GOOD WEATHERING, UV-RESISTANT UNSATURATED POLYESTER RESIN COMPRISING FUMARIC ACID

Abstract

The invention relates to an unsaturated polyester resin comprising fumaric acid and optional end-capping with an ethylenically unsaturated moiety, which is useful for the preparation of engineered stone. The unsaturated polyester resin can be further processed to obtain a formable composition which can be cured to finally yield engineered stone as composite material. The thus obtained engineered stone shows a high resistance to UV- and sunlight as well as to weathering. The invention also relates to a method for the preparation of engineered stone as well as to the use of the unsaturated polyester resin for the preparation of engineered stone.

Claims

1. An unsaturated polyester resin component for the preparation of engineered stone, wherein the unsaturated polyester resin component has a weight average molecular weight within the range of from 1000 g/mol to 7500 g/mol; and wherein the unsaturated polyester resin component is obtainable by (a) reacting a monomer mixture comprising (i) a fumaric acid component comprising fumaric acid and/or a fumaric acid ester; (ii) a polyfunctional alcohol component comprising at least one polyfunctional alcohol selected from the group consisting of aromatic polyfunctional alcohols; and aliphatic polyfunctional alcohols; (iii) optionally, a polycarboxylic acid component comprising at least one polycarboxylic acid selected from the group consisting of aromatic polycarboxylic acids, anhydrides or esters thereof; saturated aliphatic polycarboxylic acids, anhydrides or esters thereof; and unsaturated aliphatic polycarboxylic acids, anhydrides or esters thereof differing from fumaric acid and fumaric acid ester; (iv) optionally, a monocarboxylic acid component comprising at least one monocarboxylic acid selected from the group consisting of aromatic monocarboxylic acids, anhydrides or esters thereof; and aliphatic monocarboxylic acids, anhydrides or esters thereof; and (v) optionally, a monofunctional alcohol component comprising at least one monofunctional alcohol selected from the group consisting of aromatic monofunctional alcohols, and aliphatic monofunctional alcohols; wherein the molar content of the (i) fumaric acid component is within the range of from 5.0 to 50 mol.-%; and the molar content of the (ii) polyfunctional alcohol component is within the range of from 20 to 90 mol.-%; wherein said molar content in each case is relative to the total molar content of the (i) fumaric acid component, the (ii) polyfunctional alcohol component, the (iii) optionally present polycarboxylic acid component, the (iv) optionally present monocarboxylic acid component, and the (v) optionally present monofunctional alcohol component in the monomer mixture; and (b) optionally, end-capping the product of step (a).

2. The unsaturated polyester resin component according to claim 1, wherein the (i) fumaric acid component is the only component in the monomer mixture which comprises an ethylenic unsaturation; and/or the unsaturated polyester resin component is aliphatic or aromatic.

3. The unsaturated polyester resin component according to claim 1 or 2, wherein the product of step (a) has an acid value within the range of from 2 to 50; and/or a hydroxyl-value within the range of from 60 to 150.

4. The unsaturated polyester resin component according to any of the preceding claims, wherein the polyfunctional alcohol component comprises a mixture of at least two saturated aliphatic polyfunctional alcohols; and/or the optionally present polycarboxylic acid component comprises at least one saturated aliphatic polycarboxylic acid, anhydride or ester thereof.

5. The unsaturated polyester resin component according to claim 4, wherein the at least two saturated aliphatic polyfunctional alcohols are selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, propylene glycol and 1,4-butanediol; and/or the at least one saturated aliphatic polycarboxylic acid, anhydride or ester thereof is adipic acid, adipic acid anhydride or an adipic acid ester.

6. The unsaturated polyester resin component according to claim 4 or 5, wherein the molar ratio of the at least two saturated aliphatic polyfunctional alcohols is within the range of 4:1 to 1:4.

