TW201533088A - 環氧基-末端聚酯 - Google Patents
環氧基-末端聚酯 Download PDFInfo
- Publication number
- TW201533088A TW201533088A TW103138150A TW103138150A TW201533088A TW 201533088 A TW201533088 A TW 201533088A TW 103138150 A TW103138150 A TW 103138150A TW 103138150 A TW103138150 A TW 103138150A TW 201533088 A TW201533088 A TW 201533088A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- preferred
- groups
- polyester
- epoxy
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 150000001875 compounds Chemical group 0.000 description 39
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 21
- 125000001931 aliphatic group Chemical group 0.000 description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 125000002723 alicyclic group Chemical group 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 6
- -1 titanate compound Chemical class 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 101100115778 Caenorhabditis elegans dac-1 gene Proteins 0.000 description 3
- 102100035353 Cyclin-dependent kinase 2-associated protein 1 Human genes 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003335 secondary amines Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 241000857212 Varanus nebulosus Species 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- HZZUMXSLPJFMCB-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;acetate Chemical compound CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 HZZUMXSLPJFMCB-UHFFFAOYSA-M 0.000 description 2
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000001476 sodium potassium tartrate Substances 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- UISARWKNNNHPGI-UHFFFAOYSA-N terodiline Chemical compound C=1C=CC=CC=1C(CC(C)NC(C)(C)C)C1=CC=CC=C1 UISARWKNNNHPGI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- JNDKQWPBSUHORT-UHFFFAOYSA-N C1(=CC=CC=C1)NN.C(C)I Chemical compound C1(=CC=CC=C1)NN.C(C)I JNDKQWPBSUHORT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- YGHLIDRSHHCGHK-UHFFFAOYSA-N [4-(2,5-dioxabicyclo[2.1.0]pentan-3-yloxymethyl)cyclohexyl]methanol Chemical compound C1CC(CCC1CO)COC2C3C(O3)O2 YGHLIDRSHHCGHK-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- TXXACRDXEHKXKD-UHFFFAOYSA-M benzyl(trimethyl)phosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)CC1=CC=CC=C1 TXXACRDXEHKXKD-UHFFFAOYSA-M 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- ITQRVMZJBMZUBB-UHFFFAOYSA-M dimethyl(diphenyl)azanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[N+](C)(C)C1=CC=CC=C1 ITQRVMZJBMZUBB-UHFFFAOYSA-M 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229920006379 extruded polypropylene Polymers 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011140 metalized polyester Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 1
