# Patent

## Title
Glycidyl esters of alpha, alpha branched acids compositions

## Abstract

The invention relates to compositions of α,α-branched alkane carboxylic acids glycidyl esters with a define isomeric composition where the sum of the concentration of the blocked and of the highly branched isomers is at least 50%, preferably above 60% and most preferably above 75% on total composition.

## Background
The present invention relates to a composition of α,α-branched alkane carboxylic acids glycidyl esters with a defined isomeric composition; which can lead for example to improved hardness of the coatings derived thereof.
More in particular the invention relates to the compositions of aliphatic tertiary saturated carboxylic acids or α,α-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 oligomerisation process thereof, and which is defined as below.
It is generally known from e.g. U.S. Pat. Nos. 2,831,877, 2,876,241, 3,053,869, 2,967,873 and 3,061,621 that mixtures of α,α-branched alkane carboxylic acids can be produced, starting from mono-olefins, such as butenes and isomers such as isobutene, carbon monoxide and water, in the presence of a strong acid.
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, for example, neononanoic acids give different and unexpected performance in combination with some particular polymers such as polyester polyols.
The isomers are described in Table 1 and illustrated in FIG. 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, R2 and 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.
Mixture compositions of neononanoic acids glycidyl esters providing for example a high hardness of a coating, is a mixture where the sum of the concentration of the blocked and of the highly branched isomers is at least 50%, preferably above 60% and most preferably above 75% on total composition.
The composition of the glycidyl ester mixture is comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester.
The composition of the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester and 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester.
The composition of the glycidyl ester mixture in which the sum of the following content of glycidyl ester mixture, comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester, is above 25% weight, preferably above 35% weight and most preferably above 40% weight on total composition.
The composition of the glycidyl ester mixture in which the sum of the following content of glycidyl ester mixture, comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester and 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester and 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester, is above 40% weight, preferably above 50% weight and most preferably above 65% weight on total composition.
The composition of the glycidyl ester mixture in which the content of 2-methyl 2-ethyl hexanoic acid glycidyl ester is below 40% weight, preferably below 30% weight and most preferably below 20% weight on total composition.
The composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester in 1 to 99 weight % and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 1 to 99 weight % and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester in 1 to 99 weight % on total composition.
A preferred composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester in 5 to 50 weight % and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 5 to 50 weight % and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester in 5 to 50 weight % on total composition.
A further preferred composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester in 10 to 14 weight % and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 20 to 28 weight % and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester in 17 to 22 weight % on total composition.
The composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 1 to 99 weight % and 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester in 1 to 99 weight %.
A preferred composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 5 to 50 weight % and 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester in 5 to 50 weight %.
A further preferred composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 10 to 18 weight % and 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester in 15 to 22 weight %.
The above glycidyl esters compositions can be used for example, is as reactive diluent or as monomer 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 Hexion (Product Bulletin: Cardura N10 The Unique Reactive Diluent).
Other uses of the glycidyl ester are the combinations with polyester polyols, or acrylic polyols, or polyether polyols. The combination with polyester polyols such as the one used in the car industry coating leads to a fast drying coating system with attractive coating properties.
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 m×0.25 mm, df=0.2 μm
Oven program: 150° C. (1.5 min)−3.5° C./min−250° 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: 250° C.
Detector temp: 325° C.
Injection volume: 1 μL
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)—C—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 FIG. 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 1







Structure of all possible neononanoic isomers



















Retention






Methyl
Block-
time



R1
R2
R3
groups
ing
[Minutes]

