7. The unsaturated polyester resin component according to any of the preceding claims, wherein the molar content of the fumaric acid component is within the range of 2310 mole.-%; the molar content of the polyfunctional alcohol component is within the range of 5515 mole.-%; and the molar content of the optionally present polycarboxylic acid component is within the range of range of 2010 mole.-%; wherein said molar content in each case is relative to the total molar content of the (i) fumaric acid component, the (ii) polyfunctional alcohol component, the (iii) optionally present polycarboxylic acid component, the (iv) optionally present monocarboxylic acid component, and the (v) optionally present monofunctional alcohol component in the monomer mixture.

8. The unsaturated polyester resin component according to any of the preceding claims, wherein the molar content of the fumaric acid component in the monomer mixture is in the range of from 5 to 95 mole.-%, wherein said molar content is relative to the total molar content of the (i) fumaric acid component, the (iii) optionally present polycarboxylic acid component, and the (iv) optionally present monocarboxylic acid component.

9. The unsaturated polyester resin component according to any of the preceding claims, which is end-capped with moieties comprising ethylenic unsaturations.

10. The unsaturated polyester resin component according to claim 9, which is obtainable by steps (a) and (b), wherein step (b) comprises reacting the terminal hydroxyl groups or the terminal carboxyl groups of the product of step (a) with a functionalizer bearing a functional group capable of reacting with said terminal hydroxyl groups or said terminal carboxyl groups; and wherein said functionalizer (b.sub.1) either bears the ethylenic unsaturation; (b.sub.2) or does not bear the ethylenic unsaturation, but bears a functional group capable of subsequently reacting with an end-capping agent bearing the ethylenic unsaturation.

11. The unsaturated polyester resin component according to claim 10, wherein said functionalizer (b.sub.1) bears the ethylenic unsaturation and is selected from the group consisting of glycidyl(meth)acrylate; or is selected from the group consisting of allyl isocyanate, adducts of 2-hydroxyethylmethacrylate and an isocyante; or (b.sub.2) does not bear the ethylenic unsaturation and is selected from the group consisting of alicyclic polyisocyanates; aromatic polyisocyanates and aliphatic polyisocyanates; wherein said end-capping agent is selected from the group consisting of unsaturated alcohols and hydroxyl substituted acrylic and methacrylic acid esters; or is selected from the group consisting of alicyclic polyepoxides; aromatic polyepoxides and aliphatic polyepoxides; wherein said end-capping agent is at least one unsaturated carbon acid.

12. The unsaturated polyester resin component according to claim 10 or 11, wherein the functionalizer is isopherone diisocyanate and the end-capping agent is 2-hydroxyethyl-methacrylate.

13. The unsaturated polyester resin component according to any of claims 9 to 12, wherein step (b) comprises reacting the product of step (a) with a functionalizer and a catalyst; and/or an inhibitor.

14. The unsaturated polyester resin component according to claim 13, wherein the catalyst is selected from the group consisting of tetramethylammonium chloride, tetramethylammonium bromide and dibutyltindilaurate.

15. A prepromoted unsaturated polyester resin system for the preparation of engineered stone, which system comprises (i) an unsaturated polyester resin component according to any of claims 1 to 14; (ii) a metal catalyst capable of catalyzing curing of said unsaturated polyester resin component; (iii) a quaternary ammonium salt; and (iv) optionally, one or more additives selected from the group consisting of reactive diluents, accelerators, co-promoters, dispersing agents, UV absorbers, stabilizers, inhibitors and rheology modifiers.

16. The prepromoted unsaturated polyester resin system according to claim 15, wherein the metal catalyst comprises zinc, copper or cobalt.

17. The prepromoted unsaturated polyester resin system according to claim 15 or 16, wherein the quaternary ammonium salt is a benzyl-N,N,N-trialkylammonium salt or a N,N,N,N-tetraalkylammonium salt.

18. The prepromoted unsaturated polyester resin system according to any of claims 15 to 17, which comprises a reactive diluent selected from the group consisting of styrene, substituted styrene, mono-, di- and polyfunctional esters of monofunctional ethylenically unsaturated acids with alcohols or polyfunctional alcohols and/or mono-, di- and polyfunctional esters of unsaturated monofunctional alcohols with carboxylic acids or their derivatives.

19. The prepromoted unsaturated polyester resin system according to any of claims 15 to 18, wherein the content of reactive diluent is in the range of 3025 wt.-% relative to the total weight of the polyester resin system.

