Acrylic polyol resins compositions

Abstract

The invention relates to compositions of hydroxyl functional acrylic resins (acrylic polyols) comprising a mixture of ,-branched alkane carboxylic glycidyl esters derived from butene oligomers characterized in that the sum of the concentration of the blocked and of the highly branched isomers is maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition.

Claims

1. An hydroxyl functional acrylic resin composition comprising a mixture of ,-branched alkane carboxylic glycidyl esters wherein a sum of a concentration of blocked isomers and of highly branched isomers is a maximum amount of 55 wt % based on a total weight of the mixture.

2. The composition of claim 1 wherein the mixture of ,-branched alkane carboxylic glycidyl esters is based on a neononanoic (C9) acid mixture wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is a maximum amount of 55 wt % based on the total weight of the mixture.

3. The composition of claim 2 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester, 2-methyl 2-ethyl hexanoic acid glycidyl ester or 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters.

4. The composition of claim 2 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount below 40 wt % based on the total weight of the mixture.

5. The composition of claim 2 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount above 10 wt % based on the total weight of the mixture.

6. The composition of claim 2 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester, 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount above 40 wt % based on the total weight of the mixture.

7. The composition of claim 2 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester in an amount of 1 to 15 wt %, 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount of 40 to 70 wt % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount of 8 to 32 wt % based on the total weight of the mixture.

8. The composition of claim 2 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester in an amount of 2 to 10 wt %, 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount of 47 to 61 wt % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount of 10 to 25 wt % based on the total weight of the mixture.

9. A process to prepare the composition of claim 1 comprising incorporating the mixture of ,-branched alkane carboxylic glycidyl esters having epoxy groups into the hydroxyl functional acrylic resins by the reaction of the epoxy group with a carboxylic acid group of an ethylene carboxylic acid compounds from hydroxyl ethylene carboxylate ester monomers which are reacted with one or more unsaturated monomers via a radical polymerization reaction, in one step or more.

10. The composition of claim 1 wherein the hydroxyl functional acrylic resin composition has a calculated hydroxyl value between 50 and 180 mgKOH/g on solids or a number average molecular weight (Mn) between 2500 and 50000 Dalton according to a polystyrene standard.

11. A binder composition useful for a coating composition comprising the hydroxyl functional acrylic resin composition of claim 1.

12. A metal or plastic substrate coated with a coating composition comprising the binder composition of the claim 11.

13. The binder composition of claim 11 wherein the coating composition comprises 10 to 40 weight % of aliphatic isocyanate, 0-25 weight % of polyester polyol, and 40-70 weight % of the hydroxyl functional acrylic resin composition of claim 1, all weight % based on solid material after evaporation of the solvents.

14. The composition of claim 8 prepared in presence of polyester polyol.

15. An acrylic polyol copolymer resin comprising 5 to 70 weight percent of the reaction product of a secondary alcohol and maleic anhydride which has been subsequently reacted with the composition of claim 1.

16. A coating composition comprising a polyester-ether resin which is the reaction product of the composition of claim 1 and dimethylol propionic acid.

17. The composition of claim 1 wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is below 40 wt % based on the total weight of the mixture.

18. The composition of claim 1 wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is below 30 wt % based on the weight of the mixture.

19. The composition of claim 2 wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is below 40 wt % based on the total weight of the mixture.

20. The composition of claim 2 wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is below 30 wt % based on the total weight of the mixture.

21. The composition of claim 4 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount below 30 wt % based on the total weight of the mixture.

22. The composition of claim 4 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount below or equal to 25 wt % based on the total weight of the mixture.

23. The composition of claim 5 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount above 30 wt % based on the total weight of the mixture.

24. The composition of claim 5 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount above 45 wt % based on the total weight of the mixture.

25. The composition of claim 6 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester, 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount above 55 wt % based on the total weight of the mixture.

26. The composition of claim 6 wherein the mixture of ,-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester, 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount above 65 wt % based on the total weight of the mixture.

27. The composition of claim 1 wherein the mixture of ,-branched alkane carboxylic glycidyl esters is derived from butene oligomers.

