WO2011071650A1 - Résines polyester à fonction hydroxyle - Google Patents
Résines polyester à fonction hydroxyle Download PDFInfo
- Publication number
- WO2011071650A1 WO2011071650A1 PCT/US2010/056214 US2010056214W WO2011071650A1 WO 2011071650 A1 WO2011071650 A1 WO 2011071650A1 US 2010056214 W US2010056214 W US 2010056214W WO 2011071650 A1 WO2011071650 A1 WO 2011071650A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydroxyl
- functional polyester
- resin composition
- polyester resin
- weight percent
- Prior art date
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 79
- 239000004645 polyester resin Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 102
- 239000003822 epoxy resin Substances 0.000 claims abstract description 57
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 57
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- YDIZFUMZDHUHSH-UHFFFAOYSA-N 1,7-bis(ethenyl)-3,8-dioxatricyclo[5.1.0.02,4]oct-5-ene Chemical compound C12OC2C=CC2(C=C)C1(C=C)O2 YDIZFUMZDHUHSH-UHFFFAOYSA-N 0.000 claims description 25
- -1 carboxy ester Chemical class 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920003987 resole Polymers 0.000 claims description 4
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- ILSRXKFYTXYKJS-UHFFFAOYSA-N 2,4-bis(ethenyl)-3,6-dioxatetracyclo[6.4.0.02,4.05,7]dodeca-1(12),8,10-triene Chemical compound C=CC12OC1(C=C)C1=CC=CC=C1C1C2O1 ILSRXKFYTXYKJS-UHFFFAOYSA-N 0.000 claims description 2
- GLPDXGJXUWGMQJ-UHFFFAOYSA-N 4-ethenyl-7-(4-ethenylphenyl)-3,8-dioxatricyclo[5.1.0.02,4]oct-5-ene Chemical compound C(=C)C1=CC=C(C=C1)C12C(C3C(C=C1)(C=C)O3)O2 GLPDXGJXUWGMQJ-UHFFFAOYSA-N 0.000 claims description 2
- SRWLXBHGOYPTCM-UHFFFAOYSA-M acetic acid;ethyl(triphenyl)phosphanium;acetate Chemical compound CC(O)=O.CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SRWLXBHGOYPTCM-UHFFFAOYSA-M 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 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 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims 1
- 229940092714 benzenesulfonic acid Drugs 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 238000001723 curing Methods 0.000 description 31
- 239000002904 solvent Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 229920001187 thermosetting polymer Polymers 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 150000001991 dicarboxylic acids Chemical class 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 8
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000002118 epoxides Chemical group 0.000 description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- UZXQULFXZDNGSO-UHFFFAOYSA-N 1-but-1-enyl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=CC2(C=CCC)C1O2 UZXQULFXZDNGSO-UHFFFAOYSA-N 0.000 description 1
- NAMDIHYPBYVYAP-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound COCCOCCOC.COCCOCCOC NAMDIHYPBYVYAP-UHFFFAOYSA-N 0.000 description 1
- NBHKOXMOIRGJAI-UHFFFAOYSA-N 1-phenylbut-2-yne-1,4-diol Chemical compound OCC#CC(O)C1=CC=CC=C1 NBHKOXMOIRGJAI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MTCBLMPRPUTXHZ-UHFFFAOYSA-N n-(oxomethylidene)nitramide Chemical compound [O-][N+](=O)N=C=O MTCBLMPRPUTXHZ-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- 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
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
- C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to hydroxyl-functional polyester resins; and more specifically, to epoxy ester resins and/or carboxy ester resins derived from divinylarene dioxides and dicarboxylic acids; and coatings prepared from such hydroxyl-functional polyester resins.
- Hydroxyl-functional polyester resins are well known and are typically used as a coating for food containers.
- WO 2008045882 and WO 2008045884 describe compositions and processes for the preparation of soluble epoxy ester resins from aromatic epoxy resins and dicarboxylic acids having a low acid number.
- WO 2008045889 describe compositions and processes for the preparation of soluble epoxy ester resins from aromatic epoxy resins and dicarboxylic acids having a high acid number. None of the above known processes disclose the use of divinylarene dioxides as precursors for the known processes.
- the present invention is directed to providing a novel hydroxyl-functional polyester resin composition prepared from a divinylarene dioxide and a dicarboxylic acid.
- the hydroxyl-functional polyester resin compositions of the present invention which include an epoxy ester resin and/or a carboxy ester resin derived from a divinylarene dioxide, provide a resin having improved heat resistance as determined by a higher resin glass transition temperature (T g ) compared to the corresponding hydroxyl-functional polyester resin prepared from bisphenol A diglycidyl ether (BADGE) and the same dicarboxylic acid.
- One embodiment of the present invention is directed to a novel hydroxyl-functional polyester resin composition
- a novel hydroxyl-functional polyester resin composition comprising a reaction product of (a) at least one divinylarene dioxide and (b) at least one dicarboxylic acid.
- Hydroxyl-functional polyester resin compositions comprising the reaction product of divinylarene dioxides and dicarboxylic acids have greater heat resistance than their BADGE analog.
- Another embodiment of the present invention is directed to a curable hydroxyl- functional polyester resin composition
- a curable hydroxyl- functional polyester resin composition comprising (i) the above-described hydroxyl- functional polyester resin; and (ii) at least one curing agent. Curing these resins provide coatings having good solvent resistance as determined by methyletherketone (MEK) double-rub testing.
- MEK methyletherketone
- Still other embodiments of the present invention are directed to a process for preparing the hydroxyl-functional polyester resins and the curable resin compositions described above.