V901
Methyl
Methyl
n-pentyl
3
No
8.90


V902
Methyl
Methyl
2-pentyl
4
Yes
9.18


V903
Methyl
Methyl
2-methyl
4
No
8.6





butyl


V904
Methyl
Methyl
3-methyl
4
No
8.08





butyl


V905
Methyl
Methyl
1,1-dimethyl
5
Yes
10.21





propyl


V906
Methyl
Methyl
1,2-dimethy
5
Yes
9.57





propyl


V907
Methyl
Methyl
2,2-dimethyl
5
No
8.26





propyl


V908
Methyl
Methyl
3-pentyl
4
Yes
9.45


V909
Methyl
Ethyl
n-butyl
3
No
9.28


V910
Methyl
Ethyl
s-butyl
4
Yes
9.74


K1


V910
Methyl
Ethyl
s-butyl
4
Yes
9.84


K2


V911
Methyl
Ethyl
i-butyl
4
No
8.71


V912
Methyl
Ethyl
t-butyl
5
Yes
9.64


V913
Methyl
n-propyl
n-propyl
3
No
8.96


V914
Methyl
n-propyl
i-propyl
4
Yes
9.30


V915
Methyl
i-propyl
i-propyl
5
Yes
9.74


V916
Ethyl
Ethyl
n-propyl
3
No
9.44


V917
Ethyl
Ethyl
i-propyl
4
Yes
10.00









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 m×0.2 mm, df=0.52 μm
Oven: 175° C. (5 min)−1° C./min−190° C. (0 min)−10° C./min−275° C. (11.5 min)
Flow: 2.0 mL/min, constant flow
Carrier gas: Helium
Split ratio: 1:75
Injection volume: 1 μL
S/SL injector: 250° 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)—C—COO—CH2—CH(O)CH2 where 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.




Test 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 (Ww−Wd)/Ww×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 110° 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 10° 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.
Methods for the Characterization of the Clear Coats
Pot-Life
Pot-life is determined by observing the elapsed time for doubling of the initial viscosity at room temperature, usually 24.0±0.5° C. The initial viscosity of the clear coat is defined at 44-46 mPa·s for Part 1 and 93-108 mPa·s for Part 3 measured with Brookfield viscometer.
Application of Clearcoat
Q-panels are used as substrates. Then the panels are cleaned by a fast evaporating solvent methyl ethyl ketone or acetone. For Part 1 the clearcoat is spray-applied on Q-panels covered with basecoat; for Parts 2 & 3 the clearcoat is barcoated directly on Q-panels.
Dust Free Time
The dust free time (DFT) of clear coat is evaluated by vertically dropping a cotton wool ball on a flat substrate from a defined distance. When the cotton ball contacts with the substrate, the substrate is immediately turned over. The dust free time is defined as the time interval at which the cotton wool ball no longer adhered to the substrate.
Hardness Development
Hardness development is followed using pendulum hardness tester with Koenig method.
Blocking Isomers
Whereas the carbon atom in alpha position of the carboxylic acid is always a quaternary carbon atom, the carbon atom(s) in β position can either be tertiary, or quaternary. Neononanoic acids (V9) with a tertiary or a quaternary carbon atom in the β position are defined as blocking isomers (FIGS. 2 and 3).




    
    
        FIG. 2: Example of a Non-blocked V9 Structure
        
            FIG. 3: Example of a Blocked V9 Structure β
        
        
    
    


The use of the glycidyl esters compositions, discussed here above, is as reactive diluent or as monomer in binder compositions for paints and adhesives. These uses can be based on a polyester polyol resin comprising the above composition glycidyl ester and/or an acrylic polyol resin comprising the above composition glycidyl ester and/or a polyether polyol resin comprising the above composition glycidyl ester and/or an epoxy resin formulation comprising the above composition glycidyl ester.


EXAMPLES
Chemicals Used


    
    
        CarduraTM 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 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









    
    
        GE5: glycidyl ester of pivalic acid obtained by reaction of the acid with epichlorhydrin.
        Ethylene glycol from Aldrich
        Monopentaerythritol: available from Sigma-Aldrich
        Methylhexahydrophtalic anhydride: available from Sigma-Aldrich
        Boron trifluoride diethyl etherate (BF3.OEt2) from Aldrich
        Acrylic 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
        Xylene
        Di-t-Amyl Peroxide is Luperox DTA from Arkema
        tert-Butyl peroxy-3,5,5-trimethylhexanoate: available from Akzo Nobel
        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
    
    


Example 1 Comparative
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 h20 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 2
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 h18 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.
Observations: Tg of acrylic polyols is impacted by the composition of the neononanoic glycidyl ester (see examples 1, 2).
Example 3
The Adducts of Glycidyl Neononanoate, GE9H and Acrylic Acid or Methacrylic Acid
The adducts of Glycidyl neononanoate GE9H (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 3







Compositions of the adducts intakes in parts by weight












Acrylic acid
Meth acrylic 




adduct
acid adduct















Initial reactor charge





GE9H
250
250



Acrylic acid
80




Methacrylic acid

96.5



Radical Inhibitor





4-Methoxy phenol
0.463
0.463



Catalyst





DABCO T9 (0.07 wt % 
0.175
0.175



on Glycidyl 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 4
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 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.