Description

EXAMPLES

Chemicals Used

(1) Cardura E10: available from Momentive Specialty Chemicals Neononanoic glycidyl ester from Momentive Specialty Chemicals GE9S: neononanoic glycidyl ester of composition A (see Table 2 below) GE9H: neononanoic glycidyl ester of composition B (see Table 2 below) Neononanoic glycidyl ester of composition C (see Table 2 below) Neononanoic glycidyl ester of composition D (see Table 2 below) Neononanoic glycidyl ester of composition E (see Table 2 below)

(2) TABLE-US-00002 TABLE 2 Composition of the neononanoic glycidyl ester (according to the described gas chromatography method for glycidyl esters of neo-acid) Glycidyl ester of acid V9XX (described in Table 1) A (%) B (%) C (%) D (%) E (%) V901 6.5 0.1 3.7 0.1 0.1 V902 0.6 2.55 0.6 2.4 2.65 V903 1.1 0.7 0.3 1.0 0.4 V904 0.8 1 0.1 2.2 0.4 V905 0.2 13.1 0.5 4.1 14.5 V906 0.4 11.6 0.4 9.6 12.6 V907 0.2 15.4 0.1 36.4 5.6 V908 0.1 0 0.1 0.0 0.0 V909 54.8 2.55 52.8 2.4 2.65 V910 K1 7.8 0 10.0 0.0 0.0 V910 K2 7.7 0.6 12.8 0.4 0.7 V911 2.4 1.2 0.7 2.0 0.8 V912 0.0 28.3 0.0 22.4 33.5 V913 6.8 0.1 6.4 0.1 0.1 V914 4.5 0 3.8 0.0 0.0 V915 0.6 22.3 0.6 16.8 25.3 V916 4.4 0.1 5.2 0.1 0.1 V917 1.1 0.4 2.1 0.1 0.4 GES: glycidyl ester of pivalic acid obtained by reaction of the acid with epichlorhydrin. Ethylene glycol from Aldrich Monopentaerythritol: available from Sigma-Aldrich 3,3,5 Trimethyl cyclohexanol: available from Sigma-Aldrich Maleic anhydride: available from Sigma-Aldrich Methylhexahydrophtalic anhydride: available from Sigma-Aldrich Hexahydrophtalic anhydride: available from Sigma-Aldrich Boron trifluoride diethyl etherate (BF3.OEt2) from Aldrich Acrylic acid: available from Sigma-Aldrich Methacrylic acid: available from Sigma-Aldrich Hydroxyethyl methacrylate: available from Sigma-Aldrich Styrene: available from Sigma-Aldrich 2-Ethylhexyl acrylate: available from Sigma-Aldrich Methyl methacrylate: available from Sigma-Aldrich Butyl acrylate: available from Sigma-Aldrich Di-t-Amyl Peroxide is Luperox DTA from Arkema tert-Butyl peroxy-3,5,5-trimethylhexanoate: available from Akzo Nobel Xylene n-Butyl Acetate from Aldrich Dichloromethane from Biosolve Thinner: A: is a mixture of Xylene 50 wt %, Toluene 30 wt %, ShellsolA 10 wt %, 2-Ethoxyethylacetate 10 wt %. Thinner B: is butyl acetate Curing agents, HDI: 1,6-hexamethylene diisocyanate trimer, Desmodur N3390 BA from Bayer Material Science or Tolonate HDT LV2 from Perstorp Leveling agent: BYK 10 wt % which is BYK-331 diluted at 10% in butyl acetate Catalyst: DBTDL 1 wt % which is Dibutyl Tin Dilaurate diluted at 1 wt % in butyl acetate Catalyst: DBTDL 10 wt % which is Dibutyl Tin Dilaurate diluted at 10 wt % in butyl acetate

Example 01

(3) The following constituents were charged to a reaction vessel equipped with a stirrer, a condenser and a thermometer: 92.4 grams of GE9S, 24.0 grams of Butyl Acetate. That initial reactor charge has been heated up to 135 C. Then, the following mixture was added over a period of 1 h 20 while keeping the temperature constant: 30.7 grams of acrylic acid, 1.2 grams of Di-t-Amyl Peroxide, 12.0 grams of n-Butyl Acetate. After further adding 1.2 grams of Di-t-Amyl Peroxide and 20.4 grams of n-Butyl Acetate, a post-cooking was pursued at 135 C. for 1 h. The acrylic polyol had a molecular weight (Mw) of 11400 Daltons and a Tg of about 10 C.

Example 02 Comparative

(4) The following constituents were charged to a reaction vessel equipped with a stirrer, a condenser and a thermometer: 92.4 grams of GE9H, 24.0 grams of Butyl Acetate. That initial reactor charge has been heated up to 135 C. Then, the following mixture was added over a period of 1 h 18 while keeping the temperature constant: 30.2 grams of acrylic acid, 1.2 grams of Di-t-Amyl Peroxide, 12.0 grams of n-Butyl Acetate. After further adding 1.2 grams of Di-t-Amyl Peroxide and 20.4 grams of n-Butyl Acetate, a post-cooking was pursued at 135 C. for 1 h. The acrylic polyol had a molecular weight (Mw) of 8600 Daltons and a Tg of about +26 C.

(5) Observations:

(6) Tg of acrylic polyols is impacted by the composition of the neononanoic glycidyl ester (see examples 01, 02).

Example 03

(7) The adducts of Glycidyl neononanoate, GE9S and acrylic acid or methacrylic acid.

