched or unbranched, saturated alkyl group having 4 to 14 carbon atoms.
Methods [0028] The present subject matter also provides, in another embodiment, a multiple step polymerization process for making a crosslinkable acrylic copolymer having a first reactive segment with one or more self reactive functional groups provided by at least one monomer. Preferably, the monomer is an acrylic monomer. A second reactive segment is added to the first segment to form the acrylic copolymer. The second reactive segment preferably contains one or more crosslinkable functional groups and is miscible with the first segment. As used herein, the term molecularly miscible means a compound or mixture of compounds that exhibit properties in the bulk state that are indicative
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PCT/US2012/059849 of single phase behavior. With respect to the acrylic copolymer, the observation of a single Tg is indicative of polymer segment miscibility. The single Tg is intermediate between those of the constituent polymer segments and varies monotonically between these values as the relative amounts of each segment changes.
[0029] In an alternative embodiment, there is provided a process for making a crosslinkable acrylic copolymer having a first segment including self reactive functional groups, and a second segment having reactive functional groups provided by at least one monomer, which is preferably an acrylic monomer. The second segment is reacted with the first segment to form the acrylic copolymer.
[0030] With conventional free-radical polymerization, polymers are terminated when the reactive free radical end group is destroyed via termination or chain transfer reactions. The termination and chain transfer processes are typically irreversible and yield a polymer that is inactive. The result of this is a broad molecular weight distribution and little control over the distribution of monomers in the polymer backbone. Controlled radical polymerizations involve reversible radical processes in which irreversible termination and chain transfer are largely absent. There are three main types of controlled radical polymerization methodologies including atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), and stable free radical polymerization (SFRP) (of which nitroxide mediated polymerization (NMP) is a subset). RAFT and SFRP are particularly useful methods because of their tolerance to a wide array of functional groups and their efficiency and versatility in producing controlled radical polymerized polymers.
[0031] The acrylic copolymers of the subject matter are prepared using any of the controlled radical polymerization processes, which include atom-transfer radical polymerization (ATRP); rapid addition-fragmentation chain transfer (RAFT); and stable free radical polymerization (SFRP). Nitroxide-mediated polymerization (NMP) is an example of an SFRP process.
[0032] ATRP involves the chain initiation of free radical polymerization by a halogenated organic species in the presence of a metal halide species. The metal has a number of different oxidation states that allows it to abstract a halide from the organohalide, creating a radical that then starts free radical polymerization. After initiation and propagation, the radical on the chain active chain terminus is reversibly terminated (with the halide) by reacting with the catalyst in its higher oxidation state. A simplified mechanism for reversible activation-deactivation of polymer chains during ATRP is shown in Scheme 1. Thus the redox process gives rise to an equilibrium between dormant (polymer-halide) and active (polymer-radical) chains. The equilibrium is designed to heavily favor the dormant state, which effectively reduces the radical concentration to sufficiently low levels to limit bimolecular coupling.
[0033] The initiator in ATRP is usually a low molecular weight activated organic halide (RX, R=activated alkyl, X=chlorine, bromine, iodine). However, organic pseudohalides (e.g., X=thiocyanate,
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PCT/US2012/059849 azide) and compounds with weak N-X (e.g., N-bromosuccinimide) or S-X (e.g., sulfonyl halides) may be used. ATRP can be mediated by a variety of metals, including Ti, Mo, Re, Fe, Ru, Os, Rh, Co, Ni, Pd and Cu. Complexes of Cu offer the most efficient catalysts in the ATRP of a broad range of monomer in diverse media. Commonly used nitrogen-based ligands used in conjunction with Cu ATRP catalysts include derivatives of bidentate bipyridine and pyridine imine, tridentate diethylenetriamine and tetradentate tris[2-aminoethylene]amine and tetraazacyclotetradecane.
kdeact kact
Pn---X + Mtn
Scheme 1 [0034] Controlled polymerization by RAFT occurs via rapid chain transfer between growing polymer radicals and dormant polymer chains. After initiation, the control agent becomes part of the dormant polymer chain. The key mechanistic features of RAFT are illustrated in Scheme 2. Common RAFT agents contain thiocarbonyl-thio groups, and include, for example, dithioesters, dithiocarbamates, trithiocarbonates and xanthenes. Examples of useful RAFT agents include those described in The Chemistry of Radical Polymerization, Graeme Moad & David H. Solomon, 2nd rev. ed., 2006, Elsevier, p. 508-514, which is incorporated by reference herein.
[0035] Initiation and radical-radical termination occur as in conventional radical polymerization. In the early stages of the polymerization, addition of a propagating radical (Pn ) to the thiocarbonylthio compound followed by fragmentation of the intermediate radical gives rise to a polymeric thiocarbonylthio compound and a new radical (R ). Reaction of the radical (R ) with monomer forms a new propagating radical (Pm ). A rapid equilibrium between the active propagating radicals (Pn and Pm ) and the dormant polymeric thiocarbonylthio compounds provides equal probability for all chains to grow and allows for the production of narrow dispersity polymers.
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Initiation initiator l·
Pn’
Reversible chain transfer/propagation
Reinitiation
M
Kt
R-M
Pm
Reversible (degenerate) chain transfer/propagation
n
n
Termination p* + p· kt dead polymer
Scheme 2 [0036]
SFRP, and in particular, NMP achieves control with dynamic equilibrium between dormant alkoxyamines and actively propagating radicals. The use of nitroxides to mediate (i.e., control) free radical polymerization has been developed extensively. Many different types of nitroxides have been described and there are many methods for producing nitroxides in-situ. Regardless of the nitroxide or its method of generation, the key mechanistic feature of NMP is reversible coupling of the nitroxide (i.e., R2NO) to a growing polymer chain radical (P ) as shown in Scheme 3.
kdeact kact
Pn
O-R'
Scheme 3 [0037]
Examples of useful NMP agents include those described in The Chemistry of Radical
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Polymerization, Graeme Moad & David H. Solomon, 2nd rev. ed., 2006, Elsevier, p. 473-475, which is incorporated by reference herein. An example of a commercially available NMP agent is BlocBuilder*, an alkoxyamine compound that acts an initiator and control agent, available from Arkema.
[0038] The methods for forming the preferred embodiment acrylic polymers preferably use one or more polymerization catalysts. The polymerization catalyst can be, for example, organic tin compounds, metal complexes, amine compounds and other basic compounds, organic phosphate compounds, and organic acids. Examples of the organic tin compounds include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, stannous octoate, dibutyltin methoxide, dibutyltin diacetylacetate and dibutyltin diversatate. Examples of metal complexes are titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and tetraethanolamine titanate; metal salts of carboxylic acids, such as lead octoate, lead naphthoate, and cobalt naphthoate; and metal acetylacetonate complexes such as aluminum acetylacetonate complex and vanadium acetylacetonate complex. The amine compounds and other basic compounds include, for example aminisilanes such as γ-aminopropyl trimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; and straight-chain or cyclic tertiary amines or quaternary ammonium salts each containing plural nitrogen atoms. The organic phosphate compounds include monomethyl phosphate, di-n-butyl phosphate and triphenyl phosphate. Examples of organic acid catalysts include alkyl sulfonic acids such as methane sulfonic acid, aryl sulfonic acids such as p-toluene sulfonic acid, benzene sulfonic acid, styrene sulfonic acid and the like.
Adhesives [0039] Adhesives having a wide array of properties can be formed from the acrylic polymers and/or compositions described herein. Generally, the acrylic polymers described herein are crosslinked and combined with one or more components to provide an adhesive composition. The preferred embodiment adhesives are preferably pressure sensitive adhesives. The polymer may be crosslinked during post curing of the adhesive to increase the cohesive strength of the pressure sensitive adhesive. This can be achieved via covalent crosslinking such as heat, actinic or electron beam radiation, or metal based ionic crosslinking between functional groups. Table 1 below lists representative examples of crosslinkers for various functional groups of the segmented polymer.
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Table 1 - Crosslinkers
Functional Group of Segmented Polymer | Crosslinker |
Silane (Silyl) | Self-reactive |
Hydroxyl | Isocyanate, Melamine Formaldehyde, Anhydride, Epoxy, Titanium esters and Chelates |
Carboxylic acid, phosphoric acid | Aziridines, Isocyanate, Melamine Formaldehyde, Anhydride, Epoxy, Carboiimides, Metal Chelates, Titanium esters and Oxazolines |
Isocyanate | Self-reactive, Carboxylic acid, Amine, Hydroxyl |
Vinyl | Addition reaction with Silicone hydride |
(Meth)acrylate | Amine, Mercaptan, Self-reactive with radical catalyst (UV, Thermal), Acetoacetate |
Epoxy | Amine, Carboxylic acid, Phosphoric acid, Hydroxyl, Mercaptan |
Amine | Isocyanate, Melamine formaldehyde, anhydride, epoxy, acetoacetate |
Mercapto (thiol) | Isocyanate, Melamine formaldehyde, Anhydride, Epoxy |
Acetoacetate | Acrylate, Amine |
Alkoxymethylol | Acid, Hydroxyl, Thiol (Mercapto), Amine |
Cylic Ethers | Hydroxyl, Amines, Thiol (Mercapto) |
[0040] Suitable polyfunctional aziridines include, for example, trimethylolpropane tris[3aziridinylpropionate]; trimethylolpropane tris[3-(2-methylaziridinyl) propionate]; trimethylolpropane tris[2-aziridinylbutyrate]; tris(l-aziridinyl)-phosphine oxide; tris(2-methyl-l-aziridinyl)phosphine oxide; penta-erythritoltris[3-(l-aziridinyl)propionate]; and pentaerythritol tetrakis[3-(l-aziridinyl)propionate]. Combinations of more than one polyfunctional aziridine may also be used. Examples of commercially available polyfunctional aziridines include NEOCRYL CX-100 from Zeneca Resins, believed to be trimethylolpropaten tris[3-(2-methylaziridinyl)-propanoate], and Xama-2, Xama-7 and Xama-220 from Bayer Material Science.
[0041] Multifunctional aziridine amides which have the general formula (III):
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wherein R can be either an alkylene or aromatic group and R' can be a hydrogen or alkyl group and x is at least 2 may be used. Examples of suitable multifunctional aziridine amides include 1,T-(1,3 phenylenedicarbonyl)bis[2-methyl aziridine]; 2,2,4-trimethyladipoyl bis [2-ethyl aziridine]; l,l'-azelaoyl bis [2-methyl aziridine]; and 2,4,6-tris(2-ethyl-l-aziridinyl)-1,3,5 triazine.
[0042] Metal chelate crosslinking agents may be compounds prepared by coordinating multivalent metals such as Al, Fe, Zn, Sn, Ti, Sb, Mg and V with acethylacetone or ethyl acetoacetonate.
[0043] Among the isocyanate crosslinking agents that can be used are aromatic, aliphatic and cycloaliphatic diisocyanates and triisocyanates. Examples include 2,4-toluene diisocyanate, m phenylene diisocyanate, 4-chloro-l,3-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, 4,4'-diphenylene diisocyanate, xylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10 decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'methylene bis(cyclohexyl isocyanate),
1,5-tetrahydronaphthalene diisocyanate, paraxylylene diisocyanate, durene diisocyante, 1,2,4-benzene diisocyanate, isoform diisocyanate, 1,4-tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, or their reactants with polyol such as trimethylolpropane.
[0044] Other useful crosslinking agents include monomeric and polymeric melamine crosslinkers, such as Cymel 303 and 370 available from Cytec.
[0045] The crosslinking agent is typically used at a level from about 0.05% to about 5%, or from about 0.075% to about 2%, or from about 0.1% to about 1.5% by weight of adhesive solids.
[0046] Anhydride functional segmented polymers may be converted to silanes via a post polymerization reaction with amino-, mercapto- or hydroxyl-functional silanes. Examples of amino group-containing alkoxysilanes having a primary amino group alone as a reactive group include aminoalkyltrialkoxysilanes such as aminomethyltrimethoxysilane, aminomethyltriethoxysilane, β-amino ethyltrimethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltrimeth-oxysilane, γ aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltriisopropoxysilane, and y aminopropyltributoxysilane; (aminoalkyl)-alkyldialkoxysilanes such as β aminoethylmethyldimethoxysilane, y-amino-ethylmethyldiethoxysilane, y aminopropylmethyldimethoxysilane, y-aminopropyl-methyldiethoxysilane, and y13
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PCT/US2012/059849 aminopropylmethyldipropoxysilane; and corresponding aminoalkyldialkyl(mono)alkoxysilanes.
[0047] Examples of amino group-containing alkoxysilanes having a primary amino group and a secondary amino group as reactive groups include N-(aminoalkyl)aminoalkyltrialkoxysilanes such as N-p-(aminoethyl)-Y-aminopropyl-trimethoxysilane and N-p-(aminoethyl)-Yaminopropyltriethoxysilane; and N-(aminoalkyl)aminoalkylalkyldialkoxysilanes such as N-p-(aminoethyl)γ-amino-propylmethyldimethoxysilane and N-p-(aminoethyl)-y-aminopropylmethyl-diethoxysilane.