TABLE 4







Acrylic resins recipe












Weight %
in Reactor 1 L (g)















Initial Reactor Charge





GE9H or GE9S (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 5
Clear Coats for Automotive Refinish
Solvents were blended to yield a thinner mixture of the following composition (table 5):







TABLE 5







Thinner composition


A clearcoat was then formulated (table 6) 


with the following ingredients (parts by weight):











Weight % in 



Thinner
solvent blend, theory







Toluene
30.1%



ShellSolA
34.9%



2-ethoxyethyl acetate
10.0%



n-Butyl acetate
25.0%



Total
 100%

















TABLE 6







Clearcoat formulation











Resin of example
Desmodur 
BYK 10 
DBTDL 1 



ex 4
N3390
wt % in ButAc
wt % in ButAc
Thinner





80.1
27.01
0.53
1.17
40.45


























GE9S



Clearcoat properties
GE9H
(Comparative)






















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 
8.3 
s
7.1 
s



after 6 hours










Example 6
Acrylic Resins for First Finish Automotive Topcoats
GE9H 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 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%.







TABLE 7







Acrylic resins recipe











Intakes (parts by weight )














Initial reactor charge




GE9H
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

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 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
24.1



viscosity)




Properties




Solids content [% m/m]
45.3



Density [g/ml]
0.97



VOC [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 μm. 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 7
In a reactor equipped with an anchor stirrer, a thermometer, condenser and monomer/initiator feeding system, 188.6 g of GE9H 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 GE9H 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.
The polyacrylate polyol has a solids content of the solution of 90% by weight.







TABLE 9







Composition of polyol












Materials
Intake (g)















Initial charge
EPR
90




GE9H
188.6



Monomer Addition 1
AA
68




Styrene
160




GE9H
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 8 Comparative
The following constituents were charged to a reaction vessel: 0.7153 grams of a neononanoic glycidyl ester of composition C, 0.5958 grams of hexahydro-4-methylphthalic anhydride, 0.0014 grams of ethylene glycol. The reaction took place for 3 to 4 days at 140° C. The sample has been dried by evaporation. The polyester had a molecular weight (Mn) of 4700 Daltons and a Tg of +18.8° C.
Example 9
The following constituents were charged to a reaction vessel: 0.5823 grams of a neononanoic glycidyl ester of composition D, 0.4775 grams of hexahydro-4-methylphthalic anhydride, 0.0011 grams of ethylene glycol, 0.2841 grams of n-Butyl Acetate. The reaction took place for 3 to 4 days at 120-140° C. and the solvent was then thoroughly removed by evaporation. The polyester had a molecular weight (Mn) of 5000 Daltons and a Tg of +43.7° C.
Example 10
The following constituents were charged to a reaction vessel: 0.5846 grams of a neononanoic glycidyl ester of composition E, 0.4786 grams of hexahydro-4-methylphthalic anhydride, 0.0011 grams of ethylene glycol, 0.2847 grams of n-Butyl Acetate. The reaction took place for 3 to 4 days at 120-140° C. and the solvent was then thoroughly removed by evaporation. The polyester had a molecular weight (Mn) of 3800 Daltons and a Tg of +48.1° C.
Observations: Tg of polyesters is impacted by the composition of the neononanoic glycidyl ester (see examples 8, 9, 10).
The resins of the examples can be formulated in coating compositions such as 2K (polyurethane) with a low VOC (volatile organic compound) level and still providing and excellent appearance.
Example 11 Comparative
Monopentaerythritol, methylhexahydrophthalic anhydride and n-Butyl Acetate (see 1°/in Table 10) were charged to a reaction vessel and heated at 140° C. until complete conversion. Cardura E10P (see 1°/in Table 10) was then dropwise added and the reaction pursued until acceptable acid value. The polyester had a solid content of 76.0 wt %. At a suitable temperature, Cardura E10P and xylene (see 2°/in Table 10) were then added. The mixture was heated to about 157° C. and the monomers, radical initiator and solvent (see 3°/in Table 10) were fed for 6 hours at that temperature. A post-cooking (1 h) then took place with additional radical initiator (see 4°/in Table 10). After further addition of n-butyl acetate (see 5°/in Table 10), the final resin had a solid content of 66.2 wt %.
Example 12
Recipe of example 11 was used with the amount indicated in table 10 while using GE9H instead of Cardura E10P for the polyester cooking. The intermediate polyester and the final resin had a solid content of 78.4 wt % and 66.8 wt %, respectively.
Example 13
Recipe of example 12 was used with the amount indicated in table 10 while using GE9H instead of Cardura E10P for the acrylic polyol cooking. The intermediate polyester and the final resin had a solid content of 78.4 wt % and 68.3 wt %, respectively.







