EP0971968A2 - Säurefunktionelle und epoxyfunktionelle polyester-harze - Google Patents
Säurefunktionelle und epoxyfunktionelle polyester-harzeInfo
- Publication number
- EP0971968A2 EP0971968A2 EP98920497A EP98920497A EP0971968A2 EP 0971968 A2 EP0971968 A2 EP 0971968A2 EP 98920497 A EP98920497 A EP 98920497A EP 98920497 A EP98920497 A EP 98920497A EP 0971968 A2 EP0971968 A2 EP 0971968A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- ranges
- functional polyester
- polyester resins
- carboxyl functional
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 38
- 239000004645 polyester resin Substances 0.000 title claims abstract description 38
- 239000002253 acid Substances 0.000 title claims abstract description 15
- 239000004593 Epoxy Substances 0.000 title description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 25
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 23
- 239000008199 coating composition Substances 0.000 claims abstract description 23
- -1 diol compound Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 4
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 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 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- LVHOAHHFUNMKQA-UHFFFAOYSA-N 3,3-dihydroxy-2,2,5,5-tetramethyl-4-oxohexanoic acid Chemical compound CC(C)(C)C(=O)C(O)(O)C(C)(C)C(O)=O LVHOAHHFUNMKQA-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920002732 Polyanhydride Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- UWZUWNMEIDBHOF-DPMBMXLASA-M lithium;(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound [Li+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O UWZUWNMEIDBHOF-DPMBMXLASA-M 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006009 resin backbone Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 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
- C08G63/16—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
- C08G59/02—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
- 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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
Definitions
- the present invention relates to carboxyl functional polyester resins, to a process for the preparation of the resins, to polyglycidylester resins obtainable by glycidating said carboxyl functional polyester resins, to coating compositions, and in particular powder coating compositions or liquid coating compositions comprising said carboxyl functional polyester resins or said polyglycidylester resins, and to cured products obtained by using the indicated coating compositions.
- Powder coating compositions based on the solid reaction products of 2, 2-bis- ( 4-hydroxyphenyl) propane and epichlorohydrin are known already for a long time.
- the cured products prepared on the basis of these compositions are resistant against hydrolysis, however, they show a low ultraviolet resistance and are therefore not suitable for applications requiring a high degree of outdoor durability such as building parts or automotive topcoats.
- Triglycidylesters which can be used in good quality outdoor durable coatings and in moulding compositions are disclosed in European Patent Application No. 447360A (EP-A-447 , 360 ) .
- the triglycidylester produced will contain a relatively high level of hydrolizable chlorine and/or will contain low molecular weight hydrolysis products which might cause toxicity problems, as may be derived from "Water based coatings with excellent saponification stability Xlllth Int. Conf. 1987, Athens, Greece, p. 175.
- the high level of hydrolizable chlorine is reflected in example 2 of EP-A-447,360 which relates to the glycidation of the 2:1 adduct of hexahydrophthalic anhydride and dimethylolpropionic acid.
- the product obtained has a chlorine content of 1.5%.
- Such a high level of residual chlorine is generally undesirable in coating compositions.
- the triglycidylesters reported in EP-A-447,360 are liquid, they can not be applied in powder coating compositions .
- polyglycidylester resins obtainable by reacting said linear tertiary aliphatic carboxyl functional polyesters with an excess epihalohydrin in the presence of a suitable base and optional catalyst.
- the polyesters were reacted with epichlorohydrin .
- Both the specified linear polyesters and the corresponding polyglycidylesters derived therefrom were used with a cross-linking agent for powder coating compositions.
- polyester resins were obtainable by reaction of: a) at least one aromatic and/or cycloaliphatic carboxylic acid compound A comprising two aromatic- and/or secondary aliphatic carboxyl groups or the anhydride thereof, b) at least one hydroxyl compound B comprising two aliphatic hydroxyl groups, which groups each independently may be primary or secondary hydroxyl groups, c) at least one hydroxyl substituted carboxylic acid compound C comprising at least one tertiary aliphatic carboxyl group and two aliphatic hydroxyl groups, which groups each independently may be primary or secondary hydroxyl groups, and d) optionally one carboxylic acid compound D comprising one carboxyl group, the molar ratio of compounds A:B:C:D being
- polyester resins could be used together with a suitable curing agent for the production of powder coatings, or could be converted into the corresponding glycidylesters, which in combination with a suitable curing agent could be used for the production of powder coatings .
- linear tertiary aliphatic carboxyl functional polyester resins and the polyglycidylesters thereof enabled a certain progress as to the requirements of excellent outdoor durability (UV stability) and resistance against hydrolysis in the cured state, with reference to their use in modern economically applied powder coatings, there is still a need for further improvement of this combination of properties .