[0048] Examples of amino group-containing alkoxysilanes having a secondary amino group alone as a reactive group include N-phenylamino-methyltrimethoxysilane and N-phenyl-βaminoethyltrialkoxysilanes such as N-phenyl-p-aminoethyltrimethoxysilane and N-phenyl-βaminoethyltriethoxysilane; N-phenyl-y-aminopropyltrialkoxysilanes such as N-phenyl-yaminopropyltrimethoxysilane, N-phenyl-y-aminopropyltriethoxysilane, N-phenyl-yaminopropyltripropoxysilane, and N-phenyl-y-aminopropyltributoxysilane; corresponding Nphenylaminoalkyl(mono- or di-)alkyl(di- or mono-)alkoxysilanes; as well as Nalkylaminoalkyltrialkoxysilanes corresponding to the above-listed amino group-containing alkoxysilanes having a secondary amino group substituted with phenyl group, such as N-methyl-3aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, N-n-propyl-3aminopropyltrimethoxysilane, N-n-butyl-aminomethyltrimethoxysilane, N-n-butyl-2aminoethyltrimethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, N-n-butyl-3aminopropyltriethoxysilane, and N-n-butyl-3-aminopropyltripropoxysilane, and corresponding Nalkylaminoalkyl(mono- or di-)alkyl(di- or mono)alkoxysilanes. Others include Ncyclohexylaminomethylmethyldiethoxy silane and N-cyclohexylaminomethyl-triethoxysilane.
[0049] Examples of the mercapto group-containing silanes include mercaptoalkyltrialkoxysilanes such as mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, β-mercaptoethyltrimethoxysilane, β- mercapto-ethyltriethoxysilane, βmercaptoethyltripropoxysilane, β-mercaptoethyl-triisopropoxysilane, β-mercaptoethyltributoxysilane, ymercaptopropyl-trimethoxysilane, γ-mercaptopropyltriethoxysilane, y-mercaptopropyltri-propoxysilane, γ-mercaptopropyltriisopropoxysilane, and y-mercapto-propyltributoxysilane; (mercaptoalkyl)alkyldialkoxysilanes such as β-mercaptoethylmethyldimethoxysilane, βmercaptoethylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, ymercaptopropylmethyldiethoxysilane, y-mercaptopropylmethyldipropoxysilane, βmercaptopropylmethyldiisopropoxy-silane, y-mercaptopropylmethyldibutoxysilane, βmercaptopropylmethyldibutoxysilane, y-mercaptopropylethyldimethoxy-silane, y14
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[0050] Examples of hydroxyl-functional silanes include hydroxymethyltrialkoxy silanes having the formula (IV):
(iv)
Where R is an alkyl group and n is at least 1. The alkyl group is preferably a lower alkyl group having 1 to carbon atoms, and preferably 1 to 3 carbon atoms. Particularly useful are the silanes in which the alkyl group is methyl or ethyl, namely hydroxymethyltriethoxysilane and hydroxymethyltriethoxysilane when n is equal to 1.
[0051] The adhesives of the present subject matter may further comprise additives such as pigments, fillers, plasticizer, diluents, antioxidants, tackifiers and the like. Pigment, if desired, is provided in an amount sufficient to impart the desired color to the adhesive. Examples of pigments include, without limitation, solid inorganic fillers such as carbon black, titanium dioxide and the like, and organic dyes. Additional inorganic fillers such as aluminum trihydrate, christobalite, glass fibers, kaolin, precipitated or fumed silica, copper, quartz, wollasonite, mica, magnesium hydroxide, silicates (e.g.
feldspar), talc, nickel and calcium carbonate are also useful. Metal oxides such as aluminum trihydrate and magnesium hydroxide are particularly useful as flame retardants.
[0052] A wide variety of tackifiers can be used to enhance the tack and peel of the adhesive. These include rosins and rosin derivatives including rosinous materials that occur naturally in the oleoresin of pine trees, as well as derivatives thereof including rosin esters, modified rosins such as fractionated, hydrogenated, dehydrogenated, and polymerized rosins, modified rosin esters and the like.
[0053] There may also be employed terpene resins which are hydrocarbons of the formula Cio Hi6, occurring in most essential oils and oleoresins of plants, and phenol modified terpene resins like alpha pinene, beta pinene, dipentene, limonene, myrecene, bornylene, camphene, and the like. Various aliphatic hydrocarbon resins like Escorez 1304, manufactured by Exxon Chemical Co., and aromatic hydrocarbon resins based on Cg, C5, dicyclopentadiene, coumarone, indene, styrene, substituted styrenes and styrene derivatives and the like can also be used.
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PCT/US2012/059849 [0054] Hydrogenated and partially hydrogenated resins such as Regalrez 1018, Regalrez 1033, Regalrez 1078, Regalrez 1094, Regalrez 1126, Regalrez 3102, Regalrez 6108, etc., produced by Eastman Chemical Company, can be used. Various terpene phenolic resins of the type SP 560 and SP 553, manufactured and sold by Schenectady Chemical Inc., Nirez 1100, manufactured and sold by Reichold Chemical Inc., and Piccolyte S-100, manufactured and sold by Hercules Corporation, are particularly useful tackifiers for the present subject matter. Various mixed aliphatic and aromatic resins, such as Hercotex AD 1100, manufactured and sold by Hercules Corporation, can be used.
[0055] While the resins described above are quite useful for tackifying the copolymers of the instant subject matter, the particular tackifying resin and/or amount selected for a given formulation may depend upon the type of acrylic polymer being tackified. Many resins which are known in the prior art as being useful for tackifying acrylic based pressure sensitive adhesives can be effectively used in the practice of the present subject matter, although the scope of the subject matter is not limited to only such resins. Resins described in Satas, Handbook of Pressure Sensitive Adhesive Technology, Von Nostrand Reinhold, Co, Chap. 20, pages 527-584 (1989) (incorporated by reference herein) could be used.
[0056] The amount of tackifier used in the present subject matter is dependent upon the type of copolymer and tackifier used. Typically, pressure sensitive adhesive compositions prepared in accordance with the present subject matter will comprise from 5 to about 60% by weight total of one or more tackifiers.
[0057] In one embodiment, the tackifier has a ring and ball softening point of from about 100°C to about 150°C. In one embodiment, the tackifier comprises a terpene phenolic tackifier having a ring and ball softening point of from about 110°C to about 120°C.
[0058] In another embodiment, the added resin may serve a dual purpose. For example, a resin such as Wingstay l, a butylated reaction product of para-cresol and dicyclopentadiene with an average molecular weight of 650 produced by Eliokem, can serve both as a tackifier and an antioxidant.
[0059] In one embodiment, a low molecular weight polymeric additive is incorporated into the adhesive composition. The polymeric additive is polymerized from monomers selected from C1-C20 alkyl and cycloalkyl acrylates, Ci-C2o alkyl and cycloalkyl methacrylates, free radical polymerizable olefinic acids, and optionally other ethylenically unsaturated monomers. Suitable alkyl and cycloalkyl acrylates include the various esters of acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isobornyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, iso-octyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, eicosyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, and the like and mixtures thereof. Suitable alkyl and cycloalkyl methacrylate include the esters of methacrylic acid such
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[0060] Various amounts of other ethylenically-unsaturated monomers can optionally be used provided that the polymeric additive has a softening point greater than about 40°C and a number average molecular weight less than about 35,000. Optional ethylenically-unsaturated monomers suitable for use in the polymeric additive include, for example, styrene, alpha-methyl styrene, vinyl toluene, acrylonitrile, methacrylonitrile, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate t-butylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate and the like. The amount of the polymeric additive used may be in the range of about 1% to about 55% by weight, based on the total weight of the adhesive composition. Such low molecular weight additives as described in US Patent No. 4,912,169, the disclosure of which is hereby incorporated by reference.
[0061] Certain preferred embodiment adhesives have a relatively high solids content. Typically, the weight percentage of solids is greater than 50%, more preferably at least 60%, and more preferably at least 70%.
[0062] Figure 1 is a graph of viscosity as a function of solids content for several preferred embodiment polymers described herein. Specifically, these high acid polymers are prepared and evaluated as described in greater detail herein. Figure 2 is a similar graph of viscosity as a function of solids content for two preferred embodiment polymers described herein. Specifically, these low acid polymers are prepared and evaluated in greater detail herein.
EXAMPLES [0063] The following test methods were used for evaluating the adhesive properties of the acrylic adhesives.
[0064] Various 180° peel tests were used in evaluating preferred embodiment pressure sensitive adhesives prepared from preferred embodiment acrylic polymers. Also performed were shear strength tests and shear adhesion failure temperature tests (SAFT). These tests were performed as summarized in Table 2.
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Table 2 - Pressure Sensitive Adhesive Performance Test Methods
Test | Condition | |
180° | Peel | a, b |
15 Minute Dwell | ||
24 Hour Dwell | ||
72 Hour Dwell | ||
Shear Strength | c | |
Shear Adhesion Failure Temp. (SAFT) | d | |
(a) | Peel, sample applied to a stainless steel panel with a 5 pound roller with 1 pass in each direction. Samples conditioned and tested at 23°C. | |
(b) | Peel, sample applied to a high density polyethylene (HDPE) or polypropylene (PP) with a 5 pound roller with 5 passes in each direction. Samples conditioned and tested at 23°C. | |
(c) | Shear: 1 kg weight with a 1/2 inch by 1 inch overlap. Sample applied to a stainless steel panel with a 10 pound roller with 5 passes in each direction. Samples conditioned and tested at 23°C. | |
(d) | SAFT: 1000 gram weight, 1 inch by 1 inch overlap (2.2 pounds/square inch). Sample applied to a stainless steel panel with a 10 pound roller with 5 passes in each direction. Samples conditioned for 1 hour at 23°C and 15 minutes at 40°C. Temperature increased by 0.5°C/min. until failure. |
[0065] The subject matter is further described by reference to the following non-limiting examples.
Example 1: Epoxy Hybrid Functional Acrylic Polymer [0066] An acrylic copolymer with reactive functionalities positioned in the segment adjacent to the polymer chain ends is prepared as follows. Into a 1500ml vessel equipped with a heating jacket, agitator, reflux condenser, feed tanks and nitrogen gas inlet there is charged 65.06g of ethyl acetate and 10.50g of methanol. Monomers and RAFT agent are added in the following amounts to generate the segment adjacent to the polymer chain ends:
36.53g butyl acrylate
41.57g of 2 ethyl-hexyl acrylate
4.87g of dibenzyl trithiocarbonate (RAFT agent 50% solution in ethyl acetate)
6.58g of 3,4 epoxycyclohexyl methyl methacrylate (cyclo aliphatic epoxy)
0.275g of VAZO 64 (AIBN) [0067] After a 30 minute reactor sparge with nitrogen at room temperature, the reactor charge is heated to reflux conditions (reactor jacket 95°C) with a constant nitrogen purge. After a peak temperature of 75-78°C is attained, the reaction conditions are maintained for 30 minutes at which point >70% of the monomers are consumed. A reagent feed mixture with an active nitrogen purge of 230.38g ethyl acetate, 31.49g of methanol, 374.13g 2-ethyl-hexyl acrylate, 328.78g butyl acrylate,
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58.79g of acrylic acid, and 0.28g VAZO 64 is added over a period of two and one half hours to the reactor. VAZO 64 is a free radical source, commercially available from DuPont. Over the reagent feed the temperature of the reaction under reflux is held under 85°C. The reaction conditions are maintained for 3 hours after completion of the reagent feed at which point >97.0% of the monomers are consumed. The resulting solution polymer is then cooled to ambient and discharged from the reactor.
[0068] The resulting acrylic polymer contains 43.2% butyl acrylate, 49.1% 2-ethyl-hexyl acrylate, 7% acrylic acid and 0.70% 3,4 epoxycyclohexyl methyl methacrylate based on 100% by weight of the acrylic polymer. The measured molecular weight (Mn) of the acrylic polymer is 51,991 (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity is 2.12.
[0069] 0.4% based on solids aluminum acetyl acetonate (AAA) was added to the acrylic polymer. The adhesive composition is air dried for 5 minutes then placed into an air forced oven at 120°C for 10 minutes.
[0070] The adhesives are coated onto 2-mil polyethylene terephthalate at 58-62 grams per square meter (gsm) and air dried for 5 minutes followed by a 10 minute 120°C dry.
Example 2: Epoxy Hybrid Functional Acrylic Polymer [0071] An acrylic copolymer with reactive functionalities positioned in the segment adjacent to the polymer chain ends is prepared as follows. Into a 1500ml vessel equipped with a heating jacket, agitator, reflux condenser, feed tanks and nitrogen gas inlet there is charged 65.26g of ethyl acetate and 10.53g of methanol. Monomers and RAFT agent are added in the following amounts to generate the segment adjacent to the polymer chain ends:
37.05g butyl acrylate
42.11g of 2-ethyl-hexyl acrylate
4.88g of dibenzyl trithiocarbonate (RAFT agent 50% solution in ethyl acetate)
3.30g of 3,4 epoxycyclohexyl methyl methacrylate (cyclo aliphatic epoxy)
0.276g of VAZO 64 (AIBN) [0072] After a 30 minute reactor sparge with nitrogen at room temperature, the reactor charge is heated to reflux conditions (reactor jacket 95°C) with a constant nitrogen purge. After a peak temperature of 75-78°C is attained, the reaction conditions are maintained for 30 minutes at which point >70% of the monomers are consumed. A reagent feed mixture with an active nitrogen purge of 135.79g ethyl acetate, 31.58g of methanol, 378.95g 2-ethyl-hexyl acrylate, 333.47g butyl acrylate, 50.53g of acrylic acid, and 0.28g Vazo-64 is added over a period of two and one half hours to the reactor. Over the reagent feed the temperature of the reaction under reflux is held under 85°C. The
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[0073] The resulting acrylic polymer contains 43.8% butyl acrylate, 49.8% 2-ethyl-hexyl acrylate, 6% acrylic acid and 0.40% 3,4 epoxycyclohexyl methyl methacrylate based on 100% by weight of the acrylic polymer. The measured molecular weight (Mn) of the acrylic polymer is 62,898 (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity is 1.53.
