High-toughness materials based on unsaturated polyesters

Abstract

The present invention relates to unsaturated carboxylic acid ester obtained from or through the use of a source material defined below in formula (I):
A.sub.(0.9-1.2)(B+C).sub.(1.0)(I)
wherein the figures set in parentheses indicate the molar proportion of source material A to the sum of source materials B and C, and
wherein the following meanings apply:
A: unsaturated dicarboxylic acid,
B: a hard diol segment,
C: a soft diol segment selected from among compounds having a continuous chain between two hydroxyl groups, which have a length of 5 to 30 atoms, wherein the molar ratio of B:C is between 5:95 and 95:5. Furthermore, it relates to unsaturated polyester resin comprising said unsaturated carboxylic acid ester as defined above and a reactive diluents as well as molded articles, coatings, and surface textiles coated, saturated, laminated, and impregnated from or with a thermoset, which was obtained by hardening said unsaturated polyester resin.

Claims

1. Unsaturated carboxylic acid ester obtained from or through the use of source or starting materials defined in formula (I):
A.sub.(0.9-1.2)(B+C).sub.(1.0)(I) wherein the figures in parentheses indicate the molar proportion of source material A to the sum of source materials B and C, and wherein A is an unsaturated dicarboxylic acid, B is a hard diol segment, wherein a proportion of at least 40% of the atoms of the hard diol segment belong to a chain-rigid group wherein said hard diol segment B is selected from the group consisting of compounds having at least two hydroxyl groups and a continuous chain between both hydroxyl groups which has a length of 5 to 30 carbon atoms, and wherein said continuous chain comprises carbon atoms, and optionally comprises at least one of N, O and S atoms, and C is a soft diol segment selected from the group consisting of compounds having a continuous chain between two hydroxyl groups, said chain having a length of 10 to 25 atoms, wherein in said soft diol segment that proportion which belongs to a chain-rigid group makes up no more than 25% of the atoms of the compound, in each case related to the number of C atoms and, if present, N, O and S atoms, between the hydroxyl groups in the compound with the exception of the oxygen atoms of the terminal hydroxyl groups; wherein the molar ratio of B to C is between 5:95 and 95:5; and wherein the number of atoms of said continuous chain between both hydroxyl groups in said hard diol segment and the number of atoms of said continuous chain between both hydroxyl groups in said soft diol segment has a ratio of between 1:2 and 2:1.

2. Unsaturated carboxylic acid ester according to claim 1, wherein said soft diol segment does not comprise more than two hydroxyl groups.

3. Unsaturated carboxylic acid ester according to claim 1, wherein the length of a continuous chain between two hydroxyl groups in said hard diol segment and/or the length of said continuous chain between two hydroxyl groups in said soft diol segment is 10 to 24 atoms.

4. Unsaturated carboxylic acid ester according to claim 1, wherein the number of links of said continuous chain between both hydroxyl groups in said hard diol segment and the number of links of said continuous chain between both hydroxyl groups in said soft diol segment has a ratio of between 1:1.7 to 1.7:1.

5. Unsaturated carboxylic acid ester according to claim 1, wherein in the hard diol segment B, a proportion of at least 50% of the atoms of the compound belongs to a chain-rigid group, and/or wherein in the soft diol segment, less than 15% of the atoms belong to a chain-rigid group.

6. Unsaturated carboxylic acid ester according to claim 1, wherein said hard diol segment B is selected from the group consisting of dialkoxylated bisphenol A bodies, bisphenol F bodies, and bisphenol trimethylcyclohexane bodies.

7. Unsaturated carboxylic acid ester according to claim 6, wherein said soft diol segment C is selected from the group consisting of polypropylene glycols, polypropylene/polyethylene co-glycols, polytetrahydrofurans, polymers of 6-caprolactone, 1,6-hexandiolcarbonates, CO.sub.2-based polycarbonates as well as ,-hydroxy functional compounds having a chain length of 10-25 atoms, which are carbon atoms.

8. Unsaturated polyester resin, comprising an unsaturated carboxylic acid ester according to claim 1, and at least one compound having at least one CC double bond.

9. Unsaturated polyester resin according to claim 8, further comprising one or more additives selected from the group consisting of toughening agents, reinforcing fibers, fillers, pigments, dyes, and process additives.

10. Unsaturated polyester resin according to claim 9, wherein the toughening agents are selected from the group consisting of core-shell particles, rubbers, waxes, and silicones.

