The present invention relates to a composition of acrylic polyol resins based on a composition of hydroxyl functional acrylic resins (acrylic polyols) comprising a mixture of Î±,Î±-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, which lead for example to improved leveling of the coatings derived thereof.

More in particular the invention relates to acrylic polyol resins compositions comprising aliphatic tertiary saturated carboxylic acids or Î±,Î±-branched alkane carboxylic acids, which contain 9 or 13 carbon atoms and which provide glycidyl esters with a branching level of the alkyl groups depending on the olefin feedstock used and/or the oligomerization process thereof, and which is defined as below.

The glycidyl ester derived from olefins containing 5 to 10 carbon atoms in the alkyl chain are used by the industry to introduce modified resins by reaction such a glycidyl ester with acrylic resins, such as given in U.S. Pat. No. 6,136,991.

It is generally known from e.g. U.S. Pat. No. 2,831,877, U.S. Pat. No. 2,876,241, U.S. Pat. No. 3,053,869, U.S. Pat. No. 2,967,873 and U.S. Pat. No. 3,061,621 that mixtures of Î±,Î±-branched alkane carboxylic acids can be produced, starting from mono-olefins, carbon monoxide and water, in the presence of a strong acid.

One of the more recent methods has been disclosed in EP 1033360A1. The problem of providing better softening derivatives of Î±,Î±-branched acids, manufactured from alkenes, carbon monoxide and water and a nickel catalyst was solved therein by a process, which actually comprised:

- (a) oligomerization of butene;
- (b) separation of butene dimers and/or trimers from the oligomeriszate;
- (c) conversion of the butene dimers and/or trimers into carboxylic acids;
- (d) conversion of the carboxylic acids into the corresponding vinyl esters showing attractive softening properties when mixed into other polymers or if used as comonomers in coatings.

If the olefin feed is based on Raf. II or Raf III or any mixture rich in n-butene isomers on the total olefins, the subsequently mixture of neo-acid (C9 or C13 acids) derivatives will provide a mixture where the concentration of blocked and highly branched isomers is maximum 55%, preferably below 40%, and most preferably below 30%.

The glycidyl esters can be obtained according to PCT/EP2010/003334 or the U.S. Pat. No. 6,433,217.

We have discovered that well chosen blend of isomers of the glycidyl ester of mixture compositions of neo-acid (C9 or C13 acids) glycidyl ester, is providing for example a good leveling of a coating, is a mixture where the sum of the concentration of blocked and highly branched isomers is maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition.

We have further discovered that well chosen blend of isomers of the glycidyl ester of, for example, neononanoic acids give different and unexpected performance in combination with some particular polymers such as acrylic polyols.

The isomers are described in Table 1 and illustrated in Scheme 1.

We have found that the performance of the glycidyl ester compositions derived from the branched acid is depending on the branching level of the alkyl groups R¹, R²and R³, for example the neononanoic acid has 3, 4 or 5 methyl groups. Highly branched isomers are defined as isomers of neo-acids having at least 5 methyl groups.

Neo-acids, for example neononanoic acids (V9) with a secondary or a tertiary carbon atoms in the Î² position are defined as blocking isomers.

Mixture compositions of neononanoic (C9) acids glycidyl esters providing for example a good leveling of a coating, is a mixture where the sum of the concentration of the blocked and of the highly branched isomers derivatives is maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition.

Furthermore the above compositions of neononanoic acids glycidyl esters mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester or 2-methyl 2-ethyl hexanoic acid glycidyl ester or 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters.

Furthermore the above compositions of neononanoic acids glycidyl esters mixture is comprising 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) below 40%, preferably below 30% and most preferably below or equal 25% weight on total composition.

Furthermore the above compositions of neononanoic acids glycidyl esters mixture is comprising 2-methyl 2-ethyl hexanoic acid glycidyl ester above 10%, preferably above 30% and most preferably above 45% weight on total composition.

