Unsaturated polyesters are polymers having structural units linked by ester groupings, and they can be manufactured by the condensation of carboxylic acids with polyhydric alcohols. Low molecular weight unsaturated polyesters are usually produced from maleic anhydride with diethylene glycol or, alternatively, other carboxylic acids or anhydrides such as fumaric acid, and glycols such as propylene glycol are used. Typically, the obtained unsaturated polyesters are in the form of a rather viscous oil. Low molecular weight unsaturated polyesters will crosslink in the presence of a peroxide by copolymerization with reactive diluents. Unsaturated polyester resins typically contain volatile unsaturated organic monomers such as styrene as the reactive diluent. In commercially available unsaturated polyester resin applications, up to 50 % of styrene or other vinyl monomers are used. During curing, some of the organic monomer is usually lost in the atmosphere, 10-20 % of the total amount of the monomer may be lost during resin spray-up and lamination and 30-50 % during gelcoat spraying and thus these emissions cause occupational safety hazards and are also a problem because of environmental considerations. In most countries legislation introduced in recent years requires a reduction in the amount of volatile organic compounds (VOC) which may be released to the atmos- phere. Several methods have been proposed for reducing VOC emissions, for example the replacement of the reactive diluent with a less volatile reactive diluent.

This approach has led to slower curing times and/or incomplete curing at normal ambient temperatures. Another approach is a reduction in the amount of the reactive diluent in the composition. This approach has led to an increase in the viscosity of the resin beyond useable values. If the viscosity increase is compensated for by the

use of a lower molecular weight polyester then poor final product properties will result. Still another approach has been the use of a suppressant which reduces the loss of VOCs. The suppressants are often waxes which may lead to a reduction in the interlaminar adhesion of laminating layers. On the other hand, requirements for the mechanical properties and for the quality of polyester resins and of their applica- tions are constantly tightening, which can be seen especially in the field of marine applications. Thus, there is a clear need for polyester resins and their applications with low reactive diluent emissions and with superior properties and quality.

An unsaturated polyester resin is presented in DE 25 27 675 wherein the polyester resin comprises an a, ß-ethylenically unsaturated polyester, the terminal groups of which comprise a high amount of residues of monoalcohols and a copolymerizable monomer. High amounts of monoalcohols yield rather expensive polymers with shorter molecular chains and poor mechanical properties. Additionally, the use of maleic anhydride as the sole source for a carboxylic acid derivative leads to resins with inferior chemical resistance and mechanical properties.

European patent publication EP 0 475 661 relates to unsaturated polyester resins which have improved hydrolytic stability and low molecular weights (Mw) of about 300 to 2500, and which are chain-stopped or endcapped with monofunctional alcohols or acids. The chain-stopped resins can be modified by addition of polyisocyanate and hydroxy acrylate to prepare resins for artificial marble, artificial onyx, fiber glass reinforced products, laminates, sheet moulding compounds and resin transfer moulding applications. Alternatively, the resins can also be modified by adding a polyisocyanate, a hydroxy acrylate and a dicyclopentadiene based unsaturated polyester resin to produce a composition suitable for low profile marine applications. These unsaturated polyesters are prepared by the condensation of dicarboxylic acids or anhydrides with polyhydric alcohols in the presence of chain- stopping monofunctional acids or alcohols.

US 5 688 867 describes a polyester resin comprising from about 5 wt% to about 50 wt% of a reactive diluent and from about 50 wt% to about 95 wt% of an unsatu-

rated polyester resin prepared from at least one component selected from a group consisting of from about 0.5 mol% up to about 8 mol% of polyhydric alcohol having at least three hydroxyl groups, and at least one transesterification catalyst, from about 2 mol% up to about 12 mol% of a reaction product of a polyol and a fatty carboxylic acid, and from about 2 mol% up to about 12 mol% of a fatty reactant selected from the group consisting of a fatty primary alcohol, a fatty epoxide, a fatty monocarboxylic acid and mixtures thereof, wherein each member of the group has up to about 100 carbon atoms. The invention also relates to mixtures of polyester resins with conventional polyester resins. This invention provides resins and methods which have a low emission of volatile organic compounds.