(8) The adducts of Glycidyl neononanoate GE9S (see Table 3) with acrylic acid (ACE-adduct) and with methacrylic acid (MACE-adduct) are acrylic monomers that can be used to formulate hydroxyl functional (meth)acrylic polymers.

(9) TABLE-US-00003 TABLE 3 Compositions of the adducts intakes in parts by weight Acrylic acid Meth acrylic acid adduct adduct Initial reactor charge GE9S 250 250 Acrylic acid 80 Methacrylic acid 96.5 Radical Inhibitor 4-Methoxy phenol 0.463 0.463 Catalyst DABCO T9 (0.07 wt % on Glycidyl 0.175 0.175 ester) DABCO T9 and 4-Methoxy phenol (185 ppm calculated on glycidyl ester weight), are charged to the reactor. The reaction is performed under air flow (in order to recycle the radical inhibitor). The reactor charge is heated slowly under constant stirring to about 80 C., where an exothermic reaction starts, increasing the temperature to about 100 C. The temperature of 100 C. is maintained, until an Epoxy Group Content below 30 meq/kg is reached. The reaction mixture is cooled to room temperature.

Example 04

Acrylic Resins for High Solids Automotive Refinish Clearcoats

(10) A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 4) heated to 160 C. The monomer mixture including the initiator was then gradually added to the reactor via a pump over 4 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 160 C. Finally the polymer is cooled down to 135 C. and diluted to a solids content of about 68% with xylene.

(11) TABLE-US-00004 TABLE 4 Acrylic resins recipe Weight % in Reactor 1 L (g) Initial Reactor Charge GE9S or GE9H (Comparative) 28.2 169.1 Xylene 2.7 16.2 Feeding materials Acrylic acid 10 59.8 Hydroxy ethyl methacrylate 16.0 96.0 Styrene 30.0 180.0 Methyl methacrylate 15.8 95.0 Di t-Amyl peroxide 4.0 24.0 Xylene 8.3 49.8 Post cooking Di t-Amyl peroxide 1.0 6.0 Xylene 3.0 18.0 Solvent adding at 130 C. Xylene 50.8 305.0 Final solids content 61.8% Hydroxyl content 4.12%

Example 05

Clear Coats for Automotive Refinish

(12) Solvents were blended to yield a thinner mixture of the following composition (table 5):

(13) TABLE-US-00005 TABLE 5 Thinner composition Thinner Weight % in solvent blend, theory Toluene 30.1% ShellSolA 34.9% 2-ethoxyethyl acetate 10.0% n-Butyl acetate 25.0% Total 100%

(14) A clearcoat was then formulated (table 6) with the following ingredients (parts by weight):

(15) TABLE-US-00006 TABLE 6 Clearcoat formulation Resin of Desmodur BYK 10 wt % DBTDL 1 wt % example ex 04 N3390 in ButAc in ButAc Thinner 80.1 27.01 0.53 1.17 40.45

(16) TABLE-US-00007 Clearcoat properties GE9H (Comparative) GE9S Volatile organic content 480 g/l 481 g/l Initial viscosity 54 cP 54 cP Dust free time 12 minutes 14.5 minutes Koenig Hardness after 6 hours 8.3 s 7.1 s

Example 06

Acrylic Resins for First Finish Automotive Topcoats

(17) GE9S based (28%) acrylic polymers for medium solids first-finish clear coats.

(18) A reactor for acrylic polyols is flushed with nitrogen and the initial reactor charge (see Table 7) heated to 140 C. At this temperature the monomer mixture including the initiator is added over 4 hours to the reactor via a pump. Additional initiator is fed into the reactor during one hour, and then the mixture is kept at 140 C. to complete the conversion in a post reaction. Finally the polymer is cooled down and diluted with butyl acetate to a solids content of about 60%.

(19) TABLE-US-00008 TABLE 7 Acrylic resins recipe Intakes (parts by weight) Initial reactor charge GE9S 164.40 Xylene 147.84 Monomer mixture Acrylic acid 53.11 Butyl methacrylate 76.88 Butyl acrylate 48.82 Hydroxy-ethyl methacrylate 27.20 Styrene 177.41 Methyl methacrylate 47.31 Initiator Di-tert.-amyl peroxide (DTAP) 8.87 Post addition Di-tert.-amyl peroxide 5.91 Solvent (to dilute to 60% solids) Butyl acetate 246.00 Total 1000.0
Clear Lacquer Formulation

(20) Clear lacquers are formulated (see table 8) from the acrylic polymers by addition of Cymel 1158 (curing agent from CYTEC), and solvent to dilute to spray viscosity. The acidity of the polymer is sufficient to catalyze the curing process, therefore no additional acid catalyst is added. The lacquer is stirred well to obtain a homogeneous composition.

(21) TABLE-US-00009 TABLE 8 Clear lacquer formulations and properties of the polymers Intakes (part by weight) Ingredients Acrylic polymer 60.0 Cymel 1158 8.8 Butyl acetate (to application viscosity) 24.1 Properties Solids content [% m/m] 45.3 Density [g/ml] 0.97 VOC [g/l] 531
Application and Cure

(22) The coatings are applied with a barcoater on Q-panels to achieve a dry film thickness of about 40 m. The systems are flashed-off at room temperature for 15 minutes, then baked at 140 C. for 30 minutes. Tests on the cured systems are carried out after 1 day at 23 C.

Example 07

(23) In a reactor equipped with an anchor stirrer, a thermometer, condenser and monomer/initiator feeding system, 188.6 g of GE9S and 90 g of ethoxypropanol (EPR) were loaded and heated to about 150 C. (see Table 9). A mixture of 52 g of hydroxyethylmethacrylate (HEMA), 160 g of styrene, 68 g of acrylic acid (AA), 10 g of dicumylperoxide (DCP), 37.7 g of GE9S and 40 g of ethoxypropanol (EPR) were added over 2 hours 30 minutes to the reactor while keeping its content at 150 C. After the feed, the reactor content was held for 30 minutes at this temperature. After the 30 minutes hold period, 108 g of HEMA, 30 g of AA, 142 g of isobutyl methacrylate (IBMA), 5 g of DCP and 45 grams of EPR were added over 2 hours and 30 minutes at about 150 C. followed by a rinsing step for the feed system with 5 g of EPR. After the rinsing step, the content of the reactor was held for 2 hours at 150 C. The reactor content was cooled down to 100 C. and 100 parts of EPR were distilled off at atmospheric pressure.

(24) The polyacrylate polyol has a solids content of the solution of 90% by weight.

(25) TABLE-US-00010 TABLE 9 Composition of polyol Materials Intake (g) Initial charge EPR 90 GE9S 188.6 Monomer Addition 1 AA 68 Styrene 160 GE9S 37.7 HEMA 52 EPR 40 DCP 10 Monomer Addition 2 AA 30 IBMA 142 HEMA 108 DCP 5 EPR 45 TOTAL 976.3

Example 08

Maleate Diester Based Resin Prepared According to the Teaching of WO2005040241

(26) Equipment: Glass reactor equipped with an anchor stirrer, reflux condenser and nitrogen flush.

(27) Manufacturing Procedure of the Maleate Diester:

(28) Maleic anhydride was reacted with the selected alcohol (3,3,5 trimethyl cyclohexanol) in an equimolar ratio at 110 C. to form a maleate monoester in presence of around 5 wt % butyl acetate. The reaction was continued until conversion of the anhydride had reached at least 90% (Conversion of the anhydride is monitored by acid-base titration.). Methanol was added to open the remaining anhydride in a 1.2/1 molar ratio of methanol/anhydride and the reaction was continued for 30 minutes.

(29) GE9S was fed to the reactor in 30 minutes in an equimolar ratio to the remaining acid in the system whilst keeping the temperature at 110 C. The system was then allowed to react further for 1 hour at 110 C.

(30) Manufacturing Procedure of the Maleate-Acrylic Resin (See Table 10):

(31) The reactor was flushed with nitrogen and the initial reactor charge was heated to the polymerization temperature of 150 C. The first charge of Di ter-amylperoxide was then added in one shot. Immediately after this addition, the monomer-initiator mixture was dosed continuously to the reactor in 330 minutes at the same temperature. The monomer addition feed rate was halved during the last hour of monomer addition. After completion of the monomer addition, the third charge of Di ter-amylperoxide was then fed together with a small amount of the butyl acetate to the reactor in 15 minutes. The reactor was kept at this temperature for 60 more minutes. Finally, the polymer was cooled down.

(32) TABLE-US-00011 TABLE 10 Composition of TMCH maleate based resin Parts by weight Initial Reactor BuAc 8 Charge [g] Maleate diester 40.7 Initiator start [g] Di tert amyl peroxide 0.4 Monomer feed [g] BuAc 3 Hydroxyethyl methacrylate 21.5 Styrene 20 Methyl methacrylate 17.8 Methacrylic Acid 2.2 Di tert amyl peroxide 3.6 Post cooking [g] DTAP (with 10 g BuAc) 1 Total intake [g] 118.2

Example 09

Polyester-Ether Resin

(33) The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 456 g of GE9S, 134 g of dimethylolpropionic acid and 0.35 g of stannous octoate.

(34) The mixture was heated to a temperature of about 110 C. for about 1 hour and then steadily increased to 150 C. in 3 hours and then cooled down.

(35) This polyester-ether was then formulated in high solids and very high solids 2K polyurethane topcoats either as sole binder or as reactive diluent for an acrylic polyol.