20. A formable composition for the preparation of engineered stone comprising (A) a prepromoted unsaturated polyester resin system according to any of claims 15 to 19; (B) an inorganic particulate material; and (C) a peroxide component.

21. The formable composition according to claim 20, wherein the inorganic particulate material comprises silicon dioxide.

22. The formable composition according to any of claim 20 or 21, wherein the silicon dioxide has an average particle size in the range of 0.045 to 0.6 mm.

23. The formable composition according to any of claims 20 to 22, wherein the peroxide component is benzoyl peroxide (BPO) and/or tert-butyl peroxibenzoate (TBPB).

24. The formable composition according to any of claims 20 to 23, wherein the weight content of the prepromoted unsaturated polyester resin system is about 0.1 wt.-% to about 30 wt.-%, relative to the total weight of the formable composition; and/or wherein the weight content of the inorganic particulate material is about 70 wt.-% to about 99.9 wt.-%, relative to the total weight of the formable composition.

25. The formable composition according to any of claims 20 to 24, wherein the weight content of the prepromoted unsaturated polyester resin system is not more than about 10 wt.-%, relative to the total weight of the formable composition.

26. The formable composition according to any of claims 20 to 25, wherein the weight content of the inorganic particulate material is not more than about 90 wt.-% relative to the total weight of the formable composition.

27. A method for the preparation of an unsaturated polyester resin component according to any of claims 1 to 14 comprising the steps of (a) reacting a monomer mixture comprising (i) a fumaric acid component; (ii) a polyfunctional alcohol component; (iii) optionally, a polycarboxylic acid component differing from the fumaric acid component; (iv) optionally, a monocarboxylic acid component; and (v) optionally, a monofunctional alcohol component; wherein the molar content of the (i) fumaric acid component is within the range of from 5.0 to 50 mol.-%; and the molar content of the (ii) polyfunctional alcohol component is within the range of from 20 to 90 mol.-%; wherein said molar content in each case is relative to the total molar content of the (i) fumaric acid component, the (ii) polyfunctional alcohol component, the (iii) optionally present polycarboxylic acid component, the (iv) optionally present monocarboxylic acid component, and (v) the optionally present monofunctional alcohol component in the monomer mixture; and (b) optionally, end-capping the product of step (a).

28. A method for the preparation of an unsaturated polyester resin component according to claim 27, wherein the temperature of step (a) reacting a monomer mixture lies in the range of 100 to 210 C.

29. A method for the preparation of a prepromoted unsaturated polyester resin system according to any of claims 15 to 19 comprising the step of mixing (i) an unsaturated polyester resin component according to any of claims 1 to 14; (ii) a metal catalyst capable of catalyzing curing of said unsaturated polyester resin component; (iii) a quaternary ammonium salt; and (iv) optionally, one or more additives selected from the group consisting of reactive diluents, accelerators, co-promoters, dispersing agents, UV absorbers, stabilizers, inhibitors and rheology modifiers.

30. A method for the preparation of a formable composition for the preparation of engineered stone according to any of claims 20 to 26 comprising the step of mixing (A) a prepromoted unsaturated polyester resin system according to any of claims 15 to 19; (B) an inorganic particulate material; and (C) a peroxide component.

31. A method for the preparation of engineered stone comprising the steps of (a) providing a formable composition according to any of claims 20 to 26; (b) forming the composition prepared in step (a) into a desired shape; and (c) allowing the composition formed in step (b) to cure.

32. Engineered stone obtainable by the method according to claim 31.

33. Use of a unsaturated polyester resin component according to any of claims 1 to 14 for the preparation of engineered stone.

34. Use of a prepromoted unsaturated polyester resin system according to any of claims 15 to 19 for the preparation of engineered stone.