An object of the present invention is to provide unsaturated polyester resins which have a higher molecular weight, a low viscosity and which are readily soluble in reactive diluents. Another object of the present invention is to provide unsaturated polyester resins for applications such as general purpose resins and gelcoats with reduced volatile organic compound emissions in order to reduce the risk of occupa- tional safety hazards and environmental concerns. Additionally methods for the manufacture of such unsaturated polyester resins and unsaturated polyester systems including products and applications, with good physical properties such as acceptable mechanical strength, weathering resistance and with good final product properties are desired.

Characteristic features of the unsaturated polyester resins, of the manufacture thereof and of the use according to the invention are stated in the claims.

It has been found that the above-mentioned objects can be reached with the following solution. In accordance with the present invention unsaturated polyester resins are prepared by condensation of at least two unsaturated carboxylic acids or derivatives thereof and at least one of them is an unsaturated aromatic carboxylic acid or a derivative thereof, with at least two diols and at least one of them is an aliphatic branched diol, in the presence of at least one monoalcohol, and the obtained unsatu- rated polyester or mixtures of unsaturated polyesters are diluted in a reactive diluent

or in mixtures of reactive diluents. Optionally one or more other carboxylic acids and one or more polyhydric alcohols having at least three hydroxyl groups may also be used as well as one or more modifying chemicals. The specific combination of starting materials i. e. part of the unsaturated carboxylic acids are of aromatic nature, part of the alcohols are certain aliphatic branched diols, used with combination of a monoalcohol (s), yields the cured products the desired properties.

Suitably unsaturated carboxylic acids or derivatives thereof, such as maleic acid, maleic anhydride and fumaric acid and the like are used. Preferably the unsaturated aromatic carboxylic acid or a derivative thereof is phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid or hexahydrophthalic anhydride. Suitable other carboxylic acids are adipic acid, trimellitic acid, trimellitic anhydride, dimethylmalonic acid, hydroxypivalic acid, 1,4-cyclohexanedicarboxylic acid. Unsaturated aromatic and other carboxylic acids or mixtures thereof are used in a total amount of 30-70 mol% and preferably 40-60 mol%.

Suitable diols are such as ethylene glycol, propylene glycol, diethylene glycol, di- propylene glycol, neopentyl glycol, triethylene glycol, tripropylene glycol, cyclo- hexane dimethanol, hexane diol, butylene glycol, hydroxypivalyl hydroxy pivalate, 2-ethyl-1,3-hexanediol, 1,3-propanediol, 1,5-pentanediol, 2,2-diethyl-1,3- propanediol, propylene glycol, 1,2,3-propanetriol polymer with methyl oxirane, trimethylolpropane polymer with methyl oxirane, 2-methyl-1,3-propanediol and 2- methyl-2,4-pentanediol. Preferable aliphatic branched diols are 2,2,4-trimethyl-1,3- pentanediol and 2-butyl-2-ethyl-1,3-propanediol, which are used in an amount of 0.5-8 mol%, preferably 2-6 mol%. The diols or mixtures thereof are used in a total amount of 30-70 mol% and preferably 40-60 mol%. The amount of 40-60 mol% is especially suited for applications requiring extremely good weather tolerance in demanding conditions such as in gelcoats for marine applications.

Optionally, polyhydric alcohols having at least three hydroxyl groups, such as trimethylol propane, trimethylol ethane, pentane erythritol, glycerine, and the like

and mixtures thereof may be used in amounts of 0.5-20 mol% and preferably 1-10 mol%, the amount depending on the desired properties of the application. The excess of 4-25 mol% of total alcohols is suitable and preferably an excess of 5-20 mol% is used.

Monoalcohols are used as endcappers and suitable ones are benzyl alcohol, phenyl- ethanol, cyclohexanol, 2-ethylhexanol, 2-cyclohexyl ethanol, 2,2-dimethyl-1- propanol and layryl alcohol, which are used in an amount of 0.5-10 mol%, preferably 2-6 mol%.