- the present invention includes a hydroxyl-functional polyester resin comprising the reaction product of (a) a divinylarene dioxide; and (b) at least one dicarboxylic acid to provide an hydroxyl-functional polyester resin.
- the novel hydroxyl-functional polyester resins of the present invention may comprise the reaction product of a divinylarene dioxide, for example a divinylbenzene dioxide (DVBDO); and a dicarboxylic acid, for example isophthalic acid.
- the resulting hydroxyl-functional polyester resin may be used to form a curable resin composition or formulation.
- the resulting curable resin composition or formulation may include one or more optional additives well known in the art.
- the hydroxyl-functional polyester resin compositions comprising the reaction product of divinylarene dioxides and a dicarboxylic acid advantageously provide novel resins having higher heat resistance than their BADGE analogs. Curing these novel resins provide thermosets which maintain their high heat resistance.
- the hydroxyl-functional polyester resins of the present invention are suitable for the preparation of thermosets used as coatings wherein a high heat and/or solvent resistance is desirable.
- the divinylarene dioxide such as DVBDO is prepared by reacting a divinylarene and hydrogen peroxide to provide the divinylarene dioxide useful in epoxy resin compositions of the present invention.
- Such prepared divinylarene dioxide may be used to prepare the hydroxyl-functional polyester resin of the present invention.
- the divinylarene dioxides useful in the present invention are class of diepoxides which have a relatively low liquid viscosity but impart a higher heat resistance and rigidity in its derived thermosets than do conventional epoxy resins.
- the epoxide group in divinylarene dioxides is significantly less reactive than that in conventional glycidyl ethers used to prepare prior art hydroxyl-functional polyester resins.
- the divinylarene dioxide useful in the present invention may comprise, for example, any substituted or unsubstituted arene nucleus bearing two vinyl groups in any ring position.
- the arene portion of the divinylarene dioxide may consist of benzene, substituted benzenes, (substituted) ring-annulated benzenes or homologously bonded (substituted) benzenes, or mixtures thereof.
- the divinylbenzene portion of the divinylarene dioxide may be ortho, meta, or para isomers or any mixture thereof.
- Additional substituents may consist of H 2 0 2 - resistant groups including saturated alkyl, aryl, halogen, nitro, isocyanate, or RO- (where R may be a saturated alkyl or aryl).
- Ring-annulated benzenes may consist of naphthlalene, tetrahydronaphthalene, and the like.
- Homologously bonded (substituted) benzenes may consist of biphenyl, diphenylether, and the like.
- the divinylarene dioxide used in the present invention may be produced, for example, by the process described in U.S. Patent Application Serial No.
- the divinylarene dioxide used for preparing the composition of the present invention may be illustrated generally by general chemical Structures I- IV as follows:
- each Ri, R 2 , R 3 and R4 individually may be hydrogen, an alkyl, cycloalkyl, an aryl or an aralkyl group; or a H 2 0 2 -resistant group including for example a halogen, a nitro, an isocyanate, or an RO group, wherein R may be an alkyl, aryl or aralkyl; x may be an interger of 0 to 4; y may be an integer greater than or equal to 2; x+y may be an integer less than or equal to 6; z may be an interger of 0 to 6; z+y may be an integer less than or equal to 8; and Ar is an arene fragment including for example, 1,3-phenylene group.
- the divinylarene dioxide useful in the present invention may comprise, for example, divinylbenzene dioxide, divinyln
- divinylbiphenyl dioxide divinyldiphenylether dioxide, or mixtures thereof.
- the divinylarene dioxide used in the epoxy resin formulation may be for example DVBDO.
- the divinylarene dioxide used in the epoxy resin formulation may be for example DVBDO.
- divinylarene dioxide component that is useful in the present invention includes, for example, a DVBDO as illustrated by the following chemical formula of Structure V:
- Divinylarene dioxides particularly those derived from divinylbenzene such as for example DVBDO, are class of diepoxides which have a relatively low liquid viscosity but a higher rigidity and crosslink density than conventional epoxy resins.
- the present invention includes a DVBDO illustrated by any one of the above Structures individually or as a mixture thereof. Structures VI and VII above show the meta
- the ortho isomer is rare; and usually DVBDO is mostly produced generally in a range of from about 9:1 to about 1:9 ratio of meta isomer (Structure VI) to para isomer (Structure VII).
- the present invention preferably includes as one embodiment a range of from about 6:1 to about 1:6 ratio of Structure VI to Structure VII, and in other embodiments the ratio of Structure VI to Structure VII may be from about 4:1 to about 1:4 or from about 2:1 to about 1:2.
- the divinylarene dioxide may contain quantities (such as for example less than about 20 weight percent) of substituted arenes.
- the amount and structure of the substituted arenes depend on the process used in the preparation of the divinylarene precursor to the divinylarene dioxide.
- divinylbenzene (DVB) prepared by the dehydrogenation of diethylbenzene (DEB) may contain quantities of ethylvinylbenzene (EVB) and DEB.
- EVB ethylvinylbenzene
- DEB ethylvinylbenzene
- EVB ethylvinylbenzene monoxide while DEB remains unchanged.
- the presence of these compounds can increase the epoxide equivalent weight of the divinylarene dioxide to a value greater than that of the pure compound.
- the divinylarene dioxide for example DVBDO, useful in the present invention comprises a low viscosity liquid epoxy resin (LER) composition.