[0074] 0.7% based on solids aluminum acetyl acetonate was added to the acrylic polymer.
The adhesive composition is air dried for 5 minutes then placed into an air forced oven at 120 °C for 10 minutes.
[0075] The adhesives are coated onto 2-mil polyethylene terephthalate at 58-62 grams per square meter (gsm) and air dried for 5 minutes followed by a 10 minute 120°C dry.
Example 3: Epoxy Hybrid Functional Acrylic Polymer [0076] An acrylic copolymer with reactive functionalities positioned in the segment adjacent to the polymer chain ends is prepared as follows. Into a 1500ml vessel equipped with a heating jacket, agitator, reflux condenser, feed tanks and nitrogen gas inlet there is charged 59.02g of ethyl acetate and 9.52g of methanol. Monomers and RAFT agent are added in the following amounts to generate the segment adjacent to the polymer chain ends:
34.27g butyl acrylate
38.84g of 2-ethyl-hexyl acrylate
2.94g of dibenzyl trithiocarbonate (RAFT agent 50% solution in ethyl acetate)
1.99g of 3,4 epoxycyclohexyl methyl methacrylate (cyclo aliphatic epoxy)
0.083g of VAZO 64 (AIBN) [0077] After a 30 minute reactor sparge with nitrogen at room temperature, the reactor charge is heated to reflux conditions (reactor jacket 95°C) with a constant nitrogen purge. After a peak temperature of 75-78°C is attained, the reaction conditions are maintained for 30 minutes at which point >70% of the monomers are consumed. A reagent feed mixture with an active nitrogen purge of 230.38g ethyl acetate, 28.5g of methanol, 349.57g 2-ethyl-hexyl acrylate, 308.45g butyl acrylate, 30.46g of acrylic acid, and 0.08g VAZO 64 is added over a period of two and one half hours to the reactor. Over the reagent feed the temperature of the reaction under reflux is held under 85°C. The reaction
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[0078] The resulting acrylic polymer contains 44.9% butyl acrylate, 50.8% 2-ethyl-hexyl acrylate, 4% acrylic acid and 0.3% 3,4 epoxycyclohexyl methyl methacrylate based on 100% by weight of the acrylic polymer. The measured molecular weight (Mn) of the acrylic polymer is 60,369 (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity is 1.79.
[0079] 0.6% based on solids aluminum acetyl acetonate (AAA) was added to the acrylic polymer. The adhesive composition is air dried for 5 minutes then placed into an air forced oven at 120 °C for 10 minutes.
[0080] The adhesives are coated onto 2-mil polyethylene terephthalate at 58-62 grams per square meter (gsm) and air dried for 5 minutes followed by a 10 minute 120°C dry.
Example 4: Preparation of Segmented Acrylic Polymer Having Epoxy Functionality in the Endblocks and Acid Functionality Throughout Using RAFT Agent [0081] An acrylic copolymer with segmented acrylic polymer having epoxy functionality in the endblocks and acid functionality throughout is prepared as follows. Into a 1500ml reactor equipped with a heating jacket, agitator, reflux condenser, feed tanks and nitrogen gas inlet the following is charged:
142.50 g of butyl acetate
105.37g of ethyl acetate
15.00 g of methanol
3.92 g of Synasia S-100 epoxy monomer
54.00g of 2-ethylhexyl acrylate
36.61 g of methyl acrylate
9.00 g of acrylic acid
2.90 g of dibezyl trithiocarbonate (DBTTC)
02.87 g of VAZO 88 (polymerization initiator from DuPont) [0082] Into a 1000 ml feed vessel fitted with nitrogen gas inlet, monomers and solvents are added in the following amounts to generate a portion of only acid functional reactive segment at the center of the polymer chain ends of the epoxy/acid reactive polymer mode:
105.20 g of ethyl acetate
34.87 g of methanol
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486.00 g of 2-ethylhexyl acrylate
329.47 g of methyl acrylate
81.00 g of acrylic acid [0083] The reactor charge is heated to 80°C (reactor jacket 95°C) with a constant nitrogen purge and held for 30 minutes. After the hold, the reagent feed mixture with an active nitrogen purge is added over a period of 182 minutes to the reactor. During the reagent feed the temperature of the reaction is held between 80-85°C. The reaction conditions are maintained after completion of the reagent feed for 90 minutes. This is to create the remainder of the only acid reactive segment at the center of the polymer, the total theoretical Mn of the acid reactive segment is 90,000 g/mol. At this time, 0.87 g of t-amyl peroxy pivalate and 87.50 g of toluene are added and reaction conditions are maintained for 45 minutes. The resulting solution polymer is then cooled to ambient temperature and discharged from the reactor.
[0084] The resulting epoxy/acid reactive acrylic polymer contains 54.00% 2-ethylhexyl acrylate, 36.61% methyl acrylate, 9.00% acrylic acid, and 0.39% Synasia S-100 based on 100% by weight of the reactive acrylic polymer. The resulting acid only reactive polymer mode contains 54.00% 2ethylhexyl acrylate, 37.00% methyl acrylate, and 9.00% acrylic acid. The measured molecular weight (Mn) of the total acrylic polymer is 57,197 g/Mole (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity is 1.89.
[0085] Aluminum acetoacetonate in an amount of 0.60% based on solids was added to the acrylic polymer. The adhesive composition is dried at 120°C for 10 minutes to ensure complete crosslinking of the acrylic polymer.
Example 5: Preparation of Segmented Acrylic Polymer Having Epoxy Functionality in the Endblocks and Acid Functionality Throughout Using RAFT Agent [0086] An acrylic copolymer with segmented acrylic polymer having epoxy functionality in the endblocks and acid functionality throughout is prepared as follows. Into a 1500ml reactor equipped with a heating jacket, agitator, reflux condenser, feed tanks and nitrogen gas inlet the following is charged:
142.50 g of butyl acetate
105.37g of ethyl acetate
15.00 g of methanol
3.92 g of Synasia S-100 epoxy monomer
55.00g of 2-ethylhexyl acrylate
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37.61 g of methyl acrylate
7.00 g of acrylic acid
2.90 g of dibezyl trithiocarbonate (DBTTC)
2.87 g of VAZO 88 [0087] Into a 1000 ml feed vessel fitted with nitrogen gas inlet, monomers and solvents are added in the following amounts to generate a portion of only acid functional reactive segment at the center of the polymer chain ends of the epoxy/acid reactive polymer mode:
105.20 g of ethyl acetate
34.87 g of methanol
495.00 g of 2-ethylhexyl acrylate
338.47 g of methyl acrylate
63.00 g of acrylic acid [0088] The reactor charge is heated to 80°C (reactor jacket 95°C) with a constant nitrogen purge and held for 30 minutes. After the hold, the reagent feed mixture with an active nitrogen purge is added over a period of 182 minutes to the reactor. During the reagent feed the temperature of the reaction is held between 80-85°C. The reaction conditions are maintained after completion of the reagent feed for 90 minutes. This is to create the remainder of the only acid reactive segment at the center of the polymer, the total theoretical Mn of the acid reactive segment is 90,000 g/mol. At this time, 0.87 g of t-amyl peroxy pivalate and 87.50 g of toluene are added and reaction conditions are maintained for 45 minutes. The resulting solution polymer is then cooled to ambient temperature and discharged from the reactor.
[0089] The resulting epoxy/acid reactive acrylic polymer mode contains 55.00% 2-ethylhexyl acrylate, 37.61% methyl acrylate, 7.00% acrylic acid, and 0.39% Synasia S-100 based on 100% by weight of the reactive acrylic polymer mode. The resulting acid only reactive polymer mode contains 55.00% 2ethylhexyl acrylate, 38.00% methyl acrylate, and 7.00% acrylic acid. The measured molecular weight (Mn) of the total acrylic polymer is 60,592 g/Mole (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity is 1.90.
[0090] Aluminum acetoacetonate in an amount of 0.60% based on solids was added to the acrylic polymer. The adhesive composition is dried at 120°C for 10 minutes to ensure complete crosslinking of the acrylic polymer.
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Example 6: Preparation of Segmented Acrylic Polymer Having Epoxy Functionality in the Endblocks and Acid Functionality Throughout Using RAFT Agent [0091] An acrylic copolymer with segmented acrylic polymer having epoxy functionality in the endblocks and acid functionality throughout is prepared as follows. Into a 1500ml reactor equipped with a heating jacket, agitator, reflux condenser, feed tanks and nitrogen gas inlet the following is charged.
131.18 g of butyl acetate
97.00g of ethyl acetate
13.81 g of methanol
2.41 g of Synasia S-100 epoxy monomer
49.71g of 2-ethylhexyl acrylate
33.82 g of methyl acrylate
8.29 g of acrylic acid
1.78 g of dibezyl trithiocarbonate (DBTTC)
1.76 g of VAZO 88 [0092] Into a 1000 ml feed vessel fitted with nitrogen gas inlet, monomers and solvents are added in the following amounts to generate a portion of only acid functional reactive segment at the center of the polymer chain ends of the epoxy/acid reactive polymer mode:
131.18 g of ethyl acetate
32.11 g of methanol
447.40 g of 2-ethylhexyl acrylate
304.38 g of methyl acrylate
74.57 g of acrylic acid [0093] The reactor charge is heated to 80°C (reactor jacket 95°C) with a constant nitrogen purge and held for 60 minutes. After the hold, the reagent feed mixture with an active nitrogen purge is added over a period of 176 minutes to the reactor. During the reagent feed the temperature of the reaction is held between 80-85°C. The reaction conditions are maintained after completion of the reagent feed for 90 minutes. This is to create the remainder of the only acid reactive segment at the center of the polymer, the total theoretical Mn of the only acid reactive segment is 135,000 g/mol. At this time, 0.81 g of t-amyl peroxy pivalate and 80.55 g of butyl acetate are added and reaction conditions are maintained for 45 minutes. The resulting solution polymer is then cooled to ambient temperature, diluted with 87.46 g of butyl acetate and discharged from the reactor.
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PCT/US2012/059849 [0094] The resulting epoxy/acid reactive acrylic polymer mode contains 54.00% 2ethylhexyl acrylate, 36.74% methyl acrylate, 9.00% acrylic acid, and 0.26% Synasia S-100 based on 100% by weight of the reactive acrylic polymer mode. The resulting acid only reactive polymer mode contains 54.00% 2-ethylhexyl acrylate, 37.00% methyl acrylate, and 9.00% acrylic acid. The measured molecular weight (Mn) of the total acrylic polymer is 63,887 g/mole (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity is 2.11.
[0095] Aluminum acetoacetonate in an amount of 0.60% based on solids was added to the acrylic polymer. The adhesive composition is dried at 120°C for 10 minutes to ensure complete crosslinking of the acrylic polymer.
Example 7: Preparation of Segmented Acrylic Polymer Having Epoxy Functionality in the Endblocks and Acid Functionality Throughout Using RAFT Agent [0096] An acrylic copolymer with segmented acrylic polymer having epoxy functionality in the endblocks and acid functionality throughout is prepared as follows. Into a 1500ml reactor equipped with a heating jacket, agitator, reflux condenser, feed tanks and nitrogen gas inlet the following is charged:
131.18 g of butyl acetate
92.40g of ethyl acetate
13.81 g of methanol
2.41 g of Synasia S-100 epoxy monomer
50.63g of 2-ethylhexyl acrylate
34.74 g of methyl acrylate
6.44 g of acrylic acid
1.78 g of dibezyl trithiocarbonate (DBTTC)
1.76 g of VAZO 88 [0097] Into a 1000 ml feed vessel fitted with nitrogen gas inlet, monomers and solvents are added in the following amounts to generate a portion of only acid functional reactive segment at the center of the polymer chain ends of the epoxy/acid reactive polymer mode.
131.18 g of ethyl acetate
32.11 g of methanol
455.69 g of 2-ethylhexyl acrylate
312.67 g of methyl acrylate
58.00 g of acrylic acid
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PCT/US2012/059849 [0098] The reactor charge is heated to 80°C (reactor jacket 95°C) with a constant nitrogen purge and held for 60 minutes. After the hold, the reagent feed mixture with an active nitrogen purge is added over a period of 176 minutes to the reactor. During the reagent feed the temperature of the reaction is held between 80-85°C. The reaction conditions are maintained after completion of the reagent feed for 90 minutes. This is to create the remainder of the only acid reactive segment at the center of the polymer, the total theoretical Mn of the only acid reactive segment is 135,000 g/mol. At this time, 0.81 g of t-amyl peroxy pivalate and 80.55 g of butyl acetate are added and reaction conditions are maintained for 45 minutes. The resulting solution polymer is then cooled to ambient temperature, diluted with 87.46 g of butyl acetate and discharged from the reactor.