The optional modifying chemicals include monofunctional acids, such as benzoic acid, lauric acid, 2-ethylbuturic acid, 2-ethylhexanoic acid and phenylacetic acid, and glycidyl ester of neodecanoic acid, epoxystyrene and dicyclopentadiene. Mono- alcohols and optional modifying chemicals or mixtures thereof are used in a total amount of 0.5-20 mol% and preferably 4-15 mol%.

The molar ratio of aliphatic branched diols to monoalcohols is 5: 1-1: 5 and prefer- ably 2: 1-1: 2.

The reactive diluent is preferably an ethylenically unsaturated, monomeric com- pound, which compound includes allyl and vinyl compounds conventionally used for the preparation of unsaturated polyester based moldings, impregnating and coating compositions. Examples of reactive diluents include styrene, substituted styrenes, such as methoxystyrene, divinylbenzene, 4-ethylstyrene, 4-methylstyrene, 4-t- butylstyrene, p-chlorostyrene or vinyltoluene, esters of acrylic acid and methacrylic acid with alcohols or polyols, such as methyl methacrylate, butyl acrylate, ethyl- hexyl acrylate, hydroxpropyl methacrylate, lauryl acrylate, stearyl methacrylate, lauryl methacrylate, butanediol diacrylate, ethyleneglycol dimethacrylate, di- ethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, propyleneglycol dimethacrylate, dipropyleneglycol dimethacrylate, tripropyleneglycol di- methacrylate and trimethylolpropane triacrylate, allyl esters, such as diallyl phthalate, and vinyl esters, such as vinyl ethylhexanoate, vinyl pivalate, limonene,

dipentene, vinyl ethers, indene, allyl benzene, and the like and mixtures thereof.

Preferred reactive diluents are styrene, a-methylstyrene, vinyltoluene, divinyl- benzene, methyl methacrylate, hydroxpropyl methacrylate, ethyleneglycol di- methacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate and mixtures of volatile diluents with less volatile diluents such as mixtures of styrene or derivatives thereof with said methacrylates. The amount of the reactive diluent or mixtures thereof varies between 15 and 50 wt%, preferably between 20 and 35 wt%.

Preferable starting materials for the manufacture of resins especially suited for marine applications comprise phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride and hexahydrophthalic anhydride as aromatic unsaturated carboxylic acids or derivatives thereof. Maleic anhydride is a suitable unsaturated carboxylic acid or a derivative thereof, 1,4-cyclohexanedicarboxylic acid and adipic acid are suitable as other carboxylic acids or derivatives thereof. and 2- butyl-2-ethyl-1,3-propanediol are suitable aliphatic branched diols. Propylene glycol, dipropylene glycol, diethylene glycol, neopentyl glycol, cyclohexane dimethanol, hexanediol, hydroxypivalyl hybroxypivalate, 1,5-pentanediol, 1,3-propanediol, 2- ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2- methyl-2,4-pentanediol, polypropylene glycol, 1,2,3-propanetriol polymer with methyl oxirane and trimethylolpropane polymer with methyl oxirane are suitable as other diols. Trimethylol propane is suitable as an optional polyhydric alcohol. As a monoalcohol benzyl alcohol, phenyl ethanol, cyclohexanol, 2-cyclohexylethanol, 2- ethylhexanol, 2,2-dimethyl-1-propanol are suitable. Glycidyl ester of neodecanoic acid, epoxystyrene, benzoic acid, phenylacetic acid are suitable as optional modifying chemicals.