- the viscosity of the divinylarene dioxide used in the process for making the epoxy resin composition of the present invention ranges generally from about 10 mPa-s to about 100 mPa-s, preferably from about 10 mPa-s to about 50 mPa-s, and more preferably from about 10 mPa-s to about 25 mPa-s at 25 °C.
- Another advantageous property of the divinylarene dioxide useful in the present invention may be for example rigidity.
- the rigidity property of the divinylarene dioxide is measured by a calculated number of rotational degrees of freedom of the dioxide excluding side chains using the method of Bicerano described in Prediction of Polymer Properties, Dekker, New York, 1993.
- the rigidity of the divinylarene dioxide used in the present invention may range generally from about 6 to about 10, preferably from about 6 to about 9, and more preferably from about 6 to about 8 rotational degrees of freedom.
- the concentration of the divinylarene dioxide used to prepare the hydroxyl- functional polyester resin of the present invention may range generally from about
- the DVBDO epoxy resin may be used in less than stoichiometric amounts when reacted with the dicarboxylic acid which results in a carboxy ester resin product. In another embodiment, a stoichiometric excess of the DVBDO epoxy resin results in an epoxy ester resin product.
- the dicarboxylic acid, component (b), useful in the present invention may be any conventional acrylic acid known in the art.
- the dicarboxylic acid compound useful in the practice of the present invention may be for example isophthalic acid, adipic acid, and the like. Mixtures of any two or more dicarboxylic acids can also be used in the practice of the present invention.
- Other suitable dicarboxylic acid compounds useful in the present invention are described in WO 2008/045882 Al published April 17, 2008.
- Preferred examples of the dicarboxylic acid compounds useful in the present invention may include for example isophthalic acid, terephthalic acid, adipic acid; and mixtures thereof.
- the concentration of the dicarboxylic acids used to prepare the hydroxyl-functional polyester resin of the present invention may range generally from about 1 wt% to about 99 wt%; preferably, from about 2 wt% to about 98 wt%; and more preferably, from about 5 wt% to about 95 wt%.
- one embodiment of the present invention includes wherein the DVBDO epoxy resin is used in less than stoichiometric amounts when reacted with the dicarboxylic acid which results in a carboxy ester resin product. In another embodiment, a stoichiometric excess of the DVBDO epoxy resin results in an epoxy ester resin product.
- At least one unsaturated monomer may optionally be used to dissolve the dicarboxylic acid therein and facilitate the reaction between the divinylarene dioxide and the at least one dicarboxylic acid.
- the preparation of the hydroxyl-functional polyester resin of the present invention is achieved by adding to a reactor: a divinylarene dioxide, a dicarboxylic acid, optionally a catalyst, and optionally a solvent; and then allowing the components to react under reaction conditions to produce the hydroxyl-functional polyester resin.
- the components may be mixed in any order.
- the components are heated until the desired degree of reaction is achieved.
- the resulting product is allowed to cool prior to or during isolation and is immediately usable in thermoset formulations.
- the reaction conditions to form the hydroxyl-functional polyester resin include carrying out the reaction under a temperature, generally in the range of from about 100 °C to about 250 °C; preferably, from about 125 °C to about 225 °C; and more preferably, from about 150 °C to about 200 °C.
- the pressure of the reaction may be from about 0.1 bar to about 10 bar; preferably, from about 0.5 bar to about 5 bar; and more preferably, from about 0.9 bar to about 1.1 bar.
- one or more suitable reaction catalysts may be employed in the practice of the present invention.
- Catalysts used to prepare the compositions of the present invention may be selected, for example, from one or more of, an alkali metal salt, an alkaline earth metal salt, a tertiary amine, a quaternary ammonium salt, a quaternary phosphonium salt, and the like, and mixtures thereof.
- the catalyst used in the present invention is ethyltriphenylphosphonium acetate-acetic acid complex or
- the reaction catalyst is generally employed in an amount of from about 0.01 to about 10; preferably, from about 0.05 to about 5; and most preferably, from about 0.1 to about 4, weight percent based on the combined weight of the divinylarene dioxide compound and dicarboxylic acid compound used.
- the reaction process to prepare hydroxyl-functional polyester resin of the present invention may be a batch or a continuous.
- the reactor used in the process may be any reactor and ancillary equipment well known to those skilled in the art.
- the novel hydroxyl-functional polyester resin compositions of divinylarene dioxides and dicarboxylic acids have a lower viscosity with high heat resistance of derived thermosets compared to similar hydroxyl-functional polyester of the prior art.
- the viscosity of the hydroxyl-functional polyester resin prepared by the process of the process of the present invention ranges generally from about 100 mPa-s to about 200,000 mPa-s; preferably, from about 150 mPa-s to about 100,000 mPa-s; and more preferably, from about 200 mPa-s to about 50,000 mPa-s at 150 °C.
- the number average molecular weight (M n ) of the hydroxyl-functional polyester resin prepared by the process of the process of the present invention ranges generally from about 200 to about 100,000; preferably, from about 300 to about 80,000; and more preferably, from about 500 to about 50,000.
- the hydroxyl-functional polyester resin of the present invention is useful as the epoxy component in a curable or thermosettable epoxy resin formulation or composition.
- a curable hydroxyl-functional polyester resin composition which may be suitable for a coating composition may be prepared comprising a mixture of: (i) the above described hydroxyl-functional polyester resin; (ii) at least one solvent; and (iii) at least one catalyst; and (iv) optionally, at least one curing agent and/or surfactant.
- the first component (i) of the curable hydroxyl-functional polyester resin composition comprises the hydroxyl-functional polyester resin, as described above.