- 239000001521 potassium lactate Substances 0.000 description 1
- 235000011085 potassium lactate Nutrition 0.000 description 1
- 229960001304 potassium lactate Drugs 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 229940094938 stannous 2-ethylhexanoate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
Abstract
環氧基末端聚酯係具有結構:
□
其中,R1-係
□
G-係
□
-A-係二價烷基,-CA-係二價環烷基,以及,-R2-係二價有機基團。
Description
環氧基-末端化合物可用於多種用途。舉例而言,環氧基-末端化合物可與其本身反應或可與一種或多種共反應劑反應以形成具有高分子量及/或經交聯之聚合物。此等聚合物往往有用於多種目標之一者或多者如,舉例而言,作為黏著劑。
US 2008/0081883揭示了聚酯多元醇,其係2,5-呋喃二甲酸與聚環氧化物之反應產物。所欲者係提供環氧基末端化合物,其係與多胺良好地反應以形成有用之黏著劑組成物如,舉例而言,層壓黏著劑。亦所欲者係提供環氧基末端化合物,其係於自約25℃至約70℃之溫度範圍內具有所欲之低粘度。
下述者係本發明之內容。
本發明之第一態樣係環氧基末端聚酯,其係具有結構:
其中,R1-係
G-係
-A-係二價烷基,-CA-係二價環烷基,以及,-R2-係二價有機基團。
下述者係本發明之詳細說明。
除內文中明確另行指出者外,本文中,下述術語係具有指明之定義。
環氧基末端之化合物係含有一個或多個結構I之化合物:
二環氧化物係具有恰恰兩個結構I之基團的化合物。環氧丙基醚末端之化合物係含有一個或多個結構II的化合物。
酯鏈結係結構III
聚酯係具有兩個或更多個酯鏈結之化合物。多元醇係具有兩個或更多個-OH基團之化合物。二醇係具有恰恰兩個-OH基團之化合物。多胺係具有兩個或更多個胺基之化合物;胺基可係一級或二級或其混合物。二胺係具有恰恰兩個胺基之化合物;二胺可具有兩個一級胺基、兩個二級胺基、或一個一級胺基及一個二級胺基。二羧酸係具有恰恰兩個-COOH基團之化合物。
脂族基團係僅含有碳原子及氫原子且不含有芳族環之化學基團。脂環族基團係含有一個或多個環狀結構之脂族基團。烷基係不具有雙鍵之脂族基團。環烷基係含有一個或多個環狀結構之烷基。芳族基團係具有芳族環之任何基團。
本文中,當稱一比為X:1或更大時,其係意指該比為Y:1,其中,Y係大於或等於X。舉例而言,若稱一比為3:1或更大,則該比可係3:1或5:1或100:1,但不可為2:1。同樣,當稱一比為W:1或更小時,其係意指該比為Z:1,其中,Z係小於或等於W。舉例而言,若稱一比為15:1或更小,則該比可係15:1或10:1或0.1:1,但不可為20:1。
本發明之組成物係具有結構IV之環氧基末端聚酯:
於結構IV中,兩個-R1基團可係相同或相異。每一-R1基團係具有結構V:
基團-R2-係具有少於50個碳原子之二價有機基團。基團G-係具有上文中定義之結構II。基團-CA-係環烷基。基團-A-係二價烷基。
本發明之組成物除了含有一種或多種具有結構IV之化合物外,亦可含有一種或多種具有結構IVA之化合物:
其中,B1係具有結構:
B2係具有結構:
且n係1至6。
較佳地,-R2-係具有結構VI之基團:
數字p係0至20。較佳地,p係0至10;更佳係0至5。每一-R3-、每一-R4-、及每一-R5-係彼此獨立為二價有機基團。於一個-R2-基團中,若p為2或更大,則多個-R3-基團可係彼此相同或彼此相異。於一個-R2-基團中,若p為2或更大,則多個-R4-基團可係彼此相同或彼此相異。
較佳地,-R3-係選自一種或多種二價脂族及脂環族基團、一種或多種二價芳族烴基、或其混合物。於脂族基團中,較佳係烷基;更佳係線性或分支鏈烷基;更佳係線性烷基。於脂族基團中,較佳係彼等具有1個或多個碳原子者;更佳係彼等具有2個或更多個碳原子者;更佳係彼等具有3個或更多個碳原子者。於脂族基團中,較佳係彼等具有12個或更少碳原子者;更佳係彼等具有8個或更少碳原子者;更佳係彼等具有6個或更少碳原子者。於脂族基團中,較佳係-CH2CH2CH2CH2-。於脂環族基團中,較佳係1,2-環己烷、1,3-環己烷、及1,4-環己烷。於芳族基團中,較佳係彼等具有下述結構者:
包括異構物之混合物;更佳係:
對於-R5-,適宜且較佳之基團係與用於-R3-之彼等相同者。基團-R5-可與全部之-R3-基團皆不同,或-R5-可與一個或全部-R3-基團相同。
較佳地,-R4-係或為脂族基團或脂環族基團或為脂族醚基團。脂族醚基團係具有結構VII:
