CA2472035A1 - Unsaturated, amorphous polyesters based on certain dicidol isomers - Google Patents
Unsaturated, amorphous polyesters based on certain dicidol isomers Download PDFInfo
- Publication number
- CA2472035A1 CA2472035A1 CA002472035A CA2472035A CA2472035A1 CA 2472035 A1 CA2472035 A1 CA 2472035A1 CA 002472035 A CA002472035 A CA 002472035A CA 2472035 A CA2472035 A CA 2472035A CA 2472035 A1 CA2472035 A1 CA 2472035A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- unsaturated
- amorphous polyester
- present
- alcohol component
- 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.)
- Abandoned
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 42
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 7
- 239000001530 fumaric acid Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- -1 aromatic diols Chemical class 0.000 claims description 5
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 5
- 238000000034 method Methods 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 claims description 3
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 claims description 2
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 claims description 2
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical group OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 2
- 229940100573 methylpropanediol Drugs 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003504 photosensitizing agent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 239000013008 thixotropic agent Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 2
- LDQSOXHNCNMAKA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,6-diyldimethanol Chemical compound C1C(CO)C2C3C(CO)CCC3C1C2 LDQSOXHNCNMAKA-UHFFFAOYSA-N 0.000 claims 2
- ZFZDWMXUMXACHS-UHFFFAOYSA-N 28132-01-6 Chemical compound C1C2CC(CO)C1C1C2CC(CO)C1 ZFZDWMXUMXACHS-UHFFFAOYSA-N 0.000 claims 1
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 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
- 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
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
-
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to unsaturated, amorphous polyesters based on determined dicidol isomers and saturated and/or unsaturated dicarboxylic acids.
Description
, O.Z. 6007 Unsaturated, amorphous polyesters based oa certain dicidol isomers The invention relates to unsaturated, amorphous polyesters based on certain dicidol isomers and acids.
Unsaturated polyester resins (UP resins) are well known. They are prepared by condensing saturated and unsaturated dicarboxylic acids or their anhydrides with diols. Their properties depend substantially on the type and ratio of the starting materials.
The bearers of the polymerizable double bonds used are usually oc,(3-unsaturated acids, primarily malefic acid and its anhydride or fumaric acid; unsaturated diols are of minor importance. The higher the content of double bonds, i.e. the smaller the separation of the double bonds in the chain molecules, the more reactive the polyester resin. It polymerizes very rapidly with intense development of heat and extensive contraction to give a highly crosslinked and therefore comparatively brittle end product. For this reason, the reactive double bonds in the polyester molecule are "diluted" by co-condensing saturated aliphatic or aromatic dicarboxylic acids. The alcohol components used are straight-chain and branched diols. The individual UP resin types differ not only in the components used to prepare them but also in the ratio of saturated to unsaturated acids which determines the crosslinking density in the polymerization, the degree of condensation, i.e. the molar mass, the acid number and the OH number, i.e. the type of end groups in the chain molecules, the monomer content and the type of additives (Ullmann's Encyclopedia of Industrial Chemistry, VOL A21, p. 217ff., 1992).
UP resins based on dicidol as the diol component are known, for example, from DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP 934 988.
O.z. 6007 - 2 -It is an object of the present invention to provide novel unsaturated and amorphous polyester resins from the multiplicity of possibilities and diversity of the prior art which are also readily soluble without cloudiness in many solvents and are transparent as solids. This object is achieved as will be illustrated henceforth.
The invention provides unsaturated, amorphous polyesters substantially comprising at least one oc,(3-unsaturated dicarboxylic acid component and one alcohol component, wherein the alcohol component comprises a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.02'6]decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.02'6]decane and 5,8-bis(hydroxymethyl)-tricyclo [ 5 . 2 . 1 . O2' 6 ] decane, where each isomer may be present in the mixture in a proportion of from 20 to 40~ and the sum of the three isomers is from 90 to 100, and at least 5~ of the mixture is present in the alcohol component of the polyester.
The invention also provides a process for preparing unsaturated, amorphous polyesters substantially comprising at least one oc,~3-unsaturated dicarboxylic acid component and one alcohol component, wherein the alcohol component comprises a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)tricyclo [5.2.1.02~6]decane, 4,8-bis(hydroxymethyl)tricyclo [5.2.1.02'6]decane and 5,8-bis(hydroxymethyl)tricyclo 3 5 [ 5 . 2 . 1 . O2' 6 ] decane, each isomer may be present in the mixture in a proportion of from 20 to 40~ and the sum of the three isomers is from 90 to 100, O.Z. 6007 - 3 -and at least 5% of the mixture is present in the alcohol component of the polyester, by reacting the starting components at a temperature of from 150 to 270°C, preferably in an inert gas atmosphere, where the inert gas has an oxygen content of less than 50 ppm.