- the concentration of the hydroxyl-functional polyester resin used in the curable hydroxyl-functional polyester resin mixture of the present invention may range generally from about 100 weight percent (wt%) to about 10 wt%; preferably, from about 99 wt% to about 20 wt%; and more preferably, from about 90 wt% to about 30 wt%.
- the amount of hydroxyl-functional polyester resin used is selected based on the desired balance of properties of the resulting cured product.
- a solvent may be used in preparing the curable hydroxyl-functional polyester resin of the present invention.
- one or more organic solvents well known in the art may be added to the hydroxyl-functional polyester resin composition.
- aromatics such as xylene, ketones such as methyl ether ketone (MEK), and ethers such as diglyme; and mixtures thereof, may be used in the present invention.
- the concentration of the solvent used in the present invention may range generally from 0 wt% to about 90 wt%, preferably from about 0.01 wt% to about 80 wt%, more preferably from about 1 wt% to about 70 wt%, and most preferably from about 10 wt% to about 60 wt%. Viscosity is too high or solvent is wasted when the above concentration ranges are not used.
- At least one curing catalyst may be used to facilitate the reaction of the divinylarene dioxide compound with the at least one curing agent.
- the curing catalyst useful in the present invention may include, for example, an acid such as phosphoric acid or an organosulfonic acid or a base such as a tertiary amine; and mixtures thereof.
- the curing catalyst is generally employed in an amount of from about 0.01 to about 10, preferably from about 0.05 to about 5, and most preferably from about 0.1 to about 2, weight percent based on the combined weight of the hydroxyl-functional polyester resin and curing agent used.
- An optional curing agent useful for the curable hydroxyl-functional polyester resin composition of the present invention may comprise any conventional curing agent known in the art for curing epoxy resins such as for example an epoxy resin, a phenolic resole, a melamine resin, and the like; and mixtures thereof.
- the curing agent is preferably epoxy resins such as LER or SER.
- epoxy resins such as LER or SER.
- D.E.R. is a trademark of The Dow Chemical Company.
- the curing agent is preferably a phenolic resole a melamine resin, or mixtures thereof.
- the amount of the curing agent used in the curable hydroxyl-functional polyester resin composition generally is selected based on the desired balance of properties of the resulting cured product.
- An optional surfactant useful for the curable hydroxyl-functional polyester resin composition of the present invention may comprise any conventional surfactant known in the art such as for example a silicone compound, a fluorinated organic compound, a polyether, and the like; and mixtures thereof.
- the amount of the surfactant used in the curable hydroxyl-functional polyester resin composition generally ranges from about 0 wt% to about 10 wt%, preferably from about 0.01 wt% to about 2 wt%, and more preferably from about 0.1 wt% to about 1 wt%.
- An assortment of known additives useful for the preparation, storage, and curing of hydroxyl-functional polyester resins may be used as optional additional components for the resin compositions of the present invention including for example, reaction catalysts, resin stabilizers, curing catalysts, processing aids, solvents, other resins, fillers, plasticizers, catalyst de- activators, and mixtures thereof.
- a curable hydroxyl-functional polyester resin composition may comprise a reaction mixture of (i) an hydroxyl-functional polyester resin of a divinylarene dioxide and dicarboxylic acid as described above, (ii) at least one curing agent; (iii) at least one curing catalyst; and (iv) at least one other hydroxyl-functional polyester different from component (i).
- the mixture may include at least one other epoxy resin, component (v).
- the optional epoxy resin may used as a co-monomer for the epoxy ester resins of the present invention or the optional epoxy resin may used as a curing agent for carboxy ester resins of the present invention.
- Optional epoxy resins include those compounds containing at least one vicinal epoxy group.
- the optional epoxy resin may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted.
- the optional epoxy resin may also be monomeric or polymeric.
- the optional epoxy resin useful in the present invention may be selected from any known epoxy resins in the art. An extensive
- the optional epoxy resins, used in embodiments disclosed herein for component (v) of the present invention may vary and include conventional and commercially available epoxy resins, which may be used alone or in combinations of two or more. In choosing epoxy resins for compositions disclosed herein, consideration should not only be given to properties of the final product, but also to viscosity and other properties that may influence the processing of the resin composition.
- Particularly suitable optional epoxy resins known to the skilled worker are based on reaction products of polyfunctional alcohols, phenols, cyclo aliphatic carboxylic acids, aromatic amines, or aminophenols with epichlorohydrin.
- a few non-limiting embodiments include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, triglycidyl ethers of para-aminophenols and mixtures thereof.
- Other suitable epoxy resins known to the skilled worker include reaction products of
- epichlorohydrin with o-cresol and phenol novolacs respectively. It is also possible to use a mixture of two or more epoxy resins.
- the optional epoxy resin useful in the present invention for the preparation of the curable epoxy resin composition may be selected from commercially available products.
- the epoxy resin component (a) may be a liquid epoxy resin, D.E.R.
- epoxy resin having an epoxide equivalent weight (EEW) of 175-185, a viscosity of 9.5 Pa-s and a density of 1.16 gms/cc, or a solid epoxy resin, D.E.R 664 epoxy resin.
- EW epoxide equivalent weight
- Other commercial epoxy resins that can be used for the epoxy resin component can be D.E.R. 330, D.E.R. 354, or D.E.R. 332 epoxy resins.
- the optional epoxy resin useful in the composition of the present invention comprises any aromatic or aliphatic glycidyl ether or glycidyl amine or a cycloaliphatic epoxy resin.
- the choice of the optional epoxy resin used in the present invention depends on the application. However, diglycidyl ether of bisphenol A (DGEBA) and derivatives thereof are particularly preferred.