[0099] The resulting epoxy/acid reactive acrylic polymer mode contains 55.00% 2ethylhexyl acrylate, 37.74% methyl acrylate, 7.00% acrylic acid, and 0.26% Synasia S-100 based on 100% by weight of the reactive acrylic polymer mode. The resulting acid only reactive polymer mode contains 55.00% 2-ethylhexyl acrylate, 38.00% methyl acrylate, and 7.00% acrylic acid. The measured molecular weight (Mn) of the total acrylic polymer is 76,119 g/mole (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity is 2.07.
[00100] Aluminum acetoacetonate in an amount of 0.60% based on solids was added to the acrylic polymer. The adhesive composition is dried at 120°C for 10 minutes to ensure complete crosslinking of the acrylic polymer.
[00101] The adhesives were coated onto 2-mil aluminum foil at 58-62 grams per square meter (gsm) and dried at 120°C for 10 minutes.
Adhesives of Examples 1-7 [00102] Table 3 set forth below summarizes wet physical properties of adhesives prepared using the polymers of Examples 1-7 and two commercially available adhesives. Table 4 summarizes pressure sensitive adhesive properties of adhesives prepared using the polymers of Examples 1-7 and two commercially available adhesives. The first commercial adhesive designated as Commercial Adhesive 1 in Tables 3 and 4 is compositionally comparable to the preferred embodiment adhesives of Examples 1-3. And, the second commercial adhesive designated as Commercial Adhesive 2 in Tables 3 and 4 is compositionally comparable to the preferred embodiment adhesives of Examples 4-7. Referring to Table 3, it will be noted that the preferred embodiment adhesives of Examples 1-7 exhibit a significantly narrower range of molecular weights and polydispersity values, for example Pdi values range from 1.41 to 2.11 as compared to the molecular weight ranges and polydispersity values of the two commercially available adhesives, i.e. Pdi values of 6.2 and 6.75. In addition, the preferred
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[00103] Referring to Table 4, it is evident that the PSA performance of the preferred embodiment adhesives of Examples 1-7 are comparable to and in certain instances, significantly superior to those of the two commercially available adhesives.
Table 3 - Wet Physical Properties of Adhesives of Polymers of Examples 1-7
Sample Name | Monomer s | Acid Level | Tg(degC) | Molecular Weight | 0/ /0 Solids | Viscosity (cps) | |||
Targeted | Mn | Mw | Pdi | ||||||
Example 1 | EHA/BA | 7 | -60 | 100 | |||||
Example2 | EHA/BA | 6 | -60 | 100 | 62898 | 96248 | 1.53 | 72 | 10640 |
Example 3 | EHA/BA | 4 | -60 | 100 | 60506 | 85370 | 1.41 | 73 | 8300 |
Commercial Adhesive 1 | EHA/BA | 4 | -60 | NA | 57000 | 350000 | 6.2 | 50 | 4000 |
Example 4 | EHA/MA | 9 | -35 | 100 | 57197 | 107980 | 1.89 | 71 | 45400 |
Example 5 | EHA/MA | 7 | -35 | 100 | 60592 | 115500 | 1.91 | 72 | 31160 |
Example 6 | EHA/MA | 9 | -35 | 150 | 63887 | 134520 | 2.11 | 62 | 32080 |
Example 7 | EHA/MA | 7 | -35 | 150 | 76119 | 157670 | 2.07 | 63 | 28800 |
Commercial Adhesive 2 | EHA/MA | 7 | -35 | NA | 105000 | 709000 | 6.75 | 36 | 13000 |
Table 4 - Properties of Adhesives of Polymers of Examples 1-7
Sample Name | 180° Peel SS 15min (pli) | 180° Peel SS 24 hr (Pli) | 180° Peel SS 72 hr (Pli) | 180° Peel HDPE72 hr (Pli) | 180° Peel PP 72 hr (pli) | 8.81 bs/in2 Shear(min) | SAFT (°C) |
Example 1 | 5.15 m | 5.55 m | 5.71 m | 0.38 a | 3.05 a | 1904 m | >200 |
Example 2 | 3.01a | 7.03 c | 9.06 c | 0.44 a | 2.56 a | 199 m | >200 |
Example 3 | 2.66 a | 5.47 m | 6.78 m | 0.4 a | 2.72 a | 92.0 a | >200 |
Commercial Adhesive 1 | 5.64 m | 7.05 c | 7.85 c | 0.55 a | 2.56 a | 52.0 c | 90 c |
Example 4 | 4.39 a | 5.39 a | 6.18 a | NA | NA | >10000 | >200 |
Example 5 | 3.48 a | 5.21a | 6.03 a | NA | NA | >10000 | >200 |
Example 6 | 4.12 a | 5.64 a | 6.04 a | NA | NA | >10000 | >200 |
Example 7 | 4.04 a | 4.79 a | 5.48 a | NA | NA | >10000 | >200 |
Commercial Adhesive 2 | 4.07 a | 5.25 a | 5.70 a | NA | NA | >10000 | >200 |
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Examples 8-23: Analysis and Investigation of Polymers with High and Low Glass Transition Temperatures
Example 8 [00104] Various samples of polymers having high glass transition temperatures (Tg), e.g., about -35°C, and low glass transition temperatures, e.g., about -60°C, were prepared. Two different molecular weights were targeted: 100,000 (or 100 as noted below) and 150,000 (or 150). Hybrid epoxy functional polymers were formed from loadings of 4%, 6%, 7%, and 9% on monomers of acrylic acid. Tables 3-5 summarize these polymers. In the sample name designations, L is for low Tg, H is for high Tg, 4 is for 4% acid, 6 is for 6% acid, 7 is for 7% acid, 9 is for 9% acid, 150 is for 150K molecular weight, and 100 is for 100K molecular weight.
Table 5 - Summary of Examples and Sample Properties
Sample Name | Prepared According to |
L6. 100 | Example 2 |
L4. 100 | Example 3 |
H9. 100 | Example 4 |
H7. 100 | Example 5 |
H9. 150 | Example 6 |
H7. 150 | Example 7 |
Example 9 [00105] The performance of two high Tg samples, i.e. H9.100 and H9.150, were compared to one another. All samples were direct coated to 2 mil mylar at 60 gsm +/- 3, air dried for 5 min. followed by 10 min. in a 120°C forced air oven. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of performance testing are set forth below in Tables 6A and 6B. Throughout these tables, MOF refers to mode of failure. Zip refers to quick zipping peels. Sp refers to cohesive splitting. Re refers to removed. Regarding the samples, % BOS refers to percent based on solids content. And WPI refers to Williams Plasticity Index.
Table 6A - Test Results for Samples H9.100 and H9.150
180 DEG SS PEEL | |||||||||
Sample | XLINKER | %BOS | 15 MIN | MOF | AVG | 24 HR | AVG | 72 HR | AVG |
H9.100 | 4.71 | 5.86 | 6.68 | ||||||
5.06 | 4.88 | 5.99 | 5.94 | 6.91 | 6.76 | ||||
4.86 | 5.97 | 6.7 | |||||||
H9.100 | 1:3:9 AAA | 0.20% | 4.6 | 5.25 | 6.94 | ||||
4.96 | 4.74 | 5.87 | 5.73 | 6.73 | 7.00 | ||||
4.65 | 6.06 | 7.32 | |||||||
H9.100 | 1:3:9 AAA | 0.40% | 3.78 | 5.95 | 6.42 |
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3.45 | zip | 4.23 | 4.68 | 5.57 | 5.31 | 6.11 | |||
5.45 | 6.09 | 6.6 | |||||||
H9.100 | 1:3:9 AAA | 0.60% | 4.6 | 5.47 | 6.23 | ||||
4.64 | 4.39 | 5.04 | 5.39 | 5.76 | 6.18 | ||||
3.93 | zip | 5.65 | 6.54 | ||||||
H9.100 | 1:3:9 AAA | 0.80% | 3.42 | zip | 5.45 | 6.05 | |||
3.89 | zip | 3.73 | 5.32 | 5.39 | 5.93 | 6.09 | |||
3.89 | zip | 5.4 | 6.28 | ||||||
H9.150 | 1:3:9 AAA | 0.20% | 3.7 | 5.31 | 5.96 | ||||
4.19 | 4.12 | 6.15 | 5.64 | 6.58 | 6.04 | ||||
4.46 | 5.47 | 5.58 | |||||||
H9.150 | 1:3:9 AAA | 0.40% | 3.77 | 5.47 | 5.92 | ||||
3.97 | 3.66 | 5.46 | 5.25 | 5.54 | 5.65 | ||||
3.24 | 4.81 | 5.48 | |||||||
H9.150 | 1:3:9 AAA | 0.60% | 3.2 | 5.31 | 5.71 | ||||
3.33 | 3.26 | 5 | 5.05 | 5.57 | 5.62 | ||||
3.25 | 4.84 | 5.58 | |||||||
H9.150 | 1:3:9 AAA | 0.80% | 3.24 | 4.93 | 4.8 | ||||
3.02 | 3.38 | 5.1 | 4.94 | 5.32 | 5.04 | ||||
3.89 | 4.8 | 4.99 |
Table 6B -Test Results for Samples H9.100 and H9.150
8.8 LB PERSQIN SHEAR | WPI | ||||||
Sample | XLINKER | %BOS | MIN | MOF | AVG | VALUE | AVG |
H9.100 | 39.1 | sp | |||||
28.5 | sp | 33.27 | NA | ||||
32.2 | sp | ||||||
H9.100 | 1:3:9 AAA | 0.20% | 422.7 | sp | 1.9 | ||
473.7 | sp | 439.23 | 2.1 | 2 | |||
421.3 | sp | ||||||
H9.100 | 1:3:9 AAA | 0.40% | 10000 | re | 3.3 | ||
10000 | re | 10000.00 | 3.31 | 3.305 | |||
10000 | re | ||||||
H9.100 | 1:3:9 AAA | 0.60% | 10000 | re | 4.3 | ||
10000 | re | 10000.00 | 4.3 | 4.3 | |||
10000 | re | ||||||
H9.100 | 1:3:9 AAA | 0.80% | 10000 | re | 4.58 | ||
10000 | re | 10000.00 | 4.59 | 4.585 | |||
10000 | re | ||||||
H9.150 | 1:3:9 AAA | 0.20% | 10000 | re | 3.07 | ||
10000 | re | 10000.00 | 3.15 | 3.11 | |||
10000 | re | ||||||
H9.150 | 1:3:9 AAA | 0.40% | 10000 | re | 4.41 | ||
10000 | re | 10000.00 | 4.85 | 4.63 | |||
10000 | re | ||||||
H9.150 | 1:3:9 AAA | 0.60% | 10000 | re | 5.27 | ||
10000 | re | 10000.00 | 5.97 | 5.62 | |||
10000 | re |
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H9.150 | 1:3:9 AAA | 0.80% | 10000 | re | 5.48 | ||
10000 | re | 10000.00 | 5.99 | 5.735 | |||
10000 | re |
Example 10 [00106] The performance of two high Tg samples H7.100 and H7.150, were similarly compared to one another. All samples were direct coated to 2 mil mylar at 60 gsm +/-3, air dried for 5 min. followed by 10 min. in a 120°C forced air oven. All samples were conditioned for 24 hours by a controlled climate room. A summary of the samples and results of performance testing are set forth below in Tables 7A and 7B.
Table 7A - Test Results for Samples H7.100 and H7.150
180 DEG SS PEEL | ||||||||
Sample | XLINKER | %BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG |
H7.100 | 1:1:9 AAA | 0.50% | 2.96 | 3.45 | 5.37 | |||
4.64 | 3.99 | 4.48 | 4.14 | 5.71 | 5.57 | |||
4.38 | 4.49 | 5.64 | ||||||
H7.100 | 1:1:9 AAA | 0.60% | 4.12 | 4.19 | 5.38 | |||
3.11 | 3.61 | 4.08 | 4.15 | 5.24 | 5.34 | |||
3.59 | 4.19 | 5.41 | ||||||
H7.100 | 1:1:9 AAA | 0.70% | 3.26 | 4.48 | 5.39 | |||
3.67 | 3.41 | 3.85 | 4.15 | 4.82 | 5.25 | |||
3.29 | 4.12 | 5.53 | ||||||
H7.100 | 1:1:9 AAA | 0.80% | 3.29 | 3.77 | 4.85 | |||
3.36 | 3.44 | 3.66 | 3.70 | 4.99 | 4.99 | |||
3.67 | 3.66 | 5.17 | ||||||
H7.150 | 1:1:9 AAA | 0.50% | 4.74 | 4.31 | 3.85 | |||
4.53 | 4.42 | 3.83 | 4.44 | 3.97 | 4.54 | |||
4 | 5.18 | 5.8 | ||||||
H7.150 | 1:1:9 AAA | 0.60% | 3.85 | 4.39 | 5.12 | |||
3.98 | 4.04 | 4.95 | 4.79 | 5.58 | 5.48 | |||
4.3 | 5.02 | 5.73 | ||||||
H7.150 | 1:1:9 AAA | 0.70% | 4.25 | 4.66 | 5.32 | |||
3.84 | 4.12 | 4.43 | 4.58 | 5.08 | 5.15 | |||
4.26 | 4.64 | 5.06 |
Table 7B -Test Results for Samples H7.100 and H7.150
8.8 LB PERSQIN SHEAR | WPI | ||||||
Sample | XLINKER | %BOS | MIN | MOF | AVG | VALUE | AVG |
H7.100 | 1:1:9 AAA | 0.50% | 8300 | re | 4.16 | ||
8300 | re | 8300.00 | 4.01 | 4.085 | |||
8300 | re | ||||||
H7.100 | 1:1:9 AAA | 0.60% | 8300 | re | 4.4 | ||
8300 | re | 8300.00 | 4.11 | 4.255 | |||
8300 | re |
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H7.100 | 1:1:9 AAA | 0.70% | 8300 | re | 5.1 | ||
8300 | re | 8300.00 | 4.8 | 4.95 | |||
8300 | re | ||||||
H7.100 | 1:1:9 AAA | 0.80% | 8300 | re | 5.01 | ||
8300 | re | 8300.00 | 5.03 | 5.02 | |||
8300 | re | ||||||
H7.150 | 1:1:9 AAA | 0.50% | 8300 | re | 4.11 | ||
8300 | re | 8300.00 | 5.2 | 4.655 | |||
8300 | re | ||||||
H7.150 | 1:1:9 AAA | 0.60% | 8300 | re | 4.25 | ||
8300 | re | 8300.00 | 5.57 | 4.91 | |||
8300 | re | ||||||
H7.150 | 1:1:9 AAA | 0.70% | 8300 | re | 5.71 | ||
8300 | re | 8300.00 | 5.5 | 5.605 | |||
8300 | re |
Example 11 [00107] The performance of two low Tg samples L4.100 and L6.100, were compared to one another. All samples were direct coated to 2 mil mylar at 60 gsm +/- 3, air dried for 5 min. followed by 10 min. in a 120°C forced air oven. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of performance testing are set forth below in Tables 8A and 8B.