其中,-R8-、-R9-(若存在)、及-R10-係脂族基團,其中,r係0至10。基團-R8-、-R9-(若存在)、及-R10-可係彼此相同或相異。當-R4-為脂族醚基團時,下述之優選係施用至-R8-、-R9-(若存在)、-R10-、及r。較佳地,-R8-、-R9-(若存在)、及-R10-係相同。較佳地,-R8-、-R9-(若存在)、及-R10-係線性烷基。較佳地,-R8-、-R9-(若存在)、及-R10-係各自具有4個或更少碳原子;更佳3個或更少碳原子;更佳恰恰2個碳原子。較佳地,r係0至10;更佳0至5;更佳0至2;更佳為0。當-R4-為脂族或脂環族基團時,-R4-較佳係烷基;更佳係線性烷基。當-R4-為脂族或脂環族基團時,-R4-係具有1個或多個碳原子。當-R4-為脂族或脂環族基團時,-R4-較佳係具有8個或更少碳原子;更佳6個或更少碳原子;更佳4個或更少碳原子;更佳3個或更少碳原子;更佳恰恰2個碳原子。
於某些態樣(本文中稱為「混合聚酯」態樣)中,p係大於1,且某些-R3-基團係不同於其他-R3-基團。於某些混合聚酯態樣中,-R2-係具有結構VIII:
基團-R3-、-R4-、及-R5-係如上文定義者,且q為1或更高。較佳地,q係0至9;更佳1至4。對於-R6-,適宜且較佳之基團係與用於-R4-之彼等相同者。對於-R7-,適宜且較佳之基團係與用於-R3-之彼等相同者。於某些混合聚酯態樣(本文中稱為「MP1」態樣)中,-R5-係與-R3-相同,-R6-係與-R4-相同,而-R7-係與-R3-相異。於某些MP1態樣中,全部-R4-基團係彼此相同;於其他MP1態樣中,某些-R4-基團係與其他-R4-基團相異。於某些混合聚酯態樣(本文中稱為「MP2」態樣)中,-R5-係與-R7-相同,-R6-係與-R4-相同,而-R7-係與-R3-相異。於某些MP2態樣中,全部-R4-基團係彼此相同;於其他MP2態樣中,某些-R4-基團係與其他-R4-基團相異。
較佳之態樣係選自下列:(a)其中p=0之態樣;(b)其中p為1或更大,以及,其中全部-R3-係彼此相同,全部-R4-基團係彼此相同,且-R5-係與-R3-相同之態樣;(c)MP1態樣;以及(d)MP2態樣。
於結構V中,基團-A-係二價烷基。較佳地,全部基團-A-係彼此相同。較佳地,-A-係線性。較佳
地,-A-中碳原子之數目為1個至6個;更佳1個至4個;更佳1個至2個;更佳1個。
於結構V中,基團-CA-係二價環烷基。基團-CA-可經一個或多個甲基、一個或多個線性烷基、或其組合取代。基團-CA-可具有一個環狀結構或可係雙環狀結構。較佳地,-CA-中碳原子之數目為12個或更少;更佳8個或更少;更佳7個或更少。較佳地,-CA-中碳原子之數目為3個或更多;更佳4個或更多;更佳5個或更多。較佳地,-CA-係二價環己基,包括其全部異構物及其混合物。更佳地,-CA-係1,4-二價環己基。
本發明之環氧基末端聚酯將具有環氧當量(Epoxide Equivalent Weight,EEW)為275至1,500;更佳285至1,000;最佳285至750。本發明之環氧基末端聚酯的數目平均分子量將係較佳500至5,000之範圍;更佳550至3,100;更佳550至2,400。
以本發明之組成物中存在之低分子量(1,000道爾頓)物質的水準為表徵係有用的。低分子量物質之水準係定義為,以該組成物之總重為基準計,具有分子量小於或等於1,000道爾頓之物質的重量百分比。低分子量物質之水準較佳係45%或更低;更佳30%或更低;更佳25%或更低。
本發明之組成物可藉由任何方法作成。較佳之方法係包括令至少一種二環氧化物與至少一種二羧酸反應。該二環氧化物係具有結構IX:
基團G、-A-、及-CA-係如結構V中定義者。該二羧酸係具有結構X:
基團-R2-係如結構IV中定義者。使用足量之具有結構IX的化合物,故該反應係產生具有結構IV之化合物。該反應亦可產生具有結構IVA之化合物。
較佳之結構X之化合物係具有酸值(其係藉由下文揭示者量測之)為110或更高;更佳120或更高;更佳125或更高。較佳之結構X之化合物係具有酸值為770或更低;260或更低;更佳200或更低;更佳175或更低。較佳之結構X之化合物係具有分子量為146或更高;更佳430或更高;更佳560或更高;更佳640或更高。較佳之結構X之化合物係具有分子量為1,020或更低;更佳940或更低;更佳900或更低。適宜之結構X之化合物的混合物亦為適宜者。
於至少一種二環氧化物與至少一種二羧酸之反應中,環氧基團與羧酸基團之化學計量比將係較佳3.1:1或更大;更佳2.7:1或更大;更佳2.2:1或更大。環氧基團與羧酸基團之化學計量比將係較佳2:1或更小;更佳1.6:1或更小;更佳1.3:1或更小。
二環氧化物與二羧酸之反應係視需要於催化劑之存在下實施。較佳之催化劑係與可溶性鉻化合物合
用之三芳基磷化合物、四取代之鏻鹽、四級銨鹽、碳酸鹽、氫氧化物鹽、及羧酸鹽。更佳係四取代之鏻鹽、碳酸鹽、及羧酸鹽。
當三芳基磷化合物與鉻化合物合用時,較佳之三芳基磷化合物係三芳基膦。較佳之三芳基膦係三苯基膦、三-甲苯基膦、三-二甲苯基膦、及三萘基膦。當三芳基磷化合物與鉻化合物合用時,較佳之鉻化合物係三醋酸鉻及三氯化鉻。於四取代之鏻鹽中,較佳係烷基三苯基鏻鹽、四芳基鏻鹽、苄基三烷基鏻鹽、及四烷基鏻鹽;更佳係烷基三苯基鏻鹽及苄基三烷基鏻鹽。於烷基三苯基鏻鹽中,較佳係醋酸乙基三苯基鏻/乙基三苯基鏻醋酸錯合物、及碘化乙基三苯基鏻;更佳係碘化乙基三苯基鏻。於四烷基鏻鹽中,較佳係醋酸四丁基鏻/四丁基鏻醋酸錯合物。於苄基三烷基鏻鹽中,較佳係氯化苄基三甲基鏻。於四芳基鏻鹽中,較佳係溴化四苯基鏻。
於四級銨鹽中,較佳係氯化苄基三甲基銨、氯化四甲基銨、及氯化二苯基二甲基銨。於羧酸鹽中,較佳係單羧酸之鈉鹽或鉀鹽;更佳係醋酸鈉、醋酸鉀、丙酸鈉、丙酸鉀、苯甲酸鈉、苯甲酸鉀、檸檬酸鈉、檸檬酸鉀、乳酸鈉、乳酸鉀、酒石酸鈉、酒石酸鉀、及酒石酸鉀鈉。於無機鹼中,較佳係碳酸鈉、碳酸鉀、氫氧化鈉、及氫氧化鉀。