The unsaturated, amorphous polyester resins according to the invention are obtained by reacting the alcohol component with the acid component.
According to the invention, the alcohol component used is a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)tricyclo[5.2.1.02'6]decane, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02'6]decane and 5,8-bis(hydroxymethyl)tricyclo[5.2.1.02'6]decane, where each isomer may be present in the mixture in a proportion of from 20 to 40% and the sum of the three isomers is from 90 to 100%, preferably from 95 to 100%, and at least 5%
of the mixture is present in the alcohol component of the polyester. The isomer content of the dicidol mixture may be determined qualitatively and quantitatively, for example by GC analysis, or quantitatively by separating by means of preparative GC
or HPLC and subsequent NMR spectroscopy. All corresponding isomers of dicidol in the 9-position are equally suitable but, owing to the mirror symmetry of the above mentioned isomers, like the cis- and trans isomers, cannot be differentiated under normal, practical conditions.
The dicidol mixture may further comprise up to 10% of further isomers of dicidol and/or trimeric and/or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene. The alcohol component preferably consists of 20%, of 50%, preferably of 90%, more preferably of 100%, of dicidol mixture which more preferably comprises from 95 to 100% of the abovementioned three isomeric compounds.
O.Z. 6007 - 4 -In addition to the dicidol mixture, the alcohol component may comprise further linear and/or branched, aliphatic and/or cycloaliphatic and/or aromatic diols and/or polyols. The additional alcohols used are preferably ethylene glycol, 1,2- and/or 1,3-propanediol, diethylene glycol, dipropylene glycol, triethylene glycol or tetraethylene glycol, 1,2- and/or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and/or pentaerythritol.
The starting acid component present in the unsaturated, amorphous polyester resins according to the invention comprises at least one a,~-unsaturated dicarboxylic acid. The unsaturated polyester resins preferably comprise citraconic acid, fumaric acid, itaconic acid, malefic acid and/or mesaconic acid.
In addition, aromatic and/or aliphatic and/or cycloaliphatic monocarboxylic acids and/or dicarboxylic acids and/or polycarboxylic acids may also be present, for example phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, decanedicarboxylic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and/or trimellitic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid and/or azelaic acid.
The acid component may partly or entirely consist of anhydrides and/or alkyl esters, preferably methyl esters.
. O.Z. 6007 - 5 -In general, the alcohol component is present in a molar ratio of from 0.5:1 to 2.0:1 to the acid component, preferably from 0.8:1 to 1.5:1. The reaction of the alcohol component more preferably takes place in a molar ratio of from 1.0:1 to 1.1:1 to the acid component.
The unsaturated, amorphous polyesters according to the invention may have an acid number of from 1 to 200 mg KOH/g, preferably from 1 to 100 mg KOH/g, more preferably from 1 to 50 mg KOH/g, and an OH number of from 1 to 200 mg KOH/g, preferably from 1 to 100 mg KOH/g, more preferably from 1 to 50 mg KOH/g.
The Tg of the unsaturated, amorphous polyesters according to the invention varies from -30 to +80°C, preferably from -20 to +50°C, more preferably from -10 to +40°C.
In one preferred embodiment I, the unsaturated polyesters (UP resins) according to the invention consist of an alcohol component comprising at least 90~, preferably 95~, more preferably 100, of the dicidol mixture of the isomeric compounds 3,8-bis-(hydroxymethyl)tricyclo[5.2.1.02'6]decane, 4,8-bis-(hydroxymethyl)tricyclo[5.2.1.02'6]decane and 5,8-bis-(hydroxymethyl)tricyclo[5.2.1.02'6]decane, and of fumaric acid and/or malefic acid/anhydride. In a further preferred embodiment II, the polyesters comprise the abovementioned starting components as under I, but additionally a further acid selected from adipic acid and phthalic acid/anhydride, where the ratio of a,~3-unsaturated acid to the additional acid may vary from 2:1 to 1:4. Preference is given to ratios of approx.
1:1 to 1:2. These polyesters generally have acid numbers of from 1 to 200 mg KOH/g, preferably 1-100 mg KOH/g, more preferably 1-50 mg KOH/g, OH numbers of from 1 to 200 mg KOH/g, preferably 1-100 mg KOH/g, more preferably 1-50 mg KOH/g, and a Tg of from -30 to O.Z. 6007 - 6 -+80°C, preferably from -20 to +50°C, more preferably from -10 to +40°C.
The polyesters according to the invention may also comprise assistants and additives which are selected from inhibitors, water and/or organic solvents, neutralizing agents, surface-active substances, oxygen scavengers and/or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, antiskinning agents, defoamers, antistats, thickening agents, thermoplastic additives, dyes, pigments, flame retardants, internal release agents, fillers and/or blowing agents.