Table 8A - Test Results for Samples L.100 and L6.100
180 DEG SS PEEL | |||||||||||
SAMPLE | AAA | %BOS | 15 MIN | MO F | AVG | 24 HR | MOF | AVG | 72+ HR | MOF | AVG |
L4.100 | 1:1:8 AAA | 0.40% | 3.84 | sp | 4.06 | sp | 4.14 | sp | |||
4.01 | sp | 3.93 | 4.19 | sp | 4.11 | 4.21 | sp | 4.14 | |||
3.95 | sp | 4.08 | sp | 4.08 | sp | ||||||
L4.100 | 1:1:8 AAA | 0.50% | 4.52 | sp | 4.52 | sp | 4.60 | sp | |||
4.63 | sp | 4.55 | 4.53 | sp | 4.53 | 4.69 | sp | 4.64 | |||
4.50 | sp | 4.53 | sp | 4.64 | sp | ||||||
L4.100 | 1:1:8 AAA | 0.60% | 5.05 | sp | 5.17 | sp | 5.24 | sp | |||
5.31 | sp | 5.27 | 5.35 | sp | 5.28 | 5.45 | sp | 5.40 | |||
5.44 | sp | 5.31 | sp | 5.50 | sp | ||||||
L4.100 | 1:1:8 AAA | 0.70% | 5.44 | sp | 5.50 | sp | 5.72 | sp | |||
5.60 | sp | 5.56 | 5.55 | sp | 5.55 | 5.76 | sp | 5.74 | |||
5.63 | sp | 5.60 | sp | 5.74 | sp | ||||||
L4.100 | 1:1:8 AAA | 0.80% | 2.55 | 5.64 | sp | 6.11 | sp | ||||
2.40 | 2.64 | 5.87 | sp | 5.27 | 6.21 | sp | 6.21 |
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2.96 | 4.30 | 6.30 | sp | ||||||||
L6.100 | 1:1:8 AAA | 0.40% | 7.38 | sp | 7.46 | sp | 7.83 | sp | |||
7.58 | sp | 7.65 | 7.58 | sp | 7.52 | 7.86 | sp | 7.82 | |||
7.98 | sp | 7.53 | sp | 7.76 | sp | ||||||
L6.100 | 1:1:8 AAA | 0.50% | 8.58 | sp | 8.04 | sp | 8.42 | sp | |||
7.25 | sp | 8.04 | 8.36 | sp | 8.26 | 8.48 | sp | 8.47 | |||
8.28 | sp | 8.36 | sp | 8.51 | sp | ||||||
L6.100 | 1:1:8 AAA | 0.60% | 7.83 | p tr | 8.35 | sp | 8.44 | sp | |||
6.10 | p tr | 5.96 | 6.12 | Ittr | 7.18 | 3.78 | It tr | 6.95 | |||
3.94 | p tr | 7.07 | sp | 8.62 | sp | ||||||
L6.100 | 1:1:8 AAA | 0.70% | 3.40 | 7.03 | P tr/sp | 9.07 | sp | ||||
2.82 | 3.01 | 5.17 | p tr | 7.03 | 8.83 | psp | 9.307 | ||||
2.82 | 8.89 | sp | 9.30 | sp | |||||||
L6.100 | 1:1:8 AAA | 0.80% | 3.10 | 4.91 | 6.11 | ||||||
3.08 | 2.98 | 4.87 | 4.91 | 5.14 | 6.11 | ||||||
2.77 | 4.95 | 7.07 | p tr |
[00108] In Table 8A and other tables, p tr refers to partial adhesive transfer. And It tr refers to light partial adhesive transfer. And p tr/sp refers to partial cohesive splitting.
Table 8B -Test Results for Samples L.100 and L6.100
% x % x 1 kg SHEAR | |||||
SAMPLE | AAA | %BOS | MIN | MOF | AVG |
L4.100 | 1:1:8 AAA | 0.40% | 1.6 | sp | |
1.3 | sp | 1.45 | |||
L4.100 | 1:1:8 AAA | 0.50% | 13.3 | sp | |
11 | sp | 12.15 | |||
L4.100 | 1:1:8 AAA | 0.60% | 24.7 | sp | |
28.1 | sp | 26.40 | |||
L4.100 | 1:1:8 AAA | 0.70% | 50.4 | sp | |
62.1 | sp | 56.25 | |||
L4.100 | 1:1:8 AAA | 0.80% | 84.9 | sp | |
89.4 | sp | 87.15 | |||
L6.100 | 1:1:8 AAA | 0.40% | 24.9 | sp | |
25.1 | sp | 25.00 | |||
L6.100 | 1:1:8 AAA | 0.50% | 87.2 | sp | |
79 | sp | 83.10 |
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L6.100 | 1:1:8 AAA | 0.60% | 207.5 | sp | |
162.5 | sp | 185.00 | |||
L6.100 | 1:1:8 AAA | 0.70% | 196.5 | adh | |
201.8 | adh | 199.15 | |||
L6.100 | 1:1:8 AAA | 0.80% | 105.4 | adh | |
77.7 | adh | 91.55 | |||
[00109] In Table 8B and other tables, adh refers to adhesive failure.
Example 12 [00110] The performance of one of the high Tg samples H7.150 was evaluated in a coatweight study. All samples were direct coated to 2 mil. Mylar at designated coatweight, air dried for 5 min. followed by 120°C for 10 minutes. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of performance testing are set forth below in Tables 9A and 9B.
Table 9A - Test Results for Sample H7.150
AAA | 180 DEG SS PEEL | |||||||
SAMPLE | CW | %BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG |
H7.150 | 30 GSM | 0.50% | 2.42 | 4.34 | 5.27 | |||
2.64 | 2.59 | 5.48 | 4.94 | 6.34 | 5.53 | |||
2.72 | 5 | 4.97 | ||||||
H7.150 | 40 GSM | 0.50% | 3.59 | 5.31 | 5.23 | |||
3.33 | 3.24 | 5.21 | 5.06 | 5.42 | 5.09 | |||
2.79 | 4.66 | 4.61 | ||||||
H7.150 | 50 GSM | 0.50% | 5.36 | 6.63 | 6.65 | |||
4.71 | 5.03 | 6.79 | 6.84 | 6.94 | 6.89 | |||
5.01 | 7.1 | 7.09 |
Table 9B -Test Results for Sample H7.150
AAA | 8.8 LB PERSQIN SHEAR | 65C 1X1X5LB SHEARS | SAFT | |||||||
SAMPLE | CW | %BOS | MIN | AVG | MIN | SLIP/ MOF | AVG | DEG C | MOF | AVG |
H7.150 | 30 GSM | 0.50% | 10000 | 360 | ,2mm | 200 | pass | |||
10000 | 10000.00 | 360 | ,1mm | 360 | 200 | pass | 200 | |||
10000 | 360 | ,1mm | 200 | pass | ||||||
H7.150 | 40 GSM | 0.50% | 10000 | 360 | ,2mm | 200 | pass | |||
10000 | 10000.00 | 360 | ,2mm | 360 | 200 | pass | 200 |
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10000 | 360 | ,2mm | 200 | pass | ||||||
H7.150 | 50 GSM | 0.50% | 10000 | 360 | ,2mm | 200 | pass | |||
10000 | 10000.00 | 360 | ,1mm | 360 | 200 | pass | 200 | |||
10000 | 360 | ,1mm | 200 | pass |
Example 13 [00111] The performance of two high Tg samples H9.100 and H7.100, was evaluated in a coatweight study. All samples were direct coated to aluminum foil at designated coatweight, air dried for 5 min. followed by 120°C for 10 minutes. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of performance testing are set forth below in Table 10.
Table 10 -Test Results for Samples H9.100 and H7.100
SAMPLE | 1:3:9 AAA | COAT WT | 180 DEG SS PEEL | 8.8 LB PERSQIN SHEAR | |||||||
%BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG | MIN | MOF | AVG | ||
H9.100 | 0.60% | 30 gsm | 3 | 4.91 | 6.13 | 10000 | re | ||||
2.57 | 3.08 | 5.53 | 5.32 | 4.55 | 5.40 | 10000 | re | 10000.0 0 | |||
3.67 | 5.52 | 5.51 | 10000 | re | |||||||
60 gsm | 5.22 | 7.29 | 6.85 | 1647. 3 | It st | ||||||
4.84 | 5.01 | 7.01 | 7.04 | 6.5 | 6.61 | 10000 | re | 7215.77 | |||
4.97 | 6.82 | 6.49 | 10000 | re | |||||||
120 gsm | 2.94 | 4.61 | 9.26 | 362.4 | Lt st | ||||||
4.3 | 3.83 | 5.93 | 5.28 | 8.28 | 8.25 | 10000 | re | 6787.47 | |||
4.26 | 5.3 | 7.21 | 10000 | re | |||||||
H7.100 | 0.70% | 30 gsm | 4.37 | 6.29 | 4.98 | 10000 | re | ||||
3.98 | 3.85 | 5.42 | 5.93 | 5.22 | 5.28 | 10000 | re | 10000.0 0 | |||
3.21 | 6.09 | 5.65 | 10000 | re | |||||||
60 gsm | 3.1 | 4.85 | 5.37 | 10000 | re | ||||||
3.2 | 3.48 | 5.29 | 5.21 | 6.37 | 6.03 | 10000 | re | 10000.0 0 | |||
4.14 | 5.48 | 6.34 | 10000 | re | |||||||
120 gsm | 4.53 | 6.16 | 7.37 | 1993. 3 | Lt st | ||||||
3.19 | 3.62 | 5.58 | 5.66 | 6.04 | 6.59 | 10000 | re | 7331.10 | |||
3.15 | 5.24 | 6.36 | 10000 | re |
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Example 14 [00112] Samples of a high Tg sample H9.150, were subjected to a drying study. All samples were direct coated to 2 mil mylar at 60 +/- 5 gsm, air dried for 5 min. followed by the designated temperatures for 10 min. All samples were conditioned for 24 hours in a controlled climate room. A summary is set forth below in Table 11.
Table 11 -Test Results for Sample H9.150
180 DEG SS PEEL | 8.8 LB PERSQIN SHEAR | |||||||||
SAMPLE | XLINKER | % BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG | MIN | AVG |
H9.150 | 1:3:9 AAA | 0.20% | 3.76 | 5.03 | 5.6 | 10000 | ||||
dried temp | 110 | 3.86 | 4.01 | 4.94 | 5.23 | 5.34 | 5.63 | 10000 | 10000.00 | |
dry time | 10 | 4.4 | 5.73 | 5.95 | 10000 | |||||
H9.150 | 1:3:9 AAA | 0.20% | 4.77 | 5.62 | 5.95 | 10000 | ||||
dried temp | 120 | 4.53 | 4.58 | 5.75 | 5.70 | 5.94 | 6.01 | 10000 | 10000.00 | |
dry time | 10 | 4.43 | 5.73 | 6.14 | 10000 | |||||
H9.150 | 1:3:9 AAA | 0.20% | 3.85 | 5.5 | 5.77 | 10000 | ||||
dried temp | 130 | 3.94 | 3.79 | 4.9 | 5.17 | 6.02 | 5.91 | 10000 | 10000.00 | |
dry time | 10 | 3.59 | 5.11 | 5.94 | 10000 | |||||
H9.150 | 1:3:9 AAA | 0.20% | 3.34 | 5.31 | 5.87 | 10000 | ||||
dried temp | 140 | 3.25 | 3.33 | 5.04 | 5.20 | 5.95 | 5.90 | 10000 | 10000.00 | |
dry time | 10 | 3.4 | 5.24 | 5.88 | 10000 |
Example 15 [00113] Samples of low Tg polymers, e.g., L4.100 and L6.100, were subjected to quick stick testing. All samples were direct coated to 2 mil mylar at 60 gsm +/- 3, air dried for 5 min. followed by 10 min. in a 120°C forced air oven. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of quick stick testing are set forth below in Tables 12A and 12B.