用於製備環氧基末端聚酯之較佳催化劑係碘化乙基三苯基鏻、氯化苄基三甲基銨、碳酸鈉、及醋酸
鈉。
當錫或鈦酸酯化合物用於經由二醇與二羧酸之反應製備羧酸末端聚酯時,其水準較佳係0.0001至0.05重量(wt)%之範圍。
當基團-R2-具有結構VI且p為1或更大時,該具有結構X之化合物較佳係藉由一種或多種二羧酸與一種或多種二醇之一種或多種反應作成。
上文定義之態樣(a)較佳係藉由二環氧化物與具有結構HOOC-R11-COOH之二羧酸的反應作成。適宜且較佳之-R11-基團係與適宜且較佳之-R3-基團相同。
上文定義之態樣(b)較佳係藉由二環氧化物與為聚酯之二羧酸(本文中稱為「PEb1」)的反應作成。PEb1較佳係藉由單一種二羧酸(「DAb1」)與一種二醇(「DOb1」)之反應作成。DAb1係具有結構HOOC-R12-COOH。適宜且較佳之-R12-基團係與適宜且較佳之-R3-基團相同。DOb1係具有結構HOR13-OH,其中,適宜且較佳之-R13-基團係與彼等揭示用於-R4-基團者相同。-R4-基團可係,舉例而言,脂族或脂環族基團或結構VII。使用足量之DAb1,故與DOb1之反應將產生為二羧酸之聚酯。
上文定義之態樣(c)較佳係藉由二環氧化物與為聚酯之二羧酸(本文中稱為「PEc1」)的反應作成。PEc1較佳係藉由單一種二羧酸(「DAc1」)與中間體聚酯(「PEc2」)之反應作成。DAc1係具有結構HOOC-R13-COOH。適宜且較佳之-R13-基團係與適宜且較佳之-R3-基團相同。PEc2較
佳係藉由二羧酸(「DAc2」)與一種或多種二醇(「DOc1」)之反應作成。DAc2係具有結構HOOC-R14-COOH。適宜且較佳之-R14-基團係與適宜且較佳之-R3-基團相同。較佳之DAc2係與DAc1相異。DOc1係具有結構HOR15-OH,其中,適宜且較佳之-R15-基團係與彼等揭示用於-R4-基團者相同。-R4-基團可係,舉例而言,脂族或脂環族基團或結構VII。使用相應量之DOc1與DAc2,故形成顯著量之具有一個末端-OH基團及一個末端-COOH基團的產物PEc2。
上文定義之態樣(d)較佳係藉由二環氧化物與為聚酯之二羧酸(本文中稱為「PEd1」)的反應作成。PEd1較佳係藉由單一種二羧酸(「DAd1」)與中間體聚酯(「PEd2」)之反應作成。DAd1係具有結構HOOC-R16-COOH。適宜且較佳之-R16-基團係與適宜且較佳之-R3-基團相同。PEd2較佳係藉由二羧酸(「DAd2」)與一種或多種二醇(「DOd1」)之反應作成。DAd2係具有結構HOOC-R17-COOH。適宜且較佳之-R17-基團係與適宜且較佳之-R3-基團相同。較佳之DAd2係與DAd1相異。DOd1係具有結構HOR18-OH,其中,適宜且較佳之-R18-基團係與彼等揭示用於-R4-基團者相同。-R4-基團可係,舉例而言,脂族或脂環族基團或結構VII。使用相應量之DOd1與DAd2,故形成顯著量之具有兩個末端-OH基團的產物PEc2。
羧酸基團與羥基之間的反應較佳係於一種或多種催化劑之存在下實施。較佳之催化劑係錫化合物及鈦酸酯化合物。於錫化合物中,較佳係二丁基錫、四丁基
錫、四氯化錫、二辛基錫、單丁基錫、及二價錫類;更佳係氧化羥丁基錫、單丁基錫叄(2-乙基己酸)、及2-乙基己酸亞錫。於鈦酸酯化合物中,較佳係四烷基鈦酸酯;更佳係四(異丙基)鈦酸酯及四(正丁基)鈦酸酯。
對於羧酸基團與羥基之間的反應,當存在催化劑時,以承載羧酸基團之化合物加上承載羥基之化合物的重量之和為基準計,該催化劑之量較佳係0.0001wt%至0.05wt%。
本發明之組成物可用於廣泛之目標。較佳地,本發明之組成物係用作黏著劑組成物之一種組分,該組成物係用以將第一基板結合至第二基板。較佳地,本發明之一種或多種組成物係與一種或多種固化劑化合物及視需要之溶劑混合;將該混合物施用至第一基板以於該第一基板上形成層;蒸發溶劑(若存在)或令其蒸發;將第二基板帶至與該混合物之層接觸;以及,將該混合物固化或令其固化。
固化劑化合物係具有兩個或更多個能與環氧基團反應之基團的化合物。較佳之固化劑化合物係胺基化合物。較佳之胺基化合物係苯烷胺、苯烷醯胺、及胺基末端醯胺樹脂。胺基末端醯胺樹脂係二羧酸與二胺之反應產物。對於胺基末端醯胺樹脂之形成,較佳之二羧酸係二聚物酸,其係兩個不飽和脂肪酸分子之反應產物。不飽和脂肪酸係具有結構R19-COOH,其中,R19-係具有8個或更多個碳原子及一個或多個碳-碳雙鍵之脂族基團。較佳之二
胺係乙二胺、二乙三胺、三乙三胺、四乙五胺、哌、胺基乙基哌、異佛酮二胺、伸二甲苯基二胺、及其混合物。
較佳之基板係聚合物膜、金屬化聚合物膜、金屬箔、聚合物-背襯之金屬箔、陶瓷塗覆之聚合物膜、及其組合。
下述者係本發明之實施例。
下文所使用之縮寫如下:AV=酸值,藉由方法ASTM D3644-06(美國測試及材料科學會(American Society for testing and Materials),Conshohocken,PA,USA)量測之。
OHN=羥基數,藉由方法ASTM E1899-08量測之。
胺值=藉由方法ASTM D2074-07量測之,用於藉由替代指標方法測試脂肪胺之總、一級、二級、及三級胺值的測試方法。
Visc.=黏度,其係藉由採用Brookfield RV DV-II+黏度計量測之,該黏度計具有恆溫小樣本適配器及紡錘體#27,溫度於25至70℃範圍內以5℃增量變化,並令該樣本於溫度安定化20至30分鐘,再記錄黏度。
FascatTM 9100=氧化羥丁基錫,來自阿科瑪公司(Arkema,Inc.),工業級。