The polyesters according to the invention are prepared by (semi)continuous or batchwise esterification of the starting acids and alcohols in a one-stage or two-stage procedure.
The process according to the invention, as described above, is preferably operated in an inert gas atmosphere at from 150 to 270°C, preferably from 160 to 230°C, more preferably from 160 to 200°C. The inert gas used may be nitrogen or a noble gas, in particular nitrogen. The inert gas has an oxygen content of less than 50 ppm, in particular less than 20 ppm.
The polyester resins according to the invention are further illustrated by the examples which follow:
O.z. 6007 - 7 -Examples Starting component: dicidol mixture (claim 1) in an isomeric ratio of approximately 1:1:1 Example 1 Decanedicarboxylic acid and fumaric acid (ratio 0 . 6 : 0 . 4 ) are reacted with dicidol in a ratio of 1 :1 . 05 at 180°C in a nitrogen atmosphere until an acid number of 24 mg KOH/g and an OH number of 34 mg KOH/g are attained. To this end, the fumaric acid is initially esterified with dicidol over the course of one hour and then the dodecanedicarboxylic acid is added.
Mn = 2200 g/mol, Mw = 5500 g/mol, glass transition temperature 4°C.
Example 2 Adipic acid and malefic acid (ratio 1:1) are reacted with dicidol in a ratio of 1:1.05 at 180°C in a nitrogen atmosphere until an acid number of 26 mg KOH/g and an OH number of 37 mg KOH/g are attained. To this end, the malefic acid is initially esterified with dicidol over the course of one hour and then the adipic acid is added. Mn = 1800 g/mol, MW = 4300 g/mol, glass transition temperature 12°C.
C
Unsaturated polyester resins (UP resins) are well known. They are prepared by condensing saturated and unsaturated dicarboxylic acids or their anhydrides with diols. Their properties depend substantially on the type and ratio of the starting materials.
The bearers of the polymerizable double bonds used are usually oc,(3-unsaturated acids, primarily malefic acid and its anhydride or fumaric acid; unsaturated diols are of minor importance. The higher the content of double bonds, i.e. the smaller the separation of the double bonds in the chain molecules, the more reactive the polyester resin. It polymerizes very rapidly with intense development of heat and extensive contraction to give a highly crosslinked and therefore comparatively brittle end product. For this reason, the reactive double bonds in the polyester molecule are "diluted" by co-condensing saturated aliphatic or aromatic dicarboxylic acids. The alcohol components used are straight-chain and branched diols. The individual UP resin types differ not only in the components used to prepare them but also in the ratio of saturated to unsaturated acids which determines the crosslinking density in the polymerization, the degree of condensation, i.e. the molar mass, the acid number and the OH number, i.e. the type of end groups in the chain molecules, the monomer content and the type of additives (Ullmann's Encyclopedia of Industrial Chemistry, VOL A21, p. 217ff., 1992).
UP resins based on dicidol as the diol component are known, for example, from DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP 934 988.
O.z. 6007 - 2 -It is an object of the present invention to provide novel unsaturated and amorphous polyester resins from the multiplicity of possibilities and diversity of the prior art which are also readily soluble without cloudiness in many solvents and are transparent as solids. This object is achieved as will be illustrated henceforth.
The invention provides unsaturated, amorphous polyesters substantially comprising at least one oc,(3-unsaturated dicarboxylic acid component and one alcohol component, wherein the alcohol component comprises a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.02'6]decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.02'6]decane and 5,8-bis(hydroxymethyl)-tricyclo [ 5 . 2 . 1 . O2' 6 ] decane, where each isomer may be present in the mixture in a proportion of from 20 to 40~ and the sum of the three isomers is from 90 to 100, and at least 5~ of the mixture is present in the alcohol component of the polyester.
The invention also provides a process for preparing unsaturated, amorphous polyesters substantially comprising at least one oc,~3-unsaturated dicarboxylic acid component and one alcohol component, wherein the alcohol component comprises a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)tricyclo [5.2.1.02~6]decane, 4,8-bis(hydroxymethyl)tricyclo [5.2.1.02'6]decane and 5,8-bis(hydroxymethyl)tricyclo 3 5 [ 5 . 2 . 1 . O2' 6 ] decane, each isomer may be present in the mixture in a proportion of from 20 to 40~ and the sum of the three isomers is from 90 to 100, O.Z. 6007 - 3 -and at least 5% of the mixture is present in the alcohol component of the polyester, by reacting the starting components at a temperature of from 150 to 270°C, preferably in an inert gas atmosphere, where the inert gas has an oxygen content of less than 50 ppm.