- the invention provides carboxyl functional polyester resins obtainable by reaction of: a) at least a compound of the formula 0 0
- Dl trihydroxyalkane
- D2 tetrahydroxy- alkane
- the optional component A2 are meant amounts of from 0 to 10 mole%, relative to the total molar amount of Al and A2.
- the aliphatic carboxyl functional polyester resins thus produced may only contain tertiary carboxyl groups pendant of the main chain, whereas only at each end of the main chain secondary carboxyl groups originating from 1,4-cyclo- hexane dicarboxylic acid, are present.
- Dependent on the actual presence of components (Dl) or ( D2 ) the main chain will be linear (components D are absent) or branched (component Dl and/or D2 is present) .
- glycidation of these non-terminal tertiary aliphatic carboxyl groups and the terminal secondary carboxyl groups with epihalohydrin can be performed under standard alkaline conditions, whereby a polyglycidylester resin can be obtained which contains a low hydrolizable halogen content, usually lower than 1% by weight and preferably lower than 0.7% by weight, based on the total weight of the composition.
- the process for preparation of the aliphatic carboxyl functional polyester may in general be carried out according to conventional esterification methods, preferably by azeotropic condensation, taking care that the terminal secondary carboxyl groups are only originating from 1, 4-cyclohexane dicarboxylic acid.
- the condensation is carried out by charging the compounds A, B, optionally C and optionally Dl or D2 , simultaneously to the reactor whereafter the temperature is increased from room temperature to a temperature in the range of from 180 to 240 °C, preferably from 180 to 210 °C in the presence of any compound B, during a period of 3 to 8 hours, thus allowing the reaction to initiate and to proceed under continuous azeotropic removal of water.
- esterification catalyst such as for example dibutyltinoxide, paratoluenesulphonic acid, tinoctoate, zincoctoate and lithium ricinoleate may be used in the esterification process, but is in general not required.
- a part of the total batch of e.g. 1 , 4-cyclohexane dicarboxylic acid to be included may be added during the reaction and more preferably in its last stage.
- Suitable compounds B for use in the process of the present invention include branched aliphatic-, cyclo- aliphatic-, or araliphatic compounds, containing two aliphatic hydroxyl groups, each individually being either a primary or a secondary hydroxyl group, such as for example propylene glycol, neopentyl glycol, hydrogenated diphenylolpropane (HDPP) , hydrogenated 4,4' -dihydroxydiphenyl, 1, 4-cyclohexanedimethylol, 1, -dihydroxycyclohexane, hydroxypivalylhydroxypivalate and 2-butyl-2-ethyl-l , 3-propanediol or mixtures thereof; of which HDPP is particularly preferred.
- HDPP hydrogenated diphenylolpropane
- a typical example of a suitable compound C for use in the process of the present invention is dimethylol propionic acid.
- a typical and preferred example of compound Dl to be used for the preparation of the branched carboxyl functional polyesters of the present invention is trimethylol propane and a preferred example of compound D2 is pentaerythritol .
- the aliphatic carboxyl functional polyester resin obtainable according to the process of the present invention can be easily converted to a polyglycidylester resin according to methods known in the art i.e. by reaction with an excess epihalohydrin in the presence of a suitable base and optionally a catalyst. Most conveniently epichlorohydrin is used.
- the curable powder coating compositions of the invention may be prepared by addition of a cross- linking resin to either the hereinbefore specified linear or branched or star shaped aliphatic carboxyl functional polyester resins of the present invention or to the polyglycidylester resin obtainable by glycidating said linear or branched aliphatic carboxyl functional polyester resin.
- the amount of cross-linking compound used in the powder coating compositions of the invention will normally be such so as to provide about equal amounts of reactive groups of the cross-linking compound and of the aliphatic carboxyl groups present in the linear or branched aliphatic carboxyl functional polyester resin or of the epoxy groups present in the polyglycidylester resin .
- Suitable cross-linking resins for use in combination with the aliphatic carboxyl functional polyester resins of the present invention are for example outdoor durable epoxy resins, such as for example the polyglycidylester resins according to the present invention, the diglycidylesters of alpha, alpha ' -dibranched dicarboxylic acids as disclosed in
- Suitable cross-linking resins for use in combination with the polyglycidylester resins of the present invention are for example the (corresponding) acid functional polyester resin of the present invention; solid polyacids such as sebacic acid,
- 1, 12-dodecanedioic acid 1, 12-dodecanedioic acid
- anhydrides such as polyazeleic polyanhydride
- acid functional polyesters such as the reaction product of one mole of trimethylolpropane
- the powder coating compositions of the present invention may further comprise a catalyst and optionally other additives, as known in the art to be suitable for use in powder coating compositions.
- Suitable catalysts are for example quaternary ammonium and phosphonium salts; metal salts/compounds such as for example stannous (II ) octoate; basic compounds such as for example the imidazoles; and tertiary amines such as for example diazabi- cycloundecene .
- the amount of catalyst used will usually be somewhere in the range of from 0.1 to 2% by weight based on the weight of the total powder coating composition .