35. Use of a formable composition according to any of claims 20 to 26 for the preparation of engineered stone.

Description

EXAMPLES 1 AND 2 (PREPARATION OF AN UNSATURATED POLYESTER RESIN)

[0252] Unsaturated polyester resin suitable for end-capping with urethane methacrylate was prepared from the following monomers:

TABLE-US-00001 components (mol.-%) example 1 example 2 ethylene glycol 28.3 28.3 neopentyl glycol 28.3 28.3 adipic acid 17.3 29.0 fumaric acid 26.2 14.5

[0253] The monomers were charged to a resin kettle equipped with a Thermocouple, a mechanical stirrer, a fractionating column, a distillation head, a condenser and a nitrogen sparge. The mixture of each example was heated slowly to 120 C. with agitation until a homogeneous mixture was obtained. The homogeneous mixture was heated slowly to 190 C. removing water and then sparged with nitrogen, whereas the rate of sparge was maintained such that the distillation temperature was kept at 100 C. throughout the removal of water. The acid value and cone and plate viscosity were monitored during the reaction. When the mixture reached an acid value in the range of 0 to 4 it was cooled down to about 80 C. At this time the nitrogen sparge was changed to air sparge and 200 ppm hydroquinone inhibitor was added followed by methyl methacrylate to adjust the nonvolatile component to 80-90%. The resin was then cooled down to room temperature.

[0254] The acid and hydroxyl values and the molecular weight of the polymers were determined with standard methods. The results are shown in the table here below:

TABLE-US-00002 example 1 example 2 acid number 3.3 3.3 OH value 120 87 Mn (g/mol) 1,362 1,481 Mw (g/mol) 2,175 2,579 Pdi 1.6 1.74

EXAMPLES 3 AND 4 (URETHANE METHACRYLATE END-CAPPING OF THE UNSATURATED POLYESTER RESIN)

[0255] The resin of example 1 was end-capped with the components which are shown in the table here below to obtain example 3:

TABLE-US-00003 components (g) example 3 unsaturated resin of example 1 (N.V. 89.3% in MMA) 523.5 MMA 180 IPDI 222.3 4-hydroxy-TEMPO 0.4 Dabco-T12 0.12 HEMA 143.1
The resin of example 2 was end-capped with the components which are shown in the table here below to obtain example 4:

TABLE-US-00004 components (g) example 4 unsaturated resin of example 2 (N.V. 89.6% in MMA) 1,583.27 MMA 550.00 IPDI 595.76 4-hydroxy-TMPO 1.10 25% HQ solution 0.44 Dabco-T12 0.26 HEMA 314.86

[0256] The resins were end-capped according to the following method: Under a nitrogen blanket a resin flask was charged with resin solution of example 1 or 2 respectively in MMA. MMA, isophorone diisocyanate (IPDI) and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (4-hydroxy-TEMPO) and dibutyltindilaurate catalyst (DABCO T12) were added. The exothermic reaction was allowed to take place keeping the reaction temperature below 65 C. using external cooling if needed. The reaction mixture was then heated to 65 C. for additional 90 minutes. At the end of 90 minutes, 2-hydroxyethyl methacrylate (HEMA) was added and the exothermic reaction was allowed to take place keeping the temperature below 70 C. The reaction mixture was then heated at 70 C. until all the isocyanate groups had reacted. The reaction was followed by FTIR, NCO peak.

[0257] The molecular weight of the end-capped resins was measured:

TABLE-US-00005 example 3 example 4 Mn (g/mol) 2,282 2,672 Mw (g/mol) 5,320 5,824 Pdi 2.33 2.18

EXAMPLE 5 (ALTERNATIVE URETHANE METHACRYLATE END-CAPPING OF THE UNSATURATED POLYESTER RESIN)

[0258] Alternatively, end-capping of the unsaturated polyester resin can be done using the following components and procedure.