The unsaturated, amorphous polyester resins according to the invention are obtained by reacting the alcohol component with the acid component.
According to the invention, the alcohol component used is a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)tricyclo[5.2.1.02'6]decane, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02'6]decane and 5,8-bis(hydroxymethyl)tricyclo[5.2.1.02'6]decane, where each isomer may be present in the mixture in a proportion of from 20 to 40% and the sum of the three isomers is from 90 to 100%, preferably from 95 to 100%, and at least 5%
of the mixture is present in the alcohol component of the polyester. The isomer content of the dicidol mixture may be determined qualitatively and quantitatively, for example by GC analysis, or quantitatively by separating by means of preparative GC
or HPLC and subsequent NMR spectroscopy. All corresponding isomers of dicidol in the 9-position are equally suitable but, owing to the mirror symmetry of the above mentioned isomers, like the cis- and trans isomers, cannot be differentiated under normal, practical conditions.
The dicidol mixture may further comprise up to 10% of further isomers of dicidol and/or trimeric and/or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene. The alcohol component preferably consists of 20%, of 50%, preferably of 90%, more preferably of 100%, of dicidol mixture which more preferably comprises from 95 to 100% of the abovementioned three isomeric compounds.
O.Z. 6007 - 4 -In addition to the dicidol mixture, the alcohol component may comprise further linear and/or branched, aliphatic and/or cycloaliphatic and/or aromatic diols and/or polyols. The additional alcohols used are preferably ethylene glycol, 1,2- and/or 1,3-propanediol, diethylene glycol, dipropylene glycol, triethylene glycol or tetraethylene glycol, 1,2- and/or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and/or pentaerythritol.
The starting acid component present in the unsaturated, amorphous polyester resins according to the invention comprises at least one a,~-unsaturated dicarboxylic acid. The unsaturated polyester resins preferably comprise citraconic acid, fumaric acid, itaconic acid, malefic acid and/or mesaconic acid.
In addition, aromatic and/or aliphatic and/or cycloaliphatic monocarboxylic acids and/or dicarboxylic acids and/or polycarboxylic acids may also be present, for example phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, decanedicarboxylic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and/or trimellitic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid and/or azelaic acid.
The acid component may partly or entirely consist of anhydrides and/or alkyl esters, preferably methyl esters.
. O.Z. 6007 - 5 -In general, the alcohol component is present in a molar ratio of from 0.5:1 to 2.0:1 to the acid component, preferably from 0.8:1 to 1.5:1. The reaction of the alcohol component more preferably takes place in a molar ratio of from 1.0:1 to 1.1:1 to the acid component.
The unsaturated, amorphous polyesters according to the invention may have an acid number of from 1 to 200 mg KOH/g, preferably from 1 to 100 mg KOH/g, more preferably from 1 to 50 mg KOH/g, and an OH number of from 1 to 200 mg KOH/g, preferably from 1 to 100 mg KOH/g, more preferably from 1 to 50 mg KOH/g.
The Tg of the unsaturated, amorphous polyesters according to the invention varies from -30 to +80°C, preferably from -20 to +50°C, more preferably from -10 to +40°C.
In one preferred embodiment I, the unsaturated polyesters (UP resins) according to the invention consist of an alcohol component comprising at least 90~, preferably 95~, more preferably 100, of the dicidol mixture of the isomeric compounds 3,8-bis-(hydroxymethyl)tricyclo[5.2.1.02'6]decane, 4,8-bis-(hydroxymethyl)tricyclo[5.2.1.02'6]decane and 5,8-bis-(hydroxymethyl)tricyclo[5.2.1.02'6]decane, and of fumaric acid and/or malefic acid/anhydride. In a further preferred embodiment II, the polyesters comprise the abovementioned starting components as under I, but additionally a further acid selected from adipic acid and phthalic acid/anhydride, where the ratio of a,~3-unsaturated acid to the additional acid may vary from 2:1 to 1:4. Preference is given to ratios of approx.
1:1 to 1:2. These polyesters generally have acid numbers of from 1 to 200 mg KOH/g, preferably 1-100 mg KOH/g, more preferably 1-50 mg KOH/g, OH numbers of from 1 to 200 mg KOH/g, preferably 1-100 mg KOH/g, more preferably 1-50 mg KOH/g, and a Tg of from -30 to O.Z. 6007 - 6 -+80°C, preferably from -20 to +50°C, more preferably from -10 to +40°C.
The polyesters according to the invention may also comprise assistants and additives which are selected from inhibitors, water and/or organic solvents, neutralizing agents, surface-active substances, oxygen scavengers and/or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, antiskinning agents, defoamers, antistats, thickening agents, thermoplastic additives, dyes, pigments, flame retardants, internal release agents, fillers and/or blowing agents.