CHDM-DGE=1,4-環己二甲醇二環氧丙基醚(結構IX,其中,兩個-A-基團皆為-CH2-,且-CA-基團係1,4-環己基),純度大於99.0重量%;EEW為129.9,SEC分析:Mn 200,
Mw 200,Mz 200,500道爾頓者之重量分率為98.8%,1000道爾頓者之重量分率為99.9%。
粗CHDM-DGE=粗品,純度=79.5%,1,4-環己二甲醇二環氧丙基醚;含有其他單-、二-、及三-環氧化物;EEW為135.24,SEC分析:Mn 200,Mw 300,Mz 600,500道爾頓者之重量分率為77.3%,1000道爾頓者之重量分率為96.1%。
ErisysTM GE-22=CHDM-DGE,來自CVC Thermoset Specialties,工業級,純度為53.8%之1,4-環己二甲醇二環氧丙基醚。雜質為其他二環氧化物、單環氧化物等。批次A:EEW為147.61,(SEC分析:Mn 225,Mw 250,Mz 300,500道爾頓者之重量分率為96.8%,1000道爾頓者之重量分率為99.4%);批次B:156.56,(SEC分析:Mn 200,Mw 300,Mz 400,500道爾頓者之重量分率為93.0%,1000道爾頓者之重量分率為99.2%)。
UnidymeTM 22=二聚之脂肪酸,來自亞利桑那化學(Arizona Chemical),AV=192.9。
CardoliteTM NC-541LV=苯烷胺固化劑,來自卡德萊公司(Cardolite Corporation),胺值為340,活性氫當量為125。
PolypoxTM HO15=曼尼希鹼固化劑,來自陶氏化學公司(The Dow Chemical Company),胺值為375,活性氫當量為75。
PolypoxTM P370=用於環氧樹脂之聚胺基咪唑啉硬化劑,來自陶氏化學公司,胺值為485,活性氫當量為95。
EpikureTM 3140=聚醯胺固化劑,二聚之脂肪酸與多胺之反應產物,來自邁圖(Momentive),胺值為375,活性氫當量為95。
PriamineTM 1071=來自克羅達(Croda)之二聚物二胺
JeffamineTM D400=來自亨茨曼(Huntsman)之聚醚胺
Coex PP(75SLP)=美孚(Exxon Mobil)Bicor SLP取向聚丙烯,不可熱封,厚度為19微米(0.75密耳(mil))。
Coex PP(70SPW)=美孚Bicor SPW共押出聚丙烯,厚度為18微米(0.70mil)。
PET=杜邦公司(DuPont),聚酯,聚(對苯二甲酸乙二酯),厚度為23微米(92規(Gauge))厚聚酯膜。
PE(GF-19)=貝里塑膠公司(Berry Plastics Corp.),高滑低密度聚乙烯膜,厚度為25.4微米(1.0mil)。
尼龍=霍尼韋爾(Honeywell)Capran Emblem 1500,雙軸取向尼龍6膜,厚度為15微米。
PET-Met=膜技術公司(FILMTech Inc.),金屬化聚酯膜,厚度為25.4微米。
OPP-Met=AET Films,金屬化取向聚丙烯膜,MT膜,可熱封,厚度為18微米。
經背襯之箔=12微米(48Gauge)聚酯(PET)膜,以Adcote 550/共反應劑F以3.26g/m2(2.00磅(lbs)/令(ream))層壓至0.00035mil鋁(Al)箔。
PET(92LBT)=杜邦公司,聚酯,聚(對苯二甲酸乙二酯),厚度為23微米(92Gauge)。
Mn=數目平均分子量。
Mw=重量平均分子量。
Mz=z-平均分子量。
EEW=環氧當量,其係每莫耳環氧基團之質量。
活性氫當量=每莫耳活性氫之質量;活性氫係結合至胺基之氮原子的氫原子。
Wt Fraction 500=分子量小於或等於500者之重量分率。
Wt Fraction 1,000=分子量小於或等於1,000者之重量分率。
實施例1:聚酯之製備
將項目1及2充填入反應器中;對樹脂脫氣/氮氣吹掃;將樹脂混合物緩慢加熱至100℃;於100至115℃保持1.5小時(Hr);檢查AV及黏度。若AV>155,則加熱至145℃。保持於145至150℃,直至AV為約155。冷卻至約70至80℃,過濾並包裝。
最終之樹脂具有下述特性:酸值(AV)為147.94,Mn為300,Mw為700,Mz為1,100,500道爾頓者之重量分率為42.4%,1,000道爾頓者之重量分率為75.9%,25℃黏度為78,375毫帕*秒(mPa*s)。
實施例2:聚酯之製備
於周邊溫度(25至30℃),將項目1至3充填入容器中。於氮氣氛下,於攪拌下將樹脂加熱至100℃。於100℃保持0.50Hr。加熱樹脂至225℃並保持於225℃,當約80%之理論水分移除時,監控AV及製程中黏度。保持於225℃,直至AV小於(<)約180。當AV<180時,施用真空;保持在225℃及約325毫米(mm)真空,直至AV<155。冷卻樹脂至約150℃,過濾並包裝。
最終之樹脂具有下述特性:酸值(AV)為140.39,Mn為950,Mw為1,650,Mz為3,350,500道爾頓者之重量分率為11.4%,1,000道爾頓者之重量分率為32.1%,25℃黏度為4,070mPa*s。
實施例3:聚酯之製備
於周邊溫度(25至30℃),將項目1至3充填入容器中。
於氮氣氛下,於攪拌下將樹脂加熱至100℃。於100℃保持0.50Hr。加熱樹脂至225℃並保持於225℃,當約80%之理論水分移除時,監控AV及製程中黏度。保持於225℃,直至AV小於約225。當AV<225時,施用真空;保持在225℃及約325mm真空,直至AV<205。冷卻樹脂至約150℃,過濾並包裝。