Preferable starting materials for the manufacture of resins especially suited for general purpose resins and gelcoats comprise phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride and terephthalic acid as aromatic unsaturared carboxylic acids or a derivative thereof. Maleic anhydride is a suitable unsaturated carboxylic acid or a derivative thereof, trimellitic acid, dimethylmalonic acid and hydroxy- pivalic acid are suitable as other unsaturated carboxylic acids or derivatives thereof,

and 2-butyl-2-ethyl-1,3-propanediol are used as aliphatic branched diols. Propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tripropyleneglycol, neopentyl glycol, hexane- diol, butylene glycol, hydroxypivalyl hybroxypivalate, 1,5-pentanediol, hexanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, polypropylene glycol, 1,2,3-propanetriol polymer with methyloxirane and trimethylolpropane polymer with methyl oxirane are suitable as other diols and trimethylol propane, trimethylol ethane, pentane erythritol and glycerine are suitable as optional poly- hydric alcohols. Benzyl alcohol, 2-ethyl-hexanol, 2,2-dimethyl-1-propanol and layryl alcohol are suitable as monoalcohols and benzoic acid, 2-ethylhexanoic acid, lauric acid, phenyl acetic acid and dicyclopentadiene may be used as optional modifying chemicals.

General purpose resins and gelcoats are suitable for applications such as fiber glass reinforced products, artificial marble, artificial onyx, sheet moulding compounds, resin transfer moulding applications, hand and spray lamination applications, sanitary applications, pigmented and clear gelcoats and topcoats/enamels.

The unsaturated polyester resin according to the invention comprises 20-85 wt%, preferably 30-80 wt% of at least one unsaturated polyester having a weight average molecular weight of 2000-6000, preferably 2600-6000, prepared from 1) 30-70 mol%, preferably 40-60 mol% of at least two unsaturated carboxylic acids or derivatives thereof and at least one of them is an unsaturated aro- matic carboxylic acid or a derivative thereof, and optionally of a carbxylic acid or a derivative thereof; 2) 30-70 mol%, preferably 40-60 mol% of at least two diols and at least one of them is an aliphatic branched diol, preferably 2,2,4-trimethyl-1,3-pentane- diol and/or 2-butyl-2-ethyl-1,3-propanediol and the amount of the aliphatic branched diol/diols is 0.5-8 mol%, preferably 2-6 mol%.

3) 0.5-10 mol%, preferably 2-6 mol% of at least one monoalcohol, 4) optionally a modifying chemical/chemicals and the total amount of mono- alcohols and modifying chemicals is 0.5-20 mol%, preferably 1-15 mol%;

5) optionally 0.5-20 mol%, preferably 1-10 mol% of a polyhydric alcohol/ alcohols having at least three hydroxyl groups and 15-50 wt%, preferably 20-35 wt% of at least one reactive diluent.

Additionally an esterification catalyst for decreasing of reaction time may optionally be used in the manufacture of the linear unsaturated polyesters. The catalyst may be present in an amount known to a man skilled in the art. Suitable esterification catalyst include metal-containing catalysts, such as metal oxides, metal hydroxides and metal acetates. The progress of the polymerization reaction is conventionally monitored by means of acid number.

Suitable and preferred alternatives for the components in the resins according to the invention are listed above.

The unsaturated polyesters according to the invention can be prepared in a single- stage or in a two-stage process. A solvent process wherein an azeotropic solvent, such as xylene is used to facilitate water removal is also suitable. The unsaturated polyester resins according to the invention are preferably manufactured in the following manner. The alcohols and carboxylic acids or derivatives thereof are charged to a suitable reaction vessel and the reaction is carried out at a temperature of about 180-240 °C, preferably 190-230 °C and it is continued until an acid number of 1-50, preferably 3-20 and an I. C. I. (cone and plate) viscosity of 1-10 Pas/125 °C, preferably 3-8 Pas/125 °C of the linear unsaturated polyester are reached. Finally the linear unsaturated polyester or mixtures of linear unsaturated polyesters are dissolved in a suitable reactive diluent or a mixture thereof. In the case maleic anhydride and isophthalic acid or terephthalic acid are used, all acids except maleic anhydride are charged with alcohols. The reaction is then allowed to proceed until the reaction mixture is clear, and the acid number is below 70, more preferably below 30. After cooling the maleic anhydride is added. The encapper, monohydric alcohol can be added at the first or the second stage.

Components or additives generally known in the art may be employed in the process.