TABLE-US-00006 components (g) example 5 unsaturated resin of example 1 (N.V. 89.3% in MMA) 532.5 MMA 180 IPDI 222.3 BHT 0.1 Dabco-T12 0.12 HEMA (1.sup.st addition) 143 HEMA (2nd addition) 13

[0259] Under nitrogen blanket, a resin flask was charged with MMA and isophorone diisocyanate (IPDI), butyl hydroxyl toluene (BHT) and dibutyltindilaurate catalyst (DAB.sup.CO T12). This mixture was then heated to 50 C. and 2-hydroxyethy methacrylate (HEMA) was added slowly maintaining the reaction mixture below 65 C. After the HEMA addition was completed, the reaction temperature was maintained at 65 C. for an additional 90 minutes. The reaction mixture was then cooled down to 60 C. and resin of example 1 was added. The exothermic reaction was allowed to take place keeping the reaction temperature below 80 C. The reaction temperature was then maintained at 80 C. for 4 hours at which time an additional HEMA was added. The reaction was followed by FTIR until all the isocyante groups had reacted.

EXAMPLE 6: (PREPARATION OF UNSATURATED POLYESTER RESIN WITHOUT END-CAPPING)

[0260] Unsaturated polyester resin was prepared from the following monomers:

TABLE-US-00007 components (mol.-%) example 6 1,3-butanal 25.86 neopentyl glycol 25.33 adipic acid 15.38 fumaric acid 33.43

[0261] The monomers were charged to a resin kettle equipped with a Thermocouple, a mechanical stirrer, a fractionating column, a distillation head, a condenser and a nitrogen sparge. The mixture of example 6 was heated slowly to 120 C. with agitation until a homogeneous mixture was obtained. To this mixture, 35 ppm hydroquinone inhibitor, 0.033% phosphoric acid and 0.021% oxalic acid catalyst were added. The homogeneous mixture was heated slowly to 190 C. removing water and then sparged with nitrogen, whereas the rate of sparge was maintained such that the distillation temperature was kept at 100 C. throughout the removal of water. The acid number and cone and plate viscosity were monitored during the reaction. When the target acid value of 14 to 20 and viscosity of 2.9 to 3.9 P were reached, the reaction mixture was cooled down to 80 C and an additional 30 ppm of hydroquinone inhibitor was added and the air sparge started. Styrene monomer was added and the resin was cooled down to room temperature.

[0262] The acid value, viscosity and the molecular weight of example 6 were determined with standard methods. The results are shown in the table here below:

TABLE-US-00008 example 6 acid number 18 plastic viscosity C&P at 150 C. (P) 2.9 Mn (g/mol) 2,789 Mw (g/mol) 6,832 Pdi 2.45

EXAMPLES 7, 8 AND 9 (PREPARATION OF ENGINEERED STONE BASED ON END-CAPPED RESIN OF EXAMPLE 3 AND UNCAPPED RESIN OF EXAMPLE 6 AND WITH AROPOL DRL 085)

[0263] A formulation was prepared with the following components:

TABLE-US-00009 component (Mol.-%) example 7 resin of example 1 58.75 MMA 41.25 BPO 50% 2 TBPB 0.1 Vinyl-trimethoxy-silane 0.2

[0264] A corresponding example 8 was prepared with the resin of example 6 (not end-capped).

[0265] The amounts of fillers and pigments which were added to the examples 7 and 8 are shown in the following table. Further, an engineered stone slab was prepared with a comparative resin.

TABLE-US-00010 comparative example 9 components (wt.-%) example 7 example 8 Aropol DRL 085 formulation 10 10 10 quartz fillers 0.3-0.6 mm 25 25 25 quartz fillers 0.1-0.3 mm 35 35 35 quartz fillers 0.045 mm 30 30 30 TiO.sub.2white slabs 2 2 2 only part per 100)

[0266] The weathering properties and the UV-resistance of the obtained engineered stone slabs of examples 7 to 9 were investigated by exposing the stone slabs to outdoor conditions in Arizona for one year. The results of the measurements of color changes of the stone slabs after one year exposure to outdoor conditions in Arizona are summarized in the table below:

TABLE-US-00011 comparative example 9 example 7 example 8 Aropol DRL 085 white slabs db 0.26 0.37 1.2 dE 0.31 0.73 1.57 black slabs db 0.04 0.75 1.15 dE 0.4 2.99 13.53

[0267] The degree of color change due to weathering and UV-exposure is measured with the values db and dE. The value db is related to yellowing of the stone slabs, wherein an increase of the db value or a positive db value indicates that the change is to a more (darker) yellow color of the artificial stone slabs and a decrease of the db value or a negative db value indicates a change to a more blue color of the artificial stone slabs. The value dE relates to the total color change of the artificial stone slabs. It is always positive because of the way it is calculated, wherein a higher dE value indicates a more intensive change in color of the artificial stone slabs.

[0268] It becomes clear from the above comparative data that the unsaturated polyester resin according to the invention provides engineered stone having superior weathering properties and UV-resistance compared to engineered stone manufactured from conventional unsaturated polyester resins.

[0269] The white stone slab of comparative example 9 showed a considerable increase of its db value which was almost six times higher than the db value of the white stone slab of example 7 and three times higher than the db value of the white stone slab of example 8 prepared with the inventive resin. This means that the white stone slab of comparative example 9 turned to a more (darker) yellow color much more compared to the slabs prepared with the inventive resin.

[0270] The black stone slab of comparative example 9 showed a considerable decrease of its db value which was up to 28 times smaller than the db value of the black stone slab of example 7 and 1.5 times smaller than the db value of the black stone slab of example 8 prepared with the inventive resin. This means that the black stone slab of comparative example 9 turned to a blue color much more compared to the slabs comprising the inventive resin.

[0271] Further, the white and the black stone slabs prepared with the inventive unsaturated polyester resin of examples 7 and 8 showed only a rather small change of the db value compared to the slab of comparative example 9, meaning that the white slabs hardly turned to a more (darker) yellow color and the black slabs hardly turned to a more blue color.

[0272] Furthermore, the white and the black stone slabs prepared with the inventive unsaturated polyester resin of examples 7 and 8 showed a small total change in color, i.e. a small change of the dE value, compared to the stone slab prepared with conventional resin of example 9. The white stone slab of example 7 prepared with the inventive resin had a dE value which was about five times smaller than the dE value of the white stone slabs of comparative example 9. The black stone slab of example 7 prepared with the inventive resin had a dE value which was four times smaller than the value of the black stone slabs of comparative example 9.

EXAMPLES 10 TO 13 (PREPARATION OF AN UNSATURATED POLYESTER RESIN)

[0273] Unsaturated polyester resin was prepared from the following monomers:

TABLE-US-00012 example 10 example 11 component [g] [mol] mol. % [g] [mol] mol.-% propylene glycol 1150.3 15.12 40.06 1150.3 15.12 40.06 diethylene glycol 470.4 4.43 11.73 470.4 4.43 11.73 phthalic 949.1 6.41 16.98 949.1 6.41 16.98 anhydride adipic acid 0 0 fumaric acid 1368.4 11.79 31.23 1368.4 11.79 31.23 benzyl alcohol

TABLE-US-00013 example 12 example 13 component [g] [mol] mol.-% [g] [mol] mol.-% propylene glycol 1150.3 15.12 39.20 1597.7 21.00 50.53 diethylene glycol 470.4 4.43 11.49 phthalic 949.1 6.41 16.62 814.7 5.50 13.23 anhydride adipic acid 255.0 1.74 4.19 fumaric acid 1368.4 11.79 30.57 1450.9 12.50 30.08 benzyl alcohol 88.2 0.82 2.13 88.2 0.82 1.97

[0274] The monomers, hydroquinone 25% in PGMME solution (1,391 g) and potassium acetate (0,174 g) were charged to a reactor equipped with a thermocouple, a mechanical stirrer, a fractionating column, a distillation head, a condenser and a nitrogen sparge. Agitation was started as soon as a sufficient quantity of material was in the reactor. The reaction mixture was heated to 205-210 C. removing water and then sparged with nitrogen, whereas the rate of sparge was maintained such that the distillation temperature was kept at 100 C. throughout the removal of water. The acid number (mgKOH/g, 100% solids) and cone and plate viscosity (at 125 C.) were monitored during the reaction. When the acid value of 60 to 80 was reached, vacuum was applied and increased gradually. Vacuum was maintained until the target Brookfield cone and plate viscosity (at 125 C.) and the target acid number (mgKOH/g, 100% solids) were reached. Then the vacuum was released and the reaction mixture was cooled to a temperature of 1805 C. The thus obtained resin was diluted in styrene. The resin was dropped slowly to a thin tank, which was charged beforehand with styrene (904 g, 8.68 mol), hydroquinone 25% in propylene glycol monomethyl ether (PGMME) solution (0.27 g) and potassium (K15%) octoate (0.0035 g). During drop, thin tank temperature was maintained at maximum 805 C. Mixing and cooling of the thin tank was continued until temperature was decreased below 35 C.