最終之樹脂具有下述特性:酸值(AV)為203.68,Mn為650,Mw為1,150,Mz為1,600,500道爾頓者之重量分率為26.6%,1,000道爾頓者之重量分率為50.3%,35℃黏度為33,050mPa*s。
實施例4:聚酯之製備
於周邊溫度(25至30℃),將項目1至3充填入容器中。於氮氣氛下,於攪拌下將樹脂加熱至100℃。加熱樹脂至225℃並保持於225℃。當約50%之理論水分移除時,監控AV及製程中黏度。保持於225℃,直至AV小於約75。冷卻樹脂至低於125℃。加入項目4,於125至135℃保持0.50Hr。升溫至225℃並保持在225℃。監控AV及黏度;保持於225℃,直至AV小於約155。冷卻樹脂至約150℃,過
濾並包裝。
最終之樹脂具有下述特性:酸值(AV)為149.73,Mn為950,Mw為1,750,Mz為2,550,500道爾頓者之重量分率為10.6%,1,000道爾頓者之重量分率為32.1%,25℃黏度為29,500mPa*s。
實施例5:聚酯之製備
於周邊溫度(25至30℃),將項目1至4充填入容器中。於氮氣氛下,於攪拌下將樹脂加熱至100℃。加熱樹脂至225℃並保持於225℃。當約50%之理論水分移除時,監控AV及製程中黏度。保持於225℃,直至AV小於約75。冷卻樹脂至低於125℃。加入項目5,於125至135℃保持0.50Hr。升溫至225℃並保持在225℃。監控AV及黏度;保持於225℃,直至AV小於約155。冷卻樹脂至約150℃,過濾並包裝。
最終之樹脂具有下述特性:酸值(AV)為157,Mn為750,Mw為1,500,Mz為2,350,500道爾頓者之重量分率為18.1%,1,000道爾頓者之重量分率為41.3%,25℃黏度為
22,175mPa*s。
實施例6至23:環氧基末端聚酯樹脂之製備
實施例6至23之製備係類似者。將二環氧化物、一種或多種二酸、及催化劑(若有使用)充填入反應器中。緩慢加熱至135至140℃。於135至140℃保持約2Hr,隨後監控AV及黏度。保持於135至140℃並監控AV及黏度,直至AV<1.0。轉移樹脂並包裝。
實施例6至24係如下:
實施例24:胺固化劑之製備
將項目1及2充填至反應器中,緩慢加熱至200℃。於200℃保持2Hr;監控水質變化。升溫至225至230℃,保持1Hr。將樹脂轉移並包裝。
最終之樹脂係具有下述特性:胺值為217.15,25℃黏度為51,100mPa*s。
實施例25:胺固化劑之製備
將項目1及2充填至反應器中,緩慢加熱至200℃。於200℃保持2Hr;監控水質變化。將樹脂轉移並包裝。
最終之樹脂係具有下述特性:胺值為238.9,25℃黏度為49,000mPa*s。
該環氧基末端聚酯黏著特性係使用一系列層壓體構造以胺系樹脂評估之。此等兩成分之黏著劑系統係經由溶劑手工澆鑄方法及層壓器評估之。
下述縮寫係用以描述測試結果:as:黏著劑分裂;ftr:膜撕裂;fstr:膜拉伸;at:黏著劑轉移;sec:次等;zip:參差不齊的結合;pmt:部分金屬轉移。使用15mm寬之層壓體條帶於配備50牛頓(N)負載單元之Thwing-Albert拉伸強度測試儀(Model QC-3A)上以10.0公分(cm)/分鐘(min)之速率測定黏著結合強度。
實施例26至52
如下述者施行實施例26至52:以下文顯示之混合比,於50重量%濃度之乙酸乙酯中,令環氧基末端聚酯與固化劑混合。將該溶液塗覆於第一基板上以獲得乾塗層重量為1.6276g/平方公尺(m2)(1.0磅(lb)/令(ream))。將第二基板施用至乾燥塗層,將所得層壓體於室溫(約25℃)固化。檢查作為固化時間之函數的結合強度,並報導於下文中。「混合比」係環氧樹脂與固化劑之重量比,且表現為100:X。於標記為「層壓體結構」之欄中,係列述第一基板,其後為第二基板。
舉例而言,於下表中,實施例編號26係實施例6中作成之環氧樹脂與固化劑CardoliteTM NC-541LV以環氧樹脂與固化劑重量比為100:23.9混合而成的混合物。於第7天,15mm之寬度之結合強度為0.74N,而失敗案例為黏著劑分裂。
Claims (6)
- 一種環氧基末端聚酯,其係具有結構:
- 如申請專利範圍第1項所述之聚酯,其中,-A-係-(CH2)n-,其中,n係1至6。
- 如申請專利範圍第1項所述之聚酯,其中,所述-CA-係
- 如申請專利範圍第1項所述之聚酯,其中,所述-R2-係
- 如申請專利範圍第4項所述之聚酯,其中,所述-R3-係-(CH2)q-或
- 如申請專利範圍第4項所述之聚酯,其中,所述-R4-係-CH2-CH2-或-CH2-CH2-O-CH2-CH2-。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361905374P | 2013-11-18 | 2013-11-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201533088A true TW201533088A (zh) | 2015-09-01 |
TWI560210B TWI560210B (en) | 2016-12-01 |
Family
ID=52117981
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103138150A TWI560210B (en) | 2013-11-18 | 2014-11-04 | Epoxy-terminated polyester |
Country Status (10)
Country | Link |
---|---|
US (1) | US9701786B2 (zh) |
EP (1) | EP3071621B1 (zh) |
JP (1) | JP6561052B2 (zh) |
