NZ535437A - Unsaturated, amorphous polyesters based on certain dicidol isomers - Google Patents
Unsaturated, amorphous polyesters based on certain dicidol isomersInfo
- Publication number
- NZ535437A NZ535437A NZ535437A NZ53543703A NZ535437A NZ 535437 A NZ535437 A NZ 535437A NZ 535437 A NZ535437 A NZ 535437A NZ 53543703 A NZ53543703 A NZ 53543703A NZ 535437 A NZ535437 A NZ 535437A
- Authority
- NZ
- New Zealand
- Prior art keywords
- acid
- unsaturated
- amorphous polyester
- present
- alcohol component
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 51
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 18
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 16
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 15
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 14
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000001361 adipic acid Substances 0.000 claims description 9
- 235000011037 adipic acid Nutrition 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 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
- 239000011976 maleic acid Substances 0.000 claims description 7
- 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
- 238000000034 method Methods 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
- 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
- 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
- 238000004519 manufacturing process Methods 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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-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
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 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
- 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
- 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
- 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
- 239000007795 chemical reaction product Substances 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
- 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
- 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims 2
- 230000009477 glass transition Effects 0.000 claims 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims 1
- 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 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 102100033320 Lysosomal Pro-X carboxypeptidase Human genes 0.000 claims 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims 1
- 108010057284 lysosomal Pro-X carboxypeptidase Proteins 0.000 claims 1
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 abstract 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 abstract 1
- 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 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
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Disclosed is an unsaturated, amorphous polyester comprising at least one alpha,beta-unsaturated dicarboxylic acid component and one alcohol component, wherein: the alcohol component comprises a dicidiol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)-tricyclo [5.2.1.02,6]decane, 4,8-bis-(hydroxymethyl)tricycle [5.2.1.02,6]decane and 5,8-bis(hydroxymethyl)tricycle [5.2.1.02,6]decane, wherein each isomer is present in the mixture in a proportion of 20 to 40% and the sum of the three isomers is 90-100%, and at least 5% of the mixture is present in the alcohol component of the polyester.
Description
New Zealand Paient Spedficaiion for Paient Number 535437
O.Z. 6007
5354
Unsaturated/ amorphous polyesters based on certain dicidol isomers
The invention relates to unsaturated, amorphous 5 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 10 diols. Their properties depend substantially on the type and ratio of the starting materials.
The bearers of the polymerizable double bonds used are usually a,p-unsaturated acids, primarily maleic acid 15 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 2 0 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 25 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 30 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 35 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.
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, or to at least provide the public with a useful alternative. This object is_ achieved as will be illustrated henceforth.
/ j
The invention provides unsaturated, Amorphous polyesters comprising at least one a, (^-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. O2,6] decane and 5, 8-bis (hydroxymethyl) tricyclo [5.2.1. 02,s] decane,
2 0 where each isomer may be present in the mixture in a proportion of from 2 0 to 4 0% 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 a,P-unsaturated dicarboxylic acid component and one alcohol component,
3 0 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,s] decane and 5 , 8-bis (hydroxymethyl) tricyclo 35 [5.2.1.02,6] decane,
each isomer may be present in the mixture in a proportion of from 2 0 to 4 0% and the sum of the three isomers is from 90 to 100%,
,NTEI i i-fTUAL PROPERTY O'-HCE OF N.Z.
\ 3 APR eiCBIVEB
O.Z. 6007
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 5 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 10 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, 4,8-15 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 2 0 to 40% and the sum of the three isomers is from 90 to 100%, preferably from 95 to 100%,
2 0 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 25 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 abovementioned isomers, like the cis- and trans-isomers, cannot be differentiated under normal, 30 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
3 5 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
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 glycol, 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,p-unsaturated dicarboxylic acid. The unsaturated polyester resins preferably comprise citraconic acid, fumaric acid, itaconic acid, maleic 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, methyltetrahydrophthalie acid, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedicarboxylic 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
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 5 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 10 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.
2 0 In one preferred embodiment I, the saturated 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 25 [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 maleic acid/anhydride. In a further preferred embodiment II, the polyesters comprise the abovementioned starting
3 0 components as under I, but additionally a further acid selected from adipic acid and phthalic acid/anhydride,
where the ratio of a,P-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
O.Z. 6007
of from -30 to +80°C, preferably from -20 to +50°C, more preferably from -10 to +40°C.
The polyesters according to the invention may also 5 comprise assistants and additives which are selected from inhibitors, water and/or 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 are.
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.
2 0 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:
Claims (3)
- O.Z. 6007 - 7 - Examples Starting component: dicidol mixture (claim 1) in an isomeric ratio of approximately 1:1:1 5 Example 1 Dodecanedioic 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 10 end, the fumaric acid is initially esterified with dicidol over the course of one hour and then the adipic acid is added. Mn = 2200 g/mol, Mw = 5500 g/mol, glass transition temperature 4°C. 15 Example 2 Adipic acid and maleic 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 3 7 mg KOH/g are attained. To this 20 end, the maleic 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. 8 Claims: 1. An unsaturated, amorphous polyester comprising at 5 least one a,^-unsaturated dicarboxylic acid component and one alcohol component, wherein the alcohol component comprises a dicidol mixture of the isomeric compounds 3,8-bis(hydroxymethyl)-10 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 2 0 to 40% and the sum of the 15 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 20 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 25 are present.