Table 12A - Test Results for Samples L4.100 and L6.100
180 DEG SS PEEL | ||||||||
SAMPLE | AAA | % BOS | 15 MIN | MOF | AVG | 72+ HR | MOF | AVG |
L4:100 | 1:1:8AAA | 0.40% | 3.84 | sp | 4.14 | sp | ||
4.01 | sp | 3.93 | 4.21 | sp | 4.14 |
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3.95 | sp | 4.08 | sp | |||||
L4.100 | 1:1:8AAA | 0.50% | 4.52 | sp | 4.60 | sp | ||
4.63 | sp | 4.55 | 4.69 | sp | 4.64 | |||
4.50 | sp | 4.64 | sp | |||||
L4.100 | 1:1:8AAA | 0.60% | 5.05 | sp | 5.24 | sp | ||
5.31 | sp | 5.27 | 5.45 | sp | 5.40 | |||
5.44 | sp | 5.50 | sp | |||||
L4.100 | 1:1:8AAA | 0.70% | 5.44 | sp | 5.72 | sp | ||
5.60 | sp | 5.56 | 5.76 | sp | 5.74 | |||
5.63 | sp | 5.74 | sp | |||||
L4.100 | 1:1:8AAA | 0.80% | 2.55 | 6.11 | sp | |||
2.40 | 2.64 | 6.21 | sp | 6.21 | ||||
2.96 | 6.30 | sp | ||||||
L6.100 | 1:1:8AAA | 0.40% | 7.38 | sp | 7.83 | sp | ||
7.58 | sp | 7.65 | 7.86 | sp | 7.82 | |||
7.98 | sp | 7.76 | sp | |||||
L6.100 | 1:1:8AAA | 0.50% | 8.58 | sp | 8.42 | sp | ||
7.25 | sp | 8.04 | 8.48 | sp | 8.47 | |||
8.28 | sp | 8.51 | sp | |||||
L6.100 | 1:1:8AAA | 0.60% | 7.83 | p tr | 8.44 | sp | ||
6.10 | p tr | 5.96 | 3.78 | It tr | 6.95 | |||
3.94 | p tr | 8.62 | sp | |||||
L6.100 | 1:1:8AAA | 0.70% | 3.40 | 9.07 | sp | |||
2.82 | 3.01 | 8.83 | psp | 9.07 | ||||
2.82 | 9.30 | sp | ||||||
L6.100 | 1:1:8AAA | 0.80% | 3.10 | 6.11 | ||||
3.08 | 2.98 | 5.14 | 6.11 | |||||
2.77 | 7.07 | p tr |
Table 12B - Test Results for Samples L4.100 and L6.100
% x % x 1 kg SHEAR | ROLLING BALL | SS LOOPTACK | ||||||||
SAMPLE | AAA | % BOS | MIN | MO F | AVG | VALUE (mm) | AVG | VALUE (mm) | MO F | AVG |
L4:100 | 1:1:8AA A | 0.40% | 1.6 | sp | 40 | 10.54 | tr | |||
1.3 | sp | 1.45 | 50 | 45 | 9.84 | tr | 10.19 | |||
L4.100 | 1:1:8AA A | 0.50% | 13.3 | sp | 60 | 11.81 | tr | |||
11 | sp | 12.15 | 48 | 54 | 11.68 | tr | 9.51 | |||
L4.100 | 1:1:8AA A | 0.60% | 24.7 | sp | 65 | 5.05 | ||||
28.1 | sp | 26.40 | 50 | 57.5 | 5.45 | 5.25 | ||||
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L4.100 | 1:1:8AA A | 0.70% | 50.4 | sp | 50 | 4.76 | ||||
62.1 | sp | 56.25 | 50 | 50 | 4.46 | 4.61 | ||||
L4.100 | 1:1:8AA A | 0.80% | 84.9 | sp | 50 | 2.86 | ||||
89.4 | sp | 87.15 | 65 | 57.5 | 2.76 | 2.81 | ||||
L6.100 | 1:1:8AA A | 0.40% | 24.9 | sp | 135 | 7.20 | ||||
25.1 | sp | 25.00 | 140 | 137.5 | 8.41 | 7.81 | ||||
L6.100 | 1:1:8AA A | 0.50% | 87.2 | sp | 140 | 4.51 | ||||
79 | sp | 83.10 | 155 | 147.5 | 4.61 | 4.56 | ||||
L6.100 | 1:1:8AA A | 0.60% | 207.5 | sp | 164 | 3.90 | ||||
162.5 | sp | 185.0 0 | 170 | 167 | 4.28 | 4.09 | ||||
L6.100 | 1:1:8AA A | 0.70% | 196.5 | adh | 160 | 3.46 | ||||
201.8 | adh | 199.1 5 | 140 | 150 | 3.48 | 3.47 | ||||
L6.100 | 1:1:8AA A | 0.80% | 105.4 | adh | 140 | 3.40 | ||||
77.7 | adh | 91.55 | 165 | 152.5 | 3.44 | 3.42 | ||||
[00114] In Table 12B, the term adh means adhesive failure.
Example 16 [00115] Samples of low Tg polymer L4.100 and L6.100 were subjected to performance testing. All samples were direct coated to 2 mil mylar at 60 gsm +/- 3, air dried for 5 min. followed by 10 min. in a 120°C forced air oven. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of testing are set forth below in Tables 13A and 13B.
Table 13A - Test Results for Samples L4.100 and L6.100
180 DEG PP PEEL | ||||||||
SAMPLE | AAA | %BOS | 15 MIN | MOF | AVG | 72+ HR | MOF | AVG |
L4.100 | 1:1:8 AAA | 0.40% | 3.74 | sp | 4.07 | sp | ||
3.93 | sp | 3.85 | 4.24 | sp | 4.20 |
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3.87 | sp | 4.28 | sp | |||||
L4.100 | 1:1:8 AAA | 0.50% | 4.20 | sp | 4.54 | sp | ||
4.46 | sp | 4.39 | 4.77 | sp | 4.70 | |||
4.50 | sp | 4.80 | sp | |||||
L4.100 | 1:1:8 AAA | 0.60% | 0.82 | zip | 5.46 | sp | ||
0.81 | zip | 0.80 | 0.72 | zip | 2.33 | |||
0.78 | zip | 0.82 | zip | |||||
L4.100 | 1:1:8 AAA | 0.70% | 0.77 | zip | 0.64 | zip | ||
0.74 | zip | 0.76 | 0.71 | zip | 0.70 | |||
0.76 | zip | 0.74 | zip | |||||
L4.100 | 1:1:8 AAA | 0.80% | 2.16 | 2.57 | ||||
2.46 | 2.37 | 2.86 | 2.72 | |||||
2.50 | 2.72 | |||||||
L6.100 | 1:1:8 AAA | 0.40% | 0.48 | zip | 0.39 | zip | ||
0.41 | zip | 0.46 | 0.60 | zip | 0.45 | |||
0.49 | zip | 0.37 | zip | |||||
L6.100 | 1:1:8 AAA | 0.50% | 0.45 | zip | 0.34 | zip | ||
0.47 | zip | 0.46 | 0.40 | zip | 0.36 | |||
0.47 | zip | 0.34 | zip | |||||
L6.100 | 1:1:8 AAA | 0.60% | 0.41 | zip | 0.39 | zip | ||
0.40 | zip | 0.39 | 1.00 | zip | 0.58 | |||
0.36 | zip | 0.35 | zip | |||||
L6.100 | 1:1:8 AAA | 0.70% | 1.46 | si zip | 2.54 | |||
1.14 | si zip | 1.478 | 2.33 | 2.56 | ||||
1.84 | si zip | 2.77 | ||||||
L6.100 | 1:1:8 AAA | 0.80% | 1.94 | 2.22 | ||||
1.68 | 1.89 | 2.17 | 2.29 | |||||
2.04 | 2.47 |
Table 13B - Test Results for Samples L4.100 and L6.100
180 DEG HDPE PEEL | ||||||||
SAMPLE | AAA | %BOS | 15 MIN | MOF | AVG | 72+ HR | MOF | AVG |
L4.100 | 1:1:8 AAA | 0.40% | 3.99 | sp | 4.30 | sp | ||
3.96 | sp | 4.02 | 4.15 | sp | 4.25 | |||
4.12 | sp | 4.31 | sp | |||||
L4.100 | 1:1:8 AAA | 0.50% | 3.01 | p tr | 4.65 | sp |
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2.76 | p tr | 2.42 | 4.54 | sp | 4.65 | |||
1.50 | p tr | 4.75 | sp | |||||
L4.100 | 1:1:8 AAA | 0.60% | 0.61 | 0.73 | ||||
0.69 | 0.65 | 0.80 | 0.73 | |||||
0.64 | 0.65 | |||||||
L4.100 | 1:1:8 AAA | 0.70% | 0.44 | 0.51 | ||||
0.38 | 0.42 | 0.67 | 0.59 | |||||
0.45 | 0.58 | |||||||
L4.100 | 1:1:8 AAA | 0.80% | 0.31 | 0.36 | ||||
0.25 | 0.28 | 0.43 | 0.39 | |||||
0.29 | 0.38 | |||||||
L6.100 | 1:1:8 AAA | 0.40% | 0.84 | 1.21 | ||||
0.87 | 0.90 | 0.95 | 1.03 | |||||
1.00 | 0.93 | |||||||
L6.100 | 1:1:8 AAA | 0.50% | 0.66 | 0.65 | ||||
0.60 | 0.62 | 0.83 | 0.71 | |||||
0.60 | 0.64 | |||||||
L6.100 | 1:1:8 AAA | 0.60% | 0.50 | 0.64 | ||||
0.43 | 0.48 | 0.64 | 0.61 | |||||
0.52 | 0.55 | |||||||
L6.100 | 1:1:8 AAA | 0.70% | 0.40 | 0.48 | ||||
0.44 | 0.40 | 0.41 | 0.46 | |||||
0.37 | 0.48 | |||||||
L6.100 | 1:1:8 AAA | 0.80% | 0.36 | 0.33 | ||||
0.35 | 0.34 | 0.36 | 0.34 | |||||
0.30 | 0.34 |
Example 17 [00116] Samples of high Tg polymers H9.150 and H7.150, were subjected to UL testing. All samples were direct coated to foil at 60 +/- 5 gsm, air dried for 5 min. followed by 120°C for the designated minutes. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of testing are set forth below in Tables 14A and 14B.
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Table 14A - Test Results for Samples H9.150 and H7.150
180 DEG SS PEEL | ||||||||
SAMPLE | XLINKER | % BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG |
H9.150 | 1:1:8AAA | 0.40% | 6.4 | 7.66 | 8.08 | |||
5.54 | 5.29 | 6.62 | 6.80 | 6.56 | 6.52 | |||
3.92 | 6.13 | 4.91 | ||||||
H9.150 | 1:1:8AAA | 0.50% | 6.06 | 7.41 | 8.3 | |||
5.78 | 6.07 | 7.34 | 7.44 | 8.27 | 8.24 | |||
6.37 | 7.57 | 8.16 | ||||||
H9.150 | 1:1:8AAA | 0.60% | 5.62 | 7.58 | 7.99 | |||
5.36 | 4.98 | 6.81 | 6.37 | 7.11 | 7.55 | |||
3.82 | 4.73 | 7.54 | ||||||
H7.150 | 1:1:8AAA | 0.50% | 5.95 | 6.8 | 7.63 | |||
5.29 | 5.62 | 6.42 | 6.63 | 7.07 | 7.45 | |||
5.61 | 6.67 | 7.65 | ||||||
H7.150 | 1:1:8AAA | 0.60% | 4.98 | 5.7 | 6.56 | |||
5.19 | 5.00 | 5.81 | 5.69 | 5.98 | 6.25 | |||
4.82 | 5.57 | 6.21 | ||||||
H7.150 | 1:1:8AAA | 0.70% | 3.73 | 3.56 | 3.53 | |||
4.96 | 4.22 | 4.54 | 4.21 | 5.6 | 4.75 | |||
3.98 | 4.52 | 5.11 |
Table 14B -Test Results for Samples H9.150 and H7.150
1x1x10 lb | 65C 1x1x5 lb | 8.8 LB PERSQIN SHEAR | |||||||||
SAMPLE | XLINKER | % BOS | MIN | SLIP/MO F | AVG | MIN | SLIP/ MOF | AVG | MIN | MO F | AVG |
H9.150 | 1:1:8AA A | 0.40% | 720 0 | .5 mm | 163.1 0 | Sp | 100 0 | re | |||
720 0 | .6 mm | 7200.0 0 | 181.8 0 | Sp | 175.5 3 | 100 0 | re | 10000.0 0 | |||
720 0 | .6 mm | 181.7 0 | sp | 100 0 | re | ||||||
H9.150 | 1:1:8AA A | 0.50% | 720 0 | .4 mm | 360.0 0 | .9 mm | 100 0 | re | |||
720 0 | .4 mm | 7200.0 0 | 360.0 0 | .9 mm | 360.0 0 | 100 0 | re | 10000.0 0 | |||
720 0 | .4 mm | 360.0 0 | .9 mm | 100 0 | re | ||||||
H9.150 | 1:1:8AA A | 0.60% | 720 0 | .3 mm | 360.0 0 | .5 mm | 100 0 | re | |||
720 0 | .2 mm | 7200.0 0 | 360.0 0 | .4 mm | 360.0 0 | 100 0 | re | 10000.0 0 | |||
720 0 | .2 mm | 360.0 0 | .5 mm | 100 0 | re | ||||||
H7.150 | 1:1:8AA | 0.50% | 720 | .3 mm | 360.0 | .5 mm | 100 | re |
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A | 0 | 0 | 0 | ||||||||
720 0 | .3 mm | 7200.0 0 | 360.0 0 | .5 mm | 360.0 0 | 100 0 | re | 10000.0 0 | |||
720 0 | .3 mm | 360.0 0 | .5 mm | 100 0 | re | ||||||
H7.150 | 1:1:8AA A | 0.60% | 720 0 | .1 mm | 360.0 0 | .2 mm | 100 0 | re | |||
720 0 | .2 mm | 7200.0 0 | 360.0 0 | .2 mm | 360.0 0 | 100 0 | re | 10000.0 0 | |||
720 0 | .1 mm | 360.0 0 | .1 mm | 100 0 | re | ||||||
H7.150 | 1:1:8AA A | 0.70% | 720 0 | .2 mm | 360.0 0 | .2 mm | 100 0 | re | |||
720 0 | .2 mm | 7200.0 0 | 360.0 0 | .2 mm | 360.0 0 | 100 0 | re | 10000.0 0 | |||
720 0 | .2 mm | 360.0 0 | .3 mm | 100 0 | re |
Example 18 [00117] Samples of high Tg polymers, i.e., H7.100 and H9.100, were subjected to UL testing. All samples were directed coated to foil at 60 +/- 5 gsm, air dried for 5 min. followed by 120°C for the designated minutes. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of testing are set forth below in Tables 15A and 15B.