TABLE 10







Constituents for the polyester based acrylic polyol cooking











Example 11
Example 12
Example 13










1°/Polyester cooking, constituent (g)










Monopentaerythritol
4.0
4.2
3.4


Methylhexahydrophthalic 
15.2
15.9
12.7


anhydride





n-Butyl acetate
10.0
10.4
8.3


Cardura E10P
22.3




GE9H

21.9
17.5







2°/Acrylic polyol cooking, initial reactor charge (g)










Polyester (from above)
51.5
52.3
41.8


Cardura E10P
33.2
31.3
—


GE9H
—
—
24.9


Xylene
3.6
3.4
2.9







3°/Acrylic polyol cooking, feeding material (g)










Acrylic Acid
9.5
9.0
7.6


Hydroxyethyl methacrylate
23.9
22.5
19.0


Styrene
39.8
37.5
31.7


Butyl Acrylate
0.0
0.0
0.8


Methyl methacrylate
26.3
24.8
21.6


Xylene
11.0
10.4
8.8


Di-t-Amyl Peroxide
5.3
5.0
4.2







4°/Acrylic polyol post cooking, feeding material (g)










Di-t-Amyl Peroxide
1.3
1.3
1.1







5°/Acrylic polyol solid content adjustment, solvent adding (g)










n-Butyl acetate
55.7
52.6
44.4









Formulation of the Clear Coats

A clear coat is formulated with one of the polyester based acrylic polyol (from examples 11, 12 or 13, the curing agent (HDI, Desmodur N3390), the thinner, the levelling agent (BYK-331) and the catalyst (dibutyltin dilaurate, DBTDL) according to the amounts indicated in table 11.







TABLE 11







Clear coats, formulations














Binder
Binder

BYK
DBTDL 
Thinner


CE-Example
(ID)
(g)
HDI (g)
10 wt % (g)
1 wt % (g)
A (g)





CE-11
From Example 11
92.1
34.7
0.67
1.47
37.2


CE-12
From Example 12
91.3
36.0
0.66
1.46
37.4


CE-13
From Example 13
91.3
36.9
0.68
1.50
39.7









Characterization of the Clear Coats

The clearcoat formulations (from table 11) are barcoat applied on degreased Q-panel. The panels are dried at room temperature, optionally with a preliminary stoving at 60° C. for 30 min. Clear coats have been characterized among others by measuring the dust free time and Koenig hardness development (see table 12).







TABLE 12







Clear coats, drying (curing) properties











CE-11
CE-12
CE-13










1°/Dust free time (Room temperature drying panels) (min)










Dust free time (min)
39
35
24







2°/Koenig Hardness (Room temperature drying panels) (sec)










 6 hours
3
4
7


24 hours
31
38
49


 7 days
156
167
179







3°/Koenig Hardness (Stoved Q panels) (sec)