The above compositions of the glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester and 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) is above 40%, preferably 55% and most preferably 65% weight on total composition.

A preferred composition is comprising a mixture of 2,2-dimethyl heptanoic acid glycidyl ester in 1 to 15 weight % and 2-methyl 2-ethyl hexanoic acid glycidyl ester in 40 to 70 weight % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) in 8 to 32 weight % on total composition.

A further preferred composition is comprising a mixture of 2,2-dimethyl heptanoic acid glycidyl ester in 2 to 10 weight % and 2-methyl 2-ethyl hexanoic acid glycidyl ester in 47 to 61 weight % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) in 10 to 25 weight % on total composition.

The above glycidyl esters compositions can be used for example, as reactive diluent or as momomer in binder compositions for paints or adhesives.

The glycidyl esters compositions can be used as reactive diluent for epoxy based formulations such as exemplified in the technical brochure of Momentive (Product Bulletin: Cardura E10P The Unique Reactive Diluent MSC-521).

Other uses of the glycidyl ester are the combinations with polyester polyols, or acrylic polyols, or polyether polyols. The combination with acrylic polyols such as the one used in the car industry coating leads to coating system with attractive coating appearance.

Methods Used

The isomer distribution of neo-acid can be determined using gas chromatography, using a flame ionization detector (FID). 0.5 ml sample is diluted in analytical grade dichloromethane and n-octanol may be used as internal standard. The conditions presented below result in the approximate retention times given in Table 1. In that case n-octanol has a retention time of approximately 8.21 minute.

The GC method has the following settings:

Column: CP Wax 58 CB (FFAP), 50 mÃ—0.25 mm, df=0.2 Î¼m
Oven program: 150Â° C. (1.5 min)âˆ’3.5Â° C./minâˆ’250Â° C. (5 min)=35 min
Carrier gas: Helium
Flow: 2.0 mL/min constant
Split flow: 150 mL/min
Split ratio: 1:75
Injector temp: 250Â° C.
Detector temp: 325Â° C.
Injection volume: 1 Î¼L

CP Wax 58 CB is a Gas chromatography column available from Agilent Technologies.

The isomers of neononanoic acid as illustrative example have the structure (R¹R²R³)â€”Câ€”COOH where the three R groups are linear or branched alkyl groups having together a total of 7 carbon atoms.

The structures and the retention time, using the above method, of all theoretical possible neononanoic isomers are drawn in Scheme 1 and listed in Table 1. The isomers content is calculated from the relative peak area of the chromatogram obtained assuming that the response factors of all isomers are the same.

TABLE 1Structure of all possible neononanoic isomersMethylRetention timeR1R2R3groupsBlocking[Minutes]V901MethylMethyln-pentyl3No8.90V902MethylMethyl2-pentyl4Yes9.18V903MethylMethyl2-methyl butyl4No8.6V904MethylMethyl3-methyl butyl4No8.08V905MethylMethyl1,1-dimethyl propyl5Yes10.21V906MethylMethyl1,2-dimethy propyl5Yes9.57V907MethylMethyl2,2-dimethyl propyl5No8.26V908MethylMethyl3-pentyl4Yes9.45V909MethylEthyln-butyl3No9.28V910 K1MethylEthyls-butyl4Yes9.74V910 K2MethylEthyls-butyl4Yes9.84V911MethylEthyli-butyl4No8.71V912MethylEthylt-butyl5Yes9.64V913Methyln-propyln-propyl3No8.96V914Methyln-propyli-propyl4Yes9.30V915Methyli-propyli-propyl5Yes9.74V916EthylEthyln-propyl3No9.44V917EthylEthyli-propyl4Yes10.00

The isomer distribution of glycidyl esters of neo-acid can be determined by gas chromatography, using a flame ionization detector (FID). 0.5 ml sample is diluted in analytical grade dichloromethane.