- 3. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein 3 0 the acid component additionally comprises aromatic and/or aliphatic and/or cycloaliphatic monocarboxylic acids and/or dicarboxylic acids and/or polycarboxylic acids. 3 5 4. The unsaturated, amorphous polyester as claimed m any one of the preceding claims, wherein the acid component consists partly or anhydrides and/or alkyl esters. ft&PHRTY OrFICE OF N.z. 1 3 APR 2006 LfciGElVEB 9 5. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein the alcohol component comprises further linear 5 and/or branched, aliphatic and/or cycloaliphatic and/or aromatic diols and/or polyols. 6. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, 10 wherein the a,P-unsaturated dicarboxylic acid present is citraconic, fumaric, itaconic, maleic and/or mesaconic acid. 15 7. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein the additional acids present are phthalic acid, isophthalic acid, terephthalic acid, 1,4-20 cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-2 5 ethylhexanoic acid, pyromellitic acid and/or trimellitic acid, their anhydrides and/or methyl esters. 30 35 The unsaturated, amorphous polyester as claimed in any one 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, i-r-im<=>i-.hyl ol sthana trimethylolpropane and/or pentaerythrit dl! i i tl'-'iCT'JAL PROPERTY ' OFFICE OF N.Z. 1 3 APR 2006 received 10 9. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein at least 20% of the alcohol component consists of 5 the isomers of claim 1 or 2. 10. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein 10 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 one of the preceding claims, 15 wherein at least 90% of the alcohol component consists of the isomers of claim 1 or 2. 20 12. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein at least 100% of the alcohol component consists of the isomers of claim 1 or 2. 25 13. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein the a,p-unsaturated acid component present is fumaric acid and/or maleic acid/anhydride. 30 14. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein the further dicarboxylic acid component present is 35 adipic acid and/or phthalic acid/anhydride. 15. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, I .vu'rry-.L PRCr-rKTY " o-HG or N.Z. wherein 13 APR RECEDES 11 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 one of the preceding claims, 5 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 one of the preceding claims, 10 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 one of the preceding claims, 15 which has an acid number of from 1 to 200 mg KOH/g. 19. The unsaturated, amorphous polyester as claimed in claim 18, which has an acid number of from 1 to 100 mg KOH/g. 20 20. The unsaturated, amorphous polyester as claimed in claim 18 or claim 19, which has an acid number of from 1 to 50 mg KOH/g. 21. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, 25 which has an OH number of from 1 to 200 mg KOH/g. 22. The unsaturated, amorphous polyester as claimed in claim 21, , . — ~ ..;-rTUAL PROPERTY which j C^ICE OF N.Z. 30 has an OH number of from 1 to 100 mg KOH/c . 1 3 APR 2006 seseiVED , .,TrM.'-:-.TJAL PRCP -RTY OFFICE OF N.Z. 12 L 1 s APR 2006 SICK 23. The unsaturated, amorphous polyester as claimed in claim 21 or claim 22, which has an OH number from 1 to 50 mg KOH/g. 5 24. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein assistants and additives are present. 25. The unsaturated, amorphous polyester as claimed in 10 any one of the preceding claims, wherein assistants and additives are present which are selected from inhibitors, water and/or solvents, neutralizing agents, surface-active substances, 15 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 20 retardants, internal release agents, fillers and/or blowing agents. 26. The unsaturated, amorphous polyester as claimed in any one of the preceding claims, wherein 25 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. 27. The unsaturated, amorphous polyester as claimed in 30 claim 26, wherein adipic acid and/or phthalic acid/anhydride are additionally present as the acid component in a 13 i mT£L -!-.CT'JAL PRC/ sRTY Or-FICE OF N.z. 1 i APR 2006 RECHIVEB ratio of a,p-unsaturated to additional acid of from 3:1 to 1:4. 28. The unsaturated, amorphous polyester as claimed in claim 27, 5 wherein the ratio of a, {3-unsaturated to additional acid is from 1:1 to 1:2. 29. A process for preparing unsaturated, amorphous polyesters substantially comprising at least one 10 a,p-unsaturated dicarboxylic acid component and alcohol component, wherein the alcohol component comprises a dicidol mixture of the isomeric compounds 3,8-bis (hydroxymethyl) 15 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, each isomer may be present in the mixture in a proportion of from 20 to 40% and the sum of the 20 three isomers is from 90 to 100%, and at least 5% of the mixture is present in the alcohol component of the polyster, by reacting the starting components at a temperature of from 150 to 270°C. 25 30. A process for preparing unsaturated, amorphous polyesters according to claim 29 by reacting the starting components at a temperature of from 60 to 230 °C. 31. A process for preparing unsaturated, amorphous 30 polyesters according to claim 29 or claim 30 by reacting the starting components at a temperature of from 160 to 200°C. 14 % 10 15 20 32. The process as claimed in any one of claims 29 to wherein the reaction is effected in an inert gas atmosphere. 33. The process as claimed in any one of claims 29 to wherein the inert gas has an oxygen content of less than 50 ppm. 34. The process as claimed in any one of claims 29 to wherein starting components of claims 1 to 27 are used. 35. An unsaturated, amorphous polyester according to any one of claims 1 to 28, substantially as herein described with reference to Example 1 and/or Example 2. 36. The process according to any one of claims 29 to 34, substantially as herein described with reference to Example 1 and/or Example 2. 31 32 DEGUSSA AG By BALDWINS i.-iTELP.fCT'JAL PROPERTY OFFICE OF N.Z. 1 3 APR 2006 RECEIVE®
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE20212706 | 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 |
|---|---|
| NZ535437A true NZ535437A (en) | 2006-07-28 |
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ID=36694510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NZ535437A NZ535437A (en) | 2002-03-21 | 2003-02-15 | Unsaturated, amorphous polyesters based on certain dicidol isomers |
Country Status (1)
| Country | Link |
|---|---|
| NZ (1) | NZ535437A (en) |
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2003
- 2003-02-15 NZ NZ535437A patent/NZ535437A/en unknown
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