Out of the oven
12
15
24


 6 hours
15
18
29


24 hours
48
55
67


 7 days
178
180
190









Observation (see table 12): significant improvement (lower dust free time and quicker hardness development) is observed when replacing Cardura E10P by GE9H for the polyester cooking. Improvement is even more significant when Cardura E10P is complementary replaced by GE9H for the acrylic polyol cooking.
Example 14 Comparative
Monopentaerythritol/Methylhexahydrophtalic anhydride/GE9S (1/3/3 molar ratio)=CE-GE9S
80.4 g amount of butylacetate, 68.3 g of monopentaerythritol, 258.2 g of methylhexahydrophthalic anhydride are loaded in a glass reactor and heated to reflux until complete dissolution. Afterwards, the temperature is decreased down to 120° C. and 333.0 g of GE9S are added over about one hour. The cooking is pursued at 120° C. for the time needed to decrease epoxy group content and acid value down to an acid value below 15 mg KOH/g. Then, further 82.4 g of butylacetate are added. Test results are indicated in table 13.
Example 15a
Monopentaerythritol/Methylhexahydrophtalic anhydride/GE9H (1/3/3 molar ratio)=CE-GE9Ha
80.4 g amount of butylacetate, 68.3 g of monopentaerythritol, 258.2 g of methylhexahydrophthalic anhydride are loaded in a glass reactor and heated to reflux until complete dissolution. Afterwards, the temperature is decreased down to 120° C. and 337.1 g of GE9H are added over about one hour. The cooking is pursued at 120° C. for the time needed to decrease epoxy group content and acid value down to an acid value below 15 mg KOH/g. Then, further 83.4 g of butylacetate are added. Test results are indicated in table 13.
Example 15b
Monopentaerythritol/Methylhexahydrophtalic Anhydride/GE9H (1/3/3 Molar Ratio)=CE-GE9Hb
CE-GE9Hb is a duplication of Example 15a performed in very close experimental conditions.
Example 16a Comparative According to EP 0996657
Monopentaerythritol/Methylhexahydrophtalic Anhydride/GE5 (1/3/3 Molar Ratio) CE-GE5a
71.3 g amount of butylacetate, 60.5 g of monopentaerythritol, 228.90 g of methylhexahydrophthalic anhydride are loaded in a glass reactor and heated to reflux until complete dissolution. Afterwards, the temperature is decreased down to 120° C. and 214.3 g of GE5 are added over about one hour. The cooking is pursued at 120° C. for the time needed to decrease epoxy group content and acid value down to an acid value below 15 mg KOH/g. Then, further 52.1 g of butylacetate are added. Test results are indicated in table 13.
Example 16b Comparative According to EP 0996657
Monopentaerythritol/Methylhexahydrophtalic Anhydride/GE5 (1/3/3 Molar Ratio) CE-GE5b
CE-GE5b is a duplication of comparative example 16a performed in very close experimental conditions except for the higher amount of butylacetate added at the end of the reaction.







TABLE 13







Polyesters characterization














Mw
Mn
Mw/Mn



Polyester resin
SC (%)
(Da)
(Da)
(PDI)
Viscosity (cP)















CE-GE9S
78.6
974
919
1.06
2450 (25.9° C.)


CE-GE9Ha
80.0
921
877
1.05
6220







(25.9° C.)


CE-GE9Hb
80.0
1014
975
1.04
11740







(21.6° C.)


CE-GE5a
79.3
914
886
1.03
5080







(26.0° C.)


CE-GE5b
68.3
1177
1122
1.05
102.3







(22.0° C.)





SC: solids content






Example 17 Comparative
Acrylic Resin Synthesis
CarduraTM E10 Based Acrylic Polyol Resin: Acryl-CE(10)
105.0 g amount of CE10 (CarduraTM E10-glycidyl ester of Versatic acid) and 131.6 g of Shellsol A are loaded in a glass reactor and heated up to 157.5° C. Then, a mixture of monomers (37.4 g acrylic acid, 107.9 g hydroxyethyl methacrylate, 180.0 g styrene, 100.2 g butyl acrylate, 69.6 g methyl methacrylate) and initiator (12.0 g Di-tert-butyl peroxide) is fed into the reactor at a constant rate in 5 hours. Then post cooking started: a mixture of 6.0 g Di-tert-butyl peroxide and 18.0 g n-butyl acetate is fed into the reactor at a constant rate in 0.5 hour, then temperature maintained at about 157.5° C. for a further 0.5 hour. Finally, 183.2 g of n-butyl acetate is added under stirring to achieve a polyol resin with the target solids content. Test results are indicated in table 14.







TABLE 14







Acryl-CE(10) characterization














SC (%)-
Mw
Mn
Mw/Mn



Acryl-
measured
(Da)
(Da)
(PDI)







CE(10)
65.2
5094
2629
1.94










Three types of formulations have been prepared:

    
    
        Blend Acryl-CE(10) blend with CE-GEx polyester with Desmodur as hardener (Part 1)
        CE-GEx polyester alone with Tolonate HDT LV2 as hardener (0.03 wt % DBTDL)(Part 2)
        CE-GEx polyester alone with Tolonate HDT LV2 as hardener (0.09 wt % DBTDL) (Part 3)
    
    


Part 1: CE-GEx Polyesters Blend with Acryl-CE(10) Formulation







TABLE 15







Clear coats, formulations

















BYK 10
DBTDL




Binder 1
Binder 2
HDI
wt %
1 wt %
Thinner A


CE-GEx
(g)
(g)
(g)
(g)
(g)
(g)





GE9Hb
71.6
16.9
31.2
0.63
1.39
86.33


GE5b
79.1
12.4
31.2
0.63
1.39
89.30





Binder 1: Acryl-CE(10)


Binder 2: CE-GEx polyesters






Part 2—CE-GEx Polyesters Alone, No Acryl-CE(10) Formulation (0.03 wt % DBTDL)