The polyesters according to the invention are prepared by (semi)continuous or batchwise esterification of the starting acids and alcohols in a one-stage or two-stage procedure.
The process according to the invention, as described above, is preferably operated in an inert gas atmosphere at from 150 to 270°C, preferably from 160 to 230°C, more preferably from 160 to 200°C. The inert gas used may be nitrogen or a noble gas, in particular nitrogen. The inert gas has an oxygen content of less than 50 ppm, in particular less than 20 ppm.
The polyester resins according to the invention are further illustrated by the examples which follow:
O.z. 6007 - 7 -Examples Starting component: dicidol mixture (claim 1) in an isomeric ratio of approximately 1:1:1 Example 1 Decanedicarboxylic acid and fumaric acid (ratio 0 . 6 : 0 . 4 ) are reacted with dicidol in a ratio of 1 :1 . 05 at 180°C in a nitrogen atmosphere until an acid number of 24 mg KOH/g and an OH number of 34 mg KOH/g are attained. To this end, the fumaric acid is initially esterified with dicidol over the course of one hour and then the dodecanedicarboxylic acid is added.
Mn = 2200 g/mol, Mw = 5500 g/mol, glass transition temperature 4°C.
Example 2 Adipic acid and malefic acid (ratio 1:1) are reacted with dicidol in a ratio of 1:1.05 at 180°C in a nitrogen atmosphere until an acid number of 26 mg KOH/g and an OH number of 37 mg KOH/g are attained. To this end, the malefic acid is initially esterified with dicidol over the course of one hour and then the adipic acid is added. Mn = 1800 g/mol, MW = 4300 g/mol, glass transition temperature 12°C.
C
Claims (27)
1. An unsaturated, amorphous polyester comprising at least one .alpha.,.beta.-unsaturated dicarboxylic acid component and one alcohol component, wherein the alcohol component comprises a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2'6]decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2'6]decane and 5,8-bis-(hydroxymethyl)tricyclo[5.2.1.0 2,6]decane, where each isomer may be present in the mixture in a proportion of from 20 to 40% and the sum of the three isomers is from 90 to 100%, and at least 5% of the mixture is present in the alcohol component of the polyester.
2. The unsaturated, amorphous polyester as claimed in claim 1, wherein up to 10% of further isomers of dicidol and/or trimeric and/or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene are present.
3. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the acid component additionally comprises aromatic and/or aliphatic and/or cycloaliphatic monocarboxylic acids and/or dicarboxylic acids and/or polycarboxylic acids.
4. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the acid component consists partly or entirely of anhydrides and/or alkyl esters.
5. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the alcohol component comprises further linear and/or branched, aliphatic and/or cycloaliphatic and/or aromatic diols and/or polyols.
6. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the .alpha.,.beta.-unsaturated dicarboxylic acid present is citraconic, fumaric, itaconic, maleic and/or mesaconic acid.
7. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the additional acids present are phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedicarboxylic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and/or trimellitic acid, their anhydrides and/or methyl esters.
8. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the additional alcohols present are ethylene glycol, 1,2- and/or 1,3-propanediol, diethylene, dipropylene, triethylene glycol or tetraethylene glycol, 1,2- and/or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and/or pentaerythritol.
9. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein at least 20% of the alcohol component consists of the isomers of claim 1 or 2.
10. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein at least 50% of the alcohol component consists of the isomers of claim 1 or 2.
11. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein at least 90% of the alcohol component consists of the isomers of claim 1 or 2.
12. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein at least 100% of the alcohol component consists of the isomers of claim 1 or 2.
13. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the .alpha.,.beta.-unsaturated acid component present is fumaric acid and/or maleic acid/anhydride.
14. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the further dicarboxylic acid component present is adipic acid and/or phthalic acid/anhydride.
15. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the alcohol component is present in a molar ratio of from 0.5:1 to 2.0:1 to the acid component.
16. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the alcohol component is present in a molar ratio of from 0.8:1 to 1.5:1 to the acid component.
17. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the alcohol component is present in a molar ratio of from 1.0:1 to 1.1:1 to the acid component.
18. The unsaturated, amorphous polyester as claimed in any of the preceding claims, which has an acid number of from 1 to 200 mg KOH/g, preferably from 1 to 100 mg KOH/g, more preferably from 1 to 50 mg KOH/g.
19. The unsaturated, amorphous polyester as claimed in any of the preceding claims, which has an OH number of from 1 to 200 mg KOH/g, preferably from 1 to 100 mg KOH/g, more preferably from 1 to 50 mg KOH/g.
20. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein assistants and additives are present.
21. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein assistants and additives are present which are selected from inhibitors, water and/or organic solvents, neutralizing agents, surface-active substances, oxygen scavengers and/or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, antiskinning agents, defoamers, antistats, thickening agents, thermoplastic additives, dyes, pigments, flame retardants, internal release agents, fillers and/or blowing agents.
22. The unsaturated, amorphous polyester as claimed in any of the preceding claims, wherein the alcohol component consists of at least 90% of the dicidol mixture of claims 1 and 2, and fumaric acid and/or maleic acid(anhydride) are present in a diol/acid ratio of from 0.9:1 to 1.1:1.
23. The unsaturated, amorphous polyester as claimed in claim 22, wherein adipic acid and/or phthalic acid/anhydride are additionally present as the acid component in a ratio of .alpha.,.beta.-unsaturated to additional acid of from 3:1 to 1:4, preferably from 1:1 to 1:2.
24. A process for preparing unsaturated, amorphous polyesters substantially comprising at least one .alpha.,.beta.-unsaturated dicarboxylic acid component and one alcohol component, wherein the alcohol component comprises a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)tricyclo[5.2.1.0 2,6]decane, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0 2,6]decane and 5,8-bis(hydroxymethyl)tricyclo[5.2.1.0 2,6]decane, each isomer may be present in the mixture in a proportion of from 20 to 40% and the sum of the three isomers is from 90 to 100%, and at least 5% of the mixture is present in the alcohol component of the polyester, by reacting the starting components at a temperature of from 150 to 270°C, preferably from 160 to 230°C, more preferably from 160 to 200°C.
25. The process as claimed in claim 24, wherein the reaction is effected in an inert gas atmosphere.
26. The process as claimed in claim 24 or 25, wherein the inert gas has an oxygen content of less than 50 ppm.
27. The process as claimed in at least one of claims 24 to 26, wherein starting components of claims 1 to 23 are used.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10212706A DE10212706A1 (en) | 2002-03-21 | 2002-03-21 | Unsaturated, amorphous polyester based on certain dicidol isomers |
| DE10212706.9 | 2002-03-21 | ||
| PCT/EP2003/001535 WO2003080703A1 (en) | 2002-03-21 | 2003-02-15 | Unsaturated, amorphous polyesters based on determined dicidol isomers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2472035A1 true CA2472035A1 (en) | 2003-10-02 |
Family
ID=27798034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002472035A Abandoned CA2472035A1 (en) | 2002-03-21 | 2003-02-15 | Unsaturated, amorphous polyesters based on certain dicidol isomers |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US7144975B2 (en) |
| EP (1) | EP1492834A1 (en) |
| JP (1) | JP2005527660A (en) |
| KR (1) | KR20040091149A (en) |
| CN (1) | CN1643028A (en) |
| AU (1) | AU2003210284A1 (en) |
| BR (1) | BR0308572A (en) |
| CA (1) | CA2472035A1 (en) |
| DE (1) | DE10212706A1 (en) |
| MX (1) | MXPA04009041A (en) |
| MY (1) | MY134367A (en) |
| NO (1) | NO20044228L (en) |
| PL (1) | PL370838A1 (en) |
| TW (1) | TW200305591A (en) |
| WO (1) | WO2003080703A1 (en) |
| ZA (1) | ZA200407526B (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2446419C (en) * | 2001-05-31 | 2010-07-20 | Inventio Ag | Equipment for ascertaining the position of a rail-guided lift cage with a code carrier |
| DE10242265A1 (en) | 2002-09-12 | 2004-03-25 | Degussa Ag | Adhesion-improving additive made from an unsaturated, amorphous polyester |
| DE10326893A1 (en) * | 2003-06-14 | 2004-12-30 | Degussa Ag | Resins based on ketones and aldehydes with improved solubility properties and low color numbers |
| DE10338562A1 (en) * | 2003-08-22 | 2005-03-17 | Degussa Ag | Radiation-curable resins based on ketone and / or urea-aldehyde resins and a process for their preparation |
| DE10338561A1 (en) * | 2003-08-22 | 2005-04-14 | Degussa Ag | Ketone-aldehyde resins, especially low water content cyclohexanone-formaldehyde resins with high thermal and yellowing resistance, and a method of preparation and use |