Table 15A-Test Results for Samples H7.100 and H9.100
180 DEG SS PEEL | ||||||||
SAMPLE | X-LINKER | % BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG |
H7.100 | 1:1:9AAA | 0.60% | 5.31 | 6 | 6.02 | |||
5.51 | 5.00 | 5.83 | 5.56 | 7.01 | 6.29 | |||
4.19 | 4.85 | 5.83 | ||||||
H7.100 | 1:1:9AAA | 0.70% | 5.04 | 5.2 | 6.21 | |||
3.62 | 4.34 | 5.77 | 5.35 | 6.67 | 6.43 | |||
4.36 | 5.09 | 6.41 | ||||||
H7.100 | 1:1:9AAA | 0.80% | 4.34 | 4.6 | 5.13 | |||
4.57 | 4.19 | 5.78 | 5.00 | 6.2 | 5.48 | |||
3.65 | 4.63 | 5.11 | ||||||
H9.100 | 1:1:9AAA | 0.50% | 6.19 | 6.84 | 6.71 | |||
5.12 | 5.77 | 6.43 | 6.96 | 6.96 | 7.09 | |||
6.01 | 7.6 | 7.61 | ||||||
H9.100 | 1:1:9AAA | 0.60% | 6.2 | 6.41 | 5.89 | |||
5.59 | 5.67 | 6.46 | 6.27 | 7.25 | 6.44 | |||
5.23 | 5.95 | 6.19 | ||||||
H9.100 | 1:1:9AAA | 0.70% | 5.63 | 6.97 | 7.15 | |||
6.06 | 6.00 | 7.01 | 7.08 | 7.16 | 7.30 | |||
6.32 | 7.27 | 7.58 |
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Table 15B -Test Results for Samples H7.100 and H9.100
1x1x10 lb | 1x1x5 lb 65 DEG Shears | 8.8 LB PERSQIN SHEAR | |||||||||
SAMPLE | X-LINKER | % BOS | MIN | MOF | AVG | MIN | MOF | AVG | MIN | MO F | AVG |
H7.100 | 1:1:9AAA | 0.60% | 6000+ | 360.0 0 | .1 mm | 1000 | re | ||||
6000+ | 6000.0 0 | 360.0 0 | .1 mm | 360.0 0 | 1000 | re | 10000.0 0 | ||||
6000+ | 360.0 0 | .1 mm | 1000 | re | |||||||
H7.100 | 1:1:9AAA | 0.70% | 6000+ | 360.0 0 | .1 mm | 4134. 7 | Itst | ||||
6000+ | 6000.0 0 | 360.0 0 | .1 mm | 360.0 0 | 1000 | re | 8044.90 | ||||
6000+ | 360.0 0 | .2 mm | 1000 | re | |||||||
H7.100 | 1:1:9AAA | 0.80% | 6000+ | 360.0 0 | .1 mm | 1273. 1 | Itst | ||||
6000+ | < | 6000.0 0 | 360.0 0 | .1 mm | 360.0 0 | 418.9 | Itst | 3897.33 | |||
6000+ | 10000 | re | |||||||||
H9.100 | 1:1:9AAA | 0.50% | 7200.0 0 | .3 mm | 360.0 0 | .5 mm | 10000 | re | |||
7200.0 0 | .4 mm | 7200.0 0 | 360.0 0 | .5 mm | 360.0 0 | 10000 | re | 10000.0 0 | |||
7200.0 0 | .3 mm | 360.0 0 | .5 mm | 10000 | re | ||||||
H9.100 | 1:1:9AAA | 0.60% | 7200.0 0 | .3 mm | 360.0 0 | .3 mm | 10000 | re | |||
7200.0 0 | .2 mm | 7200.0 0 | 360.0 0 | .2 mm | 360.0 0 | 10000 | re | 10000.0 0 | |||
7200.0 0 | .2 mm | 360.0 0 | .2 mm | 10000 | re | ||||||
H9.100 | 1:1:9AAA | 0.70% | 7200.0 0 | .1 mm | 360.0 0 | .2 mm | 10000 | re | |||
7200.0 0 | .2 mm | 7200.0 0 | 360.0 0 | .2 mm | 360.0 0 | 10000 | re | 10000.0 0 | |||
7200.0 0 | .1 mm | 360.0 0 | .2 mm | 10000 | re |
[00118] In Tables 15B and other tables, the term It st refers to light stain.
Example 19 [00119] Samples of low Tg polymers L4.100 and L6.100 were subjected to various benchmarking trials. All experimental samples were direct coated to 2 mil mylar at 60 +/- 5 gsm, air dried for 5 min. followed by 120°C for the designated minutes. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of the trials are set forth below in Tables 16A and 16B.
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Table 16A - Test Results for Samples L4.100 and L6.100
Polymer | AAA Level | 15 MIN | MO F | AGED | MO F | AGED | MO F | AGED | MO F | AGED | MO F |
L4.100 | 0.0% | 5.56 | sp | 5.76 | sp | 0.59 | 0.7 | zip | 1.05 | ||
L4.100 | 0.80% | 2.64 | 6.21 | sp | 0.39 | 2.72 | 0.42 | ||||
L6.100 | 0.60% | 5.96 | ptr | 6.95 | sp | 0.61 | 0.58 | zip | 0.9 | ||
L6.100 | 0.70% | 3.01 | 9.07 | sp | 0.45 | 2.56 | 0.52 |
Table 16B - Test Results for Samples L4.100 and L6.100
POLYMER | AAA Level | SS LOOP-TACK | ROLLING BALL | 8.8 LB PER SQ IN |
15 MIN | VALUE (mm) | MIN | ||
L4.100 | 0.70% | 4.61 | 50.0 | 56.25 |
L4.100 | 0.80% | 2.81 | 57.5 | 87.15 |
L6.100 | 0.60% | 4.09 | 167.0 | 185.00 |
L6.100 | 0.70% | 3.47 | 150.0 | 199.15 |
Example 20 [00120] Samples of high Tg polymers H9.150 and H7.150 were subjected to various benchmarking trials. All samples were directed coated to foil at 60 +/- 5 gsm, air dried for 5 min. followed by 120°C for the designated minutes. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of benchmarking are set forth below in Tables 17A and 17B.
Table 17A - Comparative Test Results for Samples H9.150 and H7.150
180 DEG SS PEEL | 1x1x10 lb | ||||||||||
SAMPLE | XLINKER | % BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG | MIN | SLIP/MO F | AVG |
H9.150 | 1:1:8AA A | 0.60% | 4.51 | 6.54 | 7.23 | 10000 | .2 mm | ||||
4.3 | 4.34 | 6.33 | 6.20 | 7.17 | 6.42 | 10000 | .2 mm | 10000.0 0 | |||
4.22 | 5.72 | 4.85 | 10000 | .1 mm | |||||||
H7.150 | 1:1:8AA A | 0.60% | 3.97 | 5.71 | 6.27 | 10000 | .2 mm | ||||
3.36 | 3.51 | 5.27 | 5.31 | 6 | 5.83 | 10000 | .2 mm | 10000.0 0 | |||
3.2 | 4.96 | 5.21 | 10000 | .2 mm |
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Venture tape 1581A | 3.37 | 5.05 | 5.46 | 196.00 | Itst | ||||
3.45 | 3.53 | 5.17 | 5.19 | 5.59 | 5.60 | 268.10 | Itst | 242.33 | |
3.77 | 5.36 | 5.74 | 262.90 | Itst | |||||
Shurtape AF 912 | 6.3 | 7.13 | 7.61 | 126.30 | Itsp | ||||
5.35 | 5.62 | 6.44 | 6.61 | 6.79 | 7.03 | 125.50 | Itsp | 126.03 | |
5.22 | 6.25 | 6.68 | 126.30 | Itsp | |||||
Shurtape AF 100 | 3.66 | 4.81 | 5.14 | 4148.5 0 | sp | ||||
3.74 | 3.71 | 5.07 | 5.02 | 5.64 | 5.31 | 2462.0 0 | sp | 4603.50 | |
3.73 | 5.17 | 5.14 | 7200.0 0 | .1 mm | |||||
Fasson 181 AP | 3.66 | 3.67 | 5.41 | 655.10 | Itst | ||||
3.63 | 4.20 | 4.3 | 4.60 | 4.59 | 5.21 | 1641 | Itst | 1376.80 | |
5.32 | 5.83 | 5.62 | 1834.3 | Itst | |||||
Shurtape DC 181 | 2.02 | 3.21 | 4.22 | 53.5 | Itsp | ||||
1.57 | 1.71 | 3.43 | 3.31 | 3.72 | 4.82 | 62.5 | Itsp | 71.67 | |
1.54 | 3.29 | 6.52 | 99 | Itsp | |||||
Polyken 339 | 3.66 | 5.19 | 5.67 | N/A | |||||
3.80 | 3.70 | 4.59 | 4.83 | 4.07 | 4.95 | N/A | |||
3.65 | 4.72 | 5.11 |
Table 17B - Comparative Test Results for Samples H9.150 and H7.150
1x1x5 lb | 8.8 LB PERSQIN SHEAR | |||||||
SAMPLE | X-LINKER | % BOS | MIN | SLIP/MO F | AVG | MIN | MO F | AVG |
H9.150 | 1:1:8AAA | 0.60% | 360.00 | .3 mm | 10000 | re | ||
360.00 | .2 mm | 360.0 0 | 10000 | re | 10000.0 0 | |||
360.00 | .3 mm | 10000 | re | |||||
H7.150 | 1:1:8AAA | 0.60% | 360.00 | .5 mm | 10000 | re | ||
360.00 | .4 mm | 360.0 0 | 10000 | re | 10000.0 0 | |||
360.00 | .5 mm | 10000 | re | |||||
Venture tape 1581A | 71.20 | POP | 49 | Itst | ||||
33.90 | POP | 39.40 | 41.5 | Itst | 45.25 | |||
13.10 | pop | |||||||
Shurtape AF 912 | 24.00 | Itsp | 5287.1 | Itsp | ||||
14.80 | Itsp | 17.57 | 10000 | re | 7643.55 | |||
13.90 | .Itsp | |||||||
Shurtape AF 100 | 360.00 | .2 mm | 215.7 | POP | ||||
360.00 | .1 mm | 360.0 0 | 193.3 | POP | 204.50 | |||
360.00 | .2 mm | |||||||
Fasson 181 AP | 360 | .2 mm | 808.6 | Itst | ||||
360 | .2 mm | 360.0 0 | 10000 | re | 5404.30 |
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360 | .2 mm | |||||
Shurtape DC 181 | 118.5 | sp | 727 | Itsp | ||
91.4 | sp | 106.6 3 | 49.7 | Itsp | 61.20 | |
110.00 | sp | |||||
Polyken 339 | 31.8 | POP | 81 | pop | ||
52.30 | POP | 32.40 | 43.4 | pop | 62.20 | |
13.10 | pop |
[00121] In Table 17B and other tables, the term pop refers to quick adhesive failure.