- DGEBA diglycidyl ether of bisphenol A
- Other epoxy resins can be selected from, but limited to, for example; bisphenol F epoxy resins, novolac epoxy resins, glycidylamine- based epoxy resins, alicyclic epoxy resins, linear aliphatic epoxy resins,
- the at least one optional epoxy resin, component (v), may be present in the epoxy resin mixture composition at a concentration ranging generally from about 1 wt% to about 99 wt%, preferably from about 10 wt% to about 90 wt%, and more preferably from about 25 wt% to about 75 wt%.
- the curable or thermosettable composition of the present invention may optionally contain one or more other additives which are useful for their intended uses.
- the optional additives useful in the present invention composition may include, but not limited to, stabilizers, surfactants, flow modifiers, pigments or dyes, matting agents, degassing agents, flame retardants (e.g., inorganic flame retardants, halogenated flame retardants, and non-halogenated flame retardants such as phosphorus-containing materials), toughening agents, curing initiators, curing inhibitors, wetting agents, colorants or pigments, thermoplastics, processing aids, UV blocking compounds, fluorescent
- thermoplastic particles and mixtures thereof.
- UV stabilizers UV stabilizers
- inert fillers fibrous reinforcements
- antioxidants impact modifiers including thermoplastic particles, and mixtures thereof.
- impact modifiers including thermoplastic particles, and mixtures thereof.
- the above list is intended to be exemplary and not limiting.
- the preferred additives for the, formulation of the present invention may be optimized by the skilled artisan.
- the concentration of the additional additives is generally between about 0 wt% to about 90 wt%; preferably, between about 0.01 wt% to about 80 wt%; more preferably, between about 1 wt% to about 65 wt%; and most preferably, between about 10 wt% to about 50 wt% based on the weight of the total composition. If no additive or a small amount of additive is used, the effect may be insignificant; or if an additive is used greater than 90 wt%, the amount of additive may be detrimental to thermoset properties.
- the preparation of the curable hydroxyl-functional polyester resin composition of the present invention is achieved by admixing in a vessel the following components: the hydroxyl-functional polyester resin, a curing agent, optionally a catalyst, optionally another epoxy resin, and optionally an inert organic solvent; and then allowing the components to formulate into a hydroxyl-functional polyester resin composition.
- a curing agent optionally a catalyst, optionally another epoxy resin, and optionally an inert organic solvent
- the components to formulate into a hydroxyl-functional polyester resin composition There is no criticality to the order of mixture, i.e., the components of the formulation or composition of the present invention may be admixed in any order to provide the thermosettable composition of the present invention. Any of the above-mentioned optional assorted formulation additives, for example fillers, may also be added to the composition during the mixing or prior to the mixing to form the composition.
- All the components of the hydroxyl-functional polyester resin composition are typically mixed and dispersed at a temperature enabling the preparation of an effective epoxy resin composition having a low viscosity for the desired application.
- temperature during the mixing of all components may be generally from about 0 °C to about 300 °C and preferably from about 20 °C to about 200 °C.
- the hydroxyl-functional polyester resin composition of the present invention prepared from the divinylarene dioxides described above, have improved heat resistance compared to their BADGE analogs.
- the viscosity of the hydroxyl-functional polyester resin composition prepared by the process of the present invention ranges generally from about 100 mPa-s to about
- 200,000 mPa-s preferably, from about 150 mPa-s to about 100,000 mPa-s; and more preferably, from about 200 mPa-s to about 50,000 mPa-s at 150 °C.
- the number average molecular weight (M n ) of the hydroxyl-functional polyester resin composition prepared by the process of the present invention ranges generally from about 200 to about 100,000; preferably, from about 300 to about 10,000; and more preferably, from about 500 to about 5,000.
- the heat resistance of the hydroxyl-functional polyester resin based thermoset of the present invention ranges generally from about 50 °C to about 300 °C; preferably, from about 75 °C to about 275 °C; and more preferably, from about 100 °C to about 250 °C as measured by the glass transition temperature (T g ) using differential scanning calorimetry (DSC).
- thermoset The curable hydroxyl-functional polyester resin formulation or composition of the present invention can be cured under conventional processing conditions to form a thermoset.
- the resulting thermoset displays excellent thermo-mechanical properties, such as good solvent resistance.
- the process to produce the thermoset products of the present invention may be performed by gravity casting, vacuum casting, automatic pressure gelation (APG), vacuum pressure gelation (VPG), infusion, filament winding, lay up injection, transfer molding, prepreging, dipping, coating, spraying, brushing, and the like.
- the curing reaction conditions include, for example, carrying out the reaction under a temperature, generally in the range of from about 0 °C to about 300 °C; preferably, from about 20 °C to about 250 °C; and more preferably, from about 50 °C to about 200 °C.
- the pressure of the curing reaction may be carried out, for example, at a pressure of from about 0.01 bar to about 1000 bar; preferably, from about 0.1 bar to about 100 bar; and more preferably, from about 0.5 bar to about 10 bar.
- the curing of the curable or thermosettable composition may be carried out, for example, for a predetermined period of time sufficient to cure the composition.
- the curing time may be chosen between about 1 minute to about 24 hours, preferably between about 10 minutes to about 12 hours, and more preferably between about 100 minutes to about 8 hours.
- the curing process of the present invention may be a batch or a continuous process.
- the reactor used in the process may be any reactor and ancillary equipment well known to those skilled in the art.
- the cured or thermoset product prepared by curing the hydroxyl-functional polyester resin composition of the present invention advantageously exhibits a good solvent resistance.
- the cured product can be visually transparent or opalescent.
- the solvent resistance of the cured product may be demonstrated by MEK resistance as measured by ASTM D 5402-93 method.
- the MEK resistance in terms of the number of double-rubs to failure may be from about 10 to greater than 200, preferably from about 20 to greater than 200 and more preferably from about 50 to greater than 200.
- hydroxyl-functional polyester resin compositions of the present invention are useful for the preparation of epoxy thermosets or cured products in the form of coatings, films, adhesives, laminates, composites, electronics, and the like.
- the hydroxyl-functional polyester resin compositions of the present invention may be particularly suitable for several applications, such as electrical casting, electronic encapsulation, casting, molding, potting, encapsulation, tooling, injection molding, resin transfer molding, and the like.
- the present invention may be used for the fabrication of hydroxyl- functional polyester resin based composites parts, particularly for producing large hydroxyl- functional polyester resin-based parts produced by casting, potting and encapsulation.
- Coatings were prepared by mixing a coating resin, crosslinker (Methylon 75108 phenolic resole), catalyst (85% phosphoric acid), surfactant (BYK-310), and solvents (80/20 Dowanol EB/cyclohexanone) at 25 wt. % solid contents.
- the substrate used was tin free steel (TFS) panels.
- the coatings were prepared with a #20 draw down bar. The coated panels were stored in a dust free box for at least 30 minutes at room temperature (about 25 °C) before being cured in an oven at the temperature indicated below in Table I for 10 minutes.
- H 3 PO 4 is a 85% solution, ppH is based on the calculated amount of 100% acid versus total coating solids.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080055698.7A CN102666636B (zh) | 2009-12-08 | 2010-11-10 | 羟基官能聚酯树脂 |
BR112012013135A BR112012013135A8 (pt) | 2009-12-08 | 2010-11-10 | Composição de resina, processo para preparar um resina de poliésyer com funcionalidade hidroxila e processo para preparar uma composição de resina de poliéster com funcionalidade hidroxila curável |
US13/508,075 US8975343B2 (en) | 2009-12-08 | 2010-11-10 | Hydroxyl-functional polyester resins |
EP10779628.6A EP2510035B1 (fr) | 2009-12-08 | 2010-11-10 | Résines polyester à fonction hydroxyle |
JP2012543125A JP5902625B2 (ja) | 2009-12-08 | 2010-11-10 | ヒドロキシル官能性ポリエステル樹脂 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US26767209P | 2009-12-08 | 2009-12-08 | |
US61/267,672 | 2009-12-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011071650A1 true WO2011071650A1 (fr) | 2011-06-16 |
Family
ID=43477956
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/056214 WO2011071650A1 (fr) | 2009-12-08 | 2010-11-10 | Résines polyester à fonction hydroxyle |
Country Status (8)
Country | Link |
---|---|
US (1) | US8975343B2 (fr) |
EP (1) | EP2510035B1 (fr) |
JP (1) | JP5902625B2 (fr) |
KR (1) | KR20120114296A (fr) |
CN (1) | CN102666636B (fr) |
BR (1) | BR112012013135A8 (fr) |
TW (1) | TWI503341B (fr) |
WO (1) | WO2011071650A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013090010A1 (fr) * | 2011-12-15 | 2013-06-20 | Dow Global Technologies Llc | Résines d'ester à fonctionnalité hydroxy |
WO2013101531A3 (fr) * | 2011-12-29 | 2013-12-19 | Dow Global Technologies Llc | Compositions de résine époxy acrylate solubles dans l'eau, durcissables |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102906148A (zh) * | 2010-05-21 | 2013-01-30 | 陶氏环球技术有限责任公司 | 可固化组合物 |
Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US163973A (en) | 1875-06-01 | Improvement in indexes | ||
US3018262A (en) | 1957-05-01 | 1962-01-23 | Shell Oil Co | Curing polyepoxides with certain metal salts of inorganic acids |
DE1227659B (de) * | 1958-10-13 | 1966-10-27 | Union Carbide Corp | Verfahren zur Herstellung von Formteilen |
US5405688A (en) | 1990-09-11 | 1995-04-11 | Dow Corning Corporation | Epoxy resin/aminopolysiloxane/aromatic oligomer composite |
US5780582A (en) * | 1996-12-31 | 1998-07-14 | The Dow Chemical Company | Hydroxy-functionalized polyester and poly(ester ether) oligomers |
US5962547A (en) * | 1997-05-16 | 1999-10-05 | Nikolic; Nikola A. | Reactive radiation- or thermally-initiated cationically-curable epoxide monomers and compositions made from those monomers |
US6153719A (en) | 1998-02-04 | 2000-11-28 | Lord Corporation | Thiol-cured epoxy composition |
US6242083B1 (en) | 1994-06-07 | 2001-06-05 | Cytec Industries Inc. | Curable compositions |
US6572971B2 (en) | 2001-02-26 | 2003-06-03 | Ashland Chemical | Structural modified epoxy adhesive compositions |
US6632893B2 (en) | 1999-05-28 | 2003-10-14 | Henkel Loctite Corporation | Composition of epoxy resin, cyanate ester, imidazole and polysulfide tougheners |
US6887574B2 (en) | 2003-06-06 | 2005-05-03 | Dow Global Technologies Inc. | Curable flame retardant epoxy compositions |
US20050171237A1 (en) | 2002-05-24 | 2005-08-04 | Patel Ranjana C. | Jettable compositions |
US7037958B1 (en) | 2001-08-24 | 2006-05-02 | Texas Research International, Inc. | Epoxy coating |
WO2006052727A1 (fr) | 2004-11-10 | 2006-05-18 | Dow Global Technologies Inc. | Résines d’époxy durcies par copolymère bloc amphiphile et stratifiés électriques réalisés à partir de ces résines |
US20060293172A1 (en) | 2005-06-23 | 2006-12-28 | General Electric Company | Cure catalyst, composition, electronic device and associated method |
US20070221890A1 (en) | 2004-05-28 | 2007-09-27 | Joseph Gan | Phosphorus Containing Compounds Useful for Making Halogen-Free, Ignition-Resistant Polymer |
WO2008045889A1 (fr) | 2006-10-10 | 2008-04-17 | Dow Global Technologies Inc. | Procédé d'élaboration de polymères solubles avec faible taux de conversion de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères |
WO2008045882A1 (fr) | 2006-10-10 | 2008-04-17 | Dow Global Technologies Inc. | Polymères soluble à forte conversion of d'acide de résines époxy aromatiques et de diacides et revêtements réticulés en étant faits |
WO2008045884A1 (fr) | 2006-10-10 | 2008-04-17 | Dow Global Technologies Inc. | Procédé d'élaboration de polymères solubles avec taux de conversion élevé de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères |
WO2008045894A1 (fr) | 2006-10-10 | 2008-04-17 | Dow Global Technologies Inc. | Polymères solubles avec une faible conversion d'acides à partir de résines époxy aromatiques et de diacides et revêtements réticulés préparés à partir de ceux-ci |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2924580A (en) * | 1957-08-08 | 1960-02-09 | Union Carbide Corp | Divinyl benzene dioxide compositions |
GB866410A (en) * | 1958-10-11 | 1961-04-26 | Union Carbide Corp | Improvements in and relating to polymerisable epoxide compositions |
DE3671449D1 (de) * | 1985-06-06 | 1990-06-28 | Ciba Geigy Ag | 2,6-disubstituierte 4-epoxypropylphenylglycidylether und deren verwendung. |
WO1998050447A1 (fr) * | 1997-05-06 | 1998-11-12 | Ciba Specialty Chemicals Holding Inc. | Resine epoxy modifiee, et utilisation de cette derniere comme composant de formulation pour des compositions thermo-durcissables, en particulier, pour des revetements sous forme de poudres |
EP0878472A1 (fr) * | 1997-05-16 | 1998-11-18 | National Starch and Chemical Investment Holding Corporation | Monomères époxydes réactifs, durchissables cationiquement par radiation ou thermiquement et compositions les contenant |
US7163973B2 (en) | 2002-08-08 | 2007-01-16 | Henkel Corporation | Composition of bulk filler and epoxy-clay nanocomposite |
-
2010
- 2010-11-10 BR BR112012013135A patent/BR112012013135A8/pt not_active IP Right Cessation
- 2010-11-10 WO PCT/US2010/056214 patent/WO2011071650A1/fr active Application Filing
- 2010-11-10 US US13/508,075 patent/US8975343B2/en not_active Expired - Fee Related
- 2010-11-10 EP EP10779628.6A patent/EP2510035B1/fr not_active Not-in-force
- 2010-11-10 KR KR1020127017670A patent/KR20120114296A/ko not_active Application Discontinuation
- 2010-11-10 CN CN201080055698.7A patent/CN102666636B/zh not_active Expired - Fee Related
- 2010-11-10 JP JP2012543125A patent/JP5902625B2/ja not_active Expired - Fee Related
- 2010-12-07 TW TW099142556A patent/TWI503341B/zh not_active IP Right Cessation
Patent Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US163973A (en) | 1875-06-01 | Improvement in indexes | ||
US3018262A (en) | 1957-05-01 | 1962-01-23 | Shell Oil Co | Curing polyepoxides with certain metal salts of inorganic acids |
DE1227659B (de) * | 1958-10-13 | 1966-10-27 | Union Carbide Corp | Verfahren zur Herstellung von Formteilen |
US5405688A (en) | 1990-09-11 | 1995-04-11 | Dow Corning Corporation | Epoxy resin/aminopolysiloxane/aromatic oligomer composite |
US6242083B1 (en) | 1994-06-07 | 2001-06-05 | Cytec Industries Inc. | Curable compositions |
US5780582A (en) * | 1996-12-31 | 1998-07-14 | The Dow Chemical Company | Hydroxy-functionalized polyester and poly(ester ether) oligomers |
US5962547A (en) * | 1997-05-16 | 1999-10-05 | Nikolic; Nikola A. | Reactive radiation- or thermally-initiated cationically-curable epoxide monomers and compositions made from those monomers |
US6153719A (en) | 1998-02-04 | 2000-11-28 | Lord Corporation | Thiol-cured epoxy composition |
US6632893B2 (en) | 1999-05-28 | 2003-10-14 | Henkel Loctite Corporation | Composition of epoxy resin, cyanate ester, imidazole and polysulfide tougheners |
US6572971B2 (en) | 2001-02-26 | 2003-06-03 | Ashland Chemical | Structural modified epoxy adhesive compositions |
US7037958B1 (en) | 2001-08-24 | 2006-05-02 | Texas Research International, Inc. | Epoxy coating |
US20050171237A1 (en) | 2002-05-24 | 2005-08-04 | Patel Ranjana C. | Jettable compositions |
