Polymer and composition

Abstract

The present invention relates to a polyester resin obtained by reaction in a process (I) between the following components A to E to obtain a polyester P (the polyester comprising an alkyd resin and/or a saturated polyester resin), where (A) Component A (also referred to herein as the Imide and/or Imide Component) comprises one or more cyclic imides of Formula (1); where R represents a divalent optionally substituted saturated C.sub.1-30 organo moiety; and R represents H or a monovalent optionally substituted saturated C.sub.1-30 organo moiety; (A) Optional Component A comprises saturated dicarboxylic acid and/or saturated hydroxyacid and that is not optional in case component A does not comprise a dicarboxylic acid or a hydroxyacid; 1(B) Component B (also referred to herein as the Polyol and/or Polyol Component) comprises at least one saturated polyhydric alcohol; (C) Optional Component C (also referred to herein as the Rosin and/or Rosin Component) comprises naturally occurring rosin, the rosin comprising from 40 to 80 parts per hundred by weight of rosin of an unsaturated mono carboxylic acid comprising at least one C.sub.5-25 cyclohydrocarbo moiety capable of undergoing a Diels Alder or Ene reaction; (D) Optional Component D (also referred to herein as the Fatty Acid and/or Fatty Acid Component) comprises at least one linear C.sub.2-60 hydrocarbo carboxylic acid optionally comprising at least two linoleically unsaturated double bonds; 2(E) Optional Component E (also referred to as the Other Component E) which may comprise at least one monofunctional or polyfunctional monomer other than any of Components A to D. ##STR00001##

Claims

1. A polyester resin comprising an alkyd resin and/or a saturated polyester resin, wherein said polyester resin is obtained by reacting the following components A to E in a process (I): (A) Component A comprises one or more cyclic imides of Formula 1; ##STR00028## wherein R represents a divalent optionally substituted saturated aliphatic C1-30 organo moiety; and R represents H or a monovalent optionally substituted saturated C1-30 organo moiety; (A) Component A comprises a saturated dicarboxylic acid and/or a saturated hydroxy acid, wherein component A is optional only if component A comprises a dicarboxylic acid or a hydroxy acid; (B) Component B comprises at least one saturated polyhydric alcohol; (C) Optional Component C comprises naturally occurring rosin, the rosin comprising from 40 to 80 parts per hundred by weight of rosin of an unsaturated mono carboxylic acid comprising at least one C15-25 cyclohydrocarbo moiety capable of undergoing a Diels Alder or Ene reaction; (D) Optional Component D comprises at least one linear C12-60 hydrocarbo carboxylic acid optionally comprising at least two linoleically unsaturated double bonds; (E) Optional Component E other than any of Components A to D, wherein Component E is selected from the group consisting of monocarboxylic acids, amines, isocyanates, (poly)ethers, (poly)siloxanes (poly)amides and (poly)acrylates.

2. The polyester resin according to claim 1, wherein R represents a monovalent optionally substituted saturated C.sub.1-30 organo moiety.

3. The polyester resin according to claim 1, wherein R represents a monovalent substituted saturated C.sub.1-30 organo moiety.

4. The polyester resin according to claim 1, wherein R represents a divalent substituted aliphatic saturated C.sub.1-30 organo moiety and R represents a monovalent optionally substituted saturated C.sub.1-30 organo moiety.

5. The polyester resin according to claim 1, wherein R represents a divalent aliphatic substituted saturated C.sub.1-30 organo moiety and R represents a monovalent substituted saturated C.sub.1-30 organo moiety.

6. The polyester resin according to claim 1, wherein R represents a divalent substituted aliphatic saturated C.sub.1-20 hydrocarbo, and R represents a substituted saturated C.sub.1-20 hydrocarbo.

7. The polyester resin according to claim 1, wherein R represents an aliphatic saturated C.sub.1-6 hydrocarbylene substituted by one or more imido, carboxy and/or hydroxyl, and R represents a saturated C.sub.1-6 hydrocarbyl substituted by one or more imido, phenyl, carboxy and/or hydroxy.

8. The polyester resin according to claim 1, wherein the polyester resin is an alkyd resin and wherein Component D is not optional and is present in an amount of at least 20% by weight of the total amount of Components A to E.

9. The polyester resin according to claim 1, wherein the polyester resin is a saturated polyester resin and wherein the Component C and the Component D are absent.