TABLE 16







Clear coats, formulations


















DBTDL





Binder 
HDI
BYK 10
1 wt %
Thinner



CE-GEx 
2 (g)
(g)
wt % (g)
(g)
B (g)







GE9S
80.0
36.56
0.72
3.15
89.75



GE9Ha
80.4
37.27
0.73
3.20
87.83



GE5a
79.9
43.18
0.76
3.36
94.82










Part 3—CE-GEx Polyesters Alone, No Acryl-CE(10) Formulation (0.09 wt % DBTDL)







TABLE 17







Clear coats, formulations

















BYK
DBTDL





Binder 
HDI
10 wt % 
1 wt %
Thinner 



CE-GEx
2 (g)
(g)
(g)
(g)
B (g)







GE9Ha
60.0
28.10
0.54
7.18
15.40



GE5a
59.8
32.54
0.57
7.57
17.79










Characterization of the Clear Coats

The clearcoat formulations are barcoat applied on degreased Q-panel for Parts 2 & 3; sprayed for the Part 1 on Q-panel with a basecoat. The panels are dried at room temperature, optionally with a preliminary stoving at 60° C. for 30 min.
Part 1—CE-GEx Polyesters Blend with Acryl-CE(10)/Room Temperature curing







TABLE 18







Clear coats, performances
















Drying
DFT (min)



CE-GEx
SC (%)
Potlife (h)
conditions
Cotton Balls







GE9Hb
47.1
4.5
RT
15



GESb
46.2
4.0
RT
19







SC: solids content,



RT: room temperature






Part 2—CE-GEx Polyesters Alone, No Acryl-CE(10)/Room Temperature Curing and Room Temperature Drying after Stoving







TABLE 19







Clear coats, performances










DFT




(min)












SC
Drying
Cotton
Koenig Hardness (s)













CE-GEx
(%)
conditions
Balls
6 h
24 h
7 d
















GE9S
48.4
RT
223
3
17
159


GE9Ha
49.2
RT
 91
3
36
212


GE5a
49.5
RT
114
1
29
216


GE9S
48.4
Stoving 30
Dust free
4
44
174




min/60° C.
out of





oven


GE9Ha
49.2
Stoving 30
Dust free
10
55
211




min/60° C.
out of





oven


GE5a
49.5
Stoving 30
Dust free
6
49
216




min/60° C.
out of





oven









Part 3—CE-GEx Polyesters Alone, No Acryl-CE(10)/Room Temperature Curing and Room Temperature Drying after Stoving (0.09 wt % DBTDL)







TABLE 20







Clear coats, performances














DFT




Pot-

(min)













SC
life
Drying
Cotton
Koenig Hardness (s)