The unsaturated polyesters according to the invention exhibit acid numbers from 1 to 50, based on solids or nonvolatile content, and preferably the acid number is 3-20. The I. C. I viscosity of the linear unsaturated polyester is between 1-10 Pas/125 °C, preferably 3-8 Pas/125 °C, the weight average molecular weight Mw of the linear unsaturated polyester is 2000-6000, preferably 2600-6000 and the number average molecular weight Mn is 700-2500, preferably 1000-2200.

Regardless of the longer chain length and higher molecular weight, the viscosity remains low and the solubility of the unsaturated polyester in reactive diluents such as styrene is good, which significantly reduces the need for reactive diluents, down to 20-35 wt%. Because of their solubility and viscosity properties, the unsaturated polyesters can be dissolved in smaller amounts of reactive diluents, and thus the emission of VOCs from the products manufactured from the resins according to the invention are significantly lower. The low styrene content in the resin results also in a more efficient material transfer and less loss of the product in applications because the product is less atomized. Mostly due to the higher molecular weight of the unsaturated polyester, the cured unsaturated polyester resins retain the mechanical properties such as weathering resistance, chemical resistance and UV-resistance and thus they are well suited especially for demanding applications. The unsaturated polyesters according to the invention are compatible and readily soluble in reactive diluents, such as styrene and the respective resins have good curing properties.

Polyester derived products with superior surface quality, thermocycling and UV resistance and clarity are conveniently manufactured from the unsaturated polyester resins according to the invention.

The unsaturated polyester resins according to the invention are useful for a variety of applications such as general purpose resins, coating materials and reinforcing materials. They have utility as resins with reduced reactive diluent emissions for panels, laminates, fiber glass reinforced products, artificial marble, artificial onyx, sheet moulding compounds, resin transfer moulding applications, sanitary applica-

tions and as base resins, they are also well suited for demanding marine applications, and products such as pigmented or clear gelcoats and topcoats/enamels can be manufactured which meet the requirements described above.

The resins for marine applications have very tight requirements and Det Norske Veritas (DNV) approval and Lloyd's approval are required in several countries for polyester resins used for marine purposes. DNV requirements for mechanical properties of resins used in gelcoats for marine applications (Tentative Rules for Certification and Classification of Boats, Part 7 Chapter 1, Approval of Raw Materials, December 1997) are presented in the following: -Tensile strength 50 MPa.

-Tensile modulus > 3000 MPa.

-Bending temperature (HDT) 2 70 °C.

-Water absorption < 80 mg/piece/28 d.

-Barcol hardness 2 35.

The unsaturated polyester resins according to the invention may be formulated together with suitable additives known in the art to form gelcoats, resins and polyester based products.

Gelcoats are curable compositions which contain at least one of the above unsatu- rated polyester resins with additives. Suitable additives include thixotropic agents, thixotropy enhancers, suppressants, surface tension agents, co-promoters, promoters, air release agents, fillers, wetting agents, levelling agents and pigments.

The thixotropic agents comprise silica compounds such as fumed silica and precipi- tated silica and inorganic clays like bentonite and hectorite clay. Thixotropy enhancers comprise propyle glycol and ethylene glycol and derivatives thereof.

Promoters are usually added to unsaturated polyester resins to accelerate the decomposition of a peroxide initiator into free radicals and to thereby initiate or speed up the curing of the composition. The promoters are generally metal com- pounds, such as cobalt, manganese, iron, vanadium, copper, and aluminum salts of

organic acids, such as octoate or naphthenate salts. Co-promoters are widely used in promoter systems and suitable ones are organic amines like dimethylaniline, diethyl- aniline, 2-aminopyridine, N, N-dimethyl-acetoacetamide, acetoacetanilide or other organic compounds like ethyl acetoacetate, methyl acetoacetate and N, N-dimethyl-p- toluidine. Inhibitors are used for adjusting storage stability and gel time, and suitable inhibitors comprise hydroquinone, toluhydroquinone, mono-tert-butylhydroquinone, hydroquinone monomethyl ether p-benzoquinone, 2,5-di-tert-butylhydroquinone.

Gelcoats may also contain fillers such as talc, calcium carbonate, magnesium carbon- ate, barium carbonate, aluminium trihydroxide, calsium sulfate, magnesium sulfate, barium sulfate, chopped glassfiber and the like. Various pigments are typically used in gelcoats and titanium dioxide is a suitable one. Air release agents, wetting additives, surfactants or levelling additives based on silicone and fluorocarbon, and various modified polymers like acrylate and urethane may be added to gelcoats.

Suppressants for reducing organic emissions may be included in gelcoats and such as polyethers, alcanoic acid esters of propoxylated phenols, propoxylated bisphenols or hydoxypropylphthalates, polyetherpolysiloxane blockcopolymers, waxes and the like are suitable. Various peroxides for curing/crosslinking are used and peroxides like methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl peroctoate, di-t- butyl peroxide, benzoyl peroxide and the like are suitable.

The unsaturated polyester resins and applications based thereon are well suited for hand lay up lamination, spray lamination, resin lamination, pultrusion, sheet moulding compounding, bulk moulding compounding and applications well known to the man skilled in the art. The obtained products achieve to reduced volatile organic compound emissions, they have acceptable geltime, good adhesion, weather- ing resinstance, low water absorption and good final product properties. The UV- resistance, low shrinkage properties and hydrolytic stability of the products are good due to the lower reactive diluent content and due to other properties of the resins.

Following examples provide a better understanding of the present invention, how ever they are not be intended as limiting the scope thereof.

EXAMPLE 1 General purpose resins 1A, 1B, 1C and 1D

Resin Starting material (mol%) 1A 1B 1C 1D Propylene glycol 12 12 12 10 Neopentyl glycol 33 33 33 33 2-Butyl-2-ethyl-1, 3-propanediol 4 5 4 5 1,4-Cyclohexanedicarboxylicacid 4 Isophthalic acid 15 14 14 14 Adipic acid 3 3 3 Maleic anhydride 28 28 28 27 2-Ethylhexanoic acid 2 4 2-Phenylethylalcohol 4 Benzyl alcohol 3 5 2-Ethylhexanol 5 Property of linear unsaturated polyester: Cook end points: I. C. I./150 °C * (Pas) 1.3 1.7 1.4 0.8 Acid number 12 15 19 20 Property of linear unsaturated polyester in styrene: I. C. I./25 °C (Pas) 3.8 3 3.5 Styrene % 30 35 35 Mw 3200 3000 2800 3100 Mn 1700 1100 1600 1600 Mechanical properties of cured resin in styrene Tensile strength (MPa) 40 65 40 Tensile elongation (%) 3 7 6 Tensile modulus (MPa) 2600 3200 1950 HDT (°C) 59 57 50 Barcol 33 36 22 * I. C. I viscosity was measured at 150°C yielding lower values when compared with 125 °C EXAMPLE 2 General purpose resins 2A, 2B, 2C and 2D

Resin Starting material (mol%) 2A 2B 2C 2D Neopentylglycol 34 32 33 26 Propylene glycol 9 12 7 11 Dipropylene glycol 4 3 2-Butyl-2-ethyl-1,3-propanediol 5 5 6 10 Isophthalic acid 12 11 13 14 Adipic acid 5 3 Maleic anhydride 29 31 32 31 Benzyl alcohol 5 6 6 5 Property of linear polyester: Cook end points: I. C. I./125 °C (Pas) 4.3 2.8 3.4 4 Acid number 18 9 10 16 Property of linear polyester in styrene: I. C. I./25 °C (Pas) 35 % styrene 2.6 2.4 2.7 3 Mw 2800 2600 2840 2500 Mn 1300 1200 1500 1400 Mechanical properties of cured resin in 40 % styrene Tensile strength (MPa) 60 57 48 60 Tensile elong (%) 5 5 4 5 Tensile modulus (MPa) 2600 2500 2500 3000 HDT (°C) 71 70 56 71 Barcol 34 33 36 36 EXAMPLE 3 Gelcoats 3A, 3B, 3C and 3D made from resins 2A, 2B, 2C and 2D for general purpose applications