10. The polyester resin according to claim 1, wherein the cyclic imides of Formula 1 are represented by one or more citric imide derivatives of Formula 2: ##STR00029## and/or one more succinimide derivatives of Formula 3: ##STR00030## wherein R in Formulae 2 and/or 3 independently represents H or a monovalent optionally substituted saturated C1-30 organo moiety.

11. The polyester resin according to claim 1, wherein the cyclic imides of Formula 1 are represented by one or more citric imide derivatives of Formula 2: ##STR00031## wherein R in Formula 2 independently represents H or a monovalent optionally substituted saturated C1-30 organo moiety.

12. The polyester resin according to claim 1, wherein the cyclic imides of Formula 1 are selected from the group consisting of: ##STR00032##

13. The polyester resin according to claim 1, wherein the cyclic imides of Formula 1 are selected from the group consisting of: ##STR00033##

14. The polyester resin according to claim 1, wherein the Component A is present in an amount of from 1 to 90% by weight of the total amount of Components A to E and such that the amount of A to E totals 100%.

15. The polyester resin according to claim 1, wherein the Component B is present in an amount of from 1 to 40% by weight of the total amount of Components A to E and such that the amount of A to E totals 100%.

16. The polyester resin according to claim 1, wherein at least 20% by weight of the total amount of Components A to E comprise biorenewable material.

17. An emulsion comprising a polyester resin as claimed in claim 1 dispersed in an aqueous medium.

18. A coating composition comprising an emulsion as claimed in claim 17.

19. A coating composition comprising a polyester resin as claimed in claim 1.

20. The coating composition according to claim 19, wherein the coating composition is a powder coating composition.

21. A coating obtained from a coating composition as claimed in claim 19.

22. A method of preparing a coated article or a coated substrate comprising the step of coating an article or a substrate with a coating composition as claimed in claim 19.

23. The method according to claim 22, wherein the method further comprises the step of curing the coating composition.

24. An article or a substrate comprising a coating composition as claimed in claim 19.

25. An article or a substrate having coated and cured thereon a coating composition as claimed in claim 19.

Description

EXAMPLES

(1) The present invention will now be described in detail with reference to the following non limiting examples which are by way of illustration only.

Example 1: Imide

(2) As an example citric acid glycine imide (formula I1) was prepared by introducing in a 1 liter glass reactor, fitted with mechanical stirrer, nitrogen inlet, thermocouple and Dean-Stark trap, 192.1 grams (1 mole) citric acid, 75.1 grams (1 mole) glycine and 200 grams of xylene; heating the mixture to reflux at 140 C. for about 4 hours when 36 grams of water was collected in the trap; and removing the solvent by vacuum distillation. The brown viscous liquid material was poured out and solidified into a brittle and clear solid. The identity was confirmed by H NMR, and purity estimated to be at least 95%.

Example 2: Imide

(3) Citric acid phenylalanine imide (formula I3) was prepared by reacting according to the process of example 1, 192.1 grams (1 mole) citric acid and 165.2 grams (1 mole) L-phenylalanine. The resulting product was a reddish brown viscous liquid material, which solidified into a brittle and clear solid.

Example 3: Resin

(4) A citric imide alkyd was prepared by a two-step procedure using the same equipment of example 1. First an alkyd prepolymer was made by reacting 68.1 grams pentaerythritol, 71.7 grams benzoic acid and 185.2 grams soybean fatty acids to an acid value of 4.8 mgKOH/g at 230 C. using xylene azeotropic water removal. After this 143.5 grams of solid, ground imide from Example 2 was introduced at 150-170 C. in portions under stirring and temperature was raised to max 220 C. The mixture was reacted to low acid value by azeotropic water removal, and the resin was diluted in xylene and poured out.

Example 4: Imide

(5) Succinic acid glycine imide (formula I5) was prepared by introducing in a 2 liter glass reactor, fitted with mechanical stirrer, nitrogen inlet, thermocouple and Dean-Stark trap, 622.8 grams succinic acid, 377.2 grams glycine and a suitable amount of xylene; heating the mixture to reflux at 140-180 C. for about 10 hours when 176 grams of water was collected in the trap; and removing the solvent by vacuum distillation. The brown viscous liquid material was poured out and solidified into a brittle and clear solid. The identity was confirmed by H NMR.