The GC method has the following settings:

Column: CP Wax 58 CB (FFAP), 50 mÃ—0.2 mm, df=0.52 Î¼m
Oven: 175Â° C. (5 min)âˆ’1Â° C./minâˆ’190Â° C. (0 min)âˆ’10Â° C./minâˆ’275Â° C. (11.5 min)
Flow: 2.0 mL/min, constant flow
Carrier gas: Helium
Split ratio: 1:75
Injection volume: 1 Î¼L
S/SL injector: 250Â° C.

CP Wax 58 CB is a Gas chromatography column available from Agilent Technologies.

The isomers of glycidyl esters of neononanoic acid as illustrative example have the structure (R¹R²R³)â€”Câ€”COOâ€”CH₂â€”CH(O)CH₂where the three R groups are linear or branched alkyl groups having together a total of 7 carbon atoms.

The isomers content is calculated from the relative peak area of the chromatogram obtained assuming that the response factors of all isomers are the same.

GC-MS method can be used to identify the various isomers providing that the analysis is done by a skilled analytical expert.

[Image Omitted]

Methods for the Characterization of the Resins

The molecular weights of the resins are measured with gel permeation chromatography (Perkin Elmer/Water) in THF solution using polystyrene standards. Viscosity of the resins are measured with Brookfield viscometer (LVDV-I) at indicated temperature. Solids content are calculated with a function (Wwâˆ’Wd)/WwÃ—100%. Here Ww is the weight of a wet sample, Wd is the weight of the sample after dried in an oven at a temperature 110Â° C. for 1 hour.

Tg (glass transition temperature) has been determined either with a DSC 7 from Perkin Elmer or with an apparatus from TA Instruments Thermal Analysis. Scan rates were respectively 20 and 10Â° C./min. Only data obtained in the same experimental conditions have been compared. If not, the temperature difference occurring from the different scanning rate has been proved not significant for the results compared.

Blocking Isomers

Whereas the carbon atom in alpha position of the carboxylic acid is always a tertiary carbon atom, the carbon atom(s) in Î² position can either be primary, secondary or tertiary. Neononanoic acids (V9) with a secondary or a tertiary carbon atoms in the Î² position are defined as blocking (blocked) isomers (Schemes 2 and 3).

[Image Omitted]

The use of the glycidyl esters compositions, discussed here above, can be as monomer in binder compositions for paints and adhesives. These binders can be based on an acrylic polyol resin comprising the above composition glycidyl.

The acrylic polyol resins of the invention are based on a composition of hydroxyl functional acrylic resins (acrylic polyols) comprising a mixture of Î±,Î±-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.

A preferred composition is that the glycidyl ester mixture is based on neononanoic (C9) acid mixture where 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.

Further the neononanoic (C9) glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester or 2-methyl 2-ethyl hexanoic acid glycidyl ester or 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester.

Another embodiment is that the composition of the glycidyl ester mixture is comprising 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) below 40%, preferably below 30% and most preferably below or equal 25% weight on total composition.

A further embodiment is that the composition of the glycidyl ester mixture is comprising 2-methyl 2-ethyl hexanoic acid glycidyl ester above 10%, preferably above 30% and most preferably above 45% weight on total composition.

A further embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester and 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) is above 40%, preferably 55% and most preferably 65% weight on total composition.

A further embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester in 1 to 15 weight % and 2-methyl 2-ethyl hexanoic acid glycidyl ester in 40 to 70 weight % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) in 8 to 32 weight % on total composition.

A further embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester in 2 to 10 weight % and 2-methyl 2-ethyl hexanoic acid glycidyl ester in 47 to 61 weight % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) in 10 to 25 weight % on total composition.

The invention is also about the process to prepare the acrylic polyol resins compositions, which are obtained by the incorporation of the mixture of Î±,Î±-branched alkane carboxylic glycidyl esters, as characterized above, into a hydroxyl functional acrylic resins by the reaction of the epoxy group with the carboxylic acid group of ethylene carboxylic acid compounds from hydroxyl ethylene carboxylate ester monomers which are then reacted with one or more unsaturated monomers via a radical polymerization reaction, in one step or more.

The ethylene carboxylic acid compounds are for example acrylic acid, methacrylic acid, and the like.

The other unsaturated monomers are selected from the group consisting of octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, undecyl acrylate, undecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isotridecyl acrylate, isotridecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, and stearyl methacrylate, lauryl acrylate, lauryl methacrylate, styrene, alpha-methyl styrene, C1 to C10 (cyclo)alkyl acrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid or a combination thereof.

A further process to prepare the acrylic polyol resins of the invention are cooked it while having a polyester polyol or a polyether polyol or a mixture thereof as initial reactor charge.

The acrylic polyol resins of the invention prepared according to the above processes will have a calculated hydroxyl value between 50 and 180 mgKOH/g on solid and or the number average molecular weight (Mn) is between 2500 and 50000 Dalton according polystyrene standard.

The invention is also related to a binder composition useful for coating composition comprising at least any hydroxyl functional acrylic resins as prepared above.

The said binder compositions are suitable for coating metal or plastic substrates.

EXAMPLESChemicals Used

Carduraâ„¢ 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)

TABLE 2Composition of the neononanoic glycidyl ester (accordingto the described gas chromatography method for glycidylesters of neo-acid)Glycidyl ester ofacid V9XX(described inTable 1)A (%)B (%)C (%)D (%)E (%)V9016.50.13.70.10.1V9020.62.550.62.42.65V9031.10.70.31.00.4V9040.810.12.20.4V9050.213.10.54.114.5V9060.411.60.49.612.6V9070.215.40.136.45.6V9080.100.10.00.0V90954.82.5552.82.42.65V910 K17.8010.00.00.0V910 K27.70.612.80.40.7V9112.41.20.72.00.8V9120.028.30.022.433.5V9136.80.16.40.10.1V9144.503.80.00.0V9150.622.30.616.825.3V9164.40.15.20.10.1V9171.10.42.10.10.4

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 50wt %, Toluene 30wt %, 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: â€˜BYK 10 wt %â€™ which is BYK-331 diluted at 10% in butyl acetate
Catalyst: â€˜DBTDL 1 wt %â€™ which is Dibutyl Tin Dilaurate diluted at 1 wt % in butyl acetate
Catalyst: â€˜DBTDL 10 wt %â€™ which is Dibutyl Tin Dilaurate diluted at 10 wt % in butyl acetate

Example 01

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 135Â° 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 135Â° C. for 1 h. The acrylic polyol had a molecular weight (Mw) of 11400 Daltons and a Tg of about âˆ’10Â° C.

Example 02 Comparative

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 135Â° 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 135Â° C. for 1 h. The acrylic polyol had a molecular weight (Mw) of 8600 Daltons and a Tg of about +26Â° C.

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

Example 03

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

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.

TABLE 3Compositions of the adducts intakes in parts by weightAcrylic acidMeth acrylic acidadductadductInitial reactor chargeGE9S250250Acrylic acid80Methacrylic acid96.5Radical Inhibitor4-Methoxy phenol0.4630.463CatalystDABCO T9 (0.07 wt % on Glycidyl0.1750.175ester)

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 80Â° C., where an exothermic reaction starts, increasing the temperature to about 100Â° C.
The temperature of 100Â° 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

A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 4) heated to 160Â° 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 160Â° C. Finally the polymer is cooled down to 135Â° C. and diluted to a solids content of about 68% with xylene.