Gelcoat Constituent (wt%) 3A 3B 3C 3D Resin (30 % styrene) 2A 64 2B 64 2C 64 2D 64 Air release agent 0.2 0.2 0.2 0.2 Talc 7 7 7 7 Titanium dioxide 17 17 17 17 Thixotropic agent 1.3 1.3 1.3 1.3 Styrene 7.5 7.5 9.5 11 Cobalt (10 %) 0.12 0.12 0.12 0.12 Inhibitor 0.13 0.13 0.13 0.13 Property: Styrene % 28 28 29 30 Styrene emission (ppm) 145 150 185 145 Brookfield viscosity/10 RPM 11940 11400 7420 8920 Thixotropic index 5/50 RPM 5.1 5.2 4.4 4.68 Accelerated weathering test: Gloss 60° 90 89 91 92 QUV-A 250 h CIE L*a*b* (Db*) 1. 1 1 1.2 1.3 Gloss 60° 83 84 85 85 QUV-A 500 h CIE L*a*b* (Db*) 1.4 1.3 1.7 2 Gloss 60° 81 81 84 83 maximum styrene concentration in exhaust air during spraying EXAMPLE 4 Resins 4A, 4B, 4C, 4D and 4E for marine applications

Resin Starting material 4A 4B 4C 4E (mol%) Neopentyl glycol 23 30 30 30 Propylene glycol 11 10 11 12 2-Butyl-2-ethyl-1,3-6 3 3 3 propanediol Hydroxypivalyl 9 5 5 5 hydroxypivalate Isophthalic acid 16 14 14 13 Adipic acid 2 2 2 Maleic anhydride 29 30 29 29 2-Phenyl ethyl alcohol 3 3 3 Benzoic acid 6 3 3 3 Property of linear polyester: Cook end points: 3.2 2.5 2.5 1.5 I. C. I./150 °C) Pas) Acid number 42 21 18 17 Property of linear polyester in styrene: I. C. I./25 °C (Pas) 35 % 7 4.7 4.6 3.3 styrene Mw 3100 3600 3500 3000 Mn 1700 1900 1400 1500 Mechanical properties of cured resin in 40 % styrene Tensile strength (MPa) 67 87 73 65 Tensile elongation (%) 3 5 3 4 Tensile modulus (MPa) 3500 4300 3800 3400 HDT (°C) 73 75 73 64 Barcol 39 38 37 38 Water abs (28d)/ (mg)/piece 78 73 73 73 EXAMPLE 5 Gelcoats 5A, 5b, 5C, 5D and 5E made from resin 4A, 4B, 4C, 4D and 4E for marine applications and commercial isophthalic based marine gelcoat GN 10000S (Neste Oy) for reference purposes Gelcoats Reference gelcoat Constituent 5A 5B 5C 5D GN 10000S (w% a) Resin (styrene 30 %) 4A 63 4B 63 4C 67 4D 64 Air release agent 0.2 0.2 0.2 0.2 Talc 7 7 7 7 Titanium dioxide 15 15 15 15 Thixotropic agent 1.3 1.3 1.3 1.3 Styrene 13.5 14 9 12 Cobalt (10 %) 0.12 0.12 0.12 0.12 Inhibitor 0.0.13 0.13 0.13 Property: Styrene % 33 33 30 28 36 Styrene 175 210 200 190 260 emission (ppm) Brookfield 8500 4160 10560 6680 7500 viscosity/ 10 RPM Thixotropic 4.5 4.3 4.8 4.2 4.8 index 5/50 RPM Acceterated weathering test: Gloss 60° 95 88 90 87 84 QUV-A 250 h 2 1.8 0.9 1.3 1.9 CIE L*a*b* (Db*) Gloss 60° 85 84 84 84 81 QUV-A 500 h 1.7 1.2 1.9 2.4 2.9 CIE L*a*b* (Db*) Gloss 60° 84 86 83 85 81 maximum styrene concentration in exhaust air during spraying