| DE102004005208A1 (en) * | 2004-02-03 | 2005-08-11 | Degussa Ag | Use of radiation-curable resins based on hydrogenated ketone and phenol-aldehyde resins |
| DE102004020740A1 (en) * | 2004-04-27 | 2005-11-24 | Degussa Ag | Polymer compositions of carbonyl-hydrogenated ketone-aldehyde resins and polyisocyanates in reactive solvents |
| DE102004031759A1 (en) | 2004-07-01 | 2006-01-26 | Degussa Ag | Radiation-curable, adhesion-improving composition of unsaturated, amorphous polyesters and reactive diluents |
| DE102004039083A1 (en) * | 2004-08-12 | 2006-02-23 | Degussa Ag | Tin-free, high-melting reaction products of carbonyl-hydrogenated ketone-aldehyde resins, hydrogenated ketone resins and carbonyl- and ring-hydrogenated ketone-aldehyde resins based on aromatic ketones and polyisocyanates |
| DE102004041197A1 (en) * | 2004-08-26 | 2006-03-02 | Degussa Ag | Radiation sensitive mass |
| DE102004049544A1 (en) * | 2004-10-12 | 2006-04-13 | Degussa Ag | Radiation-curable modified, unsaturated, amorphous polyesters |
| DE102004051861A1 (en) * | 2004-10-26 | 2006-04-27 | Degussa Ag | Use of an aqueous dispersion based on an unsaturated, amorphous polyester based on certain dicidol isomers |
| DE102004051862A1 (en) * | 2004-10-26 | 2006-04-27 | Degussa Ag | Dispersions of sulphonic acid-containing, unsaturated and amorphous polyesters based on certain dicidole isomers |
| KR100666480B1 (en) * | 2004-11-25 | 2007-01-09 | 주식회사 새 한 | Self-curable expanded polyester resin composition and molded product produced therefrom |
| DE102005002388A1 (en) * | 2005-01-19 | 2006-07-27 | Degussa Ag | Aqueous, radiation-curable modified, unsaturated, amorphous polyester |
| DE102005013329A1 (en) * | 2005-03-23 | 2006-11-16 | Degussa Ag | Low-viscosity uretdione group-containing polyaddition compounds, process for their preparation and use |
| DE102005017200A1 (en) | 2005-04-13 | 2006-10-19 | Degussa Ag | Use of a high-viscosity, largely amorphous polyolefin for producing a film |
| DE102005026765A1 (en) * | 2005-06-10 | 2006-12-14 | Degussa Ag | Back fixation of artificial turf raw material with hot melt adhesives based on amorphous poly-alpha-olefins and / or modified, amorphous poly-alpha-olefins |
| DE102006000646A1 (en) * | 2006-01-03 | 2007-07-12 | Degussa Gmbh | Composition for the preparation of universal pigment preparations |
| DE102006000645A1 (en) * | 2006-01-03 | 2007-07-12 | Degussa Gmbh | Universal pigment preparations |
| DE102006009079A1 (en) * | 2006-02-28 | 2007-08-30 | Degussa Gmbh | New carbonylhydrogenated ketone-aldehyde resin useful in lacquer industries, coating materials and for weathering |
| DE102007034866A1 (en) | 2007-07-24 | 2009-01-29 | Evonik Degussa Gmbh | Unsaturated polyester |
| DE102007034865A1 (en) | 2007-07-24 | 2009-01-29 | Evonik Degussa Gmbh | Coating compositions |
| DE102007057057A1 (en) | 2007-11-27 | 2009-05-28 | Evonik Degussa Gmbh | Uretdione group-containing polyurethane compositions which are curable at low temperature and contain adhesion-improving resins |
| US8604105B2 (en) | 2010-09-03 | 2013-12-10 | Eastman Chemical Company | Flame retardant copolyester compositions |
| US8758862B2 (en) | 2012-06-26 | 2014-06-24 | Prc Desoto International, Inc. | Coating compositions with an isocyanate-functional prepolymer derived from a tricyclodecane polyol, methods for their use, and related coated substrates |
| JP6065645B2 (en) * | 2013-02-27 | 2017-01-25 | 三菱化学株式会社 | Photosensitive resin composition, cured product obtained by curing the same, color filter, and liquid crystal display device |
| DE102013219555A1 (en) * | 2013-09-27 | 2015-04-02 | Evonik Industries Ag | Liquid adhesion-improving additive and process for its preparation |
| EP3243863A1 (en) | 2016-05-09 | 2017-11-15 | Evonik Degussa GmbH | Use of block copolymers in adhesives |
| KR20230154919A (en) | 2021-03-12 | 2023-11-09 | 알넥스 오스트리아 게엠베하 | coating composition |
| KR102444853B1 (en) | 2021-06-04 | 2022-09-19 | 에스케이케미칼 주식회사 | Tricyclodecane dimethanol composition and method for preparing same |