- Suitable cure times and cure temperatures of the powder coating compositions of the invention are those conventionally applied in connection with powder coating systems.
- Example 1 The invention is illustrated by the following examples, however without restricting its scope to these specific embodiments.
- Example 1 The invention is illustrated by the following examples, however without restricting its scope to these specific embodiments.
- the mixture was then heated to 150 °C in 30 minutes.
- the temperature of the reaction mixture was increased in two hours to 210 °C and kept at 210 °C until at least 94% of the original hydroxyl groups have reacted.
- the acid functional polyester thus formed was discharged and allowed to cool down to room temperature .
- Numbers given represent the amount of moles of a particular compound charged to the reactor in the process of example 1 for the preparation of the linear tertiary carboxyl functional polyester resins 1 to 5.
- 1,4-CHCA 1 , 4-cyclohexanedicarboxylic acid
- HHPA hexahydrophthalic anhydride
- HDPP hydrogenated diphenylolpropane
- PENTA pentaerythritol
- MIBK methyl isobutyl ketone
- Modaflow III is an acrylic based flow aid available from Monsanto Co.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98920497A EP0971968A2 (de) | 1997-03-25 | 1998-03-24 | Säurefunktionelle und epoxyfunktionelle polyester-harze |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97200904 | 1997-03-25 | ||
| EP97200904 | 1997-03-25 | ||
| PCT/EP1998/001903 WO1998042768A2 (en) | 1997-03-25 | 1998-03-24 | Acid functional and epoxy functional polyester resins |
| EP98920497A EP0971968A2 (de) | 1997-03-25 | 1998-03-24 | Säurefunktionelle und epoxyfunktionelle polyester-harze |
| US09/048,036 US6143838A (en) | 1997-03-25 | 1998-03-25 | Acid functional and epoxy functional polyester resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0971968A2 true EP0971968A2 (de) | 2000-01-19 |
Family
ID=27222864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98920497A Withdrawn EP0971968A2 (de) | 1997-03-25 | 1998-03-24 | Säurefunktionelle und epoxyfunktionelle polyester-harze |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0971968A2 (de) |
| BR (1) | BR9808045A (de) |
| WO (1) | WO1998042768A2 (de) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6103835A (en) * | 1998-11-11 | 2000-08-15 | Shell Oil Company | Epoxy-functional polyester advanced with carboxyl-functional polyester or dicarboxylic acid (anhydride) |
| US6388024B1 (en) | 1999-10-29 | 2002-05-14 | Ronald Petrus Clemens Van Gaalen | Acid functional and epoxy functional polyester resins |
| US6451929B1 (en) | 1999-10-29 | 2002-09-17 | Resolution Performance Products, Llc | Glycidyl ester by reacting COOH polyester with epihalohydrin |
| JP2001131270A (ja) * | 1999-11-04 | 2001-05-15 | Japan Epoxy Resin Kk | 酸官能性及びエポキシ官能性ポリエステル樹脂 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138078A (en) * | 1990-03-15 | 1992-08-11 | Ciba-Geigy Corporation | Glycidyl esters of tricarboxylic acid adducts |
| WO1994001505A1 (en) * | 1992-07-06 | 1994-01-20 | Eastman Chemical Company | Thermosetting powder coating compositions |
| DE4305990A1 (de) * | 1993-02-26 | 1994-09-01 | Hoechst Ag | Sauer modifizierte Polyester und deren Verwendung in Einbrennlacken |
| JP3432278B2 (ja) * | 1993-07-15 | 2003-08-04 | ジャパンエポキシレジン株式会社 | 酸官能性ポリエステル樹脂およびそれから誘導されるポリグリシジルエステル樹脂の製造法 |
| EP0677544A1 (de) * | 1994-03-24 | 1995-10-18 | Shell Internationale Researchmaatschappij B.V. | Epoxypulverüberzugszusammensetzungen |
| US5393609A (en) * | 1994-06-13 | 1995-02-28 | Eastman Chemical Company | Weatherable powder coatings |
| EP0720997B1 (de) * | 1995-01-06 | 2001-10-17 | Resolution Research Nederland B.V. | Lineare, epoxyfunktionelle Polyesterharze |
| US5554701A (en) * | 1995-03-24 | 1996-09-10 | Eastman Chemical Company | Crosslinked polyesters made from decahydronaphthalene dimethanol |
-
1998
- 1998-03-24 EP EP98920497A patent/EP0971968A2/de not_active Withdrawn
- 1998-03-24 BR BR9808045-8A patent/BR9808045A/pt active Search and Examination
- 1998-03-24 WO PCT/EP1998/001903 patent/WO1998042768A2/en not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9842768A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998042768A3 (en) | 1999-01-21 |
| BR9808045A (pt) | 2000-03-08 |
| WO1998042768A2 (en) | 1998-10-01 |
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