TABLE 4Acrylic resins recipeWeight %in Reactor 1 L (g)Initial Reactor ChargeGE9S or GE9H (Comparative)28.2169.1Xylene2.716.2Feeding materialsAcrylic acid1059.8Hydroxy ethyl methacrylate16.096.0Styrene30.0180.0Methyl methacrylate15.895.0Di t-Amyl peroxide4.024.0Xylene8.349.8Post cookingDi t-Amyl peroxide1.06.0Xylene3.018.0Solvent adding at 130Â° C.Xylene50.8305.0Final solids content61.8%Hydroxyl content4.12%

Example 05

Clear Coats for Automotive Refinish

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

TABLE 5Thinner compositionThinnerWeight % in solvent blend, theoryToluene30.1%ShellSolA34.9%2-ethoxyethyl acetate10.0%n-Butyl acetate25.0%Totalâ€‰100%

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

TABLE 6Clearcoat formulationResin ofDesmodurBYK 10 wt % DBTDL 1 wt % example ex 04N3390in ButAcin ButAcThinner80.127.010.531.1740.45

Clearcoat propertiesGE9H (Comparative)GE9SVolatile organic content480 g/l481 g/lInitial viscosity54 cP54 cPDust free time12 minutes14.5 minutesKoenig Hardness after 6 hours8.3 s7.1 s

Example 06

Acrylic Resins for First Finish Automotive Topcoats

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

A reactor for acrylic polyols is flushed with nitrogen and the initial reactor charge (see Table 7) heated to 140Â° 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 140Â° 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%.

TABLE 7Acrylic resins recipeIntakes (parts by weight)Initial reactor chargeGE9S164.40Xylene147.84Monomer mixtureAcrylic acid53.11Butyl methacrylate76.88Butyl acrylate48.82Hydroxy-ethyl methacrylate27.20Styrene177.41Methyl methacrylate47.31InitiatorDi-tert.-amyl peroxide (DTAP)8.87Post additionDi-tert.-amyl peroxide5.91Solvent (to dilute to 60% solids)Butyl acetate246.00Total1000.0

Clear Lacquer Formulation

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.

TABLE 8Clear lacquer formulations and properties of the polymersIntakes(part by weight)IngredientsAcrylic polymer60.0Cymel 11588.8Butyl acetate (to application viscosity)24.1PropertiesSolids content [% m/m]45.3Density [g/ml]0.97VOC [g/l]531

Application and Cure

The coatings are applied with a barcoater on Q-panels to achieve a dry film thickness of about 40 Î¼m. The systems are flashed-off at room temperature for 15 minutes, then baked at 140Â° C. for 30 minutes. Tests on the cured systems are carried out after 1 day at 23Â° C.

Example 07

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 150Â° 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 150Â° 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 150Â° 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 150Â° C. The reactor content was cooled down to 100Â° C. and 100 parts of EPR were distilled off at atmospheric pressure.

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

TABLE 9Composition of polyolMaterialsIntake (g)Initial chargeEPR90GE9S188.6Monomer Addition 1AA68Styrene160GE9S37.7HEMA52EPR40DCP10Monomer Addition 2AA30IBMA142HEMA108DCP5EPR45TOTAL976.3

Example 08

Maleate Diester Based Resin Prepared According to the Teaching of WO2005040241

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

Manufacturing procedure of the maleate diester:

Maleic anhydride was reacted with the selected alcohol (3,3,5 trimethyl cyclohexanol) in an equimolar ratio at 110Â° 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.

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 110Â° C. The system was then allowed to react further for 1 hour at 110Â° C.

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

The reactor was flushed with nitrogen and the initial reactor charge was heated to the polymerization temperature of 150Â° 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.

TABLE 10Composition of TMCH maleate based resinParts byweightInitial ReactorBuAc8Charge [g]Maleate diester40.7Initiator start [g]Di tert amyl peroxide0.4Monomer feed [g]BuAc3Hydroxyethyl methacrylate21.5Styrene20Methyl methacrylate17.8Methacrylic Acid2.2Di tert amyl peroxide3.6Post cooking [g]DTAP (with 10 g BuAc)1Total intake [g]118.2

Example 09

Polyester-Ether Resin

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.

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

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.