| KR102389695B1 (en) * | 2021-06-18 | 2022-04-21 | 에스케이케미칼 주식회사 | Tricyclodecane dimethanol composition and preparation method of the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE953117C (en) | 1953-12-17 | 1956-11-29 | Huels Chemische Werke Ag | Process for the production of unsaturated polyesters |
| JPS54143494A (en) * | 1978-04-28 | 1979-11-08 | Mitsubishi Petrochem Co Ltd | Unsaturated polyester resin composition |
| US4826903A (en) * | 1988-02-22 | 1989-05-02 | Eastman Kodak Company | Condensation polymer containing the residue of an acyloxystyrl compound and shaped articles produced therefrom |
| DE19805008A1 (en) * | 1998-02-07 | 1999-08-12 | Huels Chemische Werke Ag | Coatings based on thermoplastic polyester with the addition of an unsaturated polyester as additional resin |
| DE10242265A1 (en) * | 2002-09-12 | 2004-03-25 | Degussa Ag | Adhesion-improving additive made from an unsaturated, amorphous polyester |
| DE10261006A1 (en) * | 2002-12-24 | 2004-07-08 | Degussa Ag | Dispersions of amorphous, unsaturated polyester resins based on certain dicidol isomers |
-
2002
- 2002-03-21 DE DE10212706A patent/DE10212706A1/en not_active Withdrawn
-
2003
- 2003-02-15 CN CNA038066114A patent/CN1643028A/en active Pending
- 2003-02-15 US US10/502,189 patent/US7144975B2/en not_active Expired - Fee Related
- 2003-02-15 MX MXPA04009041A patent/MXPA04009041A/en not_active Application Discontinuation
- 2003-02-15 BR BR0308572-4A patent/BR0308572A/en not_active Application Discontinuation
- 2003-02-15 JP JP2003578446A patent/JP2005527660A/en active Pending
- 2003-02-15 PL PL03370838A patent/PL370838A1/en unknown
- 2003-02-15 EP EP03744708A patent/EP1492834A1/en not_active Withdrawn
- 2003-02-15 WO PCT/EP2003/001535 patent/WO2003080703A1/en active Application Filing
- 2003-02-15 CA CA002472035A patent/CA2472035A1/en not_active Abandoned
- 2003-02-15 KR KR10-2004-7014783A patent/KR20040091149A/en not_active Withdrawn
- 2003-02-15 AU AU2003210284A patent/AU2003210284A1/en not_active Abandoned
- 2003-03-19 MY MYPI20030965A patent/MY134367A/en unknown
- 2003-03-20 TW TW092106188A patent/TW200305591A/en unknown
-
2004
- 2004-09-20 ZA ZA200407526A patent/ZA200407526B/en unknown
- 2004-10-06 NO NO20044228A patent/NO20044228L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE10212706A1 (en) | 2003-10-02 |
| KR20040091149A (en) | 2004-10-27 |
| JP2005527660A (en) | 2005-09-15 |
| TW200305591A (en) | 2003-11-01 |
| BR0308572A (en) | 2005-01-04 |
| PL370838A1 (en) | 2005-05-30 |
| US20050124780A1 (en) | 2005-06-09 |
| NO20044228L (en) | 2004-10-06 |
| US7144975B2 (en) | 2006-12-05 |
| MY134367A (en) | 2007-12-31 |
| EP1492834A1 (en) | 2005-01-05 |
| CN1643028A (en) | 2005-07-20 |
| AU2003210284A1 (en) | 2003-10-08 |
| ZA200407526B (en) | 2005-08-29 |
| WO2003080703A1 (en) | 2003-10-02 |
| MXPA04009041A (en) | 2005-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7144975B2 (en) | Unsaturated amorphous polyesters based on certain dicidol isomers | |
| US6881785B2 (en) | Dispersions of amorphous unsaturated polyester resins based on particular Dicidol isomers | |
| KR101106016B1 (en) | Branched amorphous polyester-based macropolyols with narrow molecular weight distribution | |
| CN104379553B (en) | Functional norbornanyl ester derivatives, polymers and process for preparing same | |
| US7687569B2 (en) | Radiation curable composition consisting of unsaturated amorphous polyesters and reactive dilutant agents | |
| NZ528158A (en) | Adhesion promoter additive comprising an unsaturated, non-crystalline (amorphous) polyester | |
| US7135522B2 (en) | Dispersions of amorphous urethanized unsaturated polyester resins based on particular dicidol isomers | |
| EP0031977B1 (en) | Unsaturated polyester composition, its preparation and use | |
| US6555623B1 (en) | Preparation of unsaturated polyesters | |
| NZ535437A (en) | Unsaturated, amorphous polyesters based on certain dicidol isomers | |
| EP1423450B1 (en) | Process for making reactive unsaturated polyester resins from 2-methyl-1,3-propanediol | |
| Yu | NOVEL SYNTHETIC METHODS FOR BICYCLIC COATING RESIN | |
| JPH0812729A (en) | Curable oligoester resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |