NZ535437A - Unsaturated, amorphous polyesters based on certain dicidol isomers - Google Patents

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)

1. 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. 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. 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®