Example 5: Imide

(6) Succinic acid lysine diimide (formula I7) was prepared as follows: A 50% solution of 765.3 grams succinic acid in xylene was heated to 125 C. in a 3 liter glass reactor, fitted with mechanical stirrer, nitrogen inlet, thermocouple and Dean-Stark trap. 782.5 grams of a 53% solution of lysine in water (commercially available from Ajinomoto Eurolysine SAS as LLB-50) was dosed during 2 hours while removing water azeotropically. Water removal is continued until no reaction water is formed anymore and xylene is distilled off at maximum 160 C. The brown viscous liquid material was poured out and solidified into a brittle and clear solid.

Example 6: Imide

(7) Succinic acid phenylalanine imide (formula I8) was prepared by reacting according to the process of example 4, 192.1 grams succinic acid and 165.2 grams L-phenylalanine. The resulting product was a reddish brown viscous liquid material, which solidified into a brittle and clear solid.

Examples 7-9: Resins

(8) Succinimide based alkyds were prepared by a two-step procedure using the same equipment of example 4: First a prepolymer was made from 367 grams of soybean oil fatty acids, 234 grams of pentaerythritol, 200 grams of succinimide from example 4, 5 or 6, and 193 grams of phthalic anhydride using azeotropic water removal at 230 C. After reaching an acid value below 5 mgKOH/g, 38 grams of succinic acid were added and reaction was continued until acid value dropped below 15 mgKOH/g. After cooling down further xylene was added to obtain a clear low viscosity liquid resin with properties as shown in table 1.

Comparative Example A: Resin

(9) A comparative resin was prepared by reacting in a 2 liter glass reactor, fitted with mechanical stirrer, nitrogen inlet, thermocouple and Dean-Stark trap, 368 grams of soybean oil fatty acids, 266 grams of pentaerythritol, 163 grams of benzoic acid, 285 grams of phthalic anhydride and a suitable amount of xylene using azeotropic water removal at 230 C. until an acid value below 15 mgKOH/g was obtained. After cooling down further xylene was added to obtain a clear low viscosity liquid resin with properties as shown in table 1.

(10) TABLE-US-00001 TABLE 1 Resin characteristics Solids Acid Imide content value Mn Mw Example Resin based on: example (%) mgKOH/g Da kDa 3 BA*, Phenylalanine citric 2 64.9 12 2550 10 imide 7 PA*, Glycine succinimide 4 62.1 10 3010 47 8 PA, Lysine succinic diimide 5 65.5 14 2500 13 9 PA, Phenylalanine 6 61.0 12 2630 43 succinimide Comp A PA and BA none 74.7 10 3420 37 *PA = phthalic anhydride, BA = benzoic acid

Example 10: Resin

(11) An alkyd containing succinimide and citric imide was prepared by a two-step procedure using the same equipment of example 4: 285 grams of soybean oil fatty acids, 140 grams of pentaerythritol, 40 grams of sebacic acid and 197 grams of succinic acid lysine diimide (example 5) were charged to a reactor fitted with thermocouple, stirrer, nitrogen flow and Dean-Stark trap, and heated to 220 C. After reaching an acid value below 5 mgKOH/g, the reactor was cooled to 150 C. and 181 grams of citric acid phenylalanine imide (example 2) were charged to the reactor. The reactor was heated to 180 C. under xylene reflux conditions and the distillation was stopped when the acid value dropped below 15 mgKOH/g. Next vacuum distillation was performed for removal of xylene azeotropic solvent and finally the resin was poured out.

Example 11: Emulsion Resin

(12) 301 grams of the solid resin from example 10 were emulsified as follows. The resin was heated to between 50-80 C. and 27 grams of a 30% solution of a highly branched alcohol based surfactant combining anionic and non-ionic components and 84 grams of demineralised water were added. The mixture was neutralised with a non-amine base and was stirred until homogeneous. Demineralised water was added during 2 hours until a solids content of 50% was obtained. The emulsion showed a milky appearance and was stable.

Example 12: Emulsion Resin

(13) The succinimide resin from example 8 was emulsified as follows. Xylene was removed by vacuum distillation, and the resin was dissolved in acetone at 64%. 229 grams of this solution were heated to 50 C. and neutralised with a non-amine base. 220 grams of demineralised water were added under stirring. Acetone was removed by vacuum distillation. The emulsion showed a milky appearance and was stable.

Example 13: Emulsion Resin

(14) A 1:1 (on solids) mixture of succinimide resins from example 8 and example 9 was emulsified as follows. Xylene was removed by vacuum distillation, and the resin was dissolved in acetone at 65%. 230 grams of this solution were heated to 50 C. and neutralised with a non-amine base. 225 grams of demineralised water were added under stirring. Acetone was removed by vacuum distillation. The emulsion showed a milky appearance and was stable.