CE-GEx
(%)
(min)
conditions
Balls
6 h
24 h
7 d

















GE9Ha
69.8
42.4
RT
47
3
66
193


GE5a
68.5
61.3
RT
73
3
55
191


GE9Ha
69.8
42.4
Stoving 30
Dust free
29
102
210





min/60° C.
out of






oven


GE5a
68.5
61.3
Stoving 30
Dust free
12
69
205





min/60° C.
out of






oven









Observations

Part 1

The potlife is about the same, the dust free time is shorter for GE9Hb vs. GE5b.
Part 2
The 24 h hardness order GE9H, GE5 and GE9S and the dust free time at room temperature is the best for GE9H.
Part 3
The hardness development is the best for GE9H at room temperature and heat cure, the dust free time at room temperature is quicker for GE9H than for GE5; and with a volatile organic content of 300 g/l.
Example 18
The following constituents were charged to a reaction vessel: 2.5500 grams of a neononanoic glycidyl ester of composition D, 1.1571 grams of dichloromethane, 0.0137 grams of boron trifluoride diethyl etherate. The reaction took place for 3 days at room temperature and the solvent was then thoroughly removed by evaporation. The polyether had a molecular weight (Mw) of 1900 Daltons and a Tg of −40.5° C.
Example 19 Comparative
The following constituents were charged to a reaction vessel: 2.5438 grams of a neononanoic glycidyl ester of composition C, 1.0150 grams of dichloromethane, 0.0128 grams of boron trifluoride diethyl etherate. The reaction took place for 3 days at room temperature and the solvent was then thoroughly removed by evaporation. The polyether had a molecular weight (Mw) of 1500 Daltons and a Tg of −51.1° C.
Observations: Tg of the modified polyether resin is impacted by the composition of the neononanoic glycidyl ester (see examples 18, 19).
Example 20
Polyether Resin
The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 134 grams of di-Trimethylol propane (DTMP), 900 grams of glycidyl neononanoate, GE9H, 135.5 grams of n-butylacetate (BAC) and 2.5 grams of Tin 2 Octoate. The mixture was heated to its reflux temperature of about 180° C. for about 4 hours till the glycidyl neononaoate was converted to an epoxy group content of less than 0.12 mg/g. After cooling down the polyether had a solids content of about 88%.
Example 21 Comparative
Polyether Resin
The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 28.8 grams of monopentaerythritol, 201.5 grams of Cardura E10P, 19.4 grams of n-butylacetate and 0.3552 grams of Tin (II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 6 hours till the Cardura E10P was converted to an epoxy group content of about 25 mmol/kg. After cooling down the polyether had a solids content of about 94%.
Example 22 Comparative
Polyether Resin
The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 28.8 grams of monopentaerythritol, 187.1 grams of GE9S, 18.3 grams of n-butylacetate and 0.3550 grams of Tin (II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 5.5 hours till the GE9S was converted to an epoxy group content of about 29 mmol/kg. After cooling down the polyether had a solids content of about 95%.
Example 23
Polyether Resin
The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 28.8 grams of monopentaerythritol, 189.4 grams of GE9H, 18.5 grams of n-butylacetate and 0.3572 grams of Tin (II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 4 hours till the GE9H was converted to an epoxy group content of about 27 mmol/kg. After cooling down the polyether had a solids content of about 95%.
Example 24 Comparative
Polyether Resin
The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 29.0 grams of monopentaerythritol, 136.7 grams of GE5, 14.0 grams of n-butylacetate and 0.3597 grams of Tin (II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 5.7 hours till the GE5 was converted to an epoxy group content of about 27 mmol/kg. After cooling down the polyether had a solids content of about 94%.
Formulation of the Clear Coats
A clear coat is formulated with one of the polyether (from examples 21, 22, 23 or 24, the curing agent (HDI, Desmodur N3390), the thinner (Methyl Amyl Ketone), the levelling agent (BYK-331) and the catalyst (dibutyltin dilaurate, DBTDL) according to the amounts indicated in table 21.







TABLE 21







Clear coats, formulations

















BYK
DBTDL



CEP-
Binder
Binder
HDI
10 wt %
1 wt %
Thinner


Example
(ID)
(g)
(g)
(g)
(g)
(g)
















CEP-21
From Exam-
40.1
30.7
0.47
1.03
15.1



ple 21


CEP-22
From Exam-
40.0
33.0
0.48
1.07
>12.5



ple 22


CEP-23
From Exam-
40.0
32.5
0.48
1.06
17.7



ple 23


CEP-24
From Exam-
40.1
42.9
0.54
1.20
17.7



ple 24









Characterization of the Clear Coats

The clearcoat formulations (from table 21) are barcoat applied on degreased Q-panel, optionally on basecoated Q-panel. The panels are dried at room temperature after a preliminary stoving at 60° C. for 30 min. Clear coats have been characterized among others by measuring the Koenig hardness development (see table 22).







TABLE 22







Clear coats, drying (curing) properties












CEP-21
CEP-22
CEP-23
CEP-24










1°/Koenig Hardness (Degreased Q panels) (sec)











 6 hours
8
10
11
10


24 hours
10
11
47
42


 7 days
18
20
94
122







2°/Koenig Hardness (Basecoated Q panels) (sec)











 6 hours
7
8
7
8


24 hours
8
8
14
17


 7 days
12
13
34
48









Observation (see table 22): significant improvement (quicker hardness development) is observed when replacing Cardura E10P or GE9S by GE9H for the polyether cooking. Early hardness improvement on degreased Q-panels is better for example CEP-23 than for example CEP-24.
Example 25
Preparation for Vacuum Infusion of Composite Structures
A resin for vacuum infusion of large structures such as yacht and wind turbines was prepared by mixing 27.7 part by weight of curing agent blend and 100 part of epoxy resins blend described here:
Epoxy resins blend: 850 part by weight Epikote 828 and 150 part of glycidyl neononanoate, GE9H.
Curing Agent blend: 650 part by weight of Jeffamine D230 and Jeffamine D230 is a polyoxyalkyleneamines available from Huntsman Corporation. Epikote 828 is an epoxy resin available from Momentive Specialty Chemicals.
Example 26
Example of Trowellable Floor and Patching Compound
The ingredients presented in the table 23 below were mixed for the preparation of a trowellable flooring compound