11. Molded article comprising a thermoset, which was obtained by hardening said polyester resin according to claim 8.

12. Molded article, comprising a textile fabric, which is coated, soaked, impregnated or laminated with a thermoset, wherein said thermoset was obtained by hardening said polyester resin according to claim 8.

13. Unsaturated carboxylic acid ester according to claim 1, wherein in the hard diol segment B, a proportion of at least 75% the atoms of the compound belong to a chain-rigid group, and/or wherein in the soft diol segment, less than 15% of the atoms belong to a chain-rigid group.

14. Unsaturated carboxylic acid ester according to claim 5, wherein no chain-rigid groups are present in the soft diol segment.

15. Unsaturated carboxylic acid ester according to claim 7, wherein the carbon atom chain is interrupted by O, S, NH or NR, and wherein R is an alkyl group.

16. Unsaturated polyester resin according to claim 8, further comprising an aromatic ring, a cycloaliphatic ring, or a hetero ring, which merges into a chain polymer under the influence of heat, light or ionizing radiation.

Description

(1) The following examples serve to provide additional understanding of the invention without limiting it.

RESIN EXAMPLE 1

(2) Unsaturated polyester was produced in a polycondensation reaction. 1.36 mol of maleic acid anhydride, 0.41 mol of polypropylene glycol (molar mass of 425 g/mol), 0.95 mol of bis-propoxylated bisphenol A, and 150 ppm of hydroquinone were weighed into a 1-liter four-necked round-bottom flask and thermally subjected to a polycondensation reaction. The reaction was conducted without atmospheric oxygen. The resulting reaction water was separated through distillation. Polycondensation was conducted up to an acid value of 18.43 mg of KOH/g and a melt viscosity of 436 mPas (150 C. and 10000 1/s).

(3) The resin was dissolved in 30 mass percent of styrene. The resin solution was hardened with 1.5 mass percent of tert-butyl perethylhexanoate for one hour at 80 C. and two hours at 120 C.

(4) The glass transition temperature was determined via dynamic mechanical analysis (DMA) and fracture toughness was determined via optical crack tracing (OCT) (see Table 1).

RESIN EXAMPLE 2

(5) Unsaturated polyester was produced in a polycondensation reaction. 1.35 mol of maleic acid anhydride, 0.47 mol of polypropylene glycol (molar mass of 425 g/mol), 0.88 mol of bis-propoxylated bisphenol A, and 150 ppm of hydroquinone were weighed into a 1-liter four-necked round-bottom flask and thermally subjected to a polycondensation reaction. The reaction was conducted without atmospheric oxygen. The resulting reaction water was separated through distillation. Polycondensation was conducted up to an acid value of 23.81 mg of KOH/g and a melt viscosity of 238 mPas (150 C. and 10000 1/s).

(6) The resin was dissolved in 30 mass percent of styrene. The resin solution was hardened with 1.5 mass percent of tert-butyl perethylhexanoate for one hour at 80 C. and two hours at 120 C.

(7) The glass transition temperature was determined via dynamic mechanical analysis (DMA) and fracture toughness was determined via optical crack tracing (OCT) (see Table 1).

RESIN EXAMPLE 3

(8) Unsaturated polyester was produced in a polycondensation reaction. 2.69 mol of maleic acid anhydride, 1.08 mol of polypropylene glycol (molar mass of 425 g/mol), 1.61 mol of bis-propoxylated bisphenol A, and 150 ppm of hydroquinone were weighed into a 2-liter four-necked round-bottom flask and thermally subjected to a polycondensation reaction. The reaction was conducted without atmospheric oxygen. The resulting reaction water was separated through distillation. Polycondensation was conducted up to an acid value of 22.80 mg of KOH/g and a melt viscosity of 553 mPas (150 C. and 10000 1/s).

(9) The resin was dissolved in 30 mass percent of styrene. The resin solution was hardened with 1.5 mass percent of tert-butyl perethylhexanoate for one hour at 80 C. and two hours at 120 C.

(10) The glass transition temperature was determined via dynamic mechanical analysis (DMA) and fracture toughness was determined via optical crack tracing (OCT) (see Table 1).