CN (2) | CN105683239A (zh) |
AR (1) | AR098267A1 (zh) |
BR (1) | BR112016010002B1 (zh) |
MX (1) | MX371348B (zh) |
RU (1) | RU2682168C1 (zh) |
TW (1) | TWI560210B (zh) |
WO (1) | WO2015073965A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR102914A1 (es) * | 2014-11-12 | 2017-04-05 | Dow Global Technologies Llc | Adhesivo de laminación por embutición en frío de bisfenol-a-libre |
JP6650125B2 (ja) * | 2015-06-18 | 2020-02-19 | Dic株式会社 | ポリエステル変性エポキシ樹脂及び接着剤 |
WO2018199127A1 (ja) * | 2017-04-28 | 2018-11-01 | ユニチカ株式会社 | 変性ポリアリレート樹脂 |
JP7176222B2 (ja) * | 2017-05-25 | 2022-11-22 | 三菱ケミカル株式会社 | エポキシ樹脂、エポキシ樹脂含有組成物及びその硬化物 |
MX2019014422A (es) | 2017-06-09 | 2020-02-05 | Dow Global Technologies Llc | Composiciones adhesivas a base de solvente. |
MX2022000440A (es) | 2019-07-15 | 2022-02-10 | Dow Global Technologies Llc | Adhesivo de laminacion sin isocianato. |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3395128A (en) * | 1963-06-14 | 1968-07-30 | Union Carbide Corp | Thermoplastic copolymers derived from diglycidyl ether of 1, 4-cyclohexanedimethanol |
US3576903A (en) | 1968-04-29 | 1971-04-27 | Minnesota Mining & Mfg | Epoxy-terminated adducts of carboxy terminated polyesters and polyepoxides |
US3836485A (en) | 1972-02-24 | 1974-09-17 | Dow Chemical Co | Solid epoxy resins from glycidyl ethers of hydrogenated bisphenols or hydrogenated novolacs and aromatic or cycloaliphatic dicarboxylic acids |
CH588513A5 (zh) | 1973-12-19 | 1977-06-15 | Ciba Geigy Ag | |
SU523909A1 (ru) * | 1975-01-10 | 1976-08-05 | Институт физико-органической химии АН Белорусской ССР | Эпоксипроизводные диаллиловых эфиров бициклических дикарбоновых кислот |
EP0111986B1 (en) | 1982-12-23 | 1987-02-04 | Akzo N.V. | Pigment-containing liquid coating composition |
EP0272222B1 (de) | 1986-12-19 | 1991-01-30 | Ciba-Geigy Ag | Epoxidharze enthaltend Polyester auf Polyalkylenglykolbasis |
EP0722964A1 (de) * | 1994-12-22 | 1996-07-24 | Ciba-Geigy Ag | Epoxidgruppenterminierte Polyester enthaltendes Epoxidharzgemisch |
MY133123A (en) * | 1998-04-07 | 2007-10-31 | Shell Int Research | Glycidation of carboxyl-functional polyester and 3 c-containing monocarboxylic acid or its glycidyl ester |
JP2000053843A (ja) * | 1998-08-12 | 2000-02-22 | Toto Kogyo Kk | 成形材料用エポキシ樹脂組成物及び電気・電子部品 |
US20080081883A1 (en) * | 2006-09-28 | 2008-04-03 | Battelle Memorial Institute | Polyester Polyols Derived From 2,5-Furandicarboxylic Acid, and Method |