[0275] The acid number (mgKOH/g, 100% solids), the viscosity of plastic sample (at 125 C.) and molecular weight analysis were determined with standard methods. The results are shown in the table here below:

TABLE-US-00014 example 10 example 11 example 12 example 13 acid number 39 45 46 42 (mgKOH/g, 100% solids) plastic 4.5 3.5 2.1 3.2 viscosity C&P at 125 C. (P) Mn (g/mol) 1316 1501 1279 1473 Mw (g/mol) 3190 2759 2220 2774 Mp (g/mol) 2217 2120 1763 2029 Pdi 2.42 1.84 1.74 1.88

[0276] Further, the content of not polymerized hydroxyl components in the unsaturated polyester resin was determined. The results are shown in the table here below:

TABLE-US-00015 example example components (wt.-%) example 10 example 11 12 13 free propylene glycol ND 2.92 2.64 2.4 free diethylene glycol ND 1.58 1.44 free benzyl alcohol ND 0.32

[0277] The content of fumaric acid and other acids in the in the unsaturated polyester resin was determined. The results are shown in the table here below:

TABLE-US-00016 components (wt.-%) example 10 example 11 example 12 example 13 fumaric acid 90.8 88.7 89.9 90 maleic acid 1.7 2.2 2.2 2 malic acid 7.5 9.1 7.9 8

EXAMPLES 14 TO 25

[0278] Formulations with the resins of examples 10 to 13 were composed with the following components and the physical and thermal properties of the thus obtained resins were determined. The formulations and the test results are shown in the table here below:

TABLE-US-00017 example 14 15 16 17 18 19 20 21 22 23 24 25 resin of example 10 10 11 11 11 12 12 12 13 13 13 13 content of resin (wt.-%) 62 58 62 62-63 64.5 64 64 65 66 63 65 66 styrene (wt.-%) 24 25 28 24-25 35.5 26 26 23 34 25 25 28 1 4-butanediol dimethacrylate 8 17 10 6.5 10 8 12 5 (BDDMA) (wt.-%) butyl methacrylate (BMA) (wt.-%) 6 6 10 5 6 trimethylolpropane triacrylate 2 2 TMPTMA (wt.-%) physical properties* plastic viscosity C&P at 25 C. (mPa .Math. s) 455** 530** 443 435 430 471 415 430 456 451 436 Brookfield viscosity at 25 C. (mPa .Math. s) 492** 394 392 392 380 420 426 380 tensile stress at maximum load (MPa) 68 69 68 66 67 67 65 61 tensile stress at break (MPa) 68 69 68 66 67 67 65 61 tensile modulus (MPa) 3797 3545 3700 3674 3579 3352 3194 3249 elongation at maximum load (%) 2.6 2.9 2.2 2.5 2.5 3.1 3.4 2.8 elongation at break (%) 2.6 2.9 2.2 2.5 2.5 3.1 3.4 2.8 flexural strength (MPa) 123 110 108 128 122 114 116 flex modulus (MPa) 3567 3701 3296 3620 3242 3036 3228 thermal properties* heat distortion temperature (HDT), C. 66 75 75 63 79 68 63 51 73 66 61 61 differential scanning calometry (DSC) 5.0 7.9 6.2 3.9 residual reactivity, RR (J/g) glass transition temperature, T.sub.g2 ( C.) 80 72 72 73 *Curing with 0.2% Cobalt-2-ethyl hexanoate (6%) and 2% methyl ethyl ketone peroxide for 24 hours at room temperature followed by post cure 2 hours at 90 C. For HDT, additionally post cured for 2 hours at 100 C. ** Viscosity tested at 23 C.