TABLE 23







Preparation of a trowellable flooring compound











Weight
Volume




(parts)
(parts)
Supplier





BASE





COMPONENT





EPIKOTE 828LVEL
63.2
126.3
Momentive


GE9H
11.1
22.3



Byk A530
4.8
13.4
Byk Chemie







Mix the additives into the EPIKOTE resin before filler addition










Total
79.1
162.0



FILLERS





Sand 1-2 mm
582.3
496.4
SCR Sibelco


Sand 0.2-0.6 mm
298.4
254.4
SCR Sibelco


Total
880.7
750.8








Disperse into the base component using a concrete mixer










CURING AGENT





COMPONENT





EPIKURE F205
40.2
87.2
Momentive


Total
40.2
87.2








Mix the curing agent well with the EPIKOTE resin base and Fillers before application










Total formulation
1000.0
1000.0










Example 27
Formulation for a Water Based Self-leveling Flooring
The ingredients presented in the table 24 below were mixed for the preparation of a waterbased self leveling flooring system.







TABLE 24







Preparation of a waterbased self leveling flooring system











Weight





(parts)
Supplier
Comment













CURING AGENT





COMPONENT (A)





EPIKURE 8545-W-52
164.00
Momentive



(HEW = 320 g/eq)





EPIKURE 3253
4.00
Momentive
Accelerator


BYK 045
5.00
BYK CHEMIE
defoamer


Antiterra 250
4.00
BYK CHEMIE
Dispersing


Byketol WS
5.00
BYK CHEMIE
Wetting agent


Bentone EW (3% in water)
20.00
Elementis
Anti-settling







Mix the additive into the EPIKURE curing agents before filler addition










Titanium dioxide 2056
50.00
KronosTitan








Disperse the pigment for 10 minutes at 2000 rpm.










EWO-Heavy Spar
195.00
Sachtleben 
Barium 




Chemie
sulphate


Quartz powder W8
98.00
Westdeutsche





Quarzwerke








Disperse fillers at 2000 rpm for 10 minutes










Water
55.00




Sand 0.1-0.4 min
400.00
Euroquarz



Total component A
1000.00




RESIN COMPONENT (B)





EPIKOTE 828LVEL
81.00
Momentive



GE9H
19.00




Mix (B) into (A)





Total formulation A + B
1081.00





















Formulation characteristics



















Fillers + Pigment/Binder ratio
3.9
by weight



PVC
37.7%
v/v



Density
1.9
g/ml



Water content
12.5%
m/m

## Claims

1. A composition of α,α-branched alkane carboxylic glycidyl esters from butene oligomers, comprising a glycidyl ester mixture of neo-acid based on dimer or trimer of butene having both blocked isomers and highly branched isomers wherein a sum of a concentration of the blocked isomers and of the highly branched isomers is at least 60% weight based on the weight of the composition, wherein a blocked isomer comprises neo-acids having tertiary or quaternary carbon atoms in the β position and a highly branched isomer comprises neo-acids having at least 5 methyl groups, wherein the glycidyl ester mixture comprises 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester in 10 to 14 weight %, 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 20 to 28 weight % and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester in 17 to 22 weight % based on the weight of the glycidyl ester mixture, wherein the total amount of the glycidyl ester mixture is 100 weight %.

2. A binder composition for paints or adhesives comprising the composition of claim 1 as a reactive diluent or as a monomer.

3. A resin comprising the composition of claim 1 wherein the resin is selected from the group consisting of a polyester polyol resin, an acrylic polyol resin, a polyether polyol resin, or an epoxy resin formulation.

4. A composition of α,α-branched alkane carboxylic glycidyl esters from butene oligomers, comprising a glycidyl ester mixture of neo-acid based on dimer or trimer of butene having both blocked isomers and highly branched isomers wherein a sum of a concentration of the blocked isomers and of the highly branched isomers is at least 60% weight based on the weight of the composition, wherein a blocked isomer comprises neo-acids having tertiary or quaternary carbon atoms in the β position and a highly branched isomer comprises neo-acids having at least 5 methyl groups, wherein the glycidyl ester mixture comprises 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 10 to 18 weight % and 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester in 15 to 22 weight % based on the weight of the composition.

5. A binder composition for paints or adhesives comprising the composition of claim 4 as a reactive diluent or as a monomer.

6. A resin comprising the composition of claim 4 wherein the resin is selected from the group consisting of a polyester polyol resin, an acrylic polyol resin, a polyether polyol resin, or an epoxy resin formulation.