EP1935904A1 (de) * | 2006-12-22 | 2008-06-25 | Sika Technology AG | Ester-vorverlängerte Epoxidgruppen terminierte Zähigkeitsverbesserer und Verfahren zu deren Herstellung |
WO2012050777A1 (en) * | 2010-09-30 | 2012-04-19 | Dow Global Technologies Llc | Advanced poly epoxy ester resin compositions |
WO2012044490A1 (en) | 2010-09-30 | 2012-04-05 | Dow Global Technologies Llc | Coating compositions |
EP2468792A1 (en) | 2010-12-23 | 2012-06-27 | 3M Innovative Properties Company | Curable adhesive composition |
CN102295779B (zh) * | 2011-05-17 | 2013-06-26 | 浙江大学 | 长链支化聚酯及其制备方法 |
CN103874719A (zh) * | 2011-09-02 | 2014-06-18 | 太阳化学公司 | 线性聚酯树脂和改进的平版油墨 |
CN102993422B (zh) * | 2012-11-30 | 2015-01-28 | 无锡市虎皇漆业有限公司 | 一种卷材涂料底漆用环氧改性饱和聚酯树脂及卷材涂料底漆 |
CN103497316B (zh) * | 2013-08-08 | 2015-12-02 | 山东汇盈新材料科技有限公司 | 低端羧基含量的生物降解聚酯的制备方法 |
-
2014
- 2014-11-03 AR ARP140104103A patent/AR098267A1/es active IP Right Grant
- 2014-11-04 TW TW103138150A patent/TWI560210B/zh active
- 2014-11-17 RU RU2016124166A patent/RU2682168C1/ru active
- 2014-11-17 CN CN201480060316.8A patent/CN105683239A/zh active Pending
- 2014-11-17 CN CN202110714019.2A patent/CN113248688A/zh active Pending
- 2014-11-17 MX MX2016005629A patent/MX371348B/es active IP Right Grant
- 2014-11-17 BR BR112016010002-6A patent/BR112016010002B1/pt active IP Right Grant
- 2014-11-17 EP EP14815129.3A patent/EP3071621B1/en active Active
- 2014-11-17 JP JP2016526880A patent/JP6561052B2/ja active Active
- 2014-11-17 US US15/035,782 patent/US9701786B2/en active Active
- 2014-11-17 WO PCT/US2014/065940 patent/WO2015073965A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
AR098267A1 (es) | 2016-05-18 |
RU2682168C1 (ru) | 2019-03-15 |
EP3071621B1 (en) | 2019-07-03 |
BR112016010002A2 (zh) | 2017-08-01 |
TWI560210B (en) | 2016-12-01 |
MX371348B (es) | 2020-01-27 |
US20160289376A1 (en) | 2016-10-06 |
MX2016005629A (es) | 2016-07-14 |
CN105683239A (zh) | 2016-06-15 |
JP6561052B2 (ja) | 2019-08-14 |
RU2016124166A (ru) | 2017-12-25 |
CN113248688A (zh) | 2021-08-13 |
BR112016010002B1 (pt) | 2021-09-21 |
US9701786B2 (en) | 2017-07-11 |
JP2016537458A (ja) | 2016-12-01 |
WO2015073965A1 (en) | 2015-05-21 |
EP3071621A1 (en) | 2016-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI568816B (zh) | 黏著劑組成物 | |
TW201533088A (zh) | 環氧基-末端聚酯 | |
TWI558737B (zh) | 環氧基-末端聚酯 | |
TW201623536A (zh) | 用於層壓黏合劑之可固化製劑 | |
TWI537354B (zh) | 黏著劑組成物 | |
BR112016010004B1 (pt) | Composição de duas partes |