Example 21 [00122] Samples of high Tg polymers H9.100 and H7.100, were subjected to additional benchmarking trials. All samples were direct coated to foil at 60 +/- 5 gsm, air dried for 5 min followed by 120°C for the designated minutes. All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of benchmarking are set forth below in Tables 18A and 18B
Table 18A - Comparative Test Results for Samples H9.100 and H7.100
180 DEG SS PEEL | 1x1x10 lb | ||||||||||
SAMPLE | X-LINKER | % BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG | MIN | SLIP/MO F | AVG |
H9.100 | 1:1:8AAA | 0.70% | 5.63 | 6.97 | 7.15 | 7200 | .1 mm | ||||
6.06 | 6.00 | 7.01 | 7.08 | 7.16 | 7.30 | 7200 | .2 mm | 7200.0 0 | |||
6.32 | 7.27 | 7.58 | 7200 | .1 mm | |||||||
H7.100 | 1:1:8AAA | 0.80% | 4.34 | 4.6 | 5.13 | 6000+ | n/a | ||||
4.57 | 4.19 | 5.78 | 5.00 | 6.2 | 5.48 | 6000+ | n/a | n/a | |||
3.65 | 4.63 | 5.11 | 6000+ | n/a | |||||||
Venture tape 1581A | 3.37 | 5.05 | 5.46 | 196.00 | Itst | ||||||
3.45 | 3.53 | 5.17 | 5.19 | 5.59 | 5.60 | 268.10 | Itst | 242.33 | |||
3.77 | 5.36 | 5.74 | 262.90 | Itst | |||||||
Shurtape AF 912 | 6.3 | 7.13 | 7.61 | 126.30 | Itsp | ||||||
5.35 | 5.62 | 6.44 | 6.61 | 6.79 | 7.03 | 125.50 | Itsp | 126.03 | |||
5.22 | 6.25 | 6.68 | 126.30 | Itsp | |||||||
Shurtape AF 100 | 3.66 | 4.81 | 5.14 | 4148.5 0 | sp | ||||||
3.74 | 3.71 | 5.07 | 5.02 | 5.64 | 5.31 | 2462.0 0 | sp | 4603.5 0 | |||
3.73 | 5.17 | 5.14 | 7200.0 0 | .1 mm | |||||||
Fasson 181 AP | 3.66 | 3.67 | 5.41 | 655.10 | Itst | ||||||
3.63 | 4.20 | 4.3 | 4.60 | 4.59 | 5.21 | 1641 | Itst | 1376.8 0 | |||
5.32 | 5.83 | 5.62 | 1834.3 | Itst |
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Shurtape DC 181 | 2.02 | 3.21 | 4.22 | 53.5 | Itsp | ||||
1.57 | 1.71 | 3.43 | 3.31 | 3.72 | 4.82 | 62.5 | Itsp | 71.67 | |
1.54 | 3.29 | 6.52 | 99 | Itsp | |||||
Polyken 339 | 3.66 | 5.19 | 5.67 | N/A | |||||
3.80 | 3.70 | 4.59 | 4.83 | 4.07 | 4.95 | n/a | |||
3.65 | 4.72 | 5.11 |
Table 18B - Comparative Test Results for Samples H9.100 and H7.100
1x1x5 lb | 8.8 LB PERSQIN SHEAR | |||||||
SAMPLE | X-LINKER | % BOS | MIN | SLIP/MO F | AVG | MIN | MO F | AVG |
H9.100 | 1:1:8AAA | 0.70% | 360.00 | .2 mm | 10000 | re | ||
360.00 | .2 mm | 360.0 0 | 10000 | re | 7200.00 | |||
360.00 | .2 mm | 10000 | re | |||||
H7.100 | 1:1:8AAA | 0.80% | 360.00 | .1 mm | 1273.1 | Itst | ||
360.00 | .1 mm | 360.0 0 | 418.9 | Itst | 3897.33 | |||
360.00 | .1 mm | 10000 | re | |||||
Venture tape 1581A | 71.20 | POP | 49 | Itst | ||||
33.90 | POP | 39.40 | 41.5 | Itst | 45.25 | |||
13.10 | pop | |||||||
Shurtape AF 912 | 24.00 | Itsp | 5287.1 | Itsp | ||||
14.80 | Itsp | 17.57 | 10000 | re | 7643.55 | |||
13.90 | .Itsp | |||||||
Shurtape AF 100 | 360.00 | .2 mm | 215.7 | POP | ||||
360.00 | .1 mm | 360.0 0 | 193.3 | POP | 204.50 | |||
360.00 | .2 mm | |||||||
Fasson 181 AP | 360 | .2 mm | 808.6 | Itst | ||||
360 | .2 mm | 360.0 0 | 10000 | re | 5404.30 | |||
360 | .2 mm | |||||||
Shurtape DC 181 | 118.5 | sp | 727 | Itsp | ||||
91.4 | sp | 106.6 3 | 49.7 | Itsp | 61.20 | |||
110.00 | sp | |||||||
Polyken 339 | 31.8 | pop | 81 | pop | ||||
52.30 | pop | 32.40 | 43.4 | pop | 62.20 | |||
13.10 | pop |
Example 22 [00123] Samples of High Tg polymer, i.e., H9.150, were subjected to accelerated heat aging.
Specifically, the samples were subjected to one (1) week exposure to 65°C. All samples were direct coated to 2 mil mylar at 60 +/- 5 gsm, air dried for 5 min. followed by 120°C for the designated minutes.
All samples were conditioned for 24 hours in a controlled climate room. A summary of the samples and results of testing are set below in Table 19.
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Table 19 - Comparative Test Results for Samples H9.150 and H7.150
180 DEG SS PEEL | 8.8 LB PER SQ IN SHEAR | ||||||||||
SAMPLE | XLINKER | % BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG | MIN | MO F | AVG |
H9.150 | 1:3:9 AAA | 0.40% | 4.52 | 5.08 | 6.11 | 10000 | |||||
AGED | 4.37 | 4.52 | 5 | 5.05 | 5.97 | 6.03 | 10000 | 10000.00 | |||
4.67 | 5.06 | 6.01 | 10000 | ||||||||
H9.150 | 1:3:9 AAA | 0.40% | 3.77 | 5.47 | 5.92 | 10000 | |||||
CONTROL | 3.97 | 3.66 | 5.46 | 5.25 | 5.54 | 5.65 | 10000 | 10000.00 | |||
3.24 | 4.81 | 5.48 | 10000 |
[00124] The control in Table 19 is H9.150 not heat aged.
Example 23 [00125] Additional samples of high Tg polymer, i.e., H9.150, were subjected to accelerated heat aging. All samples were direct coated to 2 mil mylar at 60 +/- 5 gsm, air dried for 5 min. followed by 120°C for the designated minutes. All samples were conditioned accordingly. A summary of the samples and results of testing are set forth below in Table 20.
Table 20 -Test Results for Sample H9.150
AAA | 180 DEG SS PEEL | 8.8 LB PERSQIN SHEAR | ||||||||
SAMPLE | DWELL | % BOS | 15 MIN | AVG | 24 HR | AVG | 72 HR | AVG | MIN | AVG |
H9.150 | 24 HR | 0.20% | 5.16 | 6.1 | 6.24 | 10000 | ||||
CONTROL | 4.56 | 4.90 | 5.78 | 6.00 | 6.12 | 6.25 | 10000 | 10000.00 | ||
4.98 | 6.12 | 6.4 | 10000 | |||||||
H9.150 | Tappi room dwell | 0.20% | 4.68 | 6.58 | 6.62 | 10000 | ||||
3.97 | 4.33 | 5.39 | 5.91 | 6.34 | 6.16 | 10000 | 10000.00 | |||
4.35 | 5.77 | 5.52 | 10000 | |||||||
H9.150 | 60° oven dwell | 0.20% | 5.1 | 5.13 | 7.08 | 10000 | ||||
4.45 | 4.89 | 5.8 | 5.55 | 6.31 | 6.27 | 10000 | 10000.00 | |||
5.12 | 5.73 | 5.42 | 10000 |
[00126] Many other benefits will not doubt become apparent from future application and development of this technology.
WO 2013/055978
PCT/US2012/059849 [00127] All patents, applications, and articles noted herein are hereby incorporated by reference in their entirety.
[00128] As described hereinabove, the present subject matter solves many problems associated with previously known compositions and methods. However, it will be appreciated that various changes in the details, materials and arrangements of components and/or operations, which have been herein described and illustrated in order to explain the nature of the subject matter, may be made by those skilled in the art without departing from the principle and scope of the subject matter as expressed in the appended claims.
2012322689 11 Nov 2015
Claims (19)
- WHAT )S CLAIMED IS:1. An acrylic polymer comprising:at least one acrylic copolymer having a first reactive segment of controlled molecular weight and position that includes at least one monomer having a functional group selected from the group consisting of a seif reactive functional group, a reactive functional group, and combinations thereof; and a second reactive segment of controlled molecular weight and position that includes at least one monomer having a reactive functional group, wherein the first reactive segment is positioned adjacent to the polymer chain ends, wherein the reactive functional groups are spaced apart along the length of the polymer chain or the reactive functional groups are positioned only in the second reactive segment, and wherein the functional groups of the first reactive segment and the second segment are capable of undergoing crosslinking reactions while remaining reactive with each other.
- 2. The acrylic polymer of claim 1 wherein the functional group of the second reactive segment is a self reactive functional group.
- 3. The acrylic polymer of claim 2 wherein the self reactive functional group of the second reactive segment is the same as the self reactive functional group of the first reactive segment.
- 4. The acrylic polymer of claim 2 wherein the self reactive functional group of the second reactive segment is different than the self reactive functional group of the first reactive segment.
- 5. The acrylic polymer of any one of claim 1-4 wherein the self reactive functional group is selected from the group consisting of silanes, anhydrides, epoxies, alkoxymethylol, and cyclic ethers.
- 6. The acrylic polymer of claim 5 wherein the self reactive functional group is an epoxy.
- 7. The acrylic polymer of any one of claims 1-6 wherein the reactive functional group is selected from the group consisting of acids, hydroxyls, amines, and thiols.
- 8. The acrylic polymer of claim 7 wherein the reactive functional group is an acid.2012322689 11 Nov 2015
- 9. An acrylic pressure sensitive adhesive composition comprising:at least one acrylic copolymer including a first reactive segment of controlled molecular weight and position that includes at least one monomer having a self reactive functional group, and a second reactive segment of controlled molecular weight and position that includes at least one monomer having a reactive functional group, wherein the first reactive segment is positioned adjacent to the polymer chain ends, wherein the reactive functional groups are spaced apart along the length of the polymer chain or the reactive functional groups are positioned only in the second reactive segment, and wherein the functional groups of the first reactive segment and the second segment are capable of undergoing crosslinking reactions while remaining reactive with each other.
- 10. The adhesive composition of claim 9 further comprising:at least one agent selected from the group consisting of pigments, fillers, plasticizers, diluents, antioxidants, tackifiers, polymeric additives, and combinations thereof.
- 11. The acrylic polymer of any one of claims 1-8, or the adhesive composition of any one of claims 9-10, wherein the polymer has a polydispersity of less than 4.0, or of less than 3.5, or of less than 3.0, or of less than 2.5, or of less than 2.0.
- 12. The acrylic polymer of any one of claims 1-8 or 11, or the adhesive composition of any one of claims 9-11 wherein the polymer has a number average molecular weight (Mn) within the range of from about 40,000 to about 150,000, or within the range of from about 50,000 to about 110,000.
- 13. A method of preparing an acrylic polymer comprising:polymerizing at least one monomer having a functional group to thereby form a first reactive segment of controlled molecular weight and position, the functional group being selected from the group consisting of a self reactive functional group, a reactive functional group, and combinations thereof;polymerizing at least one monomer having a reactive functional group to thereby form a second reactive segment of controlled molecular weight and position;wherein at least one of the first reactive segment and the second reactive segment includes an2012322689 11 Nov 2015 acrylate group;forming an acrylic polymer from the first reactive segment and the second reactive segment, wherein the first reactive segment is positioned adjacent to the polymer chain ends, wherein the reactive functional groups are spaced apart along the length of the polymer chain or the reactive functional groups are positioned only in the second reactive segment, and wherein the functional groups of the first reactive segment and the second segment are capable of undergoing crosslinking reactions while remaining reactive with each other.
- 14. The method of claim 13 wherein at least one of the first reactive segment and the second reactive segment is polymerized in the presence of a RAFT agent.
- 15. The method of any one of claims 13-14 wherein at least one of the first reactive segment and the second reactive segment is polymerized in the presence of an SFRP agent.
- 16. The method of any one of claims 13-15 further comprising the step of crosslinking the functional groups of the reactive segments.
- 17. The acrylic polymer of claim 1 wherein the functional group of the first reactive segment is a self reactive functional group.
- 18. The acrylic polymer of claim 1 wherein the glass transition temperature (Tg) of the acrylic polymer is about -35° C to about -60° C.
- 19. The acrylic pressure sensitive adhesive composition of claim 9 wherein the glass transition temperature (Tg) of the acrylic pressure sensitive adhesive composition is about -35° C to about-60° C.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161547481P | 2011-10-14 | 2011-10-14 | |
US61/547,481 | 2011-10-14 | ||
PCT/US2012/059849 WO2013055978A1 (en) | 2011-10-14 | 2012-10-12 | Controlled architecture polymers |
Publications (2)
Publication Number | Publication Date |
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AU2012322689A1 AU2012322689A1 (en) | 2014-05-01 |
AU2012322689B2 true AU2012322689B2 (en) | 2016-01-14 |
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