Comparative Example B: Emulsion Resin

(15) Commercially available Uradil AZ-760 (ex DSM Resins) was denoted as Comparative Emulsion resin B.

Example 14: Paints

(16) Paints were produced by mixing in a Cowless dissolver resin solution (44 grams solid resin), 28 grams of Tioxide TR 92 (pigment) and 0.30 grams of Nuosperse FA 601 (dispersant) and milling them into a mill paste. To this paste were added under stirring 0.26 grams Octasoligen Cobalt 10 (cobalt drier) 0.70 grams Calcium naphthenate (calcium drier), 1.83 grams Octasoligen Zirconium 12 (zirconium drier), 0.3 grams Borchinox M2 (antiskinning agent) 3-5 grams Dowanol PM (methoxypropyleneglycol) and xylene to give application viscosity.

(17) These paints showed the following properties (table 2).

(18) TABLE-US-00002 TABLE 2 Paint properties Resin from example: Comp A 3 Drying dust free (hrs:min) <0:30 1:00 Knig Hardness 1 day 24 17 Knig Hardness 28 days 70 55 Yellowing in the dark at 50 C. b* Initial 2.73 4.81 b* after 14 days 50 C. 1.38 1.48 Water resistance average value (1-5) 4.3 4.0
Results in table 2 show that properties of a paint according to the invention are (almost) equal to than those of the comparative paint. It is concluded that this type of imide can replace phthalic anhydride as a monomer in an alkyd resin.

Example 15: Paints

(19) Paints were produced by mixing in a Cowless dissolver resin solution (44 grams solid resin), 28 grams of Tioxide TR 92 (pigment) and 0.30 grams of Nuosperse FA 601 (dispersant) and milling them into a mill paste. To this paste were added under stirring 0.26 grams 0.31 grams Borchi-Oxy-Coat (iron drier), 0.70 grams Calcium naphthenate (calcium drier), 1.83 grams Octasoligen Zirconium 12 (zirconium drier), 0.3 grams Borchinox M2 (antiskinning agent) and xylene to give application viscosity.

(20) These paints showed the following properties (table 3).

(21) TABLE-US-00003 TABLE 3 Paint properties Resin from example: Comp A 7 8 9 Drying Dust free time (hrs:min) 0:24 0:19 0:16 0:23 Drying Tack free time (hrs:min) 1:39 0:34 0:31 1:38 Knig Hardness 1 day 34 31 44 53 Knig Hardness 15 days 73 76 83 89 Yellowing in the dark at 50 C. b* Initial 2.46 2.91 2.85 2.71 b* after 14 days 50 C 1.32 1.50 1.45 1.69 Water resistance average value (1-5) 4.7 4.4 4.3 4.7

(22) Results in table 3 show that properties of paints according to the invention are equal or better than those of the comparative paint. Especially hardness development and/or drying behavior are improved. It is concluded that this type of imide can replace benzoic acid as a monomer in an alkyd resin.

Example 16: Emulsion Paints

(23) A paste was produced by mixing in a Cowless dissolver 5 grams of demi water, 22.5 grams of Tioxide TR 92 (pigment), 1.1 grams of Disperbyk 2015 (dispersant) and 0.1 grams of Byk 028 antifoam agent and milling them into a mill paste. To this paste were added under stirring resin emulsion (25 grams solid resin), 0.88 grams Borchi-Oxy-Coat 1101 diluted 9:1 in demi water (iron drier), 7.2 grams of Acrysol RM2020 (thickener) and demi water to give solids content of 48%.

(24) These emulsion paints showed the following properties (table 4).

(25) TABLE-US-00004 TABLE 4 Paint properties Resin from example: Comp B 12 13 Drying Dust free time (hrs:min) 0:40 0:40 0:35 Drying Tack free time (hrs:min) 3:10 3:10 2:45 Knig Hardness 1 day 17 20 23 Knig Hardness 28 days 34 42 51 Yellowing in the dark at 50 C. b* Initial 2.40 2.58 2.59 b* after 14 days 50 C 1.86 2.05 1.93 Water resistance average value (1-5) 5.0 3.0 4.2

(26) Results in table 4 show that properties of emulsion paints according to the invention are equal or better than those of the comparative paint. Especially hardness development is improved and drying behavior is improved when applying resin of example 13. It is concluded that this type of imide can replace benzoic acid as a monomer also in an alkyd emulsion resin.