RESIN EXAMPLE 4

(11) Unsaturated polyester was produced in a polycondensation reaction. 1.33 mol of maleic acid anhydride, 0.60 mol of polypropylene glycol (molar mass of 425 g/mol), 0.73 mol of bis-propoxylated bisphenol A, and 150 ppm of hydroquinone were weighed into a 1-liter four-necked round-bottom flask and thermally subjected to a polycondensation reaction. The reaction was conducted without atmospheric oxygen. The resulting reaction water was separated through distillation. Polycondensation was conducted up to an acid value of 24.50 mg of KOH/g and a melt viscosity of 122 mPas (150 C. and 10000 1/s).

(12) The resin was dissolved in 30 mass percent of styrene. The resin solution was hardened with 1.5 mass percent of tert-butyl perethylhexanoate for one hour at 80 C. and two hours at 120 C.

(13) The glass transition temperature was determined via dynamic mechanical analysis (DMA) and fracture toughness was determined via optical crack tracing (OCT) (see Table 1).

RESIN EXAMPLE 5

(14) Unsaturated polyester was produced in a polycondensation reaction. 2.76 mol of maleic acid anhydride, 1.38 mol of polypropylene glycol (molar mass of 425 g/mol), 1.38 mol of bis-propoxylated bisphenol A, and 150 ppm of hydroquinone were weighed into a 2-liter four-necked round-bottom flask and thermally subjected to a polycondensation reaction. The reaction was conducted without atmospheric oxygen. The resulting reaction water was separated through distillation. Polycondensation was conducted up to an acid value of 26.09 mg of KOH/g and a melt viscosity of 366 mPas (150 C. and 10000 1/s).

(15) The resin was dissolved in 30 mass percent of styrene. The resin solution was hardened with 1.5 mass percent of tert-butyl perethylhexanoate for one hour at 80 C. and two hours at 120 C.

(16) The glass transition temperature was determined via dynamic mechanical analysis (DMA) and fracture toughness was determined via optical crack tracing (OCT) (see Table 1).

RESIN EXAMPLE 6

(17) Unsaturated polyester was produced in a polycondensation reaction. 2.64 mol of maleic acid anhydride, 1.45 mol of polypropylene glycol (molar mass of 425 g/mol), 1.19 mol of bis-propoxylated bisphenol A, and 150 ppm of hydroquinone were weighed into a 2-liter four-necked round-bottom flask and thermally subjected to a polycondensation reaction. The reaction was conducted without atmospheric oxygen. The resulting reaction water was separated through distillation. Polycondensation was conducted up to an acid value of 19.00 mg of KOH/g and a melt viscosity of 346 mPas (150 C. and 10000 1/s).

(18) The resin was dissolved in 30 mass percent of styrene. The resin solution was hardened with 1.5 mass percent of tert-butyl perethylhexanoate for one hour at 80 C. and two hours at 120 C.

(19) The glass transition temperature was determined via dynamic mechanical analysis (DMA) and fracture toughness was determined via optical crack tracing (OCT) (see Table 1).

RESIN EXAMPLE 7

(20) Unsaturated polyester was produced in a polycondensation reaction. 2.62 mol of maleic acid anhydride, 1.57 mol of polypropylene glycol (molar mass of 425 g/mol), 1.05 mol of bis-propoxylated bisphenol A, and 150 ppm of hydroquinone were weighed into a 2-liter four-necked round-bottom flask and thermally subjected to a polycondensation reaction. The reaction was conducted without atmospheric oxygen. The resulting reaction water was separated through distillation. Polycondensation was conducted up to an acid value of 18.42 mg of KOH/g and a melt viscosity of 112 mPas (150 C. and 10000 1/s).

(21) The resin was dissolved in 30 mass percent of styrene. The resin solution was hardened with 1.5 mass percent of tert-butyl perethylhexanoate for one hour at 80 C. and two hours at 120 C.

(22) The glass transition temperature was determined via dynamic mechanical analysis (DMA) and fracture toughness was determined via optical crack tracing (OCT) (see Table 1).

(23) TABLE-US-00001 TABLE 1 Fracture toughness and glass transition temperatures of the hardened resin examples Fracture Glass transition Resin toughness K.sub.1C temperature example [MN/m.sup.3/2] [ C.] 1 0.397 110 2 0.733 99 3 0.825 110 4 0.876 91 5 0.786 102 6 0.855 94 7 0.95 70

(24) It should be noted that the presented examples demonstrate the ability to achieve high fracture toughness in combination with favorable glass transition temperatures without embodiments having to have been used, which reflect the expected optimum effect, due to the fact that hard and soft diol segments having identical or nearly identical chain lengths were used.