US6887574B2 (en) | 2003-06-06 | 2005-05-03 | Dow Global Technologies Inc. | Curable flame retardant epoxy compositions |
US20070221890A1 (en) | 2004-05-28 | 2007-09-27 | Joseph Gan | Phosphorus Containing Compounds Useful for Making Halogen-Free, Ignition-Resistant Polymer |
WO2006052727A1 (fr) | 2004-11-10 | 2006-05-18 | Dow Global Technologies Inc. | Résines d’époxy durcies par copolymère bloc amphiphile et stratifiés électriques réalisés à partir de ces résines |
US20060293172A1 (en) | 2005-06-23 | 2006-12-28 | General Electric Company | Cure catalyst, composition, electronic device and associated method |
WO2008045889A1 (fr) | 2006-10-10 | 2008-04-17 | Dow Global Technologies Inc. | Procédé d'élaboration de polymères solubles avec faible taux de conversion de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères |
WO2008045882A1 (fr) | 2006-10-10 | 2008-04-17 | Dow Global Technologies Inc. | Polymères soluble à forte conversion of d'acide de résines époxy aromatiques et de diacides et revêtements réticulés en étant faits |
WO2008045884A1 (fr) | 2006-10-10 | 2008-04-17 | Dow Global Technologies Inc. | Procédé d'élaboration de polymères solubles avec taux de conversion élevé de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères |
WO2008045894A1 (fr) | 2006-10-10 | 2008-04-17 | Dow Global Technologies Inc. | Polymères solubles avec une faible conversion d'acides à partir de résines époxy aromatiques et de diacides et revêtements réticulés préparés à partir de ceux-ci |
Non-Patent Citations (3)
Title |
---|
"Prediction of Polymer Properties", 1993, DEKKER |
LEE, H.; NEVILLE, K.: "Handbook of Epoxy Resins", vol. 2, 1967, MCGRAW-HILL BOOK COMPANY, pages: 257 - 307 |
MARTA WORZAKOWSKA: "Influence of Cure Schedule on the Viscoelastic Properties and Thermal Degradation of Crosslinked Mono and Diepoxides Obtained During the Reaction of Hydrogen Peroxide and Divinylbenzene", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 103, 2007, pages 462 - 469, XP002618280 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013090010A1 (fr) * | 2011-12-15 | 2013-06-20 | Dow Global Technologies Llc | Résines d'ester à fonctionnalité hydroxy |
CN103998475A (zh) * | 2011-12-15 | 2014-08-20 | 陶氏环球技术有限责任公司 | 羟基酯树脂 |
JP2015505891A (ja) * | 2011-12-15 | 2015-02-26 | ダウ グローバル テクノロジーズ エルエルシー | ヒドロキシエステル樹脂 |
WO2013101531A3 (fr) * | 2011-12-29 | 2013-12-19 | Dow Global Technologies Llc | Compositions de résine époxy acrylate solubles dans l'eau, durcissables |
US20140336302A1 (en) * | 2011-12-29 | 2014-11-13 | Dow Global Technologies Llc | Curable water soluble epoxy acrylate resin compositions |
Also Published As
Publication number | Publication date |
---|---|
BR112012013135A2 (pt) | 2017-03-21 |
EP2510035B1 (fr) | 2015-08-05 |
JP5902625B2 (ja) | 2016-04-13 |
JP2013513011A (ja) | 2013-04-18 |
CN102666636B (zh) | 2015-11-25 |
US20120220750A1 (en) | 2012-08-30 |
TWI503341B (zh) | 2015-10-11 |
CN102666636A (zh) | 2012-09-12 |
TW201136975A (en) | 2011-11-01 |
BR112012013135A8 (pt) | 2017-10-24 |
EP2510035A1 (fr) | 2012-10-17 |
KR20120114296A (ko) | 2012-10-16 |
US8975343B2 (en) | 2015-03-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2013512988A (ja) | エポキシ樹脂組成物 | |
US20130059945A1 (en) | Curable compositions | |
EP2550310A2 (fr) | Agent solidifiant pour des compositions de résine époxy | |
US9169417B2 (en) | Powder coatings compositions | |
EP2746312A2 (fr) | Compositions de résine époxy, leurs procédés de fabrication et articles associés | |
JP2015212399A (ja) | エポキシ樹脂組成物 | |
JP6769540B2 (ja) | エポキシ樹脂組成物、硬化性樹脂組成物及び繊維強化複合材料 | |
EP2536775A1 (fr) | Compositions de résine à base de dioxyde de divinylarène | |
US8975343B2 (en) | Hydroxyl-functional polyester resins | |
JP2009051937A (ja) | エポキシ樹脂組成物、その硬化物、及び新規エポキシ樹脂 | |
US20120245306A1 (en) | Adducts based on divinylarene oxides | |
US20140256909A1 (en) | Curable compositions | |
JP2013108011A (ja) | エポキシ樹脂溶液、エポキシ樹脂組成物、硬化物及び接着剤 | |
JP7172180B2 (ja) | エポキシ樹脂組成物、硬化性樹脂組成物、硬化物、繊維強化複合材料、繊維強化樹脂成形品、及び繊維強化樹脂成形品の製造方法 | |
JP7412939B2 (ja) | フェノキシ樹脂の製造方法 | |
JP2000264952A (ja) | エポキシ樹脂混合物および粉体塗料用エポキシ樹脂組成物 | |
WO2011071961A2 (fr) | Résines dioxydes de divinylarènes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080055698.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10779628 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 13508075 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010779628 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 4965/CHENP/2012 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201002710 Country of ref document: TH Ref document number: 2012543125 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20127017670 Country of ref document: KR Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012013135 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012013135 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120531 |